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ImagineNano2015 Abstracts Book

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Back in 2013, ImagineNano event has strengthened its position as the main event dedicated to nanoscience and nanotechnology in Europe. The outstanding results of participation that have been reached and the interest created by the discussions, have laid the foundations for the upcoming edition. ImagineNano 2015 is now an established event and is considered one of the largest European in the field. The event is an excellent platform for communication between science and business, bringing together Nanoscience and Nanotechnology in the same place. Internationally renowned speakers will be presenting the latest trends and discoveries in Nanoscience and Nanotechnology. Under the same roof will be held 5 International Conferences (Graphene, NanoSpain Chemistry, Bio&Med, Toxicology and PPM), a huge exhibition showcasing cutting-edge advances in nanotechnology research and development, an industrial forum and a brokerage event.
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O n b e h a l f o f t h e I n t e r n a t i o n a l ,

S c i e n t i f i c a n d T e c h n i c a l

C o m m i t t e e s w e t a k e g r e a t

p l e a s u r e i n w e l c o m i n g y o u t o

B i l b a o f o r t h e t h i r d e d i t i o n o f

I m a g i n e N a n o .

Back in 2013, ImagineNano event has strengthened its position as the main event dedicated to nanoscience

and nanotechnology in Europe. The outstanding results of participation that have been reached and the

interest created by the discussions, have laid the foundations for the upcoming edition.

ImagineNano 2015 is now an established event and is considered one of the largest European in the field

event is an excellent platform for communication between science and business, bringing

Nanoscience and Nanotechnology in the same place.

Internationally renowned speakers will be presenting the latest trends and discoveries in

Nanotechnology.

Under the same roof will be held 5 International Conferences (Graphene, NanoSpain Chemistry,

Toxicology and PPM), a huge exhibition showcasing cutting-edge advances in nanotechnolog

development, an industrial forum and a brokerage event.

ImagineNano will gather the global nanotechnology community, including researchers, industry

and investors.The latest trends and discoveries in N&N from some of the world´s leading players in the field

will be discussed.

We would like to thank all participants, sponsors and exhibitors that joined us this year.

The Basque Country demonstrates its strengths in nanoscience, micro and nanotechnology, and positions

itself as a major player in the “nano” world, reason why ImagineNano will be organized for the 3

Bilbao.

There´s no doubt that ImagineNano 2015 is the right place to see and be seen.

Hope to see you again in the next edition of ImagineNano (2017).

Or

ga

nis

er

s

event has strengthened its position as the main event dedicated to nanoscience

and nanotechnology in Europe. The outstanding results of participation that have been reached and the

ming edition.

the largest European in the field. The

event is an excellent platform for communication between science and business, bringing together

Internationally renowned speakers will be presenting the latest trends and discoveries in Nanoscience and

nferences (Graphene, NanoSpain Chemistry, Bio&Med,

edge advances in nanotechnology research and

ImagineNano will gather the global nanotechnology community, including researchers, industry, policymakers

The latest trends and discoveries in N&N from some of the world´s leading players in the field

exhibitors that joined us this year.

emonstrates its strengths in nanoscience, micro and nanotechnology, and positions

itself as a major player in the “nano” world, reason why ImagineNano will be organized for the 3rd

time in

I m a g i n e N a n o 2 0 1 5

General Index

Plenary Sess ion 7

Graphene 13

NanoSpa in Bio&Med 177

NanoSpa in Chemistry 217

NanoSpa in Tox ico logy 263

PPM 291

Industr ia l Forum 339

Plenar y

Sess i o n

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I n d e x

P l e n a r y S e s s i o n C o n t r i b u t i o n s

Page

Juan Ignacio Cirac (Max Planck Institute of Quantum Optics, Germany)

Quantum simulations with atoms in nano-structures 11 Jean-Marie Lehn (University of Strasbourg, France)

The Self-Organization Approach 12

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Q u a n t u m s i m u l a t i o n s w i t h a t o m s i n

n a n o - s t r u c t u r e s

Max Planck Institut für Quantenoptik, Garching, Germany

Many-body quantum systems are very hard to

simulate with classical computers, as the running

time increases exponentially with the size of the

system. Quantum simulation offers a way to

circumvent this problem. A quantum simulator is a

system where interactions can be engineered,

such that its dynamics correspond to the ones of

the system one wants to emulate. Ultra-cold

atoms in optical lattices can be used for that

purpose; in particular, to simulate many-body

problems that appear in strongly-correlated

systems. In this talk I will briefly review the field of

quantum simulations and show how photonic

crystal structures can be used to design

subwavelength optical lattices in two dimensions

for ultracold atoms, achieving a better

performance than current experimental set-ups.

Furthermore, guided modes can be used for

photon-induced large and strongly long-range

interactions between trapped atoms, giving rise to

quantum simulations which cannot be performed

with other systems.

Juan Ignacio Cirac

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T h e S e l f - O r g a n i z a t i o n A p p r o a c h

ISIS, Université de Strasbourg, France

Supramolecular chemistry is actively exploring

systems undergoing self-organization, i.e. systems

capable of spontaneously generating well-defined

functional supramolecular architectures by self-

assembly from their components, on the basis of

the molecular information stored in the covalent

framework of the components and read out at the

supramolecular level through specific interactional

algorithms, thus behaving as programmed

chemical systems.

The implementation of molecular information

controlled, “programmed” and functional systems

allows the spontaneous but controlled generation

of well-defined, functional molecular and

supramolecular architectures of nanometric size

through self-organization by design . It represents

a means of performing programmed engineering

and processing of functional nanostructures. It

offers a very powerful alternative or complement

to nanofabrication and to nanomanipulation for

the development of nanoscience and

nanotechnology.

Supramolecular entities as well as molecules

containing reversible bonds are able to undergo a

continuous change in constitution by

reorganization and exchange of building blocks.

This capability allows for self-organisation with

selection and defines a Constitutional Dynamic

Chemistry (CDC) on both the molecular and

supramolecular levels. CDC introduces a paradigm

shift with respect to constitutionally static

chemistry. It takes advantage of dynamic

constitutional diversity to enable variation and

selection and thus adaptation.

These approaches have been implemented in the

generation of functional organic and inorganic

nanostructures for molecular and supramolecular

electronics, spintronics and mechanics.

Jean-Marie Lehn

Graph ene

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I n d e x

G r a p h e n e 2 0 1 5 C o n t r i b u t i o n s

A l p h a b e t i c a l O r d e r

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Adam, Shaffique (NUS, Singapore)

Disorder induced magnetoresistance in graphene and other materials I 21

Ahmad, Rezal Khairi (NanoMalaysia, Malaysia)

National Graphene Action Plan 2020 - Malaysia's Value Proposition

Abstract not available I -

Ajayan, Pulickel (Rice University, USA)

Materials Science of Two Dimensional Atomic Layers K 22

Akinwande, Deji (Univ. Texas at Austin, USA)

Flexible Black Phosphorus Transistors: Materials, Devices, and Radio Circuits I 23

Akinwande, Deji (Univ. Texas at Austin, USA)

NASCENT I 24

Alonso-González, Pablo (CIC nanoGUNE, Spain)

Two Dimensional Nanooptics with Graphene Plasmons O 25

Alpuim, Pedro (International Iberian Nanotechnology Laboratory, Portugal)

Wafer-scale fabrication of planar solution-gated graphene field-effect transistors for biosensing O 26

Amara, Hakim (ONERA/CNRS, France)

Nitrogen-doped graphene: a theoretical point of view O 28

Artaud, Alexandre (CEA, France)

Graphene growth by “magical sizes” graphene nanoclusters assembly on Re(0001) PhD 29

Auger, Jean-Marie (EC-Flagships Unit, Belgium)

Future plans for EU Graphene Flagship I 31

Aydin, Omur Isil (IMEP-LAHC, France)

Robust fabrication of suspended structures from CVD graphene O 32

Balan, Adrian (CEA, France)

The effect of defects produced by electron irradiation on the electrical properties of graphene and

MoS2

O 33

Balasubramanian, Kannan (Max Planck Institute for Solid State Research, Germany)

Electrochemical modification of graphene to enhance its electronic and vibrational properties O 34

Barbone, Matteo (University of Cambridge, United Kingdom)

Spin diffusion length in LSMO–graphene spin valves PhD 35

Baringhaus, Jens (Leibniz Universität, Institut für Festkörperphysik, Germany)

Exceptional ballistic transport in self-assembled sidewall graphene nanoribbons O 36

Barlas, Yafis (University of California at Riverside, USA )

Anomalous Hall Effect in ferromagnetic graphene O 37

Biel, Blanca (University of Granada, Spain)

Sensing capabilities of a single-layer MoS2 substrate for molecule detection O 38

Bonaccorso, Francesco (IIT, Italy)

Energy conversion and storage devices based on solution processed 2d crystals I 39

Bonaccorso, Francesco (IIT, Italy)

Science and technology of two-dimensional crystals @ Istituto Italiano di Tecnologia, Graphene Labs I 40

Bondavalli, Paolo (Thales Research & Technology, France)

Graphene based electrodes for high performances supercapacitors I 41

Bosca Mojena, Alberto (ISOM-UPM, Spain)

Lab-scale system for automated graphene transfer PhD 43

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Botello Méndez, Andres (IMCN - Université catholique de Louvain, Belgium)

Correlating electrical measurements of carbon nanostructures inside the TEM with first principles

calculations

O 45

Boustedt, Katarina (Graphene Flagship, Sweden)

The Graphene Flagship I 46

Cao, Jiang (IMEP-LAHC, Univ. Grenoble Alpes, CNRS, France) Quantum simulation of tunnel field-effect transistors based on transition metal dichalcogenides

PhD 47

Casademont, Hugo (CEA Saclay, France) MoS2 Transistors with Electrografted Organic Ultrathin Film as Efficient Gate Dielectric

PhD 49

Castro Neto, Antonio H. (National University of Singapore, Singapore)

From Graphene to Phospherene: the 2D zoo K 50

Chen, Chang-Hsiao (Center for Micro/Nano Science and Technology, National Cheng Kung University,

Taiwan)

Hole Mobility Enhancement and p-doping in Monolayer WSe2 by Gold Decoration

O 51

Chen, Tonglai (ICFO, Spain)

Nano-patterned graphene on polymer substrate by direct peel-off technique O 52

Chen, Yani (Institute Néel/CNRS, France)

Transistors based on graphene or double wall carbon nanotube hybrids for optoelectronics PhD 53

Chen, Yu (East China University of Science and Technology, China)

Polymer Covalently Modified Graphene for Nonvolatile Rewritable Memory O 54

Chernozatonskii, Leonid (Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,

Russia)

Bilayered MoS2/graphene structures with a Re-atom in a supercell: theoretical studies of stable

geometries and electronic properties

O 55

Colombo, Luigi (Texas Instruments, USA)

2D Materials Growth: Prospects and Challenges I 56

Cunha, Eunice (Institute for Polymers and Composites, University of Minho, Portugal)

Controlled functionalized graphene nanoribbons produced from carbon nanotubes PHD 58

de Souza, E.A. Thoroh (Mackenzie Presbyterian University, Brazil)

Research Activities at MackGraphe I 60

Dal Conte, Stefano (IFN-CNR and Politecnico di Milano, Italy)

Disentangling spin and valley dynamics in monolayer MoS2 by non-equilibrium optical techniques O 62

Decorde, Nicolas (Cambridge Graphene Center, United Kingdom)

3d printing of graphene-polymer composites O 63

De Fazio, Domenico (University of Cambridge, United Kingdom)

Graphene/MoS2 Flexible Photo-detector PhD 64

del Corro, Elena (J. Heyrovsky Institute of Physical Chemistry of the ASCR, v.v.i., Czech Republic)

Single Layer MoS2 under Direct Compression: Low Pressure Band-gap Engineering O 5

Diaz-Serrano, Madeline (University of Pennsylvania, USA )

High Yield and Scalable Fabrication of Nano/Bio Hybrid Graphene Field Effect Transistors for Cancer

Biomarker Detection

O 67

Diez, Enrique (Universidad de Salamanca, Spain)

Antiferromagnetic to Ferromagnetic phase transition in bilayer graphene O 68

dos Santos, Maria Cristina (Universidade de São Paulo, Brazil)

Large-Area Si-Doped Graphene: Controllable Synthesis and Enhanced Molecular Sensing O 69

Ermolov, Vladimir (VTT, Finland)

Opportunities and challenges of graphene application in passive micro-and millimetre wave

components

O 70

Etayo, David (Das-Nano, Spain)

High Speed – Large Area – Non destructive Graphene Characterization O 71

Fabricius, Norbert (Karlsruhe Institute of Technology, Germany)

International Standardization on Graphene-based Nanotechnology I 72

Falcon, Severino (MINECO, Spain)

FLAG-ERA: The FET Flagship ERA-NET I 73

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Fernández-García, Laura (Instituto Nacional del Carbón CSIC, Spain)

Tuning graphene properties by a multi-step thermal reduction process PhD 74

Ferrari, Andrea C. (Cambridge Graphene Centre, UK)

The European roadmap for science and technology of graphene and related materials I 76

Foa Torres, Luis (UNC, Argentina)

Harnessing light to tune the topology of materials I 77

Furchi, Marco M. (Vienna University of Technology, Austria)

Solar energy conversion in van der Waals heterostructures PhD 79

Galhena, D. Thanuja L. (University of Cambridge, United Kingdom)

Graphene Oxide Based Electrodes for Supercapacitors with Enhanced Cyclic Performance O 80

Garrido, Jose A. (TU München, Germany)

Graphene-based electronics for biomedical applications I 81

Gómez-Navarro, Cristina (Universidad Autonoma de Madrid, Spain)

Stiffening graphene by controlled defect creation O 82

Gómez Romero, Pedro (ICN2, Spain)

Graphene research at ICN2 I 83

Gómez Romero, Pedro (ICN2, Spain)

Hybrid polyoxometalate/reduced graphene oxide composites for supercapacitors O 85

Hao, Ling (National Physical Laboratory, United Kingdom)

Graphene drum mechanical resonators detected by microwaves O 86

Herrera-Ramírez, Luis Carlos (IMDEA Materials Institute, Spain)

The role of graphite nanoplatelets and carbon nanotubes on the enhanced fracture toughness and

electrical conductivity of polypropylene composites

PhD 88

Hilke, Michael (McGill University, Canada & FU Berlin, Germany)

Graphene Growth Dynamics and Phonon Engineering using Isotopes O 89

Horibe, Masahiro (AIST, JApan)

Standardization of Carbon Nanomaterials for Industrial Applications What we want, What should be

done I 90

Ivasenko, Oleksandr (KU Leuven - University of Leuven, Belgium)

Morphology and nano-manipulation of covalently grafted layers on graphene and graphitic substrates:

a step towards graphene-based integrated circuits

O 92

Jauho, Antti-Pekka (DTU Nanotech, Denmark)

CNG – Center for Nanostructured Graphene I 93

Journet, Catherine (University Lyon 1, France)

Synthesis of self-standing highly crystallizedhexagonal boron nitride (h-BN) O 94

Juang, Zhen-Yu (Center for Micro/Nano Science and Technology, Taiwan)

Cross-plane Thermoelectric Effect of Graphene-based Nanostructure O 95

Kakenov, Nurbek (Bilkent University, Turkey)

Controlling Terahertz Waves using Graphene Supercapacitors O 96

Kelaidis, Nikolaos (NCSR "Demokritos", Greece)

Chemical vapor deposition growth and characterization of graphene on Rh(111) and Ir(111) single

crystals

O 97

Kim, Hyo Won (Samsung Advanced Institute of Technology, Korea)

Strong Interaction between Graphene Edge and Metal Revealed by Scanning Tunneling Microscopy O 99

Kim, Min-Sik (Seoul National University, Korea)

Mesoepitaxy of graphene: continuous film formation PhD 100

Kis, Andras (EPFL, Switzerland)

MoS2 and dichalcogenide based devices and hybrid heterostructures I 101

Koppens, Frank (ICFO, Spain)

Photodetection and nano- photonics of graphene and heterostructures of 2d materials I 102

Kovalska, Evgeniya (Bilkent university, Turkey)

Investigation of electrolytes for graphene optical modulators O 103

Kvarnström, Carita (University of Turku, Finland)

Reduced graphene oxide based nanocomposite films for enhanced electrochromic performance O 105

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Lacovig, Paolo (Elettra - Sincrotrone Trieste S.C.p.A., Italy)

Epitaxial Growth of Single-domain Hexagonal Boron Nitride O 106

Lagoute, Jérôme (MPQ, Université Paris Diderot, France)

Nitrogen doping of graphene studied by scanning tunneling microscopy O 107

Le Lay, Guy (Aix-Marseille University, France)

From single to multilayer germanene O 108

Lee, Young Hee (SKKU, South Korea)

Towards large-area monocrystalline graphene: Synthesis and applications K 109

Lee, Young Hee (SKKU, South Korea)

Current Research Status of Korea on Graphene & Carbon Nanotubes I 110

Leibowitz, Mike (Nema, USA)

Graphene Standards: Building a Bigger Business I 111

Lemme, Max (Univ. of Siegen, Germany)

High Sensitivity of Graphene-based Sensors – Opportunities and Limitations I 112

Lombardi, Lucia (Cambridge Graphene Centre, United Kingdom)

Printed MoS2/Graphene Photodetector O 113

Lou, Fengliu (Norwegian University of Science and Technology, Norway)

Electrochemical synthesis of nitrogen doped graphene for oxygen reduction and supercapacitors O 114

Lou, Jun (Rice University, USA)

Synthesis, Characterization and Engineering of Two-Dimensional Materials I 115

Lux, Helge (Technical University of Applied Sciences Wildau, Germany)

Synthesis of Graphene-based transparent and conductive films on insulators using a modified high

current arc evaporation process

O 116

Magaud, Laurence (Institut Néel, CNRS, France)

Graphene nanoporous network: from synthesis to electronic structure calculations O 117

Marie, Xavier (INSA - Université de Toulouse, France)

Exciton Kinetics in MoS2, MoSe2 and WSe2 monolayers I 118

Marini, Andrea (ICFO, Spain)

Infrared spectroscopy with tunable graphene plasmons: a novel route for molecular sensing O 119

Messina, Elena (CNR - Istituto per i Processi Chimico-Fisici, Italy)

Enhanced Thermal Conductivity of silver filled-epoxy resin loaded with Carbon Nanotubes and

Graphene

O 120

Miseikis, Vaidotas (Istituto Italiano di Tecnologia, Italy)

Rapid CVD growth of millimetre-sized single-crystal graphene using a cold-wall reactor O 121

Morpurgo, Alberto (Univ. of Geneva, Switzerland)

New phenomena in transport through suspended graphene devices I 122

Nagler, Philipp (University of Regensburg, Germany)

Low-temperature photoluminescence of 2D Dichalcogenides and indirect excitons in their

heterostructures

PhD 123

Neumaier, Daniel (AMO GmbH, Germany)

Graphene based optical modulators and photodetectors for chip-integrated communication systems I 125

Newman , Leon (University of Manchester, United Kingdom)

Environmental remediation of oxidised graphene nanocarbons: 2D sheets degrade faster than 1D

tubular-shaped structures

PhD 126

Nguyen, Van Luan (Institute for Basic Science, Korea)

Seamless stitching of graphene domains on polished copper (111) foil O 127

Ni, Zhenhua (Southeast University, China)

Defect modulated photoresponse and thermal conductivity in graphene O 128

Nikitskiy, Ivan (ICFO - The Institute of Photonic Sciences, Spain)

Hybrid graphene–quantum dot phototransistors for IR-imaging applications PhD 129

Nikolic, Branislav K. (Univ. of Delaware, USA)

Graphene nanopores for biosensing and thermoelectric applications: First-principles quantum

transport simulation I 130

Otsuji, Taiichi (Tohoku University, Japan)

Recent advances in graphene heterostructures toward the creation of terahertz lasers I 131

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Özyilmaz, Barbaros (NUS, Singapore)

Transport Studies in Black Phosphorus Field Effect Transistors I 132

Pasternak, Iwona (Institute of Electronic Materials Technology, Poland)

Optimized graphene growth on Ge(100)/Si(100) substrates O 133

Pham, Van Dong (CNRS-Université Paris Diderot, France)

Electronic Interaction between Nitrogen-Doped Graphene and Porphyrin Molecules PhD 134

Pham, Trung T. (University of Namur, Belgium)

Influence of substrate temperature and SiC buffer layer on the quality of graphene formation directly

on Si(111)

PhD 135

Pimenta, Marcos (Departamento de Fisica, UFMG, Brazil)

Excitonic transitions in 2D transition metal dichalcogenides (MoS2, WS2 and WSe2) observed by

resonance Raman spectroscopy

O 136

Pogna, Eva Arianna Aurelia (Politecnico di Milano, Italy)

Ultrafast broadband study of photocarrier dynamics in MoS2 single layer PhD 137

Poirier, Wilfrid (Laboratoire National de Métrologie et d'Essais, France)

User-friendly graphene-based quantum resistance standards O 138

Power, Stephen (DTU Nanotech, Denmark)

Electronic transport, nanostructuring and disorder in graphene I 139

Ramasse, Quentin M. (SuperSTEM, UK)

Atom-by-atom defect engineering and characterisation in graphene and other

2-dimensional materials using scanning transmission electron microscopy

I 140

Ren, Wencai (Shenyang National Laboratory for Materials Science (SYNL), China)

Industrialization and Standardization of Graphene Materials in China I 141

Riazimehr, Sarah (University of Siegen, Germany)

Spectral Sensitivity of pn-junction Photodetectors based on 2D materials PhD 142

Rickhaus, Peter (University of Basel, Switzerland)

Electron optics in grapheme PhD 143

Riikonen, Juha (Aalto University, Finland)

All-Graphene T-Branch Thin-Film Field-Effect Rectifiers O 144

Rodin, Aleksandr (Boston Univ., USA)

Phosphorene: Graphene's Difficult Cousin I 146

Sandner, Andreas (Universität Regensburg, Germany)

Magnetotransport in high-mobility graphene antidot arrays PhD 147

Sauvajol, Jean-Louis (CNRS-University Montpellier 2, France)

Combined Raman spectroscopy and reflection/transmission measurements for grapheme

characterization

O 148

Schue, Leonard (Onera/CNRS, France)

Structural and optical characterisation of hBN layers PhD 149

Schwarz, Cornelia (Instutut Néel, CNRS, France)

Local Optical Probe for Motion and Strain Detection of Resonances in Graphene Membrane Drums PhD 150

Servant, Ania (NGI-University of Manchester, UK)

Graphene applications –Beyond the sticky tape I 152

Shin, Hyeon Jin (Samsung Advanced Institute of Technology, Korea)

Growth Mechanism of Hexagonal Boron Nitride: by Nanocrystalline Graphene Assistance and/or by B-

N molecular diffusion

O 153

Simic-Milosevic, Violeta (SPECS Surface Nano Analysis GmbH, Germany)

STM and NC-AFM investigations of Graphene on Metal Surfaces O 155

Tao, Haihua (Shanghai Jiaotong University, China)

Extraordinary photoluminescence in UV/ozone treated graphene flakes O 156

Tesch, Julia (Universität Konstanz, Germany)

Size quantization effects in quasiparticle interference on epitaxial graphene nanoflakes PhD 158

Van Tuan, Dinh (ICN2 - Catalan Institute of Nanoscience and Nanotechnology, Spain)

Spin Dynamics in High-Quality Graphene: Role of Electron-Hole Puddles and

Spin-Pseudospin Coupling

O 159

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Veliev, Farida (CNRS / Institut Néel, France)

Graphene Transistors for Detection of Neuronal Activity PhD 160

Vila Juarez, Mercedes (Universidade de Aveiro, Portugal)

Nanographene oxide-cell interactions and its potential for tumor destruction O 162

Wallbank, John (Lancaster University, United Kingdom)

Twist-controlled resonant tunnelling in graphene/boron-nitride/graphene heterostructures O 164

Wu, Ryan (University of Minnesota, USA)

The Atomic and Electronic Structure of Phosphorene PhD 165

Xenogiannopoulou, Evangelia (Institute of Nanoscience and Nanotechnology, “DEMOKRITOS”,

Greece)

Evidence for epitaxial germanene formationon AlN(0001)/Ag(111) template

O 166

Xie, Xiaoming (SIMIT - CAS, China)

Silane-Catalyzed Single-Crystalline Graphene Growth on Hexagonal Boron Nitride I 167

Yanfeng , Zhang (Peking university, China)

Growth and atomic-scale characterization of graphene-h-BN hybrids on single crystal substrates O 168

Yang, Hongxin (Spintec, France)

Switching of Magnetocrystalline Anisotropy of a Single Layer Cobalt Film by Graphene O 169

Yao, Wang (HKU, Hong Kong)

Valley and spin currents in 2D transition metal dichalcogenides I 171

Yoo, Ji-Beom (SKKU, South Korea)

Activities on Standardization of Properties of Graphene in Korea I 172

Zhao, Jiong (SungKyunKwan Univerisity, Korea)

In situ Transmission Electron Microscopy for Nanoscale Dynamics and Properties of 2D materials O 173

Zhi, Linjie (NCNST, China)

Well-defined Graphene-based Hybrids for Energy Storage Applications I 174

Zhu, Hongwei (Tsinghua University, China)

Graphene Woven Structure for Sensing Applications I 175

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D i s o r d e r i n d u c e d m a g n e t o r e s i s t a n c e i n g r a p h e n e a n d o t h e r m a t e r i a l s Yale-NUS College, Center for Advanced 2D materials and Graphene Research Center, and Department of Physics, National University of Singapore

In this work we address theoretically the classical and quantum magnetotransport in graphene [1], other two dimensional materials [2], as well as 3D Weyl semimetals [3]. At room temperature, the largest contribution to the magneto-transport is classical and we predict theoretically that a disorder induced carrier density inhomogeneity causes large classical magnetoresistance (MR) in these systems. Using effective medium calculations, we predict theoretically, and in the case of graphene demonstrate experimentally, that the characteristic signature of this effect is the crossover from quadratic dependence at low magnetic fields to linear magnetoresistance at larger field. At lower temperatures, quantum phase-coherent effects can be observed in the magnetotransport, and a careful study of available experiments reveals information about the dominant scattering mechanism in these materials. This work is supported by the Singapore National Research Foundation NRF-NRFF2012-01..

R e f e r e n c e s

[1] ] J. Ping, I. Yudhistira, N. Ramakrishnan, S. Cho,

S. Adam, M. S. Fuhrer, Phys. Rev. Lett. 113, 047206 (2014).

[2] H. Schmidt, S. Wang, L. Chu, M. Toh, R. Kumar, W. Zhao, A. H. Castro Neto, J. Martin, S. Adam, B. Özyilmaz, and G. Eda, Nano Letters, 14, 1909 (2014).

[3] N. Ramakrishnan, M. Milletari, and S. Adam; arXiv: 1501.03815 (2015).

Shaffique Adam

[email protected]

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M a t e r i a l s S c i e n c e o f T w o D i m e n s i o n a l A t o m i c L a y e r s Department of Materials Science and NanoEngineering Rice University, Houston, Texas 77005, USA

There has been tremendous interest in recent years to study isolated two-dimensional atomic layers which form the building blocks of many bulk layered materials. This interest was initiated by the spectacular discovery of graphene which has been demonstrated to have a unique set of properties. This talk will focus on the materials science of graphene and the emerging field of 2D atomic layers beyond graphene. Our group has been working on 2D materials systems such as graphene, graphene oxide, boron-nitrogen-carbon containing materials and several compositions of transition metal dichalcogenides. Several aspects that include synthesis, characterization and device fabrication of these systems will be discussed with the objective of building all 2D functional structures for future technologies. There are several challenges in growing and fabricating devices with 2D atomic layers, including scalability, uniformity, defects, stability, stacking, contacts etc. and the talk will discuss these issues and the progress made in addressing these. The concept of nanoscale engineering and the goal of creating new artificially stacked van der Waals solids will be discussed through a number of examples including graphene and other 2D layer compositions.

Pulickel M. Ajayan

[email protected]

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F l e x i b l e B l a c k P h o s p h o r u s T r a n s i s t o r s : M a t e r i a l s , D e v i c e s , a n d R a d i o C i r c u i t s University of Texas at Austin (USA)

Two dimensional atomic sheets, such as graphene and transition metal dichalcogenides (TMDs), have been widely studied as electronic materials for flexible nanoelectronics applications due to the high flexibility enabled by their natural 2D layered crystal structure. However, with the growing need for both high speed and low power consumption in realistic applications, TMDs with relatively low mobility and graphene with zero band gap are facing critical challenges to satisfy practical requirements. Recently, few-layer phosphorene, a new candidate in the portfolio of 2D crystals, has demonstrated high room temperature mobility and high on/off ratio, which is very attractive for advanced flexible nanoelectronics. In this work, we present the first black phosphorus flexible field effect transistors (BP-FETs), fundamental circuits and a radio receiver. For flexible BP-FETs based on exfoliated phosphorene films with thickness between 5nm to 15nm, clear ambipolar characteristics and negligible hysteresis were achieved (Fig. 1), attributed to a dielectric capping layer, which significantly enhanced long-term air stability. Outstanding device performance were achieved at room temperature; hole mobility and current on/off ratio are 300 cm2 /Vs and 105, respectively. With significantly enhanced ambipolar characteristics, electron mobility of 100 cm2 /Vs was observed. In this work, high performance electronic circuit blocks, including digital inverters, frequency doublers, inverting and non-inverting amplifiers were realized for the first time on plastics. Furthermore, we demonstrate a phosphorene flexible radio receiver which effectively demodulates amplitude modulated audio signals. In conclusion, our results indicate that few layer black phosphorus is the most promising 2D material for future high speed and

low power flexible electronics beyond the low mobility of TMDs and zero bandgap of graphene.

F i g u r e s

Figure 1: (up) Illustration of flexible phosphorene transistor on plastic, and (bottom) air-stable electrical characteristics.

Deji Akinwande

[email protected]

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N A S C E N T University of Texas at Austin MER 1.206L, R9900 10100 Burnet Rd. Bldg 160, Austin, TX 78758, USA

The University of Texas-Austin has an engineering center, NASCENT, focused on the translational development of graphene for roll-to-roll large area technology. The center is one the few dedicated centers in the U.S supported by the National Science Foundation (NSF) and several large and small technology companies to establish a nanomanufacturing center of excellence for end to end graphene development including graphene growth on flexible foils, in-line roll-to-roll graphene transfer and subsequent integration onto final plastic substrates for large area product prototyping. The facility is currently under development and will be opened publicly to external users for low-cost prototyping and proof-of-concept applications.

Deji Akinwande

[email protected]

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T w o D i m e n s i o n a l N a n o o p t i c s w i t h G r a p h e n e P l a s m o n s 1CIC nanoGUNE, 20018 Donostia-San Sebastián, Spain. 2I.N.T.I.–CONICET, Av. Gral. Paz 5445, Ed. 42, B1650JKA, San Martín, Bs As, Argentina. 3Graphenea SA, 20018 Donostia-San Sebastián, Spain. 4ICFO-Institut de Ciéncies Fotoniques, Mediterranean Technology Park, 08860 Casteldefells, Barcelona, Spain. 5IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain

Dye-sensitized solar cells (DSCs) have long been Forthcoming information and communication technologies demand the manipulation of not only electrons but also optical fields at the nanoscale. A promising solution for an active control of light in such small regions is the excitation and manipulation of graphene plasmons, which offer ultra-short wavelengths, long lifetimes, strong field confinement, and tuning possibilities by electrical gating. The huge momentum mismatch between graphene plasmons and photons, however, presents a major technological challenge [1]. Here, I will present a versatile platform technology that, based on resonant optical antenna structures (Fig. 1), allows for an efficient coupling of incoming light into propagating graphene plasmons. More importantly, I will show that these antennas and the use of spatial conductivity patterns (e.g. double layer graphene patches) also allow for controlling the graphene plasmons wavefronts [2], constituting an essential step for the development of graphene plasmonic circuits.

R e f e r e n c e s

[1] J. Chen, et.al. Nature 487, pp77-81 (2012). [2] P.Alonso-González, et. al. Science 344, 1369

(2014).

F i g u r e s

Figure 1: Experimental verification of an antenna-based graphene plasmon device. (A) Illustration of the near-field imaging method. An illuminating plane wave with electric field Ein drives an antenna resonance in a metal nanorod. The subsequently generated near fields at the rod extremities launch plasmons in the graphene sheet, which covers the substrate. A dielectric Si tip scans the sample surface and scatters the local near fields at the sample surface. (B) Topography image of an off- and on-resonance dipole antenna (left and right, respectively). (C,D) Experimental near-field images, showing the real part of the vertical near-field component of the antenna shown in B.

Pablo Alonso-González1,

Alexey Yu Nikitin1,5, F. Golmar1,2, A. Centeno3, A. Pesquera3, S. Vélez1, J. Chen1, F. Koppens4, A. Zurutuza3, F. Casanova1,5, L.E. Hueso1,5, and R. Hillenbrand1,5

[email protected]

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W a f e r - s c a l e f a b r i c a t i o n o f p l a n a r s o l u t i o n - g a t e d g r a p h e n e f i e l d - e f f e c t t r a n s i s t o r s f o r b i o s e n s i n g 1INL – International Iberian Nanotechnology Laboratory, Av. Mestre José Veiga, Braga, Portugal 2CFUM – Centre of Physics of the University of Minho, Campus de Gualtar, Braga, Portugal 3GNano – Nanomedicine and Nanotoxicology Group, Physics Institute of São Carlos, University of São Paulo, São Carlos-SP, Brazil

Recently, graphene has emerged as an alternative material for application in biosensors based on field effect transistors (bio-FET) due to its unique electronic properties combined with its high chemical stability and structural uniformity [1]. Although solution-gated bio-FETs offer interesting advantages compared to other types of biosensors (high sensitivity, label-free detection and large-scale fabrication), the usually large dimensions of gate electrodes (Ag/AgCl reference electrode or a metal wire made of gold, platinum or silver) represent a hindrance for miniaturization of these devices. Since this electrode is essential for gating the transistor it may preclude technological/commercial applications where such systems must work in realistic configurations. Here, we propose the wafer-scale fabrication of solutiongated graphene FETs (SG-GFETs) in which both the metal gate electrode and the transistor array were fabricated in the same wafer. This integration is critical, aiming further applications for bio-sensing, e.g. for advanced point of care testing. Graphene was deposited by CVD from gaseous mixtures of methane, hydrogen and argon on a 25 µm thick copper foil catalyst with 99.999% purity in a quartz tube reactor heated to 1020 °C. It was then transferred to the SiO2/Si wafer final substrate using PMMA as a temporary substrate and dissolving the Cu in a FeCl3 solution. The quality of graphene was assessed using Raman spectroscopy. Fig. 1a shows an optical image of a typical device structure: a 200 mm oxidized silicon wafer was patterned with 280 dies, each comprising three gold contacts: source, drain and a planar gate, with a source-drain gap of 25 µm and the ring-shaped gate at 50 µm around these two

contacts. Several squared pieces of 25 mm of graphene were transferred to cover a large portion of the wafer. Graphene was patterned using optical lithography and oxygen plasma etch keeping the gate Au contact protected by a layer of Al2O3, which is removed later in a wet etch step. The finished set of devices was characterized electrically using 0.01X phosphate buffered saline solution (PBS, pH 7.4) as the gate dielectric. The experiments were carried out by dropping a 20 µL drop of PBS onto the graphene transistor channel. Devices were gated by applying voltage to the integrated gate. A conventional Au wire was also used as gate contact in selected devices for comparison. Fig. 1b shows the transfer curves of the same device gated by conventional gold wire and using the integrated gate. The graphene is unintentionally p-doped which is related to the process and to the substrate. There is a shift in VDirac in the positive axis direction when the device is gated by the integrated gate. The gate-source leakage current is negligible (< 0.03 µA) as compared to the sourcedrain current of the SG-GFET at the same gate potential. Fig. 1c shows normalized transfer curves of eleven devices, obtained by dividing each original curve by the respective ISD maximum. The data show good transistor reproducibility, which is a key requirement for analytical devices. We are currently performing the functionalization of SG-FET channel with specific probes in order to detect disease biomarkers and water toxins. Acknowledgements: G.M.J thanks CNPq for a PhD grant. N.V is thankful to FAPESP for a post-doctoral grant.

N.C.S.Vieira1,3, J. Borme1, G.M. Junior1, M.F. Cerqueira2, P.P. Freitas1, V. Zucolotto3 and P. Alpuim

1,2

[email protected]

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R e f e r e n c e s

[1] Yan, F., Zhang, M., Li, J. Advanced Healthcare

Materials 3 (2014) 313.

F i g u r e s

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N i t r o g e n - d o p e d g r a p h e n e : a t h e o r e t i c a l p o i n t o f v i e w 1Laboratoire d’Etude des Microstructures, ONERA-CNRS, BP 72, 92322 Châtillon Cedex, France 2Physics Department (PMR), University of Namur (FUNDP), B-5000 Namur, Belgium

The introduction of local defects such as vacancies or doping impurities is a well-documented way to tune the electronic properties of graphene. In such a context, nitrogen is a natural substitute for carbon in the honeycomb structure due to both its ability to form sp2 bonds and its pentavalent character. However, a clear correlation between the atomic configuration of the chemically modified graphene and the electronic properties remains a challenging task. Scanning tunneling microscopy and spectroscopy (STM/ STS) are unique tools to measure local electronic properties of graphene and correlate them with their atomic structure [1]. The present work, based on both ab initio DFT, semi-empirical tight-binding (TB) electronic structure calculations and analytical calculations (Green function formalism [2]) aims at looking for interference effects generated by different types of defects. As a first step, the case of simple substitution of nitrogen, where longrange Coulomb effects are expected, will be presented. The Coulomb impurity screening problem in graphene which has been the subject of some debates is discussed [3] and elucidated within a local TB formalism based on the recursion method. This approach is extended to other defects such as vacancy, simple- and double-substitution of nitrogen or pyridine configurations. All the results presented here are discussed in the light of recent experimental STM data [5,6].

R e f e r e n c e s

[1] F. Joucken et al., Phys. Rev. B 85 (2012)

161408(R) [2] F. Ducastelle, Phys. Rev. B 88 (2013) 075413 [3] V.N. Kotov, V.M. Pereira, and B. Uchoa, Phys.

Rev. B 78 (2008) 075433 [4] Ph. Lambin, H. Amara, F. Ducastelle and L.

Henrard, Phys. Rev. B 86 (2012) 045448 [5] Y. Tison et al., (submitted to ACS Nano) [6] T. Mercier, L. Henrard , H. Amara, and F.

Ducastelle (in preparation) F i g u r e s

Figure 1: (a). Map of the local density of states at zero energy in the presence of a vacancy. (b) Local density of states on the nitrogen atom and carbon atoms around a second neighbour nitrogen pair.

H. Amara1,

D. Sharma2, Ph. Lambin2, L. Henrard2, F. Ducastelle1

[email protected]

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G r a p h e n e g r o w t h b y “ m a g i c a l s i z e s ” g r a p h e n e n a n o c l u s t e r s a s s e m b l y o n R e ( 0 0 0 1 ) 1INAC-SPSMS, CEA, 17 rue des Martyrs, F-38054 Grenoble cedex 9, France 2Institut NEEL, CNRS and Université Joseph Fourier, BP166, F-38042 Grenoble Cedex 9, France 2Universite Grenoble Alpes, Inst NEEL, F-38042 Grenoble, France 3CNRS, Inst NEEL, F-38042 Grenoble, France 4SIMAP, Grenoble INP, 1130 rue de la Piscine, BP 75, F-38402 Saint-Martin-d’Hères Cedex, France

Monolayer graphene shows unique electronic properties, among which ballistic electronic transport at the micrometer scale [1]. This makes graphene an ideal candidate for coherent Cooper pair transport via Andreev Bound States (ABS) between two superconducting reservoirs. Whereas evidence of a supercurrent in graphene has been given as soon as 2007 [2], no signature of ballistic ABS was found yet, due to low transparency of the graphene-superconductor interface and extrinsic disorder induced by the fabrication of the junction or by its environment. These problems can be circumvented by growing graphene epitaxially on a superconducting substrate such as Re(0001) (gr/Re). In this system, superconducting correlations have been measured using scanning tunneling microscopy-spectroscopy (STM/STS) [3]. Gaining control over graphene growth on Re(0001) is mandatory in view of designing advanced graphene-superconductor epitaxial systems, such as graphene billiards and perpendicular-to-the plane junctions with tunable graphene doping and interaction with the metal. With the help of STM and reflection-high energy electron diffraction performed in situ, in the same ultra-high vacuum where the sample has been prepared, we have explored the nucleation and first steps of the growth of gr/Re. We have found that graphene coexists with a dilute carbon phase forming a surface reconstruction, and that graphene nanoclusters of well-defined sizes (“magical sizes”) preferentially form (Figure 1). These “magical sizes”-nanoclusters are mobile and assemble to form graphene sheets [4].

They are therefore the key-intermediate to grow graphene, though their formation has only been predicted thus far. Our density functional theory calculation (Figure 2a,b) help us deciphering their electronic and structural properties.

R e f e r e n c e s

[1] Mayorov et al., Nano Letters, 12 (2012)

pp.4629-4634 [2] Heersche et al., Nature, 446 (2007) pp.56-59 [3] Tonnoir et al., Physical Review Letters, 111

(2013) 246805 [4] Artaud et al., to be submitted. F i g u r e s

Figure 1: STM topograph (1.4x1.4nm) of a typical 3-C6 graphene nanocluster on Re(0001).

Artaud A.123,

Ratter K.234, Gilles B.4, Bendiab N.2,3, Magaud L.2,3, Coraux J.2,3, Chapelier C.1

[email protected]

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Figure 2: DFT-simulated 3-C6 graphene nanocluster on a (7x7) cell of Re(0001). (a) Integrated |ψ|² over the 0 – 0.2 eV range. C atom sizes are proportional to their distance from the Re surface (b) Side-view showing the dome-like shape of the graphene nanocluster..

(a)

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F u t u r e p l a n s f o r E U G r a p h e n e F l a g s h i p EC-Flagships Unit, Belgium

In October 2013 the Commission launched through its FET scheme [1] two FET Flagships, Graphene [2] and the Human Brain Project. Each of them is implemented initially as an FP7 project preparing the ground for what will be a new kind of partnership. FET Flagships are long-term, large scale research initiatives aiming to solve ambitious S&T challenges. They are bringing together excellent research teams across various disciplines, sharing a unifying goal and an ambitious research roadmap to achieve it. In order to address their ambitious objectives Flagships require: (i) Setting up large-scale partnerships that bring together the leading researchers from a large number of research organisations, including academia and industry; (ii) Commitment to a strong science investment over a long time period that cannot be made alone by the European Commission or any single Member State. With Flagships, the Commission proposes a new partnering model for long-term European co-operative research. This model is built around a large Core Project and a number of Partnering

Projects. The Core Project ensures the scientific leadership, continuity and cohesion of the Flagship and is funded by the Commission. The Partnering Projects bring extra knowledge, skills and resources to the Flagship. They may address specific science and technology areas of the Flagship's research roadmap, focus on technology transfer activities, contribute as early users or become early adopters of the Flagships technologies, etc. For each Flagship, the Core Project elaborates a collaboration framework that defines the application procedure, selection

criteria and integration mechanisms of Partnering Projects. Both the Core Project and the Partnering Projects contribute to the management of the Flagship and the definition of its research roadmap. The implementation model of the Graphene Flagship will be presented; it is described in the Commission Staff Working Document on FET Flagships [3].

R e f e r e n c e s

[1] FET, Future and Emerging Technologies, is

the Commission’s scheme that was supporting long-term ICT programmes in FP7 and is now in the Excellence Science part of Horizon 2020.

[2] www.graphene-flagship.eu [3] SWD(2014) 283 final of 16.09. 2014

F i g u r e s

Jean-Marie Auger

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R o b u s t f a b r i c a t i o n o f s u s p e n d e d s t r u c t u r e s f r o m C V D g r a p h e n e 1IMEP-LAHC, Grenoble INP, Minatec, CS 50257, 38016 Grenoble, France 2CRANN Trinity College, Dublin 2, Ireland 3SPSMS, CEA-INAC, 17 rue des Martyrs, 38054 Grenoble Cedex 9, France 4LNCMI, CNRS-UJF-INSA-UPS, 38042 Grenoble Cedex 9, France

Suspended graphene is interesting for nanoelectromechanical systems (NEMS) due to its high stiffness combined with low mass [1] and RF applications due to the increased electrical mobility. [2] For suspended as well as supported devices, it is important to have a large-scale fabrication route. We developed a robust and scale fabrication route for suspended devices from CVD graphene towards industrial applications. By taking particular care of the etching mask/graphene interface, we repeatedly achieved fully self-supported graphene beams in all of the 14 devices on each sample but one or two. A representative SEM image can be observed as in Figure 1a. In addition, we saw that it is possible to suspend more complicated geometries as in Figure 1b which are intended for more elaborate electrical measurements including the extraction of Hall mobility and elimination of contact resistance in suspended graphene structures. Furthermore, we have seen that it was possible to promote or impede periodic fold formation perpendicular to the beam length that survived heat treatments as well as suspending. Such folds, especially sharp ones are predicted to influence local electronic properties as well as chemical reactivity. [3] Therefore, it is imperative to have control over their formation. Compressive strain is a result of the high temperatures of the CVD process in company with the negative thermal expansion coefficient of graphene. While this is partially relaxed into systematic and/or randomly distributed folds, Raman spectroscopy showed that the compression is, in fact, not fully relaxed even at the final step of fabrication. Our

preliminary electrical measurements on graphene devices on SiO2 showed promising contact resistance and Hall mobility. Our care of the interface resulted in contact resistivity values of ~ 2 – 3 Ω µm which is on the lower end of the published values for Cr/Au metals. [4] We calculated a mobility of ~1200 cm2 V-1 s-1 from Hall measurements where we swept the magnetic fields up to 11 T at 4 K and 20 K. While this value appears low, it agrees with electrical mobility in non-annealed CVD graphene devices.

R e f e r e n c e s

[1] van der Zande et al. Nano Lett., 10 (2010)

4869. [2] Happy et al., 2011 Proceedings of 41st

European Microwave Conference (EuMC 2011), (2011)

[3] Zhang and Arroyo, J. Appl. Phys., 113 (2013) 193501

[4] Nagashio et al., Jpn. J. Appl. Phys. 50, (2011) 070108

F i g u r e s

Figure 1: a) Tilted SEM image of devices patterned by optical lithography. b) SEM image of suspended devices with more complicated structures. The beam is patterned by ebeam lithography.

O.I. Aydin1,

T. Hallam2, J.L. Thomassin3, B.A. Piot4, G.S. Duesberg2, M. Mouis1

[email protected]

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T h e e f f e c t o f d e f e c t s p r o d u c e d b y e l e c t r o n i r r a d i a t i o n o n t h e e l e c t r i c a l p r o p e r t i e s o f g r a p h e n e a n d M o S 2 University of Pennsylvania, 209S 33rd St, Philadelphia PA, USA Iramis, CEA Saclay, Gif-sur-Yvette, France

We present a study of the effects of the defects produced by electron irradiation on the electrical and crystalline properties of graphene and MoS2 monolayers. We realized back or side gated electrical devices from monolayer MoS2 or graphene crystals (triangles respectively hexagons) suspended on a 50nm SiNx m. The devices are exposed to electron irradiation inside a 200kV transmission electron microscope (TEM) and we perform in situ conductance measurements [1]. The number of defects and the quality of the crystalline lattice obtained by diffraction are correlated with the observed decrease in mobility and conductivity of the devices. We observe a different behavior between MoS2 and graphene, and try to associate this with different models for conduction with defects. Finally, we use the TEM electron beam to tailor the macroscopic layers into ribbons to be used as the sensing element in MoS2 nanoribbon - nanopore devices for DNA detection and sequencing.

[5] van der Zande et al. Nano Lett., 10 (2010) 4869.

F i g u r e s

Figure 1: a) Schematic representation of the monolayers exposed to the electron beam. b) Increase of resistance of graphene with dose c) Conductance vs gate voltage for pristine and irradiated devices.

Adrian Balan, J. A. Rodriguez- Manzo, M. Puster, P. Masih Das, C. Nayor, A.T.C. Johnson, M. Drndic

[email protected]

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E l e c t r o c h e m i c a l m o d i f i c a t i o n o f g r a p h e n e t o e n h a n c e i t s e l e c t r o n i c a n d v i b r a t i o n a l p r o p e r t i e s 1Max Planck Institute for Solid State Research, Stuttgart (Germany). 2Instituto de Química de São Carlos, Universidade de São Paulo, 13560-970 (Brazil) 3Max Planck Institute for Biophysical Chemistry, 37077 Göttingen (Germany)

Chemical functionalization of graphene allows for a judicious engineering of the physical and chemical properties of graphene. Among the various schemes electrochemical modification [1] presents a versatile and straightforward strategy to fine tune the properties of graphene for a specific application, of which two examples will be presented here. On the one hand it allows us to improve the electronic and electrochemical performance, while on the other it provides us with a handle to continuously tune the extent of Raman scattering. In the first part, we show that trace metal impurities present on graphene have a significant impact on its physical and chemical properties. This observation has recently been made in a number of CVDgrown and graphite-derived graphene samples. This is analogous to the case of carbon nanotubes where trace metals were found to have a strong effect on the electrocatalytic properties of the material. We observe by direct electroanalysis that even after the usual copper etching process, trace copper impurities still remain on transferred CVD graphene. We devise an electrochemical etching procedure [2] using which we successfully eliminate at least 90% of these impurities with a clear improvement in both the electrochemical and electronic transport properties of monolayer graphene. In the second part we present an electrochemical deposition route to attach gold nanoparticles (AuNPs) controllably on to a graphene surface. Raman scattering in graphene can be significantly enhanced through the coupling of metal nanostructures. Many of the reported approaches utilize physical vapor depositon requiring

patterning of graphene or the underlying substrate. A major limitation is the inability to measure the Raman enhancement at the same location as a function of variation in particle size and / or density. Moreover, there is no direct possibility to tune the strength of enhancement after the structures are fabricated. Using our electrodeposition route, the size or density of the nanoparticles and thereby the Raman enhancement can be continuously increased through appropriate choice of electrochemical parameters. [3] We clearly show that the strength of Raman enhancement varies as a function of the frequency of the vibrational mode (D, G or 2D of graphene) and may be correlated with the plasmonic fingerprint of the attached AuNPs. An additional chemical contribution can be also deciphered through charge transfer from AuNPs on to graphene. Subsequently, we show that these devices can be efficiently utilized as SERS substrates for the detection of specifically bound non-resonant analyte molecules.

R e f e r e n c e s

[1] R.S. Sundaram, et al., Adv. Mater. 20, 3050

(2008). [2] R.M. Iost et al., ChemElectroChem Early View

DOI: 10.1002/celc.201402325 [3] L. Zuccaro, et al., Adv. Funct. Mater. 24, 6348

(2014).

Kannan Balasubramanian1,

L. Zuccaro1, R.M. Iost1,2, F.N. Crespilho2, H.K. Yu3, A.M. Wodtke3, K. Kern1

[email protected]

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S p i n d i f f u s i o n l e n g t h i n L S M O –g r a p h e n e s p i n v a l v e s 1Cambridge Graphene Centre, University of Cambridge, CB3 0FA, Cambridge, UK 2Department of Materials Science & Metallurgy, University of Cambridge, Cambridge, UK 3Department of Applied Physics, Aalto University School of Science, FI-00076, Aalto Finland 4Department of Physics, University of Parma, 43100, Parma, Italy 5Diamond Light Source, Chilton, Didcot, OX11 0DE UK

Significant progress has been made in graphene spintronics since the first demonstration of a graphene-based spin valve [1]. Due to low spin-orbit coupling [2] and hyperfine interaction [2], spin diffusion lengths have been measured in the range from 1.5 µm [3] up to 285 µm [4]. Here we present spin valves formed by combining La2/3Sr1/3MnO3 (LSMO) electrodes and few layer graphene channels. LSMO exhibits interfacial spin-polarization close to 100% at low temperature [5], making it a promising material for spin valves with highly spin-polarized electrodes [6]. We report spin transport on a device fabricated combining a 5 layer graphene and LSMO. The electrodes show a 20% X-ray magnetic circular dichroism contrast (XMCD) asymmetry at remanence after magnetic pulses, as confirmed by photoemission electron microscopy with XMCD. The transition between parallel and anti-parallel states occurs at distinct and well defined magnetic fields. This is further confirmed by magneto-optic Kerr effect microscopy. The resistance difference between the antiparallel and parallel configurations is ΔR=1.0 MΩ, corresponding to a magnetoresistance of 5.5% at 10 K (Fig. 1), and a spin diffusion length~100 μm (Fig.2). Importantly, our analysis excludes the contribution from tunnelling anisotropic magnetoresistance (TAMR), and allows us to attribute the recorded magnetoresistance entirely to spin transport.

R e f e r e n c e s

[1] E.W. Hill et al., IEEE Trans. Magn. 42 (2006)

2694. [2] D. Huertas-Hernando et al., Pys. Rev. B 74

(2006) 155426. [3] N. Tombros et al., Nature. 448 (2007) 571. [4] B. Dlubak et al., Nat. Phys. 8 (2012) 557.

[5] M.Bowen et al., Appl. Phys. Lett. 82 (2003) 233.

[6] L. Hueso et al., Nature 445 (2007) 410.

F i g u r e s

Figure 1: Magneto-transport measurements on a 5-layer graphene on LSMO electrodes. Blue and black line correspond to the directions of magnetic field sweep indicated by the arrows.

Figure 2: Simulated magnetoresistance (MR) as a function of interfacial spin polarisation γ, spin diffusion length lsf, and interfacial resistance rb

* using the drift-diffusion model. The blue line indicates the range of values derived for our device.

M. Barbone1,

W. Yan2, L. C. Phillips2, S. Hämäläinen3, A. Lombardo1, M. Ghidini2,4, X. Moya2, F. Maccherozzi5, S. van Dijken3, S. S. Dhesi5, N. D. Mathur2 and A. C. Ferrari1

[email protected]

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E x c e p t i o n a l b a l l i s t i c t r a n s p o r t i n s e l f -a s s e m b l e d s i d e w a l l g r a p h e n e n a n o r i b b o n s 1Leibniz Universität Hannover, Institut für Festkörperphysik, 30167 Hannover, Germany 2Georgia Institute of Technology, Atlanta, Georgia 30332-0430, USA

The patterning of graphene into graphene nanoribbons is an essential task for the development of future graphene based electronic devices. For such ribbons with a well-ordered edge geometry the presence of one-dimensional edge states has been predicted. We use a selective graphitization process on the sidewalls of SiC mesa structures to produce graphene nanoribbons with a width of 40 nm. The local electronic properties of the ribbons are investigated by means of a 4-tip scanning tunneling microscope (STM). In combination with a high-resolution scanning electron microscope (SEM), the precise positioning of all four tips on the nanometer range is possible to perform local transport measurements [1] (cf. Fig. 1(a)). Additionally, one of the STM tips can be used for scanning tunneling spectroscopy (STS) to gain an insight into the local density of states. The STS reveals two peaks in the local density of states at the edges of the ribbons which can be attributed to the zeroth subbands in the band structure of a ferromagnetic zig-zag graphene nanoribbon [2]. Transport experiments carried out on the very same ribbon show a conductance close to e2/h for a wide temperature range from 30 K up to room temperature and probe spacings between 1 µm and 10 µm. Description within the Landauer formalism is possible assuming ballistic transport dominated by a single channel. Transport in the second zeroth subband is only detectable for probe spacings smaller than 1 µm due to the short localization length of carriers in this subband. This manifests in the increase of the conductance to 2 e2/h at probe spacings below 200 nm (cf. Fig. 1(b)). As a consequence, it is possible to selectively measure transport in one or two ballistic channels. Remarkably, 4-point probe and 2-point probe configurations result in almost identical conductance values as expected for a ballistic

conductor measured with fully invasive probes. This invasiveness of the probes can be used to give further evidence for the ballistic nature of transport, simply by introducing one or two additional passive probes in a 2-point probe configuration. Every additional passive probe doubles or triples the observed resistance, a clear indication for single-channel ballistic transport [3]..

R e f e r e n c e s

[1] J. Baringhaus et al., Appl. Phys. Lett., 103

(2013) 111604. [2] J. Baringhaus et al., J. Phys.: Condens. Matter,

25 (2013) 392001. [3] J. Baringhaus et al., Nature, 506 (2014) 349.

F i g u r e s

Figure 1: (a) SEM image of four probes contacting a sidewall graphene nanoribbon. (b) Conductance as a function of probe spacing of a sidewall graphene nanoribbon.

Jens Baringhaus1,

Claire Berger2, Walt de Heer2, and Christoph Tegenkamp1

[email protected]

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A n o m a l o u s H a l l E f f e c t i n f e r r o m a g n e t i c g r a p h e n e University of California at Riverside, Department of Physics and Astronomy, Riverside, USA

Recent advancements in device transfer techniques have enabled transfer of graphene on ferromagnetic substrates, which leads to a proximity induced ferromagnetism of the graphene sheet [1]. The presence of ferromagnetic exchange along with Rashba spin-orbit coupling leads to an energy gap at the Dirac points [2]. When the Fermi energy is pinned in the gap this system exhibits a quantized anomalous Hall with Chern number 2. I will show that when the Fermi energy is not in the gap the system exhibits un-quantized anomalous Hall effect (AHE) due to an intrinsic (band structure effect) and an extrinsic (disorder induced effect) contribution. The AHE contributions due to the intrinsic and extrinsic mechanisms will be calculated in semi-classical Boltzmann transport. The ability to gate tune the two-dimensional carrier density of the graphene sheet allows for a more detailed study of the anomalous Hall than that previously available in ferromagnetic semi-conductors. I will compare our theoretical results with most recent experimental data.

R e f e r e n c e s

[1] Zhiyong Wang, Chi Tang, Raymond Sachs,

Yafis Barlas, Jing Shi, Proximity-induced ferromagnetism in graphene revealed by anomalous Hall effect, cond-mat/1412.1521 (to be published in PRL).

[2] Z. Qiao, H. Jiang, X. Li, Y. Yao and Q. Niu, Phys. Rev. B 85, 115439 (2012)..

Yafis Barla, Jing Shi, Roger Lake

[email protected]

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S e n s i n g c a p a b i l i t i e s o f a s i n g l e - l a y e r M o S 2 s u b s t r a t e f o r m o l e c u l e d e t e c t i o n 1Dpto. Electrónica y Tecnología de Computadores, Universidad de Granada, 18071, Granada, Spain 2Dpto. Física Teórica de la Materia Condensada, Universidad Autónoma de Madrid, 28049, Madrid, Spain

Motivated by the work of Perkins et al. [1], we investigated, by means of DFT simulations, the potential capabilities of a monolayer MoS2 to detect different molecular species. Although graphene has been proposed as the ultimate material for sensor applications, it lacks selectivity in the recognition of different chemical species. In contrast, Perkins et al. showed that monolayer MoS2 is capable to distinguish between molecules with different chemical character, hence being a good alternative to graphene as the active component of ultrascaled, 2D materials-based gas sensors. Following the experiment by Perkins et al., the molecular species chosen for our study were triethylamine, which typically behaves as an electron donor, and nitromethane, which tends to act as an electron acceptor. After the characterization of the Potential Energy Surface (PES) for both molecules on the monolayer surface, we studied the influence of two possible reconstructions of a SiO2 substrate under the molecule-on-MoS2 compounds, using both the silanol and the siloxane reconstructions to test the impact of different atomic rearrangements at the oxide/MoS2 interface. The structural and electronic properties of such systems have been analysed and in the present work the results are contrasted against the experimental evidence. The study has been extended to the interaction of the MoS2 monolayer with acetates and triflates of transition metals of the fourth period.

R e f e r e n c e s

[1] Perkins, F. K., Friedman, A. L., Cobas, E.,

Campbell, P. M., Jernigan, G. G., and Jonker, B. T., Nano Letters, 13 (2013), 668.

F i g u r e s

Figure 1: Left panel: Bandstructure of the3x3 MoS2 supercell, the TEA/MoS2, the TEA/MoS2/silanol and the NM/MoS2/siloxaneCenter panel: a triethylamine (TEA) molecule on top of the MoS2 monolayer on a silanol substrate Right panel: a nitromethane (NM) molecule on top of the MoS2 monolayer on a siloxane substrate.

Figure 2: Left panel: Bandstructures for the spin up (left) and down (right) states of the copper(II) acetate (Cu(OAc)2 ) on top of the 3x3 MoS2 supercell Center and right panels: top and side view of the Cu(OAc)2 molecule on top of the MoS2monolayer

Blanca Biel1,

Luca Donetti1, Andrés Godoy1, Francisco Gámiz1, Pablo Pou2

[email protected]

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E n e r g y c o n v e r s i o n a n d s t o r a g e d e v i c e s b a s e d o n s o l u t i o n p r o c e s s e d 2 d c r y s t a l s Istituto Italiano di Tecnologia, Graphene Labs, Via Morego 30, 16163 Genova, Italy

Energy conversion and storage are two of the grand challenges that our society is currently facing. New materials and processes [1] can improve the performance of existing devices or enable new ones [1-5] that are also environmentally friendly. In this context, graphene and other two-dimensional (2d) crystals are emerging as promising materials. [1-5] A key requirement for energy conversion and storage applications is the development of industrial-scale, reliable, inexpensive production processes, [2] while providing a balance between ease of fabrication and final material quality with on-demand properties. [2] Solution-processing [2,6] is offering a simple and cost-effective pathway to fabricate various 2d crystal-based energy devices, presenting huge integration flexibility compared to conventional methods. Here I will present an overview of graphene and other 2d crystals-based energy conversion and storage applications, starting from solution processing of the raw bulk materials, [2,7,8] the fabrication of large area electrodes [3] and their integration in lithium-ion batteries [8,9] and photovoltaic devices. [10]

R e f e r e n c e s

[1] A. C. Ferrari, F. Bonaccorso, et al., Scientific

and technological roadmap for graphene, related two-dimensional crystals, and hybrid systems. Nanoscale DOI: 10.1039/c4nr01600a (2014).

[2] F. Bonaccorso, et al., Production and processing of graphene and 2d crystals. Materials Today, 15, 564-589, (2012).

[3] F. Bonaccorso, et. al., Graphene photonics and optoelectronics. Nature Photonics 4, 611-622,(2010).

[4] F. Bonaccorso, Z. Sun, Solution processing of graphene, topological insulators and other 2d crystals for ultrafast photonics. Opt. Mater. Express 4, 63-78 (2014).

[5] G. Fiori, et al., Electronics based on two-dimensional materials. Nature Nanotech 9, , 768-779, (2014).

[6] Y. Hernandez, et al., High-yield production of graphene by liquid-phase exfoliation of graphite. Nature Nanotech 3, 563-568, (2008).

[7] O. M. Maragò, et al., Brownian motion of graphene. ACS Nano, 4, 7515-7523 (2010).

[8] J. Hassoun, et al. An advanced lithium-ion battery based on a graphene anode and a lithium iron phosphate cathode Nano Lett. 14, 4901-4906 (2014).

[9] F. Bonaccorso, et. al., Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage. Science, 347, 1246501 (2015).

[10] P. Robaeys, et al. Enhanced performance of polymer: fullerene bulk heterojunction solar cells upon graphene addition. Appl. Phys. Lett. 105, 083306 (2014).

Francesco Bonaccorso

[email protected]

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S c i e n c e a n d t e c h n o l o g y o f t w o -d i m e n s i o n a l c r y s t a l s @ I s t i t u t o I t a l i a n o d i T e c n o l o g i a , G r a p h e n e L a b s Istituto Italiano di Tecnologia, Graphene Labs, Via Morego 30, 16163 Genova, Italy

The Italian Institute of Technology (IIT) is a Foundation established in 2003 jointly by the Italian Ministry of Education, University and Research and the Ministry of Economy and Finance to promote excellence in basic and applied research. The research plan of the institute focuses on Humanoid technologies and Robotics, Neuroscience and Cognition, Nanotechnology and Materials. The Institute has a staff of about 1300 people, the central research lab being located in Genoa. IIT has a large experience with the management of large research projects and has been involved in more than 100 EU funded projects in the last 8 years. IIT headquarter in Genoa has a 30,000m2 facility equipped with state-of-the-art laboratories for robotics, nanoscience and neuroscience, and 10 Research Centres all over the country. Since September 2013 IIT graphene research is collected under the umbrella of the IIT Graphene Labs (http://graphene.iit.it), which currently involves more than 30 researchers working on different aspects of graphene and 2d crystals science and technology. IIT Graphene Labs is actively involved in realising scientific and technological targets in the field of energy conversion [1,2] and storage [3] , material production (e.g., CVD [4] and solution processing [3]), deposition [5] and composite production [6], as well as heterostructures [7] and bio-nanotechnology (e.g., biocompatibility essays, biomolecule-graphene interaction). We will also have a strong effort in dissemination and technology transfer activities. In particular, the technology transfer program of IIT Graphene Labs is developing through specific agreements with companies. At the moment we have in place agreements with more than 10 companies on different aspects of graphene technology. The relevant facilities available span from colloidal

chemistry synthesis for nanoparticle production, electron microscopies, low temperature scanning tunnelling microscopies, optical spectroscopies from femtosecond to continues wave, a class 100 clean room for nanofabrication (600m2) and finally a the processing and prototypes unit, equipped with state-of-the-art 2d crystals production and coating instruments.

R e f e r e n c e s

[1] F. Bonaccorso, et al., Science 347, 1246501,

2015. [2] G. Calogero, et al., Chem. Soc. Rev. DOI:

10.1039/c4cs00309h, 2015. [3] J. Hassoun, et al., Nano Lett. 14, 4901-4906,

2014. [4] V. Miseikis, et al., 2D Materials 2, 014006,

2015. [5] G. Fiori, et al., Nature Nanotech. 9, 768-779,

2014. [6] E. Jomehzadeh, et al., Comput. Mat. Sci. 99,

164-172, 2015. [7] A. Gamucci, et al., Nature Comm. 5, 5184,

2014.

Francesco Bonaccorso

and Vittorio Pellegrini

[email protected]

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G r a p h e n e b a s e d e l e c t r o d e s f o r h i g h p e r f o r m a n c e s s u p e r c a p a c i t o r s Head of the nanomaterial topic team, Joint unit CNRS/Thales, Physics Department Thales Research and Technology, 91120 Palaiseau, France

Supercapacitors are electrochemical energy storage devices that combine the high energy-storage-capability of conventional batteries with the high power-delivery-capability of conventional capacitors. In this contribution we will show the results of our group recently obtained on supercapacitors with electrodes obtained using mixtures of carbonaceous nanomaterials (carbon nanotubes (CNTs), graphite, graphene, oxidised graphene). The electrode fabrication has been performed using a new dynamic spray-gun based deposition process set-up at Thales Research and Technology (patented). This technique constitute a real breakthrough compared to the classical filtration method because electrodes can be deposited over large areas in a completely automated way, using different kinds of substrates and with a thickness between some nm and up to hundredth of μms. In a first step, we will show the properties of mixtures of graphite/CNTs as a function of their composition (%) and of their weight for the fabrication of electrodes and cells. In order to spray the nanomaterials on a substrate we put them in stable suspensions using specific solvents. In case of CNTs/Graphite we used N-Methyl-Pyrrolidone. To avoid the “coffee-ring” effect” we have to heat the substrate and to reach the boiling point of the solvent (~220°C for NMP). The supercapacitor electrodes were fabricated on low cost graphite current collectors (commercially available) which are flexible and highly conducting. First, we systematically studied the effect of the relative concentrations of CNTs and graphite on the energy and power density. We obtained a power increase of a factor 2.5 compared to barely CNTs based electrodes for a mixture composed by 75% of graphite. After these results, we decided to test water as a solvent in order to reduce the

heating temperature and to obtain a green type process without toxic solvents. To achieve stable suspensions we oxidised the graphene and the CNTs before putting them in water. In this way we were able to fabricate stable suspensions in less than one hour compared to three days using NMP. Finally we will show recent results obtained using graphene exfoliated by IIT, that allows us improving the power of the supercapacitors in a dramatic way, thanks to its high conductivity. All these results demonstrate the strong potential to obtaining high performance devices using an industrially suitable fabrication technique.

R e f e r e n c e s

[1] Supercapacitor electrode based on mixtures

of graphite and carbon nanotubes deposited using a new dynamic air-brush deposition technique, P Bondavalli, C.Delfaure, P.Legagneux, D.Pribat JECS 160 (4) A1-A6, 2013

[2] Non-faradic carbon nanotubes based supercapacitors : state of the art, P.Bondavalli, D.Pribat, C.Delfaure, P.Legagneux, L.Baraton, L.Gorintin, J-P. Schnell, Eur. Phys. J. Appl. Phys. 60,10401, 2012.

Paolo Bondavalli

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F i g u r e s

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L a b - s c a l e s y s t e m f o r a u t o m a t e d g r a p h e n e t r a n s f e r 1Inst. de Sistemas Optoelectrónicos y Microtecnología, UPM, Madrid, 28040, Spain 2Dpto. de Ingeniería Electrónica, E.T.S.I de Telecomunicación, UPM, Madrid, 28040, Spain 3Campus de Excelencia Internacional, Campus Moncloa UCM-UPM, Madrid, 28040, Spain 4Dpto. de Ciencia de Materiales, E.T.S.I de Caminos, Canales y Puertos, UPM, Madrid, 28040, Spain

Although chemical vapor deposition (CVD) has proven to be an excellent method for growing electronic-quality graphene, its main disadvantage is the need of transferring the graphene layer from the metal catalyst to a suitable final substrate. A manual transfer method [1] was developed to overcome this issue. It consists of protecting the graphene with a thin polymer layer, wet-etching the growth substrate, rinsing with deionized water, and finally depositing the resulting polymer/graphene membrane onto the desired target substrate. Despite this method has been strongly optimized [2,3], it still requires strong handling skills, is time consuming, and is not suitable for an industrial process. An alternative method based on a roll-to-roll system [4] can overcome some limitations of the manual method, but it is limited to flexible substrates. In this work we report on a lab-scale system designed to transfer graphene automatically to arbitrary substrates, which could be easily scaled up for industrial applications. The system is composed of several modules (Fig. 1) that control the process temperature, the liquid flow and the overall system state. An Arduino UNO microcontroller is used as the real-time control system, timing and activating the rest of modules. It also allows communication with a computer for logging purposes. The passive components of the system are depicted in Fig. 2. A polytetrafluoroethylene (PTFE) tube encloses the graphene sample during the whole process. This enclosing tube has a surface treatment that centers the polymer/graphene membrane that floats inside it. The treatment avoids mechanical stress or induced ripples in the graphene during the process. A fixed platform and a substrate holder ensure a fixed position between the final substrate and the tube center. All these pieces are

immersed into a liquid, starting with an etchant solution and changing gradually into deionized water for the final rinsing steps. Finally, graphene field-effect transistors (GFETs) were processed on the same CVD material but transferred using both the standard manual method and the novel automatic method for comparison. Raman and electrical assessment of the GFETs demonstrate that devices on the automatically-transferred graphene present systematically higher mobilities and less impurity contamination.

Acknowledgements: Supported by MINECO projects RUE (CSD2009-0046) and GRAFAGEN (ENE2013-47904-C3).

R e f e r e n c e s

[1] Alfonso Reina, Xiaoting Jia, et al., Nano Lett.,

vol. 9, 1 (2009), p. 30. [2] Wei-Hsiang Lin, Ting-Hui Chen, et al., ACS

Nano, vol. 8, 2 (2014), p. 1784. [3] Hai Li, Jumiati Wu, et al., ACS Nano, vol. 8, 7

(2014), p. 6563. [4] Sukang Bae, Hyeongkeun Ri Kim, et al., Nat.

Nanotechnol., vol. 5, August (2010), p. 1.

Alberto Boscá1, 2,

J. Pedrós1, 3, J. Martínez1, 4, F. Calle1, 2, 3

[email protected]

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F i g u r e s

Figure 1: System modules. An Arduino UNO board is used for interconnection and control.

Figure 2: Figure 2: PTFE passive components (in liquid) and the sample and final substrate.

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C o r r e l a t i n g e l e c t r i c a l m e a s u r e m e n t s o f c a r b o n n a n o s t r u c t u r e s i n s i d e t h e T E M w i t h f i r s t p r i n c i p l e s c a l c u l a t i o n s 1IMCN-NAPS Université catholique de Louvain, Chemin des étoiles 8, 1348 Louvain la neuve, Belgium 2Institut de Physique et Chimie des Matériaux de Strasbourg, UMR 7504 CNRS, University of Strasbourg, 23 rue du Loess, 67034 Strasbourg 3Department of Physics and Astronomy, University of Pennsylvania, Philadelphia, Pennsylvania 19104, USA.

The interest of carbon nanostructues as potential active or passive components in next generation electronics is in great part due to the large range of properties that these systems exhibit. For instance, it has been shown theoretically that the electronic structure of carbon nanotubes (CNTs) and carbon nanoribbons (CNRs) strongly depend on the details of their atomic structure. This represents both an opportunity to tailor the electrical properties and a challenge to achieve atomically precise synthesis and characterization. In particular, the electrical characterization of carbon nanostructures has been elusive due to the challenging task of having accurate information of both the atomic structure and the electrical response. Recent breakthroughs in the spatial resolution of electron microscopes and the possibility to make electrical measurements inside them have provided unprecedented information about the electrical behaviour of these systems. Coupled with simulations, important contributions to the understanding of the electrical behaviour of carbon nanostructures have been made. Here, the specific examples of the electronic characterization of atomic chains of carbon and CNRs are used to compare with transport calculations based on first-principles DFT and tight biniding models [1-3]. The qualitative agreement between experiment and simulation allow a solid understanding of the properties of these systems. However, the quantitative discrepancies offer challenges on both sides.

R e f e r e n c e s

[1] O. Cretu, A.R. Botello-Mendez, I. Janowska, C.

Pham-Huu, J.-C. Charlier, F. Banhart, Nano Lett. 13 (2013) 3487.

[2] Z.J. Qi, J.A. Rodríguez-Manzo, A.R. Botello-Méndez, S.J. Hong, E.A. Stach, Y.W. Park, J.-C. Charlier, M. Drndić, A.T.C. Johnson, Nano Lett. 14 (2014) 4238.

[3] A. La Torre, A.R. Botello-Mendez, J.-C. Charlier, F. Banhart, Nature Comm. (2014) submitted.

F i g u r e s

Figure 1: Schematic view of the transport through a carbon chain inside the TEM.

Andrés R. Botello-Méndez1,

O. Cretu2, A. La Torre2, Z. J. Qi3, J. A. Rodríguez-Manzo3, M. Drndic3, A.T. C. Johnson3, F. Banhart2, J.-C. Charlier1

[email protected]

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T h e G r a p h e n e F l a g s h i p Graphene Flagship, Sweden

The Graphene Flagship is a ten-year research program funded by the European Commission, EU member states and project participants. It originates from the science of graphene and related layered materials and targets a disruptive technology shift, bringing these materials from academic laboratories to society as new products, employment opportunities and economic growth. Realising this ambition is only possible by integrating the entire value chain from basic research to applied and industrial research, which requires a large consortium with corresponding resources – the total project cost is about one billion euros. The flagship covers a wide range of topics ranging from fundamental research and spintronics to flexible electronics and nanocomposites. Examples of research carried out in some of the work packages will be briefly presented, but technical details cannot be covered, in the interest of time. Ways of interacting with the Graphene Flagship will be described, as well as the planned development of the Flagship during Horizon 2020.

Katarina Boustedt

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Q u a n t u m s i m u l a t i o n o f t u n n e l f i e l d -e f f e c t t r a n s i s t o r s b a s e d o n t r a n s i t i o n m e t a l d i c h a l c o g e n i d e s 1IMEP-LAHC, Univ. Grenoble Alpes, CNRS, F-38016 Grenoble, France 2DIEG-IUNET, Via delle Scienze 208, 33100 Udine, Italy

The tunnel field-effect transistors (TFETs) may enable a more aggressive reduction of the supply voltage than the MOSFETs, by lowering the sub-threshold swing (SS) under the thermionic limit of 60mV/dec at room temperature. Promising experimental results were reported for TFETs based on silicon and III-V semiconductors. However, in nanoscale devices, quantum confinement widens the band gaps and precludes the implementation of truly broken band gap alignments in 3D semiconductors [1], while interface states degrade the SS [2]. The use of semiconducting transition metal dichalcogenides (TMDs) may represent an extremely advantageous alternative thanks to their intrinsic 2D geometry and thinness, the absence of dangling bonds, and the variety of available materials, which results in a large range of energy band gaps and band alignments. In this contribution, we predict an extremely steep sub-threshold swing for inter-layer TFETs based on WTe2 and MoS2 layers with a 1 nm thick h-BN interlayer [3]. Figure 1 shows a sketch of the device and its equivalent 2D structure. Our full-quantum simulations are based on the non-equilibrium Green’s function formalism and accurately account for the device electrostatics by a self-consistent coupling to the Poisson equation. Electron-phonon scattering is calibrated to make the simulations consistent with available mobility experiments. By means of this numerical apparatus, we investigate the role of several relevant design parameters such as chemical doping, top gate geometrical alignment and back-gate biasing (see Fig.2). Our analysis reveals that carefully designed TMD TFETs can offer excellent SS values (<30 mV/dec) and represent a promising technology for future low-power nanoelectronics.

R e f e r e n c e s

[1] S. Brocard et al., IEDM Proceedings (2013)

5.4.1. [2] M. Pala et al., IEEE TED 60 (2013) 2795. [3] M. Li et al., J. Appl. Phys. 115 (2014) 074508.

F i g u r e s

Figure 1: (a) Sketch of the TFET under study. (b) Equivalent 2D model used in the simulations. The x2D axis corresponds to the y-direction for MoS2 and to x-direction for WTe2.

Jiang Cao1,

Marco Pala1, Alessandro Cresti1 and David Esseni2

[email protected]

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Figure 2: (a) Transfer characteristics as a function of the top-gate voltage VTG for different values of the gate extension in the contact regions. The SS is 100, 27 and 17 mV/dec for Lext = 0, 5 and 10nm, respectively. (b) Output characteristics for different top-layer dopant concentration ND and back-gate voltage VBG. (c) Band profile and energy spectrum of the inter-layer current density in the transistor on-state (VTG=0.3V).

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M o S 2 T r a n s i s t o r s w i t h E l e c t r o g r a f t e d O r g a n i c U l t r a t h i n F i l m a s E f f i c i e n t G a t e D i e l e c t r i c CEA Saclay, IRAMIS / NIMBE / LICSEN, F-91191 Gif sur Yvette, France

Two dimensional layered semiconductors, and in particular transition metal dichalcogenides such as molybdenum disulfide (MoS2), have recently received increasing attention due to the combination of their unique electronic properties with their atomically thin geometry. Contrary to graphene, MoS2 has a finite band gap of 1.2-1.9 eV (depending on the number of layers), thus complying with the requirements of digital electronic applications. To maximize the potential of MoS2 as channel material in field effect transistors, it must be associated with an efficient gate dielectric. Beside the mainstream CMOS technology, other fields such as large-area and/or printable electronics, sensors and display technologies could also benefit from the combination of 2D materials and new dielectrics, especially if these dielectrics present additional advantages in terms of mechanical flexibility, low temperature processes, conformability to structured substrates, cost and simplicity of equipment and processes, etc. In this respect, the development of robust organic nano-dielectrics and their combination with new semiconductors represent a high potential route. In this context, we developed new dielectrics based on electrografted organic thin films on metallic electrodes. These dielectrics are produced at room temperature and under mild conditions. The process yields uniform films of nanometer thickness (4-8 nm range). In this work [1], we demonstrated the first transistors combining MoS2 as channel material and an electrografted organic ultrathin film as gate dielectric. The transistors exhibit high ION/IOFF ratio together with steep subthreshold slope as low as 110 mV/decade. Besides, the transfer characteristics of these transistors have no-hysteresis due to the

hydrophobic and trap-free nature of our electrografted dielectric. The transistors reported in [1] were fabricated on rigid substrates and using mechanically exfoliated MoS2. Their potential in large scale (based on CVD MoS2) and flexible electronics will be discussed on the basis of our latest results.

R e f e r e n c e s

[1] H. Casademont, L. Fillaud, X. Lefèvre, B.

Jousselme, V. Derycke, submitted. F i g u r e s

Hugo Casademont,

Laure Fillaud, Xavier Lefevre, Renaud Cornut, Bruno Jousselme, Vincent Derycke

[email protected]

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F r o m G r a p h e n e t o P h o s p h e r e n e : t h e 2 D z o o Centre for Advanced 2D Materials and Graphene Research Centre National University of Singapore 6 Science Drive 2, Singapore 117546

The field of two dimensional materials is rapidly expanding with the isolation and synthesis of many atomically thin crystals that present a broad variety of physical and chemical properties which can be exploited in different areas of science and engineering. In this talk I will review the progress in this exciting new area of research.

Antonio H. Castro Neto

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H o l e M o b i l i t y E n h a n c e m e n t a n d p -d o p i n g i n M o n o l a y e r W S e 2 b y G o l d D e c o r a t i o n 1Center for Micro/Nano Science and Technology, National Cheng Kung Uni., Tainan, Taiwan 2Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, 11529, Taiwan 3Department of Applied Physics, Waseda University, Tokyo 169-8555, Japan 4Physical Sciences and Engineering, King Abdullah University of Science and Technology, Thuwal, 23955-6900, Kingdom of Saudi Arabia

Tungsten diselenide (WSe2) is an attractive transition metal dichalcogenide material, since its Fermi energy close to the mid gap makes it an excellent candidate for realizing p–n junction devices and complementary digital logic applications. Doping is one of the most important technologies for controlling the Fermi energy in semiconductors, including 2D materials. Moreover, the Fermi level engineering or doping in monolayer WSe2 is still relatively unexplored. Recently, Fang et al have reported transistors based on WSe2 using high-k materials as the gate dielectrics, where the chemically doped source/drain contacts exhibit low contact resistances. Selective treatment with potassium is able to form degenerately doped n+ contacts for electron injection while NO2 treatment forms p+ contacts [1–3]. Liu et al have demonstrated the n-type WSe2 FET by using indium as a contact metal [4]. Chuang et al have revealed that graphene can be a work-function-tunable electrode material for few-nanometre WSe2 FETs [5]. It is noted that the small molecules adsorbed on the 2D materials tend to desorb from the surfaces and the alkali metals are known to be sensitive to moisture and oxygen. Here we present a simple, stable and controllable p-doping technique on a WSe2 monolayer, where a more p-typed WSe2 field effect transistor is realized by electron transfer from the WSe2 to the gold (Au) decorated on the WSe2 surfaces. Related changes in Raman spectroscopy are also reported. The p-doping caused by Au on WSe2 monolayers lowers the channel resistance by orders of magnitude. The effective hole mobility is ∼100 (cm2/Vs) and the near ideal subthreshold swing of ∼60 mV/decade and high on/off current ratio of >106 are observed. The Au deposited on the WSe2 also serves as a protection layer to prevent a reaction between the WSe2 and the environment,

making the doping stable and promising for future scalable fabrication. R e f e r e n c e s

[1] Tosun M, Chuang S, Fang H, Sachid A B, Hettick M,

Lin Y, Zeng Y and Javey A, ACS Nano, 8 (2014) pp. 4948–53.

[2] Fang H, Tosun M, Seol G, Chang C T, Takei K, Guo J and Javey A, Nano Letters, 13 (2013) pp.1991–5.

[3] Fang H, Chuang S, Chang C T, Takei K, Takahashi T and Javey A, Nano Letters, 12 (2012) pp. 3788–92.

[4] Liu W, Kang J, Sarkar D, Khatami Y, Jena D and Banerjee K, Nano Letters, 13 (2013) pp.1983–90.

[5] Chuang H J, Tan X, Ghimire N J, Perera M M, Chamlagain B, Cheng M M C, Yan J, Mandrus D, Tománek D and Zhou Z, Nano Letters, 14 (2014) pp.3594–601.

F i g u r e s

Chang-Hsiao Chen1,

Chun-Lan Wu2, Jiang Pu3, Ming-Hui Chiu4, Pushpendra Kumar2, Taishi Takenobu3, Lain-Jong Li4

[email protected]

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N a n o - p a t t e r n e d g r a p h e n e o n p o l y m e r s u b s t r a t e b y d i r e c t p e e l - o f f t e c h n i q u e 1ICFO-Institut de Ciències Fotòniques, Mediterranean Technology Park, 08860 Castelldefels, Barcelona, Spain 2ICREA- Institució Catalana de Recerca i Estudis Avançats, 08010, Barcelona, Spain

A graphene on polyimide polymer film (Gr-PI film), obtained by direct peel-off technique, is proposed and investigated. Thanks to its high transparency, electrical conductivity, mechanical strength and chemical durability, the Gr-PI film is an ideal substrate for flexible electronic and optoelectronic devices, including transistors, light emitting diodes and plasmonic antennas. It is obtained using a straightforward method. After spin-coating and curing a PI film on graphene previously grown on copper, one can separate the Gr-PI film from the copper foil thanks to the difference in adhesive energy between the graphene-copper and graphene-PI interfaces. The resulting Gr-PI film shows an average electrical sheet-resistance ranging from 520 Ω/sq to 860 Ω/sq and very high optical transmission (>90%), which have allowed the demonstration of a transparent heater. The surface morphology of the Gr-PI film follows that of the copper foil, with the latter maintaining its surface properties and allowing in this way its re-use in subsequent chemical-vapor-deposition growths. The method can also be applied to patterned graphene, as it is demonstrated for nano size ribbons with a width of a few tens of nm.

F i g u r e s

T. L. Chen1,

D. S. Ghosh1, M. Marchena1 and V. Pruneri1,2

[email protected] and [email protected]

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T r a n s i s t o r s b a s e d o n g r a p h e n e o r d o u b l e w a l l c a r b o n n a n o t u b e h y b r i d s f o r o p t o e l e c t r o n i c s 1Institut Néel /CNRS, Univ. Grenoble Alpes, F-38000 Grenoble, France 2Département de Chimie Moléculaire, UMR CNRS-5250, Ins. de Chimie Moléculaire de Grenoble, FR CNRS-2607, Univ.Joseph Fourier Grenoble I, BP 53, 38041 Grenoble Cedex 9, France 3Université de Toulouse, UPS, INP, Institut Carnot CIRIMAT, 118 Route de Narbonne, 31062 Toulouse Cedex 9, France

Graphene and carbon nanotubes (CNTs) are ideal platforms for realizing new functional devices such as ultrasensitive gas detectors, molecular scale logics and quantum devices, due to their outstanding electrical properties. Particularly, double walled nanotubes (DWNTs) consisting of two concentric single walled CNTs, can be treated as structures of two twisted and stretched graphene bilayers that exhibit peculiar electronic properties, visible using molecule grafting on the outer wall [1]. Photo active molecules such as porphyrin molecules and terpyridine complex have the ability to reversibly switch between two or more stable states in response to external stimuli such as light, temperature or an electrical current, and can thus find application in molecular optoelectronics [2]. A few studies have already demonstrated the efficient photo induced charge transfer in CNT/porphyrin hybrid systems by using electrochemical methods, photoluminescence excitation experiments [3] as well as absorption spectra. Here we use Raman spectroscopy as a powerful tool both for the investigation of isolated DWNT and graphene and to study the charge transfer between the chemical dopants and sp2 carbon. We demonstrate field effect transistors based on isolated DWNT (or graphene) and functionalized with photo active molecules probed with combined Raman spectroscopy and electrical transport measurements. The role of light in the control of the state of the hybrid will be manifested and elucidated in terms of photo-induced charge transfer.

R e f e r e n c e s

[1] D. Bouilly, et al. ACS nano 5, (2011), pp.

4927-4934. [2] C. B. Winkelmann, et al. Nano lett. 7 (2007),

pp. 1454-1458. [3] F. Vialla, et al. Phys. Rev. Lett. 111 (2013),

pp.137402. F i g u r e s

Figure 1: Principle of the chromophore-DWNT transistors. The molecule is deposited on chip on the transistor. Light excitation of the chromophore acts as an optical gate.

Yani Chen1,

Frederic Lafollet2, Saioa Cobo2, Guy Royal2, Emmanuel Flahaut3, Dipankar Kalita1, Vincent Bouchiat1, Laëtitia Marty1, Nedjma Bendiab1

[email protected]

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P o l y m e r C o v a l e n t l y M o d i f i e d G r a p h e n e f o r N o n v o l a t i l e R e w r i t a b l e M e m o r y 1Key Lab for Advanced Materials, Institute of Applied Chemistry, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China 2Dep. of Polymer Science and Engineering, College of Chemistry and Chemical Engineering, Shanghai Jiao Tong Un., 800 Dongchuan Road, Shanghai 200240, China

The data storage performance, stability and reliability of the graphene memories have advanced significantly towards practical information storage applications. [1,2] A number of essential strategies can be employed to control and optimize the switching characteristics of graphene memories for practical information storage applications. Covalent functionalization of graphene oxide(GO) or, reduced graphene oxide(RGO) with electroactive polymers is an effective and versatile approach to tuning the electronic properties of graphene. The facile engineering of GO/RGO energy bandgap through polymer functionalization also provides an alternative route to supplement the lithographical patterning of graphene sheets into low dimensional nanostructures and chemical modification of graphene nanoribbons. By using the “grafting to” or “grafting from” method, we have synthesized a new series of soluble polymer-covalently grafted GO/RGO functional materials. Bistable electrical switching effects and non-volatile rewritable memory effects were observed in the ITO/graphene-based polymer/Al sandwiched devices (Fig.1), with small switch-on voltage of about -1~-2 V and the ON/OFF current ratio of more than 103. The non-volatile nature of the ON state and the ability to write, read and erase the electrical states fulfilled the functionality of a rewritable memory. Both the ON and OFF states were stable under a constant voltage stress for more than 104 s and survived up to 108 read cycles at a read voltage of -1.0 V.

R e f e r e n c e s

[1] Y. Chen, B. Zhang,G. Liu et al.,Chem. Soc. Rev.

41(2012)4688–4707.

[2] Y. Chen,G. Liu, C. Wang, W. Zhang, R.-W. Li, L. Wang, Mater. Horiz. 1(2014) 489-506.

F i g u r e s

Figure 1: Typical current density-voltage characteristics of a 0.16 mm2 Al/graphene-based polymer/ITO device.

Luxing Wang1, Cheng Wang1, Xiaodong Zhuang2, Bin Zhang1 and Yu Chen

*1

[email protected]

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B i l a y e r e d M o S 2 / g r a p h e n e s t r u c t u r e s w i t h a R e - a t o m i n a s u p e r c e l l : t h e o r e t i c a l s t u d i e s o f s t a b l e g e o m e t r i e s a n d e l e c t r o n i c p r o p e r t i e s Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, 4 Kosigin Street, 119334, Moscow, Russia

Last time quasi-two-dimensional transition metal dichalcogenides Mo(W)S2(Se2) are taking attention by their semiconducting properties in contrast to semimetallic graphene ones, that they have advantage of their using in semiconductor electronics [1]. At the same time multi-layer structures [2] including bilayers of Mo(W)S2 and graphene (G) are of interest by possibilities of controlling of the electronic and electro-optic properties. We propose new energetically stable MoS2/G90o form of bi-layers with 90o rotated graphene (G) regarding MoS2 layer, and consider by DFT simulations Mo(Re)S2/G structures with renium atom as a doping one in MoS2 supercell, or as an embedded atom between these two layers – MoS2/(Re)/G structures. Insertion of Re atoms into the MoS2-graphene structures determines their metallic properties, especially in MoS2/(Re)/G90o structure (Fig.) with high electronic density of states near Fermi level unlike semi-metallic graphene and Mo(Re)S2/G bilayer [3]. These structures may be important for the application as good metal nanoelements in electronics. Acknowledgements: This work was supported by RSF 14-12-01217. The calculations were performed using resources of the Supercomputer Complex of MSU and the Joint Supercomputer Center of the RAS.

R e f e r e n c e s

[1] H. Terrones, F. López-Urías, M. Terrones, Sci.

Rep. 3 (2013), 1549. [2] A. K. Geim, I. V. Grigorieva, Nature 499

(2013), 419.

[3] B. Sachs, L. Britnell,. T. O. Wehling, A. Eckmann, R. Jalil, B. D. Belle, A. I. Lichtenstein, M. I. Katsnelson, K.S. Novoselov. Appl. Phys. Letters 103 (2013), 251607.

F i g u r e s

Figure 1: Structures with the rhenium atom between MoS2 and G layers: a common view of MoS2/(Re)/G modification(a) and bellow the band energy structure with unit cell in inset (EF= -3.52 eV), the similar schemes of the MoS2/(Re)/G90o bilayer - (b), (EF= -3.38 eV).

L.A. Chernozatonskii and V.А. Demin

[email protected]

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2 D M a t e r i a l s G r o w t h : P r o s p e c t s a n d C h a l l e n g e s Texas Instruments Incorporated, Dallas, TX, USA

The isolation of graphene [1] now almost a decade ago has given rise to the revitalization of an old full set of materials, twodimensional materials (2DM) that have exceptional electrical, chemical and physical properties. Some of the materials under investigation in addition to graphene are hexagonal boron nitride (h-BN), semiconducting, metallic, and superconducting, transition metal dichalcogenides (TMD) with a general chemical formula, MX2 where M is for example equal to Mo, W, Ta, Nb, Zr, Ti, and X = S, Se and Te, and others. While h-BN is an excellent 2D insulator, TMD materials provide what neither graphene nor h-BN can, bandgap engineering that, in principle, can be used to create devices that cannot be fabricated with h-BN and graphene. Therefore, there is hope to integrate these materials for numerous device types for many applications ranging from inkjet printing, photonic applications, flexible electronics, and high performance electronics. However, before the engineering community can develop these products that use 2DM, basic material properties for each application needs full definition so as to select the most appropriate techniques for material preparation and growth. A number of deposition techniques have been used to prepare large area graphene, growth on SiC through the evaporation of Si at high temperatures [2], precipitation of carbon from metals [3], and chemical vapor deposition on Cu [4]. Direct growth of good quality graphene on dielectrics/semiconductors other than SiC has only been reported recently on Ge [5], but not on others. Considering that before 2004 only small flakes of isolated graphene could be grown, the community has madesignificant progress on large area continuous graphene films on Cu and Ge [6].

In addition, there are numerous chemical exfoliating techniques used to form graphene with a range of sizes [7]. CVD graphene and graphene on SiC have been shown exceptional transport properties, equivalent to the best graphene exfoliated from mined graphite. Thin film growth of h-BN on the other hand has been found to be more difficult than graphene nevertheless there are many reports on large area growth on metals but the quality is still not equivalent to h-BN exfoliated from “bulk grown h-BN” when used as a substrate or as a gate dielectric for graphene devices. Transition metal dichalcogenides present altogether different opportunities and difficulties in the preparation of low defect density large area single crystals. Of the many TMDs to select from, a lot of attention has been dedicated to MoS2 because of its long history in rheological applications and availability of naturally occurring crystals and at this time it is used as a platform for materials growth development techniques. Vapor transport, chemical vapor deposition, and molecular beam epitaxy are being developed to produce these materials for initial studies of materials physics device fabrication [8,9]. In this presentation I will present the state of the art results of graphene, h-BN, and a few TMD materials and their prospects for future electronic device applications.

R e f e r e n c e s

[1] Novoselov, K. S. et al. Two-dimensional

atomic crystals. Proceedings of the National Academy of Sciences of the United States of

Luigi Colombo

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America 102, 10451-10453, doi:10.1073/pnas.0502848102 (2005).

[2] Berger, C. et al. Ultrathin Epitaxial Graphite: 2D Electron Gas Properties and a Route toward Graphene-based Nanoelectronics. The Journal of Physical Chemistry B 108, 19912-19916, doi:10.1021/jp040650f (2004).

[3] Karu, A. E. & Beer, M. Pyrolitic Formation of Highly Crystalline Graphite Films. Journal of Applied Physics 37, 2179, doi: 10.1063 /1.1708759 (1966).

[4] Li, X. S. et al. Large-Area Synthesis of High-Quality and Uniform Graphene Films on Copper Foils. Science 324, 1312-1314, doi:10.1126/science.1171245 (2009).

[5] Lee, J.-H. et al. Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium. Science 344, 286-289, doi: 10.1126 /science.1252268 (2014).

[6] Lee, J. H. et al. Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium. Science 344, 286-289, doi: 10.1126 /science.1252268 (2014).

[7] Bonaccorso, F. et al. Production and processing of graphene and 2d crystals. Materials Today 15, 564-589 (2012).

[8] Zhan, Y., Liu, Z., Najmaei, S., Ajayan, P. M. & Lou, J. Large-Area Vapor-Phase Growth and Characterization of MoS2 Atomic Layers on a SiO2 Substrate. Small 8, 966-971, doi:10.1002/smll.201102654 (2012).

[9] Lee, Y.-H. et al. Synthesis of Large-Area MoS2 Atomic Layers with Chemical Vapor Deposition. Advanced Materials 24, 2320- 2325, doi:10.1002/adma.201104798 (2012).

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C o n t r o l l e d f u n c t i o n a l i z e d g r a p h e n e n a n o r i b b o n s p r o d u c e d f r o m c a r b o n n a n o t u b e s 1Institute for Polymers and Composites/I3N, University of Minho, Campus de Azurém, 4800-058 Guimarães, Portugal, 2Department of Chemistry, University of Minho, Campus de Gualtar, 4710-057 Braga, Portugal 3Pole for Innovation in Polymer Engineering (PIEP), Uni of Minho, 4800-058 Guimarães, Portugal, 4International Iberian Nanotechnology Laboratory (INL), Av. Mestre José Veiga, 4715-330 Braga, Portugal 5Computer Science and Technology Center, Uni. of Minho, 4710-057 Braga, Portugal 6Materials Science Centre, School of Materials, Uni. of Manchester, Manchester M13 9PL, U.K. 7Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Aarhus University, Building 1521, Ny Munkegade, 8000 Aarhus C, Denmark

Graphene nanoribbons (GNR) have received a great deal of attention due their promise for electronics and optoelectronic applications [1]. Recently, the formation of GNR was observed “in situ” by unzipping of carbon nanotubes under ultra-high vacuum scanning tunneling microscopy (UHV STM) [2]. The CNT under observation were functionalized by the 1,3-dipolar cycloaddition reaction [3], in which the concentration of covalently bonded functional groups can be controlled by the experimental functionalization conditions. This functionalization route was responsible for the unzipping of the CNT, and thus the GNR formation by unzipping of functionalized CNT was repeated in ethanol suspension. The present work demonstrates the formation of graphene nanoribbons in solution by unzipping of functionalized carbon nanotubes. The formation of the GNR prepared in solution was studied by UV visible spectroscopy, and the GNR obtained by solvent evaporation were analyzed by Raman spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) and scanning tunneling microscopy (STM). TEM and STM images demonstrated the formation of few layer graphene ribbons, and this result was confirmed by Raman spectroscopy. Molecular modeling was applied to study the crystalline stacking of functionalized GNRs yielding interlayer distances of 0.51 nm, in agreement with STM and XRD analysis. It was demonstrated that this interlayer distance was required to accommodate the functional groups attached to the graphene. Figure 1 depicts the Raman spectra of the functionalized carbon nanotubes and resulting GNR, showing evidence for the formation of few-layer graphene.

Acknowledgements: The authors acknowledge Fundação para a Ciência e Tecnologia (FCT) for project PEst-C/CTM/LA0025/2013 (Strategic Project - LA 25 - 2013-2014), and for E. Cunha’s PhD grant SFRH/BD/87214/2012. M. Melle-Franco acknowledges support by FCT through the program Ciência 2008 and the project SeARCH (Services and Advanced Research Computing with HTC/HPC clusters) funded under contract CONC-REEQ/443/2005. R e f e r e n c e s

[1] M. Terrones, A. Botello-Méndez, J. Campos-

Delgado, F. López-Urías, Y. Vega-Cantú, F. Rodríguez-Macías, A. Elías, E. Muñoz-Sandoval, A. Cano-Márquez, J. Charlier, H. Terrones, Nano Today, 5 (2010) 351.

[2] M. C. Paiva, W. Xu, M. F. Proença, R. M. Novais, E. Lægsgaard, F. Besenbacher, Nano Letters, 10 (2010) 1764.

[3] M. C. Paiva, F. Simon, R. M. Novais, T. Ferreira, M. F. Proença, W. Xu, F. Besenbacher, ACS Nano 4, (2010) 7379.

Eunice Cunha1,

Helena Rocha1, Maria C. Paiva1, M. Fernanda Proença2, Paulo E. C. Lopes3, Mariam Debs4, Manuel Melle-Franco5, Francis L. Deepak4, Robert Young6, Liv Hornekaer7

[email protected]

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F i g u r e s

Figure 1: Raman spectra of the carbon nanotubes, the functionalized carbon nanotubes and the graphene nanoribbons.

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R e s e a r c h A c t i v i t i e s a t M a c k G r a p h e MackGraphe – Graphene and Nanomaterials Reseach Center Mackenzie Presbyterian University, Sao Paulo- Brazil

MackGraphe initiated its activities in 2013 and has a start-up fund of approximately US$ 20,000,000.00, which includes the construction of a new building. The aim is to carry out graphene and nanomaterials synthesis (via both CVD growth and exfoliation), characterization, and device development, with special attention to photonic devices. The mission of MackGraphe is to investigate properties of graphene and nanomaterials with an applied engineering thinking. We expect strong collaboration with industries to develop technologies that meet the society needs. We are focused on seeking novelty in science and in technology innovation; recruiting the best and brightest students and researchers; and creating an environment to encourage long-term thinking. We present some results we obtained in modeling of current flow in biased bilayer graphene [1], a new method of direct dry transfer of chemical vapor deposition graphene to polymeric substrates [2], and application of nanomaterials in the generation of ultrashort pulses [3].

R e f e r e n c e s

[1] C. J. Páez, D. A. Bahamon, and Ana L. C.

Pereira, Current flow in biased bilayer graphene: Role of sublattices”, Phys. Rev. B 90, 125426 – Published 17 September 2014.

[2] Fechine, Guilhermino J. M.; Martin-Fernandez, Iñigo; Yiapanis, George; et al, “Direct dry transfer of chemical vapor deposition graphene to polymeric substrates”, Carbon Volume: 83, Pages: 224-231 Published: 2015

[3] H. G. Rosa, D. Steinberg, and E. A. Thoroh de Souza, “Explaining simultaneous dual-band carbon nanotube mode-locking Erbium-doped fiber laser by net gain cross section variation“, Optics Express, Vol. 22, Issue 23, pp. 28711-28718 (2014).

F i g u r e s

Figure 1: Perspective of the new building under construction which includes a clean room class 1000.

Figure 2 (a) Schematic representation of a BLG nanoribbon, with zigzag edges and width W, between left (L) and right (R) semi-infinite contacts. Spatial distribution of charge densities (left) and current densities (right) over each layer of the BLG [1].

E.A. Thoroh de Souza

[email protected]

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Figure 3 Schematic of the transfer method and sample after transfer. (a–d) Schematic: (a) graphene/metal and polymer film before transfer. (b) Polymer application step to form the metal/graphene/polymer stack. (c) Peeling of the metal step. (d) Final graphene/polymer stack. [2].

Figure 4 Output spectrum from a dual-wavelength EDFL based on CNT [3].

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D i s e n t a n g l i n g s p i n a n d v a l l e y d y n a m i c s i n m o n o l a y e r M o S 2 b y n o n -e q u i l i b r i u m o p t i c a l t e c h n i q u e s 1IFN-CNR, Piazza L. da Vinci 32, I-20133 Milano, Italy 2Dipartimento di Fisica, Politecnico di Milano, Piazza L. da Vinci 32, I-20133 Milano, Italy 3Dipartimento di Elettronica, Politecnico di Milano and IU.NET, I-20133 Milano, Italy 4Cambridge Graphene Centre, University of Cambridge, 9 JJ Thomson Avenue, Cambridge CB3 0FA, United Kingdom

The ability to control the valley degrees of freedom is the foundation of the emerging field of valleytronics [1]. Atomically thin Transition Metal Dichalcogenides (TMDs) are a promising platform for the implementation of new devices exploiting the valley degrees of freedom [2]. The lack of inversion symmetry, combined with a large spin-orbit interaction, leads to a conduction (valence) band with different spin-polarized minima (maxima) having equal energies [3]. These peculiar properties offer the possibility to develop a new valley-based electronics where information is carried not only by the spin, but also by the crystal momentum at multiple extreme points of the band structure. Any implementation of these concepts, however, needs to consider the robustness of valley and spin degrees of freedom, which are deeply intertwined. To this aim, here we measure separately the spin and valley relaxation dynamics of both electrons and holes in the prototypical TMD MoS2. We disentangle the different processes by the combination of ultrafast optical spectroscopy techniques, i.e. Time Resolved Circular Dichroism (TRCD) and Time Resolved Faraday Rotation (TRFR). TRCD experiments are performed by exciting the sample with an ultrashort circularly polarized pulse, resonant with the optical gap (650 nm), and measuring the difference between the transient absorption response probed by co- and counter- circularly polarized pulses. The transient absorption is measured on a broad energy range including the A (λ = 650 nm) and B (λ = 605 nm) excitonic transitions at K and K’. These measurements reveal an extremely fast intravalley relaxation of the spin of the photoexcited electrons at the bottom of the conduction band. Furthermore, our data demonstrate that the two non-equivalent valleys K

and K’ are strongly coupled and the valley polarization is strongly quenched after few ps [4]. In TRFR experiments the pump pulse, in analogy with TRCD, creates a spin polarized population of electrons/holes in the conduction/valence band, while the rotation angle of the linearly polarized probe pulse is measured by a balanced photodiode bridge technique. We use a two-color TRFR configuration, in which the energy of the probe pulse is tuned well below the absorption gap. In these conditions, the TRFR signal is only sensitive to the helicity-dependent light scattering of the photoexcited electron and hole populations. Since the probe pulse couples with the carrier orbital degree of freedom, the Faraday rotation signal is related to an unbalanced distribution of the photoexcited carrier orbital degrees of freedom. The orbital momentum in MoS2 single layer is locked with the valley index. Thus, the two color TRFR measurements probe exclusively the intervalley dynamics of electrons and holes. The combination of TRFR and TRCD allows us to disentangle intervalley and intravalley dynamics. Both TRCD and TRFR experiments are quantitatively explained by a set of rate equations which take into account intervalley and intravalley relaxation channels. These results are very useful for the engineering of spintronic and valleytronic devices based on single layer TMDs. R e f e r e n c e s

[1] Nebel C. E., Nature Materials 12, 690–691 (2013) [2] Bahnia, K., Nature Nanotech. 7, 488–489 (2012) [3] Zeng, H., Dai, J., Yao, W., Xiao, D., & Cui, X. Nature

Nanotech. 7, 490–3 (2012) [4] Wang, Q., et al. ACS Nano 7, 11087–93 (2013).

S. Dal Conte1,2,

F. Bottegoni2, E. A. A. Pogna2, S. Ambrogio3, D. De Fazio4, A. Lombardo4, M. Bruna4, A.C. Ferrari4, F. Ciccacci2, G. Cerullo2, M. Finazzi2

[email protected]

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3 d p r i n t i n g o f g r a p h e n e - p o l y m e r c o m p o s i t e s 1Cambridge Graphene Centre, University of Cambridge, Cambridge CB3 0FA, UK 2Cambridge Nanosystems, Cambridge CB5 8HY, UK

3d printing is a rapidly growing field. It consists in the deterministic layer-by-layer printing of 3d objects of almost any shape, from a Computer Aided Design source file. Its versatility [1], the limited number of process steps [1] and reproducibility [2], make 3d printing one of the most promising techniques for rapid design and prototyping. Fused Modeling Deposition (FMD) (i.e. layer-by-layer deposition of melted and extruded polymer through a nozzle [3]) is the most popular 3d printing technique thus far, because of its simplicity and the use of common thermoplastic polymers, such as Poly Lactic Acid (PLA) [4], Acrylonitrile Butadiene Styrene (ABS) [4], Polycarbonate (PC) [4], etc. However, polymer composites with Young’s Modulus higher than few GPa [5] or electrical conductivity higher than few S/m [6], or with a combination of both properties are still not available. Graphene’s electrical, thermal, optical and mechanical properties can be used to create composites with higher electrical and mechanical properties than the starting materials [7]. Here, we demonstrate 3d printing of a graphene-polymer filament by FMD. Graphene powder produced from methane plasma cracking (Fig1.a) is blended with PLA using two different routes: wet mixing in chloroform and dry mixing at 250°C. The composite is then extruded at 160°C into a solid filament (Fig1.c) and 3d printed by FMD. Figs.1d,e show pure polymer and graphene composite 3d-printed objects. The electrical and mechanical properties of the 3d printed structures are investigated by conductivity and tensile strength measurements. Ink-jet printing of graphene, as first reported in Ref. [8], is now an ever growing field, with increasing industrial interest, now

including a variety of other 2d materials. We believe our demonstration of 3d printing of graphene will also stimulate a new field, soon to include a variety of other layered materials. R e f e r e n c e s

[1] E M. Sachs, et al. Three-dimensional printing

techniques, US5204055 [2] D. Dimitrov, et al. CIRP Annals -

Manufacturing Technology, 52, 189 (2003). [3] S.S. Crump, Apparatus and method for

creating three-dimensional objects, US5121329

[4] L. Novakova-Marcincinova et al. World Academy of Science, Engineering and Technology 70, 396 (2012).

[5] M. Nikzad,et al. Materials & Design 32, 3448 (2011).

[6] S.J. Leigh et al. PLoS ONE 7, e49365 (2012). [7] A.C. Ferrari et al. Nanoscale

10.1039/C4NR01600A (2014). [8] Torrisi et al. ACS Nano, 6, 2992 (2012). F i g u r e s

Figure 1: (a) Graphene Powder, (b) PLA pellets (c) Filament of PLA (White) and Graphene-PLA (Black), (d) Printed structure with pure PLA and (e) graphene-PLA composite.

N. Decorde1,

R.C.T. Howe1, F. Tomarchio1, C. Paukner2, J. Joaug2, K. Koziol2, T. Hasan1, A.C. Ferrari1, F. Torrisi1

[email protected]

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G r a p h e n e / M o S 2 F l e x i b l e P h o t o -d e t e c t o r 1Cambridge Graphene Centre, University of Cambridge, Cambridge, UK 2Electrical Engineering Institute, Ecole Polytechnique Federale de Lausanne, Lausanne, Switzerland

We present a large area, flexible photodetector for visible wavelengths fabricated by stacking centimetre-scale chemical vapor deposited (CVD) graphene and CVD MoS2, both wet transferred onto a flexible polyethylene terephthalate (PET) substrate (fig. 1). In this configuration, MoS2 acts as an absorbing material for visible wavelengths, while graphene is primarily used as a conductive channel for photocurrent flow. When electron-hole pairs are generated in MoS2 upon illumination of the stack, MoS2 donates electrons to the p-doped graphene channel [1], resulting in a decrease of the total source-drain current. In this configuration, the device responsivity can be enhanced either by promoting the injection process from MoS2 to graphene through side-gating using a polymer electrolyte (fig. 2), a technique that is suitable for a flexible platform [2,3], or by increasing the photoconductive gain in the graphene channel by applying larger source-drain voltage. The photodetector has an internal responsivity as high as ~30A/W at 642nm. This is at least two orders of magnitude higher than previously reported values for bulk-semiconductor flexible membranes [4,5] and for other flexible photodetectors based on a combination of graphene and MoS2 [6,7,8]. The photocurrent is stable at different bending angles, with variations less than 15% for radiuses of curvature down to 6cm. R e f e r e n c e s

[1] ] W. J. Zhang, et al. Sci. Rep. 4 (2014). [2] H. Sirringhaus et al. Science 290 (2000) 2123. [3] A. Das et al. Nature Nanotech. 3 (2008) 210.

[4] W. Yang et al. Appl. Phys. Lett. 96 (2010) 121107.

[5] H. C. Yuan et al. Appl. Phys. Lett. 94 (2009) 013102.

[6] F. Withers et al. Nano Lett. 14 (2014) 3987. [7] D. J. Finn et al. J. Mater. Chem. C 2 (2014)

925. [8] Koppens et al. Nature Nanotech. 9, (2014)

780. F i g u r e s

Figure 1: Sketch of the flexible photodetector.

Figure 2: V trans-characteristics of the device at different optical powers.

D. De Fazio1, I. Goykhman1, M.

Bruna1, A. Eiden1, U. Sassi1, M. Barbone1, D. Dumcenco2 K. Marinov2 A. Kis2 and A.C. Ferrari1

[email protected]

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S i n g l e L a y e r M o S 2 u n d e r D i r e c t C o m p r e s s i o n : L o w P r e s s u r e B a n d - g a p E n g i n e e r i n g 1J. Heyrovsky Institute of Physical Chemistry of the ASCR, v.v.i., Dolejškova 2155/3, 182 23, Prague, Czech Republic 2Department of Physical and Macromolecular Chemistry, Faculty of Science, Charles University in Prague, Hlavova 2030, CZ-128 40, Prague 2, Czech Republic

Recently, the unique electronic properties of few layered transition metal dichalcogenides, such as MoS2, have been revealed. Monolayer MoS2 present a direct gap which evolves into an indirect one, as the number of layers increases [1]. Moreover, it has been observed that monolayer MoS2 may turn into an indirect gap semiconductor itself by applying stress, and even transform into a semimetal if the strain is increased [2,3,4]. The regime of the deformation (uniaxial, biaxial, hydrostatic…) and its sign (tensile or compressive) governs the possibility of achieving such electronic transformations, as well as the level of strain required for achieving the changes. In this work, we subject monolayer MoS2 samples to uniaxial compression along the c axis (up to 5 GPa), using a high pressure anvil cell, while monitoring the evolution of the samples with both Raman spectroscopy and photoluminescence measurements. From the evolution of the Raman frequencies of the normal modes with pressure we can distinguish three different electronic states: the direct and indirect gap semiconductor and the semimetal. But interestingly, and in contrast with previous works, the pressure levels required for observing these electronic changes are quite low and they are easily accessible under our experimental configuration: MoS2 samples directly compressed between two hard materials. The change to indirect gap semiconductor is observed just by closing the gem anvil cell, at around 0.5 GPa, and the transition to semimetal is achieved when pressure is increased above 2 GPa. Such results were confirmed by means of theoretical calculations and photoluminescence measurements. The later also provided information about the reversibility of the electronic changes observed under pressure. The transition from direct to indirect semiconductor is

a reversible process; however, once the semimetal state is reached the sample does not recover its semiconductor character after the pressure release. These results open new avenues for the application and development of optoelectronic devices based on these new materials of the family of molybdenum disulphide. Acknowledgements: This work was funded by Czech Science Foundation (project No. 14-15357S). R e f e r e n c e s

[1] Kin F. Mak, Changgu Lee, James Hone, Jie

Shan, Tony F. Heinz, Phys. Rev. Lett. 105 (2010) 2-5.

[2] Xiuming Dou, Kun Ding, Desheng Jiang, Baoquan Sun, ACS Nano, 8 (2014) 7458.

[3] Emilio Scalise, Michel Houssa, Geoffrey Pourtois, Valery Afanas’ev, André Stesmans, Nano Res. 5 (2012) 43.

[4] Hiram J. Conley, Bin Wang, Jed I. Ziegler, Richard F. Haglund, Jr., Sokrates T. Pantelides,Kirill I. Bolotin, Nano Lett. 13 (2013) 3626.

Elena del Corro1

Miriam Peña Álvarez1, Ángel Morales2, Ladislav Kavan1, Martin Kalbac1 and Otakar Frank1

[email protected]

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F i g u r e s

Figure 1: Schematic lateral view of a single layer MoS2 directly compressed in a gem anvil cell. Raman frequencies of the active normal modes of MoS2 as a function of loading pressure.

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H i g h Y i e l d a n d S c a l a b l e F a b r i c a t i o n o f N a n o / B i o H y b r i d G r a p h e n e F i e l d E f f e c t T r a n s i s t o r s f o r C a n c e r B i o m a r k e r D e t e c t i o n 1Department of Physics and Astronomy, 209 South 33rd Street, University of Pennsylvania, Philadelphia, PA, USA 2Fox Chase Cancer Center, 333 Cottman Avenue, Philadelphia, PA, USA

Graphene field effect transistors (GFETs) hold tremendous promise for use as biosensor transduction elements due to graphene's high mobility, low noise and all-surface structure with every atom exposed to the environment [1]. We developed a GFET array fabrication based on two approaches, pre-patterned transfer and post-transfer photolithography [1-2]. Both approaches are scalable, high yield, and electrically stable. Functional groups for protein immobilization were added to the GFET using various bi-functional pyrene-based linkers. One approach immobilized an azide engineered protein through a “Staudinger Reaction” chemistry with NHS-phosphine reacting with a 1-aminopyrene linker. Another approach bound an engineered antibody via 1-pyrene butanoic acid succinimidyl ester, where an amine group of the antibody reacts to the succinimide of the linker. GFETs were studied by Raman spectroscopy, AFM and current-gate voltage (I-Vg) characterization at several steps of the fabrication process. A sensing response was obtained for a breast cancer biomarker (HER2) as a function of target concentration (Figure 1). We have started to design multiplexed sensor arrays by adding several functional groups to GFETs on a single chip. Simultaneous detection with these devices will be discussed.

R e f e r e n c e s

[1] M. B. Lerner, et.al. Nano Letter, 14 (2014)

2709. [2] N. J. Kybert, et. al. Nano Research, 7 (2014),

95.

F i g u r e s

Figure 1: Illustration of anti-HER2 single chain variable fragments bounds to the graphene FET.

Madeline Díaz-Serrano1,

Pedro Ducos1, Matthew Robinson2, A.T. Charlie Johnson1

[email protected]

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A n t i f e r r o m a g n e t i c t o F e r r o m a g n e t i c p h a s e t r a n s i t i o n i n b i l a y e r g r a p h e n e 1Laboratorio de Bajas Temperaturas, Universidad de Salamanca, E-37008 Salamanca, Spain 2Dipartimento di Fisica, Universit`a degli studi di Pavia, I-27100 Pavia, Italy 3Laboratoire National des Champs Magn´etiques Intenses, CNRS-UJF-UPS-INSA, F-38042 Grenoble, France

We report on magnetotransport measurements up to 30 T performed on a bilayer graphene Hall bar, enclosed by two thin hexagonal boron nitride flakes. In the quantum Hall regime, our high-mobility sample exhibits an insulating state at the neutrality point which evolves into a metallic phase when a strong in-plane field is applied, as expected for a transition from a canted antiferromagnetic to a ferromagnetic spin-ordered phase. We individuate a temperature-independent crossing in the four-terminal resistance as a function of the total magnetic field, corresponding to the critical point of the transition. We show that the critical field scales linearly with the perpendicular component of the field, as expected from the underlying competition between the Zeeman energy and interaction-induced anisotropies. A clear scaling of the resistance is also found and a universal behavior is proposed in the vicinity of the transition [1]. Acknowledgements: This work has been supported by the following projects: JCYL SA226U13, FPU AP2009-2619, MINECO MAT2013-46308-C2-1-R, and European Union CTA-228043-EuroMagNET II Programme

R e f e r e n c e s

[1] S. Pezzini, C. Cobaleda, B. A. Piot,V. Bellani,

and E. Diez Physical Review B 90, 121404(R) (2014).

F i g u r e s

Figure 1: (a) Rxx as a function of Vg for increasing temperatures at B⊥ = Btot = 7 T. (b) Insulating T dependence of the longitudinal resistance at the neutrality point : the red line is a fit to Rxx∝ exp (Δ/2kBT). Inset: Optical microscopy image of the sample (the scale bar corresponds to 5 μm). (c) Rxx as a function of Vg for increasing B with fixed B⊥ = 5 T, at T 1.2 K. Inset: Gxx as a function of the filling factor for the same values of B. (d) Metallic T -dependence of Rxx. Inset: Gxx as a function of the filling factor for increasing temperatures in strong B.

E. Diez1,

S. Pezzini1,2, C. Cobaleda1 B. A. Piot3, V. Bellani2

[email protected]

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L a r g e - A r e a S i - D o p e d G r a p h e n e : C o n t r o l l a b l e S y n t h e s i s a n d E n h a n c e d M o l e c u l a r S e n s i n g 1Instituto de Física, Universidade de São Paulo, 05508-090 São Paulo SP, Brazil 2Key Laboratory of Advanced Materials (MOE), School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, China 3Department of Materials Science & Engineering, Universidad Carlos III de Madrid, Madrid, Spain 4Department of Physics and Center for 2-Dimensional and Layered Materials, The Pennsylvania State University, University Park, PA 16802, USA 5Institute of Carbon Science and Technology, Shinshu University, Wakasato 4-17-1, Nagano 380-853, Japan 6Advanced Materials Department, IPICYT, Camino a la Presa San José 2055, Col. L omas 4a sección, San Luis Potosí S.L.P., 78216, México 7Department of Physics, Advanced Physics and Astronomy, Rensselaer Polytechnic Institute, 100 Eighth Street Troy, NY, 12180, USA 8Department of Chemistry, Department of Materials Science and Engineering and Materials Research Institute, The Pennsylvania State University, University Park, PA 16802, USA

Chemical doping of graphene with different heteroatoms (e.g. B, N) is becoming a powerful way to tailor its electrical and chemical properties. Extensive studies have been carried out on N- and B-doped graphene. However, there are few reports on Si-doped graphene (SiG) so far. Here we report the controllable synthesis of large-area SiG sheets for the first time using methoxytrimethylsilane (MTMS) and hexane as precursors in a bubbler-assisted chemical vapor deposition (BA-CVD) setup. As a proof-of-concept, their application in probing different organic molecules (e.g. crystal violet, rhodamine B, methylene blue) was successfully demonstrated. We noted that significant enhanced molecular sensing was achieved when SiG was used as a probing surface in virtue of their enhanced Raman scattering effect. This unique enhancement of SiG was explained using ab initio calculations, in which local distortions caused by the presence of Si atoms increase the interaction of the dye molecules with the doped graphene surface, in addition to the presence of an incomplete valence electron caused by the Si atom. Subsequently, the laser electronic excitation generated in SiG is then transferred to the molecule, and give rise to the strong Raman scattering in which both graphene and the molecular vibrations of the dyes are detected [1].

R e f e r e n c e s

[1] Ruitao Lv et al., Adv. Mater. 26 (2014)7593–

7599.

Maria Cristina dos Santos1,

Ruitao Lv2 , Claire Antonelli3, Simin Feng4, Kazunori Fujisawa4, Ayse Berkdemir4, Rodolfo Cruz-Silva5, Ana Laura Elías4, Nestor Perea-Lopez4, Florentino López-Urías6, Humberto Terrones7 & Mauricio Terrones4,5,8

[email protected]

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O p p o r t u n i t i e s a n d c h a l l e n g e s o f

g r a p h e n e a p p l i c a t i o n i n p a s s i v e m i c r o -

a n d m i l l i m e t r e w a v e c o m p o n e n t s

Technical Research Centre of Finland, Tietotie 3, FI-02150 Espoo, Finland

Graphene was first isolated in 2004 and since numerous application concepts based on graphene have been demonstrated [1]. Graphene been recognized from the very beginning as promising candidates for future radio electronics because graphene shows extraordinarily large carrier mobility [2].

Up to now most of the radio related research focuses very much on development of high frequency graphene transistors. In just a few years, high frequency graphene transistors have reached a performance level rivalling the best semiconductor devices that have over sixty years research effort behind them [2,3].

However other unique properties of graphene have not been utilized so much in high frequency analog electronics so far. For example single-layer graphene has very low density of states, which leads to a strong quantum capacitance effect. Quantum capacitance of the graphene depends on applied voltage [4]. This effect has been used in varactors.

No radio circuitry can be built without passive components. It would be important to understand how visible to use graphene for fabrication passive radio components.

In this paper we evaluate opportunities of usage of graphene in passive micro- and millimetre wave components. The paper is presenting the physical properties of graphene in terms

of its application in passive micro and millimeter wave components;

review of applications of graphene in passive components including antennas, transmission lines, inductors and varactors

new type of a phase shifter based on effect of dependence of quantum capacitance on

applied voltage are proposed and theoretically analyzed.

Analysis shows that high resistance of single layer graphene is the main challenge of usage of graphene in passive devices. Though graphene is the best electrical conductor known, it is mono-atomic and thus the surface resistance is very high compared to metals at micro and mm-waves frequencies, even with the possibility of doping and electric field biasing of graphene. In these frequency ranges graphene is thus mostly a moderate to bad conductive surface. At microwave and mm-wave frequencies, graphene conductivity is essentially real and the electric field bias allows controlling this resistivity over a certain range.

The picture is quite different at terahertz frequency range above 500 GHz, as a result of the plasmonic nature of the imaginary conductivity allowing plasmonic modes. At terahertz electric field affects strongly the imaginary part of the graphene conductivity. This mode can be used in tunable terahertz devices, for example terahertz antennas and filters.

R e f e r e n c e s

[1] A. K. Geim & K. S. Novoselov , Nature Materials, 6, (2007), pp 183 - 191

[2] P. Avouris, Nano letters, 10, (2010), pp 4285–4294.

[3] F. Schwierz, Nature nanotechnology, 5, (2010), pp 487–496.

[4] A.S Mayorov, K.S Novoselov, M.I Katsnelson, A.K Geim, 105, (2010) Physical review, pp 136801(4).

[5] J. S. Gómez-Díaz and J. Perruisseau-Carrier, International Symposium on Antennas and Propagation (ISAP12), Nagoya (Japan), (2012), pp 239-242.

Vladimir Ermolov, Jan Saijets

[email protected]

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H i g h S p e e d – L a r g e A r e a – N o n d e s t r u c t i v e G r a p h e n e C h a r a c t e r i z a t i o n 1das-Nano, P.I. Mutilva Baja Calle G-6. E-31192 Mutilva Baja, Navarra. Spain 2CIC nanoGUNE. Tolosa Hiribidea, 76. E-20018 Donostia-San Sebastián, Spain 3Graphenea. Tolosa Hiribidea, 76. E-20018 Donostia-San Sebastián, Spain 4Dept. Fisica Fundamental, Universitat de Barcelona. C. de Martí i Franquès, 1,08028 Barcelona,Spain

In this paper we will present a new, ultra-fast device (Figure 1) for quality inspection of thin film materials. This machine inspects and determines the quality of thin film materials such as graphene (mono-layer and multilayer), PEDOT or ITO by a repeatable and reproducible [1] measurement process. The materials cited above are currently characterized by nano-scale tools (such as confocal Raman Spectroscopy, Atomic Force Microscopy or Transmission Electron Microscopy), and/or macro-scale methods (for example van der Pauw resistivity technique or optical microscopy) [2]. Our Thin Film Inspector covers the gap between the nano-scale tools and the macro-scale methods allowing the ultra-fast determination of the existence of inhomogeneities in the material. Our Thin Film Inspector is non-invasive (metallic contacts are not required), non-destructive (thin film material is not modified) and non-ionizing. Furthermore, our Thin Film inspector can measure the full area of the sample under examination and provide a quality map (Figure 2) at a very high speed (over 10.000 mm2,@ 1 mm2 resolution), and with a spatial resolution of 100 μm. R e f e r e n c e s

[1] Rouhi et al., Nano Research, (2012), Volume

5, Issue 10, pp 667-678 [2] Buron et al., Nano Letters (2012), Volume 12

Issue 10, pp 5074–5081

F i g u r e s

Figure 1: Thin Film Inspector.

Figure 2: Quality maps of several samples of Monolayer Graphene.

David Etayo1, Alex Lopez1,

Magdalena Chudzik1, Luis E. Hueso2, Amaia Zurutuza3, Javier Tejada4 and Eduardo Azanza1

[email protected]

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I n t e r n a t i o n a l S t a n d a r d i z a t i o n o n G r a p h e n e - b a s e d N a n o t e c h n o l o g y 1PTConsulting, 45144 Essen, Germany 2Karlsruher Institut für Technologie, 76344 Eggenstein-Leopoldshafen, Germany

International standards are more and more recognized as a tool for dissemination and exploitation of research results for developing industrial applications. To be successful in facilitating this transition, the process of standardization needs to be started as early as possible even if fundamental research has not established a satisfactory level of knowledge and industrial fabrication processes are not mature enough for commercialization. In the area of nanotechnology, international standardization started 10 years ago driven by the International Electrotechnical Commission (IEC) and the International Standardization Organization (ISO) with the establishment of the two technical committees IEC/TC 113 and ISO/TC 229. Currently, over 100 standards are published or under development. They cover a broad range of nanotechnologies topics from nanomaterials to nano-enabled batteries and nano-enabled photovoltaics as well as standards regarding environmental, health and safety aspects and the development of a comprehensive nanotechnology vocabulary. With the rise of graphene-based technologies, this topic was adopted by the committees IEC/TC 113 and ISO/TC 229 leading to the establishment of currently 8 graphene projects. On the European level, graphene standardization was identified as an important activity within the Graphene Flagship. Here standardization is not only needed from a technical point of view to ensure that material specifications and measurement methods are developed in consensus with the involved stakeholders. It also helps to improve the exchange of information across work packages and

supports the development process along the roadmap from research to commercialization. This workshop will introduce to the international standardization on graphene technologies and present the status reached. This includes the activities within the IEC and ISO nanotechnology committees and the recently established Graphene Flagship Standardization Committee which is now organizing the CENELEC Workshop on Specifications for Graphene Related Materials (WS SGRM). All this activities are well linked together to ensure the establishment of a comprehensive system of standards for graphene-based technologies. Furthermore, it should become clear how important it is especially for the industry to actively participate in the standardization process and what kind of service IEC and ISO provide to make this investment most efficient for its stakeholders. .

Alexandra Fabricius1 and Norbert Fabricius

2

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F L A G - E R A : T h e F E T F l a g s h i p E R A - N E T

MINECO, Spain

The FET Flagship ERA-NET, called FLAG-ERA, gathers national and regional funding organisation with the goal of supporting the FET Flagship initiatives and more generally the FET Flagship concept. Most funding organisations in Europe participate, either directly or as associated members. The project also fosters international cooperation with funding organisations outside Europe. FLAG-ERA thus offers a platform to coordinate a wide range of sources of funding towards the realization of very ambitious research goals. FLAG-ERA contributes to the construction of the two Flagship initiatives on Graphene and Human Brain research, and also offers support to the four non-selected pilots to progress towards their goals with adapted means. It does so through a range of activities: • In order to enable researchers funded through various sources to work in tight cooperation with each other in the context of the two Flagships, the funding organisations in FLAG-ERA coordinate their funding framework conditions. • In order to enhance complementarities and synergies of regional, national and European research programmes and initiatives, the funding organisations share information on these programmes and initiatives, identify gaps and overlaps, and can thus adapt their thematic program and launch new initiatives according to the identified needs. In particular, they launch Joint Transnational Call (JTC) enabling researchers from different countries to propose joint contributions to the Flagships. The FLAG-ERA JTC 2015 was closed on January 27th 2015. A total of 108 proposals were submited

with 408 participats. The proposals will be assessed by an independent international Scientific Evaluation Panel (SEP) with the help of external reviewers, experts in the Flagship topic/areas. The final funding decision by the National and/or Regional Research Funding Organisations (NRFOs) participating in the JTC is expected by September 2015. • Additionally, in order to encourage the actual construction of the Flagships and take-up of their results, the funding organisations organise networking sessions for the research communities and other stakeholders, including industry. The activities in FLAG-ERA are organised around periodic events gathering all stakeholders and structured in sessions dedicated to the various objectives and related tasks of the project. All activities are done with the long-term vision of the Flagship programme in mind, and the project extends slightly beyond the ramp-up phase in order to accompany the transition to the fully operational phase of the Flagships. F i g u r e s

Severino Falcon

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T u n i n g g r a p h e n e p r o p e r t i e s b y a m u l t i - s t e p t h e r m a l r e d u c t i o n p r o c e s s 1Instituto Nacional del Carbón, INCAR-CSIC, Apdo. 73, 33080 Oviedo, Spain. 2REPSOL, Centro de Tecnología, Carretera de Extremadura, km 18, 28935 Mostoles, Madrid

The chemical methods for producing graphene materials, via the formation of graphite oxide which must be subsequently exfoliated and reduced to obtain the final graphene, are among the most valuable due to their simplicity and easy scalability. The characteristics of the graphene materials obtained (rGO), which will determine their applicability, are greatly affected by the experimental conditions.[1,2] In any case, the use of single-step thermal treatment does not allow the properties of the materials obtained to be tuned as once the final temperature has been fixed, the resulting properties (C/O ratio, BET surface area, processability into suitable electroders, etc.) are also fixed. The aim of this work is to design a route for the preparation of rGOs of enhanced BET surface area as well as maximizing their suitability as electrodes in energy devices. For that, a GO obtained by a modified Hummers method was thermally exfoliated/reduced at 700 and 1000ºC by two single step procedures (ramp and flash pyrolisis) and by a novel multi-step procedure. The ramp pyrolisis in a single step gave rise to rGOs with low BET surface areas (~200 m2g-1) which are easily conformed into stable electrodes (Figure 1a). In contrast, by flash pyrolisis in a single step, high BET surface areas were obtained (~500 m2g-1) but it is not possible to conform them into stable electrodes (Figure 1b). By using the multi-step procedure developed herein it is possible to prepare rGOs that have an increased BET surface area (compared to that of the material prepared by the single-step ramp-heated material) and that are easily conformed into stable electrodes for electrochemical energy storage devices (Figure 1c). SEM images of the

rGOs indicate the formation of tridimensional structures derived from the expansion of the graphite oxide on heating, which is the factor responsible for the development of porosity in these graphene materials. In the case of the flash-pyrolized sample (Figure 2a) cavities with sizes more in the range of mesopores are observed, contributing to an increment in the BET surface area and to the loss of suitability as electrodes. These structures are not so abundant in the ramp-heated sample, which explains its lower BET surface area (Figure 2b). An intermediate situation is obtained by the multi-step procedure, which explains the high BET surface area and good suitability as electrode of these materials. Acknowledgements: The authors thank REPSOL for their financial support; project SAVE Dr. P. Alvarez also acknowledges MICINN for her Ramon y Cajal contract. Work patented (ref: EP14382352.4).

R e f e r e n c e s

[1] McAllister MJ et al. Chem Mater 19 (2007)

4396. [2] Botas C et al. Carbon 50 (2012) 275.

Laura Fernández-García1,

Patricia Álvarez1, Marcos Granda1, Clara Blanco1, Ricardo Santamaría1, Patricia Blanco1, Zoraida González1, Uriel Sierra1, Antonio Páez2, Rosa Menéndez1*

[email protected]

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F i g u r e s

Figure 1: Thin Film Inspector.

Figure 2: Quality maps of several samples of Monolayer Graphene.

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T h e E u r o p e a n r o a d m a p f o r s c i e n c e a n d t e c h n o l o g y o f g r a p h e n e a n d r e l a t e d m a t e r i a l s Cambridge Graphene Centre, Cambridge CB3 OFA, UK

I will present the science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems developed within the framework of the European Graphene Flagship[1]. I will focus on some emerging application areas, such as the integration of graphene with silicon photonics, and flexible devices. R e f e r e n c e s

[1] AC. Ferrari et al., Nanoscale, 2014, DOI:

10.1039/C4NR01600A

Andrea C. Ferrari

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H a r n e s s i n g l i g h t t o t u n e t h e t o p o l o g y o f m a t e r i a l s 1Ins. de Física Enrique Gaviola (CONICET) and Univ. Nacional de Córdoba, Argentina 2Universidad Técnica Federico Santa María, Valparaíso, Chile 3CONICET, Centro Atómico Bariloche and Instituto Balseiro, Comisión Nacional de Energía Atómica, 8400 San Carlos de Bariloche, Argentina

The understanding lightmatter interaction has led to many practical applications. Raman spectroscopy, an outstanding tool for graphene characterization, is a prominent example. But beyond characterization, several studies proposed much deeper effects of laser illumination on the electronic properties of a material like switching off the conduction in graphene [1,2], thereby allowing to tune the material's response with optical means, or even inducing new (tunable) topological phases in otherwise trivial materials [1,3,4] (i.e. a Floquet topological insulator ). The latter is very promising as it would enormously expand the playground of topological insulators to a broader set of materials. Recently, laserinduced bandgaps have been experimentally verified at the surface of a topological insulator [5] adding much thrill to this area. In this talk I will provide an overview of the recent developments in this field with a focus on the generation of Floquet chiral edge states in graphene [6,7] (Fig. 1(a)), bilayer graphene [8] and other materials [9,10]. The emergence of a Hall response without Landau levels [11,12] (see scheme in Fig. 1(b)), similarities and differences with the integer quantum Hall effect (like the breakdown of the connection between usual topological invariants and the Hall conductance [11]), and a few open problems will also be highlighted.

R e f e r e n c e s

[1] T. Oka and H. Aoki, Phys. Rev. B 79 (2009)

081406. [2] H. L. Calvo, H. M. Pastawski, S. Roche, and L.

E. F. Foa Torres, Appl. Phys. Lett. 98 (2011) 232103;H. L. Calvo, P. M. PerezPiskunow, S. Roche, and L. E. F. Foa Torres, Appl. Phys. Lett. 101 (2012) 253506 (2012).

[3] N. H. Lindner, G. Refael, and V. Galitski, Nat. Phys. 7 (2011) 490.

[4] T. Kitagawa, T. Oka, A. Brataas, L. Fu, and E. Demler, Phys. Rev. B 84 (2011) 235108.

[5] Y. H. Wang, H. Steinberg, P. JarilloHerrero, and N. Gedik, Science 342 (2013) 453.

[6] P.M. PerezPiskunow, G. Usaj, C. A. Balseiro, and L. E. F. Foa Torres Phys. Rev. B, 89 (2014) 121401(R).

[7] G. Usaj, P. M. PerezPiskunow, L. E. F. Foa Torres, and C. A. Balseiro Phys. Rev. B, 90 (2014) 115423.

[8] E. Suárez Morell and L. E. F. Foa Torres Phys. Rev. B, 86 (2012) 125449.

[9] H. L. Calvo, L. E. F. Foa Torres, P. M. PerezPiskunow, C. A. Balseiro, G. Usaj, to be published .

[10] V. Dal Lago, L. E. F. Foa Torres, to be published .

[11] L. E. F. Foa Torres, P. M. PerezPiskunow, C. A. Balseiro, and G. Usaj Phys. Rev. Lett., 113 (2014) 266801.

[12] Related publications and updates available at http://nanocarbon.famaf.unc.edu.ar/

P. M. PerezPiskunow1 , H. L. Calvo1 , V. Dal Lago1 , E. Suárez Morell2 , C. A. Balseiro3 , G. Usaj3 and Luis E. F. Foa Torres

1

[email protected]

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F i g u r e s

Figure 1: The scheme in (a) represents the chiral edge states predicted in illuminated graphene. These chiral edge states lead, in a multiterminal setup as shown in panel (b), to a Hall response.

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S o l a r e n e r g y c o n v e r s i o n i n v a n d e r W a a l s h e t e r o s t r u c t u r e s 1Institute of Photonics, Vienna University of Technology, Gusshausstrasse 27-29, 1040 Vienna, Austria 2Institute for Theoretical Physics, Vienna University of Technology, Wiedener Hauptstrasse 8-10,1040 Vienna, Austria

Photovoltaic cells for solar energy harvesting are today mainly made out of crystalline semiconductors or organic compounds. Beside the high production costs, crystalline semiconductor cells have the drawback of being heavy and bulky. Organic cells, on the other hand, suffer from low carrier mobility and short lifetime of the organic material. To overcome these drawbacks, we engineered a new type of solar cell based on atomically thin transition metal dichalcogenide (TMDC) layers. Due to the thickness of the used materials the advantages of low raw material costs, high flexibility and semi-transparency are intrinsic parameters. This, combined with the wide range of available band gaps and the good carrier mobility make atomically thin TMDC crystals a promising candidate for next generation solar cells[1]. Recent work demonstrated that atomically thin WSe2 can be electrostatically doped such that hole and electron conduction is achieved and that it can be used to realize a lateral hetero-junction which can be operated as a solar cell[2]. The main drawback of the mentioned structure is the small interaction area. To overcome this limitation, we fabricated planar van der Waals heterojunctions by stacking two[3], and also multiple, atomically thin TMDC layers. Figure 1a shows that such a planar p-n can indeed be used for efficient solar energy harvesting. Besides measurements of electrical transport and the photovoltaic properties, we will present photoluminescence measurements that clarify the working principle of these devices. In addition we will present improved cells, formed by a triple TMDC heterojunction as schematically depicted in Figure 1b.

R e f e r e n c e s

[1] D. Jariwala et al., ACS Nano, 8 (2014) 1102-

1120. [2] A. Pospischil et al., Nature Nanotechnology, 9

(2014) 257-261. [3] M.M. Furchi et al., Nano Letters, 14 (2014)

4785-4791. F i g u r e s

Figure 1: (a) I-V characteristic of the MoS2 – WSe2 heterostructure device under optical illumination with Popt =180…6400 W/m2. (b) Schematic illustration of a triple junction heterostructure device.

Marco M. Furchi1,

Andreas Pospischil1, Armin A. Zechmeister1, Florian Libisch2, Joachim Burgdörfer2 and Thomas Mueller1

[email protected]

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G r a p h e n e O x i d e B a s e d E l e c t r o d e s f o r S u p e r c a p a c i t o r s w i t h E n h a n c e d C y c l i c P e r f o r m a n c e Centre for Advanced Photonics and Electronics, Department of Engineering, University of Cambridge, 9 J. J. Thomson Ave., CB3 0FA, Cambridge, UK.

Graphene and graphene-based materials have attracted significant recent attention because of their unique properties and have emerged as a new class of promising electrode material in supercapacitors. Among the various approaches, chemical exfoliation of graphite has provided an affordable route to the large scale processing of graphene-based materials. The most common chemical means of graphite exfoliation is the use of strong oxidizing agents to yield graphene oxide (GO). For GO, contiguous aromatic lattice of graphene is interrupted by epoxides, alcohols, ketone carbonyls and carboxylic groups. These surface oxides make GO electrically insulating but, hydrophilic and thus, allow intercalation of water and polar solvent molecules between the GO layers. Although GO is not a preferred electrode material for supercapacitors due to its electrically insulating nature, in this study we exploit the ability of GO to interact with organic solvents to enhance the cyclic performance of GO based supercapacitors. Deviating from the normal supercapacitor behaviour, for GO based supercapacitors, a gradual increase in specific capacitance was observed with the cycle number. Free standing, flexible GO paper was synthesised using graphite oxide derived from vein graphite following Hummer’s method and used as the electrode material. The morphology and chemical structure of the material were characterized by means of scanning electron microscopy, Raman spectroscopy, X-ray diffraction and Fourier transform infrared spectroscopy. Thermal properties were investigated using thermo gravimetric analysis. The electrochemical properties of as obtained GO paper were investigated, together with its thermally reduced component (r-GO) for comparison. For electrochemical characterisation, two-electrode symmetrical supercapacitor cells were constructed and characterized by cyclic voltammetry and electrochemical impedance spectroscopy. Tetraethylammonium tetrafluoroborate (TEABF4) in

Propylene Carbonate (PC) was used as the electrolyte. The results showed that for GO based supercapacitors, the specific capacitance increased by approximately six times (from 71 mF g-1 to 422 mF g-1) after 24,000 cycles. After 24,000 cycles, the specific capacitance decreased gradually, but even after 85,000 cycles the value did not drop below the initial specific capacitance (258 mF g-1 after 85,400 cycles). However, for r-GO based supercapacitors, the specific capacitance decreased gradually with cycle number revealing the usual supercapacitor behaviour. This confirms that, the enhanced cyclic performance of GO based supercapacitors can be attributed to the presence of functional groups on GO. Their ability to interact with PC, allows PC molecules to intercalate between the graphene sheets, facilitating exfoliation of graphene sheets as confirmed by X-ray diffraction data. Subsequent increase in the electrochemically accessible surface area of the electrode material increases the specific capacitance of GO based supercapacitors. Although GO based supercapacitors exhibit relatively lower specific capacitance due to the electrically insulating nature of GO, when GO is mixed with a suitable conductive electrode material, the resulting composite may benefit from the presence of GO to enhance the cyclic performance. R e f e r e n c e s

[1] Hummers Jr., W. S., Offeman, R. E, J. Am. Chem.

Soc., 80 (1958), 1339–1339 [2] Dikin, D. A. et al. , Nature Letters, 448 (2007),

457-460

D. Thanuja L. Galhena Bernhard C. Bayer, Stephan Hofmann and Gehan A. J. Amaratunga

[email protected]

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G r a p h e n e - b a s e d e l e c t r o n i c s f o r b i o m e d i c a l a p p l i c a t i o n s Walter Schottky Institut, Technische Universität München, Am Coulombwall 4, Garching, Germany

Graphene and graphene-based materials possess a rather exclusive set of physicochemical properties holding great potential for medical and biomedical applications. In this presentation, I will provide an overview on fundamentals and applications of several graphene-based technologies and devices, namely solution-gated field-effect transistors and microelectrode arrays based on CVD-grown graphene. I will first introduce the science and technology of such electronic devices, both on rigid and flexible substrates, discussing the influence of the intrinsic properties of CVD graphene (e.g. grain boundaries) and comparing their performance with other competing technologies. The presentation will further discuss on the functionalization of these devices aiming at the introduction of specific sensing mechanisms, which is of particular relevance for the development of chemical and biochemical sensors. Based on these technologies, I will also report on experiments aiming at the bidirectional communication with electrogenic cells as well as the detection of neurotransmitters, suggesting a bright future for graphene-based technologies in the field of neuroprosthetics.

Jose A. Garrido

[email protected]

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S t i f f e n i n g g r a p h e n e b y c o n t r o l l e d d e f e c t c r e a t i o n 1Departamento de Física de la Materia Condensada, Universidad Autónoma de Madrid, 28049, Madrid, Spain

Graphene, due to its extremely high in plane stiffness and low bending rigidity, presents important out of plane thermal fluctuations crucial for the understanding of its mechanical properties. In this work we measure the variation of the stiffness of graphene with induced vacancy density using AFM nanoindentations. Unlike predicted, we find that the stiffness of graphene increases with defect content until a vacancy density of 0.2 percent, where it doubles its initial value. For higher defect density the elastic modulus exhibits a decreasing tendency. We attribute the initial increase in stiffness to the quenching of the out of plane oscillations of graphene due to defects [1]. In order to validate this interpretation we also study the dependence of the elastic modulus with strain. We observe an increase of the Young’s modulus at pre-strains higher than 0.5 percent where it again doubles its initial value. R e f e r e n c e s

[1] Lopez-Polin et al. Nature Physics accepted

C. Gómez-Navarro1,

G. López-Polín1, V. Parente, F. Guinea, M. I. Katsnelson, F. Pérez-Murano, J. Gómez-Herrero1

[email protected]

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G r a p h e n e r e s e a r c h a t I C N 2 1ICN2 - Institut Català de Nanociència i Nanotecnologia 2CSIC - Consejo Superior de Investigaciones Científicas Edifici ICN2, Campus UAB, 08193 Bellaterra, Spain

ICN2 is turning research into marketable technologies with the expertise of over 200 scientists and technicians that put their work in the whole value chain, from fundamental research all the way to design, fabrication, and evaluation of nanotechnology-based devices. The Institute offers a full suite of advanced instruments available for research and innovation in fields such as energy, biosystems (medical and environmental), and information and communication technologies. Our activities take place in a stimulating environment, close to Barcelona, where over 500 researchers and 200 technicians work on materials science and micro/nanotechnologies within the Barcelona Nanotechnology Cluster - Bellaterra (www.bnc-b.net), a cluster comprising several public and private research centers, the Universitat Autónoma de Barcelona, and the ALBA Synchrotron. Graphene research is one of the cornerstones of the work developed by ICN2’s multidisciplinary groups. The Institute promotes collaboration among scientists from diverse backgrounds (physics, chemistry, biology, engineering) to conduct basic and applied research, always seeking interaction with local and global industries. In this sense, graphene is one of the basic tools that ICN2 uses to develop its science and technology. The ultimate goal is to produce devices for real life applications, which can be only developed from the discovery and deep knowledge of the most fundamental aspects of the materials and nanostructures.

Graphene research at ICN2

encompasses four major

areas:

Predictive modelling of materials and devices. Theoreticians and experimentalists work together to create, validate, and refine models that predict the behavior of graphene. Production methods. ICN2 conducts research to achieve higher levels of control over size, shape, and layers, to develop large-scale fabrication processes and to produce customized graphene-based materials. Characterization and testing. ICN2 research groups define properties of graphene, measure electronic thermal and quantum phenomena in graphene-based devices, and test how graphene reacts to realistic external forces. Device design, fabrication and evaluation. Graphene-based biosensors, solar cells, supercapacitors, and information and communication devices are being developed. F i g u r e s

Figure 1: Simulated charge mobility of polycrystalline graphene. D.V. Tuan, J. Kotakoski, T. Louvet, F. Ortmann, J. C. Meyer, and S. Roche, Nano Letters, 13(4), 1730-1735 (2013).

Pedro Gómez-Romero1,2

www.icn2.cat/graphene [email protected]

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Figure 2: Top: Scanning Tunnelling Microscopy image of a triangular graphene nanoisland grown on a Ni(111) surface. Middle: Suspended graphene multiply connected. Bottom: Silicon chip covered with graphene.

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H y b r i d p o l y o x o m e t a l a t e / r e d u c e d g r a p h e n e o x i d e c o m p o s i t e s f o r s u p e r c a p a c i t o r s 1Institut Català de Nanociència i Nanotecnología, ICN2-CSIC,UAB Campus 08193 Bellaterra, Spain. Phone: +34 937373608 2Present Address: European Commission, DG Joint Research Centre, Institute for Energy and Transport, P.O. Box 2, 1755 ZG Petten, The Netherlands

In this work, we present the novel synthesis and electrochemical study of polyoxometalate-graphene oxide hybrid materials to be used as electrode in Supercapacitors (SCs). The synthesis involves the reduction of graphene oxide (GO) with simultaneous incorporation of polyoxometalate (POM).1 The existence of the strong chemisorption between polyoxometalate and graphene oxide makes it possible to construct stable hybrid carbon structures. Hybrid materials were carried out in a single step by means of a hydrothermal treatment (120 °C, 24 h) of an aqueous solution of polyoxometalate: H3PMo12O40.10H2O (PMo12) and exfoliated graphene oxide (GO). The resulting materials (labeled HT-RGO-PMo12) was filtered-off, washed and dried at 50 °C overnight. The amount of POM impregnated was determined by TGA. A similar treatment of a GO sample without POM added was carried out for comparison (sample HT-RGO). Figure 1 shows the HR-TEM images of the blank HT-RGO sample (Fig, 1A) and HT-RGO-PMo12 (Fig. 1B). The presences of the inorganic POM clusters on the surface graphene are clearly detected in the latter image, and are evenly distributed at a truly molecular level and no agglomerate or nanocrystal could be detected. The electrochemical characterization of the hybrid materials was tested by cyclic voltammetry and galvanostatic charge-discharge test in two- and three- electrodes configurations, where platinum wire and Ag|AgCl were used as counter and reference electrode, respectively. 1 M H2SO4 was the electrolyte.

R e f e r e n c e s

[1] [1] Suárez-Guevara, J.; Ruiz, V.; Gomez-

Romero, P. J. Mater. Chem. A, 2 (2014), 1014 – 1021.

F i g u r e s

Figure 1: HR-TEM images of HT-RGO (A) and HT-RGO-PMo12 (B). Scale bars are 10 nm.

Jullieth Suarez-Guevara1, Vanesa Ruiz1,2 and

Pedro Gomez-Romero1*

[email protected], jullieth.suarez@gmail,com, [email protected]

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G r a p h e n e d r u m m e c h a n i c a l r e s o n a t o r s d e t e c t e d b y m i c r o w a v e s National Physical Laboratory, Teddington TW11 0LW, UK 1Imperial College London, Department of Materials, London SW7 2AZ, UK 2Wroclaw University of Technology, ul. Janiszewskiego, 11/17, 50-372 Wroclaw, Poland

The self-supporting monolayer material which is graphene has excited enormous interest over the ten years since its discovery due to its remarkable electrical, mechanical, thermal and chemical properties. We describe transfer of graphene onto a patterned SiO2/Si substrate which provides freely suspended graphene drums ranging in size from 2m to 40m which are being explored as nano-electromechanical (NEMS) resonators. An SEM image of an array of patterned structures for our graphene NEMS resonators is shown in Fig. 1a. An AFM scan across a 5m square graphene suspended membrane is shown in fig. 1b). As electromechanical devices become smaller, approaching the nanoscale, the oscillation displacement amplitude scales down in proportion to size. Thus new ultra-sensitive transducer techniques and low dissipation excitation schemes are needed to operate NEMS sensors. Microwave measurement using high Q resonators becomes attractive due to the high sensitivity of frequency measurement and the very low phase noise from synthesized microwave sources, in contrast with optical systems. We have developed a novel near-field microwave probe system which is able to simultaneously excite and readout the oscillation of a range of mechanical resonators, from hundreds of microns to sub-micron size. By using a quarter wave microwave coaxial resonator with the open end connected to a sharp tip we can produce a very localized intense microwave field in a very limited region close to the tip. The spatial range of this high field region is on the order of the radius of curvature of the tip, which can be, comparable to the smallest mechanical resonator dimensions.

We report experimental data on these drums using a variety of microwave excitation and readout methods. An important issue is that there is strong coupling between graphene and microwave fields. This relates to the relatively close matching of the impedance of free space, or a confined geometry like a microwave resonator, and the sheet resistance of high quality graphene [1], making the microwave method particularly suitable for application to graphene NEMS resonator based sensors [2]. R e f e r e n c e s

[1] L. Hao, J. Gallop, S. Goniszewski, O.

Shaforost, N. Klein and R. Yakimova, ‘Non-contact method for measurement of the microwave conductivity of graphene’, Appl. Phys. Lett. Vol.103, 123103 (2013)

[2] Ling Hao, Stefan Goniszewski, Jie Chen and John Gallop, ‘Microwave excitation and readout of nano- and micron scale cantilevers’, Applied Surface Science vol. 258 pp. 2192-5 (2012).

Ling Hao, Stefan Goniszewski1, Trupti Patel, K. Gajewski2 and John Gallop

[email protected]

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F i g u r e s

Figure 1: a) SEM image of the fabricated substrate showing the array of features for graphene suspension. b) AFM image of a 5μm square graphene drum, with line scan across central region.

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T h e r o l e o f g r a p h i t e n a n o p l a t e l e t s a n d c a r b o n n a n o t u b e s o n t h e e n h a n c e d f r a c t u r e t o u g h n e s s a n d e l e c t r i c a l c o n d u c t i v i t y o f p o l y p r o p y l e n e c o m p o s i t e s 1IMDEA Materials Institute, C/ Eric Kandel 2, 28906, Getafe, Madrid, Spain 2AITIIP Centro Tecnológico, P. I. Empresarium, C/ Romero 12, 50720, Zaragoza, Spain 3Dep. of Mechanical Engineering, University of Zaragoza, EINA, Av. María de Luna 3, 50018, Zaragoza, Spain

In recent years, materials researchers have focused their interest on polymer nanocomposites[1], being carbon-based nanostructures envisioned as promising nanofillers, due to its outstanding mechanical, electrical and thermal properties[2,3]. In this work, commercially available carbon nanotubes (CNT) and graphite nanoplatelets (GNP), composed by multiple graphene layers stacked together by van der Waals forces, have been used to produce polypropylene (PP) nanocomposites. This materials were manufactured following an industrial approach as it is the masterbatch technique[4,5]. The CNT/PP composites, shows a significant increase in the electrical conductivity for the nanocomposites with 5 and 10 wt.% of CNT. A processing-induced anisotropy[6,7] is observed in the electrical conductivity, being different in the three directions of the injection-moulded bars. The fracture toughness has been determined applying a single-specimen technique, the Spb parameter method[8]. For the nanocomposites manufactured, the fracture mechanism has been identified as void nucleation and growth, by scanning electron microscopy. This is also the fracture mechanism that takes place in the neat PP. The manufactured nanocomposites presents an improved fracture toughness with loadings up to 10 and 2.5 wt.% of CNT and GNP, respectively. The results obtained by the strain field analysis around the crack tip, performed by digital image correlation, indicates that this may be explained in terms of variation of size of the deformation zone ahead the crack tip.

Finally, in this work it has been demonstrated how an scalable machine and an industrial masterbatch compounding approach can be applied to a thermoplastic, in order to obtain nanocomposites with improved fracture toughness and electrical conductivity, opening the way to a wider industrial utilization of these materials. R e f e r e n c e s

[1] E. T. Thostenson, C. Li, T.-W. Chou, Compos.

Sci. Technol., 65 (2005), 491. [2] G. Mittal, V. Dhand, K. Y. Rhee, S.-J. Park, W.

R. Lee, J. Ind. Eng. Chem. n.d., DOI 10.1016/j.jiec.2014.03.022.

[3] Y. Zhu, S. Murali, W. Cai, X. Li, J. W. Suk, J. R. Potts, R. S. Ruoff, Adv. Mater., 22 (2010), 3906.

[4] K. Prashantha, J. Soulestin, M. F. Lacrampe, P. Krawczak, G. Dupin, M. Claes, Compos. Sci. Technol., 69 (2009), 1756.

[5] Y.-C. Li, G.-H. Chen, Polym. Eng. Sci., 47 (2007), 882.

[6] M. Ganß, B. K. Satapathy, M. Thunga, R. Weidisch, P. Pötschke, D. Jehnichen, Acta Mater., 56 (2008), 2247.

[7] R. J. Kuriger, M. K. Alam, D. P. Anderson, R. L. Jacobsen, Compos. Part Appl. Sci. Manuf., 33 (2002), 53.

[8] L.C. Herrera-Ramírez, P. Castell, J.P. Fernández-Blázquez, A. Fernández Cuello, R. Guzmán de Villoria, Compos. Sci. Technol., Submitted article (2014)

L. C. Herrera-Ramírez1,

P. Castell2, A. Fernández Cuello2,3 and R. Guzmán de Villoria1,*

[email protected]

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G r a p h e n e G r o w t h D y n a m i c s a n d P h o n o n E n g i n e e r i n g u s i n g I s o t o p e s 1McGill University, 3600 rue University, Montreal, Canada 2FU Berlin, Arnimallee 14, 14195 Berlin, Germany

3Graphene is grown by chemical vapor deposition (CVD) on copper using different relative concentrations of C12 and C13 isotopes. This allows us to extract the growth history by correlating the isotope concentrations with the Raman peak positions [1] as shown in figure (a) and extract important growth parameters. This is done for regular shaped graphene as well as for fractal graphene (graphlocons) [2], which can be modeled using phase field models. This approach can also be applied to multilayer growth. Beyond growth dynamics, graphene with different or alternating isotopes enables the experimental realization of new phonon modes such as phonon Anderson localization for random distribution of isotopes, or phonon waveguides, like phonon quantum wires in alternating isotopes as shown in figure (b) and (c), or more generally phonon engineering. Some of these modes have particular signatures in the Raman spectrum, particularly at high frequencies and can be spacially detected via Raman spectroscopy and will also be discussed here. R e f e r e n c e s

[1] S Bernard, E Whiteway, V Yu, DG Austing, ans

M Hilke, Phys. Rev. B, 86, (2012) 085409 [2] M Massicotte, V Yu, E Whiteway, D Vatnik,

and M Hilke, Nanotechnology, 24 (2013) 325601.

F i g u r e s

Figure 1: Caption: CVD graphene grown with different carbon isotopes. -a- shows the Raman map of the 2D peak position of graphene for C13 carbon varying between 0 and 100%. -b- the colormap indicates the Raman G-peak height of C12 graphene. –c- a numerical evaluation of a high energy phonon mode corresponding to a 1Dconfined mode.

Michael Hilke1,2,

Eric Whteway1, Wayne Yang1 and Victor Yu1

[email protected]

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S t a n d a r d i z a t i o n o f C a r b o n N a n o m a t e r i a l s f o r I n d u s t r i a l A p p l i c a t i o n s W h a t w e w a n t , W h a t s h o u l d b e d o n e National Institute of Advanced Industrial Science and Technology, National Metrology Institute of Japan, 1-1-1 Umezono, Tsukuba, Ibaraki, 305-8563, Japan

Recent years, new materials are demanded from broad industry area, electronics, heavy industry, healthcare, etc.. On the ITRS roadmap [1], graphene and carbon nanotubes (CNT) device, interconnect technology and frontier materials are demanded. In addition, electromagnetic application, mobile telecommunication equipment (smart phone), and automotive radar system are become explosively popularized. In the case of mobile telecommunications and automotive industry demand excellent electromagnetic properties, i.e. electromagnetic compatibility, electronics performance, as minimum requirement for commercialization in the products. Mobile telecommunication industry have interest around new materials to realize not only excellent electromagnetic performance but also lightweight and/or thinner. Researches and developments in the nanotechnology turn out innovative new materials, CNT and graphene, etc., in the scientific sectors. The standardization activity of nanotechnology is giving a boost to commercialization of them in the industries. In this occasions, IEC standards undertake a role to suggest as follows; - Terms and definition, - Product and its specification, - Testing and measurement methods. Terms and definition give the common knowledge and an effective way to communicate with many kinds of industrial sectors, i.e. telecommunication, automotive, life-science and material providers, etc. Product (material) specifications proclaim technical superiority in the material science and are compared to initial requirements in the

industrial production. In the standards of testing and measurement methods, there are two type of nature. One is for analysis in material science, another is testing for industrial acceptable to production. In the former case, standard measurement method is specific for the nanotechnology society. However, researchers and engineers working in broad industry area have interests under the latter circumstance. In the IEC TC113, many standards of electromagnetic property measurements are strongly related to other broad industry area. Then, the many industries establish each IEC Technical Committee. If we want to establish successful standardization in nanotechnology area, IEC TC113 needs aggressively to make collaboration with other specific technical committee, TC46, TC47, TC48 and TC86 etc. They have soma knowledge, industrial needs and trends, business strategy and history on the each business. In Japan, we are communicating to IEC TC46 around electromagnetic measurements standardizations proposed in IEC TC113. Other consideration in the standards for the testing and measurements, calibration, measurement traceability and uncertainty analysis under the ISO/IEC 17025 are required in the IEC and other standards. This trend are demanded from the quality control and conformance to a requirement in the regulations. R e f e r e n c e s

[1] International Technology Roadmap For

Semiconductors Edition 2013 (ITRS2013), Interconnect.

Masahiro Horibe

[email protected], [email protected]

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Figure 1: Advanced interconnects and native device listed in ITRS 2013.

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M o r p h o l o g y a n d n a n o - m a n i p u l a t i o n o f c o v a l e n t l y g r a f t e d l a y e r s o n g r a p h e n e a n d g r a p h i t i c s u b s t r a t e s : a s t e p t o w a r d s g r a p h e n e - b a s e d i n t e g r a t e d c i r c u i t s 1Department of Chemistry, Division of Molecular Imaging and Photonics, KU Leuven-University of Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium 2Vienna University of Technology, Institute of Applied Physics, Wiedner Hauptstraße 8-10/E134, A-1040, Vienna, Austria 3Division of Frontier Materials Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan

Covalent grafting by reactive radicals opens up exciting possibilities to modify and tune graphene properties and structure: from highly conductive pristine graphene to electrical insulators- graphane, perfluorographane, and the like. Thus, the seamless integration of nanopatterned graphene and graphane was predicted to create powerful platform for different devices.[1] The full realization of graphene-based electronics requires high level of control over graphene structure and functionalization all the way down to the nanometer scale. Unfortunately, many techniques that can confirm successful covalent grafting do not have necessary spatial resolution at nanoscale, and as a result, the progress in nano-structuring of covalently grafted graphene and graphitic surfaces has been slow. In this work we show how scanning tunneling microscopy (STM) can be used for direct visualization of covalently grafted sites. Focusing on aryl-grafting of graphene and highly oriented pyrolytic graphite (HOPG), we were able to not only visualize and characterize covalently grafted sites, but also to develop rationale for the design and fabrication of highly dense, uniform aryl-grafted monolayers. Furthermore, we demonstrated that scanning probes (STM and AFM) could be used to selectively break grafting bonds efficiently restoring defect-free sp2-carbon

network of graphene with nanometer precision. This important finding allows for quick prototyping of complex graphene architectures via scanning probe lithography. R e f e r e n c e s

[1] A. K. Singh and B. I. Yakobson, Nano Lett., 9

(2009) 1540. F i g u r e s

Oleksandr Ivasenko1

John Greenwood1, Thanh Hai Phan1, Yasuhiko Fujita1, Zhi Li1, Willem Vanderlinden1, Hans Van Gorp1, Wout Frederickx1, Gang Lu1, Stijn Mertens2, Kazukuni Tahara3, Yoshito Tobe3, Hiroshi Ujii1 and Steven De Feyter1

[email protected]; [email protected]

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C N G – C e n t e r f o r N a n o s t r u c t u r e d G r a p h e n e CNG, DTU Nanotech, Technical University of Denmark, Building 345 East, Oersteds Plads, KongensLyngby, DK 2800, Denmark

CNG – Center for Nanostructured Graphene – is funded by the Danish National Research Foundation with a 54 MDKr (7.2 M€) grant, starting in February 2012, and running initially for six years with a possibility for a four year extension, pending a successful evaluation. The main stake-holder in CNG is DTU Nanotech, and additional partners include two other departments from DTU campus, DTU Fotonik and DTU Fysik, the center for electron nanoscopy DTU Cen, and the Physics Department from Aalborg University. DTU Danchip, the state-of-the-art clean room facility on DTU Campus is an important component in CNG’s experimental research. In addition, many other researchers on the DTU campus are independently financed stake-holders in CNG’s research program, so that all in all more than sixty persons contribute towards CNG’s goals. The graphene research program at DTU Nanotech also receives important support from various EU financial instruments, including the Graphene Flagship, where CNG researchers participate in two work-packages (Fast Electronics, and Sensors). CNG focuses on basic research, but all its research projects have long-time perspectives with the aim of applications. Its research profile has a broad range: it involves polymer chemists, nanofabrication specialists, experimental physicists, and condensed matter theorists using a wide palette of analytical and numerical tools, including large scale simulations of nanodevices, ab initio electronic structure calculations, and theory of quantum transport. The key word in CNG’s research program is “control”: we want to achieve an increased control of the electrical, thermal, and optical properties of

graphene, and other novel two-dimensional materials, by adding carefully designed nanoscale features to the pristine material.

Antti-Pekka Jauho

[email protected]

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S y n t h e s i s o f s e l f - s t a n d i n g h i g h l y c r y s t a l l i z e d h e x a g o n a l b o r o n n i t r i d e ( h - B N ) Université de Lyon, F-69000, Lyon, France ; Université Lyon 1, F-69622, Villeurbanne, France ; CNRS, UMR 5615, Laboratoire des Multimatériaux et Interfaces, F-69622, Villeurbanne, France.

2D-nanomaterials present a remarkable potential to be used for electronic applications and they have been intensively studied in the past few years. Among these materials, graphene appears as the next potential superstar material for the electronics industry, with a thinner, stronger and much faster electron conductor than silicon. However, while graphene shows promise for transistors, it has one major problem: graphene is vulnerable to perturbations from its supporting substrate and graphene devices on standard SiO2 substrates are highly disordered, exhibiting characteristics that are far inferior to the expected intrinsic properties of graphene. Therefore, the promising future development of practical graphene devices seems strongly linked to the choice of a substrate that does not disturb the electronic structure of graphene. One of the most suitable substrates appears to be hexagonal boron nitride (h-BN, also called “white graphite”), which is isostructural / isoelectronic with graphene with a lattice matching with that of graphene. Since many years, our group is particularly interested in the preparation of such h-BN based 2D nanomaterials and we recently demonstrated that self-standing highly crystallized h-BN few-layers and monolayers can be easily obtained by a versatile method modifying the original synthesis by using an additive agent and, as a consequence, decreasing the temperature for the ceramization step (1200– 1400°C) [1, 2]. This synthesis is based on the polymer-derived ceramics (PDCs) route using liquid-state polyborazylene (PBN) mixed with lithium nitride (Li3N) micro-powders as additive agent. We have demonstrated that incorporation of Li3N as a crystallization promoter allows the onset of crystallization of h-BN at lower temperatures. Consequently, a high crystallization rate can be obtained from 1000 °C for bulk boron

nitride, whereas the temperature has to be 1600–1800 °C under classical conditions. A series of samples incorporating Li3N (5 wt.-%) and annealed at various temperatures from 600 to 1400°C was prepared and structurally characterized by Raman spectroscopy, XRD analyis, and TEM. A simple ultra sonication process has been used to obtain nanostructures. Hence, we were able to produce highly crystallized hexagonal boron nitride (h-BN) sheets. The hexagonal structure was confirmed by both electron and X-ray diffraction (Figure 1). R e f e r e n c e s

[1] S. Yuan, B. Toury, C. Journet, A. Brioude,

Nanoscale 6 (2014) 7838. [2] S. Yuan, B. Toury, S. Benayoun, R. Chiriac, F.

Gombault, C. Journet and A. Brioude, Eur. J. Inorg. Chem. 2014 (2014) 5507.

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Figure 1: HRTEM image of h-BN few-layers presenting an atomic-scale Moiré pattern typical from the hexagonal atomic network.

Catherine Journet, Sheng Yuan, François Gombault, Bérangère Toury, Arnaud Brioude

[email protected]

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C r o s s - p l a n e T h e r m o e l e c t r i c E f f e c t o f G r a p h e n e - b a s e d N a n o s t r u c t u r e Center for Micro/Nano Science and Technology in National Cheng Kung University, No.1, University Road, Tainan City 701, Taiwan

The cross-plane thermoelectric (XPTE) nanostructure was fabricated by few-layer graphene and intercalated C60 clusters. The effective thermoelectric figure of merit (ZT) of this all-carbon sandwich nanostructure in cross-plane direction was measured by transient Harman’s method. The results of ZT value has great potential to compete with nowadays commercial TE materials. A suggested mechanism for XPTE nanostructure implies the ZT could be further pushed to higher value, and reveals the high temperature-to-electricity conversion efficiency at a wild temperature range. In addition, due to graphene is an atomic thick 2D material with high transparency and flexibility, a transparent and flexible TE device of graphene-based nanostructure is demonstrated herein.

Zhen-Yu Juang

and Chien-Chih Tseng

[email protected]

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C o n t r o l l i n g T e r a h e r t z W a v e s u s i n g G r a p h e n e S u p e r c a p a c i t o r s Bilkent University Department of Physics, 06800, Ankara, Turkey

In this work, we demonstrate a terahertz intensity modulator using a graphene supercapacitor which consists of two large area graphene electrodes and electrolyte medium. The mutual electrolyte gating between the graphene electrodes provides a very efficient electrostatic doping with Fermi energies of 1 eV and charge density of 8x1013 cm-2. We show that, the graphene supercapacitor yields more than 50% modulation between 0.1 to 1.4 THz with operation voltages less than 3 V. The low insertion losses, the simplicity of the device structure and polarization independent device performance are the key attributes of graphene supercapacitors for THz applications. R e f e r e n c e s

[1] Rahm, M.; Li, J. S.; Padilla, W. J. J Infrared

Millim Te 2013, 34, (1), 1-27 [2] Sirtori, C.; Barbieri, S.; Colombelli, R. Nature

Photonics 2013, 7, (9), 691-701. [3] Tonouchi, M. Nature Photonics 2007, 1, (2),

97-105.

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Figure 1: (a) Schematic representation of the graphene supercapacitor used as a broad-band terahertz modulator. The supercapacitor consists of ionic liquid electrolyte sandwiched between two large area graphene electrodes. The charge density on graphene electrodes is modulated efficiently by an external voltage applied between the graphene electrodes. (b) Schematic band structure of electrostatically doped graphene electrodes. The arrows represent the interband and intraband electronic transitions. (c) The equivalent transmission line model of the graphene layer. (d) Calculated optical absorption of single layer graphene plotted against the frequency for different doping levels. (e) The change of reflection, transmission and absorption of graphene as a function of sheet resistance. The shaded area indicates experimentally accessible sheet resistance for CVD graphene.

Nurbek Kakenov, Osman Balci, Emre O. Polat, Hakan Altan, Coskun Kocabas

[email protected]

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C h e m i c a l v a p o r d e p o s i t i o n g r o w t h a n d c h a r a c t e r i z a t i o n o f g r a p h e n e o n R h ( 1 1 1 ) a n d I r ( 1 1 1 ) s i n g l e c r y s t a l s Institute of Nanoscience and Nanotechnology, National Center for Scientific Research “DEMOKRITOS”, 15310, Athens, Greece

Few studies exist on graphene on Rh(111) single crystal substrates [1,2]. Graphene on Ir(111) has been studied more, but in both cases the usual mode of preparation is under Ultra High Vacuum (UHV). In this study, we perform Chemical Vapor Deposition (CVD) of graphene on Ir(111) at 1200o C and Rh(111) at 1000oC using methane (CH4) as the carbon precursor at low and atmospheric pressure respectively (non-UHV conditions). Due to the high carbon solubility of the catalytic substrates a moderate cooling rate is preferred. Graphene covers the whole surface in both cases. Structural characterization by ARPES, STM and RAMAN is performed. Few layer graphene is grown on Rh(111) single crystal. The electronic band structure as investigated by ARPES at room temperature shows the valence band structure imaging of the system along the ΓΚ direction of Rh(111) surface Brillouin zone (Fig. 1(a)). Graphene’s σ and π bands are observed with σ-bands dispersing from 4eV binding energy at Γ-point downwards along ΓΚ, while π band disperses from 8.5eV binding energy at Γ-point upwards up to Fermi level at 1.703 Å-1, forming a Dirac cone at KGR-point. Detail of the APRES constant energy contour kx-ky is shown in Fig. 1b). Good epitaxial orientation is observed in agreement with RHEED data (not shown here) where ΓΚ direction of graphene is aligned with the ΓK direction of Rh(111). Single layer graphene is grown on Ir(111) single crystal and studied by STM (Fig.1(b)). A well-structured honeycomb lattice is observed. The bright points correspond to higher regions whereas the dark areas correspond to shallower regions. The high quality graphene extends to the whole scanning area surface. Raman characterization spectra (not shown here)

lack the typical imaging because of the high noise/signal ratio. Acknowledgements: ERC AdG SMARTGATE (Grant No 291260)/ Greek Program for Excellence ARISTEIA-TOP-ELECTRONICS (Grant No. 745). R e f e r e n c e s

[1] Mengxi Liu, Yanfeng Zhang, Yubin Chen, Yabo

Gao ,Teng Gao , Donglin Ma, Qingqing Ji , Yu Zhang, Cong Li and Zhongfan Liu, ACS Nano, 6 (2012), 10581.

[2] G C Dong, D W van Baarle, M J Rost and J W M Frenken, New Journal of Physics, 14 (2012), 05303

[3] Choon-Ming Seah, Siang-Piao Chai, Abdul Rahman Mohamed, Carbon, 70 (2014), 1

N. Kelaidis, A. Kordatos, P. Tsipas, E. Xenogiannopoulou, J. Marquez-Velasco, S.A. Giamini and A. Dimoulas

[email protected]

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F i g u r e s

Figure 1: (a) ARPES imaging (He-I 21.22eV) of the valence band structure for Graphene on Rh(111) along the ΓΚ direction of Rh(111) surface Brillouin zone (SBZ). The π-band disperses linearly up to Fermi level at KGR point. (b) Detail of the APRES constant energy contour kx-ky plot. (c) HRSTM imaging (2.2x2.2nm2) of the crystallographic structure for the Graphene on Ir(111) system.

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S t r o n g I n t e r a c t i o n b e t w e e n G r a p h e n e E d g e a n d M e t a l R e v e a l e d b y S c a n n i n g T u n n e l i n g M i c r o s c o p y 1Samsung Advanced Institute of Technology, Suwon 443-803, Korea, 2Department of Mechanical Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Korea

3 The interaction between a graphene edge and the underlying metal is investigated through the use of scanning tunneling microscopy (STM) and density functional theory (DFT) calculations and found to influence the geometrical structure of the graphene edge and its electronic properties [1]. STM study reveals that graphene nanoislands grow on a Pt(111) surface with the considerable bending of the graphene at the edge arising from the strong graphene-edge–Pt-substrate interactions. Periodic ripples along the graphene edge due to both the strong interaction and the lattice mismatch with the underlying metal were seen. DFT calculations confirm such significant bending and also reproduce the periodic ripples along the graphene edge. The highly distorted edge geometry causes strain-induced pseudo-magnetic fields, which are manifested as Landau levels in the scanning tunneling spectroscopy. The electronic properties of the graphene edge are thus concluded to be strongly influenced by the curvature rather than the localized states along the zigzag edge as was previously predicted. R e f e r e n c e s

[1] Kim, H. W. et al. Carbon, 78 (2014), 190.

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Figure 1: STM of Graphene grown a Pt (111) substrate and side view of the graphene ribbon on the Pt model system by DFT calculation.

Hyo Won Kim1,

JiYeon Ku1, Wonhee Ko1, Insu Jeon1, Hyeokshin Kwon1, Seunghwa Ryu2, Se-Jong Kahng1,3, Sung-Hoon Lee1, Sung Woo Hwang1, and Hwansoo Suh1

[email protected]

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M e s o e p i t a x y o f g r a p h e n e : c o n t i n u o u s f i l m f o r m a t i o n Department of Materials Science and Engineering, Seoul National University, Korea

Polycrystalline nature of graphene is a major issue to be overcame in real application of CVD graphene. Recently, liquid Cu was used as catalytic substrate for graphene growth, and due to liquid surface nature, self-assembly of graphene islands was observed. However, stitching of each graphene islands still need to be investigated since thermal stress may result cracks. We verified that typical growth conditions for self-assembly of graphene on liquid Cu are not adequate for obtaining continuous graphene film, due to low supersaturation ratio. Two-step growth method was suggested in order to reduce thermal induced cracks, and fill the narrow gaps between graphene islands. Also, the transport behavior was studied via Van der Pauw measurement of the graphene film, and TLM patterning of two adjacent graphene islands. Self-assembled graphene shows lower resistance compared to randomly grown graphene islands which are typically observed on solid Cu.

Seong-Yong Cho, Min-Sik Kim, Hyun-Mi Kim, Min-Su Kim, Ki-Ju Kim, Sang-Hoon Lee, and Ki-Bum Kim*

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M o S 2 a n d d i c h a l c o g e n i d e b a s e d d e v i c e s a n d h y b r i d h e t e r o s t r u c t u r e s EPFL, Lausanne, Switzerland

MoS2 and transition metal dichalcogenides have opened numerous research directions and potential applications for this diverse family of nanomaterials. The combination of these 2D materials in heterostructures can result in a huge number of potentially interesting new materials. Most of the attention in this field is focused on heterostructures composed of different 2D materials. In my talk, I will present some of our recent efforts in this direction, oriented towards realizing combinations of 2D and 3D materials into van der Waals heterostructures. I will report on high-performance photodetectors based on 2D/3D heterostructures that can operate with internal gain and high sensitivity. Our devices also show very low noise, due to the unique architecture of the 2D/3D heterojunction. Next, I will give an update on our efforts to realize high-performance electrical circuits based on TMD materials.

Andras Kis

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P h o t o d e t e c t i o n a n d n a n o - p h o t o n i c s o f g r a p h e n e a n d h e t e r o s t r u c t u r e s o f 2 d m a t e r i a l s The Institute of Photonics Sciences (Barcelona)

The interaction of light with graphene and heterostructures of related 2d materials embodies a wide variety of physical processes such as ultra-fast photoconversion, strong light-matter interactions and highly confined plasmons, with strong potential for disruptive opto-electronic technologies. In this talk, several examples of the ultra-fast opto-electronic and nano-photonic capabilities of novel 2d material heterostructures are being addressed. We argue that graphene encapsulated in hexagonal boron nitride (h-BN) is a material system with remarkable nano-photonic properties. First, we find that it is an excellent host for extremely strongly confined light with reduced plasmon losses. We identify experimentally and theoretically the main damping channels. Second, h-BN itself is an interesting optical material as it shows natural hyperbolic behaviour, meaning that the in- and out-of-plane component of the permittivity have opposite signs in the reststrahlen frequency bands. This implies that h-BN supports deep subwavelength slow-light phonon polariton modes within those bands. Combining h-BN with graphene gives rise to unconventional plasmon–phonon hybridization and this hybrid system can be used for tailoring novel subwavelength metama-terials. Next, we address recent photovoltage generation experiments with unprecented time resolution, applied to graphene and heterostructures of 2 materials. We control and study the underlying carrier-carrier interactions and charge carrier transfer dynamics.

R e f e r e n c e s

[1] Electrical Control of Optical Emitter Relaxation

Pathways enabled by Graphene. K.J. Tielrooij, L. Orona, A. Ferrier, M. Badioli, G. Navickaite, S. Coop, S. Nanot, B. Kalinic, T. Cesca, L. Gaudreau, Q. Ma, A. Centeno, A. Pesquera, A. Zurutuza, H. de Riedmatten, P. Goldner, F.J. García de Abajo, P. Jarillo-Herrero, F.H.L. Koppens Nature Physics [online DOI: 10.1038/nphys3204] (2015)

[2] Highly confined low-loss plasmons in

graphene–boron nitride heterostructures. A. Woessner, M. B. Lundeberg, Y. Gao, A. Principi, P. Alonso-González, M. Carrega, K. Watanabe, T. Taniguchi, G. Vignale, M. Polini, J. Hone, R. Hillenbrand, F. H. L. Koppens Nature Materials [online DOI: 10.1038/NMAT4169] (2014)

[3] Ultrafast electronic read-out of diamond NV

centers coupled to graphene. Andreas Brenneis, Louis Gaudreau, Max Seifert, Helmut Karl, Martin S. Brandt, Hans Huebl, Jose A. Garrido , Frank H.L. Koppens, Alexander W. Holleitner Nature Nanotechnoly [online DOI: 10.1038/nnano.2014.276] (2014)

[4] Hybrid 2D–0D MoS2–PbS Quantum Dot

Photodetectors. Kufer, Dominik, Ivan Nikitskiy, Tania Lasanta, Gabriele Navickaite, Frank HL Koppens, and Gerasimos Konstantatos Advanced Materials 27, no. 1, 176-180 (2015)

[5] Photodetectors based on graphene, other two-

dimensional materials and hybrid systems. F. H. L. Koppens, T. Mueller, Ph. Avouris, A. C. Ferrari, M. S. Vitiello, M. Polini Nature Nanotechnol. 9, 780-793 (2014)

[6] Phonon-mediated mid-infrared photoresponse

of graphene. M. Badioli , A. Woessner, K. J. Tielrooij, S. Nanot, G. Navickaite, T. Stauber, F. J. Garcia de Abajo, F. H. L. Koppens Nano Lett. 14, 6374–6381 (2014)

Frank Koppens

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I n v e s t i g a t i o n o f e l e c t r o l y t e s f o r g r a p h e n e o p t i c a l m o d u l a t o r s Department of physics, Bilkent university, 06800, Ankara, Turkey

Notably, atomically thin 2 dimensional (2d) crystals provide new perspective for novel optoelectronic devices. Since the thickness of 2d crystals is much shorter than the wavelength of light, their response originates from the free charge carriers. Recently graphene provides new opportunities for optoelectronic devices. Ability to tune the free carrier on graphene through electrostatic doping, enables to control optical absorption in a very broad spectrum. Controlling optical properties in the visible spectra, however, remains as a challenge due to requirements of very large charge densities in the order of 1014 cm-2. Recently [1] we discovered a very simple device structure to control optical properties of graphene using a supercapacitor structure (Figure 1a). In this device architecture, we used two graphene electrodes and electrolyte medium. Application of a voltage bias polarized the electrolyte and yield large shift in the Fermi energy in the order of 1.5 eV with corresponding charge densities of 1014cm-2. The electrical and chemical properties of the electrolyte are the key parameters that define the performance of these optical modulators. In this report, we will talk about our investigation of various organic electrolytes (EL) for graphene optical modulators: liquid EL - PC/LiBOB (propylene carbonate/lithium bis(oxalato)borate), gel EL - PVA/LiBOB (polyvinyl alcohol/lithium bis(oxalato)borate) and solid EL - p(VDF-HFP)/IL (poly (vinylidene fluoride-co-hexafluoropropylene) fluoroelastomer/ionic liquid). Thereby, based on electrical and optical results we have established higher capacitance at 78 μF in the case of a gel EL, using during the changing of the transmission versus the wavelength for various

bias voltages. Also, we have found the increasing of transmission at 3 times for solid EL (Figure 1b) in comparison with liquid and gel Els and have detected the possibilities of gel EL to work in negative region. Analyzing obtained results we suggest the best and most suitable solid EL for fabrication graphene-based SC devices permitting to increase the modulation efficiencies by increasing the interaction of light with graphene electrodes. We anticipate that using namely of solid EL, except getting the desired electro-optical properties, will allow us to minimize the size of the SC and to vary the its form. R e f e r e n c e s

[1] E.O. Polat and C. Kocabas, Nano Lett, 13

(2013) 5851−5857.

Evgeniya Kovalska

and Coskun Kocabas

[email protected]

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F i g u r e s

Figure 1: Schematic representation of graphene optical modulators (a); optical spectra of graphene optical modulators (b) based on solid electrolyte (p(VDF-HFP)/IL).

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R e d u c e d g r a p h e n e o x i d e b a s e d n a n o c o m p o s i t e f i l m s f o r e n h a n c e d e l e c t r o c h r o m i c p e r f o r m a n c e University of Turku, Turku University Centre for Materials and Surfaces (MATSURF), Laboratory of Materials Chemistry and Chemical Analysis, Vatselankatu 2, FIN-20014 Turku, Finland

Reduced graphene oxide has been investigated [1,2] and applied as component in polymer composites. Polyviologen (PV)-reduced graphene oxide (rGO) nanocomposite films were fabricated by simple, onestep reductive electropolymerization of cyanopyridinium based precursor monomer (CNP) in an aqueous dispersion of graphene oxide (GO). Since the polymer formation and reduction of graphene oxide occurs within the same potential window, electrocodeposition method was preferred for obtaining nanostructured PV-rGO films. Cyclic voltammetry experiments of PV-rGO displayed two well resolved, reversible one-electron redox processes typical of viologen. Being a redox polymer, incorporation of rGO further enhances the electroactivity of the PV in the composite films. Vibrational spectral analysis with surface characterization revealed structural changes after composite formation along with subsequent reduction of GO within the polymer matrix. The PV-rGO nanostructured film exhibits a highcontrast electrochromism with low driving voltage induced striking color changes from transparent (0 V) to purple (-0.6 V), high coloration efficiency, fast response times and better cycling stability compared to a pristine PV film [3,4]. This performance can be attributed to the high stability of the electrochrome in the composite assembly induced by electrostatically driven non-covalent interactions between redox PV2+ and negatively charged rGO, improved electrical conductivity and enlarged surface area accessed through reinforced nanostructured graphene sheets for tethering PV molecules.

R e f e r e n c e s

[1] Jussi Kauppila, Peter Kunnas, Pia Damlin,

Antti Viinikanoja, Carita Kvarnströms. Electrochim. Acta. 89 (2013) 84

[2] A. Viinikanoja, X. Wang, J. Kauppila, C. Kvarnström, Phys. Chem. Chem. Phys. 14 (2012) 14003.

[3] Gadgil B, Damlin P, Ääritalo T, Kankare J, Kvarnström C. Electrochim Acta 97 (2013) 378-85.

[4] Gadgil B, Damlin P, Ääritalo T, Kvarnström C. Electrochim Acta 133 (2014) 268-74.

F i g u r e s

Figure 1: Changes in the UV-vis absorption spectra for bleached state (0 V) and colored state (-0.6 V) for PV (blue line) and PV-rGO (red line) films with 0.1 M KCl in water.

Bhushan Gadgil, Pia Damlin and Carita Kvarnström

[email protected]

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E p i t a x i a l G r o w t h o f S i n g l e - d o m a i n H e x a g o n a l B o r o n N i t r i d e 1Elettra-Sincrotrone Trieste S.C.p.A., AREA Science Park, S.S. 14 km 163.5, 34149 Trieste, Italy 2Physics Department and CENMAT, University of Trieste, Via Valerio 2, 34127 Trieste, Italy 3National Institute of Materials Physics, Atomistilor 105b, 077125 Magurele-Ilfov, Romania 4CNR-Institute for Complex Systems, Via Fosso del Cavaliere 100, 00133 Roma, Italy 5IOM-CNR, Laboratorio TASC, AREA Science Park, S.S. 14 km 163.5, 34149 Trieste, Italy

3d printing is a rapidly growing field. It consists in The rising interest of the scientific community in graphene (GR), motivated by its fascinating properties and wide range of potential applications, has triggered substantial interest also on other twodimensional (2D) atomic crystals and, in particular, on hexagonal boron nitride (h-BN) [1], which provides a superior insulating platform for high-performance GR devices [2]. However, a number of challenges still awaits the scientific community before the full potential of 2D atomic crystals can be exploited, such as the development of reliable methods for the growth of high-quality GR and h-BN single layers. For instance, it is still challenging to obtain large h-BN single crystalline domains because of the formation of rotated phases that give rise to grain boundaries and other 1D defects [3,4]. A deeper understanding of the h-BN growth mechanism is therefore highly desirable in order to find the optimum approach to grow high-quality films. Here, we investigate the structure of h-BN grown on Ir(111) by chemical vapor deposition (CVD) of borazine [5]. Using synchrotron radiation photoelectron spectroscopy, photoelectron diffraction and low energy electron diffraction we show that hightemperature borazine deposition gives rise to a h-BN monolayer formed by domains with opposite orientation, while a h-BN monolayer with single orientation can be synthesized by dosing borazine at room temperature and subsequently annealing the sample [6]. Our results provide new insight into the strategies for producing h -BN monolayers with single orientation.

R e f e r e n c e s

[1] M. Corso et al., Science, 303 (2004) 217. [2] C. R. Dean et al., Nature Nanotechnology, 5

(2010) 722. [3] W. Auwärter et al., Surface Science, 545

(2003) L735. [4] G. Dong et al., Physical Review Letters, 104

(2010) 096102. [5] F. Orlando et al., Journal of Physical

Chemistry C, 115 (2012) 157. [6] F. Orlando et al., ACS Nano, DOI:

10.1021/nn5058968 (2014) in print.

Paolo Lacovig1,

Fabrizio Orlando2, Luca Omiciuolo2, Nicoleta G. Apostol1,3, Rosanna Larciprete4, Alessandro Baraldi2,5, and Silvano Lizzit 1

[email protected]

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N i t r o g e n d o p i n g o f g r a p h e n e s t u d i e d b y s c a n n i n g t u n n e l i n g m i c r o s c o p y 1Laboratoire Matériaux et Phénomènes Quantiques, Université Paris diderot 10 rue Alice Domon et Léonie duquet, Paris France 2Research Center in Physics of Matter and Radiation, Université de Namur, 61 Rue de Bruxelles, 5000 Namur, Belgium 3Laboratoire d'Etude des Microstructures, ONERA-CNRS, 92322 Châtillon Cedex, France

Tuning the electronic properties of graphene is a key to the development of carbon-based electronics or other applications taking advantages of the properties of this 2D-material. Among the possible strategies to achieve this goal, the insertion of nitrogen atoms in the carbon lattice appears to be particularly interesting as it allows to perform regular doping with minimal atomic relaxation. Several studies have focused on the properties of nitrogen doped graphene down to the atomic scale using scanning tunneling microscopy (STM). Here we report on the systematic investigation of nitrogen doped graphene on SiC(000-1) using STM and scanning tunneling spectroscopy (STS). The spectroscopic measurements show that the doping induces a shift of the Dirac point that does not follow the expected behavior from a rigid band model. This point will be discussed. In addition to single substituted nitrogen the inserted atoms can have different local environments: pyridinic where the nitrogen is combined with a vacancy, and pairs of nitrogen with different interatomic distances (see figure). The isolated single nitrogen atoms have been found to be the most common characterized by a localized resonance in valence band [1]. On nitrogen pairs, the local density of states is different from that of single graphitic nitrogen suggesting that an electronic interaction occurs between N atoms even when they are separated by several atomic sites. The properties of these complex atomic configurations will be shown and discussed. The extensive measure by STM/STS of N-doped graphene allow to provide a detailed background

to better understand the electronic properties of chemically doped graphene. R e f e r e n c e s

[1] F. Joucken et al., Phys; rev. B, 85 (2012)

161408 (R). F i g u r e s

Figure 1: STM image of nitrogen doped graphene revealing different atomic configurations of the doping sites. Local spectroscopy showing the difference between spectra measured on different types of doping sites.

J. Lagoute1,

F. Joucken2, Y. Tison1, V. Repain1, C. Chacon1, Y. Girard1, A. Bellec1, H. Amara3, F. Ducastelle3, L. Henrard2, R. Sporken2, S. Rousset1

[email protected]

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F r o m s i n g l e t o m u l t i l a y e r g e r m a n e n e Aix-Marseille University, CNRS-PIIIM, Campus de St Jérôme, F-13297 Marseille Cedex, France, Instituto de Ciencia de Materiales de Madrid, ICMM-CSIC, C/Sor Juana Inés de la Cruz, 3 Cantoblanco, 28049 Madrid, Spain

There is a surge of works on new artificial elemental honeycomb two-dimensional materials beyond graphene, especially silicene sheets, first synthesized in 2012 on Ag(111) substrates [1], and germanene single layer ones, epitaxially grown, just very recently in 2014, on a Au(111) template [2]. The amazingly fast fabrication of a Room Temperature silicene Field Effect Transistor [3] will surely give a strong boost to research on these novel synthetic 2D materials, which do not exist in nature and which are, per se, directly compatible with the ubiquitous Si-based microelectronics processes. Here, we will present further advances on germanene, possibly a 2D topological insulator robust up to nearly RT, upon reporting novel results acquired by STM and Synchrotron Radiation PhotoElectron Spectroscopy on multilayer germanene sheets [4]. R e f e r e n c e s

[1] P. Vogt et al., Phys. Rev. Lett., 108 (2012)

155501. [2] M. E. Dávila, L. Xian, S. Cahangirov, A. Rubio

and G. Le Lay, New J. Phys., 16 (2014) 095002.

[3] L. Tao et al., Nature Nanotechnol., in press. [4] M.E. Dávila and G. Le Lay, to be published.

Guy Le Lay, Maria Eugenia Dávila

[email protected]

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T o w a r d s l a r g e - a r e a m o n o c r y s t a l l i n e g r a p h e n e : S y n t h e s i s a n d a p p l i c a t i o n s 1Center for Integrated Nanostructure Physics, Institute for Basic Science, Sungkyunkwan University,Suwon, Kyunggi-do 440-746, South Korea 2Department of Energy Science, Department of Physics, Sungkyunkwan University,Suwon, Kyunggi-do 440-746, South Korea

Grain boundaries in graphene are formed via the stitching of islands during the initial growth stage, and these boundaries govern transport properties and related device performance. Graphene can be ideally grown from a single nucleation seed, but its growth to large-area graphene can be terminated by several unknown self-limiting growth factors. Another approach is to start with numerous nucleation seeds and allow them to grow and coalesce together to produce large-area graphene. However, graphene grain boundaries (GGBs) are inevitably formed via stitching of graphene flakes, consequently limiting the graphene quality. We will describe several growth factors to achieve monocrystalline graphene growth during CVD. In addition, we will also describe how the grain boundaries can be modified by functional groups and influence transport properties at the grain boundaries. In addition, applications to electronics and energy storage done recently in our laboratory will be discussed further.

Young Hee Lee

[email protected]

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C u r r e n t R e s e a r c h S t a t u s o f K o r e a o n G r a p h e n e & C a r b o n N a n o t u b e s 1IBS Center for Integrated Nanostructure Physics, Institute for Basic Science, Sungkyunkwan University, Suwon 440-746, Republic of Korea. 2Department of Energy Science, Department of Physics, Sungkyunkwan University, Suwon 440-746,Republic of Korea.

Nanoscience and nanotechnology have been considered to be one of the most important sciences and technologies for electronics, energy storage and production, and biological and medical applications to drive future industries of Korea. Therefore, Korean Government set the Integral Development Plan for Nanotechnology, for the first time in 2001, which has been modified and enhanced every 5 years, taking the change in technologies and industrial environments into consideration. Since Korean Government started supporting the research on nanotechnology with these plans, about $ 3.138 billion have been invested in it for 13 years. Among the amount, $ 2.485 billion (79.2%) were supplied for research and development, and $ 493 billion (15.7%) and $ 160 billion (5.1%) were provided to build the infrastructures and to foster manpower, respectively. It is quite meaningful for us to look into the research progress of carbon nanomaterials, such as carbon nanotubes and graphene, which have played a main role in promoting the early nanoscience of Korea, because we can speculate how Korean nanoscience is structured, which can predict change in the future nanoscience by analyzing funds and publications.

Young Hee Lee1,2

[email protected]

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G r a p h e n e S t a n d a r d s : B u i l d i n g a B i g g e r B u s i n e s s National Electrical Manufacturers Association (NEMA) 1300 North 17th Street, Suite 900 Rosslyn, Virginia 22209, USA

Electrotechnical products, from the standpoint of their individual components, function as a system. For example, today’s smart phones offer unprecedented functionality in our everyday lives, but this made possible only by integrating of different technologies, like the software, the luminescent materials, the touch screen or the audio capabilities, into a system through standardization. Standards are at the core of not only every end use product, but to each of the components of that product because these components must perform adequately to work together. However the graphene industry is faced with a worldwide challenge – gaining the trust of its customers. Claims about performance and characteristics do not currently have the standardized requirements and measurement techniques behind them in place to give customers confidence that the bottle of graphene they bought indeed contains what the supplier claims is in there, and that it will do what it’s supposed to, will do it reliably, and do it reliability for a long time. Graphene suppliers can solve this dilemma by developing standards will help facilitate this over the long-term because they create a baseline for expanding markets and building new solutions. This starts at the basic level of making sure suppliers and customers are speaking the same language in terms of vocabulary, measurements, and test procedures. This can only be accomplished by working together to create value for the customer.

Mike Leibowitz

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H i g h S e n s i t i v i t y o f G r a p h e n e - b a s e d S e n s o r s – O p p o r t u n i t i e s a n d L i m i t a t i o n s University of Siegen, Department of Electrical Engineering and Computer Science, Siegen,Germany

The two-dimensional nature of graphene leads to an extremely high surface-to-volume ratio, which promises ultrahigh sensitivity of graphene-based sensors [1]. The ultimate thinness and high Young’s modulus of graphene may be utilized in membrane-based devices with very high resonant frequencies for mass sensing applications [2]. In combination with an impressive stretchability, this may further lead to applications as piezoresistive graphene membrane-based sensors [3]. While the fundamental properties of graphene apparently make it an ideal candidate for such applications, in reality one has to deal with a number of parasitic effects that can influence and falsify the response of a graphene sensor. This talk aims to carefully balance the discussion about the merits and disadvantages of graphenebased sensors based on experimental data. R e f e r e n c e s

[1] F. Schedin, A. K. Geim, S. V. Morozov, E. W.

Hill, P. Blake, M. I. Katsnelson, and K. S. Novoselov, “Detection of individual gas molecules adsorbed on graphene,” Nat Mater, vol. 6, pp. 652–655, 2007.

[2] T. Mashoff, M. Pratzer, V. Geringer, T. J. Echtermeyer, M. C. Lemme, M. Liebmann, and M. Morgenstern, “Bistability and Oscillatory Motion of Natural Nanomembranes Appearing within Monolayer Graphene on Silicon Dioxide,” Nano Lett., vol. 10, pp. 461–465, 2010.

[3] A. D. Smith, F. Niklaus, A. Paussa, S. Vaziri, A. C. Fischer, M. Sterner, F. Forsberg, A. Delin, D. Esseni, P. Palestri, M. Östling, and M. C. Lemme, “Electromechanical Piezoresistive

Sensing in Suspended Graphene Membranes,” Nano Lett., vol. 13, no. 7, pp. 3237–3242, Jul. 2013.

Max C. Lemme

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P r i n t e d M o S 2 / G r a p h e n e P h o t o d e t e c t o r Cambridge Graphene Centre, 9 JJ Thomson Avenue Cambridge CB3 0FA, UK

The electrical and optical properties of graphene and other 2d crystals are ideal for flexible, transparent, conductive electrodes [1], thin film transistors (TFTs) [2], photodetectors (PDs) [3], flexible batteries and smart textiles [2]. Liquid phase exfoliation (LPE) allows one to produce printable inks [4, 5] based on graphene and 2d crystals. LPE can be used to control concentration and morphology of 2d flakes at room temperature in a wide range of solvents [6, 7]. Inkjet-printed graphene/MoS2 PDs were reported with an external responsivity of few tens of nA/W at drain voltage of 40V [8]. Here we report a graphene/MoS2 PD, Fig.1 (a) fabricated by inkjet-printing on polyethylene terephthalate (PET) a 40μm MoS2 channel and then contacted by two inkjet printed graphene electrodes. In this configuration, graphene acts as conductive electrode, while MoS2 is the active layer where light absorption takes place. The device has an external responsivity of 960 nA/W, measured at 514nm and drain voltage of 30V, Fig.1 (b). This is 2 orders of magnitude higher than the previous reports [8]. Our device has an internal responsivity up to 0.2mA/W. This result demonstrates the viability of inkjet printed 2d-material inks for PDs, suitable for flexible, printed optoelectronics. R e f e r e n c e s

[1] F. Bonaccorso et al., Nat. Photon., 4 (2010)

611. [2] A.C. Ferrari et al., Nanoscale, DOI:

10.1039/c4nr01600a, (2014). [3] F.H.L. Koppens et al., Nat. Nanotec., 10

(2014) 780. [4] F. Torrisi et al., ACS Nano, 6 (2012) 4.

[5] F. Torrisi et al., Nat. Nanotec., 10 (2014) 738. [6] J.N. Coleman et al., Science, 331 (2011) 568. [7] Y. Hernandez et al., Nat. Nanotec., 3 (2008)

563. [8] J. Finn et al., J. Mater. Chem. C, 2 (2014) 925. F i g u r e s

Figure 1: a) Printed graphene/MoS2 photodetector. b) Time domain photoresponse of the graphene/MoS2 photodetector measured at 514nm and at +30V bias voltage.

L. Lombardi, F.Torrisi, F.Tomarchio and A. C. Ferrari

[email protected]

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E l e c t r o c h e m i c a l s y n t h e s i s o f n i t r o g e n d o p e d g r a p h e n e f o r o x y g e n r e d u c t i o n a n d s u p e r c a p a c i t o r s Department of Chemical Engineering Norwegian University of Science and Technology, N-7491 Trondheim, Norway

Graphene, a two dimensional monolayer of sp2-hybrided carbon sheet, has received wide attention due to its huge specific surface area, high chemical stability, excellent thermal and electrical conductivity, great mechanical strength, and inherent flexibility as well as ultrahigh electron mobility. However, the zero band gap characteristic limited the wide application of graphene. Fortunately, the introduction of heteroatoms into graphene presents the potential to tweak its electronic and electrochemical properties by changing the electronic density within the graphene sheet. [1] In previous reports, nitrogen doped graphene was either prepared from graphene or graphene oxide by post treatment, such as thermal, plasma, or hydrothermal treatment, or obtained through a bottom up approach, such as chemical vapor deposition or hydrothermal process.[1] Therefore, developing a low-cost, scalable, and ecofriendly method is still of great interest. A one-step electrochemical method to produce bulk quantities of nitrogen doped graphene was developed in this work. The simultaneous production and nitrogen doping of graphene was realized by electrochemical exfoliation of graphite foil in the nitrogen containing sulfate salt electrolyte. The highest doping level of about 5 at% N can be achieved (Figure 1A). The mechanism of nitrogen doping was proposed based on analysis the exhausted gas and the obtained graphene. The obtained nitrogen doped graphene was tested as catalyst for electrochemical oxygen reduction reaction and as electrode for supercapacitors

which shows improved performance (Figure 1B and C). R e f e r e n c e s

[1] Higgins, D. C.; Hoque, M. A.; Hassan, F.; Choi,

J.-Y.; Kim, B.; Chen, Z., ACS Catalysis, 4 (2014) 2734-2740.

F i g u r e s

Figure 1: XPS spectra (A), RDE measurements (B), and electron transfer number (C) of Graphene and NGraphene.

Fengliu Lou, Navaneethan Muthuswamy, Marthe Emelie Melandsø Buana, Magnus Rønning and De Chen

[email protected]

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S y n t h e s i s , C h a r a c t e r i z a t i o n a n d E n g i n e e r i n g o f T w o - D i m e n s i o n a l M a t e r i a l s Department of Materials Science and NanoEngineering Rice University, Houston, TX 77005, USA

In this talk, we first report the controlled vapor phase synthesis of transition metal dichalcogenide atomic layers and their heterostructures. The atomic structure and morphology of the grains and their boundaries are examined and first-principles calculations are applied to investigate their energy landscape. More importantly, if precise two-dimensional domains of metallic, semiconducting and insulating atomic layers can be seamlessly stitched together, in-plane heterostructures with interesting electronic applications could potentially be created. Here, we show that planar graphene/h-BN/h-BNC heterostructures can be formed either by growing graphene in lithographically-patterned h-BN atomic layers or by a direct chemical conversion process. Next, we report the in situ tensile testing of suspended graphene using a nanomechanical device to measure the fracture toughness of graphene. Our combined experiment and modeling verify the applicability of the classic Griffith theory of brittle fracture to graphene. The implications of the effects of defects such as grain boundaries on mechanical and electrical properties of two-dimensional atomic layers will also be discussed. Finally, we demonstrate how self-assembled monolayers with a variety of end termination chemistries can be utilized to tailor the physical properties of single-crystalline MoS2 atomic-layers. Our data suggests that combined interface-related effects of charge transfer, built-in molecular polarities, varied densities of defects, and remote interfacial phonons strongly modify the electrical and optical properties of MoS2, illustrating an engineering approach for local and universal property modulations in two-dimensional atomic-layers.

Jun Lou

[email protected]

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S y n t h e s i s o f G r a p h e n e - b a s e d t r a n s p a r e n t a n d c o n d u c t i v e f i l m s o n i n s u l a t o r s u s i n g a m o d i f i e d h i g h c u r r e n t a r c e v a p o r a t i o n p r o c e s s 1Technical University of Applied Sciences Wildau, Hochschulring 1, Germany 2Arc Precision GmbH, Schwartzkopffstraße 2, 15745 Wildau, Germany 3University of Roma - Tor Vergata, Department of Industrial Engineering, Via del Politecnico, 1 00133 Roma, Italy 4Univ. of Roma - Tor Vergata, Dep. of Physics, Via della Ricerca Scientifica, Roma, Italy 5IHP Innovations for High Performance Microelectronics, Frankfurt (Oder), Germanym

We present a simple and stable approach to deposit graphene-containing transparent and conductive carbon coatings directly on arbitrary insulating substrates (fused quartz, sapphire, boron crone glass) using a solid carbon source. In contrast to established CVD-processes, we do not need any catalytic metal substrate or coating. The current process uses a pulsed filtered high current arc evaporation

(Φ-HCA) to deposit a small but well defined amount of carbon homogeneously on heated substrates. To from graphene-containing coatings instead of ta:C (tetrahedral amorphous carbon) as it normally occurs by using such a carbon source, the substrate is heated and the chamber is filled with different functional and/or inert gases. In contrast to the processes reported in literature [1,2], the complex deposition parameters, which are a result of a systematic optimization process, are able to effectively avoid the formation of perpendicular grown graphitic carbon. TEM measurements show a predominantly flat lying graphitic structure with a high portion of graphene flakes. This result is in contrast to the well-known thermal modification (annealing) of ta:C, where the sp3- content of the coatings is quite constant, resulting in a strongly reduced resistivity [3,4,5]. Consequently, our coatings provide a specific resistivity, which is more than 4 orders of magnitude lower. Furthermore, the electrical properties (sheet resistance, charge carrier mobility) are comparable to the published values of reduced Graphene oxide. The coatings has been characterized using confocal Raman microscopy (Figure 1a), TEM, STM (Figure 1b),

AFM, Hall measurements, Spectral photometry (transmission, reflection), and Spectral ellipsometry. The best carbon layers have a surface resistance of 5 KΩ, with an absorption of only 12%. The filtered high current arc evaporation provides a completely metal free process for the fabrication of transparent and conductive graphene-containing carbon coatings on insulating substrates. It can be used as a stable, large area production, which can be compatible to established CMOS and other semiconductor fabrication. R e f e r e n c e s

[1] ] Y. Yin et al, Nuclear Instruments and

Methods in Physics Research B 119 (1996) [2] N.A. Marks et al., APPLIED PHYSICS LETTERS

89 (2006) [3] A. Ilie et al., J. Appl. Phys. 90, 2024 (2001) [4] A.C. Ferrari et al., Journal of Applied Physics

85 (1999) [5] D.S. Grierson et al., Journal of Applied Physics

107 (2010) F i g u r e s

Figure 1: a) Raman Spectrum of a Graphene-based coating, b) STM image of the same coating.

H. Lux1, C. Villringer1, P.

Siemroth2, M. Casalboni3, A. Sgarlata4, M.A. Schubert5 and S. Schrader1

[email protected]

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G r a p h e n e n a n o p o r o u s n e t w o r k : f r o m s y n t h e s i s t o e l e c t r o n i c s t r u c t u r e c a l c u l a t i o n s 1University of Grenoble Alpes, Institut Néel, F-38042 Grenoble, France 2CNRS, Institut Néel, F38042 Grenoble, France 3Institut FEMTO-ST, Université de France-Comté, CNRS, ENSMM, 32 Avenue de l'Observatoire, F-25044 Besançon, France

The family of two-dimensional materials is a rapidly growing one that emerged with graphene synthesis ten years ago. Tailoring the structure of these materials allows engineering their properties. One example is the change in the topology of graphene band structure as a function of the number of layer and their stacking. [1] Porous versions of graphene such as antidot lattice [2] (GAL) offer new degrees of freedom for structure-engineering of the properties: gap opening, anisotropic renormalization of Dirac velocity, spin qubit.... Up to now, experimental realization of GAL are mostly based on top-down approach and relied on lithography performed on graphene sheets. [3] We report here a convergent surface polymerization reaction scheme on Au(111), based on a triple aldol condensation, yielding a purely carbon, covalent nanoporous two-dimensional network whose formation and structure are studied with scanning tunneling microscopy. [4] Ab initio calculations including van der Waals interactions have been performed on the free standing network as well as on the network on Au(111) to analyse the role of the substrate in the convergent reaction. The electronic structure of the free standing network shows Kagome lattice like features: flat band and bands with linear dispersion together with a wide band gap. The possibility to enhance spin-orbit coupling in the system and then to turn it into a topological insulator will be discussed.

R e f e r e n c e s

[1] Ohta, T.; Bostwick, A.; McChesney, J. L.;

Seyller, T.; Horn, K.; Rotenberg, E. Phys. Rev. Lett. 98 (2007) 206802

[2] Pedersen, T. G.; Flindt, C.; Pedersen, J.; Mortensen, N. A.; Jauho, A. P.; Pedersen, K. Phys. Rev. Lett. 100 (2008) 136804

[3] Bai, J. W.; Zhong, X.; Jiang, S.; Huang, Y.; Duan, X. F. Nat. Nanotechnol. 5 (2010) 190.

[4] Landers, J.; Coraux, J; De Santis, Maurizio; Bendiab, N.; Lamare, Simon.; Magaud, L.; Cherioux, F., 2D Materials 1 (2014) 034005

F i g u r e s

Figure 1: :(Left) Scanning tunnel microscopy (STM) image of a fully conjugated carbon network synthesized on Au(111). (Right) Density functional theory (DFT) calculations showing the stable structure on Au(111). Middle inset shows the reaction based on a novel convergent approach via a triple aldolisation.

Magaud1,2

, Laurence, Landers1,2, John; Coraux1,2, Johann; Hallal, Ali 1,2;De Santis1,2, Maurizio; Bendiab Nedjma1,2; Lamare, Simon3; Cherioux3, Frédéric

[email protected]

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E x c i t o n K i n e t i c s i n M o S 2 , M o S e 2 a n d W S e 2 m o n o l a y e r s 1Université de Toulouse, INSA-CNRS-UPS, LPCNO, 135 Avenue de Rangueil, 31077 Toulouse, France 2Ioffe Physical-Technical Institute of the RAS, 194021 St. Petersburg, Russia 3Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Beijing 100190, China

We have investigated the optical and valley properties for both neutral and charged exciton in transition metal dichalcogenide monolayers (ML): MoS2, MoSe2 and WSe2. In WSe2 MLs, we have combined linear and non-linear optical spectroscopy (one and two-photons PLE, Second Harmonic Generation spectroscopy) in order to evidence the neutral exciton excited states. The clear identification of exciton excited states combined with first principle calculations allows us to determine an exciton binding energy of the order of 600 meV. The deviation of the excited exciton spectrum from the standard Rydberg series will be discussed. Moreover we show that exciton valley coherence can be achieved following one or two-photons excitation [1]. The neutral and charged exciton dynamics have been measured by time-resolved photoluminescence and pump-probe Kerr rotation dynamics [2,3]. The neutral exciton valley depolarization is about 6 ps, a fast relaxation time resulting from the strong electron-hole Coulomb exchange interaction in bright excitons [4]. Its temperature dependence is well explained by the developed theory, taking into account the long-range Coulomb exchange interaction [5]. In contrast the valley polarization decay time for the charged exciton is much longer (~1ns). The large neutral exciton valley polarization induced by polarized light measured in stationary conditions is mainly explained by the very short recombination time [3, 6].

Finally we will compare the exciton dynamics in WSe2 mono and bi-layers [7]. R e f e r e n c e s

[1] G. Wang et al, arXiv:1404.0056 (2014) [2] G. Wang et al, Phys. Rev. B 90, 075413 (2014) [3] D. Lagarde et al, Phys. Rev. Lett 112, 047401

(2014) [4] C.R. Zhu et al, Phys. Rev.B 90, 161302(R)

(2014) [5] M. Glazov et al, Phys. Rev. B 89, 201302(R)

(2014) [6] G. Sallen, Phys. Rev. B 86, 081301(R) (2012) [7] G. Wang et al, Applied Phys. Lett. 105,

182105 (2014)

NG. Wang1 , L. Bouet1 , D. Lagarde1 , I. Gerber1, M. Glazov2, A. Balocchi1 , T. Amand1 , B.L. Liu3, B. Urbaszek1 and X. Marie

1

[email protected]

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I n f r a r e d s p e c t r o s c o p y w i t h t u n a b l e g r a p h e n e p l a s m o n s : a n o v e l r o u t e f o r m o l e c u l a r s e n s i n g 1ICFO-Institut de Ciencies Fotoniques, Mediterranean Technology Park, 08860 Castelldefels, Barcelona, Spain 2ICREA-Institució Catalana de Recerca i Estudis Avançats, Passeig Lluís Companys, 23, 08010 Barcelona, Spain Infrared spectroscopy is an important field of research as it enables sensing of molecules through the measurement of their resonances, acting as molecular fingerprints. Nanophotonics is tightly bound to this field of research as the engineering of nano-scaled plasmonic structures is crucial for enhancing the local electromagnetic field. The high local field is mainly responsible for the giant surface-induced enhancement of infrared absorption (SEIRA) and Raman scattering (SERS) by molecules in close proximity of metallic nanoparticles. These techniques have brought a number of viable, cheap and efficient commercial applications, e.g., pregnancy tests based on metal colloids [1], and promise further revolutionary applications in plasmonic sensing, although they suffer from some drawbacks. Indeed, plasmon resonances in metal-based nanoparticles are fixed by the underpinning geometric details of the plasmonic structure and lack of efficient external tunability. Besides, their spectral width can not cover the whole broad spectrum of roto-vibrational infrared transitions, and thus they enhance only few molecular resonances. Multi-frequency sensors based on subwavelength hole arrays and optical antennas have been proposed for overcoming this limitation and for achieving broadband surface-enhanced spectroscopy [2, 3]. In the last years, doped graphene has emerged as an attractive alternative to noble metals for the exploitation of surface plasmons at infrared (IR) and terahertz (THz) frequencies. Here, we develop a theoretical framework accounting for SEIRA and SERS by molecules adsorbed on graphene nano-disks. We evaluate the efficiency of these graphene-based infrared sensors finding that, thanks to the outstanding tunability of graphene through externally applied gate voltage, broadband SEIRA and SERS can be achieved. The

calculated enhancement factors with respect to molecular cross-sections in the gas-phase (in the absence of graphene), are of the order of 103 for SEIRA and 104 for SERS, thus making these techniques highly appealing for sensing devices. R e f e r e n c e s [1] M. I. Stockman, Phys. Today 64, 39 (2011). [2] O. Limaj et al., J. Phys. Chem. C 117, 19119

(2013). [3] H. Aouani et al., ACS Nano 7, 669 (2013). F i g u r e s

Figure 1: (a) Sketch of the structure analyzed in this work, i.e. a graphene nano-disk of diameter D = 300nm surrounded by pyridine molecules at the coordinates R,h. (b) Absorption cross-section spectrum of the doped graphene nanodisk in the local-RPA limit with EF = 0.4eV. Insets depict the position-dependent induced-field amplitudes and the radial profiles of the induced charge density at the three resonant photon energies ℏω1 = 0.10eV, ℏω2 = 0.19eV, ℏω3 = 0.22eV where surface plasmon modes are excited. (c) Spectral change in the extinction cross-section induced by a single pyridine molecule placed at R = 0, h = 1nm. Labels A, B indicate the two leading absorption lines of pyridine. (d,e) Extinction cross-section map as a function of the molecule position in the x-z plane for (d) EF = 0.34eV, Ephot = 0.087eV, and (e) EF = 0.38eV, Ephot = 0.092eV.

Andrea Marini1, Iván Silveiro1 and F.

Javier García de Abajo1,2

[email protected]

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E n h a n c e d T h e r m a l C o n d u c t i v i t y o f s i l v e r f i l l e d - e p o x y r e s i n l o a d e d w i t h C a r b o n N a n o t u b e s a n d G r a p h e n e 1 CNR-IPCF, Viale F. Stagno D’Alcontres 37, 98158 Messina, Italy 2 CNR-ISMN, Area della Ricerca RM1-Montelibretti, 00016 Monterotondo Scalo, Rome, Italy 3 Selex ES Via Villagrazia 79 90125 Palermo, Italy

The development of property-designed conductive adhesives represents an important technological step in the development of smart packaging systems for next generation applications in avionics and power electronics. Silver-filled epoxy resins, such as the EPO TEK H20E (a standard for high speed chip bonding), feature remarkable thermal conductivity (~ 2.5 W/mK) and low electrical resistivity (~ 4x10-4 ohm-cm) characteristics, thanks to the presence of micrometric metallic particles embedded in the epoxy matrix. Furthermore, in the last few years, researchers have made many studies in performing multifunctional polymer nanocomposites based on Carbon Nanotubes (CNTs) and graphene sheets due to the extraordinary intrinsic properties of these reinforcement [1,2]. Intense research has been carried out in the recent years to improve the conductivity properties of epoxies. Haddon and coworkers dispersed a GNPs into a epoxy resin, and showed thermal conductivity reaching 6.44 W/mK in resin containing 25 vol% GPs[3]. Song and coworkers reported a good enhanced of thermal conductivity with 10wt% graphene flakes.[4] Here we show that the addition of Graphene nanoplatelets (GNPs) and Carbon Nanotubes (CNTs) allows to improve by a factor ca. 5 the conductivity properties of the EPO TEK H20E reaching optimal values of 11 W/mK

and 5x10-5 ohm-cm for the thermal conductivity and the electrical resistivity, respectively. Our procedure allows to prepare epoxies capable to host different carbon nanostructures (DWCNTs and Graphene) and exhibit improved conductivity properties even at low fillers loadings, down to 1wt% and 0.01 wt%, for CNT and graphene, without compromising the mechanical and thermodynamic performances. Raman Spectroscopy and Scanning Electron Microscopy provide insight on the crucial role played by the CNTs and graphene in bridging together the silver micro-particles within the epoxy matrix, filling and reinforcing the structure of the nanocomposite material, at the same time. Acknowledgements: This work has been supported by the Programma Operativo Nazionale Ricerca e Competitività 2007-2013, PON01_01322 PANREX. R e f e r e n c e s [1] M. F. L. De Voelder, et al., Science, 339 (2013)

535. [2] K.M. F. Shahil, et al., Nano Lett., 12 (2012) 861. [3] A.Yu et all, J. Phys Chem C, 111 (2007) 7565. [4] S. H. Song, et al, Advance Materials 25 (2013)

732-737.

E. Messina1, N. Leone1, A. Foti1, C.

D’Andrea1, B. Fazio1, O. M. Maragò1, G. Di Marco1, C. Vasi1, G. Di Carlo2, C. Riccucci2, G.M. Ingo2, A. F. Cassata3, P. G. Gucciardi1

[email protected]

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R a p i d C V D g r o w t h o f m i l l i m e t r e - s i z e d s i n g l e - c r y s t a l g r a p h e n e u s i n g a c o l d -w a l l r e a c t o r 1 Center for Nanotechnology Innovation @NEST, Istituto Italiano di Tecnologia, Piazza San Silvestro 12, 56127 Pisa, Italy 2 Graphene Labs, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italy This work presents a simple pathway to obtain large single-crystal graphene on copper (Cu) foils with high growth rates using a commercially available cold-wall chemical vapour deposition (CVD) reactor. We identify a series of steps of substrate preparation and growth which allow a highly repeatable and fast growth of large single-crystals of graphene, making the technique suitable for device applications. We demonstrate the importance of each of these steps, namely: i) using passivated Cu foils, ii) pre-annealing in an inert argon atmosphere and iii) enclosing the sample during the growth. Optimisation of these steps allows us to achieve a low graphene nucleation density and high growth rates of 14.7 and 17.5 μm per minute on flat and folded foils, respectively. Thus, single crystals with lateral size of nearly one millimetre can be obtained on flat foil in just one hour and 3.5 mm crystals can be grown inside copper “pockets” in 3 hours. The samples are characterised by optical microscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy as well as selected area electron diffraction (SAED) and low-energy electron

diffraction (LEED), which confirm the high quality and homogeneity of the graphene. The development of a process for the quick production of large grain graphene in a commonly used commercial CVD reactor is a significant step towards an increased accessibility to millimetre-sized graphene crystals. F i g u r e s

Vaidotas Miseikis1, Domenica

Convertino1,2, Neeraj Mishra1, Mauro Gemmi1, Vincenzo Piazza1 and Camilla Coletti1,2

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N e w p h e n o m e n a i n t r a n s p o r t t h r o u g h s u s p e n d e d g r a p h e n e d e v i c e s University of Geneva, Switzerland

Some of the most interesting electronic properties of graphene –and of its multilayers– occur when the Fermi level is positioned very close to the charge neutrality point, where valence and conduction bands touch. For devices where graphene is in direct contact with a substrate, the possibility to position the Fermi level close to the charge neutrality point is limited by the presence of charge inhomogeneity, which so far has not be reduced below ~5 1010 cm-2 even in the best systems. In suspended graphene devices –where graphene is not in direct contact with a gate dielectric material– this limit can be improved by nearly a factor of 50, enabling the observation of new phenomena. Here, I will discuss transport experiments that we have performed on devices of this high quality, by probing transport in a multi-terminal configuration –something that had not been successfully done until now.

After giving some background about suspended graphene devices and presenting the characterization of our structures, I will discuss two main topics. The first is the fractional quantum Hall effect in graphene bilayers, where the phenomenon occurs in new regimes, resulting in predicted exotic states, whose manifestations seems to be present in our data. The second is the opening of a gap at charge neutrality induced by electron-electron interactions that is known to occur in bilayers, and that we now observe also in four-layer graphene. Our experimental results suggest the presence of an even-odd effect of interactions with layer thickness that persists even in multilayers that are so thick to be normally considered to be graphite, as long as no structural defects are present.

Alberto Morpurgo

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L o w - t e m p e r a t u r e p h o t o l u m i n e s c e n c e o f 2 D D i c h a l c o g e n i d e s a n d i n d i r e c t e x c i t o n s i n t h e i r h e t e r o s t r u c t u r e s 1Institut für Experimentelle und Angewandte Physik, Universität Regensburg, D-93040 Regensburg, Germany 2Physikalisches Institut, Westfälische Wilhelms-Universität Münster, D-48149 Münster, Germany

Two-dimensional transition-metal dichalcogenides (TMD) have recently emerged as a promising class of novel ultrathin semiconductors. Once thinned down to the monolayer level, many of them like MoS2 or WSe2 exhibit a direct band gap, which renders them especially suitable for future optical devices.

Here, we present low-temperature photoluminescence (PL) measurements and temperature series of the four most prominent TMDs, namely MoS2, MoSe2, WS2 and WSe2 (see Fig. 1). At 4K the diselenides and WS2 show a clear splitting of neutral exciton and trion which enables us to deduce the binding energy of the trion for these materials, in good agreement to recent literature (~ 30meV) [1]. Owing to the two-dimensional nature of the material and the resulting confinement effects, the observed binding energies of the trions are an order of magnitude larger than in well-known GaAs quantum well structures. For most of the materials we also observe additional peaks at low temperature which we attribute to surface-bound states [2]. Additional insight is gained by power-dependent measurements at low temperatures. Thereby, we can influence the relative intensities of excitons and trions and observe saturation effects for certain materials. Temperature series on all four materials allow us to deduce the temperature-induced shift of the bandgap which lies in the region of 70-80meV.

Additionally, by using a recently developed deterministic all-dry transfer technique [3] we are able to fabricate large area van-der-Waals heterostructures consisting of different 2D-TMDs (Fig. 2a). In PL-scanning measurements at room temperature we observe the emergence of indirect excitons at the interface (Fig. 2b,c,d).

These quasi-particles stem from a spatial separation of electrons and holes which is caused by the type-II alignment of the two semiconductors [4,5,6]. Excitation-density dependent PL measurements on the heterostructures allow us to alter the excitonic regime where we observe saturation effects of the indirect exciton, which probably result from longer recombination times compared to the direct transitions.

Acknowledgements: Financial support by the DFG via GRK 1570, SFB689 and KO3612/1-1 is gratefully acknowledged. R e f e r e n c e s

[1] J. S. Ross, S. Wu, H. Yu, N. J. Ghimire, A. M. Jones, G. Aivazian, J. Yan, D. G. Madrus, D. Xiao, W. Yao and X. Xu, Nature Commun. 4, 1474 (2013).

[2] T. Korn, S. Heydrich, M. Hirmer, J. Schmutzler and C. Schüller, Appl. Phys. Lett. 99 ,102109 (2011).

[3] A. Castellanos-Gomez, M. Buscema, R. Molenaar, V. Singh, L. Janssen, H. S. J. van der Zant, G. A. Steele, 2D Materials 1, 011002 (2014).

[4] J. Kang, S. Tongay, J. Zhou, J. Li and J. Wu, Appl. Phys. Lett. 102, 012111 (2013).

[5] K. Kośminder and J. Fernández-Rossier, Phys. Rev. B 87, 075451 (2013)

[6] H. Fang, C. Battaglia, C. Carraro, S. Nemsak, B. Ozdol, J. S. Kang, H. A. Bechtel, S. B. Desai, F. Kronast, A. A. Unal, G. Conti, C. Conlon, G. K. Palsson, M. C. Matrin, A. M. Minor, C. S.Fadley, E. Yablonovitch, R. Maboudian and A. Javey, Proc. Natl. Acad. Sci. USA, 111, 6198-6202 (2014).

P. Nagler1, G. Plechinger1, P.

Tonndorf2, S. Michaelis de Vasconcellos2, R. Bratschitsch2, C. Schüller1 and T. Korn1

[email protected]

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F i g u r e s

Figure 1: Low-temperature (4K) PL spectra of monolayer MoSe2, WSe2, MoS2 and WS2. The diselenides and WS2 show a splitting of neutral exciton (A) and the trion (T). All materials except MoSe2

show surface-bound states (S) at low temperatures.

Figure 2: (a) Two-dimensional heterostructure consisting of a WSe2 monolayer on a MoS2 monolayer. The white square marks the area of the PL scan. Within the yellow triangle we observe the indirect exciton (b) False color map of the PL intensity (c) False color map of the PL peak energy (d) Representative PL spectra of the three different regions. The emission of the indirect exciton is weak and red-shifted compared to the emission of the isolated monolayers.

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G r a p h e n e b a s e d o p t i c a l m o d u l a t o r s a n d p h o t o d e t e c t o r s f o r c h i p -i n t e g r a t e d c o m m u n i c a t i o n s y s t e m s AMO GmbH Otto-Blumenthal-Strasse 25 52074 Aachen Germany

High frequency opto-electronic devices like photodetectors and electro-optical modulators are the core of modern information and communication systems. Those devices have been recognized from the very beginning as one of the most promising fields of applications for graphene having the potential to significant outperform their counterparts based on Silicon and III/V semiconductors in terms of speed. This expectation has mainly been fuelled by graphene’s tunable, broadband optical interaction, the outstanding charge carrier mobility, and the possibility to integrate graphene on nearly any platform. The on-chip integration of different optical components is the major route for further increasing the bandwidth and reducing cost. While silicon is a perfect material for guiding and routing infrared light, the low light-interaction of silicon requires hetero-integration of other materials for realizing compact modulators and photodetectors. This offers an excellent opportunity for graphene to enter silicon technology by adding missing functionalities. In this talk I will discuss our latest results on grapheme based photodetectors and modulators integrated on silicon waveguides [1,2]. Key parameters will be assessed and compared with competing technologies. R e f e r e n c e s [1] D. Schall, et al. 50 GBit/s photodetectors

based on wafer-scale graphene for integrated silicon photonic communication systems ACS Photonics 1, 781 (2014)

[2] M. Mohsin, D. Schall, M. Otto, A. Noculak, D. Neumaier, and H. Kurz, Graphene based low insertion loss electro-absorption modulator on SOI waveguide Optics Express. 22, 15292 (2014).

F i g u r e s

Daniel Neumaier

[email protected]

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E n v i r o n m e n t a l r e m e d i a t i o n o f o x i d i s e d g r a p h e n e n a n o c a r b o n s : 2 D s h e e t s d e g r a d e f a s t e r t h a n 1 D t u b u l a r - s h a p e d s t r u c t u r e s 1Nanomedicine Lab, Faculty of Medical & Human Sciences & National Graphene Institute, University of Manchester, AV Hill Building, Manchester M13 9PT, United Kingdom 2Nanotube Research Center, National Institute of Advanced Industrial Science and Technology, Tsukuba 305-8565, Japan

Graphene nanocarbons are currently fuelling a revolution in science and technology in areas ranging from aerospace engineering to electronics [1]. Unlike their pristine forms, the oxidised derivatives of those nanostructures are water dispersible that allows their application to areas such as biology and medicine [2]. There is a need for efficient and viable means of degrading these engineered structures that is relevant to their potential biological uses but also for environmental purposes [2, 3]. The aim of the present study was to assess the potential of the widely used sodium hypochlorite, NaClO, (1% by chlorine content) to degrade oxidised graphene nanocarbons within a week. NaClO was found by a risk assessment report completed by the European Union (EEC 793/93) to be safe for the environment with regards to its standard usage which includes domestic sanitation as well as municipal water and waste disinfection. We compared the morphological changes that occur during degradation of graphene oxide to two other oxidised graphene nanocarbons, namely oxidised multiwalled carbon nanotubes and oxidised carbon nanohorns. Degradation was monitored closely using a battery of techniques including UV-Vis, Raman spectroscopy, transmission electron microscopy and atomic force microscopy. The results demonstrate that graphene oxide was degraded into a dominantly amorphous structure lacking the characteristic Raman signature and microscopic (TEM/AFM) morphology. Oxidised carbon nanotubes underwent degradation via a wall exfoliation mechanism, yet maintained a large fraction of the sp2 carbon backbone, while the degradation rate of oxidised carbon nanohorns was observed at a somewhat intermediate rate to that for the other two types of nanostructures.

R e f e r e n c e s [1] Geim, A. K. & Novoselov, K. S., Nat Mater, 6

(2007) 183-91. [2] Kostarelos, K. & Novoselov, K. S., Science,

344 (2014) 261-263. [3] Lalwani, G., Xing, W. & Sitharaman, B., J

Mater Chem B Mater Biol Med, 2 (2014) 6354 6362.

F i g u r e s

Figure 1: Schematic representation of the inferred progressive decay of structural integrity of graphene oxide, oxidised multiwalled carbon nanotubes and oxidised carbon Nanohorns over time when incubated in NaClO 1%.

LDD. Newman1, N. Lozano1, M.

Zhang2, M. Yudasaka M2, C. Bussy1, K. Kostarelos1

[email protected] [email protected] [email protected]

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S e a m l e s s s t i t c h i n g o f g r a p h e n e d o m a i n s o n p o l i s h e d c o p p e r ( 1 1 1 ) f o i l

IBS Center for Integrated Nanostructure Physics Institute for Basic Science (IBS), Sungkyunkwan University Suwon, 440-746, Republic of Korea

Graphene grain boundaries (GGBs) are inevitably formed via stitching of graphene flakes, consequently limiting the graphene quality. There have been numerous reports that GGBs are a primary carrier scattering source, thus degrading the related device performance. Therefore, it is always desired to obtain large-area graphene without forming GGBs. Two approaches exit for to synthesizing monocrystalline graphene. One approach is to reduce the number of nucleation seeds. However, large-area growth is terminated by an unknown self-limiting growth factor and requires long growth time. Another approach entails the alignment of graphene domains while leading them to stitch together to form uniform single monocrystalline graphene. Thus, seamless stitching of graphene domains during chemical vapor deposition (CVD) is an ideal concept to realize large-area monocrystalline graphene. Cu(111) substrate maintains hexagonal symmetry with minimum lattice mismatch with graphene and has been tried to grow graphene but no evidence for seamless stitching has been provided. Use of copper substrate is technologically relevant, since monolayer graphene is easily tailored due to the limited carbon solubility in copper, and moreover the surface morphology can be controlled at large area with low cost. In this work, we prove the concept of seamless stitching without forming GGBs by preparing a polished Cu(111) foil for CVD. The seamless stitching was realized by merging hexagonal graphene domains in the same orientation and verified by not only at atomic scale by scanning tunneling microscopy (STM) and transmission electron microscopy (TEM) but also at macro-scale by optical microscopy after UV-treatment[1]. This was markedly distinct from the clear GGBs formed by the similar hexagonal

domains in different orientations, in congruent with our density-functional calculations. This concept was extended to synthesize monocrystalline graphene of 3x6 cm2 size by CVD for an hour by merging multiple hexagonal graphene domains in the same orientation on Cu(111) foil. The mono-crystalinity of the large-area sample was confirmed by new observation method achieved by correlating confocal Raman mapping on overlapped graphene bilayers to polarized optical microscopy (POM) on spin-casted nematic liquid crystal (NLC) layer, combined with transport measurements at the stitched region. R e f e r e n c e s [1] Van Luan Nguyen et al, Advanced Materials,

(2014), just accepted F i g u r e s

Van Luan Nguyen, Young Hee Lee

[email protected]

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D e f e c t m o d u l a t e d p h o t o r e s p o n s e a n d t h e r m a l c o n d u c t i v i t y i n g r a p h e n e 1 Department of Physics, Southeast University, Nanjing 211189, China 2 School of mechanical engineering, Southeast University, Nanjing 211189, China 3 Graphene Research and Characterization Center, Taizhou Sunano New Energy Co., Ltd. Taizhou, 225300, China There is a great need for controlling the properties of two dimensional (2D) materials to fulfill the requirements of various applications.[1-4] Here, we present our results on the modulation of the properties of graphene by controllably introducing different types of defects. Firstly, the graphene-based photodetector with tunable p-p+-p junctions has been successfully fabricated using a simple laser modification method. Distinct photoresponse was observed at the graphene (G)- laser-modified graphene (LMG) junction through scanning photocurrent measurements, and Raman spectra reveal that defects are created at the LMG region. Detailed investigation suggests that the photo-thermoelectric effect, instead of the photovoltaic effect, dominates the photocurrent generation at the G-LMG junctions. Secondly, we adopted molecular dynamics simulations and non-contact optothermal Raman measurements to identify the correlation between the lattice defects and thermal conduction transport in graphene. We find that the thermal conductivity of graphene can be significantly reduced even at extremely low defect concentration (~83% reduction for ~1‰ defects), where defects act as localized scatters and greatly reduce the conductivity. Our findings provide fundamental insights into the physics of thermal transport in graphene, and two-dimensional materials in general, which could help on the future design of functional applications such as optothermal and electrothermal devices. R e f e r e n c e s [1] Ni ZH, Ponomarenko LA, Nair RR, Yang R,

Anissimova S, Grigorieva IV, Schedin F, Shen ZX, Hill EH, Novoselov KS, Geim AK On

resonant scatterers as a factor limiting carrier mobility in grapheme, Nano Letters 10, 3868-3872 (2010).

[2] Zhan D, Yan JX, Lai LF, Ni ZH, Liu L, Shen ZX Engineering the electronic structure of grapheme, Advanced Materials 24, 4055-4069 (2012).

[3] Liu YL, Nan HY, Wu X, Pan W, Wang WH, Bai J, Zhao WW, Sun LT, Wang XR, Ni ZH* Layer-by-Layer Thinning of MoS2 by Plasma. ACS Nano 7, 4202, (2013).

[4] Nan HY, Wang ZL, Wang WH, Liang Z, Lu Y, Chen Q, He DW, Tan PH, Miao F, Wang XR, Wang JL*, Ni ZH* Strong Photoluminescence Enhancement of MoS2 through Defect Engineering and Oxygen Bonding ACS Nano 8, 5738 (2014).

F i g u r e s

Figure 1: Photocurrent image of graphene before (a) and after laser modification at different positions: P1 (b), P2 (c), P3 (d), respectively. (e) Photoswitching characteristic at the bottom spot near LMG (P3) (P3(B)). (f) Photocurrents as function of the laser power detected at regions near P3 and graphene-metal contacts as marked in (d).

Zhenhua Ni1, Wenhui Wang1,

Weiwei Zhao2, Zheng Liang3

[email protected]

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H y b r i d g r a p h e n e – q u a n t u m d o t p h o t o t r a n s i s t o r s f o r I R - i m a g i n g a p p l i c a t i o n s 1 ICFO – The Institute of Photonic Sciences, Av. Carl Friedrich Gauss 3, 08860 Castelldefels (Barcelona), Spain

Graphene is an appealing material for optoelectronics and photodetection applications. It has various extraordinary properties, including ultrahigh mobility at room temperature, which enables fast response times. Colloidal quantum dots exhibit unique optical properties of spectral tunability and high absorption coefficients. We combine the favourable electronic properties of graphene with the optical characteristics of colloidal quantum dots to realize a novel hybrid graphene-quantum dot photodetector for visible and short-wave infrared frequencies. [1] The unique electronic properties of graphene offer a gate-tunable carrier density and polarity that enabl us to tune the sensitivity and operating speed of the detector. Here, we exploit this to maximize the photoconductive gain or to fully reduce it to zero, which is useful for pixelated imaging applications, while the implementation of nanoscale local gates enables a locally tunable photoresponse. We also demonstrate our novel approach to fully suppress dark currents in graphene-based photodetectors and increase operation speed of our devices. At

the current state our single- and multipixel photodetectors can operate at 30, 60 and up to 90 frames-per-second. The resulting technology is extremely promising for visible and, more importantly, short-wave infrared (SWIR) imaging applications. Sensing and imaging in SWIR range lies at the heart of safety and security applications in civil and military surveillance, night vision applications, automotive vision systems for driver safety, food and pharmaceutical inspection and environmental monitoring. Operation of a prototype device sensitive to visible and IR light in the auditorium will be demonstrated during the talk. R e f e r e n c e s [1] Gerasimos Konstantatos, Michela Badioli,

Louis Gaudreau, Johann Osmond, Maria Bernechea, F. Pelayo Garcia de Arquer, Fabio Gatti and Frank H. L. Koppens, Nature Nanotechnology, 7 (2012) 363–368.

Ivan Nikitskiy1, A.M. Goossens1, G.

Navickaite1, J. J. Piqueras1, G. Konstantatos1 and F.H. L. Koppens1

[email protected]

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G r a p h e n e n a n o p o r e s f o r b i o s e n s i n g a n d t h e r m o e l e c t r i c a p p l i c a t i o n s : F i r s t -p r i n c i p l e s q u a n t u m t r a n s p o r t s i m u l a t i o n Department of Physics & Astronomy, University of Delaware Newark, DE 19716, USA https://wiki.physics.udel.edu/qttg

Mechanical stability of graphene and advances in nanofabrication have recently made possible drilling of tiny holes (or arrays of such holes) of nanoscale diameter within graphene sheets. The experimental demonstration of DNA translocation through graphene nanopores has opened new avenues for third-generation DNA sequencing, where unlike traditionally considered biological or solid-state nanopores, one-atom-thickness of graphene means that only one nucleobase is present within the nanopore. However, the poor signal-to-noise ratio achieved in sensing of nucleobases within the nanopore via vertical ionic current calls for new ideas to exploit electronic transport in the plane of graphene. Using nonequilibrium Green function formalism combined with density functional theory (NEGF+DFT) simulations, we have predicted [1,2] that using edge currents in zigzag or chiral graphene nanoribbons (GNR) could significantly improve signal-to-noise ratio, thereby enabling ultrafast DNA sequencing.

An array of graphene nanopores can also be used to significantly impede the lattice thermal conduction through GNRs, decorated with heavy adatoms to locally enhance spin-orbit coupling and convert GNR into a two-dimensional topological insulator. The nanopores do not affect electronic current carried by helical edge states, which generate a highly optimized power factor per helical conducting channel due to narrow boxcar-function-shaped electronic transmission (surpassing even the so-called Mahan-Sofo limit obtained for delta function-shaped electronic transmission). In Ref. [3], we have predicted that thermoelectric figure of merit of GNR + heavy adatoms + nanopores system would reach its maximum ZT~3 at low temperatures, T~40 K,

which paves a way to design high-ZT materials by exploiting the nontrivial topology of electronic states through nanostructuring.

In this talk, I will overview these two classes of graphene nanopore devices, illustrated in Fig. 1, as well as challenges for NEGF+DFT simulations applied to their design and modeling.

R e f e r e n c e s

[1] K. K. Saha, M. Drndić, and B. K. Nikolić, Nano Lett. 12, 50 (2012).

[2] P.-H. Chang, H. Liu, and B. K. Nikolić, J. Comput. Electron. 13, 847 (2014).

[3] P.-H. Chang, M. S. Bahramy, N. Nagaosa, and B. K. Nikolić, Nano Lett. 14, 3779 (2014).

F i g u r e s

Figure 1: Schematic view of a single nanopore within GNR with zigzag or chiral edges for ultrafast DNA sequencing (top panel) [1,2]; or an array of nanopores within GNR (with arbitrary edges) and heavy adatoms for high-ZT thermoelectric applications by exploiting the nontrivial topology of electronic states (bottom panel) [3].

Branislav K. Nikolić

[email protected]

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R e c e n t a d v a n c e s i n g r a p h e n e h e t e r o s t r u c t u r e s t o w a r d t h e c r e a t i o n o f t e r a h e r t z l a s e r s Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 9808577, Japan

This paper reviews recent advances in graphene heterostructures toward the creation of terahertz (THz) lasers. Interband-transition-originated population inversion in the pumped graphene can produce a weak gain (up to 2.3%) in the THz range (Fig. 1) [1]. The current-injection pumping with the equivalent pumping photon energy as low as tens of meV can minimize carrier heating and increase the gain [2].

Excitation of graphene plasmon polaritons can dramatically enhance the THz gain (Fig. 2) [3, 4], which has recently been experimentally verified [5]. The graphene-channel FET structure with an asymmetric dual grating gate is a possible structure enabling current-injection plasmonic THz lasing (Fig. 3) [6].

We propose to use photo-emission-assisted resonant tunneling in a gated double-graphene-layer (DGL) capacitor as another physical mechanism to obtain a giant THz gain using current-injection pumping (Fig. 4) [7]. In such structures, the entire excess carriers in the n-type graphene layer can contribute to THz spontaneous emission (with the photon energy being equal to the band offset between the DGL) via interlayer radiative tunneling to the p-type graphene layer. Quantitative discussions of the lasing performance will be presented in detail. Acknowledgements: This work was supported by JSPS GA-SPR (#23000008), Japan. R e f e r e n c e s [1] V. Ryzhii, M. Ryzhii, T. Otsuji, J. Appl. Phys. 101

(2007) 083114. [2] V. Ryzhii, M. Ryzhii, V. Mitin, T. Otsuji, J. Appl.

Phys. 110 (2011) 094503.

[3] A.A. Dubinov, Y.V. Aleshkin, V. Mitin, T. Otsuji, V. Ryzhii, J. Phys.: Condens. Matter 23 (2011) 145302.

[4] Y. Takatsuka, K. Takahagi, E. Sano, V. Ryzhii, T. Otsuji, J. Appl. Physl. 112 (2012) 033103.

[5] T. Watanabe, T. Fukushima, Y. Yabe, S.A. Boubanga Tombet, A. Satou, A.A. Dubinov, V. Ya Aleshkin, V. Mitin, V. Ryzhii, T. Otsuji, New J. Phys. 15 (2013) 075003.

[6] V.V. Popov, O.V. Polischuk, A.R. Davoyan, V. Ryzhii, T. Otsuji, M.S. Shur, Phys. Rev. B 86 (2012) 195437.

[7] V. Ryzhii, A.A. Dubinov, T. Otsuji, V.Ya. Aleshkin, M. Ryzhii, M. Shur, Opt. Express 21 (2013) 31569-31579.

F i g u r e s

Figure 1: Interband photoexcitation and resultant THz gain in optically pumped graphene

Figure 2: Giant THz gain enhancement via excitation of surface plasmon polaritons in inverted grapheme. .

Taiichi Otsuji, Stephane A. Boubanga-Tombet, and Victor Ryzhii

[email protected]

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T r a n s p o r t S t u d i e s i n B l a c k P h o s p h o r u s F i e l d E f f e c t T r a n s i s t o r s Centre for Advanced 2D Materials and Graphene Research Centre National University of Singapore Singapore 117546 Department of Physics National University of Singapore Singapore 117542

Ultrathin black phosphorus (BP), or phosphorene is the second known elementary two-dimensional material that can be exfoliated from a bulk van der Waals crystal. Unlike graphene it is a semiconductor with a sizeable band gap that allows both high carrier mobility and large on/off ratios. Its excellent electronic properties make it attractive for applications in transistor, logic, and optoelectronic devices. However, it is also the first widely investigated two dimensional electronic material to undergo degradation upon exposure to ambient air. Therefore a passivation method is required to study the intrinsic material properties,

understand how oxidation affects the physical transport properties and to enable future application of phosphorene. I will show that atomically thin graphene and hexagonal boron nitride crystals can be used for passivation of ultrathin black phosphorus. I will also discuss experiments where we characterize few-layer black phosphorus field effect transistors on hexagonal boron nitride (BN) and compare with results obtained with BP fully encapsulated with BN.

Barbaros Özyilmaz

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O p t i m i z e d g r a p h e n e g r o w t h o n G e ( 1 0 0 ) / S i ( 1 0 0 ) s u b s t r a t e s 1 Institute of Electronic Materials Technology, Wolczynska 133, 01-919 Warsaw, Poland 2 IHP, Im Technologiepark 25, 15236 Frankfurt (Oder), Germany 3 Institute of Optoelectronics, Military University of Technology, Gen. S. Kaliskiego 2, 00-908 Warsaw, Poland

In order to widen the range of possible graphene applications, for example in high frequency electronics, it is desirable to grow graphene films directly on arbitrary insulator or semiconductor surfaces instead of on a most commonly used copper substrate. Ideally such insulating or semiconducting layers are deposited on Si wafers used commonly in integrated circuit (IC) manufacturing. Growing graphene directly on Si wafer surface is extremely challenging due to the tendency to form carbides. This tendency is much weaker when Ge is used as the substrate instead of Si [1], which has been exploited to grow high quality graphene on Ge(110)/Si(110) wafers [2]. Here, we present for the first time a CVD growth of graphene on monocrystalline Ge(100) “virtual substrates” deposited on Si(100) wafers which is the preferred wafer orientation in the mainstream Si IC fabrication. This approach benefits from the cost advantage and manufacturing compatibility of Si(100) wafers and avoids the metal contamination problems and complexity associated with graphene transfer from Cu. A clean, high quality graphene grown on Ge(100)/Si(100) wafers can be subsequently either transferred using wafer bonding approaches or used directly for fabrication of e.g. graphene THz devices [3] thus opening the way for this new material to the integration with Si microelectronics. In the present work graphene films were synthesized in a 6-inch Black Magic system by the CVD method. As a substrate we used both 1 µm and 3 µm thick (100) oriented Ge deposited on Si(100). To ensure optimal temperature conditions,

thus preventing Si diffusion through a Ge layer and Ge melting the temperature was chosen in the range between 900ºC and 930ºC with a slow ramp. During the process of graphene deposition the pressure of 700 mbar was sustained. Methane gas was used as a carbon precursor in the mixture of Ar and H2. We optimized the ratio of Ar/H2/CH4 gases, growth time and temperature so that a continuous film was created. Furthermore, we developed the process of transferring graphene from Ge/Si wafers onto dielectric substrates aimed at showing clear and non-contaminated graphene films. The assessment of the properties of graphene grown on Ge/Si substrates was performed using Raman spectroscopy, which confirmed the formation of graphitic structures and their quality, and SEM imaging, which showed the morphology of the graphene/Ge/Si interaction. For the purpose of electrical measurements by the Hall method and the contamination detection by performing the ToF-SIMS analysis, we developed a protocol of graphene transfer onto a dielectric substrate. R e f e r e n c e s [1] G. Lippert, et al Carbon 75, 104 (2014). [2] Lee et al, Science Vol. 344 no. 6181 (2014) pp.

286-289. [3] V. Di Lecce, R. Grassi, A. Gnudi, E. Gnani, S.

Reggiani, G. Baccarani, Trans. Electron Dev., 60 (2013) 4263.

.

I. Pasternak1, M. Lukosius2, Y.

Yamamoto2, A. Krajewska1,3, G. Lupina2

and W. Strupinski1

[email protected]

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E l e c t r o n i c I n t e r a c t i o n b e t w e e n N i t r o g e n - D o p e d G r a p h e n e a n d P o r p h y r i n M o l e c u l e s 1 Matériaux et phénomènes quantiques. CNRS-Université Paris Diderot, 10, rue Alice Domon et Léonie Duquet 75205 Paris Cedex 13, France 2 Research center in Physics of Matter and radiation, Université de Namur, 61, rue de Bruxelles, Namur, Belgium

Controlling the properties of graphene and mastering its interaction with molecules is a cornerstone for the realization of graphene-based devices. One of the promising routes explored to tune the properties of graphene is the doping by nitrogen atoms inserted in the carbon lattice. Here, we present an extensive study of the interaction of porphyrin molecules (H2TPP) with nitrogen doped graphene. Using scanning tunneling microscopy and spectroscopy (STM and STS) we evidenced the decoupling effect by the opening of the HOMO-LUMO gap of the porphyrin molecules adsorbed on graphene (3.3 eV) as compared to Au (111) (2.4 eV). The comparison of the spectroscopy of molecules on carbon and nitrogen sites reveals a downshift of the molecular levels typical of a charge transfer towards the molecule at the nitrogen sites. This shift induces a clear topographic contrast in the STM images that allows us to discriminate the molecules above the nitrogen sites (that appear bright) compared to those on the carbon sites at +2V (see Figure), which is attributed to the purely electronic effect. These results show a fascinating understanding at the atomic scale of the porphyrin molecules on graphene, in which the electronic interaction of molecules with graphene, particularly, on doped graphene, the sensitive charge transfer at nitrogen sites provide new strategic study for the further investigation of graphene as well as graphene-based devices. R e f e r e n c e s [1] Georgiou et al., Nature Nanotechnology, 8

(2013), 100.

[2] F. Schedin et al., Nature Materials 6 (2007), 652.

[3] Bruno F. Machado et al., Catal. Sci. Technol. 2 (2012) 54.

[4] Yan et al., ACS Nano, 8 (2014) 4720. F i g u r e s

Figure 1: Topography image reveals the molecule island on N doped graphene in which the red molecules correspond to those adsorbed on N sites. Comparative dI/dV spectra recorded on H2TPP molecules on carbon (blue) and nitrogen (red) sites showing the energy shifts of the HOMO and LUMO states measured on the molecular island. .

V. D. Pham1, J. Lagoute1, O. Mouhoub1,

Y. Tison1, V. Repain1, C. Chacon1, A. Bellec1, Y. Girard1, F. Joucken2, S. Rousset

[email protected]

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I n f l u e n c e o f s u b s t r a t e t e m p e r a t u r e a n d S i C b u f f e r l a y e r o n t h e q u a l i t y o f g r a p h e n e f o r m a t i o n d i r e c t l y o n S i ( 1 1 1 ) 1

Research Center in Physics of Matter and Radiation (PMR), University of Namur (FUNDP), 61 Rue de Bruxelles, 5000 Namur, Belgium 2 Nanoscopic physics (NAPS), Institute of Condensed Matter and Nanosciences (IMCN), Université catholique de Louvain (UCL), 2 chemin du Cyclotron, Louvain-la-Neuve, Belgium 3 Electrical Engineering (ELEN), Institute of Information and Communication Technologies, Electronicsand Applied Mathematics (ICTEAM), Université catholique de Louvain (UCL), 3 place du Levant, Louvain-la-Neuve, Belgium

Evidence for the epitaxial growth of graphene films directly on Si(111) 7×7 surface reconstruction was demonstrated (Fig. 1), however the production of low surface roughness and large area graphene on Si wafer is still a challenge in the context of direct deposition of carbon atoms using an electron beam evaporator [1, 2]. Therefore, in order to optimize this film for approaching industrial applications, in this paper we continue investigating the structural and electronic properties of our material at various substrate temperatures using covered SiC buffer layers with different thicknesses under appropriate preparation by Auger electron spectroscopy, X-ray photoemission spectroscopy, Raman spectroscopy, scanning electron microscopy and scanning tunneling microscopy. Recorded experimental results confirm this significant influence on the quality of graphene formation. This method might be very promising for graphene-based electronics and its integration into the silicon technology. R e f e r e n c e s [1] Pham Thanh Trung, Frederic Joucken, Jessica

Campos-Delgado, Jean-Pierre Raskin, Benoit Hackens, and Robert Sporken, Appl. Phys. Lett. 102, 013118 (2013).

[2] Pham Thanh Trung, Jessica Campos-Delgado, Frédéric Joucken, Jean-François Colomer, Benoıt Hackens, Jean-Pierre Raskin, Cristiane N. Santos, and Sporken Robert, J. Appl.Phys. 115, 223704 (2014).

F i g u r e s

Figure 1: An atomic resolution STM image of 30×30Å2 (VSample = -0.12V, IT = 10nA) from graphene films on Si(111) 7x7 surface reconstruction showing the AB (Bernal) stacking order of a typical graphene lattice [2].

Trung T. Pham1, Cristiane N. Santos2,

Frédéric Joucken1, Benoît Hackens2, Jean-Pierre Raskin3 and Robert Sporken1

[email protected]

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E x c i t o n i c t r a n s i t i o n s i n 2 D t r a n s i t i o n m e t a l d i c h a l c o g e n i d e s ( M o S 2 , W S 2 a n d W S e 2 ) 1 Departamento de Fisica Universidade Federal de Minas Gerais (UFMG), Brazil 2 Department of Physics, Applied Physics and Astronomy, RPI, Troy, NY, USA 3 Department of Physics and Center for 2-D and Layered Materials, The Pennsylvania State University, University Park, USA

Resonance Raman spectroscopy (RRS) is a very useful tool to provide information about excitons and their couplings with phonons. We will present in this work a RRS study of different samples of 2D transition metal dichalcogenides (MoS2, WS2 and WSe2) with one, two and three layers (1L, 2L, 3L) and bulk samples, using more than 30 different laser excitation lines covering the visible range. We have observed that all Raman features are enhanced by resonanceswith excitonic transitions. From the laser energy dependence of the Raman excitation profile (REP) we obtained the energies of the excitonic states and their dependence with

the number of atomic layers. The first and second-order Raman features exhibit different resonance behaviors, in agreement with the double resonance mechanism for the second-order Raman features. In the case of MoS2, we observed that the electronphonon coupling is symmetry dependent, and we provide evidence of the C exciton recently predicted theoretically. The RRS results WSe2 show that the Raman modes are enhanced by the excited excitonic states (A’ and B’) and we will present the dependence of the excited states energies on the number of layers.

Marcos A. Pimenta1, Elena del Corro1,

Bruno R. Carvalho1, Leandro M. Malard1, Juliana M. Alves1, Humberto Terrones2, Ana L. Elias3, Mauricio Terrones3 and Cristiano Fantini1

[email protected]

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U l t r a f a s t b r o a d b a n d s t u d y o f p h o t o c a r r i e r d y n a m i c s i n M o S 2 s i n g l e l a y e r 1 Politecnico di Milano, P.zza Leonardo da Vinci 32, 20133, Milano, Italy 2 CNR-Istituto Nanoscienze, 41125 Modena, Italy 3 CNR-Istituto di Struttura della Materia, Montelibretti, Italy 4 Cambridge Graphene Centre, Cambridge, CB3 OFA, UK

We present a time-resolved study of charge carrier dynamics in single-layer MoS2 (1L-MoS2) by ultrafast transient absorption spectroscopy. Using tunable pump pulses and broadband probing, we monitor the relaxation dynamics of the photo-excited states with unprecedented spectral coverage (the entire visible range). The sample is a 10 x 30 µm2 1L-MoS2 prepared by micromechanical exfoliation and transferred onto a transparent fused silica substrate [1]. The transient absorption spectrum has three prominent features, each consisting of a bleaching at the energies of the excitonic transitions A, B C (at 1.9, 2.1 and 2.9 eV) and a red-shifted photoinduced absorption, Fig. 1. These features do not depend on the excitation energy, which is tuned to be resonant and non-resonant with the excitonic transitions. Pauli blocking cannot explain, alone, the simultaneous bleaching of the three excitonic transitions and the corresponding photoinduced absorption. Instead, we believe that a transient band gap renormalization caused by the presence of photo-excited carriers should be also considered. A static strong renormalization of both electronic band gap and exciton binding energy was previously reported in MoSe2 due to the interaction with the substrate [2]. Here we compare our data with simulations combining non-equilibrium Green's functions with ab-initio methods [3,4]. The comparison of experimental data with simulations allows us to shed light on the delicate interplay among Pauli blocking, band gap renormalization and electron-phonon relaxation, which are the key phenomena governing the carrier dynamics after photo-excitation.

R e f e r e n c e s [1] Bonaccorso et al.Materials Today, 15 (2012)

564-589.

[2] M. M. Ugeda et al., Nat. Mat., 13 (2014) 1091-1095.

[3] A. Marini, J. Phys.: Conf. Ser. 427 (2013) 012003; D. Sangalli and A. Marini, arXiv:1409.1706 (2014).

[4] A. Marini, C. Hogan, M Grüning, and D. Varsano, Comp. Phys. Comm., 180 (2009) 1392.

F i g u r e s

Figure 1: Transient Absorption of 1L-MoS2. 100 fs-pulse excitation in the visible range determines simultaneous bleaching of the A, B, C excitons, with the absorption surviving up to hundreds ps. a)

Transient absorption map with λpump= 400nm; b) Transient absorption spectrum at fixed delays; c) Relaxation dynamics of C-

exciton bleaching with λpump = 400, 600 and 650 nm.

E.A.A. Pogna1, S. Dal Conte1, M.

Marsili2, D. Prezzi2, D. Sangalli3, C.Manzoni1, A. Marini3, D. De Fazio4, M. Bruna4, I. Goykhman4, A. C. Ferrari4, G. Cerullo1

[email protected]

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U s e r - f r i e n d l y g r a p h e n e - b a s e d q u a n t u m r e s i s t a n c e s t a n d a r d s 1 Laboratoire National de Métrologie et d’Essais, Trappes, 78190, France 2Laboratoire de Photonique et Nanostructures, CNRS, Marcoussis, 91460, France 3CRHEA, CNRS, Valbonne, 06560, France 4Laboratoire Charles Coulomb, Université de Montpellier 2, CNRS, Montpellier, 34095, France 5NOVASiC, Le Bourget du Lac, 73370, France

The quantum Hall effect (QHE) provides a universal standard of electrical resistance in terms of the Planck constant h and the electron charge e. One hallmark of the graphene Dirac physics is a unique QHE which is exceptionally robust. An ongoing goal of metrologists is to use this advantage to develop graphene-based quantum resistance standards (G-QHRS) operating in more convenient experimental conditions than the usual standards made of GaAs/AlGaAs heterostructures which operate at high magnetic fields (B~10 T), low temperatures (T~1.3 K) and currents (I~40 μA). This would reduce the operating cost of the ohm maintaining in national metrology institutes and would improve the dissemination towards industrial end-users. Although the 10-9 accuracy of the quantized Hall resistance (QHR) on the ν=2 plateau (ν is the Landau level filling factor) was demonstrated in a few graphene devices [1], this was obtained at still high and not competitive operating magnetic fields up to now. We will present measurements of the QHR on the ν=2 plateau carried out in large (100 × 420 μm2) Hall bars based on graphene grown by chemical vapor deposition of propane under hydrogen on the Si-face of SiC substrates, a hybrid scalable growth technique recently developed [2]. Fig. 1 demonstrates the 10-9 accuracy of the QHR (RH) over an exceptionally wide range of magnetic fields from B = 10 T in a device that can therefore operate, for the first time, in cryomagnetic conditions similar to those of GaAs-QHRS [3]. Achieving lower carrier density (down to 2x1011cm-2) and higher carrier mobilities (up to 9000 cm2V-1s-1) graphene, we recently showed that a G-QHRS can outperform GaAs-QHRS and operate with an accuracy of 1×10-9 in experimental conditions unattainable to any usual

semiconductors: B as low as 3.5 T, T as high as 5.1 K, and I up to 280 μA. This is a breakthrough in the resistance metrology application since it opens the era of user-friendly helium-free quantum resistance standards able to be widely disseminated. R e f e r e n c e s

[1] T. J. B. M Janssen et al, Metrologia 49 (2012), 294.

[2] A. Michon et al., Appl.Phys. Lett. 97 (2010), 171909.

[3] F. Lafont et al. arXiv:1407.3615 (2014). F i g u r e s

Figure 1: (a) Relative deviation of the Hall resistance to the quantized value ΔRH/RH versus magnetic field B. b) Hall resistance RH

and longitudinal resistance Rxx versus B (in green for GaAs sample). c) Accurate measurements of the longitudinal resistance Rxx versus

B.

W. Poirier1, F. Lafont1, R. Ribeiro-Palau1,

D. Kazazis2, A. Michon3, B. Jouault4, O. Couturaud4, C. Consejo4, M. Zielinski5, Th. Chassagne5, M. Portail3, B. Jouault4, F. Schopfer1

[email protected]

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E l e c t r o n i c t r a n s p o r t , n a n o s t r u c t u r i n g a n d d i s o r d e r i n g r a p h e n e Center for Nanostructured Graphene (CNG), Department of Micro- and Nanotechnology (DTU Nanotech), Technical University of Denmark, Denmark

Nanoscale patterning has been suggested as a possible route towards achieving the elusive electronic band-gap required to incorporate graphene, with its many superlative properties, into conventional semiconductor devices. Of particular interest are so-called graphene antidot

lattices (GALs), consisting of sheets of graphene with periodic perforations, which theory predicts should display sizable band-gaps [1]. In this talk I demonstrate that the geometric disorders inherent in fabrication techniques severely hamper the performance of many GAL-based devices. Furthermore, control over antidot edge geometry may allow the detrimental effects of such disorders to be minimized [2]. I will also discuss techniques we have developed to characterize individual defects and nanostructures using multiple point-probes or STM tips. Computational methods developed to extend this type of analysis from simple defects to larger nanostructures such as perforations or gas-filled blisters will be demonstrated [3]. Finally, I will discuss two alternative routes towards achieving desirable electronic properties in graphene, namely bilayer systems with single layer nanostructuring [4] and graphene with selective sublattice doping [5]. R e f e r e n c e s [1] Pederden, T. G. et al, Phys. Rev. B, 77 (2008)

245431. [2] Power, S. R. and Jauho, A.-P., Phys. Rev. B, 90

(2014), 115408. [3] Settnes, M. et al, preprint arXiv:1501.06036

(2015).

[4] Gregersen, S. S. et al, preprint arXiv:1410.5196 (2015)

[5] Aktor et al, in preparation (2015) F i g u r e s

Figure 1: (Top) Schematic of graphene patterned with circular antidots arranged in a triangular superlattice, showing the unit cell of the 7,3 antidot lattice system. (Bottom) Transmission through finite-width antidot barriers for the pristine case, and with edge roughness disorder in the form of weak random potentials on the antidot edge sites (shown for a single instance and for configurationally averaged disorder)

Stephen R. Power, Mikkel Settnes, Søren Schou Gregersen, Thomas Aktor, Antti-Pekka Jauho

spow @ nanotech.dtu.dk

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A t o m - b y - a t o m d e f e c t e n g i n e e r i n g a n d c h a r a c t e r i s a t i o n i n g r a p h e n e a n d o t h e r 2 - d i m e n s i o n a l m a t e r i a l s u s i n g s c a n n i n g t r a n s m i s s i o n e l e c t r o n m i c r o s c o p y 1 SuperSTEM Laboratory, SciTech Daresbury Campus, Keckwick Lane, Daresbury WA4 4AD, U.K. 2Institute for Materials Research, SCAPE, University of Leeds, Leeds LS2 9JT, U.K. 3Faculty of Physics, University of Vienna, Boltzmanngasse 5, A-1090 Vienna, Austria 4Department of Physics and Energy, University of Limerick, Limerick, Ireland

Modern aberration-corrected scanning transmission electron microscopes (STEMs) have been optimised to provide improved data collection ability and greater flexibility even at low acceleration voltages, to the great benefit of the field of graphene and two-dimensional materials. By reducing the acceleration voltage to overcome knock-on damage limitations, many of these structures can be imaged directly at atomic resolution, revealing for instance the successful low energy ion implantation of single N or B dopants in graphene with retention rates consistent with theoretical predictions, a technique commonly used by the modern semiconductor industry and which has the potential to revolutionize graphene technology [1]. Furthermore, the sensitivity of complementary analytical techniques such as electron energy loss spectroscopy (EELS) is such that it also possible to study precisely how these atoms bonded to one another and how minute structural differences affect their electronic configuration [2,3]. In particular, EELS fine structure differences can distinguish unambiguously between tri- and tetravalent bonding configurations of single Si contaminants in graphene [2], while a clear signature in the near-edge fine structure of the B and N EELS K edges but also that of neighboring C atoms and their EELS K edges (Figure 1) provide evidence of electronic structure modifications due to presence of the dopants. Ab initio calculations are used simulate experimental spectra and to rationalize the experimental observations, thus providing further insight into the nature of bonding around the foreign species [3]. Finally, these otherwise 'gentle' STEM observation conditions can also be precisely tailored to engineer and modify defects in 2-dimensional materials: the electron beam can thus drive the

diffusion of substitutional Si dopants through graphene (Figure 2), one atomic jump at a time [4].

R e f e r e n c e s

[1] U. Bangert, W. Pierce, D.M. Kepaptsoglou et al., Nano Lett. 13 (2013), p. 4902.

[2] Q.M. Ramasse, C.R. Seabourne, D.M. Kepaptsoglou et al., Nano Lett. 12 (2012), p. 3936.

[3] D.M. Kepaptsoglou, C.R. Seabourne, R. Nicholls et al., Submitted (2015).

[4] T. Susi, J. Kotakoski, D. Kepaptsoglou et al., Phys. Rev. Lett. 113 (2014), 115501.

F i g u r e s

Figure 1: Atomically resolved EELS map (b), showing a single N dopant in the graphene lattice (a-b). C K edge spectra (d) from neighboring C atoms, show changes in their near-edge fine structure.

Figure 2: A single Si substitutional impurity in graphene can undergo a bond inversion with its neighbouring C atoms under a 60kV electron beam.

Quentin M. Ramasse1, Demie M.

Kepaptsoglou1, Che R. Seabourne2, Trevor Hardcastle2, Andrew Scott2, Toma Susi3, Jani Kotakoski3, Jannik C. Meyer3, Recep Zan4 and Ursel Bangert4

[email protected]

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I n d u s t r i a l i z a t i o n a n d S t a n d a r d i z a t i o n o f G r a p h e n e M a t e r i a l s i n C h i n a Shenyang National Laboratory for Materials Science Institute of Metal Research, Chinese Academy of Sciences Shenyang 110016, P.R. China

Graphene materials have attracted increasing interest from academic and industrial societies because of their excellent properties and a wide range of promising applications. In particular, the research and industrialization of graphene materials in China has been developing very rapidly in the past several years. Many graphene-related companies have been established for large-

scale production of grapheme materials aimed at industrial applications, which makes an urgent call for the standardization of graphene materials. This talk will briefly summarize the progress of industrialization and standardization of graphene materials in China, and challenges and prospects in these fields will be discussed.

Wencai Ren

[email protected]

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S p e c t r a l S e n s i t i v i t y o f p n - j u n c t i o n P h o t o d e t e c t o r s b a s e d o n 2 D m a t e r i a l s 1 University of Siegen, Hölderlinstrasse 3, 57076 Siegen, Germany 2 School of Chemistry, Trinity College Dublin, Dublin 2, Ireland

Broad spectral range detection is interesting for several technological applications such as imaging, sensing, communication and spectroscopy. Two-dimensional (2D) materials are very promising for such applications. Graphene is a suitable material for broadband detection due to its absorbance covering the entire spectrum from ultraviolet to terahertz, which is a consequence of its linear dispersion and zero bandgap characteristic [1], [2]. In contrast to graphene, molybdenum disulfide (MoS2) is an n-type semiconducting 2D material. MoS2 shows a more limited spectral response due to its band structure. Monolayer MoS2 has a direct band gap of ~1.8 eV, whereas bulk MoS2 has an additional indirect band gap of ~1.3 eV [3].

In this work, we investigate graphene – silicon Schottky barrier diodes composed of chemical vapor deposited (CVD) graphene on n-type Si substrates. A device schematic along with its cross-section is shown in Fig. 1a and 1b, respectively. The effects of incident light intensity and wavelength are investigated. Fig. 1c shows the band diagram of the device in reverse bias under illumination. The diodes exhibit good rectifying behavior and high sensitivity to changes of incident light, as shown in Fig. 1d. A broad spectral response (SR) of 60 - 407 mAW-1 at reverse dc bias of 2V is measured from ultraviolet (UV) to near infrared (NIR) light (Fig. 2a). In our previous work on MoS2/Si diodes, we reported a maximum SR of 8.6 mA/W (Fig. 2b, [4]). This is 47 times less than the Si-graphene diode value presented in this work, even though multilayer MoS2 should have higher absorbance than graphene. We attribute the greatly enhanced SR to an optimized design, with larger contact electrodes that were also placed closer to the active device area. This results in an increased external electrical field. Therefore, more photo-generated electron-hole pairs can be

captured before recombination and consequently, the overall photodetection efficiency is improved.

R e f e r e n c e s

[1] R. R. Nair, et al., Science, vol. 320, no. 5881, (2008) 1308–1308.

[2] K. F. Mak, et al., Solid State Commun., vol. 152, no. 15,( 2012) 1341–1349.

[3] K. F. Mak, et al., Phys. Rev. Lett., vol. 105, no. 13, (2010). 136805.

[4] C. Yim, et al., Sci. Rep., vol. 4, (2014). 1-7.

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Figure 1: a) Schematic, (b) Cross-section of the graphene/n-Si heterojunction diode and (c) its band diagram in reverse bias under illumination. (d) J-V plot of the diode on a semi-logarithmic scale under various light intensities of 20%, 60% and 100% compared to the dark-state.

Figure 2: Absolute spectral response (Abs. SR) vs. wavelength (lower x-axis) and energy (upper x-axis) of the (a) graphene/ n-Si photodiode and for comparison (b) MoS2 /p-Si photodiode at zero bias and reverse bias of 1 and 2 V taken from [our previous paper].

Sarah Riazimehr1, Daniel Schneider1,

Chanyoung Yim2, Satender Kataria1, Vikram Passi1, Andreas Bablich1, Georg S. Duesberg2 and Max C. Lemme1*

[email protected]

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E l e c t r o n o p t i c s i n g r a p h e n e 1 1Dept. of Physics, University of Basel, Switzerland 2 Institute of Theoretical Physics, University of Regensburg, Germany 3 Dept. of Physics, Budapest University of Technology and Economics, Hungary

In ballistic graphene, electrons behave in many ways similar to photons. By changing the electrostatic potential locally, we realized elements in graphene that are known from optics. But in contrast to conventional optics, gapless p-n interfaces can be formed showing a negative index of refraction and the effect of Klein tunneling. Even more, electron trajectories can be bent by applying a magnetic field. The electron-optics devices that we will show were fabricated using high-mobility suspended monolayer graphene on organic lift-off resists. We extended the technology introduced by N. Tombros et al. [1] allowing to add a multitude of bottom and top gates [2]. Recently we have demonstrated that with this technique a ballistic p-n junction can be created forming a Fabry-Pérot etalon. We will go beyond our recent publication [3] and discuss the observed transition from the Fabry-Pérot to the Quantum Hall regime that is observed once a magnetic field is applied. We will show striking features that can be traced to the formation of snake state trajectories along a pn interface. By this we can guide electrons along arbitrary interfaces already at very small magnetic fields of 100 mT. Beyond that we will demonstrate that electrons in ballistic graphene can be guided by gate potentials (Fig.1a) the same way as photons in an optical fiber, and that the formation of a p-n interface increases the guiding efficiency due to Klein filtering. We will show that we can fill the electrostatic guiding channel mode by mode. A further electron-optics element that we will present is a four terminal device that involves a tilted gate structure (Fig.1b) which acts as a mirror. Theoretical calculations [4] clearly reproduce the measured features of the different electron-optics devices, and the simulated current density plots give further insight to the nature of the discussed effects.

R e f e r e n c e s [1] N. Tombros et al. Journal of Applied Physics

109, 093702 (2011). [2] R. Maurand, P.Rickhaus, P.Makk et. al. Carbon

79, 486 (2014). [3] P. Rickhaus, P.Makk, M.-H. Liu et al., Nature

Communications 4, 2342 (2013). [4] M.-H.Liu, P.Rickhaus, P.Makk et.al.,

arXiv:1407.5620 (2014). F i g u r e s

Figure 1: (Top) False color image of a suspended graphene flake (blue) with side contacts (gray) and bottomgates (yellow) that can be used for electron guiding. (Bottom) Another four-terminal device with a tilted gate structure allows studying the reflection at the pn-interface and acts as a mirror.

P. Rickhaus1, M.-H. Liu2, P. Makk1, S.

Hess1, R. Maurand1, E. Tovari3, M. Weiss1, K. Richter2 and C. Schönenberger1

[email protected]

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A l l - G r a p h e n e T - B r a n c h T h i n - F i l m F i e l d - E f f e c t R e c t i f i e r s 1 Aalto University, Department of Micro and Nanosciences, P.O.Box 13500, Espoo, Finland 2Departament d'Enginyeria Electrònica, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain

Charge carrier transport in a two-dimensional electron gas (2-DEG) has been widely studied for the past decades to exploit its nonlinear properties arising in the ballistic regime for nanoelectronics. For example, T-branch (three-terminal junction) devices fabricated on 2-DEG exhibit electrical rectification as predicted by theoretical models. Whereas III-V compound semiconductors are well known materials for 2DEG devices, graphene has recently attracted attention as a 2-DEG material because it has exceptional electronic properties. The lack of band gap in graphene does not set similar limitations for the device performance as in the case of graphene field-effect transistors (GFETs). Consequently, nonlinear behavior of three-terminal graphene nanojunctions have been studied using mechanically exfoliated [1] and silicon carbide [2] graphene. However, these nanoscale graphene three-terminal junctions with ballistic (or quasi-ballistic) operation have shown rectifications with relatively low efficiency. Large-scale graphene prepared by chemical vapor deposition (CVD) has the potential to deliver true monolithic integrated circuits (ICs) as one continuous monolayer graphene film can be utilized as a channel, gate, interconnect, and even as passive components such as resistors. Here, all-graphene thin-film devices are realized as T-branch channels and gate electrodes are both fabricated utilizing graphene synthesized by photo-thermal CVD (PTCVD) [3] as depicted in Figure 1a. The top gate electrode is deposited on a 30-nm-thick Al2O3 by atomic layer deposited (ALD). It is intriguing to note that Raman fingerprint of high quality graphene and high mobility (~ 4700 cm2/Vs) is achieved on PTCVD grown graphene despite the fact the graphene grain size is relatively small (2-3 µm) compared to typical CVD graphene. Moreover, small grain size is generally considered detrimental

to the electronic transport characteristics. We note that PTCVD is an interesting alternative for graphene mass-production as a monolayer film can be deposited only in ~30 s on copper. For the microscale T-branch devices, we present highly tunable and switchable room temperature full-wave rectification for 100 kHz of AC (Figure 1b). Instead of ballistic theory, we explain the rectification characteristics through an electric field capacitive model based on self-gating in the high drain-source bias regime. The model and experimental results are shown in Figure 1c. These findings open new possibilities for practical applications, as ballistic operation is impractical for flexible and transparent application due to nanoscale size requirements. The device architecture introduced here is not dependent on the substrate and therefore the concept can be utilized for transparent and flexible electronics. By comparing with invasive metal center probe structures, we demonstrate that graphene itself acts also an excellent electrode for the signal detection. Finally, examining devices with varying channel dimensions, we find the relation of the micrometer-size scaling to the device performance. R e f e r e n c e s [1] Fadzli Rahman, S.; Kasai, S.; Manaf Hashim, A.,

Appl. Phys. Lett. 100 (2012) 193116. [2] Göckeritz, R.; Pezoldt, J.; Schwierz, F. Appl.

Phys. Lett. 99 (2011) 173111. [3] Riikonen, J.; Kim, W.; Li, C.; Svensk, O.;

Arpiainen, S.; Kainlauri, M.; Lipsanen, H., Carbon, 62 (2013) 43.

Juha Riikonen1, David Jiménez2,

Wonjae Kim1, Changfeng Li1, and Harri Lipsanen1

[email protected]

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Figure 1: (a) Illustration of the all-graphene T-branch junction device. (b) Rectifier characteristics for the 100 kHz push-pull inputs (for left and right terminals) under two different DC gate fields. Solid lines are the center branch outputs for hole (VG= -1V) and electron region (VG= 1 V), respectively. (c) Comparison of measured and calculated rectification curves.

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P h o s p h o r e n e : G r a p h e n e ' s D i f f i c u l t C o u s i n Centre for Advanced 2D Materials and Graphene Research Centre National University of Singapore, 6 Science Drive 2, 117546, Singapore

From all the two-dimensional materials discovered after graphene, phosphorene holds a special place due to the fact that it is composed of a single atom type. Its corrugated structure gives rise to a highly anisotropic dispersion and the presence of a gap makes it an appealing candidate for potential applications. The size of the gap can be modified by applying uniaxial strain, which can potentially even lead to the closing of the gap. Unfortunately, unlike graphene, which can be modeled using the tight binding model, phosphorene's bands cannot be described using a simple nearest-neighbor approximation. As a consequence, one typically has to resort to ab initio calculations. Using the first principles calculations, we study nanoribbons in phosphorene and show that depending on the edge type, the ribbons can give rise to localized edge states. While the analytical treatment of the problem is non-trivial, it is possible to make some definite predictions for one of the edge types. Having obtained the band structure using numerical methods, we address the issue of excitons in anisotropic two-dimensional systems. Employing a combination of analytical and numerical methods, we obtain the binding energies for excitons and show how they change

with the substrate and applied strain. Our results compare favorably with those reported earlier using different approaches. Additionally, we study the dynamic polarization in monolayer and double-layer phosphorene. We show that double-layer systems give rise to two distinct plasmonic branches, as was previously reported for graphene. Here, however, the system anisotropy introduces additional effects, such as anisotropic Landau damping and effective gating due to relative twist between the layers. R e f e r e n c e s [1] A. S. Rodin, A. Carvalho, A. H. Castro Neto,

"Strain-induced gap modification in black phosphorus", Phys. Rev. Lett. 112, 176801 (2014).

[2] A. Carvalho, A. S. Rodin, A. H. Castro Neto, "Phosphorene Nanoribbons'', EPL 108, 47005 (2014).

[3] A. S. Rodin, A. Carvalho, A. H. Castro Neto, "Excitons in anisotropic 2D semiconducting crystals", Phys. Rev. B 90, 075429 (2014).

Aleksandr Rodin, Alexandra Carvalho, Leandro Seixas, Antonio H. Castro Neto

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M a g n e t o t r a n s p o r t i n h i g h - m o b i l i t y g r a p h e n e a n t i d o t a r r a y s 1 Institut für Experimentelle und Angewandte Physik, Universität Regensburg 93040 Regensburg, Germany 2 National Institute for Materials Science, 1-1 Namiki, Tsukuba, 305-0044, Japan

We report on the observation of antidot peaks in in monolayer-graphene (MLG), encapsulated between hexagonal boron nitride (hBN). The hBN-MLG-hBN heterostructures were fabricated with a dry transfer pick-up technique; subsequently mesas were etched in Hall bar geometry and contacted with 1-dimensional side contacts [1]. The periodic antidot lattice was defined in a following step by additional electron-beam lithography and reactive ion etching (see fig. 1). We performed measurements on stacks with different antidot lattice periods down to 100 nm. Several peaks in magnetoresistance can be identified and assigned to orbits around one and several antidots (see fig. 2) [2]. This proves ballistic transport in our graphene heterostructures, in spite of the critical etching step for small lattice periods. We show measurements at different temperatures and can study antidot peaks down to very low carrier densities (n = 2・1011 cm−2) and magnetic fields (B = 0.5 T). At higher magnetic fields, well defined quantum Hall plateaus with filling factors down to = 1 are observed, even at an antidot period of 100 nm. R e f e r e n c e s [1] L. Wang et al., Science 342, 614 (2013). [2] D. Weiss et al., Phys. Rev. Lett. 66, 2790

(1991).

F i g u r e s

Figure 1: SEM image of a hBN/MLG/hBN heterostructure with a patterned antidot array (lattice constant d = 100 nm). The stack is contacted by Cr/Au leads.

Figure 2: Magnetoresistance (black) and Hall resistance (red) of a patterned sample (antidot lattice period d = 100 nm) as a function of magnetic field at 1.4 K. For small perpendicular magnetic fields, additional peaks rise in , which can be assigned to orbits around 1, 2 and 4 antidots. At higher fields (B ≥ 5 T), we can see pronounced plateaus from the QHE. The inset shows a sketch of electron orbits around a different number of antidots.

A. Sandner1, T. Preis1, C. Schell1, P.

Giudici1, K. Watanabe2, T. Taniguchi2, D. Weiss1 and J. Eroms1

[email protected]

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C o m b i n e d R a m a n s p e c t r o s c o p y a n d r e f l e c t i o n / t r a n s m i s s i o n m e a s u r e m e n t s f o r g r a p h e n e c h a r a c t e r i z a t i o n Laboratoire Charles Coulomb, University of Montpellier–CNRS 34400 Montpellier, France

Raman spectroscopy (RS) of graphene-related materials (GRM) is being considered as a fast, versatile, powerful and non-destructive characterization technique. RS is sensitive to the number of layers, their stacking order, the nature and density of defects, the charge carrier density and in-plane strain variations. However, the positions, linewidths, profiles, intensities of the graphene/MLG Raman bands are not only affected by all these perturbations but also depends on the uniformity across the probed area (laser spot size and field depth) and on the substrate (through optical interference effects, dielectric screening, doping…) [1]. An accurate interpretation of Raman spectra becomes then extremely complex and deserves the combined use of complementary diagnosis. We recently developed an expertise in terms graphene/MLG characterization. This know-how is based on instrumental developments (including laser power, transmission, reflection and Raman signal simultaneous monitoring), as well as the

development of data treatment (including specific algorithms to subtract the substrate Raman background), interpretation tools and a detailed modeling of the Raman scattering and optical properties of graphene/MLG on a wide set of substrates (including SiC, Cu, SiO2/Si,…). Special care was paid to define protocols that ensure a high reproducibility and repeatability of calibrated measurements. In this contribution, we apply this tool for counting the number of layers of any kind of graphene samples and we propose standard procedures for GRM characterization on different substrates.. R e f e r e n c e s [1] A. Tiberj, M. Rubio-Roy, M. Paillet, J. -R

Huntzinger, P. Landois, M. Mikolasek, S. Contreras, J.-L. Sauvajol, E. Dujardin and A.-A Zahab, Reversible optical doping of graphene, Scientific Report, 3 (2013) 2355.

J.-L. Sauvajol, M. Paillet, J.-R. Huntzinger, A. Tiberj, P. Landois, M. Bayle, A. A. Zahab

[email protected]

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S t r u c t u r a l a n d o p t i c a l c h a r a c t e r i s a t i o n o f h - B N l a y e r s 1 LEM, ONERA-CNRS, 29 avenue de la Division Leclerc, Châtillon, France 2 GEMAC, Université Versailles St Quentin – CNRS, 45 avenue des Etats Unis Versailles, France

Hexagonal boron nitride is a wide band gap semiconductor (~ 6.5 eV), which meets a growing interest for graphene engineering [1]. In particular electron mobility of graphene is shown to be preserved when graphene is supported by a h-BN film. We attempt to have a better comprehension of the optical and electronic properties of thin BN layers, in correlation with their structural properties and to better know how electronic properties of graphene can be impacted by underlying BN layers. Until recently, these properties were poorly known due to both the scarcity of crystals and suitable investigation tools. This situation has changed thanks, first, to the development of dedicated cathodoluminescence (CL) experiments running at 5K and adapted to the detection in the far UV range [2], and second to the avaibility of high quality single crystals [3]. H-BN has been shown to display original optical properties, governed, in the energy range 5.2 – 6 eV, by strong Frenkel-type excitonic effects [2, 4]. In this work, we first investigate by CL the luminescence properties of hBN samples synthesized by three different processes (HPHT, PDCs and a commercial powder). We observe in CL spectra the same features of the S series, in the energy range 5.7 – 6 eV. This reveals the intrinsic

origin of these excitonic recombinations unlike the D series previously attributed to excitons trapped on defects such as dislocations or grain boundaries and observed at lower energy (5.2 – 5.7 eV) [5]. Besides, thin hBN layers have been obtained by mechanical exfoliation from small crystallites of a commercial powder and single crystal. We performed CL measurements on several flakes with various thicknesses from 100L to 6L and observed a significant effect of the confinement on the luminescence of hBN, especially in the energy range 5.7 – 6 eV previously mentioned. Indeed, CL spectra exhibit S series with different features depending on the hBN thickness. This strongly suggests that this signal (S series) could arise from distinct contributions that we will discuss. R e f e r e n c e s [1] C.R. Dean et al. Nature Nanotechnology, 5

(2010) 722. [2] P. Jaffrennou el al., Phys. Rev. B, 77 (2008)

235422. [3] Y. Kubota et al., Science, 317 (2007) 932. [4] L. Museur et al., Phys. Stat. Sol. RRL, 5 (2011)

414. [5] A. Pierret et al., Phys. Rev. B, 89 (2014)

035214.

L. Schue1,2, A. Pierret1, F. Fossard1, F.

Ducastelle1, J. Barjon2 and A. Loiseau1

[email protected]

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L o c a l O p t i c a l P r o b e f o r M o t i o n a n d S t r a i n D e t e c t i o n o f R e s o n a n c e s i n G r a p h e n e M e m b r a n e D r u m s Univ. Grenoble Alpes, F-38000 Grenoble, France CNRS, Inst Néel, F-38000 Grenoble, France

Nanoelectromechanical systems (NEMSs) are emerging nanoscale elements at the crossroads between mechanics, optics and electronics, with significant potential for actuation and sensing applications. The reduction of dimensions compared to their micronic counterparts brings new effects including sensitivity to very low mass, resonant frequencies in the radiofrequency range, mechanical non-linearities and observation of quantum mechanical effects. An important issue of NEMS is the understanding of fundamental physical properties conditioning dissipation mechanisms, known to limit mechanical quality factors and to induce aging due to material degradation. There is a need for detection methods tailored for these systems which allow probing material parameters, motion and stress at the nanometer scale. Graphene, as a one-atom-thick layer, provides an ultimate membrane with a very low mass along with high Young modulus. Moreover its vibrational properties make it a new playground to probe strain in an actuated NEMS. Here, we show a non-invasive local optical probe for the measurement of motion and stress within a monolayer graphene NEMS with a well-defined geometry provided by a combination of reflection measurements and Raman spectroscopy. The system studied consists of a monolayer graphene sheet grown by chemical vapour deposition (CVD) that is suspended over prepatterned holes in a silicon dioxide substrate. Thus the geometry of the resonators is well- controlled and diameters up to 10 µm are reached. The graphene membrane is actuated electrically by applying a voltage to the silicon backgate or mechanically with a piezo crystal. The actuation ranges from a quasi-static load up to the mechanical resonance at some MHz.

With reflection measurements of the actuated membrane the resonance frequencies of up to the first eight vibrational membrane modes can be determined. Furthermore mechanical non-linearities of the graphene are revealed by reflection measurements at high excitation powers. Raman measurements comparing the static and actuated state allow to determine the strain induced in the driven graphene membrane. In summary, a geometrically well-defined monolayer graphene resonator is presented which allows to study graphene material properties by reflection measurements. The latter are complemented by Raman spectroscopy measurements which open the route towards the nanoscale spatial detection of strain induced in a mechanical resonance mode of the graphene. Such spectroscopic detection reveals the coupling between a strained nano-resonator and the energy of an inelastically scattered photon, and thus offers a new approach to optomechanics. R e f e r e n c e s [1] A. Reserbat-Plantey et al., Nat Nano, 7 (2012),

151-155). [2] A. Reserbat-Plantey et al., J. Opt., 15 (2013),

114010. [3] O. Frank et al ACS Nano, 5 (2011), 2231–2239.

C. Schwarz, B. Pigeau, A. Kuhn, D. Kalita, Z. Han, L. Marty, O. Arcizet, N. Bendiab, V. Bouchiat

[email protected]

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F i g u r e s

Figure 1: SEM micrograph of a suspended monolayer graphene drum.

Figure 2: Mechanical resonance modes of suspended monolayer graphene drum.

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G r a p h e n e a p p l i c a t i o n s – B e y o n d t h e s t i c k y t a p e Knowledge Exchange Fellow, National Graphene Institute The University of Manchester, UK

Graphene - the so called "wonder material" could change the world with what seems endless applications and capabilities. Challenges exist in achieving this commercialisation and a key will be the creation of partnerships and collaborations to make these real from structures, to membranes and electronic applications. The National Graphene Institute (NGI) will house state of the art instruments and techniques to characterize graphene and to work with graphene and other 2D materials. The NGI will also collaborate on research projects with industry leaders. The building is specifically designed for industry to come and collaborate on academic research in order to push for the commercialization of Graphene enabling industry to work hand in hand with academics, and gain access to the science and the expertise it has to offer. The university is also focusing on a variety on Graphene applications such as electronics, membranes and coatings, energy storage, composition structure, the standard characterization of graphene, and Bio- Medical application.

F i g u r e s

Ania Servant

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G r o w t h M e c h a n i s m o f H e x a g o n a l B o r o n N i t r i d e : b y N a n o c r y s t a l l i n e G r a p h e n e A s s i s t a n c e a n d / o r b y B - N m o l e c u l a r d i f f u s i o n 1 Device Lab., Samsung Advanced Institute of Technology, Suwon 443-801 Republic of Korea 2School of Advanced Materials Science and Engineering, SKKU Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University (SKKU), Suwon 440-746 Republic of Korea

Hexagonal boron nitride (h-BN) has received a great deal of attention as a substrate material for high-performance graphene electronics because it has an atomically smooth surface, lattice constant similar to that of graphene, large optical phonon modes, and a large electrical band gap. Herein, we discuss In the first part, we report the large scale synthesis of high-quality h-BN nanosheets in a chemical vapor deposition (CVD) process by controlling the surface morphologies of the copper (Cu) catalysts [1]. It was found that morphology control of the Cu foil is much critical for the formation of the pure h-BN nanosheets as well as the improvement of their crystallinity. We demonstrate the performance enhancement of CVD based graphene devices with large-scale h-BN nanosheets. The mobility of the graphene device on the h-BN nanosheets was increased 3 times compared to that without the h-BN nanosheets. The on-off ratio of the drain current is 2 times higher than that of the graphene device without h-BN. We can determine occasionally nanocrystalline graphene (nc-G) on Cu foil during h-BN growth process. Unintentionally formed nanocrystalline graphene (nc-G) can act as a useful seed for the large-area synthesis of hexagonal boron nitride (h-BN) nanosheets with an atomically flat surface that is comparable to that of exfoliated single crystal h-BN. A wafer-scale dielectric h-BN nanosheets was successfully synthesized on a bare sapphire substrate by assistance of nc-G without metal catalyst [2]. We systematically discuss the growth mechanism of these nc-G-tailored h-BN nanosheets in the second part.

Until now, because of the low solubility of N atoms in metals, hexagonal boron nitride (h-BN) growth has explained by surface reaction on metal rather than by penetration/precipitation of B and N atoms in metal. In the third part, we present an impressive pathway of h-BN formation at the interface between Ni and oxide substrate based on B-N molecular diffusion into Ni through individual atomic vacancies [3]. First-principles calculations confirmed the formation energies of the h-BN layers on and under the metal and the probability of B-N molecular diffusion in metal. The interface growth behavior depends on the species of metal catalysts, and these simulation results well support experimental results. These approaches provide a novel method for preparing high-quality two-dimensional materials on a large surface. R e f e r e n c e s [1] Kang Hyuck Lee, Hyeon-Jin Shin, Jinyeong Lee,

In-yeal Lee, Gil-Ho Kim, Jae-Young Choi, and Sang-Woo Kim, Nano Lett., 12 (2), 714-718 (2012).

[2] Kang Hyuck Lee, Hyeon-Jin Shin, Brijesh Kumar, Han Sol Kim, Jinyeong Lee, Ravi Bhatia, Sang-Hyeob Kim, In-Yeal Lee, Hyo Sug Lee, Gil-Ho Kim, Ji-Beom Yoo, Jae-Young Choi and Sang-Woo Kim, Angew. Chem. Int. Edi. 53 (43), 11493-11497 (2014).

[3] Seongjun Park, Jinyeong Lee, Han Sol Kim, Jong-Bong Park, Kang Hyuck Lee, Sang A Han, Sungwoo Hwang, Sang-Woo Kim and Hyeon-Jin Shin, ACS Nano, online published.

Hyeon-Jin Shin1, Seongjun Park1, Kang

Hyuck Lee2, Jinyeong Lee2, Sang-Woo Kim2

[email protected]

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S T M a n d N C - A F M i n v e s t i g a t i o n s o f G r a p h e n e o n M e t a l S u r f a c e s 1 SPECS Surface Nano Analysis GmbH, Voltastrasse. 5, 13355 Berlin, Germany

We present recently obtained results in graphene-based systems as measured with STM and NC-AFM techniques. We highlight the latest state-of-the-art developments in these two techniques and show how these techniques are applied in the latest graphene research as well in other experimental systems. The SPM Aarhus 150 is an ideal instrument for investigating lattice mismatched surfaces, with a focus in the present talk of SPM measurements on the graphene/Ir(111) system [1]. Microscopy experiments were performed in constant current / constant frequency shift (CC/CFS) and constant height (CH) modes, exploiting a combination of the STM and NC-AFM capabilities of the system. We found that in STM imaging the electronic contribution is prevailing compared to the topographic one and the inversion of the contrast can be assigned to the particular features in the electronic structure of graphene on Ir(111). Contrast changes observed in constant height AFM measurements [1] are analyzed on the basis of the energy, force, and frequency shift curves, obtained in DFT calculations, reflecting the interaction of the W-tip with the surface and are attributed to the difference in the height and the different interaction strength for high-symmetry cites within the moirè unit cell of graphene on Ir(111).The presented findings are of general importance for the understanding of the properties of the lattice-

mismatched graphene/metal systems especially with regard to possible applications as templates for molecules or clusters. R e f e r e n c e s [1] E. N. Voloshina et al., Nature Sci. Rep. 3, 1072

(2013). F i g u r e s

Figure 1: Gr/Ir(111) moirés (left) are contrasted with STM/NC-AFM measurements, with feedback switched ‘on-the-fly’ (right) at tunnelling voltages of +0.46 (top-right) and -0.2 V (bottom-right). The top of each image demonstrates the effect of feedback via tunnelling current and the bottom feedback in NC-AFM modeshows STM, the bottom Δf (AFM)

V. Simic-Milosevic, Y. Dedkov, A. Kaiser, S. Schmitt, S. Bahr, O. Schaff, A. Thissen

[email protected]

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E x t r a o r d i n a r y p h o t o l u m i n e s c e n c e i n U V / o z o n e t r e a t e d g r a p h e n e f l a k e s 1 Department of Physics and Astronomy, Shanghai Jiao Tong University, Shanghai 200240, China 2 State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050, China 3 Department of Physics, Southeast University, Nanjing 211189, China

Photoluminescence (PL) originating from two dimensional materials is attracting intense attention due to emergence of graphene and other direct bandgap materials like phosphorene and monolayer MoS2/WS2 [1-3]. In 2013, H. R. Gutiérrez et. al. observed extraordinary PL from edges of the chemically grown triangular WS2 and MoS2 monolayer flakes [2]. They proposed that the edge structure and chemistry of as-grown monolayer WS2/MoS2 are crucial for localized PL enhancement even though the actual mechanism leading to the edge-enhanced PL is still to be determined. Different from direct-bandgap monolayer metal dichalcogenides, luminescent graphene-based nanostructures usually have two distinct characteristics, i.e., shrinking nanometer scale structures and adsorbed surface chemical functional groups [1,4]. Aside from regular chemical synthesis routes, realizing in-situ PL in high-quality graphene flakes is significant in the future photonic and optoelectronic applications [1]. As previously reported, UV/ozone photochemical oxidation has a unique capability of carving few layer graphene (FLG) into about one nanometer deep patterns [4,5]. In this talk, we present extraordinary PL imaged by a confocal laser scanning microscope (CLSM) in the suspended and edge area of UV/ozone treated FLG flakes [Fig. 1]. Atomic force microscopy (AFM) and confocal Raman spectroscopy analyses [Fig. 2] indicate that monolayer graphene, the most adequate for characterizing ozonation, turn into some isolated amorphous nano-dots with an average size of ~20 nm. In addition, no obvious topographic difference can be detected between the suspended and Si/SiO2 (300 nm) supported FLG. X-ray photoelectron spectroscopy (XPS) results [Fig. 3] indicate a minute amount of luminescent-inducing

surface chemical groups are created after the ozonation. We think the properly etched nanostructures and luminescent-inducing surface chemical groups contribute together to the PL in FLG. However, the subjacent intact carbon layers and charge impurities resided in SiO2 substrate can cause severe PL quenching, and as a consequence result in non-detectable PL in the mono-/bilayer graphene and substrate supported FLG [6]. Our results deviate from report by Gokus et al. that they could detect PL only in monolayer graphene flakes instead of in FLG after oxygen plasma treatment [1]. We conclude the simultaneously ozonized graphene bottom layers, which are ascertained by high temperature vacuum annealing process, can efficiently decrease PL quenching and facilitate PL detection in the suspended and edge area of FLG. Our work may shed light on the understanding of luminescent two dimensional materials as well as contribute to building graphene-based nanophotonics and optoelectronics. R e f e r e n c e s [1] T. Gokus, R. R. Nair, A. Bonetti, M. Böhmler, A.

Lombardo, K. S. Novoselov, A. K. Geim, A. C. Ferrari, and A. Hartschuh, ACS Nano 3, 3963 (2009).

[2] H. R. Gutiérrez, N. P.-López, A. L. Elías, A. Berkdemir, B. Wang, R. Lv, F. L.-Urías, V. H. Crespi, H. Terrones, and M. Terrones, Nano Lett. 13, 3447 (2013).

[3] S. Zhang, J. Yang, R. Xu, F. Wang, W. Li, M. Ghufran, Y.-W. Zhang, Z. Yu, G. Zhang, Q. Qin, and Y. Lu, ACS Nano 8, 9590 (2014).

[4] N. Leconte, J. Moser, P. Ordejón, H. Tao, A. Lherbier, A. Bachtold, F. Alsina, C. M.

Haihua Tao1, Ziyu Zhang1, Hao Li1,

Guqiao Ding2, Zhenhua Ni3, Xianfeng Chen1

[email protected] [email protected]

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Sotomayor Torres, J.-C. Charlier, and S. Roche, ACS Nano 4, 4033 (2010).

[5] H. Tao, J. Moser, F. Alzina, Q. Wang, C. M. Sotomayor-Torres, J. Phys. Chem. C 115, 18257 (2011).

[6] X. T. Guo, Z. H. Ni, C. Y. Liao. H. Y. Nan, Y. Zhang, W. W. Zhao, and W. H. Wang, Appl. Phys. Lett. 103, 201909 (2013).

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Figure 1: (a) Optical image of a graphene flake composed of bilayer and FLG elements; (b) its CLSM picture excited at 364 nm after proper UV/ozone treatment with a low initial oxygen pressure. Each scale bar is 20 μm.

Figure 2: (a) AFM image and (b) Raman spectrum of UV/ozone treated monolayer graphene; AFM image of (c) bi-/hexalayer FLG adjacent to the suspended region in Fig. 1; (d) AFM comparison of the supported (top) and suspended (bottom) regions of FLG (~6L thick). All samples are the same UV/ozone treated as photoluminescent FLG.

Figure 3: Highly resolved narrow band (a) C1s and (b) O1s XPS spectra of the freshly cleaved and ozonized Kish graphite; (c) Fitting C1s spectrum of the ozonized Kish graphite with six mixed Gaussian- Lorentzian curves.

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S i z e q u a n t i z a t i o n e f f e c t s i n q u a s i p a r t i c l e i n t e r f e r e n c e o n e p i t a x i a l g r a p h e n e n a n o f l a k e s 1 Universität Konstanz, Konstanz, Germany 2 Chalmers University of Technology, Göteborg, Sweden

Graphene nanostructures represent an exciting topic for research, as a strong spatial confinement together with the edge structure impose new electronic properties, making them promising candidates for future nanoscale electronic units. By means of low-temperature scanning tunnelling microscopy and spectroscopy we investigate the electronic properties of elongated quasi-freestanding epitaxial graphene nanoflakes (GNFs) on Ag(111) and Au(111). Samples are prepared by temperature programmed growth of graphene flakes on Ir(111) and subsequent intercalation of noble metals. This procedure allows us to produce GNFs of different shapes and sizes exhibiting no substantial edge bonding towards the substrate [1]. The edges display an edge configuration with long-range zigzag or rougher zigzag sections with single hydrogen termination.

We implement local density of states (LDOS) mapping to analyze standing wave patterns arising from elastic scattering processes within single nanoflakes [2,3]. The Fourier analysis of the obtained LDOS maps shows that characteristic ringlike features due to the intervalley and intravalley scattering observed for large graphene sheets are also visible on the GNFs with lateral sizes down to 20nm. For GNFs, additional features appear inside the ringlike structures, which can be related to the transverse confinement in a nanoflake [4]. The scattering processes between the confinement-induced discrete bands in the nanoribbon electronic structure observed in flakes with a width of 100 nm indicate a large electron coherence length, though these features appeared less prominent within the Fourier transform for larger flakes. Our experimental results are supported by tight-binding calculations of realistic flakes, which very well reproduce the experimentally observed fingerprints of confinement in the Fourier transform of the

standing wave patterns and confirm the strong influence of edge type as well as confinement direction and dimensions on the scattering in GNFs.

R e f e r e n c e s

[5] P. Leicht et al., ACS Nano, 8 (2014) 3735. [6] G.M. Rutter et al., Science, 317 (2007) 219. [7] L. Simon et al., J. Phys. D: Appl. Phys., 44

(2011) 464010. [8] A. Bergvall et al., Phys. Rev. B, 87 (2013)

205431.

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Figure 1: (a) Topography of an investigated graphene flake on Ag(111). (b) QPI mapping with atomic resolution (scanning parameters: 54x54 nm2, V = -10mV, I = 0.8 nA, Vmod = 3 mV), the inset indicates the mapping position on the flake. (c) FFT of the obtained mapping. The inset shows a magnification of the intervalley scattering rings with clearly visible confinement features inside the characteristic trigonally warped circles. All measurements were carried out at 10 K

Julia Tesch1, Philipp Leicht1, Felix

Blumenschein1, Anders Bergvall2, Tomas Löfwander2, Luca Gragnaniello1, Mikhail Fonin1

[email protected]

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S p i n D y n a m i c s i n H i g h - Q u a l i t y G r a p h e n e : R o l e o f E l e c t r o n - H o l e P u d d l e s a n d S p i n - P s e u d o s p i n C o u p l i n g 1 ICN2 - Institut Catala de Nanociencia i Nanotecnologia, Campus UAB, 08193 Bellaterra (Barcelona), Spain 2 Department of Physics, Universitat Autónoma de Barcelona, Campus UAB, 08193 Bellaterra, Spain 3 Institute for Materials Science and Max Bergmann Center of Biomaterials, Technische Universität Dresden, 01062 Dresden, Germany 4 ICREA, Institució Catalana de Recerca i Estudis Avancats, 08070 Barcelona, Spain

We report a strong spin dephasing effect induced by electron-hole puddles [1, 2] and spin-pseudospin coupling in ultraclean graphene, with long mean free path and uniform Rashba spin-orbit coupling as low as a few tens of µeV [3] . From the time dependence of spin dynamics of propagating wave packets, spin relaxation times typically on the order of few hundreds of picoseconds to the nanosecond scale are extracted, depending on the substrate-induced electron-hole characteristics. The energy dependence of spin relaxation times [4], together with the obtained ratio for spins pointing out-of-plane to spins in-plane (

/∥),

and scaling of spin lifetimes with disorder provide a consistent description of fundamentals of spin lifetimes [5] in the ultraclean grapheme limit. R e f e r e n c e s [1] J. Martin et al., Nature Physics 4, 144-148

(2008). [2] Y. Zhang et al., Nature Physics 5, 722 (2009). [3] C. R. Ast and I. Gierz, Phys. Rev. B 86, 085105

(2012) [4] Dinh Van Tuan, Frank Ortmann, David Soriano,

Sergio O. Valenzuela and Stephan Roche, Pseudospindriven spin relaxation mechanism in graphene. Nature Physics 10, 857-863 (2014).

[5] Dinh Van Tuan, Frank Ortmann, Aron W. Cummings, David Soriano, Sergio O. Valenzuela and Stephan Roche, Spin Dynamics in High-Quality Graphene: Role of Electron-Hole Puddles and Spin-Pseudospin Coupling. Submitted to Phys. Rev. Lett.

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Figure 1: Spin polarizations for out-of-plane (a) and in-plane (b) spin injections. (c): Illustration of parallel (green) and perpendicular (violet) components. The projection of parallel component in x direction is shown in blue.

Figure 2: Time-dependent spin polarization for in- plane and out-of-plane polarized wavepacket in grapheme on hBN and SiO2 substrates. Inset: Onsite energy distribution of the carbon atoms in the graphene sample, which mimics the chemical potential induced by hBN (green) and SiO2 (black) substrates together with their Gaussian fitting lines.

Dinh Van Tuan1,2

, Frank Ortmann1,3, Aron W. Cummings1, David Soriano1, Sergio O. Valenzuela1,4 and Stephan Roche1,4

[email protected]

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G r a p h e n e T r a n s i s t o r s f o r D e t e c t i o n o f N e u r o n a l A c t i v i t y 1 Institut Néel, CNRS, 25 Rue des Martyrs, 38042 Grenoble, France 2 Université Grenobel Alpes, HP2 & INSERM U1042, 38041 Grenoble, France

Due to its outstanding properties graphene offers an ideal platform for sensing and culturing neural networks. Its biocompatible, soft, and chemically inert nature associated to the lack of dangling bonds offers novel perspectives for direct integration in bioelectric probes. The presence of readily accessible surface charges gives the unprecedented possibility to realize a strong electrical coupling with cells. Moreover, the possibility to transfer it on transparent and flexible substrates opens the way to a variety of applications for in-vitro studies and in-vivo implants with reduced inflammatory response [1]. Here we present a study of our CVD grown SL graphene [2] with regard to its biocompatibility and bioelectrical interfacing. We found, that while on any other substrate an adhesive coating (such as polyL-lysine) is needed to assure neuronal growth in culture, graphene actively promotes the growth even without a coating. Moreover, in comparison to other frequently used substrates the neuron density and the neurite length are significantly higher for neurons cultured on uncoated graphene as shown in Fig. 1. Further, in order to prove the ability of graphene based devices to detect neuronal signals, we realized graphene FET arrays on Si/SiO2, glass and polyimide substrates and performed characterization measurements in cell culture medium with a Pt gate electrode. To mimic the neuronal spiking we superimposed 1ms long Gaussian pulses on the DC offset of the Pt-electrode. All graphene FETs showed reproducible electrical properties with a mobility around 6000

cm2V

-1s

-1 and a sensitivity to potential changes up to 2 mS/V allowing a rapid detection of very small (around 200µV) potential spikes comparable with

neuronal signaling [3]. Also, neurons were shown to survive on graphene FETs for periods up to 19-21 days achieving the regular maturation stage. In conclusion, our studies show the enormous potential of graphene based devices as neuronal growth support and bioelectrical sensors R e f e r e n c e s [1] V.S. Polikov, P.A. Tresco, W.M. Reichert,

Journal of Neuroscience Methods 148 (2005) 1–18.

[2] Z. Han, A. Kimoche, D. Kalita, A. Allain, H. Arjmandi-Tash, A. Reserbat-Plantey, L. Marty, S. Pairis, N. Bendiab, J. Coraux, V. Bouchiat, Adv. Func. Mat., 24 (2014) 964-970.

[3] J.J. Pancrazio, J.C. Keefer, W. Ma, D.A. Stenger, G.W. Gross, NeuroToxicology, 22 (2001) 393-400.

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Figure 1: Coating-free graphene promotes neuronal growth. a) Coating-free glass and graphene with neurons after 4 days in culture. The neurons survive only on graphene. b) Neuron density on day 1 and day 2 of and c) the average neurite length on day 2 of culture on different substrates: Ctrl - glass control sample, Gr - graphene, Gr-noPLL – coating-free graphene, Par-C – parylene-C and PI – polyimide.

Farida Veliev1, A. Briancon-Marjollet2,

A. Bourrier1 , D. Kalita1, V. Bouchiat1 and C. Delacour1

[email protected] [email protected]

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Figure 2: Graphene FET characteristics. a) Optical micrograph of a typical device. b) Conductance variation (black line) and device sensitivity (red line) as function of front liquid gate potential measured in cell culture medium. c) Detection of 1 ms long 250 µV Gaussian potential spike applied to the medium through a Pt-electrode using graphene FET.

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N a n o g r a p h e n e o x i d e - c e l l i n t e r a c t i o n s a n d i t s p o t e n t i a l f o r t u m o r d e s t r u c t i o n 1 Nanotechnology Research Division-TEMA, Mechanical Engineering Dpt University of Aveiro, 3810-193 Aveiro, Portugal 2 Department of Biochemistry and Molecular Biology I Faculty of Chemistry, Universidad Complutense, 28040-Madrid, Spain 3 Department of Inorganic and Bioinorganic Chemistry Faculty of Pharmacy, Universidad Complutense, 28040-Madrid, Spain 4 Networking Research Center on Bioengineering, Biomaterials and Nanomedicine CIBER-BBN, Spain

Many applications of graphene in the area of bio and nanomedicine have been proposed and it is important to review its potential with a fine-tooth comb with two main specific objectives: to evaluate if it could possess all the parameters that make a material suitable for its use on the human body, and to specify conditions, applications and materials modifications that could assure materials biocompatibility and a positive biological response. For example, one of the most novel fields of nanomedicine applied to cancer research is using nanoparticles (NPs) but their application will not be feasible without a previous understanding of NPscell/tissue interactions, possible toxicity and accumulation risks. [1] These cancer therapies work through the NPs preferential accumulation in cancerous tissue after intravenous injection due to the combination of leaky vasculature and poor lymphatic drainage which results in what is known as the enhanced and permeability retention effect (EPR). Simultaneously, among the new arising therapies, the hyperthermia of tumours has been investigated as a minimally invasive alternative to surgery that can induce lethal damage to cellular components at temperatures above 40 ºC. Unfortunately, simple heating techniques have trouble discriminating between tumours and surrounding healthy tissues. Thus, by the combination of these two concepts, the localized nanoparticle-based hyperthermia raised as a powerful and potential treatment on its own. Amongst hyperthermia potential agents, nano graphene oxide (nGO) has been proposed due to its strong Near-Infrared (NIR 700-1100 nm range) optical absorption ability and its unique 2-dimensional aspect ratio. [3] Restricting all dimensions at nanoscale could allow unique

performing when compared to any other nanoparticle, but it is mandatory to deeply study the hyperthermia route and the kind of nGO-cell interactions induced in the process. By optimizing the nGO synthesis, it is possible to diminish the initial cell-particle interactions to reduce possible future toxicity in healthy cells.[4] nGO cell exposure and its influence on both the innate and the adaptive immune responses was evaluated in murine lymphocytes and there was no stimulation of proinflammatory cytokine secretion assuring a good biocompatibility. [5] Moreover, the nGO incorporation kinetics and mechanisms by different cell types either in the absence or in the presence of eight endocytosis inhibitors showed that macropynocitosis is the general mechanism of nGO internalization, but that it can also entry through clathrin-dependent mechanisms in hepatocytes and macrophages. [6] This fact gives light to which will be the key surface factors in a future design of targeted delivery of this NPs by means of active moieties. Cell internalization kinetics were established for producing a safe and efficient tumor cell destruction avoiding damage on untreated cells as well as an evaluation of the nature of tumor destruction that could be produced by this hyperthermia treatment.The type of cell damage and toxicity produced by NIR laser irradiation was evaluated as a function of exposure time and laser power in order to control the temperature rise and consequent damage in the nGO containing cell culture medium. The results suggested that controlling the type of cell death, the threshold for producing soft or harmful damage could be precisely ontrolled and so, the increase of

M. Vila1,3,4, , M. C. Matesanz2 , G.

Gonçalves1 , M. J. Feito2, J. Linares2,P.A.A.P. Marques1, , M.T. Portolés2, M.Vallet-Regic4

[email protected]

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cytokine release to the medium, having this a direct impact on immune system reactions.[7] R e f e r e n c e s [1] Day ES, Morton JG, West JL. J Biomed Eng

2009 ;131:074001. [2] Yang K, Wan J, Zhang et al. ACS Nano

2011;5:516-22. [3] Gonçalves G, Vila M, et al. Adv. Healthcare

Materials. 2013; 2(8):1072. [4] Vila M, Portolés MT, Marques PAAP, Feito et

al. Nanotechnology 2012; 23:465103. [5] MJ. Feito, M. Vila , MC. Matesanz et al J

Colloid Interface Science 2014; 432, 221. [6] J.Linares, M. C. Matesanz, M. Vila et al ACS

applied materials & interfaces 2014; 27,13697. [7] Vila M, Matesanz MC, Gonçalves G, et al.

Nanotechnology 2014 (25) 035101.

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Figure 1: Morphology evaluation by confocal microscopy of cultured human Saos-2 osteoblasts in the presence of GOs, before (left) and after 7 min of 1.5 W/cm2 laser irradiation showing necrotic cells (right).

.

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T w i s t - c o n t r o l l e d r e s o n a n t t u n n e l l i n g i n g r a p h e n e / b o r o n - n i t r i d e / g r a p h e n e h e t e r o s t r u c t u r e s Department of Physics, Lancaster University, Lancaster, LA1 4YB, UK

Recent developments in van der Waals heterostructures made from stacks of two-dimensional crystals have already led to the observation of new physical phenomena, such as the metal-insulator transition and Coulomb drag, and to the realisation of functional devices, such as tunnel diodes, and tunnel transistors. An unprecedented degree of control of the electronic properties is available not only by means of the selection of materials in the stack, but also by adjusting the relative orientation of the component layers. In this talk I shall discuss how careful alignment of the crystallographic orientation of two graphene electrodes, separated by a layer of hexagonal boron nitride (hBN) in a transistor device, can achieve resonant tunnelling with conservation of electron energy, momentum and, potentially, chirality [1]. This leads to resonance peaks and negative differential conductances in the device characteristics, which, in turn, can be used to induce a tuneable radio-frequency oscillatory current. Also, the application of a magnetic field in the plane of the two graphene layers can be used to reveal the effects of graphene's chirality on the tunnelling current, and may lead to valley polarised currents. Finally, I note that the momentum and velocity distribution of the tunnelling electrons is highly anisotropic, which may lead to interesting effects in a ballistic device. R e f e r e n c e s [1] A. Mishchenko, J. S. Tu, Y. Cao, R. V.

Gorbachev, J. R. Wallbank, M.T. Greenaway, V. E. Morozov, S. V. Morozov, M. J. Zhu, S. L. Wong, F. Withers, C. R. Woods, Y.-J. Kim, K.

Watanabe, T. Taniguchi, E. E. Vdovin, O. Makarovsky, T. M. Fromhold, V. I. Falko, A. K. Geim, L. Eaves, K. S. Novoselov, Nature Nanotechnology 9, 808 (2014) D. Weiss et al., Phys. Rev. Lett. 66, 2790 (1991).

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Figure 1: (a) The measured (solid curve) and theoretically calculated (dashed curve) tunnelling currents, displaying the resonant peak at a bias voltage of Vb≈0.8V. (b-d) The conditions of energy and momentum conservation, which enable the tunnelling of Dirac electrons, are visualized in the left panels by the line of intersection (red) of the Dirac cones in the two graphene layers. The shift of these in momentum is set by the misalignment of the Brillouin zones of the two graphene layers (see inset of (a)), while the displacement along the energy axis is controlled by the applied bias voltage. Importantly, panel (c) displays the conditions for which the main resonant peak occurs. The tunneling probability for an electron is also modulated by the interference between the electron amplitudes on graphene's A/B carbon sites (right panels).

AJ. R. Wallbank, A. Mishchenko, J.S. Tu, Y. Cao, R.V. Gorbachev, M.T. Greenaway, V.E. Morozov, S.V.Morozov, M.J. Zhu, S.L. Wong, F. Withers, C.R. Woods, Y.-J. Kim, K. Watanabe, T. Taniguchi, E.E. Vdovin, O. Makarovsky, T.M. Fromhold, V.I. Falko, A.K. Geim, L.Eaves, K.S. Novoselov

[email protected]

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T h e A t o m i c a n d E l e c t r o n i c S t r u c t u r e o f P h o s p h o r e n e 1 Department of Chemical Engineering and Material Science 2 Department of Electrical and Computer Engineering University of Minnesota, Minneapolis, MN, USA

Black phosphorus or phosphorene received considerable scientific interest over half a century ago due to its unusual stability compared to other phosphorus allotropes as a result of its unique crystal and electronic structure [1]. The recent emergence in 2-dimensional materials, however, has led to a rediscovery of phosphorene as a layered 2D material with considerable applicability [2]. While first principle studies have predicted both the atomic and electronic structure of phosphorene, atomic resolution experimental evidence to support the theoretical predictions would verify and further our understanding of this material. In this work, scanning transmission electron microscopy (STEM) was used to image few-layer phosphorene with atomic resolution to provide directly interpretable images of its crystal structure in three different zone axes models of which are shown in Figure 1. The experimentally measured lattice parameters match those predicted by simulation [4]. In addition, low-loss and core-loss electron energy loss spectroscopy (EELS) were used to analyze the electronic structure of this material. The resulting conduction band density of states measurements closely resembled those from DFT calculations. The effects of oxidation of phosphorene were also explored

using a STEMEELS approach which explained the degradation observed in devices. R e f e r e n c e s [1] Keyes, R. W, Physical Review, 92 (1953). 580-

584. [2] Xia, F., Wang, H. & Jia, Y., Nat Commun 5

(2014). 4458. [3] Rudenko, A. N. & Katsnelson, M. I., Physical

Review B 89 (2014). 201408. [4] Dai, J. & Zeng, X. C. The Journal of Physical

Chemistry Letters 5, (2014) 1289-1293. F i g u r e s

Figure 1: Structure of Black Phosphorus. a) top down view or [001] zone axis. b) 17.5 degrees off of [001] or [101] zone axis. c) cross sectional view or [100] zone axis.

Ryan J. Wu1, Jong Seok. Jeong1, Matt

Robbins2, Nazila Haratipour2, Mehmet Topsakal1, Renata M. M. Wentzcovich1 , Steven J. Koester2, K. Andre Mkhoyan1

[email protected]

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E v i d e n c e f o r e p i t a x i a l g e r m a n e n e f o r m a t i o n o n A l N ( 0 0 0 1 ) / A g ( 1 1 1 ) t e m p l a t e 1 Institute of Nanoscience and Nanotechnology, National Center for Scientific Research ‘DEMOKRITOS’, GR-15310, Athens, Greece 2 CNR-IOM-OGG c/o European Synchrotron Radiation Facility, 71 Avenue des Martyrs, F-38043 Grenoble, France

Free standing silicene and germanene, has been predicted to be stable in the low buckled (LB) configuration, preserving the Dirac cone at K-points of Brillouin zone (BZ) although observation of π-bands remain elusive [1]. The first experimental works on germanene growth appeared only recently, reporting on the germanene formation on Pt(111) [2] and Au(111) [3] substrates. Nevertheless, the growth of metal-supported germanene/silicene has drawbacks because of the strong interactions between the substrate and the 2D layers. The deposition of Ge on Ag(111) at 1/3 coverage show strong cone-like features which are attributed to strong Ge-Ag interactions forming Ag2Ge surface alloy [4]. On the other hand, it has been theoretical predicted that germanene can stably attach through weak van der Waals interactions on another 2D graphite-like material, such as hexagonal (h-) boron nitride (BN) [5].

In this work we present the growth of Ge layer on 2D hexagonal (h)-AlN nanosheets on Ag(111) [6]. Ge layers were deposited by molecular beam epitaxy (MBE) on Ag(111) with and without h-AlN buffer layer and were structurally characterized by RHEED, EXAFS measurements and first-principle calculationsDFT. The RHEED spectra of Ge layer on h-AlN (Fig. 1) present a (4x4) Ge reconstruction with respect to (1x1) h-AlN, or a (3x3) reconstruction with respect to (1x1) germanene. EXAFS structural analysis on the Ge layers deposited on the pure Ag surface shows a Ge-Ge distance that is typical of Ge bulk islands, while the Ge deposited on the buffer h-AlN layer presents a significant structural difference indicating buckled germanene with Ge-Ge bond length near the free standing value. Acknowledgements: This work was supported by

the FP7/FET “2D-NANOLATTICES”-270749 project of the European Commission.

R e f e r e n c e s

[1] For a recent review see e.g. A. Dimoulas, Microelectron. Eng. 131 (2015) 68–78.

[2] L. Li, S. Z. Lu, J. Pan, Z. Qin, Y. Q. Wang, Y. Wang, G. Y. Cao, S. Du, H. J. Gao, Adv. Mater. 26 (2014) 4820.

[3] M. E. Dávila, L. Xian, S. Cahangirov, A. Rubio, G. Le Lay, New J. Phys. 16 (2014) 095002.

[4] E. Golias, E. Xenogiannopoulou. D. Tsoutsou, P. Tsipas, S. A. Giamini, A. Dimoulas, Phys. Rev. B 88 (2013) 075403.

[5] L. Li, M. Zhao, Phys. Chem. Chem. Phys. 15, (2013) 16853.

[6] P. Tsipas, S. Kassavetis, D. Tsoutsou, E. Xenogiannopoulou, E. Golias, S.A. Giamini, C. Grazianetti, D. Chiappe, A. Molle, M. Fanciulli, A. Dimoulas, Appl. Phys. Lett. 103 (2013) 251605.

F i g u r e s

Figure 1: RHEED patterns of: (a) bare Ag(111), (b) epitaxial AlN buffer layer on Ag(111) and (c) 1ML Ge deposited on epitaxial AlN/Ag(111) template, along [110] (left) and [11-2] (right) azimuths of silver, respectively. The white and red arrows indicate the AlN and Ge diffraction streaks, respectively. In (b) the (1x1) hexagonal AlN reconstruction is shown while in (c) after the Ge deposition, a (4x4) Ge reconstruction with respect to (1x1) hexagonal-AlN is observed.

Evangelia Xenogiannopoulou1 ,

Polychronis Tsipas1, Jose Marquez Velasco1 , Dimitra Tsoutsou1, Francesco d’Acapito2, Simona Torrengo2 and Athanasios Dimoulas1

[email protected]

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S i l a n e - C a t a l y z e d S i n g l e - C r y s t a l l i n e G r a p h e n e G r o w t h o n H e x a g o n a l B o r o n N i t r i d e 1 State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences, 865 Changning Road, Shanghai 200050, P.R. China 2 Division of Physics and Applied Physics, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore 637371 3 Institute of Textiles and Clothing, Hong Kong Polytechnic University, Kowloon, Hong Kong, 999077, P. R. China

Hexagonal boron nitride (h-BN) is considered as an ideal substrate for graphene, on which superior graphene properties are demonstrated. Direct grapheme growth on h-BN by chemical vapor deposition (CVD) were already realized but with very low growth rate, because of the absence of catalyst. With extensive investigations, we discovered that silane, can serve as a gaseous catalyst, boosting the graphene growth rate by 2-3 orders of magnitude, yielding in single crystalline graphene domain size up to 20 μm, with more than 90% of the grains aligned precisely with the h-BN substrate. Preliminary results show that the

edges of grapheme can be tuned from pure armchair to pure zigzag. The results may stimulate further research on the graphene/h-BN hetero-structure and graphene/h-BN super-lattice, which may have profound impact on graphene research in the future. Most recent results on the CVD synthesis of single layered h-BN grains over 100 µm and inch-sized single crystal graphene wafer will also be briefly presented.

Shujie Tang1, Haomin Wang1, Ting Yu2, Feng Ding3 and Xiaoming Xie

1

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G r o w t h a n d a t o m i c - s c a l e c h a r a c t e r i z a t i o n o f g r a p h e n e - h - B N h y b r i d s o n s i n g l e c r y s t a l s u b s t r a t e s Department of Materials Science and Engineering, College of Engineering; Center for Nanochemistry (CNC), Peking University, Beijing, China

We have performed systematic STM studies of the growth and the microscopic structure of graphene on Cu, Pt, Rh etc. foil substrates, and clarified their growth mechanisms along with the aid of traditional methods like Raman spectroscopy, scanning electron microscopy (SEM) and so on [4]. Interestingly, we found that randomly stacked bilayer or few layer segregated graphene on Rh foils usually exhibit various moiré patterns, on which angel-dependent van hove singularities was observed by STM/STS [5,6]. Moreover, we showed that h-BN, a structural analogue of graphene, can be patched onto graphene to form a monolayer hybrid on Rh(111). This hybrid formation was considered be promising for opening up a small band gap of graphene, and most of the efforts were performed by growing the sample on Cu foil substrates. In our work, we show that, on the deliberately selected Rh(111) and Ir(111) substrates with strong and weak interface interactions with graphene and h-BN, a monolayer hybrid of G-h-BN can be constructed with atomic scale continuity at their interfaces mostly with a preferred zigzag type, as identified by STM and also verified by DFT calculations. The influence of the substrates on the electronic properties of the two analogue materials were also presented.

R e f e r e n c e s [1] Y. F. Zhang, Z.F. Liu*, et al., et al., ACS Nano,

5(2011)4014. [2] Y.F. Zhang*, Z.F. Liu*, et al., ACS Nano

6(2012)10581. [3] Y. F. Zhang*, L. He*, et al., Phys. Rev. Lett.

109(2012)126801. [4] Y. F. Zhang*, Z. F. Liu*, et al., Nano Lett.

13(2013)3439. [5] Y. F. Zhang*, Z. F. Liu*, et al., Nano Lett.

14(2014)6342. F i g u r e s

Yanfeng Zhang

[email protected]

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S w i t c h i n g o f M a g n e t o c r y s t a l l i n e A n i s o t r o p y o f a S i n g l e L a y e r C o b a l t F i l m b y G r a p h e n e SPINTEC, UMR CEA/CNRS/UJF-Grenoble 1/Grenoble-INP, INAC 38054 Grenoble, France

Two-dimensional graphene has demonstrated outstanding physical properties such as exceptional electrical, thermal, and mechanical properties [1,2], but also very long spin diffusion lengths at room temperature [3–7]. This offers an unprecedented platform for the advent of lateral spintronics. For instance, graphene interfaced with insulators/semiconductors (SiC, SiO2, Al2O3), magnetic insulator EuO [8,9], and magnetic metals have been intensively studied in recent years. Among many interesting phenomena which have been recently proposed for graphene/magnetic metal interfaces, perpendicular magnetic anisotropy (PMA) has been attracting much attention in a view of its general interest for spintronics. In particular, PMA has been reported in Co/graphene interface [10]. However, a single layer of Co film, either free standing or on substrates (e.g. Pt, Au, etc.), persists in-plane anisotropy and switching it to the out-of-plane one is a big challenge. In this work, we report graphene proximity induced switching of magnetocrystalline anisotropy of single layer Co film from the in-plane to out-of-plane orientation with a large PMA value comparable to thicker Co films. The calculations were performed in two steps using Vienna Ab-Initio Simulation Package (VASP), which is based on density functional theory with generalized gradient approximation (PBE), for the exchange correlation potential and projector augmented wave based pseudopotentials [11]. First, the structures are relaxed with no spin-orbit interaction taken into account for determining the most favorable adsorption geometry of graphene on Co. Then the spin-orbit coupling was included and the total energy of the system was determined as a function of the orientation of the magnetic moments. The 19×19×1 k-point mesh was used in

all calculations and the energy cutoff was set to 520 eV. The atomic structures were relaxed until the forces were smaller than 1 meV/Å. For the anisotropy calculations, the total energies were converged to with precision of 10-7 eV. First, the magnetocrystalline anisotropy of a free standing Co layer was calculated and found to be about -2.17 mJ/m2 favoring in-plane anisotropy. Next, we optimized one Co single layer on graphene sheet. Two high symmetric structures are considered: BC stacking (Co sitting on the center of hexagonal cell of graphene) and AB stacking (Co is placed on top of carbon atoms). We found that BC stacking is a semi-stable phase and it preserves the in-plane anisotropy with a bit larger absolute value of 2.23 mJ/m2. Interestingly, for the stable phase of AB stacking the anisotropy switches to out-of-plane direction with a value of 1.43 mJ/m2, which is comparable to thicker Co films. We find that the hybridization between C-pz and Co-dZ2 plays the crucial role in switching the anisotropy of Co film. At the same time, the Dirac point of graphene is also modified by Co presence. Acknowledgements: This work is supported by EU Future Emerging Technology Flagship "Graphene" and ANR NMGEM. R e f e r e n c e s [1] A. H. Castro Neto, et al., Rev. Mod. Phys. 8,

109 (2009). [2] A. K. Geim and K. S. Novoselov, Nat. Mater. 6,

183 (2007). [3] N. Tombros, C. Jozsa, M. Popinciuc, H. T.

Jonkman, and B. J. van Wees, Nature 448, 571 (2007).

Hongxin Yang and Mairbek Chshiev

[email protected]

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[4] M. Popinciuc, et al., Phys. Rev. B 80, 214427 (2009).

[5] B. Dlubak, et al., Appl. Phys. Lett. 97, 092502 (2010).

[6] W. Han and R. K. Kawakami, Phys. Rev. Lett. 107, 047207 (2011).

[7] T.-Y. Yang, et al., Phys. Rev. Lett. 107, 047206 (2011).

[8] H. X. Yang, A. Hallal, D. Terrade, X. Waintal, S. Roche, and M. Chshiev, Phys. Rev. Lett. 110, 046603 (2013).

[9] A. G. Swartz, et al., ACS Nano 6, 10063 (2012). [10] Chi Vo-Van, Z. Kassir-Bodon, H.X. Yang, J.

Coraux, et al., New J. Phys. 12, 103040 (2010). [11] G. Kresse and J. Hafner, Phys. Rev. B 47, 558

(1993); G. Kresse and J. Furthmuller, Phys. Rev. B 54 (1996); P. E. Blochl, Phys. Rev. B 50, 17953 (1994).

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V a l l e y a n d s p i n c u r r e n t s i n 2 D t r a n s i t i o n m e t a l d i c h a l c o g e n i d e s Department of Physics and Center of Theoretical and Computational Physics, The University of Hong Kong, Hong Kong, China

The recent emergence of two-dimensional transition metal dichalcogenides (TMDs) provides a new laboratory for exploring the internal quantum degrees of freedom of electrons for new electronics. These include the electron spin and the valley pseudospin that labels the degenerate band extrema in momentum space. In 2D TMDs, the valley pseudospin acquires physical properties which allow its quantum manipulations in ways similar to the control of spins, making possible valley-based electronics [1]. The generation and control of spin and valley pseudospin currents are at the heart of spin and valley based electronics. Two mechanisms will be discussed for generating spin and valley currents of electrons in 2D TMDs: (I) the valley and spin Hall current arising from the Berry curvatures [2]; and (II) the nonlinear valley and spin currents arising from Fermi pocket anisotropy [3]. The two effects have distinct scaling with the field and different dependence of the current direction on the field direction and crystalline axis. The nonlinear current response further allows two unprecedented possibilities to

generate pure spin and valley flows without net charge current, either by an AC bias or by an inhomogeneous temperature distribution [3]. This points to a new route towards electrical and thermal generations of spin and valley currents for spintronic and valleytronic applications. I will also discuss the valley Hall effect of charged excitons in monolayer TMDs arising from the exchange interaction between the electron and hole constituents of the exciton [4]. R e f e r e n c e s [1] X. Xu, W. Yao, D. Xiao and T. F. Heinz, Nature

Physics, 10 (2014) 343. [2] D. Xiao, G. Liu, W. Feng, X. Xu and W. Yao,

Physical Review Letters, 108 (2012) 196802. [3] H. Yu, Y. Wu, G. Liu, X. Xu and W. Yao, Physical

Review Letters, 113 (2014) 156603. [4] H. Yu, G. Liu, P. Gong, X. Xu and W. Yao,

Nature Communications, 5 (2014) 3876.

Wang Yao

[email protected]

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A c t i v i t i e s o n S t a n d a r d i z a t i o n o f P r o p e r t i e s o f G r a p h e n e i n K o r e a SAINT (SKKU Advanced Institute of Nanotechnology) Sungkyunkwan University Suwon, Korea

Graphene with two dimensional honeycomb structures of carbon atoms is known as having exceptional electrical, thermal, and mechanical properties. Their applications are expected to be in high speed, flexible, and transparent devices. Research activities on graphene in Korea have been focused on commercialization of graphene based materials and devices. Activities of

standardization of graphene in Korea will be presented. Topics in standardization of graphene discussed are followings: Characterization of electrical properties of graphene, Evaluation of the number of layers of graphene, and Evaluation of domain boundaries of graphene. Other activities of standardization of carbon materials will be introduced as well.

Ji-Beom Yoo

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I n s i t u T r a n s m i s s i o n E l e c t r o n M i c r o s c o p y f o r N a n o s c a l e D y n a m i c s a n d P r o p e r t i e s o f 2 D m a t e r i a l s 1 Center for Integrated Nanostructure Physics, Institute for Basic Science(IBS), Sungkyunkwan University, Suwon 440-746. Korea 2 Institute of Solid State Research, Leibniz-institut fur Festkorper und Werkstoffforschung Dresden, D-01171 Dresden, Germany

With the development of transmission electron microscopy, many in situ experiments can now be carried out inside the transmission electron microscopes (TEM). We utilized low voltage aberration corrected TEMs for real-time observations of the dynamics in our two dimensional samples, up to the atomic scale. The electron beam irradiation will be stressed. With proper selection of the samples and TEM conditions, the graphene edges, the hetero-structure between metallic atoms and graphene, or the novel 1D structures derived from 2D materials will be introduced in detail. High resolution observation is another critical point for our observations which can be directly related to state-of-art density functional theoretical calculations or even dynamical simulations. The samples used in these studies covered many kinds of 2D materials, like graphene, carbon nanotubes, and transition metal dichalcogenide (MoS2, WSe2), etc. This presentation will give an overview of the in

situ TEM on 2D materials as well as insights into several topics related to new structure determination, anomalous diffusion, phase transition or mechanical analysis. R e f e r e n c e s [1] Zhao Jiong, Deng Qingming, Sandeep M.

Gorantla, Alicia Bachmatuk, Alex Popov, Jurgen Eckert, Mark, Rummeli, “Free-standing

single-atom thick iron membranes suspended in graphene pores”, SCIENCE ,343(2014)1228-1232.

[2] Zhao Jiong, Deng Qingming, Stanislav Avdoshenko, Jurgen Eckert, Mark Rummeli, “Direct Observation of catalytical processes and anomalous diffusion of single Fe atom on grapheme edges, (2014), PNAS, 111(2014)15641-15646.

F i g u r e s

Jiong Zhao1,2, Qingming Deng2

[email protected]

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W e l l - d e f i n e d G r a p h e n e - b a s e d H y b r i d s f o r E n e r g y S t o r a g e A p p l i c a t i o n s National Center for Nanoscience and Technology, Beiyitiao 11, Zhongguancun Beijing, 100190, P. R., China

The preparation of high performance electrode materials is critically important for the development of powerful batteries. Graphene-based materials have attracted great attention recently as electrode in various energy storage devices, including lithium ion batteries and supercapacitors. However, the rational control of the structures and functions of the material is always a big challenge. In this work, graphene-based materials with well-defined structures and functions, such as the graphene/SnXn nanocomposites with rationallly desinged interfaces, the graphene/Si nanocomposites with systematic structure control, have been developed by the rational design of various chemical approaches. Interestingly, the rational design of structures and functions of the electrode material provides efficient strategies for the development of high performance materials in lithium ion batteries.

R e f e r e n c e s [1] Z Fan, J Yan, L Zhi, Q Zhang, T Wei, J Feng, M

Zhang, W Qian, F Wei, Adv. Mater. 2010, 22, 3723.

[2] S Yang, X Feng, L Zhi, Q Cao, J Maier, K Müllen, Adv. Mater. 2010, 22, 838.

[3] B Luo, Y Fang, B Wang, J Zhou, H Song, and L Zhi, Energy Environ. Sci. 2012, 5, 5226.

[4] B Luo, B Wang, X Li, Y Jia, M Liang, L Zhi, Adv. Mater., 2012, 24, 3538.

[5] B Wang, B Luo, X Li, L Zhi, Mater. Today, 2012, 15(12), 544-552.

[6] B Luo, B Wang, X Li, Y Jia, M Liang, L Zhi, Adv. Mater., 2012, 24, 3538-3543.

[7] B Wang, X Li, X Zhang, B Luo, Y Zhang, L Zhi, Nano Lett. 2013, 13, 5578-5584.

[8] B Wang, X Li, X Zhang, B Luo, Y Zhang, L Zhi, Adv. Mater., 2013, 25, 3560-3565.

F i g u r e s

Linjie Zhi, Bin Luo, Bin Wang

[email protected]

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G r a p h e n e W o v e n S t r u c t u r e f o r S e n s i n g A p p l i c a t i o n s School of Materials Science and Engineering, Tsinghua University Beijing 100084, China

Sensing strain and vibration with soft materials in small scale has attracted increasing attention. Graphene has the potential for creating thin film devices, owing to its two-dimensionality and structural flatness. We demonstrated several interesting examples of potential applications of graphene woven structure in highly sensitive strain sensing (Figure 1) [1,2].

A rational strategy was proposed to fabricate flexible touch sensors easily and effectively with the full usage of the mechanical and electrical properties of graphene (Figure 2) [3]. The resistance of the woven structure was highly sensitive to macro-deformation or microdefect. Compared to commercial and traditional touch sensing, the graphene-on-polymer piezoresistor is structurally flexible that is demanded under special conditions and meanwhile makes the piezoresistor to have excellent durability.

Detection and analysis of volatile organic compounds as pollutants in the atmosphere and liquids are of great significance because of their detrimental effects. A polymer-coated graphene micro-tube piping structure with a cross-linked and interconnected channel network was synthesized for liquid sensing (Figure 3) [4]. Due to the capillary force, the interfaces of the 3D structures could speed up the penetration of solvents into the polymer, thus promoted distinct selectivity within seconds and significantly decrease the response time. Owing to their good selectivity, high sensitivity, rapid response and flexibility, and the ease of use of the sensors and the simplicity of the fabrication processes, the composites should be a good candidate for liquid sensing.

Torsion is another deformation occurring in everyday life, but was less well understood. In our

previous study a torsion sensor was prepared by wrapping woven graphene fabrics around a polymer rod at a specific winding angle (Figure 4) [5]. The sensor showed an ultra-high sensitivity with a detection limit as low as 0.3 rad/m, indicating its potential application in the precise measurement of low torsions.

A flexible and wearable strain sensor was assembled by adhering graphene on polymer and medical tape composite film. The sensor exhibited the following features: ultra-light, relatively good sensitivity, high reversibility, superior physical robustness, easy fabrication, ease to follow human skin deformation (Figure 5) [6]. Some weak body motion were chosen to test the notable resistance change, including hand clenching, phonation, expression change, blink, breath, and pulse. A highly sensitive sensor for sound signal acquisition and recognition was further fabricated from thin films of special crisscross graphene woven structures. The ultra-high sensitivity of the sensor could realize fast and low frequency sampling of speech by extracting the signature characteristics of sound waves (Figure 6) [7]. Representative signals of 26 English letters, typical Chinese characters and tones, even phrases and sentences, were tested with obvious resistance changes. Furthermore, resistance changes of grapheme sensor responded perfectly with sounds.

By future combining artificial intelligence with digital signal processing, the graphene based sensing system will represent a new smart tool to classify and analyze signals in wide potential applications in fields of the displays, robotics, fatigue detection, body monitoring, in vitro diagnostics, and advanced therapies.

Hongwei Zhu

[email protected]

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R e f e r e n c e s [1] X. Li, P. Z. Sun, L. L. Fan, M. Zhu, K. L. Wang, M.

L. Zhong, J. Q. Wei, D. H. Wu, Y. Cheng, H. W. Zhu*, Sci. Rep., 2 (2012) 395

[2] X. Li, R. J. Zhang, W. J. Yu, K. L. Wang, J. Q. Wei, D. H. Wu, A. Y. Cao, Z. H. Li, Y. Cheng, Q. S. Zheng, R. S. Ruoff, H. W. Zhu*, Sci. Rep., 2 (2012) 870.

[3] X. Lee, T. T. Yang, X. Li, R. J. Zhang, M. Zhu, H. Z. Zhang, D. Xie, J. Q. Wei, M. L. Zhong, K. L. Wang, D. H. Wu, Z. H. Li, H. W. Zhu*, Appl. Phys. Lett., 102 (2013) 163117.

[4] T. T. Yang, H. Z. Zhang, Y. Wang, X. Li, K. L. Wang, J. Q. Wei, D. H. Wu, Z. H. Li, H. W. Zhu*, Nano Res., 7 (2014) 869–876.

[5] T. T. Yang, Y. Wang, X. M. Li, Y. Y. Zhang, X. Li, K. L. Wang, D. H. Wu, H. Jin, Z. H. Li, H. W. Zhu*, Nanoscale, 6 (2014) 13053-13059.

[6] Y. Wang, L. Wang, T. T. Yang, X. Li, X. B. Zang, M. Zhu, K. L. Wang, D. H. Wu, H. W. Zhu*, Adv. Funct. Mater., 24 (2014) 4666–4670.

[7] Y. Wang, T. T. Yang, J. C. Lao, R. J. Zhang, Y. Y. Zhang, M. Zhu, X. Li, X. B. Zang, K. L. Wang, H. Jin, L. Wang, H. W. Zhu*, Nano Res., in press (2015).

F i g u r e s

Figure 1: Graphene woven structure.

Figure 2: Touch senor.

Figure 3: Liquid sensor.

Figure 4: Torsion sensor.

Figure 5: Skin sensor.

Figure 6: Sound sensor.

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A l p h a b e t i c a l O r d e r

K : K e y n o t e / O : O r a l Page

Axpe, Eneko (University of the Basque Country - UPV/EHU, Spain)

Free Volume: a New Physical Parameter in Biomaterials and Cancer O 181

Barenholz, Yechezkel (The Hebrew University, Israel) Abstract not available

K -

Benita, Simon (The Hebrew University, Israel)

Development of novel nanodelivery systems of hydrophilic biomacromolecules for improved cells uptake and

therapy K 182

Benny, Ofra (The Hebrew University, Israel)

Nanomedicine Approach for Targeting the Tumor Microenvironment K 183

Blank, Fabian (Univ. of Bern, Switzerland)

Biomedical nanopacarriers: the importance of size and surface charge in modulating the

pulmonary immune system K 184

Correa Duarte, Miguel A. (Univ. of Vigo, Spain)

Synthesis and Applications of Confined Plasmonic Nanoparticles is Hollow Structures K 185

Fanarraga, Monica (Universidad de Cantabria, Spain)

Carbon nanotubes display intrinsic anticancer properties O 186

Fink, Alke (Univ. of Fribourg, Switzerland)

Designing smart vesicles for drug delivery K 187

Flors, Cristina (IMDEA Nanociencia, Spain)

Correlative atomic force and super-resolution fluor escence microscopy: a novel tool for

characterization at the nanoscale O 188

Friedler, Assaf (The Hebrew University, Israel)

Using peptides to study and modulate protein interactions for therapeutic purposes K 189

Garcia-Martin, Jose Miguel (IMM-CSIC, Spain)

NANOIMPLANT: nanostructured biocompatible coatings to prevent orthopedic implant infections O 190

Goiriena-Goikoetxea, Maite (UPV/EHU, Spain)

Permalloy Nanodisks for Biomedical Applications O 191

Grinyte, Ruta (CICbiomagune, Spain)

Application of Photocatalytical Activity of CdS Nanoparticles to Development of Sensitive Colorimetric

Enzymatic Assays Using 3,3’,5,5’- tetramethylbenzidine (TMB) as a Universal Chromogenic Compound O 192

İlk, Sedef (Niğde University, Turkey)

Decolorization for Industrial Wastewater Treatment with Immobilization of Laccase to the

Nanocomposite Matrix O 193

Kara, Göknur (Institution of Graduate Studies in Science, Turkey)

Chitosan Nanoparticles for siRNA Based Gene Silencing Therapy for Cancer O 194

Lazaro-Carrillo, Ana (Universidad Autonoma Madrid / IMDEA Nanociencia, Spain)

Ferromagnetic nanoparticles as delivery system of antitumor drugs for targeting breast cancer cells O 195

Lechuga, Laura (ICN2, Spain)

Nanophotonic lab-on-chip biosensors for the next diagnostics generation K 196

Lisjak, Darja (Jozef Stefan Institute, Slovenia)

Influence of chemical composition on the dissolution ofAYF4:Yb,Tm (A = Na, K or Li) upconverting

nanoparticles in water O 197

Lúcio, Marlene (Universidade do Minho, Portugal)

Design of Multifunctional liposomal drug formulations for cancer therapy O 198

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Martínez de la Fuente, Jesús (ICMA, Spain)

Dissecting the Molecular Mechanism of Apoptosis during Photothermal Therapy using Gold Nanoprisms K 199

Martinez-Perdiguero, Josu (CIC microGUNE, Spain)

Innovative Biosensors for New Point-of-Care Devices O 200

Meseguer, Francisco Javier (CSIC, Spain)

Silicon nanoparticles as Trojan horses for Potential breast cancer therapy O 201

Morant-Miñana, Maria Carmen (CIC microGUNE, Spain)

Microscale Electrodes integrated on non-conventional substrates for Real Sample Campylobacter spp.

detection O 202

Nebot Carda, Vicent J (Centro de Investigación Príncipe Felipe, Spain)

Polymer therapeutics for the treatment of chronic spinal cord injuries O 203

Pavlov, Valery (CIC BiomaGUNE, Spain)

Biosensing Based on Enzymatic Modulation of Growth of Nanoparticles O 204

Pinto, Artur (LEPABE, Portugal)

Biodegradation influence on PLA/graphene-nanoplatelets composite biomaterials mechanical

properties and biocompatibility

O 206

Reichardt, Niels (CIC biomaGUNE, Spain)

Nanostructured Materials in Matrix-free Laser Desorption Ionisation Mass Spectrometry K 208

Richter, Shachar (Tel-Aviv University, Israel)

Proteins: A Material-Science Point of View K 209

Rodrigues, Rita (University of Minho, Portugal)

Magnetic liposomes based on nickel ferrite nanoparticles as nanocarriers for new potential antitumor

compounds O 210

Rossi-Bergmann, Bartira (Universidade Federal do Rio de Janeiro, Brazil)

Treatment of cutaneous leishmaniasis with a subcutaneous implant consisting of drug-loaded

biodegradable nano and microparticles O 211

Salomé, Laurence (IPBA UPS/CNRS, UMR 5089, France)

A single-DNA chip for biosensing K 212

Schroeder, Avi (Technion, Israel)

Targeted drug deliveryand personalized nano-medicine K 213

Serrano Núñez, Juan Manuel (Sesderma Laboratories, Spain)

Repair of uv light-induced DNA damage O 214

Tamayo, Javier (IMM-CNM/CSIC, Spain)

Biosensors based on nanomechanical systems K 216

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F r e e V o l u m e : a N e w P h y s i c a l P a r a m e t e r i n B i o m a t e r i a l s a n d C a n c e r 1University of the Basque Country, Sarriena s/n 48940, Bilbao, Spain 2University of Oxford, Clarendon Laboratory, Parks Road OX1 3PU, Oxford, United Kingdom

Free volume is a key parameter in physics, nanomechanics and diffusion properties of biopolymers, biomembranes and other biomaterials. Positron annihilation lifetime spectroscopy (PALS) is a unique technique for measuring the free volume void sizes and distributions inside these materials. Previous work has shown the potential of PALS in biophysics and cancer research. In this presentation we are introducing the concept of free volume in biomaterials and discuss the results of PALS in combination with other techniques in (i) biopolymer-based scaffolds, (ii) biomembranes and (iii) living cultured cancer cells [1]. The approach used here can serve as a framework for rational design of materials for tissue engineering and contributes to a better understanding of the biophysics behind biomembranes and cancer.

R e f e r e n c e s

[1] Eneko Axpe, Tamara Lopez-Euba, Ainara

Castellanos-Rubio, David Merida, Jose Angel Garcia, Leticia Plaza-Izurieta, Nora Fernandez-Jimenez, Fernando Plazaola and Jose Ramon Bilbao, PLoS ONE, 9 (2014) 1.

Eneko Axpe1,2

, Sonia Contera2, Jose Angel García1, Fernando Plazaola1

[email protected]

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D e v e l o p m e n t o f n o v e l n a n o d e l i v e r y s y s t e m s o f h y d r o p h i l i c b i o m a c r o m o l e c u l e s f o r i m p r o v e d c e l l s u p t a k e a n d t h e r a p y 1The Institute for Drug Research of the School of Pharmacy, Faculty of Medicine, the Hebrew University 2Hadassah Hebrew University Medical Center of Jerusalem and 3Schneider Children's Medical Center, Israel Proteins, peptides, oligonucleotides, and small interfering RNA duplex (siRNAs) typically exhibit poor membrane permeability and high sensitivity to heat, pH, and enzymatic degradation. Furthermore, these hydrophilic biomacromolecules suffer from short biological half-lives and rapid clearance limiting their clinical applications. Most of the drawbacks can be overcome by incorporating such active macromolecules in adequate nanocarriers which can prolong their blood circulation and intracellular delivery in targeted pathological tissues. Two types of hydrophilic biomacromolecules were used in this research: (1) an siRNA (19-30 bp) known to produce gene silencing via a well-defined mechanism. (2) An antisense oligonucleotide (ASO) with great potential for the treatment of Duchenne muscular dystrophy (DMD) caused by mutated pre-mRNA, and currently is the most promising therapy for DMD patients. Although, both macromolecules are currently in clinical trials (naked or loaded in different delivery systems including: liposomes, lipid or polymeric nanoparticles), there is no approved delivery system yet for them in the market. The issue of limited dosage (mostly due to nephrotoxicity and hepatotoxicity) hampers their potential activity and still needs to be addressed. The objective of the present study was to develop novel nanodelivery systems that will double-encapsulate such biomacromolecules and provide protection, sustained release, and improved cells uptake and therapy, compared to their parenteral administration in solution following administration of much lower dosage of siRNA/ASO, avoiding or minimizing possible side effects and renal toxicities. The first line of protection is achieved by loading the siRNA (or ASO) into primary nanoparticles (PNPs ~100 nm) made from crosslinked human serum albumin (HSA), containing the cationic lipid DOTAP (1,2-dioleoyl-3-trimethylammonium-propane), added to increase

loading of the negatively charged RNA molecules and to further facilitate endosomal escape following cell internalization. The second line of stability is obtained by further encapsulating the PNPs into sub-micron capsules (i.e. nanocapsules or DNCs <1µm), made from PLGA (Poly D,L-lactic-co-glycolic acid), with or without PEG moieties, using a novel technique of nano spray drying (launched by Buchi in 2009). The main findings up to now are that a weekly administration of PNPs up to 2 mg/mouse (loaded with 100µg of active ASO) was well tolerated by the mice (n=3). Pathology of the spleen, liver, kidney, lungs, heart and brain found all examined tissues to be within normal range. New formation of dystrophin was observed in quadriceps muscle's, already at the low dosage (1 mg/mouse), with significantly more positive dystrophin fibers formation in the mice treated with 2 mg/mouse. It should be emphasized that a weekly administration of up to 3 mg/mouse, was well tolerated for Blank DNCs but not for active DNCs (loaded with 60µg ASO) whereas a weekly administration of active DNCs 1.5mg/mouse (30µg ASO), produced modest positive dystrophin fibers. To the best of our knowledge, this work is the first attempt to produce double-nanocarriers using the nano spray drying technique. The main advantage of the platform developed in this project is the preparation of the final product in the form of dry powder easily dispersed prior to injection. Encouraging results were achieved in terms of loading capacity, drug content, extended in vitro drug release without a burst effect, cellular uptake, and preliminary efficacy results in animal models.

Amsalem, O. 1, Nassar, T. 1, Yanai, N. 2, Benhamron, S. 1, Lazarovici, P. 1, Yavin, E. 1, Nevo, Y. 2,3 and Benita, S.

1

[email protected]

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N a n o m e d i c i n e A p p r o a c h f o r T a r g e t i n g t h e T u m o r M i c r o e n v i r o n m e n t Institute for Drug Research, Faculty of Medicine The Hebrew University of Jerusalem, Jerusalem Israel

Tumor metastases are the principal cause of mortality in the majority of cancer patients. A hospitable tumor microenvironment, of which the vascular system is a significant component, is crucial in the implantation of disseminated tumor cells. Angiogenesis, the formation of new blood vessels, is a multifactorial process that is critical for tumor progression and metastasis. Anti-angiogenic compounds, has been widely investigated as a strategy to treat cancer. However, several of these drugs are limited by poor pharmacological properties, such as low bioavailability, undesired biodistribution and short half-life necessitating their use in high intravenous doses which expose the patients to adverse size-effects due to off-target activity. To overcome these drug limitations, we developed a formulation of self-assembled nanomicelles composed of short di-block polymers, polyethylene glycol-polylactic acid (PEG-PLA), for conjugating small molecule drugs. We present a case of re-formulating a broad spectrum anti-angiogenic drug from the fumagillin family

which originally had several clinical limitations. In the new formulation, unlike the free compound, the drug showed high oral availability, improved tumor targeting and reduced toxicity. Dramatic anti-cancer activity was obtained in eight different tumor types (60-90% growth inhibition) in mice, and, importantly, the treatment was able to prevent liver metastases due to the shift from intravenous to oral administration. The activity was associated with reduction of microvessel density and increased tumor apoptosis. Nanomicelle drug delivery system has been shown to be an efficient approach for improving pharmacological properties of drugs and

F i g u r e s

Figure 1 Polymeric Nanomicelles Delivery System

Ofra Benny

[email protected]

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B i o m e d i c a l n a n o p a c a r r i e r s : t h e i m p o r t a n c e o f s i z e a n d s u r f a c e c h a r g e i n m o d u l a t i n g t h e p u l m o n a r y i m m u n e s y s t e m 1 Respiratory Medicine, Bern University Hospital, Bern, Switzerland 2 Telethon institute for Child Health Research, Perth, Australia 3 School of Veterinary and Biomedical Sciences, Faculty of Health Sciences, Murdoch University, Perth, Australia 4 Centre for Child Health Research University of Western Australia, Perth Australia 5 Adolphe Merkle Institute, University of Fribourg, Fribourg, Switzerland

Due to its vast surface area provided by the gas exchange region, limited local proteolytic activity, non-invasiveness, fine anatomical barriers for systemic access and a number of different antigen presenting cell (APC) populations, the respiratory tract is an attractive target for the delivery of vaccine antigens. Nano-sized carriers have been proposed as promising novel diagnostic, therapeutic, and vaccination approaches for a variety of human diseases. Pulmonary APC are considered as sentinels of the immune system due to their strategic localization, their phagocytic activity, and their ability to present antigen. To improve efficiency of vaccination and develop new strategies, a well-founded knowledge about composition and characterization of APC populations throughout the respiratory tract is essential. In particular, respiratory tract dendritic cells, as key APC in the lung, constitute an ideal target for vaccine delivery. Furthermore, carrier size is a key factor when designing new inhalable vaccines, as size determines not only deposition in different respiratory tract compartments, but also how an antigen and its carrier will interact with lung tissue components and immune cells. Recent studies have also emphasized the importance of particle surface charge, when interacting with biological interfaces, since charge may strongly affect interactions with cells, e.g. regarding rate of uptake and intra-cellular trafficking. Clarifying which APC / dendritic cell populations primarily interact different sized and charged nanocarriers and traffic these from different respiratory tract compartments to lung draining lymph nodes is paramount to understanding related downstream inflammatory and immune responses. Such data will be fundamental to rationally develop future novel particulate systems in the nano-size range

for therapeutic or diagnostic applications in the respiratory tract. Acknowledgements: Grant funding by the Swiss National Science Foundation the Swiss Society for Pneumology and the Swiss Lung League

F Blank1, E Seydoux1, P

Stumbles2,3,4, D Strickland2, R Blom1, B Rothen-Rutishauser5, A Petri-Fink5, P Holt2, Ch von Garnier1

[email protected]

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S y n t h e s i s a n d A p p l i c a t i o n s o f C o n f i n e d P l a s m o n i c N a n o p a r t i c l e s i s H o l l o w S t r u c t u r e s Department of Physical Chemistry, Universidade de Vigo, 36310 Vigo, Spain

The synthetic architectures of complex nanostructures, including multifunctional hollow capsules, are expected to play key roles in many different applications, such as drug delivery, photonic crystals, nanoreactors, and sensing. Implementation of novel strategies for the fabrication of such materials is needed because of the infancy of this knowledge, which still limits progress in certain areas. We report herein the design of plasmonic hollow nanoreactors capable of concentrating light at the nanometer scale for the simultaneous performance and optical monitoring of thermal-activated reactions. These reactors feature the encapsulation of plasmonic nanoparticles on the inner walls of a mesoporous silica capsule. A Diels-Alder cy-cloaddition reaction was carried out in the inner cavities of these nanoreactors to evidence their efficacy. Thus, it is demonstrated that reactions can be accomplished in a confined volume without alteration of the temperature of the bulk solvent while allowing a real time monitoring of the reaction progress.

Additionally, these plasmonic nanoprobes have been shown as an advanced intracellular hybrid SERS sensor for relevant signaling molecules (NO). After their inner functionalization with a NO chemoreceptor, the sensor is quantitative and can perform in-situ, real-time monitoring of the dynamics of intracellular NO in living cells while remains fully biocompatible. Its sophisticated design prevents the interaction of cytosolic macromolecules within the active optical material and the enzymatic degradation of the sensor. It additionally facilitates the diffusion of small molecules between the interior and exterior thanks to the plasmonic thermal gradients generated upon their illumination.

F i g u r e s

Figure 1 Schematic cross-section view of the plamonic nanoreactors developed in this work where reactants and products diffuse through the mesoporous silica shell and a NIR-laser irradiation promotes the chemical reaction allowing a simultaneous in situ SERS monitoring of the process.

Miguel A. Correa-Duarte

[email protected]

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C a r b o n n a n o t u b e s d i s p l a y i n t r i n s i c a n t i c a n c e r p r o p e r t i e s Universidad de Cantabria, Santander, Spain

Carbon nanotubes (CNTs) have been proposed as the technological counterpart of nature’s microtubules (MTs) [1]. MTs are 25 nm diameter protein polymer nanotubes that constitute the cellular cytoskeleton and are essential for cell proliferation and migration. CNTs and MTs share various aspects of their architecture and properties [1]. They have similar dimensions, (ii) a similar tubular morphology that ensures structural efficiency, have analogous mechanical behaviors, and are exceptionally resilient [2,3]. Their similarities are quite likely to be responsible for their association in vitro [4] and in vivo [5]. There is, however, a big difference between these polymers that has critical implications in the in vivo system, while CNTs are very stable polymers, microtubules are highly dynamic structures that are continuously undergoing assembly/disassembly cycles in a process known as dynamic instability [6]. Functionalized CNTs are easily translocated intracellularly [5,7]. Inside cells they assemble mixed polymers with tubulin [5]. Due to the scaffolding effect of CNTs, MTs display an enhanced stability that is critical during cell division, triggering mitotic arrest and cell death [5,8]. Interestingly, CNTs behave as microtubule stabilizing cytotoxic agents interfering with microtubule dynamics, leading to anti-proliferative, anti-migratory and pro-apoptotic effects [9]. These findings support the idea that CNTs represent a ground-breaking type of synthetic microtubule-stabilizing agents that could play a pivotal role in future cancer treatments in combination to traditional antineoplastic drugs. R e f e r e n c e s

[1] Pampaloni F, Florin EL. Microtubule Architecture:

Inspiration for Novel Carbon Nanotube-Based Biomimetic Materials. Trends Biotechnol 26 (2008) 302.

[2] Odde DJ, et al. Microtubule bending and breaking in living fibroblast cells. J Cell Sci. 112 (1999) 3283.

[3] de Pablo PJ, et al. Deformation and collapse of microtubules on the nanometer scale. Phys Rev Lett 91 (2003) 98101.

[4] Dinu CZ, et al. Tubulin Encapsulation of CNTs into Functional Hybrid Assemblies. Small 5 (2009) 310.

[5] Rodriguez-Fernandez, et al. Multiwalled carbon nanotubes display microtubule biomimetic properties in vivo, enhancing microtubule assembly and stabilization. ACS Nano 6, (2012) 6614.

[6] Jordan MA, Wilson L. Microtubules as a Target for Anticancer Drugs. Nat Rev Cancer 4 (2004) 253.

[7] Lacerda L, et al. Translocation Mechanisms of chemically functionalised carbon nanotubes across plasma membranes. Biomaterials 33 (2012) 3334.

[8] Sargent L, et al. Single-Walled Carbon Nanotube-Induced Mitotic Disruption. Mutat Res 14 (2012) 28.

[9] García-Hevia L, et al. Nanotube interactions with microtubules: implications for cancer medicine. Nanomedicine (Lond). 9 (2014) 1581.

F i g u r e s

Figure 1: Confocal microscopy image of a mitotic spindle of a dividing HeLa cell treated with MWCNT during 70 h displaying an abnormal microtubule/chromosomal organization. Microtubules are shown in the in the red channel immunostained with anti-tubulin antibody-Cy3. Chromosome miss-positioning is observed in the blue channel, Hoechst staining. Scale bar 2μm.

García-Hevia L, Valiente, R, González J, Villegas JC, Fanarraga ML.

[email protected]

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D e s i g n i n g s m a r t v e s i c l e s f o r d r u g d e l i v e r y Adolphe Merkle Institute, University of Fribourg & Chemistry Department, University of Fribourg

Delivering and releasing drugs at their target in a controlled fashion remains a key determinant of successful treatment. Liposomes acting as basic drug carriers are forerunners in this development, and combining them with various stimuli-responsive nanoparticles – which act as release triggers - has become an increasingly popular methodology to control the spatial and temporal release of an encapsulated drug. Developing such hybrids however requires an interdisciplinary bottom-up approach which starts from basic chemical synthesis over precise microscopic characterization to biological settings. In our research group, we apply nanoparticles of different materials (i.e. superparamagnetic iron oxide nanoparticles/SPIONs and gold nanorods/AuNRs) and combine them with thermoresponsive liposomes, either by incorporating them directly in the vesicle bilayer (i.e. via self-assembly) or by functionalizing them to the surface (i.e. via cross-linking). These materials are biocompatible and meticulously tuned to react to a maximum degree to various stimuli (i.e. magnetic and light) - which are presently found in medical

settings - to consequently facilitate the transition from bench to bedside. To optimize our systems, we characterize these nanoscopic hybrids with state-of-the-art cryogenic microscopy techniques to assess their structural and architectural properties under unadulterated conditions. This approach has recently led to the development of Janus magnetic liposomes[1], which were designed by deeply understanding and steering of the liposome self-assembly process. With this research, we hope to contribute to the development of next-generation drug carriers by providing effective, well-characterized and reliable materials to treat conditions such as cancer and inflammatory diseases. R e f e r e n c e s

[1] Bonnaud, C.*, Monnier, C. A.*, Demurtas, D., Jud, C., Vanhecke, D., Montet, X., . & Petri-Fink, A. (2014). Insertion of Nanoparticle Clusters into Vesicle Bilayers. ACS Nano, 8(4), 3451-3460.

F i g u r e s

Alke Fink,

[email protected]

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C o r r e l a t i v e a t o m i c f o r c e a n d s u p e r -r e s o l u t i o n f l u o r e s c e n c e m i c r o s c o p y : a n o v e l t o o l f o r c h a r a c t e r i z a t i o n a t t h e n a n o s c a l e IMDEA Nanociencia, C/ Faraday 9, Ciudad Universitaria de Cantoblanco, Madrid 28049, Spain

Fluorescence microscopy is an essential tool in many fields of science, particularly in biological and biomedical research. However, its spatial resolution is limited by light diffraction to about 200 nm, which precludes its application to the study of subcellular structures and its wide implementation in nanoscience. Currently, approaches for improving the spatial resolution in fluorescence microscopy are experiencing a spectacular expansion and recognition, including the recent award of the Nobel Prize in Chemistry 2014. Several imaging schemes have been successful in breaking the diffraction limit and achieving a spatial resolution of tens of nm [1]. One alternative for super-resolution imaging is photoactivated-localization microscopy (PALM), also termed stochastic optical reconstruction microscopy (STORM). PALM, STORM and related techniques rely on the combination of photoswitchable fluorescent labels, a wide-field fluorescence microscope with single-molecule sensitivity, and image post-processing. These techniques are in continuous development, and new fluorescence labelling and image analysis methods need to be tested. Both labelling and postprocessing analysis are prone to imaging artifacts, therefore new tools that allow robust validation o super-resolution images are needed. For that purpose, we have implemented a novel correlative microscope that allows sequential in situ imaging of the same sample area by atomic force microscopy (AFM) and PALM/STORM [2]. The technical aspects of the correlative microscope, including image alignment and sample preparation requirements will be discussed, as well as its application in optimizing DNA super-resolution imaging. The combination of super-resolution and AFM is not only a useful tool to improve current nanoscopy methods but also to answer new biological questions.

R e f e r e n c e s

[1] S. W. Hell, Nat. Methods, 6 (2009) 24. [2] A. Monserrate, S. Casado, C. Flors,

ChemPhysChem, 15 (2014) 647.

Aitor Monserrate, Santiago Casado, Cristina Flors

[email protected]

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U s i n g p e p t i d e s t o s t u d y a n d m o d u l a t e p r o t e i n i n t e r a c t i o n s f o r t h e r a p e u t i c p u r p o s e s Institute of Chemistry, the Hebrew University of Jerusalem, Givat Ram, Jerusalem, Israel

Our group is interested in using peptides for the quantitative biophysical and structural analysis of protein-protein interactions (PPI) in health and disease. Based on this, we develop lead compounds that modulate PPI for therapeutic purposes. Peptides serve as major tools both for studying PPI and for modulating them (by inhibition or activation). In my talk I will present an overview of our research, focusing on the following examples:

1. Using peptides to modulate the oligomeric state of proteins [1,2]. Many disease-related proteins are in equilibrium between active and inactive oligomeric states. Specific binding of peptides to one of the oligomeric states of such protein should result in stabilization of this state and consequently in shift of the oligomerization equilibrium towards it. We term peptides with such activity as “shiftides”, and they can be utilized therapeutically in two manners: (i) inhibiting a protein by shiftides that bind preferentially to its inactive oligomeric state and stabilize it; (ii) activating a protein by shiftides that bind preferentially to the active oligomeric state and stabilize it. Examples for shiftides developed in o ur lab will be described for the HIV-1 integrase [2,3].

2. Development of new synthetic methods for peptide modifications. We developed a new approach for peptide cyclization during solid phase synthesis under highly acidic conditions [4]. Our approach involves simultaneous in situ deprotection, cyclization and TFA cleavage of the peptide, which is achieved by forming an amide bond between a lysine side chain and a succinic acid linker at the peptide N-terminus. The reaction proceeds via a highly active succini mide intermediate, which was isolated and characterized. Our new methodology is applicable for the formation of macrocycles in solid phase synthesis of peptides and organic molecules. We also developed a new general N-acetylation method for solid phase synthesis [5]. Malonic acid is used as precursor and the reaction proceeds by

in situ formation of a reactive ketene intermediate at room temperature.

3. Intrinsically disordered proteins as drug targets: About one third of the genome encodes for intrinsically disordered proteins (IDPs) or disordered regions in proteins (IDRs). These lack stable tertiary structures and are composed of a large ensemble of extended and flexible conformations interchanging dynamically. IDPs are involved in many human diseases, making them attractive targets for drug design. However, more than 90% of current drug targets are enzymes or receptors and IDPs still cannot be targeted due to the lack of specific binding pockets for small molecules. Our research focuses on how intrinsic protein disorder regulates protein activity with the ultimate goal of setting IDPs and IDRs as therapeutic targets. In my talk I will describe our studies regarding several IDRs including: (1) the pro-apoptotic ASPP2 protein [6,7]; (2) The HIV - 1 Rev protein [8]; (3) the centrosomal STIL protein, which is upregulated in cancer [9].

R e f e r e n c e s

[1] Gabizon, R. and Friedler A. (2014) Front

Chem.;2:9 [2] Hayouka, Z., et al., (2007) Proc Natl Acad Sci U

S A,. 104(20): p. 8316-21. [3] Hayouka, Z., et al., (2010) Bioorg Med Chem,.

18(23): p. 8388-95. [4] Chandra K, et al.(2014; Angew Chem Int Ed

Eng, 53(36):9450-5 [5] Chandra K, et al. (2014) Org Biomol Chem.

12(12):1879-84 [6] Rotem, S. et al. (2008) J Biol Chem 283, 18990-

1899, [7] Rotem-Bamberger, S. et al. (2013) PLoS One

8,e58470, [8] Faust, O. et al. (2014) Chem Comm

50(74):10797-800 [9] Amartely, H. et al. (2014) Chem Comm,

50(40):5245-7.

Assaf Friedler

[email protected]

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N A N O I M P L A N T : n a n o s t r u c t u r e d b i o c o m p a t i b l e c o a t i n g s t o p r e v e n t o r t h o p e d i c i m p l a n t i n f e c t i o n s 1 IMM-Instituto de Microelectronica de Madrid (CNM-CSIC), Isaac Newton 8, 28760 Tres Cantos, Madrid, Spain 2 Dpto. Quimica Inorganica y Bioinorganica. Universidad Complutense de Madrid. Instituto de Investigacion Sanitaria Hospital 12 de Octubre i+12, 28040 Madrid, Spain 3 CIBER de Bioingenieria, Biomateriales y Nanomedicina (CIBER-BBN), Spain 4 Instituto de Ciencia de Materiales de Sevilla (CSIC-US), Seville,Spain 5 Department of Clinical Microbiology. IIS-Fundacion Jimenez Diaz, UAM, Spain

Bacterial colonization and biofilm formation on orthopedic implants is one of the worst possible scenarios in orthopedic surgery, in terms of both patient prognosis and healthcare costs [1]. Tailoring the surface of these orthopedic implants to actively promote bone bonding, while avoiding bacterial colonization, represents an interesting challenge to reach better clinical outcomes [2]. Currently, it has been demonstrated a strong dependence of structural features in the nano-scale with antibacterial effects. Several naturally existing surfaces such as plant leaves and insect wings are capable of maintaining a contaminant-free status despite the innate abundance of contaminants in their surrounding environments [3]. These properties are related to the presence of a periodic topography of hexagonal arrays of nanopillar on their surfaces. By mimicking the nature, and to translate this effect to orthopedic metallic biomaterials, a Ti6Al4V alloy of medical grade has been coated with Ti nanostructures employing the glancing angle deposition technique by magnetron sputtering. The resulting surfaces have a high density of nanocolumnar structures based on Ti, providing high roughness and a notable decrease of wettability. These nanostructured coatings exhibit a selective behavior towards osteoblast and bacteria proliferation. While these nanotextured surfaces strongly impair bacteria adhesion and inhibit biofilm formation, the osteoblasts exhibit almost identical behavior than that obtained onto the initial Ti6Al4V substrates. This selective behavior is discussed on the basis of a “lotus leaf effect” induced by the nanostructured surface and the different size of osteoblasts and bacteria. The obtained results provide new perspectives for manufacturing Ti6Al4V-based implants to prevent infections. Moreover, it is also worth noticing that our work has won the 2014 IDEA² Madrid Award of

the Madrid-MIT M+Vision Consortium, a partnership of the regional government of Madrid and the Massachusetts Institute of Technology (MIT), which fosters innovation in biotechnology [4].

R e f e r e n c e s

[1] Arcos D, Boccaccini AR, Bohner M, Diez-Perez A,

Epple M, et al. Opinion paper. Acta Biomater(2014), http://dx.doi.org/10.1016/j.actbio.2014.01.004

[2] Campoccia D, Montanaro L, Arciola CR. Biomaterials 34 (2013) 8533.

[3] E.P. Ivanova, J. Hasan, H.K. Webb , V. K. Truong, et al. Small 8 (2012) 2489.

[4] http://mvisionconsortium.mit.edu/idea2

J.M. Garcia-Martin1,

I. Izquierdo-Barba2,3, D. Arcos2,3, R. Alvarez4, A. Palmero4, J. Esteban5, C. Perez-Jorge5, M. Vallet-Regi2,3

[email protected]

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P e r m a l l o y N a n o d i s k s f o r B i o m e d i c a l A p p l i c a t i o n s 1 BCMaterials, Universidad del País Vasco (UPV/EHU), Barrio de Sarriena s/n, 48940, Leioa, Spain. 2 Departamento de Electricidad y Electrónica, Universidad del País Vasco (UPV/EHU), Barrio de Sarriena s/n, 48940, Leioa, Spain.

Magnetic nanoparticles are extensively studied for biomedical applications because their size are comparable to biological entities, while providing remote capabilities of actuation [1]. Disk shaped ferromagnetic nanoparticles add attractive possibilities to these characteristics. First, Permalloy (Py) nanodisks display much higher saturation magnetization values than oxide nanoparticles and second, depending on their geometry, they can present a spin vortex configuration which leads to net zero magnetization at remanence, eliminating the problem of particle agglomeration. Therefore, Py nanodisks present a huge potential for biomedical applications, ranging from cancer cell destroy by hyperthermia or mechanical actuation to MRI contrast enhancement and drug delivery [2].

While oxide nanoparticles are chemically synthetized, nanodisk physical fabrication methods offer higher control on particle size and the possibility of choosing among a larger spectrum of materials. Electron beam lithography (EBL) and Photolithography allow for tightly controlled fabrication of particles with virtually any size, shape and composition. The use of these techniques, though, imply a very low yield production (in the case of EBL) and the use of quite sophisticated and expensive equipment. As an alternative, self-assembling fabrication routes provide high volume and low cost production of well-defined Py nanodisks.

In this work we present the results obtained by Hole-mask Colloidal Lithography (HCL) [3]. HCL utilizes the definition of a dense hole-pattern in a sacrificial resist layer onto which a layer of Py is deposited. Py disks are produced after lift-of of the resist layer.

The results obtained show promising structures. The magnetic characterization performed by Magneto-Optical Kerr Effect (MOKE) indicates that vortex and single-domain states can be present [4].

R e f e r e n c e s

[1] Q. A. Pankhurst et al., Journal of Physics D: Applied Physics (2003), 167.

[2] D.-H. Kim, et. al., Nature Materials (2009), 9 165. [3] H. Fredriksson et al., Advanced Materials (2007),

19 4297. [4] G. Shimon et al., Physical Review B (2013), 87

214422. F i g u r e s

Figure 1: Hole-patterned resist.

Figure 2: Permalloy nanodisks on SiO2 substrate.

M. Goiriena-Goikoetxea1,

J. Feuchtwanger2, M.L. Fdez-Gubieda1,2 and A. García-Arribas1,2

[email protected]

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A p p l i c a t i o n o f P h o t o c a t a l y t i c a l A c t i v i t y o f C d S N a n o p a r t i c l e s t o D e v e l o p m e n t o f S e n s i t i v e C o l o r i m e t r i c E n z y m a t i c A s s a y s U s i n g 3 , 3 , 5 , 5 ’ - t e t r a m e t h y l b e n z i d i n e ( T M B ) a s a U n i v e r s a l C h r o m o g e n i c C o m p o u n d Biofunctional Nanomaterials, CIC biomaGUNE, Parque Tecnológico de San Sebastian, Paseo Miramon 182, 20009 Donostia- San Sebastian, Spain

Metallic and semiconductor nanoparticles (NPs) can be very conveniently employed for signal transduction and signal amplification by physical methods. Their chemical and physical properties are defined by three dimensional structure of NPs, therefore very slight changes in shape and size lead to drastic variation in absorption and emission spectra. Semiconductor NPs can be photo-excited producing electron/hole couples, which recombine to yield emission of light. Quantum effects in inorganic NPs give rise to fluorescence, therefore such fluorescent particles are referred to in the literature as quantum dots (QDs) [1].

Our laboratory has introduced application of in situ growth of QDs to development of flourogenic enzymatic assays [2]. This concept is based on registration of fluorescence originating from CdS QDs influenced by products of an enzymatic reaction. Those fluorogenic assays showed low detection limits and high signal to noise ratio, but unfortunately the read-out signal was not stable with time. The size of semiconductor QDs defines quantum effects governing fluorescence emission. It was found out that semiconductor CdS nanoparticles (NPs) are able to catalyze photo-oxidation of the well known chromogenic enzymatic substrate 3,3’,5,5’-tetramethylbenzidine (TMB), traditionally employed in quantification of peroxidase activity in the presence of hydrogen peroxide. The photocatalytical oxidation of TMB by oxygen does not require hydrogen peroxide and its rate is directly proportional to the quantity of CdS NPs produced in situ through the interaction of Cd2+ and S2- ions in an aqueous medium. The present concept permits to extend utility of the enzymatic substrate TMB, traditionally employed for detection of horseradish peroxidase activity, to other enzymes participating in formation of semiconductor NPs. In other words, the new approach allows to employ

inexpensive commercially available TMB as a universal chromogenic substrate for quantification of different classes of enzymes.

This phenomenon was applied to development of colorimetric sensitive assays for glucose oxidase and glutathione reductase based on enzymatic generation of CdS NPs acting as light-powered catalysts as demonstrated in Figure 1. Sensitivity of the developed chromogenic assays was of the same order of magnitude or even better than that of relevant fluorogenic assays. The present approach opens the possibility for the design of simple and sensitive colorimetric assays for a number of enzymes using inexpensive and available TMB as a universal chromogenic compound.

R e f e r e n c e s

[1] Parak, W. J.; Manna, L.; Simmel, F. C.; Gerion, D.; Alivisatos, P. In Nanoparticles; Wiley-VCH Verlag GmbH & Co. KGaA, (2005) 4-49

[2] Malashikhina, N.; Garai-Ibabe, G.; Pavlov, V. Anal Chem, 85 (2013) 6866-6870.

F i g u r e s

Figure 1: Chromogenic detection of enzyme activity using photocatalytical oxidation of TMB enhanced by enzymaticaly produced CdS NPs.

Ruta Grinyte, Gaizka Garai-Ibabe, Laura Saa, Valery Pavlov

[email protected]

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D e c o l o r i z a t i o n f o r I n d u s t r i a l W a s t e w a t e r T r e a t m e n t w i t h I m m o b i l i z a t i o n o f L a c c a s e t o t h e N a n o c o m p o s i t e M a t r i x 1 Faculty of Agricultural Sciences and Technologies, Nigde University, Nigde, Turkey 2 Institute of Graduate in Science & Engineering, Division of Nanotechnology and Nanomedicine, Hacettepe University, Beytepe, Ankara, Turkey Abstract -In this study, laccase enzyme (E.C.1.10.3.2.) that produced Trametes versicolor was immobilized through physical adsorption to the nanocomposite structure which used for decolorization of reactive coloring substance (Reactive Red 5) in the industrial originated wastewaters. Optimum physiological conditions such as optimum pH, temperature, the initial colored substance concentration, time-dependent decolorization rate were determinated for the laccase immobilization and these datas were applied and compared both free and immobilized laccase for effective decolorization of industrial wastewater at lab scale.

Keywords: Nanocomposites, enzyme immobilization, laccase, removing of azo dyes.

Introduction-Using of microorganismal originated enzymes for decolorization of industrial waste water offers considerable advantages. This nanobiotechnological process is cheap and economic, also the last products that obtained during mineralization are not toxic [1, 2]. Even though physico-chemical methods are effective in dye removal, some problems such as the overall cost, regeneration, secondary pollutants, limited versatility, interactions with other wastewater constituents and residual sludge generation limit their usage [3]. As an alternative, biological treatments are a relatively inexpensive way to remove dyes from wastewater [4]. In this work, fungal originated laccase enzymes were studied with a nanotechnological way for this kind of removal process.

Experimental-Laccase immobilization to the synthesized poly(maleic anhydride-alt-methyl vinyl ether)/octadecylamine-montmorillonite nanostructures were examined under the optimum conditions (pH, temperature, laccase initial concentration and time). After then, for effectively decolorization process, the optimum conditions (pH, temperature, the initial coloring substance concentration, time-dependent

decolorization rate) were determined for both free and immobilized laccase enzymes.

Results and Discussion-The optimum conditions for the fungal originated laccase immobilization to the poly(maleic anhydride-alt-methyl vinyl ether)/octadecylamine-montmorillonite nanocomposites were determined as 4.5 pH, 37oC temperature, 0.025 mg/ml laccase initial concentration, and 60 minutes at the first stage of the study. After then, for effectively decolorization, the optimum pH was stated as 5.0 and temperature was also stated as 20 0C for both free and immobilized laccase. Moreover, the initial coloring substance concentration was 0,025 mg/L and 0,05 mg/L for free and immobilized laccase, respectively. In our research was determinated as optimum time 120 min.(63% decolorization rate) and 90 min. (70% decolorization rate) for free enzyme and immobilized laccase respectively. At the end of 27 days, while immobilized laccase activity was 65%, free enzyme activity was 33%. Lastly, laccase productivity was found as 77.3% for reusing in effectively decolorization at 10 times over in a period of three days.

R e f e r e n c e s

[1] Duran N., Rosa M.A., D’annibale A., Gianfreda L.. Applications of laccases and tyrosinases (phenoloxidases) immobilized on different supports: a review, Enzyme Microbiol. Technol. 2002; 31, 907–931.

[2] Esther Forgacsa, Tibor Cserhati, Gyula Oros, Removal of synthetic dyes from wastewaters: a review, Environment international, 2004; 30, 953–971.

[3] Mohan S.V., Rao N.C., Sarma P.N., Simulated acid azo dye (Acid black 210) wastewater treatment by periodic discontinuous batch mode operation under anoxic-aerobic-anoxic microenvironment conditions, Ecol. Eng., 2007; 31, 242-250.

[4] Davies L.C., Carias C.C., Novais J.M., Martins-Dias S., Phytoremediation of textile effluents containing azo dye by using Phragmites australis in a vertical flow intermittent feeding constructed wetland, Ecol. Eng., 2005; 25, 594-605.

Sedef Ilk1, Necdet Sağlam2, Zakir

M.O. Rzayev2

[email protected]

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C h i t o s a n N a n o p a r t i c l e s f o r s i R N A B a s e d G e n e S i l e n c i n g T h e r a p y f o r C a n c e r 1 Nanotechnology and Nanomedicine Division, Hacettepe University, Beytepe, 06800, Ankara, Turkey 2 Chemistry Department, Biochemistry Division, Hacettepe University, Beytepe, 06800, Ankara, Turkey 3 Bioengineering Department, Kırıkkale University, Yahşihan, 71451, Kırıkkale, Turkey

Small interfering RNA (siRNA) based gene silencing that reduces the synthesis of specific harmful protein at mRNA level is one of the effective targeted therapies for cancer [1,2]. However, siRNA delivery into the cells is limited due to its rapid decomposition by nucleases and poor cellular uptake [3]. The polycationic, non-toxic, biodegradable and biocompatible polymer such as chitosan (CS) can be bound effectively to siRNA molecule and it can be protected against to enzymatic degradation [4]. In this study CS nanoparticles (NPs) were produced via ionic gelation method and sodium tripolyphosphate (TPP) was used as crosslinker. pH value of the CS solution (4.0 to 5.0) and CS/TPP mass ratio (2.5:1 to 5:1) were changed to optimize the NPs size and surface charge for efficient gene transfection. Morphological characterization of the CS-NPs was evaluated by AFM and SEM. The genes for ABCE1 (ATP-binding casette E1) and eRF3 (eukaryotic release factor 3) proteins which play significant roles in protein synthesis were chosen as target genes to be loaded with CS-NPs, individually and together. Loading efficiencies of 98.69%±0.051 and 98.83%±0.047 were achieved when ABCE1 siRNA and eRF3 siRNA were entrapped into the NPs, respectively. Cellular uptake of fluorescein labeled CS-NPs into MCF-7 cells, WST-1 cytotoxicity and Real Time Cell Analyzer (RTCA) assays of the NPs were carried out. Mean diameter of the CS-NPs was obtained between 105-230 nm and the zeta potential was 27 mV at pH 4.5 and 3:1 CS/TPP mass ratio values. Fig. 1 shows that CS-NPs are spherical in shape by SEM analysis. Both WST- 1 and RTCA assays revealed that ABCE1 siRNA, eRF3 siRNA and ABCE1/eRF3 siRNA loaded NPs significantly reduced the cell viabilty and proliferation (Figure 2). This work demonstrated that the CS-NPs suitable in size and surface charge are promising vectors for siRNA based targeted cancer therapy.

R e f e r e n c e s

[1] Ozpolat B, Sood AK, Lopez-Berestein G,

Advanced Drug Delivery Reviews, 66 (2014) 110-116.

[2] Oh YK, Park TG, Advanced Drug Delivery Reviews, 61 (2009) 850-862.

[3] Piao L, Li H, Teng L, Yung BC, Sugimoto Y, Brueggemeier RW, Lee RJ, Nanomedicine-Nanotechnology, Biology and Medicine, 9 (2013) 122-129.

[4] Ravi Kumar MNV, Reactive Functional Polymers 46 (2000) 1-27.

F i g u r e s

Figure 1: SEM micrographs of CS-NPs.

Figure 2: Cell proliferation curve of MCF-7 cells treated with control and siRNA loaded CS-NPs

Burcu Bağdat Cengiz1, Mehmet Doğan Aşık 1, Göknur Kara

2, Mustafa Türk 3,

Emir Baki Denkbaş 2

[email protected]

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F e r r o m a g n e t i c n a n o p a r t i c l e s a s d e l i v e r y s y s t e m o f a n t i t u m o r d r u g s f o r t a r g e t i n g b r e a s t c a n c e r c e l l s 1 Universidad Autónoma de Madrid, Departamento de Biología, Darwin 2, 28049 Madrid, Spain. 2 Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanociencia), Faraday 9, 28049 Madrid, Spain. 3 Universidad Autónoma Madrid, Departamento de Física de la Materia Condensada, Francisco Tomás y Valiente 7, 28049 Madrid, Spain.

In the last century there has been a spectacular development of chemotherapeutic drugs against cancer. Nowadays a huge amount of cancer types are treated with different antitumor agents, however they produce multiple side effects. Nanotechnology-based approaches hold substantial potential for improving the care of patients with cancer.

In this work we have used biocompatible magnetic nanoparticles (MNPs) coated with dimercaptosuccinic acid (DMSA) called MF66. Anti-neoplastic drug doxorubicin (DOX) and pseudopeptide Nucant (N6L) have been immobilized onto DMSA coating by electrostatic interactions.

After 24 h incubation MNP-DOX were efficiently internalized by human breast cancer cells (MDA-MB-231). This fact was confirmed by fluorescence microscopy and Prussian blue staining, producing an increased uptake by MNP-N6L. We assessed DOX linked to MNPs was more efficiently retained into cells than free DOX. Up to 48 h after MNP-DOX incubation aberrant mitosis were appeared and later, 72 h after treatment, apoptosis and mitotic catastrophe cell death were triggered. We confirmed these results by α-tubulin (see Fig. 1) and

caspase 3 immunofluorescence and flow cytometry and in addition this process was filmed by time-lapse video microscopy. Finally Alamar blue assay and Trypan blue were carried out to evaluate cytotoxicity of these formulation, showing a great pharmacological activity of the drug reducing cell viability approximately to 50% and many of the remaining cells enter senescence state.

In summary, these multifunctionalized magnetic nanoparticles seems a promising tool as therapeutic agent, due their ability to produce efficient drug delivery and cancer cells inactivation.

This work was partially supported by grants from EU-FP7 (no 262943) and Spanish Ministry of Economy and Competitiveness (CTQ2013-48767-C3-3-R)

R e f e r e n c e s

[1] Calero, M.; Gutiérrez, L.; Salas, G.; Luengo, Y.; Lázaro, A.; Acedo, P.; Morales, MP.; Miranda, R.; Villanueva, A. Nanomedicine 10 [2014] 733-43.

F i g u r e s

Figure 1: Immunofluorescence for α-tubulin (green) and DNA counterstained with Hoechst-33258 in MDA-MB-231 cells. Left image: cells incubated with MF66 without functionalization. Right image: cells incubated with MF66-DOX at the same magnification, where doxorubicin induced increased cell size.

Ana Lazaro-Carrillo*1,2,

Macarena Calero1,2, Pierre Couleaud2, Antonio Aires2, Alfonso Latorre2, Álvaro Somoza2, Aitziber L. Cortajarena2, Rodolfo Miranda2,3

and Angeles Villanueva1,2

[email protected] [email protected]

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N a n o p h o t o n i c l a b - o n - c h i p b i o s e n s o r s f o r t h e n e x t d i a g n o s t i c s g e n e r a t i o n Nanobiosensors and Bioanalytical Applications Group, Institut Català de Nanociència i Nanotecnologia (ICN2) CSIC and CIBER-BBN, Barcelona, Spain

Modern healthcare is demanding novel diagnostic tools that could enable quick, accurate, reliable, and cost-effective results so that appropriate treatments can be implemented in time, leading to improved clinical outcome. Such hand-held point-of-care (POC) devices, able to deliver an instant diagnostics of our health status at home, at doctor's office, at bed side or at resource-limited settings, could become a reality soon thanks to the last advances in nanobiosensors, lab-on-a-chip, wireless and smart-phone technologies which promise to surpass the existing challenges, opening the door to a global health access. Remarkable progress towards POC systems appears continuously in the scientific literature as for example POC technologies coupled to smart-phones, Google glass or paper-based biosensors. However there is still a lack of commercial POC devices as general diagnostic tools due to the many technical challenges to be overcome. The driving force of our research is to achieve such ultrasensitive platforms for POC label-free analysis accomplishing the requirements of disposability and portability. We are using an innovative design

of a nanophotonic biosensor fabricated with silicon photonics technology (an heteromodal nanointerferometer). Full lab-on-chip integration is pursued by incorporating grating couplers for light coupling, independent microfluidics for each sensing channel, photodetectors for the read-out nd signal processing. Advantages as miniaturization, sensitivities clinically relevant, robustness, reliability, potential for multiplexing and mass production at low cost can be offered by our nanodevices. We have demonstrated the suitability of our lab-on-chip photonic biosensor for the clinical diagnostics with extremely sensitivity, directly using untreated human samples, as for the evaluation of hormones related to endocrine disorders and tumours (below 0.1 pg/ml), the detection of infectious microorganisms (at few cfu/ml) or the detection of microRNA biomarkers related to cancer progression, among others.

F i g u r e s

Figure.1: (right) wafer containing nanophotonic biosensors. (left) LOC device containing 16 nanophotonic waveguide sensors integrated with a polymer microfluidics network.

Laura M. Lechuga

[email protected]

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I n f l u e n c e o f c h e m i c a l c o m p o s i t i o n o n t h e d i s s o l u t i o n o f A Y F 4 : Y b , T m ( A = N a , K o r L i ) u p c o n v e r t i n g n a n o p a r t i c l e s i n w a t e r 1 Jožef Stefan Institute, Jamova 39, 1000 Ljubljana, Slovenia 2 Jožef Stefan International Postgraduate School, Jamova 39, 1000 Ljubljana, Slovenia

Lanthanide-doped fluoride nanoparticles, which exhibit upconversion (UC) fluorescence have a great potential for biomaging and also as components in nanotheranostics.The UC process is characterized by the emission of light with shorter wavelength than that of the excitation source. Of particular interest for bioimaging is the UC at near infrared (NIR) wavelengths, so-called NIR to-NIR UC, which is characteristic for the NPs co-doped with Yb3+ and Tm3+ [1]. Ternary fluorides, like for example NaYF4, were proven to be one of the most suitable host matrices, which allow for efficient NIR-to-NIR UC. Despite the known chemical stability of bulk fluorides (i.e., low solubility in water) [2] our preliminary study [3] revealed that NaYF4:Yb3+,Tm3+ NPs can partly dissolve in water. This is not encouraging for biomedical applications, since lanthanide and flouride ions are cytotoxic in sufficiently large concentrations [4-6]. The aim of this work was to study the effect of chemical composition of ternary alkali fluoride NPs (AYF4, where A = Li, Na or K) on the dissolution degree. The AYF4 NPs co-doped with Yb3+ and Tm3+ (Ln-NPs) were synthesized solvothermally at 200 °C. The synthesis time was adjusted in such a way that the Ln-NPs sizes were several tenths of nanometers. This was inspected with transmission electron microscopy while their crystal structures were analyzed with X-ray powder diffraction. The NIR UC emission of the Ln-NPs around 800 nm was much more intense than the blue emission at 450-470 nm. Aqueous suspensions with 1 mg/ml of Ln-NPs were aged from 1h and up to 3 days at room temperature and at pH~7.4 (similar to that of blood). The solutions, which were obtained after ultrafiltration of the Ln-NPs, were analyzed for the dissolved F− and cations using a combined fluoride ion selective electrode and optical emission spectroscopy, respectively. Partial dissolution of all

the studied Ln-NPs was confirmed and will be discussed in terms of their composition.

R e f e r e n c e s

[1] F. Wang, X. Liu, Chem. Soc. Rev., 38 (2009) 976 [2] H. Itoh, H. Hachiya, M. Tsuchiya, Y. Suzuki, Y.

Asano, Bull. Chem. Soc. Jpn., 57 (1984) 1689 [3] O. Plohl, D. Lisjak, M. Ponikvar-Svet, S. Kralj, D.

Makovec, Proc. of the 6th Jožef Stefan International Postgraduate School Student's Conference – Part 1, Ljubljana, 2015, 255

[4] [4] N. I. Agalakova, G. P. Gusev, ISRN Cell Biol., (2012) 403835

[5] H. Q. Xiao, F. L. Li, Z. Y. Zhang, L. X. Feng, Z. J. Li, J. H. Yang, Z. F. Chai, Toxicol. Lett., 155 (2005) 247

[6] T. Grobner, Dial. Transplant, 21 (2006) 1194

Darja Lisjak1, Olivija Plohl1,2,

Boris Majaron1, Maja Ponikvar-Svet1

[email protected]

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D e s i g n o f m u l t i f u n c t i o n a l l i p o s o m a l d r u g f o r m u l a t i o n s f o r c a n c e r t h e r a p y 1CFUM - Centre of Physics of University of Minho, Campus of Gualtar, Braga, Portugal 2CBMA - Centre of Molecular and Environmental Biology of University of Minho, Campus of Gualtar, 4710-057 Braga, Portugal 3Nanodelivery – I&D em Bionanotechnologia, Lda., Department of Biology, University of Minho, Campus of Gualtar, 4710-057 Braga, Portugal

Cancer remains a global health problem and a major cause of death worldwide. Statistical analysis published by the International Agency for Research on Cancer from the World Health Organization reveals that if the estimated trends continue, the incidence of all cancer cases will raise from 12.7 million new cases in 2008 to 21.2 million by 2030 [1]. Doxorubicin (DOX) is considered one of the main “first-line” anticancer drugs for a broad spectrum of tumor types, but this drug has the disadvantage of being toxic for other healthy organs and tissues. The use of liposomes as carriers of DOX is thus very appealing to counteract this disadvantage and protect the healthy tissues from contact with the DOX toxicity. Despite several liposomal formulations were already proposed for the delivery of DOX, the majority uses “active loading” methods and the small number of liposomal formulations that use “passive loading” methods achieve small encapsulation efficiency (EE) of the drug. The “active loading” methods are used to increase DOX amounts in the nanocarriers, but have however the disadvantage of drug precipitation and formation of dimers for which the therapeutic value is yet to be proved [2]. In this work it is proposed a nanocarrier system of Dioctadecyldimethylammonium Bromide (DODAB) and 1-oleoyl-rac-glycerol (Monoolein (MO)) (1:2) that has previously been studied as a system with great potentiality of encapsulating drugs, not only at the DODAB enriched bilayer level, but also at the inverted non-lamellar MO-enriched phases at the vesicle interior [3]. Therefore with this innovative polymorphic system the lipophylic area is greatly increased thus increasing the system capacity to increase the payload content even by a passive encapsulation. Three methods of DOX passive encapsulation in the formulation DODAB:MO (1:2) were tested and characterized measuring the size and zeta potential of the liposomes overtime by dynamic and electrophoretic light scattering and measuring DOX EE (evaluated through UV/Vis spectrophotometry). EE studies revealed high encapsulation values of

DOX (87 %) turning the developed formulation in a very promising nanocarrier system for DOX. The study of the partition coefficient of DOX has confirmed that it is highly distributed in the lipid formulation. The biophysical effects of DOX in the formulation indicated an increase in the cooperativity of the phase transition confirming DOX distribution at the membrane level. Furthermore, thermodynamical parameters of DOX partitioning indicated that the drug distribution in the lipid formulation occurred spontaneously. Cytotoxicity assays were also performed in a cancer cell line and it was concluded that the formulation with DOX encapsulated in DODAB:MO (1:2) has a better cytostatic effect than the free drug, confirming the potentiality of the developed formulation to be used in cancer treatment. Finally controlled release assays were carried out in media with different relevant physiological pH values (5 and 7.4) to predict the pharmacokinetic behavior of the drug when loaded in the developed nanocarriers. Currently we are exploiting a distinct virtue of the co-delivery system, which is taking advantage of the positive charge of the nanocarrier to deveop hybrid co-delivery nanocarriers that combine chemotherapeutic agents with small interfering ribonucleic acids (siRNA targeted to MRP1 mRNA and siRNA targeted to BCL2 mRNA as suppressors of multidrug resistance).

This work was supported by FEDER through POFC – COMPETE and by national funds from FCT through the projects PEst-OE/BIA/UI4050/2014 and PEST-C/FIS/UI607/2013 and PTDC/QUI/69795/2006. Marlene Lucio holds a position of Researcher FCT with the reference IF/00498/2012. .

R e f e r e n c e s

[1] Bray, F.; Jemal, A.; Grey, N.; Ferlay, J.; Forman, D., The Lancet Oncology, 13 (2012), 790-801.

[2] Barenholz, Y., Journal of Control Release, 160 (2012), 117-134.

[3] Neves Silva, J.P.N; Oliveira, A.C.N.; Lúcio, M; Gomes, A.C.; Coutinho, P.J.G.; Real Oliveira, M.E.C.D., Colloids and Surfaces B: Biointerfaces, 121 (2014), 371-379.

Marlene Lúcio1, Eduarda Bárbara1,

Ana Oliveira1,2, Odete Gonçalves1,3, Andreia C. Gomes2 and M.E.C.D. Real Oliveira1,2

[email protected]

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D i s s e c t i n g t h e M o l e c u l a r M e c h a n i s m o f A p o p t o s i s d u r i n g P h o t o t h e r m a l T h e r a p y u s i n g G o l d N a n o p r i s m s 1 Instituto Universitario de Nanociencia de Aragón, Universidad de Zaragoza, Spain 2Aragón Health Research Institute, Zaragoza, Spain 3CICBiomaGUNE, San Sebastián. Spain 4 Fundacion ARAID, Spain 5 Instituto de Carboquímica, CSIC, Zaragoza, Spain. 6 Faculty of Physics, Philipps-Universität Marburg, Germany 7 Instituto de Ciencia de Materiales de Aragón, CSIC-Universidad de Zaragoza, Spain 8 Shanghai Jiao Tong University, P.R. China

Nature has been utilizing nanostructures for millions of years. The following two properties, (i) being about the size of “typical” biological objects and (ii) the possibility of tailoring their properties by changing their size or their shape, make nanoparticles attractive for biomedical applications. One the most promising application for gold nanoparticles (NPs) is their use as “heaters” during photothermal therapy of solid carcinomas using near-infrared laser light (NIR). The most common cellular response to photothermal therapy treatment (PTT) using this kind of nanomaterials is necrosis, producing detrimental inflammatory responses. Here we report the use of PTT using gold nanoprisms (NPRs)

to specifically induce apoptosis in cells. In order to understand the different molecuar pathways involved in this cellular death, we have analysed the mechanism of apoptosis using embryonic fibrobast cells from different knock out mice, which are deficient in proteins involved in the different routes of apoptosis. Our results show that “hot” NPRs activate the intrinsic/mitochondrial pathway of apoptosis mediated by Bak and Bax through the activation of the BH3-only protein Bid. Finally, apoptosis and cell death is dependent on the presence of both caspase-9 and caspase-3.

Marta Pérez-Hernández1,2, Pablo del Pino,1,3, Scott G. Mitchell1, María Moros1, Grazyna Stepien1, Beatriz Pelaz6, Wolfgang J. Parak6, 3, Eva M. Gálvez5, 2 , Julián Pardo, 1 2,4 and Jesús M. de la Fuente

7, 8

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I n n o v a t i v e B i o s e n s o r s f o r N e w P o i n t - o f - C a r e D e v i c e s 1 CIC microGUNE, Arrasate-Mondragón, Spain 2 Micro-Nanofabrication Unit, IK4-Tekniker, Eibar, Spain

There is a general need in healthcare systems all around the world to reduce costs in terms of time and money without compromising patient outcome. Point-of-Care (POC) testing is currently being used in some applications (e.g. coagulation devices) as an alternative to already established standard central laboratory tests to overcome sample transportation and long turnaround times. The main objective of this investigation is to develop innovative technologies for their integration into POC platforms. In this research, a model protein biomarker was selected as an excuse to prove the potential of the biosensors developed. Tumour Necrosis Factor-alpha (TNF-α) was chosen because it was considered a challenging goal due to its extremely low presence in blood/serum/plasma samples. In addition, assaying of this biomarker is interesting for many immunological studies. For instance, the binding inhibition of circulating TNF-α to its receptors by biological drugs has been seen to alleviate the symptoms of certain diseases such as rheumatoid arthritis or Crohn's disease. With the above-mentioned framework in mind, three different technologies were investigated: Firstly, an electrochemical immunoassay for the detection of proteins in human serum based on the combination of amperometric measurements, magnetic microbeads (MBs) and disposable screen-printed carbon electrodes (SPCEs) has been developed. The specifically modified microbeads were magnetically captured onto the working electrode surface and the electrodic and enzymatic reactions of the H2O2-hydroquinone mediated reduction was amperometrically monitored [1]. Secondly, a novel solid-phase assay based on a magnetic bead-mediated proximity ligation assay (PLA) has been developed in which one of the assay proximity probes was directly immobilized onto streptavidin-coated magnetic beads. The portable device was based on a disposable and single-use cyclo olefin polymer (COP) microfluidic

chip interfaced with a quantitative real-time polymerase chain reaction (qPCR) device [2]. Finally, a simple method for the detection of biomarkers in human serum with great sensitivity has been developed using a surface plasmon resonance (SPR) biosensor. Signal amplification based on a sandwich immunoassay including gold nanoparticles was used. Detection in serum proved to be challenging due to high undesirable non-specific binding to the sensor surface stemming from the matrix nature of the sample [3]. The simplicity, robustness and the clinically interesting LODs obtained with the three methods presented here proved them as good contenders for real clinical application. The knowledge acquired could be horizontally applied to the other interesting protein or DNA biomarkers. The POC platforms envisioned in this project could potentially help in increasing the quality of patient care by reducing turnaround times and improving clinical decision making. It should also be emphasized the possibility of integrating high-throughput, multiplex detection and automatization into the platforms. These advantages may have a significant positive impact on cost in terms of time and money on governmental health service budgets.

R e f e r e n c e s

[1] U. Eletxigerra, J. Martinez-Perdiguero, S. Merino, R. Villalonga, J.M. Pingarrón, S. Campuzano, Anal. Chim. Acta 838 (2014) 37–44.

[2] V. Castro-Lopez, J. Elizalde, M. Pacek, E. Hijona, L. Bujanda, Biosens. Bioelec., 54 (2014) 499-505

[3] J. Martinez-Perdiguero, A. Retolaza, L. Bujanda , S. Merino, Talanta 119 (2014) 492–497

Josu Martínez-Perdiguero1,

Vanessa Castro-López1, Unai Eletxigerra1,2

[email protected]

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S i l i c o n n a n o p a r t i c l e s a s T r o j a n h o r s e s f o r p o t e n t i a l b r e a s t c a n c e r t h e r a p y 1 Centro de Tecnologías Físicas, Unidad Asociada CSIC-UPV, Universidad Politécnica de Valencia, Av. Los Naranjos s/n, Valencia, 46022 Spain 2 Servicio de Oncología, Hospital Universitario Madrid-Torrelodones, Madrid, Spain 3 Departamento de Química Orgánica, Universidade de Vigo, Vigo, 36310 Spain 4 Fachbereich Physik, Philipps Universität Marburg, Marburg, 35037 Germany 5 Medcomtech SA. C/ Catalunya, 83-85 Viladecans, Barcelona, 08840 Spain 6 Departamento de Química Física e Inorgánica, Universitat Rovira i Virgili and Centro de Tecnología Química de Catalunya, Carrer de Marcel•lí Domingo s/n, 43007 Tarragona, Spain 7 ICREA, Passeig Lluís Companys 23, 08010 Barcelona, Spain

Over the last two decades nanoparticles have proven to have a great potential for drug delivery and disease treatment, particularly in cancer therapy strategies [1]. In the last years porous silicon nanoparticles have shown excellent properties as drug delivery carriers for cancer therapy due to their excellent biocompatibility and biodegradability [2]. It is well known from silicon producers that porous silicon nanoparticles present extremely high, and even explosive, oxidation reactions with enthalpy values exceeding that of Trinitrotoluene (TNT) [3]. Here we show that silicon nanoparticles can be used themselves as a cancer cell killer drug [4], thus avoiding the use any additional anticancer drug with serious side-effects. Targeted cells are destroyed through a mechanism that takes advantage of both the violent reaction of degradation of silicon in aqueous medium and the enzymatic machinery of eukaryotic cells. The use of silicon nanoparticle properly protected to avoid an extracellular solubilization, and coupled to an appropriated antibody, allows the selective destruction of the cancer cells, which is followed by the degradation of silicon into excretable biocomponents of the body. Figure 1 shows an example of how the breast cancerous cells (SK-BR3) viability dramatically decreases with porous silicon nanoparticles properly functionalized with the directing vector HER-2 positive breast cancer.

R e f e r e n c e s

[1] Prasad, P.N. Introduction to Nanomedicine and Nanobioengineering. (Wiley, New York; 2012)

[2] Park, J.-H. et al. Nat Mater 8, (2009) 331; Popplewell, J.F. et al. J. Inorg. Biochem. 69 (1998) 177; Shabir, Q. et al. Silicon 3 (2011) 173

[3] Mikulec, et al., Advanced Materials, 14 (2002) 38-41

[4] Fenollosa, R., et al., Journal of Nanobiotechnology 12 (2014) 35

F i g u r e s

Figure 1: Cell viability. Relative cell viability after incubation of SK-BR-3 and MDA-MB-435 cells with PSiPs and PSiPs-HER-2 for 48 h.

Roberto Fenollosa,1 Eduardo Garcia-Rico,2 Susana Alvarez,3 Rosana Alvarez,3 Xiang Yu,4 Isabelle Rodriguez5, Susana Carregal-Romero,4 Carlos Villanueva,5 Pilar Rivera-Gil,5 Angel R. de Lera,3 Wolfgang J. Parak,4 Francisco Meseguer,

1

Ramón A. Alvarez-Puebla,6,7

[email protected]

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M i c r o s c a l e E l e c t r o d e s i n t e g r a t e d o n n o n - c o n v e n t i o n a l s u b s t r a t e s f o r R e a l S a m p l e C a m p y l o b a c t e r s p p . d e t e c t i o n 1 CIC microGUNE, Goiru kalea, 9, Polo de Innovación Garaia, 20500, Mondragón, Spain 2 IK4-Ikerlan, Pº JMª Arizmendiarrieta 2, 20500 Arrasate-Mondragón, Gipuzkoa, Spain.

Campylobacter spp. are responsible of acute bacterial diseases in human worldwide. Nowadays campilobacteriosis is considered the most common foodborne illness in the European Union [1]. To our knowledge, there no commercial biosensors and very few examples of detection of Campylobacter spp in food matrices [2]. In this work the first electrochemical genosensor based on thin-film gold electrodes deposited onto Cyclo Olefin Polymer (COP) substrates was fabricated for the detection of Campylobacter spp in food matrices. The sensing element is characterized by several surface techniques and the sensitivity of the biosensor has been analyzed. A good linear relationship was obtained for the concentrations of PCR amplicon of Campylobacter spp. between 1 and 25 nM with a LOD of 90 pM. Real samples have been validated with poultry meat samples and results were comparable with the PCR product samples. The experimental CVs and SWVs obtained before and after hybridization suggest that the device presents a high potential to integrate

electrochemistry and microfluidics for analysis of microorganism in food and therefore the samples with current values lower that 30 μA can be considered as negative. This is the last step for the fabrication of a Lab on a Chip (LOC), a biodevice integrating DNA sensor technology into microfluidic system, believed to perform an automated and complete assay, including sample preparation, PCR amplification, and electrochemical detection of Campylobacter spp. in raw poultry meat sample.

R e f e r e n c e s

[1] Coker AO; Isokpehi RD; Thomas BN; Ko, A.; CL.,

O., Emerging Infectious Diseases, 8, (2002) 237- 243

[2] Yang, X.; Kirsch, J.; Simonian, A., Journal of microbiological methods, 95, (2013), 48-56.

F i g u r e s

Figure 1: Image of the electrochemical sensor with three-electrode configuration sputtered onto the COP layer and Square-Wave Voltammograms (SWV) before and after hybridization

M. Carmen Morant-Miñana1,

J. Elizalde1,2, A. Rodriguez1

[email protected]

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P o l y m e r T h e r a p e u t i c s f o r t h e T r e a t m e n t o f C h r o n i c S p i n a l C o r d I n j u r i e s Centro de Investigación Príncipe Felipe. Eduardo Primo Yúfera 3, 46012 Valencia. 1 Polymer Therapeutics Laboratory. 2 Neuronal and Tissue Regeneration Research group.

The medical application of nanotechnology has enormous potential to improve human health, especially in serious chronic disease such as cancer and neurodegeneration [1-3]. In this sense, Polymer Therapeutics represents an outstanding approach for the treatment of several pathologies, being one of the first nanomedicines with more than 16 polymer-drug conjugates in advanced clinical trials and several already transferred to routine clinical use. Although considerable experimental improvements in neuronal activity in acute and subacute stages after Spinal Cord Injury (SCI) have been made in the last decade, little progress has been made in the chronic stage. In the chronic scenario, tissue degeneration and reactive scarring isolate the injured area from the potential re-growing axons [4]. However, there are currently no studies which cover all fundamental criteria: cell replacement, neuroprotection and axonal growth promotion strategies and even fewer in chronic stages. Considering all tissue degeneration and the massive cell loss that occurs, transplantation of spinal cord derived and functional compatible cells result mandatory for tissue repair. Based on the multifaceted lesion that occurs, a combinatory therapeutic approach is clearly required [5]. We aim to the design of a nanomedicine for neuroprotection and axonal growth promotion. The property of multivalency provided by the use of polymeric carriers allows the conjugation of several bioactive agents in the same polymer in such a way that for SCI, the combination of a neuroprotector with an axonal growth inductor and other active principle such as chondroitinase, for glial scar disruption could markedly enhance the therapeutic value of these macromolecules. In this communication we present a first approach for the combinatorial treatment of SCI, where an axonal growth inductor (Fasudil®) conjugated to a multifunctional and biodegradable polymer such as Poly-L-Glutamic acid (PGA) is evaluated for combination with stem cell transplantation.

The conjugation of Fasudil to PGA has been achieved through different biodegradable linkers (amide and carbamate) and the different release rate profiles and toxicities of the conjugates has been evaluated in vitro showing different release rates depending on the linkage and no associated toxicities. Furthermore, the conjugation of a fluorescent dye (Oregon Green) enabled the study of the cellular uptake on injury activated ependymal cells and points to an energy dependent endocytosis internalization mechanism. In vitro tests on ROCK inhibition activity and axonal elongation has been carried out. All these results are promising for a therapy towards the treatment of SCI based on the combination of polymer conjugates and stem cells transplantation.

R e f e r e n c e s

[1] Ferrari M. Nature Rev. Cancer, 5 (2005), 161. [2] Duncan R. Nat. Rev. Drug. Discov., 2 (2003) ,

347. [3] Fabiana Canal; Joaquin Sanchis; María J. Vicent

22 – 6 (2011), 894. [4] Thuret S., Moon L.D.F., Gage F.H., Nat. Rev. 7

(2006), 628. [5] a) Moreno-Manzano V. et al., 27 (2009), 733.;

b) Moreno-Manzano V. et al. Stem Cells, 30 (2012), 2221.

V. J. Nebot,1 A. Armiñan,1

A. Alastrue-Agudo,2 R. Requejo-Aguilar,2 V. Moreno-Manzano,2 M. J. Vicent.1

[email protected]

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B i o s e n s i n g B a s e d o n E n z y m a t i c M o d u l a t i o n o f G r o w t h o f N a n o p a r t i c l e s CIC BiomaGUNE, Paseo Miramon 182, San Sebastian, Spain

Semiconductor nanoparticles (SNPs) can be very conveniently employed in biosensing for signal transduction. Their chemical and physical properties are defined by three dimensional structure of NPs, therefore very slight changes in shape and size lead to drastic variation in absorption and emissionspectra. We pioneered enzymatic assays in which formation of CdS nanoparticles according to the equation Cd2+ + S2- = CdS is caused by biocatalytic processes yielding S2- ions [1]. The second group of QDs-generating fluorogenic enzymatic assays developed by us relies on modulating the growth of CdS QDs with the products of biocatalytic transformation through inhibition or enhancement. This novel concept has been applied by us to a number of assays, including, the highly sensitive and inexpensive detection of reduced glutathione (GSH), over its oxidized form (GSSG), and glutathione reductase (GR) in human serum [2]. This new fluorogenic bioanalytical system is based on the GR-mediated stabilization of growing CdS nanoparticles (Scheme 1). The sensitivity of this new assay is 5 pM of GR, which is 3 orders of magnitude better than other fluorogenic methods previously reported in the literature. We also managed to show how the growth of fluorescent CdS can be modulated by the DNAzyme having peroxidase activity. The system is based on the affinity interaction between the peroxidase-DNAzyme bearing hairpin sequence and the analyte (DNA or low molecular weight molecule), which changes the folding of the hairpin structure and consequently the activity of peroxidase-DNAzyme [3] (Scheme 2).

Recognition events, such as specific interaction of target analytes with a number of enzymes or affinity interaction in enzyme-linked immunosorbent assays, may lead to formation of fluorescent quantum dots with photocatalytic activity. Our latest experimental results confirm that CdS QDs, grown under the influence of products of biocatalytic transformations, are photo-catalysts enhancing oxidation of commercially available enzymatic chromogenic substrates such as 3,3',5,5'-

tetramethylbenzidine (TMB) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS). The photocatalysis did not take place under ambient laboratory light but occurred only under irradiation with a standard UV lamp, resulting in high repeatability. We applied this colorimetric method to analytical assays in which the growth of SNPs in situ is modulated by products of enzymatic reactions catalyzed by GOx and GR. The detection limits demonstrated by two developed chromogenic assays were comparable with or better than those of corresponding fluorogenic assays relying on registration of emission light arising from CdS NPs. Due to stability of 3,3’,5’5-tetramethylbenzidine diimine the read-out signal was very stable and standard deviation was quite small [4].

R e f e r e n c e s

[1] V. Pavlov, Part. Part. Syst., 31 (2014) 36. [2] G. Garai-Ibabe, L. Saa, V. Pavlov, Anal. Chem.,

85, (2013) 5542. [3] G. Garai-Ibabe, M. Möller, L. Saa, R. Grinyte, V.

Pavlov, Anal. Chem., 86 (2014) 10059. [4] R. Grinyté, G. Garai, L. Saa, V. Pavlov, Anal.

Chem. In Press.

Valery Pavlov, Ruta Grinyte, Laura Saa, Gaizka Garrai

[email protected]

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F i g u r e s

Scheme 1: Detection of PON1 activity by the enzymatic inhibition of growth of fluorescent CdS QDs.

Scheme 2: DNA detection through peroxidase-DNAzyme modulated growth of CdS QDs in situ.

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B i o d e g r a d a t i o n i n f l u e n c e o n P L A / g r a p h e n e - n a n o p l a t e l e t s c o m p o s i t e b i o m a t e r i a l s m e c h a n i c a l p r o p e r t i e s a n d b i o c o m p a t i b i l i t y 1LEPABE, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal 2INEB, Universidade do Porto, Rua do Campo Alegre, 823, 4150-180 Porto, Portugal

Two types of graphene-nanoplatelets (GNPs) were incorporated in PLA (poly(lactic acid)) by melt blending. Materials were biodegraded during 6 months and characterized by XRD, tensile tests, DMA and biocompatibility assays. For both fillers, low loadings (0.25 wt.%) improved mechanical properties and decreased decay until 6 months biodegradation. PLA degradation decreased its toughness (AUC) by 10 fold, while for PLA/GNP-M and C, toughness was only reduced by 3.3 and 1.7 fold, respectively. Comparing with PLA, PLA/GNP-M and C composites presented similar (HFF-1) fibroblasts adhesion and proliferation at the surface and did not released toxic products (6 months).

Introduction

A commercial available product, with reduced cost comparing with single layer graphene, GNPs, are constituted by few stacked graphene layers. These materials present high aspect ratio and possess oxygen-containing functional groups in the platelet edges, which may facilitate extensive interfacial interaction with polymer matrices. [1] Some typical composite production techniques like solvent mixing and electrostatic deposition lead to obtainment of toxic materials. [1,2] Thus, melt blending, which assures complete embedding of GNPs in polymer matrix preventing filler leaching, is studied in this work as a green method for production of PLA/GNPs composites.

Materials and Methods

PLA 2003D (Natureworks), GNPs (XG Sciences). Composites were prepared by melt blending and moulded in a hot press into thin sheets (0.3-0.5 mm). Samples were immersed in PBS and incubated for 6 months (37 °C, 100 rpm). Tensile properties were measured (Mecmesin Multitest-1d, Mecmesin BF 1000N) using a strain rate of 10 mm min-1. Creep/recovery assays were performed using a DMA 242 E Artemis (Netzsch). Biocompatibility of materials was evaluated using HFF-1 cells cultured at the surface of composite

films and in direct contact with materials extracts obtained after 6 months degradation. Metabolic activity was determined using resazurin assay.

Results and discussion

XRD

GNP-M and C powders present similar XRD spectra, typical of carbon materials. PLA, before (0M) and after 6 months (6M) biodegradation, presents similar spectra, also typical for this polymer. In composites PLA and GNPs peaks were observed. Degradation did not affected spectra.

Tensile tests

Incorporation of GNP-C and M in PLA increased its Young´s modulus by 14 %. Also, tensile strength is increased by 20% for GNP-C and by 6% for GNP-M. After 6 months biodegradation, decreases in tensile strength, elongation at break, and toughness are respectively, for PLA of 2.6, 2.5, and 10 fold, for PLA/GNP-M of 1.6, 1.8 and 3.3 fold, and for GNP-C of 1.4, 1.4 and 1.7 fold.

Creep/recovery

Figure 1 shows that for undegraded PLA, dLf (final, at 6N) after 10 creep/recovery cycles was of 14.2 µm, being of 13.7 and 13.2 µm for PLA/GNP-M and C 0.25 wt.%, respectively. After 6 months degradation, PLA sample ruptured after 4 cycles (1.A) reaching a dLf of 56.3 µm. PLA/GNP-M and C 0.25 wt.% did not rupture (1.B,C) and presented only a slight increase in dLf, of 16.8 and 16.7 µm, respectively. Materials degradation was confirmed in terms of molecular weight decrease and changes in surface morphology (results not shown).

Biocompatibility evaluation

PLA/GNP-M and C 0.25 wt.%, metabolic activity never decreased below 90%, for both composites in comparison with PLA. Composites degradation products are not toxic (24, 48, 72h), comparing with PLA 6M. Also, cell morphology is normal and similar for all conditions tested (images not shown).

Artur M. Pinto1,2,

Carolina Gonçalves1, Inês C. Gonçalves2, Fernão D. Magalhães1

[email protected]

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Conclusions

GNP-M and GNP-C incorporation in PLA (0.25 wt.%) improved mechanical properties and decreased their decay after 6 months biodegradation. GNPs can be used to tune PLA mechanical performance during biodegradation in biomedical applications, since they did not decrease cell proliferation or cause toxicity.

R e f e r e n c e s

[1] Lahiri D, Rupak D, Cheng Z, Socarraz-Novoa I, Bhat A, Ramaswamy S, Agarwal A, ACS Appl. Mater. Interfaces, 4 (2012) 2234.

[2] Pinto AM, Gonçalves IC, Magalhães FD, Colloids and Surf B Biointerfaces, 111 (2013) 188

F i g u r e s

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N a n o s t r u c t u r e d M a t e r i a l s i n M a t r i x -f r e e L a s e r D e s o r p t i o n I o n i s a t i o n M a s s S p e c t r o m e t r y Glycotechnology Laboratory, CIC biomaGUNE, paseo Miramon 182, San Sebastian Spain

Nanostructured surfaces and nanoparticles have contributed enormously to the development of surface based matrix-free soft ionisation techniques like SALDI-MS with important applications in small molecule analysis and imaging mass Spectrometry. This lecture will try to provide brief overview of materials and concepts employed for surface and particle based LDI-MS and discuss in more detail two materials recently developed in the authors laboratory namely, nanostructured indium tin oxide thin films [1] and polished weathering steel [2]. Applications covering imaging mass spectrometry of tissues samples, serum metabolite analysis of quantification of lactose in milk have been chosen to demonstrate the versatility of the materials in a broad range of analytical problems.

R e f e r e n c e s

[1] López, de L. C., Beloqui, A., Yate, L., Calvo, J.,

Puigivila, M., Llop, J., and Reichardt, N. (2015) Nanostructured Indium Tin Oxide Slides for Small-Molecule Profiling and Imaging Mass Spectrometry of Metabolites by Surface-Assisted Laser Desorption Ionization MS. Analytical chemistry 87, 431.

[2] Etxebarria, J., Calvo, J., and Reichardt, N.-C. (2014) Nanostructured weathering steel for matrix-free laser desorption ionisation mass spectrometry and imaging of metabolites, drugs and complex glycans. Analyst 139, 2873–2883

F i g u r e s

Niels-Christian Reichardt

[email protected]

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P r o t e i n s : A M a t e r i a l - S c i e n c e P o i n t o f V i e w Department of Materials Science and Engineering & University Center for Nano Science and Nanotechnology, Tel-Aviv University, Tel-Aviv, Israel

Proteins form the very basis of life. They regulate a variety of activities in all known organisms, from replication of the genetic code to transporting oxygen, and are generally responsible for regulating the cellular machinery and determining the phenotype of an organism. From a material-science point of view, proteins can serve as excellent building blocks for the development of new structures, composites, and devices. In this talk I will describe some of our efforts in this direction. Specifically I will address the followings: (i)Engineered Light-emitting bio-materials, (ii)Control over the electrical properties of nano-sized junctions via “natural” site-controlled doping of proteins monolayers, (iii)Bioinspired photovoltaic cells(iv)

R e f e r e n c e s

[1] Gordiichuk, P. I. et al.. Adv. Mater. 26,

(2014).4863. [2] Mentovich, E. D. et al. J. Phys. Chem. C 117,

(2013) 8468. [3] Mentovich, E., Belgorodsky, B., Gozin, M.,

Richter, S. & Cohen, H. J. Am. Chem. Soc. 134, (2012) 8468.

[4] Hendler, N. et al.. Chem Commun 47, (2011) 7419.

[5] Hendler, N.,et al. Adv. Mater. 23, (2011) 4261. [6] Hendler, N. et al. Macromol. Biosci. 14, (2014)

320. [7] Carmeli, I. et al. Nano Lett. 10, (2010) 2069.

F i g u r e s

Shachar Richter, Netta Hendelr Edith Beilis, Elad Mentovich, Katya Glhih, Antonina Melinchuk, Roman Nudelman, Guy Hershtig, Tamila Gulakhmedov, Itai Carmeli, Liron Reshef, Dolev Rimerman

[email protected]

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M a g n e t i c l i p o s o m e s b a s e d o n n i c k e l f e r r i t e n a n o p a r t i c l e s a s n a n o c a r r i e r s f o r n e w p o t e n t i a l a n t i t u m o r c o m p o u n d s 1Centro de Física, Universidade do Minho, Campus de Gualtar, Braga, Portugal 2IFIMUP/IN - Instituto de Nanociência e Nanotecnologia, R. Campo Alegre, Porto, Portugal 3Centro de Química, Universidade do Minho, Campus de Gualtar, Braga, Portugal

Guided transport of biologically active molecules (most of them toxic and with systemic side effects) to target specific sites in human body has been a focus of research in therapeutics in the past years. Magnetoliposomes (liposomes entrapping magnetic nanoparticles) are of large importance, as they can overcome many pharmacokinetics problems and can be guided and localized to the therapeutic site of interest by external magnetic field gradients [1,2]. In this work, nickel ferrite nanoparticles (NPs) with size distribution of 11±5 nm were obtained. Synthesized NPs show superparamagnetic behaviour at room temperature (magnetic squareness of 7.2×10-5 and coercivity field of 12 Oe), being suitable for biological applications. These NPs were either entrapped in liposomes, originating aqueous magnetoliposomes (AMLs), or covered with a lipid bilayer, forming dry magnetoliposomes (DMLs), the last ones prepared by a new promising route. Recently, AMLs and DMLs containing nickel-based nanoparticles were successfully prepared and characterized [3]. A potential antitumor compound [4] was successfully incorporated into the lipid bilayer of magnetoliposomes. DMLs structure was evaluated by FRET (Förster Resonance Energy Transfer) measurements between the fluorescent-labeled lipids NBD-C12-HPC (donor) included in the second lipid layer and rhodamine B DOPE (acceptor) in the first lipid layer. A FRET efficiency of 23% was calculated, with a corresponding donor-acceptor distance (r) of 3.11 nm, confirming DMLs structure. Preliminary assays of the non-specific interactions of both types of magnetoliposomes with biological membranes (modeled by giant unilamellar vesicles, GUVs) were performed, keeping in mind future applications of drug delivery using this type of magnetic systems. Membrane fusion between magnetoliposomes and GUVs was confirmed by FRET.

R e f e r e n c e s

[1] A. S. Lubbe, C. Bergemann, J. Brock, D. G. McClure,

J. Magn. Magn. Mat. 194 (1999) 149-155. [2] S. Dandamudi, R. B: Campbell, Biomaterials 28

(2007) 4673-4683. [3] A.R.O. Rodrigues, I.T. Gomes, B.G. Almeida, J.P.

Araújo, E.M.S. Castanheira, P.J.G. Coutinho, Mat. Chem. Phys. 148 (2014) 978-987.

[4] C.N.C. Costa, A.C.L. Hortelão, J.M.F. Ramos, A.D.S. Oliveira, R.C. Calhelha, M.-J.R.P. Queiroz, P.J.G. Coutinho, E.M.S. Castanheira, Photochem. Photobiol. Sci. 13 (2014) 1730-1740.

F i g u r e s

Figure 1: A. Fluorescence spectra (λexc=470 nm) of DMLs labeled with NBD-C12-HPC and Rhodamine B-DOPE, before and after interaction with GUVs. B: Illustration of the fusion between the GUVs and DMLs labeled with both NBD-C12-HPC and Rhodamine B-DOPE.

Ana Rita O. Rodrigues1, I.T. Gomes1,2,

Bernardo G. Almeida1 ,J. P. Araújo2, Maria João R.P. Queiroz3, Elisabete M. S. Castanheira1, Paulo J. G. Coutinho1

[email protected]

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T r e a t m e n t o f c u t a n e o u s l e i s h m a n i a s i s w i t h a s u b c u t a n e o u s i m p l a n t c o n s i s t i n g o f d r u g - l o a d e d b i o d e g r a d a b l e n a n o a n d m i c r o p a r t i c l e s 1Universidade Federal do Rio de Janeiro, Rio de Janeiro, Brazil. 2Centre Rapsodee, École des Mines d’Albi, Albi, France

Leishmaniasis is a neglected tropical disease that is very difficult to treat. Its cutaneous form, although not fatal as the visceral form, may develop into morbid disfiguring lesions. Despite its skin localization, conventional therapy of cutaneous leishmaniasis is based on multiple parenteral injections with systemically toxic drugs [1]. Aiming at a localized therapy for cutaneous leishmaniasis, we have used a biodegradable system for sustained subcutaneous release of an antileishmanial drug. For that, poly-(lactide-co-glycolide) PLGA particles loaded with 10 % of a novel lipophylic antileishmanial nitro chalcone CH8 [2] (CH8/PLGA) were prepared by multiple emulsion and solvent evaporation methods. Particles measured in average 6 µm and had -12 mV zeta potential. When tested in

vitro on Leishmania amazonensis-infected macrophages, CH8/PLGA promoted higher parasite killing than free CH8 drug, in a manner independent of macrophage activation for the production of microbicidal reactive oxygen and nitrogen reactive species. Also, CH8/PLGA was not cytotoxic to macrophages at the range of parasite-toxic concentrations. In vivo, their efficacy was tested in BALB/c mice subcutaneously infected in the ear with fluorescent L. amazonensis-GFP. On days 9, 16 and 23 of infection, the animals received at the infection site a subcutaneous depot injection with CH8/PLGA containing 30 µg of CH8. Controls received free CH8, empty PLGA particles, 30 µg of the reference drug Glucantime, or 10 µl of PBS vehicle alone. Treatment efficacy was monitored by measuring the ear

tickeness throughout infection, and parasite loads on days 30 or 90 of infection by Limiting Dilution Assay and fluorometry. Systemic toxicity was biochemically evaluated by measuring the levels of transaminases and creatinine in the serum. Skin inflammation and implant degradation were monitored by histopathology at different times after treatment. The results showed that CH8/PLGA treatment was significantly more effective and durable than the free drug in controlling lesion and parasite growth, and in the prevention of lesion ulceration (Fig 1). A single dose with CH8/PLGA on day 9 was as effective as 3 doses with free CH8.No signs of toxicity were detected in the serum, and histopathological studies showed a transient ear inflammation on day 7 that was resolved by day 30. These findings show that PLGA nano and microparticle subcutaneous implant promoted a sustained chalcone CH8 drug release at the lesion site, with a durable and safe therapeutic effect, supporting its use for localized treatment of cutaneous leishmaniasis.

R e f e r e n c e s

[1] Croft, S. L. and Olliaro, P. Clinical Microbiology and Infection, 17 (2011): 1478-1483.

[2] Boeck, P.; Falcão, C.A.B.F.; Leal, P;V.; Cechinel-Filho, V.; Torres-Santos, E.C.; Yunes, R.A. and Rossi-Bergmann, B. 14 (2006) Bioorganic and Medicinal Chemistry: 1538-1545.

F i g u r e s

Rossi-Bergmann, B.1,

Pacienza-Lima,W.1, Batista, A.J.S. 1 and Ré, M. I.2

[email protected]

Figure 1: Figure1: Mice were infected with Leishmania in the ear. Then, they were given a single (1x, day 9) or 3 injections (3x, days 9, 16 and 23) with CH8/PLGA or control drugs or vehicle as indicated. A) The lesion growth with time. B) Ear appearances on day 70of infection.

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A s i n g l e - D N A c h i p f o r b i o s e n s i n g 1 Centre National de la Recherche Scientifique, University of Toulouse, Institut de Pharmacologie et de Biologie Structurale, 205 route de Narbonne, Toulouse, France 2 Centre National de la Recherche Scientifique, Université de Toulouse, UPS, Laboratoire de Microbiologie et Génétique Moléculaires, 118, route de Narbonne, Toulouse, France

The last two decades have seen the emergence of single-molecule experiments [1]. By avoiding the ensemble averaging inherent to traditional bulk-phase biochemistry, the study of molecular machineries at the single-molecule level permits a better understanding of the behavior of living systems. Indeed the dynamics of the machineries processes can be characterized and rare subpopulations can be identified [2]. In our laboratory, we implemented the Tethered Particle Motion (TPM) technique to monitor the conformational dynamics of single DNA molecules. To increase the output of this powerful but time-consuming single-molecule assay, we have developed a novel single DNA chip allowing the simultaneous analysis of hundreds of single DNA molecules (see Fig 1). The principle of a TPM experiment consists in tracking a bead tethered at the free end of a DNA molecule immobilized by the other end to a coverslip by means of optical videomicroscopy coupled to image analysis. The amplitude of the Brownian motion of the bead is related to the effective length of the DNA molecule [3]. In our biochip, the controlled positioning of individual DNA molecules is achieved by self-assembly on nanoscale arrays fabricated through a standard

microcontact printing method. Using this improved patented method, we currently analyze more than 500 single DNA molecules in parallel [4, 5]. After the description of our technology, we will discuss the capacities of the single DNA biochip, the sensitivity of our methodology and, the future developments and industrial applications in the field of biosensing.

R e f e r e n c e s

[1] Cornish P.V., Ha T., ACS Chemical Biology 1 (2007) 53.

[2] Van Oijen A.M., Nature Chemical Biology 8 (2008) 440.

[3] Yin H., Landick R., Gelles J., Biophys. J. 6 (1994) 2468.

[4] Plénat T., Tardin C., Rousseau P. and Salomé L. High-throughput single-molecule analysis of DNA-protein interactions by Tethered Particle Motion. Nucleic Acids Research 40, (2012) e89.

[5] Plénat T., Salomé, L., Tardin C., Thibault C., Trévisiol E., Vieu C. Biopuces pour l’analyse de la dynamique d’acides nucléiques. French Patent 10 57031, 3 Sept 2010.

F i g u r e s

Figure 1: A nanoarray for the parallel analysis of DNA conformational changes by Tethered Particle Motion.

C. Tardin1, M. Fils1, P. Rousseau2 and L. Salomé

1

[email protected]

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T a r g e t e d d r u g d e l i v e r y a n d p e r s o n a l i z e d n a n o - m e d i c i n e Technion – Israel Institute of Technology (Israel)

The field of medicine is taking its first steps towards patient-specific care. Our research is aimed at tailoring treatments to address each person’s individualized needs and unique disease presentation. Specifically, we are developing nanoparticles that target disease sites, where they perform a programmed therapeutic task. These systems utilize molecular–machines and cellular recognition to improve efficacy and reduce side effects. Two examples will be described: the first involves a nanoscale theranostic system for predicting the therapeutic potency of drugs against metastatic cancer. The system provides patient- specific drug activity data with single-cell resolution. The system makes use of barcoded nanoparticles to predict the therapeutic effect differ rent drugs will have on the tumor microenvironment.

The second system makes use of enzymes, loaded into a biodegradable chip, to perform a programed therapeutic task–surgery with molecular precision. Collagenase is an enzyme that cleaves collagen, but not other tissues. This enzyme was loaded into the biodegradable chip and placed in the periodontal pocket. Once the collagenase releases from the chip, collagen fibers that connect between the teeth and the underlying bone are relaxed, thereby enabling enhance dorthodontic corrective motion and reducing pain. This new field is termed BioSurgery. The clinical implications of these approaches will be discussed.

Avi Schroeder

[email protected]

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R e p a i r o f U V L i g h t - I n d u c e d D N A D a m a g e Sesderma Laboratories, Polígono Industrial Rafelbuñol C/Massamagrell 3, Rafelbuñol Bionos Biotech, Biopolo La Fe, Valencia, Spain

Aim

Evaluate whether DNA repair, in UV-irradiated Medaka eleutheroembryos, could be enhanced through topical application of a preparation containing DNA repair enzymes, amino acids, teprenone and Zn+ (EZ). In order to assure nuclear delivery, each ingredient was encapsulated individually into liposomes. Results

We assayed endogenous DNA repairing mechanisms in cells from Medaka fish embryos by measuring the reduction of cyclobutane pyrimidine dimers (CPDs), after UV irradiation. By comparing the amount of CPDs formed immediately after UV light irradiation on cells treated with a control formulation (EZ minus active ingredients) and cells treated with EZ, we observed a significant decrease (36%) in the formation of CPDs. p53 helps preventing genome mutation, due to its crucial role in regulating cellular responses to various DNA-damaging agents, including UV radiation. p21 is directly linked to p53 because its expression is tightly controlled by the protein p53. We also studied the effect of UV light in the expression levels of p53 and p21 by comparing samples with or without irradiation. We found that the expression levels of p53 and p21 did not change in embryos not irradiated or embryos irradiated with UV light at t=0 minutes or t=15 minutes indicating that at 15 min a p53-mediated response is not yet active. On the other hand, we observed that EZ treatment reduced the endogenous level of p53, allowing for an early damage response to UV light (t=15 min after UV irradiation) increasing the levels of p53. This early response induced by EZ treatment provoked in turn an increase in p21 expression of 130% as early as 15 min after irradiation. c-Fos is required for excision repair processes triggered by DNA lesions produced by UV radiation. Therefore, we measured c-Fos expression level in

control embryos and embryos treated with EZ, exposed or not to UV light. Results show that c-Fos does not significantly increase 15 minutes after UV radiation in control embryos. On the the contrary, 15 minutes after UV radiation c-Fos is overexpressed in embryos previously treated with EZ. In addition, we measured cell cycle immediately after irradiation with UV light and 15 minutes post irradiation, and we found that there were no significant changes in cell distribution in each cell cycle phase. Furthermore, we measured cell cycle immediately after UV light irradiation on cells treated with the control preparation and embryos treated with EZ, and we did not observe any significant changes in cell distribution further indicating that the above gene expression changes detected, were not a consequence of changes in the cell cycle. Conclusions

EZ protects cells against UV light-induced damage by reducing the amount of CPDs in the DNA and triggers the endogenous DNA repair mechanisms that involve the action of p53, p21 and c- Fos.

R e f e r e n c e s

[1] Yarosh DB. DNA repair, immunosuppression, and skin cancer. 2004. Cutis.74(5 Suppl):10-13.

[2] Karakoula A, Evans MD, Podmore ID, Hutchinson PE, Lunec J, Cooke MS. Quantification of UVR-induced DNA damage: global- versus gene-specific levels of CPDs. J Immunol Methods. 2003 Jun 1; 277(1-2):27-37.

[3] Elmets, C. A. & Mukhtar, H. (1996) Prog. Dermatol. 30, 1–16.

[4] Brash DE, Rudolph JA, Simon JA, Lin A, McKenna GJ, Baden HP, Halperin AJ, Ponten J (1991) Proc Natl Acad Sci USA 88:10124–10128. 3.

[5] Ziegler A, Leffell DJ, Kunala S, Sharma HW, Gailani M, Simon JA, Halperin AJ, Baden HP,

Juan Manuel Serrano, Bea Salesa, Ana V. Sánchez-Sánchez, José Luis Mullor

[email protected] [email protected]

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Shapiro PE, Bale AE, Brash DE (1993) Proc Natl Acad Sci USA 90:4216 – 4220. 4.

[6] Dumaz N, Drougard C, Sarasin A, Daya-Grosjean L (1993) Proc Natl Acad Sci USA90:10529 –10533.

[7] Tron VA, Li G, Ho V, Trotter MJ. Ultraviolet radiation-induced p53 responses in the epidermis are differentiation-dependent. J Cutan Med Surg. 1999 Jul;3(5):280-3.

[8] Halicka HD, Huang X, Traganos F, King MA, Dai W, Darzynkiewicz Z. Histone H2AX phosphorylation after cell irradiation with UV-B: relationship to cell cycle phase and induction of apoptosis. Cell Cycle. 2005 Feb;4(2):339-45.

[9] Zhao H, Traganos F, Darzynkiewicz Z. Kinetics of the UV-induced DNA damage response in relation to cell cycle phase. Correlation with DNA replication. Cytometry A. 2010 Mar;77(3):285-93.

[10] Kastan MB, Onyekwere O, Sidransky D, Vogelstein B, Craig RW. Participation of p53 protein in the cellular response to DNA damage. Cancer Res. 1991 Dec 1;51(23 Pt 1):6304-11.

[11] Smith ML, Ford JM, Hollander MC, Bortnick RA, Amundson SA, Seo YR, Deng CX, Hanawalt PC, Fornace AJ Jr. p53-mediated DNA repair responses to UV radiation: studies of mouse cells lacking p53, p21, and/or gadd45 genes. Mol Cell Biol. 2000 May;20(10):3705-14.

[12] Christmann M, Tomicic MT, Origer J, Aasland D, Kaina B. c-Fos is required for excision repair of UV-light induced DNA lesions by triggering the re-synthesis of XPF. Nucleic Acids Res. 2006;34(22):6530-9. Epub 2006 Nov 27.

[13] Gasparro, F. P., Mitchnick, M. & Nash, J. F. (1998) Photochem. Photobiol. 68, 243–256.

[14] Emanuele E, Altabas V, Altabas K, Berardesca E. Topical Application of Preparations Containing DNA Repair Enzymes Prevents Ultraviolet-Induced Telomere Shortening and c-FOS Proto-Oncogene Hyperexpression in Human Skin: An Experimental Pilot Study. J Drugs Dermatol. 2013 Sep 1;12(9):1017-21.

[15] Berardesca E, Bertona M, Altabas K, Altabas V, Emanuele E. Reduced ultraviolet-induced DNA damage and apoptosis in human skin with topical application of a photolyase-containing DNA repair enzyme cream: clues to skin

cancer prevention. Mol Med Rep. 2012 Feb;5(2):570-4.

[16] Wittbrodt J, Shima A, Schartl M (2002) Medaka - a model organism from the far East. Nat Rev Genet3:53-64.

[17] Reinhardt HC, Schumacher B. The p53 network: cellular and systemic DNA damage responses in aging and cancer.Trends Genet. 2012 Mar;28(3):128-36.

[18] Mirzayans R, Andrais B, Scott A, Murray D. New insights into p53 signaling and cancer cell response to DNA damage: implications for cancer therapy. J Biomed Biotechnol. 2012;2012:170325.

[19] Cazzalini O, Scovassi AI, Savio M, Stivala LA, Prosperi E. Multiple roles of the cell cycle inhibitor p21(CDKN1A) in the DNA damage response. Mutat Res. 2010 Apr-Jun;704(1-3):12-20.

[20] Leeman MF, Curran S, Murray GI. The structure, regulation, and function of human matrix metalloproteinase-13. Crit Rev Biochem Mol Biol. 2002;37(3):149-66.

[21] Kuivanen TT, Jeskanen L, Kyllönen L, Impola U, Saarialho-Kere UK Transformation-specific matrix metalloproteinases, MMP-7 and MMP-13, are present in epithelial cells of keratoacanthomas. Mod Pathol. 2006 Sep;19(9):1203-12.

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B i o s e n s o r s B a s e d o n N a n o m e c h a n i c a l S y s t e m s Bionanomechanics lab, Institute of Microelectronics of Madrid, CSIC, Isaac Newton 8 (PTM), Tres Cantos, 28760 Madrid, Spain

The advances in micro- and nanofabrication technologies are enabling increasingly smaller mechanical transducers capable of detecting the forces, motion, mechanical properties and masses that emerge in biomolecular interactions and fundamental biological processes. Thus, biosensors based on nanomechanical systems have gained considerable relevance in the last decade. This talk will provide insight into the mechanical phenomena that occur in suspended mechanical structures when either biological adsorption or interactions take place on their surface. The talk will guides through the parameters that change as a consequence of biomolecular adsorption: mass, surface stress, effective Young’s modulus and viscoelasticity. The mathematical background needed to correctly interpret the output signals from nanomechanical biosensors will also be outlined. Other practical issues reviewed are the immobilization of biomolecular receptors on the surface of nanomechanical systems and methods to attain that in large arrays of sensors. I will describe then some relevant realizations nanomechanical systems that harness some of the mechanical effects cited above to achieve ultrasensitive biological detection. In this context, I will show our developments in optical instrumentation to obtain complete information about the nanomechanical phenomena that emerges in nanomechanical systems. The results open the door for the development of hybrid optomechanical devices for biological sensing. I will show several applications running in our laboratory that include: i) protein biomarker detection, ii) cancer cell nanomechanics, iii) DNA detection, and iv) protein nanomechanical spectrometry.

R e f e r e n c e s

[1] Domínguez, C.M. et al. Label-free DNA-based

detection of mycobacterium tuberculosis and rifampicin resistance through hydration induced stress in microcantilevers. Analytical chemistry 2015.

[2] Kosaka et al. Detection of cancer biomarkers in serum using a hybrid mechanical and optoplasmonic nanosensor. Nature Nanotechnology 2014.

[3] Ruz, J. et al. Physics of nanomechanical spectrometry of viruses. Scientific Reports 2014, 4

Javier Tamayo, P.M. Kosaka, V. Pini, J.J. Ruz, O. Malvar, C. Dominguez, M. Encinar, A. Calzado, D. Ramos, A. San Paulo, and M. Calleja

[email protected] www.imm-cnm.csic.es/bionano/en

NanoS pa in

Chemi s t ry

201 5

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I n d e x

N a n o S p a i n C h e m i s t r y 2 0 1 5

C o n t r i b u t i o n s

A l p h a b e t i c a l O r d e r

I : I n v i t e d / K : K e y n o t e / O : O r a l Page

Bahmani Jalali, Houman (Istanbul Technical University, Turkey)

A comparative study on optical properties of silver doped and silver decorated TiO2 thin films prepared

by sol-gel dip-coating method”

O 221

Benito-Lopez, Fernando (CIC microGUNE, Spain)

Building Smarter Microfluidic Devices with Functional Materials O 222

Bondarchuk, Alex (CIC energiGUNE, Spain)

Vanadium Nitride Thin Films And Nanoclusters: Growth And Electrochemical/XPS Characterization O 223

Bonifazi, Davide (Univ. of Namur, Belgium)

Molecular engineering through serendipity K 224

Cabrera Lara, Lourdes Isabel (Instituto de Química, UNAM, CCIQS, Mexico)

Design of a Photoanode for its Application in a Photoelectrochemical Cell O 225

Calzolai, Luigi (European Commission - JRC, Italy)

Methods to Measure the Particle Size Distribution of Nanoparticles in Complex Matrices O 226

Cano, Laida (University of the Basque Country (UPV/EHU), Spain)

Hybrid nanocomposite films based on polystyrene-block-polymethyl methacrylate block

copolymer and synthesized colloidal nanoparticles

O 227

Castillo, Juan R (Environmenta Sciences Institute. University Zaragoza, Spain)

Environmental Nanotechnology: An Analytical Platform for the characterization of Engineered

Nanomaterials

O 229

De Teresa, Jose M. (CSIC-University of Zaragoza, Spain)

Three-dimensional magnetic nanostructures grown by Focused Electron Beam Induced deposition O 231

Driess, Matthias (Technische Universität Berlin, Germany)

How to Unify Catalytic Processes for Energy Technologies? Merging Oxygen Evolution and Oxygen

Reduction Reactions With Multifunctional Metal Oxide Catalysts

K 232

Glaria, Arnaud (INSA Toulouse - Laboratoire de Physique et Chimie des Nano-Objets, France)

Coating of pure iron nanoparticles: towards a more efficient agent for hyperthermia O 233

Gourdon, André (CEMES/CNRS, France)

Advances in on-surface synthesis K 235

Klajn, Rafal (Weizmann Institute of Science, Israel)

Light-controlled self-assembly of non-photoresponsive nanoparticles K 236

Knez, Mato (CIC nanoGUNE, Spain)

Hybrid inorganic-(bio) organic materials through molecularlevel modification with vapor-phase

infiltration

K 237

Lee, Seunghwan (Technical University of Denmark, Denmark)

Proteolytic digestionof bovine submaxillary mucin (BSM)and its impacts on adsorption and lubricity at a

hydrophobic surface

O 238

Lewis, David (Nanonics Imaging Ltd, Israel)

Multidimensional characterization of Graphene at ultralow temperatures O 239

Licini, Giulia (Univ. of Padova, Italy)

Highly Symmetric Multidentate Ligands for Catalysis and Functional Materials K 240

Lizundia, Erlantz (University of the Basque Country (UPV/EHU), Spain)

Covalent grafting effects on the thermal properties of renewable Poly(L-lactide)/cellulose nanocrystal

nanocomposites

O 241

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I : I n v i t e d / K : K e y n o t e / O : O r a l Page

Matxain, Jon M. (UPV/EHU and DIPC, Spain)

Novel Solid Phases by Self-Assembling of Nanoclusters K 243

Morlieras, Jessica (CEA, France)

Lipid nanoparticles as delivery vehicle for bio-macromolecules O 244

Nijhuis, Christian Albertus (NUS, Singapore)

The Equivalent Circuits of Molecular Tunnel Junctions K 245

Okuda, Mitsuhiro (CIC nanoGUNE, Spain)

Protein and Peptide Chemistry for Nanotechnology: Biomineralization, Crystallization, Patterning and

Self-organization

K 247

Porath, Danny (The Hebrew University, Israel)

The Quest for Charge Transport in single Adsorbed Long DNA-Based Molecules K 248

Ravaine, Serge (University of Bordeaux, France)

Recent progress on patchy nanoparticles and their directional bonding K 250

Rocha, João (CICECO/University of Aveiro, Portugal)

SensingMolecules and Temperature at the Nanoscale K 252

Sadigh Akbari, Sina (Istanbul Technical University, Turkey)

Mechanical properties of zirconium dioxide and silicon nitride composites O 253

Salawu, Omobayo (King Fahd University of Petroleum and Minerals, Saudi Arabia)

Biosynthesis of Silver Nanoparticles and its Application in the Removal of Mercury (II) from Water O 254

Sola, Rebeca (Universidad del País Vasco, Spain)

Encapsulation of xanthene dyes into nanochannels of MgAPO-11 for optical applications O 256

Torres, Tomás (UAM, Spain)

Phthalocyanines for Artificial Photosynthetic Systems and Molecular Photovoltaics K 257

Yerushalmi, Roie (The Hebrew University, Israel)

Adjusting Metal Oxide Photocatalysis using Organic-Inorganic Hybrid Films Obtained by Molecular

Layer Deposition

K 258

Zamora, Felix (Universidad Autónoma de Madrid, Spain)

2D Materials based on Covalent Organic Frameworks O 259

Zhou, Zhongfu (Aberystwyth University, United Kingdom)

Synthesis of Functionalized Nano Zeolite and Zeolitic Imidazolate Framework Crystal O 260

Zukalova, Marketa (J. Heyrovsky Institute of Physical Chemistry, AS CR, Czech Republic)

Electrochemical, photoelectrochemical and photocatalytic properties of anatase with exposed (001)

facets

O 261

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A c o m p a r a t i v e s t u d y o n o p t i c a l

p r o p e r t i e s o f s i l v e r d o p e d a n d s i l v e r

d e c o r a t e d T i O 2 t h i n f i l m s p r e p a r e d b y

s o l - g e l d i p - c o a t i n g m e t h o d

1 Department of Nano Science and Nano Engineering, Istanbul Technical University,

Istanbul, Turkey 2 Department of Mechanical Engineering, Istanbul Technical University, Istanbul,

Turkey 3

Department of Materials Engineering, Istanbul Technical University, Istanbul, Turkey

In this study, silver doped and silver decorated TiO2

thin films were prepared by sol-gel dip-coating

method. Silver nitrate was dissolved in the TiO2 sol

to obtain Ag-doped samples with different dopant

concentration. The silver decorated TiO2 samples

were prepared by dip-coating pure TiO2 thin film in

AgNO3 aqueous solution. Thermal decomposition

of AgNO3 at 414 °C was the idea to prepare silver

decorated TiO2 thin films and coated samples were

annealed at different temperatures. The structure

and composition of prepared samples were

characterized by X-Ray diffraction (XRD) and X-Ray

photoelectron spectroscopy (XPS). The optical

transmission spectra of the samples were

measured using UV-Vis spectroscopy. The

refractive index of thin films was recorded by NKD.

The optical band gap was calculated using Tauc

plot (variation of (αhυ) 0.5 with hυ), obtained from

the absorption spectra of the samples.

Surprisingly, it was observed that silver cations

were reduced to metallic silver in sample which

was annealed at 120 °C [1]. The high band gap

value of pure and silver doped TiO2 thin films are

attributed to thermal stress effects produced in

the films [2-5].

Acknowledgements: The authors acknowledge the

Portuguese National Science Foundation (FCT) for

financial support under the contract PTDC/EQU-

EQU/101397/2008 and Programa Ciência 2007.

LEPAE, CEFT, LCM and DEMM at FEUP are greatly

acknowledged for the much appreciated facilities.

R e f e r e n c e s

[1] Ji-Woon Kwon et al., Bull. Korean Chem. Soc.

2005, Vol. 26, No. 5

[2] S.A Tomas et al, Thin Solid Films, 518, (2009),

1337–1340

[3] J. Yu et al. , Appl. Catal. B 60 (2005) 211

[4] T. Ivanova et al., Optical Materials 36 (2013)

207–213

[5] Ch. Yang et al. , Appl. Surf. Sci. 254 (2008)

2685–2689

F i g u r e s

Figure 1UV-Vis absorption spectra of prepared samples

Figure 2 Tauc plot of prepared samples

Houman Bahmani Jalali1, Hatice

Turhan2, Prof. Levent Trabzon

1,2,

Associate Prof. Huseyin Kizil1,3

[email protected]

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B u i l d i n g S m a r t e r M i c r o f l u i d i c

D e v i c e s w i t h F u n c t i o n a l M a t e r i a l s

1 CIC microGUNE, Arrasate-Mondragón. Spain

2 National Centre for Sensor Research, Dublin City University, Ireland

Nowadays, microfluidic technology is one of the

most expanding fields of research, having its

mayor contribution in the life science and

biotechnology sectors trough the development of

point-of care diagnostics tools and analytical

devices for environmental monitoring, food and

chemical analysis.[1]

The integration of chemical and/or biosensors in

the microchannels of microfluidic devices using

smart materials has several technological

advantages compared to bench based sensor

devices, such as reduction of the volume that is

needed to monitor certain analytes, minimisation

of cross contamination from the surrounding

environment and continuous flow operation,

among others, Fig. 1a.[2] Moreover, the

incorporation of stimuli responsive materials in

microfluidics is enabling new ways of fluidic

control and manipulation that overpasses existing

technology, opening new avenues for the

commercialization of these devices (Fig. 1b).[3]

In this contribution we present the latest advances

carried out at CIC microGUNE on the integration of

smart materials in microfluidic chips, in order to

provide new functionalities to microfluidic

platforms.

R e f e r e n c e s

[1] R. Byrne, F. Benito-Lopez, D. Diamond,

Materials Today, 16 July-August (2010) 16.

[2] L. Florea, C. Fay, E. Lahiff, T. Phelan, N. E.

O’Connor, B. Corcoran, D. Diamond, F. Benito-

Lopez, Lab Chip, 13 (2013) 1079.

[3] F. Benito-Lopez, M. Antoñana-Díez, V. F.

Curto, D. Diamond, V. Castro-López, Lab Chip,

14 (2014) 3530.

F i g u r e s

Figure 1:(a) Pictures of polyaniline functionalised PDMS chips, acidic

on the top and basic on the bottom, as pH sensor. (b) Picture of an

ionogel microvalve (7 μL) inserted in the holder with integrated

heaters at the bottom for fluid control.

J. Saez,1 Tuğçe Akyazi,

1

L. Florea, 2 D. Diamond,

2

F. Benito-Lopez1, 2

[email protected]

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V a n a d i u m N i t r i d e T h i n F i l m s A n d

N a n o c l u s t e r s : G r o w t h A n d

E l e c t r o c h e m i c a l / X P S

CIC energiGUNE

C/ Albert Einstein 48, 01510 Minano, Alava, Spain

Pseudocapacitive or electrochemically active

materials can achieve capacitance values up to 10

times greater than those obtained by materials

based only on an electric double layer (EDL)

mechanism. The pseudocapacitive behavior of

transition metal oxides has been extensively

studied in the last decades and assigned to redox

reactions occurring at the surface of the material.

Very recently, transition metal nitrides such as

MoxN, VN or TiN have emerged as promising

electrode materials for electrochemical capacitors.

These materials are inexpensive, have a high molar

density good chemical resistance and, most

importantly, in contrast to oxides they exhibit very

high electronic conductivity value. Extremely high

specific capacitance values of 1340 F g-1

was

reported for nanostructured VN [1]. To shed some

light on the mechanism of such huge capacitance

we have carried out a comparative study of VN

thin films and VN nanoclusters grown and

characterized in-situ to relate electrochemical

properties with the structure and composition of

the surface of vanadium nitride.

An UHV system (SPECS) equipped with tools for

XPS, e-beam assisted evaporation of metals, high

pressure cell and electrochemical cell for I-V

cycling was used for in-situ synthesis and

characterization.

A recipe to grow VN thin films and nanoclusters via

direct nitridation of thin vanadium film in

atmosphere of 1 bar N2 at temperature 800oC has

been developed. Stoichiometry of the VNxOy

compounds can be controlled by post oxidation of

VN in oxygen atmosphere at elevated

temperature. Growth of VN nanoclusters using the

same procedure has been performed on HOPG

surface.

Electrochemical characterization of VN thin films

demonstrated impressive areal capacitance of

~2000 µFcm-2

in 1M KOH electrolyte at scan rate

1Vs-1

. XPS characterization was applied to

elucidate electrochemical reactions occurring on

the surface of VN films.

R e f e r e n c e s

[1] R. Byrne, F. Benito-Lopez, D. Diamond,

Materials Today, 16 July-August (2010) 16.

Oleksandr Bondarchuk,

Yan Zhang, Eider Goikolea, Teófilo Rojo,

Roman Mysyk

[email protected]

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M o l e c u l a r e n g i n e e r i n g t h r o u g h

s e r e n d i p i t y

Namur Research College (NARC) and Department of Chemistry

University of Namur, Rue de Bruxelles 61 , 5000, Namur, Belgium

Organic architectures are considered amongst the

most promising candidates for engineering

molecular-based devices. It is however necessary

to develop systems that can form at interfaces

organized molecular assemblies featuring

addressable and controllable arrangements. In this

respect, the hierarchical self-assembly of organic

molecules featuring complementary non-covalent

recognition sites allowing the simultaneous

assembly of several units and long-range order is

one of the most promising approaches.

In this talk, I will describe our approaches to

engineer multidimensional structures through the

exploitation of weak interactions established by

programmed organic-based molecules. Quoting a

letter (dated 28 January 1754) from Horace

Walpole to Horace Mann, he said he formed it

from the Persian fairy tale “The Three Princes of

Serendip”, whose heroes "were always making

discoveries, by accidents and sagacity, of things

they were not in quest of". Therefore, specific

serendipitous examples will be discussed with the

attempt to answer to the question of whether and

how the supramolecular approach can bridge

organic chemistry with molecular organization and

to which extend we can achieve macroscopic

functions solely through molecular engineering.

Davide Bonifazi

[email protected]

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D e s i g n o f a P h o t o a n o d e f o r i t s

A p p l i c a t i o n i n a P h o t o e l e c t r o c h e m i c a l

C e l l

Chemistry Insitute, Universidad Nacional Autónoma de México; Centro Conjunto en

Investigación Química Sustentable UAEMex-UNAM Km. 14.5 Carretera

Toluca-Atlacomulco C.P. 50200, Toluca, Estado de México, México

Since the pioneering work of Michael Grätzel on

utilizing TiO2 nanoparticles in dye sensitized solar

cell (DSSC), much research has been devoted to

DSSC research. However, there are a number of

challenging issues remaining, for example,

insufficient sunlight harvesting by the sensitizer,

inefficient electron transport in the

photoelectrode and the stability concern. The aim

of this work was to investigate ZnO as a

semiconductor material in the construction of

photoanodes for enhanced DSSC efficiency [1-3].

Au and AuCu nanoparticles are also used in the

design of photoanodes. Even when this work has

been performed, the use of electrochemical

techniques for its construction is of interest, since

no treatment has been given to the system after

its construction.

The ZnO/Au and ZnO/AuCu photoanodes with the

ZnO structure being nanosheet/nanorod on

Indium-tin oxide glass from substrate to surface

was prepared by electrodeposition method [1-3].

Gold nanoparticles and AuCu nanoparticles are

electrodeposited without the presence of an

organic stabilizer. The systems ZnO/Au and

ZnO/AuCu (electrochemically constructed) are

compared with other photoanodes, where Au

nanoparticles and AuCu nanoparticles have been

anchored to ZnO nanorods by means of an organic

stabilizer (colloidally constructed) (Figure 1).

Photoanodes were characterized by several

analytical methods, X ray diffraction, scanning

electron microscopy, UV-Vis and Raman

spectroscopy, and electrochemically. Structural

differences were observed between colloidally and

electrochemically constructed systems, specially

by electrochemical characterization.

Acknowledgements: The authors will like to

acknowledgment financial support from PAPIIT

(UNAM) with the project number IB200113-

RR260113. Also, the authors acknowledge

Professor Abel Moreno, Ph.D. Ivan García Orozco,

Ph.D. Rosa María Gómez Espinosa, M. SC.

Alejandra Núñez, M. Sc. Lizbeth Triana, and Ph.D.

Marco Antonio Camacho López for their support in

the analytical characterization.

R e f e r e n c e s

[1] Tanujjal Bora,Htet H. Kyaw, Soumik Sarkar,

Samir K. Pal, and Joydeep Dutta, Beilstein J.

Nanotechnol., 2 (2011), 681.

[2] Tanujjal Bora, Htet H. Kyaw, and Joydeep

Dutta, Materials Science Forum, 771 (2014),

91.

[3] C. K. N. Peh, L. KE, G. W. Ho, Materials Letters,

12 (2010), 1372.

F i g u r e s

Figure 1: Schematic diagram for the preparation of ZnO/Au systems

by using a colloidal method or an electrochemical method.

Lourdes I. Cabrera Lara,

A. Laura González Mendoza,

Raúl Torres Cadena,

C. Carina Pareja Riv

[email protected]

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M e t h o d s t o M e a s u r e t h e P a r t i c l e S i z e

D i s t r i b u t i o n o f N a n o p a r t i c l e s i n

C o m p l e x M a t r i c e s

European Commission - DG Joint Research Centre.

Institute for Health and Consumer Protection, Italy

Nowadays, microfluidic technology is one of the

Nanoparticles are already used in several

consumer products including food, food packaging

and cosmetics and their detection and

measurement represent a particularly difficult

challenge [1].

The European Commission has published in

October 2011 its recommendation on the

definition of nanomaterial [2]. This definition calls

for the measurement of the number based particle

size distribution in the 1-100 nm size range of all

the primary particles present in the sample

independently of whether they are in a free,

unbound state or as part of an

aggregate/agglomerate. This definition does

present great technical challenges for developing

measuring methods [3].

In this presentation we will illustrate the

development of techniques for the size

measurement of nanoparticles when addressing

this new definition of nanomaterials. These new

methods are based on the combination of size

separation techniques, such as flow field flow

fractionation [4], with identification and

quantification techniques, such as ICP-MS.

The problems to be overcome in measuring

nanoparticles in food and consumer products will

be illustrated with some practical examples,

including interlaboratory performance studies

organized by JRC.

R e f e r e n c e s

[1] Calzolai L. et al., Review on Measuring

Nanoparticles Size Distribution in Food and

Consumer Products. Food Additives &

Contaminants 2012, Part A 29: 1183-1193.

[2] Recommendation on the Definition of

nanomaterials (2011/696/EU).

[3] T. Linsinger et al., Requirements on

measurements for the implementation of the

European Commission definition of the term

'nanomaterial'. JRC Reference Reports. EUR

25404 EN (2012).

[4] Calzolai L. Et al., Separation and

characterization of gold nanoparticle

mixtures by flow-field-flow fractionation. J

Chromatogr A. 2011 Jul 8; 1218(27): 4234-9.

L. Calzolai,

C. Cascio, D. Gilliland, F. Rossi

[email protected]

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H y b r i d n a n o c o m p o s i t e f i l m s b a s e d o n

p o l y s t y r e n e - b l o c k - p o l y m e t h y l

m e t h a c r y l a t e b l o c k c o p o l y m e r a n d

s y n t h e s i z e d c o l l o i d a l n a n o p a r t i c l e s

1 Group `Materials + Technologies´, Chemical Engineering and Environmental

Department, Polytechnic School, University of the Basque Country (UPV/EHU), Plaza

Europa 1, 20018 Donostia-n, Spain 2 CNR-IPCF Bari Division, Chemistry Department, University of Bari, Via Orabona 4,

70126 Bari, Italy

The development of novel hybrid nanocomposites

by means of the combination of block copolymers

acting as matrices with nanometric materials is

gaining increasing interest in the material science

field. Block copolymers are ideal materials for this

purpose as chemically different blocks are

covalently linked with each other, giving them the

ability to self-assemble into different ordered

nanoscale morphologies. On the other hand,

nanoscale materials, in particular nanoparticles,

possess interesting properties, such as electrical,

magnetic, mechanical or optical, among others.

Thus, the combination between nanostructured

block copolymers and nanoparticles will result in

hybrid inorganic/organic materials with functional

properties.

In the past decade, many researchers have used

polystyrene-block-polymethyl methacrylate (PS-b-

PMMA) block copolymer as a template to create

hybrid inorganic/organic nanocomposites by

adding different inorganic nanoparticles (NP) to

the polymeric matrix [1-4]. In this case, both ex-

situ synthesized titanium oxide nanorods and iron

oxide nanocrystals have been incorporated into

the PS-b-PMMA block copolymer [3,4]. The

synthesis procedure carried out to obtain colloidal

titanium oxide nanorods and iron oxide

nanocrystals [5] led to oleic acid capped

nanoparticles, which make them more compatible

with one block of the block copolymer, the PS

block in particular. The characterization of the

nanoparticles was performed by transmission

electron microscopy (TEM) and Fourier transform

infrared spectroscopy (FTIR) in order to analyze

the size and shape of nanoparticles and to confirm

the presence of surfactant on their surface. Thank

to this capping layer, the content of nanoparticles

in the block copolymer can achieve values up to

50-60 wt % in respect to the block copolymer

content. NP/PS-b-PMMA nanocomposites were

characterized in terms of their morphology by

atomic force microscopy (AFM) and scanning force

microscopy (SEM) and also their optical, electrical

and magnetic properties were studied.

Acknowledgements: Financial support from

Spanish Ministry of Economy and Competitiveness

in the frame of MAT2012-31675 project and from

the Basque Government funded Grupos

Consolidados project (IT776-13) is gratefully

acknowledged. L. C. thanks Basque Government

for the PhD Fellowship (Programas de becas para

formación y perfeccionamiento de personal

investigador (BFI-2011-218)).

R e f e r e n c e s

[1] Weng C. C., Wei K. H., Chemistry of Materials,

15 (2003) 2936-2941.

[2] Xu C., Ohno K., Ladmiral V., Milkie D. E.,

Kikkawa J. M., Composto, R. J.,

Macromolecules, 42 (2009) 1219−1228.

[3] Cano L., Gutierrez J., Tercjak A., Journal of

Physical Chemistry C, 117 (2013) 1151-1156.

[4] Cano L., Di Mauro A. E., Striccoli M., Curri M.

L., Tercjak A., Applied Materials & Interfaces, 6

(2014) 11805-11814.

[5] Buonsanti R., Grillo V., Carlino E., Giannini C.,

Curri M. L., Innocenti C., Sangregorio C.,

Achterhold K., Parak F. G., Agostiano A.,

Cozzoli P. D., Journal of the American Chemical

Society, 128 (2006) 16953-16970.

L. Cano1, A. E. Di Mauro

2,

J. Gutierrez1, M. Striccoli

2,

M. L. Curri2, A. Tercjak

1

[email protected]

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F i g u r e s

Figure 1: AFM phase images (2 µm x 2 µm) of a) neat PS-b-PMMA diblock copolymer and its nanocomposites with b) 1, c) 10 and d) 50 wt %

synthesized TiO2 nanorods

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E N V I R O N M E N T A L N A N O T E C H N O L O G Y :

A n A n a l y t i c a l P l a t f o r m f o r t h e

c h a r a c t e r i z a t i o n o f E n g i n e e r e d

N a n o m a t e r i a l s

Group of Analytical Spectroscopy and Sensors (GEAS),

Institute of Environmental Sciences (IUCA), University of Zaragoza,

Pedro Cerbuna 12, Zaragoza, 50009, Spain

The lack of reliable methods to determine

nanoparticles identity, characteristics and

concentrations, as well as their transformations in

complex systems (environmental and biological) is

one of the most significant troubles in

nanosciences. In the case of environmental

nanosciences analysis at environmentally relevant

concentrations adds an extra level of difficulty.

Inductively coupled plasma mass spectrometry

(ICPMS) is a multielemental-specific

technique,which is used routinely for the

quantification of the elemental content of

nanoparticles and nanomaterials. However, novel

approaches based on the use of ICPMS are

emerging. Direct analysis based on the detection

of individual nanoparticles (single particle-ICPMS)

[1] and hyphenation of flow field flow fractionation

(FlFFF) techniques to ICPMS [2] are two of the

most promising ones. Whereas FlFFF-ICPMS allows

the separation and quantification of nanoparticles

according to their size, single particle detection

ICPMS provides information about dissolved and

nanoparticle forms of an element, size

distributions, and number and mass concentration

without previous separation. The use of

ultrafiltration in combination with ICP-MS analysis

allows to fractionate an element in a suspension as

dissolved and nanoparticle forms, complementing

and supporting the information provided by the

two other methods. A platform of analytical

methods based in ultrafiltration-ICPMS, single

particle-ICPMS and FlFFFICPMS is proposed to face

and solve different types of nanometrological

problems, which are current challenges in

nanosciences, as well as in analytical chemistry.

When NPs reach a biological environment,

medium components, especially proteins, compete

for binding to the NP’s surface, leading to

development of a new interface, commonly

referred to as the “protein corona”. The rich

protein shell gives the NPs a biological identity that

can be very different from their synthetic one, in

terms of their chemical-physical properties. There

are many factors influencing the detailed nature of

the NP biomolecule corona, with NP size, shape,

surface charge, and solubility all playing a role in

the interaction of the NPs with proteins.

Understanding NP-protein interaction is crucial for

both the bioapplications and safety of

nanomaterials. Optimización of different

electrophoretic methods (PAGE and especially

AGE) will be shown for AgNP-proteins corona

characterization.

The physicochemical characterization of CeO2 NPs

entails a series of analytical challenges related to

their small size, nature, and solution

physicochemistry, as well as to small concentration

in environmental samples. Sensitive methods

providing low limits of detection is required. We

will shown methods to couple a fractionation

technique (Field Flow Fractionation, FFF) to a

sensitive detector (ICP-MS) to reach a fine

characterization of CeO2 NPs based on the particle

size.

State of the art of the analytical platform

methodologies will be presented, discussing their

performance, challenges, limitations and

complementarity. Application to selected cases

about releasing of nanoparticles from

nanocomposites will also be presented, specially

for Ag and CeO2 nanomaterials.

J.R. Castillo,

F.Laborda E. Bolea I. Abad J. Jiménez-

Lamana , L.Sanchez-Garcia,

C.Cubel, M.S Jimenez, M.T Gomez

[email protected]

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Acknowledgements: This work was supported by

the Spanish Ministry of Economy and

Competitiveness, project CTQ2012-38091-C02-01.

R e f e r e n c e s

[1] F. Laborda, E. Bolea, J. Jimenez-Lamana.

Single Particle Inductively Coupled Plasma

Mass Spectrometry: A Powerful Tool for

Nanoanalysis. Anal. Chem., 86, 2270, 2014.

[2] E. Bolea, J. Jimenez-Lamana, F. Laborda, I.

Abad-Alvaro, C. Blade, L. Arola, J. R. Castillo.

Detection and characterization of silver

nanoparticles and dissolved species of silver

in culture medium and cells by AsFlFFF-UV-

Vis-ICPMS: application to nanotoxicity tests.

Analyst, 139, 914, 2014.

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T h r e e - d i m e n s i o n a l m a g n e t i c

n a n o s t r u c t u r e s g r o w n b y

F o c u s e d E l e c t r o n

B e a m I n d u c e d d e p o s i t i o n

1

Instituto de Ciencia de Materiales de Aragón (ICMA), CSIC-University of Zaragoza and

Department of Condensed Matter Physics, Faculty of Sciences, 50009, Zaragoza, Spain 2

CEMES-CNRS 29, rue Jeanne Marvig, B.P. 94347 F-31055, Toulouse Cedex, France 3 Thin Film Magnetism Group, Cavendish Laboratory, University of Cambridge, JJ

Thomson Avenue, CB3 0HE, Cambridge UK 4

Laboratorio de Microscopias Avanzadas (LMA), Instituto de Nanociencia de Aragón

(INA),University of Zaragoza, 50018, Zaragoza, Spain

Focused Electron Beam Induced deposition (FEBID)

can be assimilated to a local Chemical Vapour

Deposition (CVD) technique where the dissociation

energy to break the precursor molecules is not

provided thermally but through a focused electron

beam [1]. By using Cobased and Fe-based

metallorganic precursors, a large variety of two-

dimensional magnetic nanostructures have been

created by FEBID, as recently reviewed by De

Teresa and Fernández-Pacheco [2]. We have

recently succeeded in the growth of three-

dimensional cobalt nanowires by FEBID, which

show good magnetic response as probed by

magneto-optical Kerr effect [3]. In the present

contribution, we will report the subsequent effort

towards the understanding of the growth

strategies that permit to fabricate three-

dimensional cobalt nanowires with high cobalt

content and aspect ratio. Our work demonstrate

that this can be achieved using a pulsed deposition

technique and the appropriate precursor flux,

electron dwell time and refresh time.

R e f e r e n c e s

[1] Book “Nanofabrication using focused ion and

electron beams: principles and

applications(2012), Editors: P. E. Russell, I.

Utke, S. Moshkalev, Oxford University Press

[2] J.M. De Teresa and A. Fernández-Pacheco,

Appl. Phys. A 117 (2014) 1645

[3] A. Fernández-Pacheco et al., Sci. Rep. 3 (2013)

1492

[4] L. Serrano-Ramón et al., manuscript in

preparation

F i g u r e s

Figure 1: Figure caption. Left. Two-loop three-dimensional cobalt nanowire grown by FEBID. Middle: High aspect-ratio three-dimensional

cobalt nanowire grown by FEBID. Right: Magnetic signal obtained in the electron holography experiments performed in one of the cobalt

nanowires grown by FEBID.

L. Serrano-Ramón1,2

,

A. Fernández-Pacheco3,

L. A. Rodríguez4, C. Magén

4,

C. Gatel2, E. Snoeck

2,

M.R. Ibarra4, J. M. De Teresa

1,4

[email protected]

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H o w t o U n i f y C a t a l y t i c P r o c e s s e s f o r

E n e r g y T e c h n o l o g i e s ?

M e r g i n g O x y g e n E v o l u t i o n a n d

O x y g e n R e d u c t i o n R e a c t i o n s

W i t h M u l t i f u n c t i o n a l M e t a l O x i d e

C a t a l y s t s

Department of Chemistry: Metalorganics and Inorganic Materials, Technische

Universität Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany

Attaining efficient catalysis of both the oxygen

evolution reaction (OER) and oxygen reduction

reaction (ORR) plays a major role in energy

conversion and storage devices, especially in fuel

cells, metal-air batteries, electrolysis cells, and in

solar fuel synthetic reactors.[1-8]

Design and

development of active materials that are naturally

abundant, eco-friendly and economically viable

have still remained an unresolved problem in

energy conversion and storage. Interestingly, in

nature, OER occurs in photosystem II (PS II) that is

present in the green plants, algae and

cyanobacteria The reaction proceeds in the PS II

and is catalyzed by a Mn4Ca cluster, the oxygen

evolution center (OEC) by the four-electron and

four-proton redox reaction, and has been the

inspiration to resolve the predicament of

sustainable energy production. Although

numerous efforts have been made to utilize the

naturally occurring enzymes towards

electrochemical OER, the instability of such

enzymes at operating conditions causes the major

concern for commercialization. Over the years,

extensive investigations have been carried out to

find suitable OER catalysts which could work very

efficiently for the reaction of water splitting (solar

fuels). The best known materials for OER are based

on ruthenium and iridium species. However, the

scarcity of such materials limits their large scale

application. On the other hand, platinum-based

materials are known to be the most active for the

reverse reaction of OER, i.e., for ORR in fuel cells

and metal-air batteries. The main drawback of

using platinum as the catalyst is the high cost and

their deactivation during continuous operation.

Similarly, the attempts have also been also made

to couple (or even merge) OER and ORR with the

respective high performance catalysts to explore

bifunctionality. The highly active ruthenium- or

iridium-based OER catalysts are less effective for

ORR and the efficient platinum-based ORR

materials are moderately active for their reverse

reaction, OER.

Recently, we could show that the OER and ORR

processes can be merged in single multifunctional

metal oxide catalysts which are easily accessible by

the single-source precursor approach.

For example, we reported on cobalt manganese

spinels 1 and iron cobalt oxides 2 which represent

unprecedented multifunctional catalysts that are

highly active, remarkably stable, and unify

electrochemical oxygen evolution reaction (OER) at

both alkaline and neutral pH, oxidant-driven,

photochemical water oxidation in various pH, and

electrochemical oxygen reduction reaction (ORR)

in alkaline medium. These and related materials

syntheses with the ultimate aim to unify catalytic

processes for energy technology will be discussed

in the talk.

R e f e r e n c e s

1. P. W. Menezes, A. Indra, N. R. Sahraie, A.

Bergmann,P. Strasser, and M. Driess

ChemSusChem 2015, 8, 164.

2. A. Indra, P. W. Menezes, N. R. Sahraie, A.

Bergmann, C. Das, M. Tallarida, D. Schmeißer,

P. Strasser, and M. Driess J. Am. Chem. Soc.

2014, 136, 17530.

Matthias Driess, Prashanth Menezes

and Arindam Indra

[email protected]

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C o a t i n g o f p u r e i r o n n a n o p a r t i c l e s :

t o w a r d s a m o r e e f f i c i e n t a g e n t f o r

h y p e r t h e r m i a

Laboratoire de Physique et Chimie des Nano-Objets (LPCNO)

UMR INSA/UPS/CNRS 5215

35 avenue de Rangueil, 31077 Toulouse CEDEX 04, France

Major breakthroughs on the design of

nanoparticles (NPs) for theranostic purposes have

been reported over the past years.[1] Among all

the different techniques available that enable NPs-

mediated treatment, magnetic hyperthermia

appears as a powerful one. Indeed, many reports

have showed that iron oxides particles can

efficiently increase locally the temperature and kill

malignant cells either in vitro or in vivo.[2] One

other material of interest is pure iron NPs which

exhibit a higher saturation magnetization than the

iron oxides generally used. Indeed, using iron

would permit to obtain values of the Specific

Absorption Rate (SAR) more than two times larger

than the ones obtained with its classical oxide

counterparts (Figure 1a).[3] However, the use of

these NPs for treatment needs water transfer

where one great challenge is to avoid the oxidation

of the metal and thus the loss of the magnetic

properties. To tackle this phenomenon, we have

developed an efficient protocol to perfectly coat

the metallic particles with a silica shell in a non

alcoholic media.[4] Here, we will describe in details

this approach applied to Fe NPs (Figure 1b) and

show that whatever the thickness of the coating,

the iron core of the particles is preserved.

Moreover, depending on the experimental

conditions, it is possible to modulate the number

of NPs encapsulated and to independently study

magnetic coupling between the metallic cores.

One last important point is the transfer of these

nanomaterials in biological media and we will

present an overview of our recent findings. Finally,

we will explain how the control of the surface

functionalization as well as the NPs aggregation

will be of great importance for future

hyperthermia

measurements performed in vitro.

R e f e r e n c e s

[1] (a) A. Louie, Chem. Rev., 110 (2010) 3146; (c)

Q. Le Trequesser, H. Seznec, M.-H. Delville,

Nanotechnol. Rev., 2 (2013) 125. (b) E.-K.

Lim, T. Kim, S. Paik, S. Haam, Y.-M. Huh, K.

Lee, Chem. Rev., DOI: 10.1021/cr300213b.

[2] (a) L. H. Reddy, J. L. Arias, J. Nicolas, P.

Couvreur, Chem. Rev., 112 (2012) 5818; (b)

D. Yoo, J.-H. Lee, T.-H. Shin, J. Cheon, Acc.

Chem. Res., 44 (2011) 863.

[3] (a) J. Carrey, M. Mehdaoui, M. Respaud, J.

App. Phys., 109 (2011) 083921; (b) B.

Mehdaoui, A. Meffre, J. Carrey, S. Lachaize,

L.-M. Lacroix, M. Gougeon, B. Chaudret, M.

Respaud, Adv. Funct. Mater., 21 (2011),

4573.

[4] (a) N. El-Hawi, C. Nayral, F. Delpech, Y.

Coppel, A. Cornejo, A. Castel, B. Chaudret,

Langmuir, 25 (2009) 7540; (b) F. Delpech, C.

Nayral, N. El-Hawi, patent WO 2009071794.

Arnaud Glaria,

Wilfried Sojo Ojo, Sébastien Lachaize,

Fabien Delpech, Bruno Chaudret,

Céline Nayral, Nicolas Hallali,

Reasmey Tan, Julian Carrey

[email protected],

[email protected],

[email protected]

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F i g u r e s

Figure 1: (a) hysteresis loops calculated for different diameters of Fe NPs; (b) TEM micrographs ofFe(0) NPs before and after coating.

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A d v a n c e s i n o n - s u r f a c e s y n t h e s i s

The NanoSciences Group, CEMES-CNRS, 29 Rue Marvig 31055 Toulouse,

France

In less than a decade, on-surface synthesis by

covalent coupling of reactive precursors adsorbed

on metallic, semi-conducting or insulating films has

emerged as a powerful approach for the

fabrication of novel molecular architectures with

potential applications in nanoelectronics,

optoelectronics and other fields where new low-

dimensional materials with tailored properties are

needed [1 , 2].

Using this bottom-up route, atomically precise

grapheme nanoribbons,

polyphthalocyanines films, metal

coordination frameworks,

porous metal networks,

superhoneycomb frameworks,

etc. have been synthesized.

We will introduce current

developments in this field such

as new reactions, mechanisms,

optimization of the syntheses, semi-conducting

surfaces and perspectives [2].

Recent advances of thermally or photochemically

activated coupling reactions on bulk insulators that

have opened new avenues for molecular

electronics and the fabrication of molecular logic

gates will also be presented.

R e f e r e n c e s

[1] G.Franc and A.Gourdon, Phys. Chem. Chem.

Phys. 13, (2011)14283–14292.

[2] J. Méndez, M. Francisca López and José A.

Martín-Gago, Chem. Soc. Rev. 40, (2011) 4578-

4590.

[3] “On-surface chemistry”in “Advances in Atom

and Single Molecule Machines”, Springer

Series Ed. A. Gourdon (2016) In the press.

[4] R. Lindner, P. Rahe, M. Kittelmann, A.

Gourdon, R. Bechstein, and A.Kühnle, Angew.

Chem. Int. Ed. Engl. 53, (2014) 7952-7955

F i g u r e s

Figure 1: Surface controlled polymerization of a C60 monolayer on

calcite [3]

André Gourdon

[email protected]

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L i g h t - c o n t r o l l e d s e l f - a s s e m b l y o f n o n -

p h o t o r e s p o n s i v e n a n o p a r t i c l e s

Department of Organic Chemistry, Weizmann Institute of Science,

Rehovot 76100, Israel

The ability to reversibly guide the assembly of

nanosized objects with external stimuli, in

particular light, is of fundamental importance, and

it contributes to the development of applications

as diverse as nanofabrication [1] and controlled

drug delivery [2]. However, all systems described

to date are based on nanoparticles that are

inherently photoresponsive, which makes their

preparation cumbersome, and can significantly

hamper their performance [3]. Here, we describe a

conceptually new methodology to reversibly

assemble nanoparticles using light, which does not

require that the particles be functionalized with

light-sensitive ligands. Our strategy is based on the

use of a photoswitchable medium that responds to

light in such a way that it modulates the

interparticle interactions. Nanoparticle assembly

proceeds quantitatively and without apparent

fatigue in solution as well as in gels. Exposing the

gels to light in a spatially controlled manner

allowed us to draw images that spontaneously

disappeared after a specific period of time.

R e f e r e n c e s

[1] Nie, Z. H.; Petukhova, A.; Kumacheva, E. Nat.

Nanotech. 5 (2010), 15.

[2] Sun, C.; Lee, J. S. H.; Zhang, M. Q. Adv. Drug

Deliv. Rev. 60 (2008), 1252.

[3] Klajn, R.; Stoddart, J. F.; Grzybowski, B. A.

Chem. Soc. Rev. 39 (2010), 2203.

Rafal Klajn

[email protected]

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H y b r i d i n o r g a n i c - ( b i o ) o r g a n i c

m a t e r i a l s t h r o u g h m o l e c u l a r l e v e l

m o d i f i c a t i o n w i t h v a p o r - p h a s e

i n f i l t r a t i o n 1CIC nanoGUNE, 20018 Donostia-San Sebastian,Spain

2Centrode Física de Materiales, Material PhysicsCenter, 20018

Donostia-San Sebastian, Spain 3IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain

Polymeric materials of various types are

anticipated being the most important building

blocks for future applications. The reasons lie in

their established processes for mass production in

various shapes, mechanical flexibility for easy

handling, compatibility for roll-to-roll production

processes, versatility in functionalization, etc.

While for many applications synthetic polymers

are still without alternative, manyapproaches seek

for a sustainable substitute, whenever suitability is

given.

Cellulose represents the most abundant

biopolymers on Earth and is the fundamental

building block of plants and their subsequent

products such as paper and cotton. Furthermore

recent and significant interest has been expressed

in using cellulose based materials in a wide variety

of applications, in everything from

supercapacitors, batteries, and solar cells, to

advanced functional filters in waste water

treatment, and even wearable electronics. Several

techniques have been proposed for the

functionalization of these next generation

materials including, sol-gel, CVD, etc.However, one

of the most promising techniques is atomic layer

deposition (ALD).ALD is a similar, though

chemically distinct, form of CVD that allows low

temperature deposition, often below 100°C,

monolayer material growth, and extreme

conformality over even the most stringent

geometries. A recent modification to ALD, termed

vapor phase metal infiltration, allows for molecular

scale modification of a variety of biological and

syntheticsubstrates and scaffolds including; spider

silk, collagen, porphyrins, and

polytetrafluoroethylene (PTFE) towards and

entirely new class of hybrid materials. As well

asamore detailed understanding of the reaction

between these organic substrates and the metal-

organic precursors commonly used in standard

ALD processes.

Here we report the modification of a variety of

polymers, including spider silk, collagen, PTFE,

Kevlar, cellulose and cotton with common ALD

precursors, trimethyl aluminum and diethyl zinc.

Our findings show that the precursors induce

small, but important changes to the polymer upon

chemical interaction and that each precursorhas

different potential reaction pathways. For

characterization a variety of methods have been

applied, including FTIR, XRD, NMR, XPSand Raman

spectroscopy. We also discuss how these small

molecular scale changes lead to large changes in

the bulk mechanical properties of the substrates as

studied through uniaxial tensile testing. These

experiments point at the possibility of using this

infiltration method to alter the properties of the

materials by hybridizing inorganic ceramics with a

polymeric substrate.

K.E. Gregorczyk1, M. Garcia

1,

I. Azpitarte1, D. Pickup

2, C. Rogero

2,

and M. Knez1,3

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P r o t e o l y t i c d i g e s t i o n o f b o v i n e

s u b m a x i l l a r y m u c i n ( B S M ) a n d i t s

i m p a c t s o n a d s o r p t i o n a n d l u b r i c i t y a t

a h y d r o p h o b i c s u r f a c e

1Technical University of Denmark, Department of Mechanical Engineering, DK-2800

Kgs. Lyngby, Denmark, 2Enzyme and Protein Chemistry, Department of Systems Biology, Technical University

of Denmark, DK-2800 Kgs. Lyngby, Denmark

Mucin is the major constituent of the mucous

secretions that cover epithelial surfaces exposed

to the environment in human/animals. The

primary function of mucous gels is known to

provide protection to epithelial surfaces from

invasive microbes and physical insults by forming a

lubricating layer. About 50 to 80% of the molecular

weight of mucin is attributed from post-

translational N- and O-linked glycosidic

modifications. The ability of the glycosidic

modifications to retain water at the epithelial

surface facilitates lubrication. N- and C-terminal

interactions and also entanglement of the

glycosidic modifications lead to a viscoelastic

material that offers excellent lubrication

properties [1-4]. Since mucins are composed of

various biochemical functional moieties, it is

expected that biochemical treatments of mucins

lead to alteration in the structure, conformation,

capabilities to adsorb onto engineering material

surfaces, and consequently lubricity. In this study,

proteolytic digestion on bovine submaxillary mucin

(BSM) and its impacts on the size, structure,

surface adsorption, and lubricating properties

were studied. Two proteases with distinctly

different cleavage specificities, namely trypsin and

pepsin, were employed. SDS-PAGE analysis using

two staining methods showed that only the

unglycosylated terminal regions of BSM were

degraded by the proteases and the central,

glycosylated regions remain nearly unaffected. Size

exclusion chromatography (SEC) and dynamic light

scattering (DLS) studies indicated that tryptic

digestion mainly led to the reduction in size,

whereas pepsin digestion rather led to the

increase in size of BSM. Less complete cleavage of

terminal peptides by pepsin and subsequent

aggregation between BSMs were thought to be

responsible for the increased size. Far-UV circular

dichroism (CD) spectra of the protease-treated

BSMs showed a slight change in the secondary

structure owing to the removal of terminal

domains, but the overall random coil structural

conformation by the central glycosylated regions

remained dominant and essentially unchanged.

Surface adsorption properties as characterized by

optical waveguide lightmode spectroscopy (OWLS)

showed that tryptic and pepsin digestion of BSM

resulted in a decrease and a slight increase in the

adsorbed mass onto a hydrophobic surface

(polydimethylsiloxane (PDMS)), respectively,

compared to intact BSM. This is related to the

partial preservation of peptide residues after

pepsin digestion as confirmed by SEC and DLS

studies. Despite a contrast in the adsorbed amount

of the protease-treated BSMs onto the PDMS

surface, both proteases substantially deteriorated

the lubricating capabilities of BSM at the self-

mated sliding interface of PDMS. The present

study supports the notion that the terminal

domains of BSM are critical to the adsorption and

lubricating properties of BSM at hydrophobic

interfaces.

R e f e r e n c e s

[1] J.B. Madsen, K.I. Pakkanen, L. Duelund, B.

Svensson, M. Abou Hachem, S. Lee, Prep.

Biochem. Biotech, 45 (2015) 84-99.

[2] N. Nikogeorgos, J.B. Madsen, S. Lee, Coll. Surf.

B: Biointerfaces, 122 (2014) 760-766.

[3] J. Sotres, J.B. Madsen, T. Arnebrand, S. Lee, J

Coll. Interf. Sci. 428 (2014), 242-250.

[4] N. Nikogeorgos, P. Efler, A.B. Kayitmazer, . S.

Lee, Soft Matter 11 (2015), 489-498

Seunghwan Lee,1

Jan Busk Madsen,1 Birte Svensson,

2

Maher Abou Hachem2

[email protected]

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M u l t i d i m e n s i o n a l c h a r a c t e r i z t i o n o f

G r a p h e n e a t u l t r a l o w t e m p e r a t u r e s

Rachel and Selim Benin School of Engineering and Applied Science, The Hebrew

University of Jerusalem and 2Nanonics Imaging Ltd, Jerusalem, Israel

(www.nanonics.co.il)

It is a challenge to study 2D materials, such as

Graphene, MoS2, WeSe2, etc. at temperatures

down to 10oK when one considers the wide variety

of physical phenomena that have to be applied to

get a full picture of the functionality of these

materials. A variety of properties of these 2D

materials are important to understand at low

temperature including their chemistry (Raman),

structure, nanoscale photoconductivity, electrical

and thermal properties, and near-field optical. The

ability to simultaneously measure these properties

is especially important so that correlations and

interactions between these properties at these low

temperatures can be understood. All of these

phenomena are common not only to 2D materials

but also to carbon nanotubes and related

nanomaterials.

This presentation will describe the development of

cryogenic multiple SPM probe instrumentation to

probe this variety of properties of graphene and

other 2D materials. The system that will be

described has a completely free optical axis from

above and below that is not obscured by electrical

or other probes. This design permits on-line AFM-

Raman and Tip Enhanced NanoRaman Scattering

(TERS). With such a system we have investigated

graphene and HfO2 using multiprobe electrical,

Kelvin probe, NSOM and on-line Raman. The

results have yielded new insights into the chemical

changes that are correlated to the electrical

conductivity.

Aaron Lewis, Oleg Zinoviev,

Anatoly Komissar, Eran Maayan

and David Lewis

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H i g h l y S y m m e t r i c M u l t i d e n t a t e

L i g a n d s f o r C a t a l y s i s a n d F u n c t i o n a l

M a t e r i a l s Dipartimento Scienze Chimiche, Università di Padova, Via Marzolo 1,

35131, Padova, Italy

The use of modular, multidentate ligands is one of

the current trends in catalyst design. Advantages

include the high stability of the corresponding

metal complexes, which often allows low catalyst

concentrations without loss of catalyst integrity.

Secondly, a nearly complete filling of all

coordination sites of the metal by a single ligand

reduces the chances of formation of multimeric

and often undefined metal-species under catalytic

conditions. The presence of only a single

catalytically active species greatly facilitates

mechanistic studies and catalyst optimization. In

the last years our group has been involved in the

study of early transition metal complexes with

triphenolate ligands and their application in

catalysis.[1,2]

In this communication, we will report on most

recent results related to the effective post

modifications of the ligand backbones that allow

obtaining supramolecular hybrid functional

systems with dimensions spanning from single

molecules to much larger aggregates. In particular,

the synthesis and characterization of novel

systems bearing multiple ion-TAGs, gelator,

fluorescent or organic radical residues will be

described together with preliminary results of

applications in catalysis and functional materials

R e f e r e n c e s

[1] G. Licini, M. Mba, C. Zonta, Dalton Trans.27,

(2009) 5265; M. Mba, C. Zonta, G. Licini

(2014) “Coordination chemistry and

applications of nitrilotris (N-

methylenephenoxy)-metal complexes” in

Patai’s Chemistry of Functional Groups,

edited by I. Marek. John Wiley & Sons, Ltd:

Chichester, UK.

[2] C. Zonta, G. Licini Chem. Eur. J., 29, (2013)

9438 and reference therein

F i g u r e s

Giulia Licini

[email protected]

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C o v a l e n t g r a f t i n g e f f e c t s o n t h e

t h e r m a l p r o p e r t i e s o f r e n e w a b l e

P o l y ( L - l a c t i d e ) / c e l l u l o s e n a n o c r y s t a l

n a n o c o m p o s i t e s

1 Macromolecular Chemistry Research Group. Dept. of Physical Chemistry. Faculty of

Science and Technology. University of the Basque Country (UPV/EHU), Leioa 48940,

Spain. 2Basque Center for Materials, Applications and Nanostructures (BCMaterials), Parque

Tecnológico de Bizkaia, Ed. 500, Derio 48160, Spain.

Poly(L-lactide) (PLLA) is a semicrystalline

thermoplastic which belongs to a biocompatible,

biodegradable and bioresorbable polymers. PLLA

also fulfills many requirements of the traditional

non-biodegradable packaging materials and it is

therefore considered of great value from an

ecological point of view due to its biobased

character. Nonetheless, there are several aspects

such as its slow crystal growth rate, its marked

physical aging when used in ambient conditions

and its poor thermal stability which limit the use of

PLLA as a commodity plastic [1].

Nanocomposite approach could be viewed as an

efficient strategy to overcome the aforementioned

drawbacks. In accordance with the 12 Principles of

Green Chemistry [2], which underline the basis to

develop ecologically friendly materials, in this work

fully renewable PLLA nanocomposites have been

obtained. Among all the available naturally-

occurring nanoreinforcements, the rod-like

cellulose nanocrystals (CNC) are of special interest

due to their outstanding mechanical properties,

low density, low cost and its huge potential for

chemical modification. Unfortunately, its strong

hydrogen self-association behaviour in nonpolar

systems makes CNC difficult to disperse, reducing

their efficiency as reinforcing phase. In this sense,

grafting-from approach has been carried out with

the aim of improving the interfacial adhesion and

CNC dispersion within the polymer matrix. PLLA

chains are initiated from the surface hydroxyl

groups of CNC by a surface-initiated ring opening

polymerization (SI-ROP) [3].

Results show the crystallization rate is increased by

1.7-5 times in presence cellulose nanocrystals.

Additionally, structural relaxation kinetics of PLLA

chains has been drastically reduced by 53% and

27% with the addition of neat and grafted CNC

respectively. Those results suggest that neat CNC

reduce structural relaxation of bulk material to a

greater extent than grafted CNC because of the

reduction of the available PLLA/CNC interfaces

given by SI-ROP process. The thermal degradation

activation energy (E) determined from

thermogavrimetric analysis reveal a reduction on

the thermal stability when in presence of CNC-g-

PLLA, while raw CNC slightly increases the thermal

stability of PLLA. Those results confirm that the

presence of residual catalyst in CNC-g-PLLA plays a

pivotal role in the thermal degradation behavior of

nanocomposites. In this framework, the

improvement of the SI-ROP process would be the

next important step towards the development of

renewable materials with enhanced functional

properties.

R e f e r e n c e s

[1] E Lizundia, JR Sarasua, Macromolecular

Symposia 321 (2012) 118.

[2] PT Anastas, JC Warner, Green Chemistry:

Theory and Practice; Oxford University Press,

148 (1998).

[3] A Dufresne, Materials Today, 13 (2013) 220.

E. Lizundia1,

J. L. Vilas2, L. M. León

1

[email protected]

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F i g u r e s

Figure 1: Scheme showing surface-initiated ROP of L-lactide (L-LA) to obtain CNC-g-PLLA+(Sn(Oct)2).

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N o v e l S o l i d P h a s e s b y S e l f - A s s e m b l i n g

o f N a n o c l u s t e r s

1Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU) and Donostia

International Physics Center (DIPC), PK 1072, 20080 Donostia, Euskadi (Spain)

The theoretical search for novel polymorphs of

inorganic compounds have increased significatively

in the last years. One of the routes to build such

compounds is the so-called nanocluster

assembling, where nanometer-sized structures are

used as building blocks for the formation of 3D

periodic systems. Hollow cage-like structures are

ideal candidates for such assembling, resembling

the case of carbon fullerenes in fullerites.

In this work we focus on the assembling of bare

and endohedrally doped hollow nanoclusters of II-

VI materials, concretely, ZniSi and CdiSi, (i=12,16)

which were predicted to be

the global minima. The

considered dopant atoms

were several alkali metals,

halogens and transition

metals [1-3].

Different polymorphs were

characterized for all cases

[4,5]. Most of them were

stable towards vibration. In addition to phonon

calculations, quantum molecular dynamics

simulations, E vs V calculations were carried out in

order to provide some theoretical evidence of the

metastability of these compounds. In Figure 1, one

of the characterized metastable structure, FAU, is

shown.

R e f e r e n c e s

[1] E. Jimenez-Izal, J. M. Azpiroz, R. Gupta, J. M.

Matxain, J. M. Ugalde, J. Mol. Model. 20,

(2014) 2227.

[2] E. Jimenez-Izal, J. M. Matxain, M. Piris, J. M.

Ugalde, Comput. 1 (2013) 31.

[3] E. Jimenez-Izal, J. M. Matxain, M. Piris, J. M.

Ugalde, J. Phys.l Che. C 115, (2011) 7829.

[4] E. Jimenez-Izal, J. M. Matxain, M. Piris, J. M.

Ugalde, Phys. Chem. Chem. Phys. 14 (2012)

9676.

[5] J. M. Matxain, M. Piris, X. Lopez, J. M. Ugalde,

Chem. Eur. J. 15 (2009) 5138.

F i g u r e s

Figure 1: Characterized metastable FAU polymorph build by

Cd12S12 clusters.

Jon M. Matxain1

[email protected]

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L i p i d n a n o p a r t i c l e s a s d e l i v e r y v e h i c l e

f o r b i o - m a c r o m o l e c u l e s

1Univ. Grenoble Alpes, Grenoble, F-38000, France;

2CEA, LETI MINATEC, Technologies for Healthcare and Biology Division, 17 rue des

martyrs, 38054 Grenoble Cedex 9, France 3Institut Albert Bonniot - UJF/INSERM U823, Rond-point de la Chantourne,

38042 Grenoble Cedex 9, France.

Nanomedicine, the application of nanotechnology

to medicine, is a growing field for decades. Several

nanoparticles are already on the market, especially

for tumour diagnosis or therapy. Their applications

are based on their ability to reach the tumour

tissue due to the well-known “enhanced

permeability and retention” (EPR) effect where

they can accumulate locally in the tumour and

increase thus the efficiency of their contents. Most

of these drugs are hydrophobic small molecule

compounds whereas new therapeutic strategies in

development are basedon larger molecules from

biological origin such as peptides, proteins or

nucleic acids. Novel nanoparticle formulations are

now highly anticipated for delivery of these bio-

macromolecules, in particular for applications

beyond cancer therapy. We designed lipid

nanoparticles able to deliver either nucleic acids,

or antigen proteins. A panel of chemical strategies

have been explored for loading the bio-

macromolecules into/onto the particles, ranging

from simple electrostatic interaction to covalent

grafting by using modified polymers. The resulting

particles presented not only a high colloidal

stability, but also a good safety profile. Moreover,

their efficacy for the concerned applications were

improved either to transfect nucleic acids into cells

or to elicit immune responses in mice whenever

the protein antigens are coupled to the

nanoparticles. Further preclinical evaluation of

these particles containing bio-macromolecules in

different animal models is now ongoing and will

contribute to their successful clinical translation.

Jessica Morlieras1,2

, Alan Hibbitts1,2

,

Thomas Courant1,2

, Emilie Bayon1,2

,

Hei Lanne Reynaud3,Christian

Villiers3, Mathilde Menneteau

1,2,

Patrice Marche3

and Fabrice Navarro1,2

[email protected]

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T h e E q u i v a l e n t C i r c u i t s o f M o l e c u l a r

T u n n e l J u n c t i o n s

Chemistry Depart of the National University of Singapore

Department of Chemistry, 3 Science Drive 3, Singapore 117543

Molecular junctions of the form of electrode–

SAM–electrode(SAM=self-assembled monolayer)

are appealing because of their potential of

inducing, and controlling, electronic function at the

nanometer length scales.[1,2]Understanding the

nature of the molecule-electrode contacts in these

two-terminal junctions is crucial but it is mostly

poorly understood.[3]The reason is the electrical

properties of electrode–SAM–electrode junctions

are usually studied by two-terminal DC

measurements which only determine the total

current(impeded by all components of the

junction) as a function of applied bias. Hence,

these methods do not distinguish the contributions

of each component (the SAM, the electrodes, and

the two SAM–electrode interfaces)to the

measured current and are not suitable to measure

the dielectric response.

Recently we showed that impedance spectroscopy

makes it possible to isolate the contribution of

each component in the junctions to the total

impedance of EGaIn based junctions(Figure

1).[4,5]Here I will present that temperature

dependent and potentiodynamic impedance

spectroscopy make it possible to elucidate the bias

and temperature dependency of each circuit

component(contact resistance, SAM resistance,

and the capacitance of the SAM)of two-terminal

SAM-based junctions, unlike DC measurements,

independently from each other. We found that the

metal–electrode contact resistance is independent

of the temperature or applied bias and more than

4 orders of magnitude smaller than the thinnest

SAM measured, the thin conductive oxide layer

plays an insignificant role. We also find that by

introducing large polarizable atoms the dielectric

response can be engineered at the molecular level.

We believe that impedance spectroscopy as a

function of temperature and applied bias is a

useful and complementary tool to DC

measurements to elucidate how each component

of two-terminal SAM-based junctions impedes

charge transfer and it opens the door to

investigate dielectric response in 2-terminal

junctions at the molecular scale.

R e f e r e n c e s

[1] Nerngchanmnong, N.; Yuan, L.; Qi, D. C.;

Jiang, L.; Thompson, D.; Nijhuis, C. A. Nature

Nanotechnol.2013, 8, 113.

[2] Tan, S. F., Wu, L., Yang, K. L. W., Bai, P.,

Bosman, M., Nijhuis, C. A. Science, 2014, 343,

1496.

[3] Yuan, L.; Nerngchamnong, N.; Li, J.; Qi, D.-C.;

Hamoudi, H.; del Barco, E.; Roemer, M.;

Sriramula, R. K.; Thompson, D.; Damien

Thompson; Nijhuis, C. ANat. Commun.2015,

6, 6324.

[4] Wan, A.; Jiang, L.; Suchand Sangeeth, C. S.;

Nijhuis, C. A. Adv. Funct. Mater.201424,

4442.

[5] Suchand, S.S.C.; Wang, A.; Nijhuis, C.A. J. Am.

Chem. Soc.2014, 136, 11134–11144. Heitzer,

H. M.; Marks, T.J.;Ratner,M.A. ACS Nano,

2014, 8, 12587.

Christian A. Nijhuis

[email protected]

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F i g u r e s

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P r o t e i n a n d P e p t i d e C h e m i s t r y f o r

N a n o t e c h n o l o g y : B i o m i n e r a l i z a t i o n ,

C r y s t a l l i z a t i o n , P a t t e r n i n g a n d S e l f -

o r g a n i z a t i o n

1CIC nanoGUNE, 20018, Donostia-San Sebastian, Basque Country, Spain

2Universidad del Pais Vasco (UPV/EHU), 48940, Leioa, Basque Country, Spain

3Ikerbasque, Basque Foundation for Science, 48011, Bilbao, Basque Country, Spain

In biology, a huge number of protein and peptide

molecules established self-organizing systems with

sophisticated abilities, for example, detection of

light by our eyes, and detection of sound by our

ears. Therefore, our world can utilize such

biomolecules to develop more complex structures

for nanotechnology. On the way, we have

developed fabrication methods for inorganic NPs

and the assembly of the NPs, based on structure

and function of proteins and peptides

Biomineralization is one of the processes to build

bio-inorganic materials such as bone and teeth.

Some proteins can generate inorganic material

through specific aminoacid sequences,distributed

in protein structures, which enable us to use them

as bio-cargos for NPs .For example, the cage shape

protein Dps (DNA binding protein in starved cell,

diameter: 12 nm) can form metal oxide NPs with in

its cavity (diameter 5 nm)by assembling iron ions

and nucleating NPs at specific sites[1].The NP

species can be changed by designing the synthesis

solution, allowing for the fabrication of artificial

NPs. There are many types of cage-shaped

proteins in nature, such as ferritin and virus

capsids (Fig.1).In addition, tube-shaped viruses

such as TMV (Tobacco Mosaic Virus, inner

diameter: 4nm) can be used to fabricate rod-

shaped in organic NPs. Many types NPs and rods

have been fabricated in such cavities.

NPs containing bio-cargo scan self-assemble into

two-or three-dimensional crystals through protein-

protein interactions based on typical crystallization

techniques [2].In addition, the patterning of NPs

can be optimized with bio-cargos functionalized

using specific peptides. Peptides with certain

biochemical functions can recognize the surface of

specific inorganic materials [3]. A bio-cargo that is

functionalized with such a peptide can be

patterned on a surface of a target material. These

protein and peptide techniques have been utilized

to develop a range of devices [3].

In this talk, we will also show how to design self-

organization systems through bio-cargo structures,

and affinity peptides to fabricate complex NP

structures.

R e f e r e n c e s

[1] Mitsuhiro Okuda, et al. NanoSpain Bio&Med,

ImagineNano, (2015) poster.

[2] Mitsuhiro Okuda et al. Chem commun, 46

(2010) 8797.

[3] K.-I. Sano, et al. Langmuir, 29 (2013) 12483.

F i g u r e s

Figure 1.Schematics of apoferritin (a) viewed from the four fold

symmetry axis. (b) shows the cavity.(c)Schematic drawing of Dps.

(d) Schematic drawing of CCMV.

Mitsuhiro Okuda1,3

, Kornelius Zeth2,3

and Alexander Bittner1,3

[email protected]

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T h e Q u e s t f o r C h a r g e T r a n s p o r t i n

s i n g l e A d s o r b e d L o n g D N A - B a s e d

M o l e c u l e s

Institute of Chemistry and Center for Nanoscience and Nanotechnology

The Hebrew University of Jerusalem, 91904 Israel

DNA and DNA-based polymers have been at the

focus of molecular electronics owing to their

programmable structural versatility. The variability

in the measured molecules and experimental

setups, caused largely by the contact problem, has

produced a wide range of partial or seemingly

contradictory results, highlighting the challenge to

transport significant current through individual

DNA-based molecules. A well-controlled

experiment that would provide clear insight into

the charge transport mechanism through a single

long molecule deposited on a hard substrate has

never been accomplished. In this lecture I will

report on detailed and reproducible charge

transport in G4-DNA, adsorbed on a mica

substrate. Using a novel benchmark process for

testing molecular conductance in single polymer

wires, we observed currents of tens to over 100 pA

in many G4-DNA molecules over distances ranging

from tens to over 100 nm, compatible with a long-

range thermal hopping between multi-tetrad

segments. With this report, we answer a long-

standing question about the ability of individual

polymers to transport significant current over long

distances when adsorbed a hard substrate, and its

mechanism. These results may re-ignite the

interest in DNA-based wires and devices towards a

practical implementation of these wires in

programmable circuits.

R e f e r e n c e s

[1] "Direct measurement of electrical transport

through DNA molecules", Danny Porath,

Alexey Bezryadin, Simon de Vries and Cees

Dekker, Nature 403, 635 (2000).

[2] "Charge Transport in DNA-based Devices",

Danny Porath, Rosa Di Felice and Gianaurelio

Cuniberti, Topics in Current Chemistry Vol.

237, pp. 183-228 Ed. Gary Shuster. Springer

Verlag, 2004.

[3] “Direct Measurement of Electrical Transport

Through Single DNA Molecules of Complex

Sequence”, Hezy Cohen, Claude Nogues, Ron

Naaman and Danny Porath, PNAS 102, 11589

(2005).

[4] “Long Monomolecular G4-DNA Nanowires”,

Alexander Kotlyar, Nataly Borovok, Tatiana

Molotsky, Hezy Cohen, Errez Shapir and Danny

Porath, Advanced Materials 17, 1901 (2005).

[5] “Electrical characterization of self-assembled

single- and double-stranded DNA monolayers

using conductive AFM”, Hezy Cohen et al.,

Faraday Discussions 131, 367 (2006).

[6] “High-Resolution STM Imaging of Novel

Poly(G)-Poly(C)DNA Molecules”, Errez Shapir,

Hezy Cohen, Natalia Borovok, Alexander B.

Kotlyar and Danny Porath, J. Phys. Chem. B

110, 4430 (2006).

[7] "Polarizability of G4-DNA Observed by

Electrostatic Force Microscopy

Measurements", Hezy Cohen et al., Nano

Letters 7(4), 981 (2007).

[8] “Electronic structure of single DNA molecules

resolved by transverse scanning tunneling

spectroscopy”, Errez Shapir et al., Nature

Materials 7, 68 (2008).

[9] “A DNA sequence scanned”, Danny Porath,

Nature Nanotechnology 4, 476 (2009).

[10] “The Electronic Structure of G4-DNA by

Scanning Tunneling Spectroscopy”, Errez

Shapir, et.al., J. Phys. Chem. C 114, 22079

(2010).

Danny Porath

[email protected]

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[11] “Energy gap reduction in DNA by

complexation with metal ions”, Errez Shapir,

G. Brancolini, Tatiana Molotsky, Alexander B.

Kotlyar, Rosa Di Felice, and Danny Porath,

Advanced Maerials 23, 4290 (2011).

[12] "Quasi 3D imaging of DNA-gold nanoparticle

tetrahedral structures", Avigail Stern, Dvir

Rotem, Inna Popov and Danny Porath, J. Phys.

Cond. Mat. 24, 164203 (2012).

[13] "Comparative electrostatic force microscopy

of tetra- and intra-molecular G4-DNA", Gideon

I. Livshits, Jamal Ghabboun, Natalia Borovok,

Alexander B. Kotlyar, Danny Porath, Advanced

materials 26, 4981 (2014).

[14] "Long-range charge transport in single G4-DNA

molecules", Gideon I. Livshits et. al., Nature

Nanotechnology 9, 1040 (2014).

F i g u r e s

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R e c e n t p r o g r e s s o n p a t c h y

n a n o p a r t i c l e s a n d t h e i r d i r e c t i o n a l

b o n d i n g

1 CNRS, Univ. Bordeaux, CRPP, UPR 8641, F-33600 Pessac, France.

2Univ. Bordeaux, CNRS, ISM, UMR 5255, F-33405 Talence, France

3CNRS, Univ. Bordeaux, ICMCB, UPR 9048, F-33600 Pessac, France

Compared to standard fabrication methods based

on top-down approaches such as optical

lithography, colloidal self-assembly offers the

potential for easier fabrication and manipulation

of nano-and microstructures, especially in three

dimensions. In most cases, these building blocks

may not naturally assemble into any desired

structures. One emerging approach to confer

colloidal particles predetermined “instructions” for

assembly is to decorate the surface of the particles

with “sticky patches” made, for example, of

synthetic organic or biological molecules. This

strategy draws its inspiration in part from biology,

where the precision of self-assembled structures

such as viruses and organelles originates in the

selectivity of the interactions between their

constituents. In this talk, we report on a new route

to synthesize patchy nanoparticles with a

controlled number of patches or dimples as well as

on their potential use as building blocks for the

elaboration of new supracolloids with unusual

morphology and optical properties.

The so-patchy particles were derived from colloidal

molecules [1] made of a central silica

coresurrounded by a precise number, n, of

polystyrene satellite nodules [2,3].We succeeded

in promoting the growth of the silica core of these

colloidal molecules. While growing, the silica

surface conforms to the shape of the PS nodules.

After functionalization of the inter-nodule surface

area and dissolution of the polystyrene nodules,

homogeneous batches of silica particles with n

well-located patches at their surface can be

produced in large quantities [4]. The patchy

character of the silica particles was evidenced by

TEM characterization (see Figure). The controlled

assembly of patchy nanoparticles offers the unique

capability of creating new supraparticles [5]or

superlattice structures. We will present some

recent results on the self-assembly of the

multivalent silica nanoparticles.

These patchy particles can also be used for

creating new nano-objects suitable for many

applications such as sensing, metamaterials,

photonics, etc. For example, they can be used to

elaborate nanocages of noble metal with a

controlled number of holes

R e f e r e n c e s

[1] E. Duguet, A. Désert, A. Perro and S. Ravaine,

Chem. Soc.Rev.40(2011) 941

[2] A. Perro, E. Duguet, O. Lambert, J. C. Taveau,

E. Bourgea-Lami and S. Ravaine, Angew.

Chem.,Int. Ed.48(2009) 361.

[3] A. Désert, I. Chaduc, S. Fouilloux, J.C. Taveau,

O. Lambert, M. Lansalot, E. Bourgeat-Lami, A.

Thill, O. Spalla, S. Ravaine and E. Duguet,

Polym. Chem.3(2012)1130

[4] A. Désert, C. Hubert, Z. Fu, L. Moulet, J.

Majimel, P. Barboteau, A. Thill, M. Lansalot,

E. Bourgeat-Lami, E. Duguet and S. Ravaine,

Angew. Chem. Int. Ed.52 (2013)11068.

[5] C. Hubert, C. Chomette, A. Désert, M. Sun, M.

Treguer-Delapierre, S. Mornet, A. Perro, E.

Duguet and S.Ravaine, Faraday Discussions,

2015, DOI: 10.1039/C4FD00241E.

Serge Ravaine1, Céline Hubert

1,2,

Cyril Chomette3, Anthony Désert

3,

Adeline Perro-Marre2,

StéphaneMornet3, MonaTréguer-

Delapierre3, Etienne Duguet

3

[email protected]

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F i g u r e s

Figure:TEM images of a) silica particles surrounded by 4 polystyrene satellite nodules, b) silica particles with 4 dimples and c) a dimpled silica

particle regioselectively decorated with gold nanoparticles [4]

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S e n s i n g M o l e c u l e s a n d T e m p e r a t u r e a t

t h e N a n o s c a l e

University of Aveiro, Department of Chemistry

CICECO-Aveiro Institute of Materials, 3810-193 Aveiro, Portugal

In this talk I shall review some of the work carried

out in Aveiro in the last 6 years, or so, on the

design, synthesis and characterisation of

lanthanide (Ln) -bearing nanostructures for sensing

small molecules and temperature. Selected

examples of (i) nanoporous metal-organic

frameworks and silicates, and (ii) gold and Ln

oxides nanoparticles systems will be given.

Nanoporous metal-organic frameworks (MOFs) are

crystalline materials consisting of metal ions

bridged by organic linkers and exhibiting porosity

reminiscent of zeolites. Ln3+-organic frameworks

are very promising materials for tackling the

challenges in engineering of luminescent centres,

also presenting much potential as multifunctional

systems, combining light emission with properties

such as microporosity, magnetism, chirality,

molecule and ion sensing, catalysis and activity as

multimodal imaging contrast agents [1]. Only 10%

or so of MOFs are effectively nanoporous,

exhibiting zeolite-type behaviour, and

photoluminescent. The combination of porosity

and light emission allows the design of intriguing

new types of chemical species and temperature

sensors, which I shall highlight here [2-6].

In general, the thermal stability of MOFs is limited

and materials such as silicates present interesting

alternatives for certain applications. We have

recently reported a new Ln silicate orthorhombic

system, Na[(Gd1-aEua)SiO4], exhibiting

uncommon photoluminescence properties due to

structural disorder and a phase transition. This

system constitutes the first example of a

ratiometric thermometer based on a Ln3+ silicate,

particularly sensitive at cryogenic temperatures

(<100 K) [7].

While the use of plasmonic nanoparticles as

sources of heat have attracted much interest in

the last decade, research into ratiometric

nanothermometers with high-spatial resolution is

comparatively new. Suitable nanoplatforms

integrating heaters and thermometers, however,

have not been realized, despite their great

potential in nanophotonics and biomedicine. In

this talk I shall report a step forward towards

assessing the local temperature of laser-excited

gold nanostructures using an all-in-one

nanoplatform comprising (Gd,Yb,Er)2O3 nanorods

(thermometers, NR) that were surface-decorated

with gold nanoparticles (heaters, AuNPs) [8].

R e f e r e n c e s

[1] Rocha J., Carlos L. D., Paz F. A. A., Ananias D.,

Chem. Soc. Rev. 2011, 40, 926-940.

[2] Shi F. N., Cunha-Silva L., Ferreira R. A. S.,

Mafra L., Trindade T., Carlos L. D., Paz F. A. A.,

Rocha, J., J. Am. Chem. Soc. 2008, 130, 150-

167.

[3] Harbuzaru B. V., Corma A., Rey F., Atienzar P.,

Jordá J. L., García H., Ananias D., Carlos L. D.,

Rocha J., Angew. Chem. Int. Ed. 2008, 47,

1080-1083.

[4] Harbuzaru B. V., Corma A., Rey F., Jordá J. L.,

Ananias D., Carlos L. D., Rocha J., Angew.

Chem. Intl. Ed., 2009, 48, 6476-6479.

[5] Cadiau A., Brites C. D. S., Costa P. M. F. J.,

Ferreira R. A. S., Rocha J., Carlos L. D., ACS

Nano 2013, 7, 7213-7218.

[6] Abdelhameed R. M., Carlos L. D., Silva A.,

Rocha J., Chem. Commun. 2013, 49, (2013),

5019- 5021.

[7] Ananias, D., Almeida Paz, F. A., Yufit, D. S.,

Carlos, L. D., Rocha, J., J. Am. Chem. Soc.,

http://dx.doi.org/10.1021/ja512745y.

[8] 1) Debasu, M. L., Ananias, D., Pastoriza-

Santos, I., Liz-Marzan, L. M., Rocha, J., Carlos

L. D., Adv. Mater. 2013, 35, 4868-4874.

João Rocha

[email protected];

http://www.ciceco.ua.pt/jr

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M e c h a n i c a l p r o p e r t i e s o f z i r c o n i u m

d i o x i d e a n d s i l i c o n n i t r i d e c o m p o s i t e s

Department of Metallurgical and Materials Engineering, Istanbul

Technical University, 34469 Maslak, Istanbul, Turkey

In this study, the mechanical properties of ZrO2-

Si3N4 composites containing 3.12 mass% MgO as a

stabilizer sintered at 1600˚C for 4 hr in a nitrogen

atmosphere has been investigated. XRD phase

analysis showed addition of Si3N4 destabilized

tetragonal zirconia phase and caused the

formation of monoclinic zirconia phase, also

zirconium oxide nitride phase was formed in the

sample with 10 and 15 mass% Si3N4 [1]. SEM

microstructure revealed that the grain size of the

specimens decreased with increasing content of

Si3N4. EDS analysis displays magnesium content

increased in the grain boundaries with adding

Si3N4. The results indicated that ZrO2 containing 10

and 15 mass% Si3N4 were performed higher

hardness values than stabilized zirconia[2]. The

room temperature mechanical properties of

flexural strength decreased with 5 mass% Si3N4

then increased with increasing Si3N4 content.

R e f e r e n c e s

[1] S. Berendts, M. Lerch, Journal of Crystal

Growth, 336 (2011) 106–111.

[2] S. Chockalingam, V. R.W. Amarakoon, Journal

of the Ceramic Society of Japan, 116 [6]

(2008) 700-705.

F i g u r e s

Sina Sadigh Akbari

Serdar Ozgen

[email protected]

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B i o s y n t h e s i s o f S i l v e r N a n o p a r t i c l e s

a n d i t s A p p l i c a t i o n i n t h e R e m o v a l o f

M e r c u r y ( I I ) f r o m W a t e r

1Department of Earth Science, King Fahd University of Petroleum and minerals,

Dhahran 31261, Saudi Arabia 2Department of Chemistry, King Fahd University of Petroleum and minerals, Dhahran

31261, Saudi Arabia

The synthesis of nanoparticle using chemical

sources is gradually being replaced by bio-

synthesized nanoparticle to alleviate

environmental concerns posed by chemically

synthesized nanoparticle. Biosynthesized

nanoparticle continues to gain prominence in

various applications including water treatment.

This study is aimed at exploiting the amalgam

relationship between mercury and silver to

remove mercury from water samples. Local plant

leaves; Aloe vera and Basil are utilized in

synthesizing nanoparticles. They both showed

silver nitrate reduction capabilities to form silver

nanoparticles which were confirmed by UV-Visible

analysis. The biosynthesized nanoparticles were

characterized using Scanning Electron Microscopy

(SEM) and X-ray Diffraction (XRD). Mercury

removal was further carried out using porous

membranes functionalized silver nanoparticle

membrane filter and the analysis of mercury was

performed using cold vapour atomic fluorescence

spectroscopy.

R e f e r e n c e s

[1] I. Bhatt and B. N. Tripathi, Chemosphere, vol.

82, no. 3, Jan. (2011) pp. 308–17.

[2] B. Nowack and T. D. Bucheli, Environ. Pollut.,

vol. 150, no. 1, Nov. (2007) pp. 5–22.

[3] D. Ashok, Int. Res. J. Pharm., vol. 3, no. 2,

(2012) pp. 169–173.

[4] T. Yordanova, P. Vasileva, I. Karadjova, and D.

Nihtianova, Analyst, vol. 139, no. Mar. (2014)

6, pp. 1532–40.

[5] E. Bernalte, C. Marín Sánchez, and E. Pinilla

Gil, Anal. Chim. Acta, vol. 689, no. 1, Mar.

(2011) pp. 60–4.

[6] N. E. Selin, Annu. Rev. Environ. Resour., vol.

34, no. 1, Nov. (2009) pp. 43–63.

[7] D. K. Tiwari, J. Behari, and P. Sen, Water Res.,

vol. 3, no. 3, (2008) pp. 417–433.

[8] K. Leopold, M. Foulkes, and P. Worsfold,

Anal. Chim. Acta, vol. 663, no. 2, Mar. (2010)

pp. 127–38.

[9] K. Tyagi, J. Toxicol. Environ. Heal. Sci., vol. 5,

no. 9, Sep. (2013) pp. 172–177.

[10] E. K. Elumalai, T. N. V. K. V Prasad, J.

Hemachandran, and S. V. Therasa, J. of

Pharmaceutical Sci. Res., vol. 2, no. 9, (2010)

pp. 549–554.

[11] M. Vanaja, G. Gnanajobitha, K. Paulkumar, S.

Rajeshkumar, C. Malarkodi, and G.

Annadurai, J. Nanostructure Chem., vol. 3,

no. 1, (2013) p. 17.

1Salawu Adio Omobayo,

2Basheer Chanbsha

[email protected]

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F i g u r e s

Figure 2: From left to right, Mixture of silver nitrate and plant

extract at 0, 15 and 30 minutes respectively.

Figure 3: UV- visible spectra of effect of time on the formation of

nanoparticles.

Figure 4: UV – Visible spectra of effect of broth concentration on

formation of AgNP.

Figure 5: UV- visible spectrum of the effect of different precursor

concentration on nanoparticles formed.

Figure 7: Effect of pH on formation of AgNP.

Figure 8: Biosynthesized AgNP at 2mM, 25oC, 1:25 broth

concentration, 20 minutes and pH 10.

Figure 10: SEM image of biosynthesized AgNP.

Figure 11: SEM image of biosynthesized AgNP.

Figure 12: Reaction of AgNP with 100pm mercury solution.

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E n c a p s u l a t i o n o f x a n t h e n e d y e s i n t o

n a n o c h a n n e l s o f M g A P O - 1 1 f o r o p t i c a l

a p p l i c a t i o n s

1 Universidad del País Vasco (UPV/EHU), Aptdo 644, 48080 Bilbao, Spain

2Instituto de Catálisis y Petroleoquímica (CSIC), Marie Curie 2, 28049, Madrid, Spain

The incorporation of photoactive molecules

into ordered nanostructured systems is an

emerging field for the development of new

functional optical materials. In particular, one-

dimensional nanochanneled crystalline systems

allow a supramolecular organization of the

embedded molecules and an improvement of

their properties. For this purpose, several

xanthene type dyes with absorption and

emission bands in the whole visible spectrum

range have been encapsulated into magnesium

aluminophosphate-11 (MgAPO-11) by inclusion

during crystallization. The selected host

material, owing to the special size and topology

of the nanochannels allows a tight fit to the

molecular dimensions of the forementioned

dyes. As a result, highly luminescent materials

have been obtained, since the encapsulation of

monomeric units of the dyes is only allowed.

Not only do we improve the luminescence

properties of the dyes in the hybrid material,

but we have also obtained a particular

anisotropic response of the particles under

polarized light, due to the preferential

alignment of the dye molecules along the 1D

MgAPO-11 channels. Pursuing new enhanced

properties, two dyes have been encapsulated in

this host, acridine (AC) and pyronine Y (PY),

with perpendicular orientation of their

transition dipole moments. This property,

together with an appropriate dye-loading rate

that enables a FRET process, has resulted into a

blue-to-green color switching, instantaneous,

efficient, reversible, reproducible and with high

fatigue resistance.

R e f e r e n c e s

[1] Martínez-Martínez, V.; García, R.; Gómez-

Hortigüela, L.; Pérez-Pariente, J.; López-

Arbeloa, I., Chem. Eur. J., 19 (2013) 9859.

[2] Martínez-Martínez, V.; García, R.; Gómez-

Hortigüela, L.; Sola Llano, R.; Pérez-

Pariente, J.; López-Arbeloa, I., ACS

Photonics, 1 (2014) 205.

F i g u r e s

Figure 1: (Right) Fluorescence image of a PY-AC/MgAPO-11

particle upon UV excitation light, with parallel (up) and

perpendicular (down) polarizations to the MgAPO-11 channels’

c-axis. (Left) Their corresponding emission colors in CIE.

1Rebeca Sola Llano,

1Virginia Martínez-Martínez,

2Raquel García,

bLuis Gómez Hortigüela,

2Joaquín Pérez-Pariente,

1Iñigo López-Arbeloa

[email protected]

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P h t h a l o c y a n i n e s a s c o m p o n e n t s o f

p h o t o v o l t a i c a n d a r t i f i c i a l

p h o t o s y n t h e t i c s y s t e m s

Organic Chemistry Department, Autonoma University of Madrid, Cantoblanco, Madrid,

28049, Spain and IMDEA Nanoscience, Cantoblanco, 28049-Madrid, Spain

Porphyrinoids are employed as components of

photovoltaic and artificial photosynthetic devices.

However, synthetic porphyrin analogues such as

phthalocyanines [1-3] have the advantage, as

photon harvesters, of exhibiting very high

extinction coefficients in a wavelength range that

extends to around 700 nm, where the maximum of

the solar photon flux occurs. Consequently, Pcs

have emerged as excellent light harvesting

antennas for incorporation into donor-acceptor

systems, mainly in connection with carbon

nanostructures as acceptor moieties.

Phthalocyanines (Pcs) constitute also promising

dyes as DSCphotosensitizers. [4]

On the other hand, Subphthalocyanines (SubPcs)

[5,6] are the lowest homologues of

phthalocyanines. Their pi-electron aromatic core

along with their non-planar cone-shaped structure

make them attractive compounds with singular

chemical and physical properties.

Subphthalocyanines are currently emerging as

excellent chromophoric systems for studying

electron and excitation transfer processes with

applications in photovoltaic devices.

During this talk an overview of the results obtained

by our group in Madrid will be given.

R e f e r e n c e s

[1] De la Torre, G.; Claessens, C.G.; Torres, T

Chem. Commun. 2007, 2000-2015.

[2] Martínez-Díaz, M. D.; de la Torre, G.; Torres,

T. Chem. Commun. 2010, 46, 7090-7108.

[3] Bottari, G.; de la Torre, G.; Guldi, D.M.;

Torres, T. Chem. Rev. 2010, 110, 6768– 6816.

[4] Ragoussi, M.E.; Cid, J.J.; Yum, J.H.; de la

Torre, G.; Di Censo, D.; Graetzel, M.;

Nazeeruddin, M.K.; Torres, T. Angew. Chem.

Int. Ed. Eng. 2012, 51, 4375 –4378.

[5] Claessens, C. G.; González-Rodríguez, D.;

Rodríguez-Morgade, M. S.; Medina, A.;

Torres, T. Chem. Rev., 2014,114, 2192-2277.

[6] Verreet, B.; Cheyns, D.; Heremans, P.;

Stesmans, A.;Zango, G.; Claessens, C. G.;

Torres, T.; Rand, B. P. Adv. Energy

Mater.2014, 4,(8) 201301413.

T. Torres, L. Tejerina , B.Kuhn,

W. A. Borzecka, D. P. Medina,

M. Medel, M.-E. Ragoussi, M. Ince,

E. Fazio, N. Bill, O. Trukhina,

[email protected]

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A d j u s t i n g M e t a l O x i d e P h o t o c a t a l y s i s

u s i n g O r g a n i c - I n o r g a n i c H y b r i d F i l m s

O b t a i n e d b y M o l e c u l a r L a y e r

D e p o s i t i o n

Institute of Chemistry and the Center for Nanoscience and Nanotechnology

Metal Oxides (MOs) are used for numerous

applications including catalysis, sensing, photonics,

optoelectronic devices, renewable energy,

electrochemistry and more. MOs exhibit a unique

combination of properties including their high

chemical and physical stability, durability, rich

surface reactivity, catalytic and photocatalytic

functions. MO photocatalytic properties and

performance is typically optimized by control over

the crystalline phases, incorporation of impurities

in the MO lattice, also commonly termed doping,

formation of noble metal-MOs hybrids, and more.

In particular, the photocatalytic performance of

TiO2 thin films is widely studied with well

established understanding of the roles of grain

size, phase composition (anatase vs. rutile),

supporting substrate, and deposition conditions.

Recent studies highlight the importance of non-

stoichiometric oxides for tuning and optimizing the

reactivity and performances of MO catalysts.

Specifically for MOs, oxygen vacancies (OVs) are

important structural defect that alter the reactivity

of MOs by introduction of new electronic states

within the band gap (BG). In addition, OV often

function as adsorption sites for Lewis acids and

bases making them surface active sites for

heterogeneous catalysis. OV design offers

additional valuable handles for optimizing MO

electronic structure further to control over the

crystalline phase and impurity doping. One of the

most widely studied MOs in the context of OV is

non-stoichiometric Titania, with deviation from

ideal oxide stoichiometry. The electronic structure,

charge transport, and surface properties of TiO2-δ

are closely related to the details of the defects and

OV.

Here we demonstrate the use of hybrid organic-

inorganic thin obtained by molecular layer

deposition films for attaining oxygen-deficient

Titania and tuning of the photoctalytic properties

of the films. The decomposition of the organic

components and formation of the carbon-rich

oxide offers control over the resulting oxide

electronic properties. Ti-EG films annealed at 650

oC exhibit superior reactivity for degradation of

organic molecules while Ti-EG films annealed at

520 oC yield the direct photoctalytic production of

hydrogen peroxide (H2O2).1,2

Both systems exhibit

activities that are not typically attainable by Titania

owing to the adjustable electronic structure of

annealed Ti-EG films.

R e f e r e n c e s

[1] Ishchuk et al, ACS Nano, 2012, (8), pp 7263–

7269

[2] Kaynan et al, J Mat Chem A, 2014, (2), pp

13822-13826

Roie Yerushalmi

[email protected]

http://chem.ch.huji.ac.il/~roie/

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2 D M a t e r i a l s b a s e d o n C o v a l e n t

O r g a n i c F r a m e w o r k s

1Departamento de Química Inorgánica, Universidad Autónoma de Madrid, 28049

Madrid (Spain). 2

Departamento de Química Organica. Fac. de Ciencias Químicas. Universidad

Complutense de Madrid. Avda. Complutense s/n. 28040 Madrid (Spain). 3

CNR-IMM, Instituto per la Microelettronica e Microsistemi, via P. Gobetti 101, I-40129

Bologna (Italy). 4

Instituto Madrileño de Estudios Avanzados en Nanociencia (IMDEA Nanociencia),

Cantoblanco, 28049 Madrid (Spain).

Rational design of Covalent Organic Frameworks

(COFs) is an emerging subject with potential

implications from basic to applied sciences.1 These

porous materials are constructed by assembling

organic building blocks, containing diverse

functionalities, by strong covalent bonds. Thus, for

COF based materials are envisioned diverse

applications, such as gas storage, adsorption,

optoelectronics and catalysis. However, current

synthetic methods, together with COFs’ limited

processability, restrict massive production and

applications.

In this talk, I will summarized our most recent

results on liquid phase exfoliation of several types

of COFs to isolated few layers. I will focus on

different COFs going from well-known boronate

ester-linked networks2 to polyacetylenic porous

3

and polyimines layered organic frameworks. I will

show a simple procedure to produce laminar

imine-based COFs with interesting physico-

chemical properties.4 Different procedures to

process and structure these materials as very

stable gels (xerogels, aerogels,..) and transparent

films will be presented. Finally, I will show some

possibilities to pattern these materials on several

substrates using ink-jet printer and wet

lithography techniques.

R e f e r e n c e s

[1] Berlanga, I.; Ruiz-Gonzalez, M. L.; Gonzalez-

Calbet, J. M.; Fierro, J. L. G.; Mas-Balleste, R.;

Zamora, F. Small 2011, 7, 1207.

[2] Berlanga, I.; Mas-Balleste, R.; Zamora, F. Chem

Commun 2012, 48, 7976.

[3] Zamora, F.; Mas-Balleste, R.; Rodriguez, D.;

Segura, J. L.; de la Peña, A. Method for the

synthesis of Covalent Organic Frameworks.

PCT/ES2014/070621. 2013.

F i g u r e s

Félix Zamora1,4

,

Alejandro de la Peña Ruigómez1,2

,

David Rodríguez San-Miguel1,4

,

Fabiola Licio3, Ruben Mas-Ballesté

1,

José Luis Segura2

[email protected]

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S y n t h e s i s o f F u n c t i o n a l i z e d N a n o

Z e o l i t e a n d Z e o l i t i c I m i d a z o l a t e

F r a m e w o r k C r y s t a l s

1Department of Physics, Aberystwyth University, Aberystwyth SY23 3BZ, UK

2Shanghai Key Laboratory of Modern Metallurgy and Materials Processing, Shanghai

University, Shanghai 200072, China 3College of Chemistry, Liaoning University, Shenyang 110031, China

Zeolite and zeolitic imidazolate framework (ZIF)

crystals have a characteristic cage-like structure,

which are the ideal candidates for building host-

guest material systems. The nano zeolites and

nano ZIFs have a shorter diffusion channel and a

larger surface area than the regular ones.They are

functional materials or raw materials for producing

other advanced materials. Nano zeolites are

prepared by microwave hydrothermal synthesis

method in our experiments. Comparing with

conventional hydrothermal synthesis method,

microwave heating significantly reduces the

reaction time. Also, the microwave energy directly

interacts with the reactant molecules, which

ensures the internal and external of the sample is

adequately heated to eliminate the temperature

gradient, leaving a uniform heating system. Apart

from these, the advantages of microwave

synthesis such as mild conditions, low energy

consumption, fast reaction rate, uniform and small

grain size contribute to achieve a fast, energy

saving and continuous method for manufacturing

functional glass. The other synthetic method of the

zeolitic crystals is using the so called “reverse

crystallization mechanism” [1,2]. The initial gel of is

prepared using a method in the literature [3].

Functional cores then can be wrapped by the gel.

The functional ions of the core can be well

protected during the surface-to-core growth and

thus the functional zeolitic core-shell structures

can be prepared without a complex procedure.

The obtained product materials are characterized

using transmission electron microscopy, scanning

electron microscopy, cryogenic temperature

transmission electron microscopy, X-ray

diffraction, thermo gravimetric analyzer, solid

state NMR, FTIR, and N2 adsorption–desorption

analysis.

R e f e r e n c e s

[1] Wuzong Zhou, Adv. Mater, 22(2010) 3086–

3092.

[2] Xueying Chen, Minghua Qiao, Songhai Xie,

Kangnian Fan, Wuzong Zhou, and Heyong He,

J. AM. CHEM. SOC, 129(2007) 13305-13312.

[3] R.W. Thompson, K.C. Franklin, in: H. Robson,

K.P. Lillerud (Eds.), Verified Synthesis of

Zeolitic Materials, Elsevier, Amsterdam, 2001,

p.156.

F i g u r e s

Figure 1: Illustration of the reverse crystallization mechanism..

Zhongfu Zhou1,2

Qingqing Sun2,3

, Jingfeng Wang2

Fang Guo3, George Neville Greaves

1

[email protected]

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E l e c t r o c h e m i c a l , p h o t o e l e c t r o c h e m i c a l

a n d p h o t o c a t a l y t i c p r o p e r t i e s o f

a n a t a s e w i t h e x p o s e d ( 0 0 1 ) f a c e t s

1 J. Heyrovský Institute of Physical Chemistry, v.v.i., Academy of Sciences of the Czech

Republic, Dolejskova 3, 18223 Prague 8, Czech 2Institute of Inorganic Chemistry of the AS CR, v.v.i. CZ−250 68 Husinec-Rez 1001,

Czech Republic

In general, the catalytic activity of inorganic

(nano)crystals is governed not only by their surface

composition but also by the physicochemical

properties of their exposed surfaces, which are

related to their surface atomic arrangement and

coordination. A typical example is titanium dioxide

(TiO2), which has promising energy and

environmental applications. For example, (001)

facets of anatase TiO2 are considered to be more

reactive than (101). Both (001) and (010) facets are

called “high-energy” or “reactive” ones, and they

show interesting activity in catalysis and

photocatalysis [1].

Anatase (001) for our study was prepared by a

commonly used hydrolysis of Ti butoxide in the

presence hydrofluoric acid followed by

hydrothermal treatment in autoclave. Its

electrochemical behavior was studied by cyclic

voltammetry of Li insertion and

chronoamperometry [2]. Both methods proved its

higher activity toward Li insertion compared to

that of anatase (101).

Nanocrystalline TiO2 (anatase) in two different

crystal morphologies exposing mainly the (001) or

(101) crystal faces was employed as a photoanode

material in dye sensitized solar cells. The (001) face

adsorbs smaller amount of the used dye sensitizer

(C101) but provides larger open circuit voltage

(Uoc) of the solar cell. Among other possible

factors, the negative shift of flatband potential is

suggested to be responsible for the observed

enhancement of Uoc. The flatband potential of

both anatase (001) and anatase (101) was

determined by spectroelectrochemical

measurement of thin film electrodes at gradually

decreasing potentials from 0 V to -1.2 or 1.4 V vs

SCE. Anatase (001) exhibited the negative shift of

absorbance/potential profiles as compared that of

anatase (101).

High-resolution FT-IR spectroscopy was used to

study the kinetics of oxygen mobility between

gaseous isotopically labeled C18

O2 and solid phase

Ti16

O2 nanocrystalline anatase (001) [3]. Analysis of

the isotopic composition of the gases produced

has revealed that anatase (001) calcinated at

temperatures under 500 °C is a very weakly

reactive material and exhibits a low exchange

mobility of oxygen atoms between the gas phase

molecules of CO2 and the TiO2 lattice. Isotope

exchange is blocked by both residual HF adsorbed

onto the TiO2 surface and TiOF2 impurities. The

presence of TiOF2 was confirmed by electron

diffraction (TEM) and by X-ray diffraction, and to

the best of our knowledge, its presence in

moderately calcined anatase (001) prepared by the

standard procedure is here reported for the first

time. However, the anatase (001) sample became

slightly active after annealing at temperatures

greater than 500 °C and upon UV illumination.

Nevertheless, the effective rate constant is still

3.45 times lower than that observed for the

spontaneous exchange between C18

O2 and anatase

(101) material calcinated at 500 °C. Obviously, the

release of HF adsorbed on the surface of

moderately calcined anatase (001) and the

decomposition of TiOF2 impurity are complete at

temperatures higher than 500 °C.

Acknowledgements: This work was supported by

the Grant Agency of the Czech Republic (No.

P108/12/0814) and by the Ministry of Education,

Youth and Sports of the Czech Republic (LD 13060,

COST CM1104).

Marketa Zukalova1, Barbora

Laskova1, Martin Ferus

1, Mariana

Klementová2, Svatopluk Civiš

1 and

Ladislav Kavan1

marketa.zukalova@jh-

inst.cas.cz

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R e f e r e n c e s

[1] Laskova, B.; Zukalova, M.; Kavan, L.; Chou, A.;

Liska, P.; Wei, Z.; Bin, L.; Kubat, P.; Ghadiri, E.;

Moser, J. E.; Gratzel, M. Journal of Solid State

Electrochemistry 2012, 16, (9), 2993-3001.

[2] Bousa, M.; Laskova, B.; Zukalova, M.;

Prochazka, J.; Chou, A.; Kavan, L. Journal of the

Electrochemical Society 2010, 157, (10),

A1108-A1112.

[3] Ferus, M.; Kavan, L.; Zukalová, M.; Zukal, A.;

Klementová, M.; Civiš, S. The Journal of

Physical Chemistry C 2014, 118, (46), 26845-

26850.

NanoS pa in

Tox ico logy

201 5

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I n d e x

N a n o S p a i n T o x i c o l o g y 2 0 1 5

C o n t r i b u t i o n s

A l p h a b e t i c a l O r d e r

K : K e y n o t e / O : O r a l Page

Araque, Eva (ITENE, Spain)

Environmental toxicity evaluation of PET-Ag new polymeric nanocomposites with multitrophic

bioassays batteries

O 267

Blasco, Julian (ICMAN-CSIC, Spain)

Behavior and toxicity of metallic nanoparticles: from freshwater to saltwate K 268

Caballero Diaz, Encarnacion (University of Cordoba, Spain)

Nanotoxicity: gold nanoparticles under study O 269

Cajaraville, Miren P. (UPV/EHU, Spain)

An integrated multispecies two-tiered approach for the environmental risk assessment of nanomaterials: a

case study with Ag NPs

K 271

De Lapuente, Joaquin (Univ. of Barcelona, Spain)

An approach in product regulation and substances in nanotechnologies K 273

Domat, Maidá (ITENE, Spain)

Effectiveness of N95 Disposable Particulate Respirators and FPP3 Half Mask Respirators against target NMs

for the pigment and inks industry

O 274

Duroudier, Nerea (University of the Basque Country, Spain)

Molecular and cellular responses of mussels Mytilus galloprovincialis fed with the microalgae Isochrysis

galbana exposed to PVP/PEI-coated silver nanoparticles at different seasons

O 276

Freese, Christian (University Medical Center Mainz, Germany)

Prediction of the effects of nanoparticles on humans: Impact of amorphous silica nanoparticles on

various complex in vitro organ models

O 277

Garcia-Velasco, Nerea (University of the Basque Country, Spain)

Toxicity screening of AgNPs and integrative assessment of soil health through biomarker responses in

Eisenia fetida earthworm at different levels of biological organization

O 279

Jimeno, Alba (UPV/EHU, Spain)

Routes of internalisation and subcellular distribution patterns of metal-bearing nanoparticles in mussel,

Mytilus galloprovincialis, as a function of nanoparticle characteristics

O 281

Lacave, Jose Maria (University of the Basque Country, Spain)

Nanotoxicogenomics: transcription profiling for the assessment of nanomaterials toxicity mechanisms O 282

Navas, Jose M. (INIA, Spain)

Mechanisms of toxic action of manufactured nanomaterials unraveled by means of in vitro systems K 284

Rallo, Roberto (URV, Spain)

In silico nanotoxicology: development and validation of nano-QSARs K -

Rodea Palomares, Ismael (Universidad Autónoma de Madrid, Spain)

Colloidal Stability has a crucial role for nanomaterials toxicity testing in-vitro: nZVI-algae colloidal

system as case study

O 286

Rosal, Roberto (Universidad de Alcalá, Spain)

Internalization and toxicity of amine and hydroxyl terminated poly(amidoamine) dendrimers to

photosynthetic microorganisms

O 287

Sabbioni, Enrico (ECSIN, VenetoNanotech&SIN, Italy)

10 years of nanotoxicology research- what have we learned? K 288

Suarez Merino, Blanca (Fundación GAIKER, Spain)

Towards a harmonized Safety Assessment of Nanomaterials O 289

Vaquero, Celina (TECNALIA, Spain)

Safe manufacturing and occupational exposure to nano-TiO2 O 290

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E n v i r o n m e n t a l t o x i c i t y e v a l u a t i o n o f

P E T - A g n e w p o l y m e r i c n a n o c o m p o s i t e s

w i t h m u l t i t r o p h i c b i o a s s a y s b a t t e r i e s

1 Instituto Tecnológico del Embalaje, Transporte y Logística. Albert Einstein, 1. Paterna

(Spain) 2 Xenobiotics, S.L. Parc Científic Universitat de València. C/ Catedrático Agustín

Escardino, nº 9. Paterna ( Spain)

In the packaging industry, silver NPs have

attractive proprieties that make them appropriate

for being combined with PET, the most commonly

used polymer in this sector. Nevertheless, silver

NPs have a potential ecotoxicity that could limit

the use of PET-silver composite.

The characteristics of Sivler NPs, freshly made and

weathered composite were analyzed. PET-Ag

ecotoxicity was evaluated in organisms from

different food chain levels and it was compared to

Ag NPs ecotoxicity.

The composites possessed around 4 % of NPs

stably and uniformly scattered in the polymeric

matrix. ZnO NPs turned out to be extremely toxic

to Pseudokirchneriella subcapitata and toxic to

Daphnia magna and Brachionus plicatilis. PET-Ag

was not toxic to any of the organisms, and its

weathered form only presented a moderate

toxicity to P. subcapitata.

A c k n o w l e d g e m e n t s

This research is supported by the European Project

‘NanoSafePack’, a collaborative project funded

under the ‘Research For SME Association, SME-

2011-2’ Theme of the European Commission's 7th

Framework Programme, managed by REA-

Research Executive Agency ([FP7/2007-2013]

[FP7/2007-2011]) under Grant Agreement No.

286362

T a b l e

Table 1: Ecotoxicity test conducted

Eva Araque1, Ana Guillem

1, Carlos

Fito, Oscar Andreu2

[email protected]

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B e h a v i o r a n d t o x i c i t y o f m e t a l l i c

n a n o p a r t i c l e s : f r o m f r e s h w a t e r t o

s a l t w a t e r

Instituto de Ciencias Marinas de Andalucía (CSIC). Campus Río San Pedro

11510 Puerto Real(Cádiz). Spain2I

The increasing use of nanomaterials in industrial

applications for the last decade implies an increase

of the concern about potential toxic effects of

released engineered nanoparticles to the

environment. In fact, aquatic ecosystems are the

main receptors of chemical pollution, including

nanoparticles. Surface waters and, to a greater

extent, oceans, will be the final receptors for all

wasted NPs (Fabrega et al., 2011; Gong et al.,

2011; Whiteley et al., 2013). The transition from

freshwater to estuarine and marine ecosystems

represents drastic changes in ionic strength,

organic matter and other physicochemical

properties, which affect to particle propertiesand

their fate and behavior. Nevertheless, knowledge

about the effects and the mechanisms of toxicity

of the different NPs on the aquatic and, over all,

marine biota is quite far away to be complete

(Boxall et al.; 2007; Baun et al., 2008;

Chinnapongse etal., 2011; Walters et al., 2014).

Toxicity of metallic nanoparticles to aquatic

organisms seems to be related to the physical and

chemical properties of those nanoparticles as well

as their behavior in aquatic media where

dissolution, aggregation and agglomeration

processes occur. These ones affect to metal

bioavailability. In this study a review of fate,

behavior and toxicity of metallic nanoparticles is

carried out taken in account the differences

between fresh and marine environment with

special emphasis on phytoplankton.

R e f e r e n c e s

[1] 1. Baun, A.; Hartmann, N.B.; Grieger, K.D.

& Kusk, K.O. Ecotoxicology, 17 (2008) 387-395.

[2] Boxall, A.B.A.; Tiede, K. & Chaudhry, Q.

Nanomedicine, 2(6) (2007) 919-927.

[3] Chinnapongse, S.L.; MacCuspie, R.I. & Hackley,

V.A. 2011. Science of the Total Environment,

409(12) (2011) 2443-2450.

[4] Fabrega, J., Luoma, S.N., Tyler, C.R., Galloway,

T.S., Lead, J.R. Environment International,

37(2) (2011) 517-531.

[5] Gong, N.; Shao, K.; Feng, W.; Lin, Z.; Liang, C. &

Sun, Y. Chemosphere, 83 (2011) 510-516.

[6] Walters, C.R.; Pool, E.J. & Somerset, V.S..

Journal of Environmental Science and Health,

Part A, 49 (2014) 1588-1601.

[7] Whiteley, C.M.; Valle, M.D.; Jones, K.C. &

Sweetman, A.J. Environmental Sciences:

Processes and Impacts, 15(11) (2013) 2050-

2058.

A c k n o w l e d g e m e n t s

This work has been funded by the projects PE2011-

RNM-7812 Junta Andalucía and CTM2012-38720-

C03-03 Plan Nacional Investigación (MINECO)

Julián Blasco, Ignacio Moreno-

Garrido, Marta Sendra, Sara Pérez,

Moritz Volland, Chiara Trombini,Luis

M. Lubián, Miriam Hampel, Antonio

Tovar

[email protected]

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Nanotoxicity: gold nanoparticles under study

Department of Analytical Chemistry, University of Córdoba, Annex “Marie Curie”

building, Campus de Rabanales, Córdoba, Spain

The outstanding properties of nanoparticles along

with their widespread use in consumer and

industrial products have aroused global concern

for the consequences of their interaction with

biological systems in toxicological terms. In this

regard, nanoparticles with applications in

Biomedicine field, such as gold nanoparticles

(AuNPs), require necessarily an exhaustive

investigation on their possible adverse effects and

how these can be alleviated.

Toxicity arising from nanoparticles is directly

related to their ability for cellular internalization.

Different mechanisms have been established to

explain the cellular uptake of nanoparticles, most

of which involve endocytic processes [1]. It should

be noted that each type of nanoparticle exhibits a

preferred internalization pathway which is mainly

determined by its physicochemical properties

including surface chemistry, size and shape. As far

as surface chemistry is concerned, there are many

examples in literature that associate the toxicity

derived from AuNPs with the surfactant located on

their surface and used for their synthesis and

stabilization, in particular, CTAB [2]. On the other

hand, positively charged AuNPs are likely to exhibit

a greater cellular uptake as a consequence of their

favored electrostatic interactions with negatively

charged cell membrane [3]. Size-dependent

toxicity of AuNPs has been also confirmed in

several works where smaller AuNPs were more

efficiently internalized than larger ones and

therefore, caused a greater cytotoxicity [4]. As

regards to nanoparticle shape, different cellular

responses were reported for cells exposed to gold

nanorods or gold nanospheres [5].

Once internalized and stored, AuNPs can induce

harmful effects on cells principally due to their

catalytic ability. It has described that AuNPs

damage the DNA as a consequence of their strong

affinity for DNA grooves, which have negative

environment [6]. The endogenous production of

reactive oxygen species (ROS) and the depletion of

natural intracellular antioxidants represent other

important mechanisms of toxicity induced by

AuNPs, which may disturb the equilibrium

between antioxidant and oxidant intracellular

processes. ROS can be produced directly by the

AuNPs themselves as a result of their surface

reactivity, or degradation of their coating shell or

inorganic core with the consequent leakage of free

ions to the intracellular environment. Indirectly,

AuNPs may also interact with intracellular

organelles and biomolecules following the

activation of oxidative stress response pathways.

Moreover, protein and polyunsaturated fatty acid

oxidation are other secondary effects derived from

oxidative stress, and lead to mitochondrial

alterations (e.g. increased membrane

permeability) that ultimately prompt cell death.

Lipid membrane thinning effects or alterations on

protein conformation or activity are other

potential toxicity mechanisms.

Methods for AuNP toxicity assessment include

both in vitro and in vivo studies. However, the vast

majority of the currently performed assays are in

vitro and only allow examining the effects at

cellular level. The scenario for evaluation of

nanoparticle toxicity becomes even more complex

when other additional influential factors come into

play. In this respect, nanoparticles tend to

aggregate in contact with cell media thus

modifying their physicochemical properties and

ultimately, their degree of interaction with cells.

Different cell lines and culture media are other

determinants that can modify the resulting toxicity

Encarnación Caballero Díaz,

Miguel Valcárcel Cases

[email protected]

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even when the same nanoparticles are considered.

In addition, interferences between AuNPs and

some cytotoxicity assays have been also reported

what definitely complicate the interpretation of

the obtained results. Consequently, considerable

efforts have to be made to overcome the

limitations found in the currently available

evaluation methods..

R e f e r e n c e s

[1] H. Kettiger, A. Schipanski, P. Wick, J. Huwyler,

Int. J. Nanomed. 8 (2013) 3255.

[2] M. Alkilany, P.K. Nagaria, C.R. Hexel, T.J.

Shaw, C.J. Murphy, M.D. Wyatt, Small 5

(2009)701.

[3] T.S. Hauck, A.A. Ghazani, W.C.W. Chan, Small

4 (2008) 153.

[4] B.D. Chithrani, W.C.W. Chan, Nano Lett. 7

(2007) 1542.

[5] N.M. Schaeublin, L.K. Braydich-Stolle, E.I.

Maurer, K. Park, R.I. MacCuspie, A.R.M.

Nabiul-Afrooz, R.A. Vaia, N.B. Saleh, S.M.

Hussain, Langmuir 28 (2012) 3248.

[6] P. Rivera Gil, D. Huhn, L.L. del Mercato, D.

Sasse, W.J. Parak, Pharmacol. Res. 62 (2010)

115.

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A n i n t e g r a t e d m u l t i s p e c i e s t w o - t i e r e d

a p p r o a c h f o r t h e e n v i r o n m e n t a l r i s k

a s s e s s m e n t o f n a n o m a t e r i a l s : a c a s e

s t u d y w i t h A g N P s

CBET Research Group, Dept. Zoology and Animal Cell Biology; Faculty of Science and

Technology and Research Centre for Experimental Marine Biology and Biotechnology

PIE, University of the Basque Country UPV/EHU, Basque Country, Spain

Due to the great increase in the use of

nanomaterials for a variety of biomedical,

domestic and industrial applications, the input of

nanoparticles (NPs) and other nanomaterials in the

aquatic environment is expected to rise in the

following years. In spite of this, there is only

limited information on the fate, distribution and

toxicity of NPs to aquatic organisms. The aims of

our study were to investigate the bioavailability of

metal bearing NPs in mussels Mytilus

galloprovincialis and zebrafish Danio rerio and to

determine the possible adverse effects of NPs in

comparison to bulk and ionic forms on the same

target organisms. For this, a two-tiered strategy

was developed combining both in vitro and in vivo

approaches. In vitro techniques provide a quick

and reproducible tool for the screening of NP

toxicity. In tier 1, cytotoxicity of a variety of NPs

(Au, ZnO, SiO2, TiO2, CdS, Ag and CuO) at a wide

range of concentrations was tested in isolated

mussel hemocytes and gill cells and LC50s were

calculated. In tier 2, sublethal concentrations

below the LC25 were selected to investigate in

vitro uptake and reactivity of NPs and to discover

putative mechanisms of toxicity in both cell types.

In vivo studies with mussels comprised short-term

(1-3 d) experiments to determine bioavailability

and lysosomal membrane stability as a general

indicator of health (tier 1) and medium-term (21 d)

experiments to assess adverse effects using a

battery of molecular, cellular and tissue-level

biomarkers (tier 2). Similarly, studies in zebrafish

started with short-term embryo toxicity tests (tier

1) followed by 21 d experiments (tier 2) in case

significant toxicity was found in tier 1. Results

allowed to classify studied NPs based on their

toxicity to mussel cells in vitro and to zebrafish

embryos. Overall, NP toxicity depended on their

physico-chemical properties and their behaviour in

exposure media. Maltose-coated Ag NPs of 20 nm

resulted the most toxic NPs tested in the two

model organisms. At sublethal concentrations, Ag

NPs increased ROS production and induced

antioxidant enzyme activity, increased DNA

damage and activated lysosomal acid phosphatase

activity and multixenobiotic resistance MXR

transport activity in mussel cells. Further, Ag NPs

decreased Na-K-ATPase activity in gill cells and

affected the actin cytoskeleton in hemocytes.

Exposure to the ionic form of Ag produced similar

effects, although at a higher magnitude, suggesting

that observed responses were due at least in part

to dissolved Ag. Exceptionally, the stimulatory

effect on hemocyte phagocytic activity was

nanoparticle specific. In agreement, in in vivo

experiments with mussels exposed to the same

NPs, Ag was accumulated significantly in soft

tissues, being localized mainly in the endo -

lysosomal system at the subcellular level. This was

associated to a significant reduction in lysosomal

membrane stability and altered the structure of

the digestive gland as a result of massive digestive

cell loss. Accordingly, Ag NPs were highly toxic to

developing zebrafish embryos, causing mortality or

a variety of severe malformations at lower

exposure concentrations. Exposure of adult

zebrafish to the same Ag NPs resulted in Ag

internalization that lead to an array of sublethal

effects from changes in liver transcriptome to gill

histopathologies. Obtained data may contribute to

the risk assessment of nanomaterials in the

aquatic environment.the currently available

evaluation methods.

A c k n o w l e d g e m e n t s

Funded by EU 7th FP (NanoReTox CP-FP 214478-2),

Cost action Enter ES1205, Spanish Ministry

M.P. Cajaraville, A. Katsumiti, A.

Jimeno- Romero, J.M. Lacave, I.

Marigómez, M. Soto and A. Orbea

[email protected]

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2

(NanoCancer CTM2009-13477 and

Nanosilveromics MAT2012-39372), Basque

Governmen (consolidated research group IT810-

13and SaiotekS-PE13UN142) and University of the

Basque Country (UFI 11/37). Thanks are due to Dr.

D Gilliland (JRC, Ispra) for characterization of Ag

NPs.

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A n a p p r o a c h i n p r o d u c t r e g u l a t i o n a n d

s u b s t a n c e s i n n a n o t e c h n o l o g i e s

Unit of Experimental Toxicology and Ecotoxicology; CERETOX; Barcelona Science Park;

c/ Baldiri i Reixac 10-12; 08028 Barcelona, Spain

Nanotechnologies hold enormous potential to

revolutionise the field of cosmetic, medicine,

medical devices, electronics, biomaterials energy

production, and consumer products through

manifold applications. In the field of biomedicine,

for example, cost-effective tissue engineering or

the creation of bespoke implant, target delivery

and bioavailability of existing or new medical

substances are rapidly improving. In field of

diagnostic, the sensitivity and specificity of rapid

detection processes using lab-on-a-chip divise are

also improving.

These improvements are raising questions about

safety in short and long term of nanoscale

materials. Scientists are debating the current and

the future implications of nanotechnologies in our

life. This has caused an increase of the scientific

literature in the field of nanoscience, and the

emergence of new journals on the subject. At the

same time many countries are increasing public

and private budgets invested in research,

development and innovation on manufactured

nanomaterials.

The authorities should ensure the safety to

humans and the environment due to increasing

production of nanomaterials that has occurred in

recent years and what may go as far in the future.

Some countries are launching strategic programs

on safety evaluation and risk assessment of

manufactured nanomaterials. This is the case of

the Organisation for Economic Co-operation and

Development (OECD) that develops programs to

assist in the implementation of national policies.

Other Organizations as Environment Pollutant

Agency (EPA) are in the same way, and both are

working together in some aspects. Currently many

advances have been achieved in the field of

regulation and more work is being done towards a

safer nanotechnology every day.

F i g u r e s

Figure 1: http://www.nanotech-now.com/news.cgi?story_id=36306

de Lapuente J, Miles V.,

González-Linares J., Ramos-López D.

and Serret J

[email protected]

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E f f e c t i v e n e s s o f N 9 5 D i s p o s a b l e

P a r t i c u l a t e R e s p i r a t o r s a n d F P P 3 H a l f

M a s k R e s p i r a t o r s a g a i n s t t a r g e t N M s

f o r t h e p i g m e n t a n d i n k s i n d u s t r y

1 Instituto Tecnológico del Embalaje, Transporte y Logística. Albert Einstein, 1. Paterna

(Spain) 2 Flemish institute for technological research. Boeretang 200, 2400 Mol, Bélgica (Spain)

In the particular case of the pigment, ink and paint

industry, the use of engineered nanoparticles

(ENPs), have a great potential for new applications,

leading to products with new or enhanced

properties, and opening new market

opportunities. Consequently, many promising

applications emerge nowadays, based on the use

of ENPs such as Fe3O4, TiO2 or ZnO or quantum

dots (QDs).

Along with the benefits, there is an on-going

debate about their potential effects on human

health or the environment, considering as a key

issue the potential adverse effects of ENPs on

workers upon inhalation. In this sense, it has been

demonstrated that ENPs can become airborne

during common industrial activities, some of them

related with the production of nano-pigments

and/or nano-inks. These airborne particles,

including nanoparticles and ultrafine particles may

enter into the human respiratory tract via

inhalation.

Considering the growing production of

nanoparticles to develop high-tech applications,

there is an urgent need to define adequate risk

management measures to mitigate and control the

exposure. A first step to protect workers is to

enhance the knowledge on the effectiveness of

current risk management measures, including

personal protective equipment (PPE) and

engineering controls (OC).

A complete evaluation of the effectiveness of

common RMMs against ENPs at the workplace has

being carried out under the scope of the FP7

project NanoMICEX (NMP4-SL-2012-280713) and

the LIFE+ Project NanoRISK (LIFE12/ENV/ES/178).

We present here the results encountered during

the evalaution of the protection factor (APF) and

leakage efficacy effectivness of two different types

of respirators, including a N95 Disposable

Particulate Respirator and a FPP 3 reusable half

mask respirator. The selected RMMs were

evaluated in the testing chamber designed and

developed by ITENE. A picture of the testing

chamber and the Sheffield head employed during

the test are depicted in figure 1.

The experimental protection factor was defined by

the ratio between the number concentration of

particles upside the protective device (Cupstream)

and the concentration within that device

(Cdownstream). The concentrations upstream

were measured by means of a Philips Nanotracer,

which detects particles below 300 nm and an

Optical Particle Sizer (OPS-TSI), which detects

particles up to 10 microns. Downstream the

particles where detected by means of a CPS

System (CPC model 9007 – TSI). To conduct the

tests with our target ENPs, it was necessary to use

a powder aerosolizer, in this case, the Naneum

powder aerolizer PA100.

Average penetration levels for the two different

masks were between 26 and 2%., with a minimum

penetration level for the Reusable Half Mask

respirator. The results showed significative

differences in the penetration factor for the

models studied. It shall be noted also that the PF

characterized are higher than the recommended

5%, which means that none of the mask tested are

effective enough against ENPs.

Maidá Domat1, Enrique de la Cruz*

1,

Carlos Fito1, Jaime Gonzalez, Evelien

Frinjs2

[email protected]

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F i g u r e s

Figure 1: Sheffield head (Courtesy of the INSHT) and the Aerosol Testing Chamber developed by ITENE

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M o l e c u l a r a n d c e l l u l a r r e s p o n s e s o f

m u s s e l s M y t i l u s g a l l o p r o v i n c i a l i s f e d

w i t h t h e m i c r o a l g a e I s o c h r y s i s

g a l b a n a e x p o s e d t o P V P / P E I - c o a t e d

s i l v e r n a n o p a r t i c l e s a t d i f f e r e n t

s e a s o n s 1

CBET Research Group, Science and Technology Faculty and Plentzia Marine Station,

University of the Basque Country (UPV/EHU), Basque Country, Spain 2

Univ. Bordeaux, UMR 5805 EPOC, Allée Geoffroy St Hilaire, 33615 Pessac Cedex,

France

Bivalve mollusks have been identified as an

important target group for nanoparticle (NP)

toxicity because they are filter-feeding organisms

able to uptake and process particles of different

sizes. Several studies have been carried out in

mussels exposed to NPs via water; however, there

is scarce information on the effects of NPs

ingested through the diet, especially at

environmentally relevant concentrations. Further,

the potential influence of season on mussel´s

responses to NPs has not been explored. Silver NPs

(Ag NPs) are being increasingly used due to their

antimicrobial properties and therefore, concerns

about their potential input and hazards in aquatic

ecosystems are growing. Thus, with the aim of

determining molecular and cellular responses to

Ag NP exposure in mussels Mytilus

galloprovincialis, dietary exposure experiments

were performed both in autumn and in spring.

Mussels were fed daily with the microalgae

Isochrysis galbana previously exposed for 24 h to

two different doses of PVP-PEI coated 5 nm Ag

NPs: a dose of 1 μg Ag/L of Ag NPs close to

estimated environmental levels and a higher dose

of 10 μg/L Ag NPs. After 24 h of exposure, Ag

concentration was measured in algae by ICP-MS

while TEM and SEM analysis were performed in

order to study NP fate. After 1, 7 and 21 days of

mussel dietary exposure, total Ag concentration

was measured in mussel soft tissues by ICP-MS and

Ag deposits were measured at the light microscope

after autometallography and localized by TEM

followed by X-ray microanalysis. Microarray

studies were performed to get a specific gene

expression signature. Lysosomal membrane

stability was measured in digestive cells as a

general indicator of health status and genotoxic

effects were assessed in hemocytes by Comet

assay and the micronucleus test. Chemical analysis

showed that microalgae exposed to 10 μg/L Ag

NPs significantly accumulated Ag after 24 h. By

TEM, electron dense deposits were observed

between the scales and the membrane of

microalgae and inside cells, indicating

internalization of Ag NPs in algae. Mussels fed with

exposed microalgae significantly accumulated Ag

after 7 and 21 days in both seasons. Regarding

genotoxic effects, DNA strand breaks increased

significantly along the 21 days in spring and

micronuclei frequency showed an increasing trend

after 1 and 7 days of exposure to 1 μg/L Ag NPs in

spring and to 10 μg/L in both seasons. Thus, PVP-

PEI coated 5 nm Ag NPs were successfully

transferred from algae to mussels and caused

significant alterations in mussels.

A c k n o w l e d g e m e n t s

Spanish MINECO (MAT2012-39372), Basque

Government (SAIOTEK SPE13UN142 and GIC IT810-

13), UPV/EHU (UFI11/37 and PhD fellowship to

N.D.) and French Ministry of Higher Education and

Research (PhD fellowship to M.M.)

Nerea Duroudier1, Alberto

Katsumiti1, Alba Jimeno-Romero

1,

Leire Basarte1, Mathilde Mikolaczyk

2,

Jörg Schäfer2, Eider Bilbao

1 and

Miren P. Cajaraville1

[email protected]

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P r e d i c t i o n o f t h e e f f e c t s o f

n a n o p a r t i c l e s o n h u m a n s : I m p a c t o f

a m o r p h o u s s i l i c a n a n o p a r t i c l e s o n

v a r i o u s c o m p l e x i n v i t r o o r g a n m o d e l s

REPAIR-lab, Institute of Pathology, University Medical Center of the Johannes

Gutenberg University Mainz, Mainz, Germany

Nanoparticle-cell interactions have been

investigated since years and their evaluation in

terms of health and safety is of essential

importance. However, effects on single cells are

not reflecting the effects on organs or even living

organisms. A sophisticated approach to analyse

and predict their impact on humans much more

precisely is the use of complex in vitro multiculture

systems. These model systems have many

advantages since it is known that cell

communication could play a pivotal role in the

effect of NPs to organs (inflammatory response,

cell stress, etc.) [1]. In principal, two main concerns

of nanoparticles exposure should be considered in

detail and can be summarized as following: (1)

Uptake routes of nanoparticles into the body (lung,

skin, intestine) and (2) the impact on organs (e.g.

brain). Thus, we decided to utilize our expertise in

the development of complex cell culture model

systems (coand triple-cultures under standard and

air-liquid-interface conditions) simulating the

major physiological barriers for the investigation of

the effects of nanoparticles and nanoparticle-cell

interactions [2-4].

We started our examinations with amorphous

silica nanoparticles of different sizes (30nm, 70nm)

and various surface modifications (carboxy-,

amino, hydroxyl groups) and used these particles

as model nanoparticles due to the monodispersity,

good fluorescent properties and standardized

synthesis procedures.

Our aim was not to compare the different model

systems but to generate as much data as possible

to predict how those nanoparticles could affect

living organisms.

The results show that silica particles regardless

which size (30nm or 70nm) or surface modification

did not overcome the stratum corneum of the skin.

Histological analysis indicated that the

nanoparticles stacked to the stratum corneum but

did not interact with viable keratinocytes. In

contrast, bronchial epithelial cells internalized all

kinds of nanoparticles. However, the amounts of

nanoparticles that were internalized and located in

the perinuclear region were different dependent

from their surface modification. Moreover it could

be demonstrated that a smaller size of the

particles allowed a transcytosis across the

epithelial cell layer following an interaction with

fibroblasts. In addition to that we also investigated

the effect of the particles on the blood-brain

barrier that is one of the tightest barriers in our

body and protects the brain from xenobiotic and

endobiotic substances by expressing tight

junctions and ABC efflux transporters. The results

indicated that the barrier built by endothelial cells

is not affected and that the nanoparticles did not

induce an expression of pro-inflammatory

mediators in endothelial cells even the particles

have been internalized.

This study shows that highly complex in vitro

barrier models represent an excellent tool to

assess the impact of nanoparticles on animals or

humans more precisely. More detailed

experiments will furthermore enable the

examination of the effects and functionality of

nanoparticles designed for medical applications

(drug delivery, improved imaging, etc.).

R e f e r e n c e s

[1] Kasper J, Hermanns MI, Bantz C, Maskos M,

Stauber R, Pohl C, Unger RE, Kirkpatrick

Christian Freese, Verena Grützner,

Laura Anspach, Jennifer Kasper,

Ronald E. Unger, C. James Kirkpatrick

[email protected]

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JC.:Inflammatory and cytotoxic responses of

an alveolar-capillary coculture model to silica

nanoparticles: comparison with conventional

monocultures. 2011. Part Fibre Toxicol. 8(1):6.

doi: 10.1186/1743-8977-8-6.

[2] Freese C, Reinhardt S, Hefner G, Unger RE,

Kirkpatrick CJ, Endres K.: A novel blood-brain

barrier co-culture system for drug targeting of

Alzheimer's disease: establishment by using

acitretin as a model drug. 2014. PLoS One.

9(3):e91003. doi:

10.1371/journal.pone.0091003. eCollection

2014.

[3] Hermanns MI, Fuchs S, Bock M, Wenzel K,

Mayer E, Kehe K, Bittinger F, Kirkpatrick CJ.:

Primary human coculture model of alveolo-

capillary unit to study mechanisms of injury to

peripheral lung. 2009. Cell Tissue Res.

336(1):91-105. doi: 10.1007/s00441-008-

0750-1.

[4] Pohl C, Hermanns MI, Uboldi C, Bock M, Fuchs

S, Dei-Anang J, Mayer E, Kehe K, Kummer

W,Kirkpatrick CJ. 2009. Barrier functions and

paracellular integrity in human cell culture

models of theproximal respiratory unit. 2009

Eur J Pharm Biopharm. 72(2):339-49. doi:

10.1016/j.ejpb.2008.07.012.

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T o x i c i t y s c r e e n i n g o f A g N P s a n d

i n t e g r a t i v e a s s e s s m e n t o f s o i l h e a l t h

t h r o u g h b i o m a r k e r r e s p o n s e s i n

E i s e n i a f e t i d a e a r t h w o r m a t d i f f e r e n t

l e v e l s o f b i o l o g i c a l o r g a n i z a t i o n

CBET Research Group, Dept. Zoology and Animal Cell Biology; Research Centre for

Experimental Marine Biology & Biotechnology PiE-UPV/EHU, Univ. Basque Country

UPV/EHU, Basque Country, Spain

In recent years the number of applications and

products containing silver nanoparticles (AgNP)

has widely increased, mainly due to the

antimicrobial properties of silver, thus their release

into different environmental compartments such

as soil is already occurring. The major source of

AgNP deposition onto soil is currently though the

disposal of wastewater treatments plant sludge

(after land application of the sludge or incineration

and posterior deposition) which could modify the

terrestrial community. However, the hazards of

nanosized silver in soils are poorly investigated

despite the great complexity of soil matrix and the

potential interactions of its components with

pollutants. Besides, little is known about the

effects of AgNPs on organisms inhabiting soils.

Earthworms have been broadly used for soil health

assessment due to their pivotal role in the soil and

their quick and measurable responses after

exposures to pollutants. Soil health can be

assessed measuring these responses in model

organisms at different levels of biological

organization. Recently, in vitro assays with primary

cultures of earthworm immune cells,

coelomocytes, have been set up as rapid tools for

toxicity assessment of chemicals. At organism-

level, as earthworms are able to take up chemicals

from soil ingestion as well as from soil pore water,

through the outer skin, the Paper Contact Toxicity

Test (OECD-207) is an initial screening method to

identify toxic substances and to obtain relevant

toxicity data (LC50 and EC50). Such screening

reflects dermal contact exposure while the

Artificial Soil Toxicity Test (OECD-207) gives a more

representative toxicity data after earthworm

exposure though soils. Regarding population-level,

the Earthworm Reproduction Test (OECD-222) is

designed to be used for assessing the effects of

chemicals in soil on the reproductive output. The

aims of this work were (a) to determine the

toxicity profile of AgNPs with responses achieved

at different levels of biological organization, cell-

level biomarkers and viability test (Neutral Red

Uptake -NRU- and Calcein-AM Viability assays)

combined with organism and population level

bioassays performed with the aid of Standard

Toxicity Tests (OECD-207 and 222) and (b) to

establish toxicity threshold of AgNPs which will be

helpful to obtain an integrative view of the

biological responses in Eisenia fetida earthworms.

For that purpose, at cell-level, coelomocytes

extruded from E. fetida were maintained in

primary cultures and exposed to PVP-PEI coated

Ag-NP (5.5±2 nm, water dispersed) in

concentrations ranging 0-100 mg/l, and to PVP-PEI

coating agent separately (0.0001-10,4 mg/l) for 24

h. After exposure NRU and Calcein-AM cytotoxicity

and viability assays, and flow cytometric analyses

were applied in order to decipher coelomocyte

subpopulation dynamics and their sensitivity

against AgNPs. For the Paper Contact toxicity test

E. fetida earthworms were exposed to PVP-PEI

coated Ag-NPs and to PVP-PEI agent as well, in a

range of concentrations (0-200 μg/cm2). After 48 h

mortality and weight loss were assessed,

morphological alterations in the digestive tract and

in the epidermis were addressed after Alcian Blue

staining, and Ag concentrations were quantified by

ICP-MS in earthworm tissues. In the Artificial soil

test, earthworms were maintained in OECD

standard soils spiked with 0-500 mg AgNP/kg for 3

and 14 days. Complementarily NRU and Calcein-

AM Viability tests were performed in

coelomocytes extruded from exposed earthworms,

autometallography was applied on fixed tissue

sections (5 μm) to address the distribution of Ag in

tissues, and Ag concentrations in soils and tissues

were quantified by ICP-MS. Effects on

Garcia-Velasco N., Irizar A.,

Gandariasbeitia M.,

Urionabarrenetxea E., Soto M.

[email protected]

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reproduction were assessed after 8 weeks by

counting the number of cocoons (hatched/no-

hatched) and juveniles present in the soils. PVP-PEI

appeared not to be cytotoxic while coated AgNPs

exerted an initial stress at low doses and severe

toxicity at highest concentrations as revealed NRU

and Calcein AM assays. In addition, a clear

difference in the sensitivity of the cell-types was

detected. Paper Contact test revealed a LC50 of

346.5 ppm Ag-NP and Artificial Soil test of 144.2

mg Ag-NP/kg. Histological and histochemical

analyses proved that the primary uptake of AgNPs

was via soil ingestion. A decrease in the number of

viable cells occurred after 3 d of exposure to 50 mg

Ag-NP/kg and after 14 d to 5 mg Ag-NP/kg.

Reproduction was severely impaired at high Ag-NP

doses. All measurements were integrated in the

Integrated Biomarker Response (IBR) index. In

conclusion, the combination of in vitro test with

the Standard Toxicity Tests was useful to establish

AgNPs toxicity thresholds and thus this approach

can be used for assessing the potential risks of

AgNPs in soils. The IBR provided complementary

information concerning the mechanisms of

biological response to AgNP exposure.

R e f e r e n c e s

[1] Earthworm, Acute Toxicity Tests-207. OECD

guideline for testing of chemicals. 1984.

[2] Earthworm Reproduction Test (Eisenia fetida /

Eisenia andrei)-222. OECD guideline for testing

of chemicals. 2004.

A c k n o w l e d g e m e n t s

Basque Government (Cons. Res. Groups; IT810-13),

Univ. Basque Country (UFI 11/37) and Spanish

MINECO (Nanosilveromics Project, MAT2012-

39372).

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R o u t e s o f i n t e r n a l i s a t i o n a n d

s u b c e l l u l a r d i s t r i b u t i o n p a t t e r n s o f

m e t a l - b e a r i n g n a n o p a r t i c l e s i n

m u s s e l , M y t i l u s g a l l o p r o v i n c i a l i s , a s a

f u n c t i o n o f n a n o p a r t i c l e

c h a r a c t e r i s t i c s 1 CBET Research Group, Dept. Zoology and Animal Cell Biology, Science and Technology

Faculty and Plentzia Marine Station, University of the Basque Country (UPV/EHU) Spain 2 Centre for Ultrastructural Imaging, Guy’s Campus, King’s College London. London, UK

The aim of the present investigation is to

contribute to the understanding of internalisation

and subcellular distribution of metal-bearing

nanoparticles (NPs) in different cell compartments

within the digestive gland of the marine mussel

Mytilus galloprovincialis depending on NP physico-

chemical characteristics (size, additives, solubility,

dispersion). At the subcellular level, transmission

electron microscopy (TEM) and X-ray microanalysis

were applied after in vivo short-term exposure (3

d) of mussels to different concentrations of NPs

(TiO2, ZnO, Au, Ag andCdS QDs -quantum dots-) of

different sizes either with or without additives

such as citrate, maltose or the surfactant DSLS.

Small NPs (5-20 nm: Au5-Cit; Ag20-Mal) produced

small aggregates (15-25 nm) and mid-sized

aggregates (25-40 nm) that were readily

incorporated via phagocytosis and endocytosis,

respectively, into the digestive cell endo-lysosomal

system. The internalisation of large NPs (>40 nm:

Au40-Cit; Ag40-Mal; Ag90-Mal) in digestive cell

lysosomes was less marked, most likely because

only individual NPs followed the endocytic route.

After exposure to TiO2, Au and Ag NPs and CdS

QDs, electron-dense particles were observed in the

lumen of the digestive diverticula, associated to

cell debris (e.g., within heterolysosomes and

residual bodies). Whilst TiO2 and Au NPs and CdS

QDs remained apparently unchanged after being

processed within the acidic endo-lysosomal system

of the digestive cells, the size of Ag NPs was

reduced in the heterolysosomes, which has been

interpreted as the result of a partial dissolution of

internalised NPs. Unlike in the former cases,

electron-dense particles resembling NPs were not

clearly observed in the case of ZnO NP exposures,

except some scant electron-dense particles that

were only occasionally found in the lumen of the

digestive gland diverticula and the stomach, and in

the blood sinuses. It seems plausible that ZnO NPs

are rapidly dissolved. As a whole, the subcellular

distribution of metal-bearing NPs is seemingly

dependent on their size and solubility (this latter

being affected by the presence of additives); which

determine the uptake mechanisms in digestive

cells (e.g. endocytosis), their fate in the endo-

lysosomal system and the mode of release from

digestive cells.

A c k n o w l e d g e m e n t s

This work was funded by EU 7th FP (NanoReTox

project, CP-FP 214478-2), Spanish Ministry

(NanoCancer project CTM2009-13477 and

NanoSilverOmics project MAT2012-39372), Basque

Government (consolidated research group IT810-

13) and University of the Basque Country (UFI

11/37, and predoctoral fellowship to A. J-R).

Alba Jimeno-Romero1, Alice

Warley2, Miren P. Cajaraville

1, Manu

Soto1, Ionan Marigómez1

[email protected]

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N a n o t o x i c o g e n o m i c s : t r a n s c r i p t i o n

p r o f i l i n g f o r t h e a s s e s s m e n t o f

n a n o m a t e r i a l s t o x i c i t y m e c h a n i s m s

CBET Research group, Dept. of Zoology and Animal Cell Biology; Research Centre for

Experimental Marine Biology and Biotechnology PIE, University of Basque Country

(UPV/EHU). Sarriena z/g, E-48940, Leioa, Basque Country, Spain.

Recent studies show that certain nanomaterials

(NMs) are toxic to living organisms, both in in vitro

and in vivo studies. Main common mechanisms of

toxicity, such as immunotoxicity, inflammation and

increased production of oxygen reactive species

which, in turn, provoke oxidative stress, have been

already demonstrated for NMs. Nevertheless,

specific mechanisms for different materials and

key properties (i.e., solubility, size, shape)

influencing toxicity remain to be elucidated.

Toxicogenomics is a high throughput tool to

investigate the molecular and cellular mechanisms

of action of chemicals and other environmental

stressors, including NMs, on biological systems,

predicting toxicity before any functional damages,

and allows classification of materials based on

signatures of gene expression [1].In this work, we

studied the transcriptomic response in the liver of

adult zebrafish (Danio rerio) exposed to 10 μg

metal/L of CuO nanoparticles (NPs) of ~100 nm,

maltose-coated Ag NPs of 20 nm and CdS quantum

dots (QDs) of 3.5-4 nm, as well as to their ionic

counterparts (CuCl2, AgNO3 or CdCl2). After 3 and

21 days of exposure, the liver of 20 males was

dissected out and a microarray study was

performed using the Agilent technology Zebrafish

(v3), 4x44k Gene Expression Microarray.

Copper exposures caused a weak effect on liver

transcriptome compared to the response elicited

by silver and cadmium compounds. CuO NPs

differentially regulated 69 transcripts (LIMMA

adjusted p<0.05 value) after 3 days of exposure

while ionic copper significantly altered the

expression of 30 transcripts after 21 days of

exposure. Most of the GO terms (9 out of the 11)

were shared in both treatments. General terms

involving basic biological processes, such as

“cellular process”, “single organism process”,

“metabolic process”, “biological regulation” and

“responses to stimulus” appeared enriched.

Sequences related to “rhythmic process” were

only regulated after 3 weeks of exposure to ionic

copper. Exposure to silver for 3 days significantly

regulated 243 different genes (Ag NPs) or 399

genes (ionic silver). After 21 days, the opposite

trend was found: ionic silver regulated 265

transcripts and Ag NPs altered 990 different genes.

At 3 days, ionic silver produced a strong

disturbance of the energetic metabolism, inducing

fatty acid catabolism, biosynthesis of unsatured

fatty acids and peroxisome proliferator activated

receptor signaling pathway and inhibiting

glycolysis, among others. All these alterations did

not remain after 21 days. Exposure for 3 days to Ag

NPs inhibited steroid biosynthesis and induced

fatty acid catabolism and several amino acids

catabolism. After 21 days, pentose phosphate

pathway, ether lipid metabolism, most of the

amino acids metabolism and many ribosomal

proteins were up-regulated. CdS QDs significantly

regulated 9 and 3638 genes after 3 and 21 days,

respectively, while the ionic form regulated 37 and

11224 genes. Both cadmium forms up-regulated

RNA degradation related biological processes after

21 days. In addition, ionic cadmium altered the

DNA repair metabolism and down-regulated the

carboxylic acid, alcohol and glycerol metabolic

José M. Lacave, Unai Vicario-Parés,

Eider Bilbao, Miren P. Cajaraville,

Amaia Orbea*

[email protected]

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processes and amino acid and derivative metabolic

processes, among others. QDs exposure inhibited

actin cytoskeleton including focal adhesions and

metabolism of carbohydrates and some amino

acids, among others.

Overall, these results show distinct gene

transcription signatures for the three metals, being

the non-essential metals, silver and cadmium,

those eliciting the strongest response in the

zebrafish liver. Copper only altered general

biological processes. In addition, transcription

profiles distinguished metal forms (NP versus ionic

form) and exposure times (3 versus 21 days),

appearing as an useful tool to unveil nano-specific

mechanisms of toxicity.

R e f e r e n c e s

Funded by EU 7th FP (CP-FP 214478-2), Spanish

MICINN and MINECO (CTM2009-13477 and

MAT2012-39372), UPV/EHU (UFI 11/37), and

Basque Government (IT810-13). Technical and

human support provided by the UPV/EHU SGiker is

acknowledged.

R e f e r e n c e s

[1] Zhou T, Chou J, Watkins PB, Kaufmann WK. In:

Molecular, Clinical and Environmental

Toxicology. Vol 1: Molecular Toxicology. Ed.

Luch A. 2009. Birkhäuser Verlag/Switzerland.

Pp 325-366

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M e c h a n i s m s o f t o x i c a c t i o n o f

m a n u f a c t u r e d n a n o m a t e r i a l s

u n r a v e l e d b y m e a n s o f i n v i t r o

s y s t e m s

INIA (National Institute for Agricultural and Food Research and Technology)

Dpt. of Environment; Ctra de la Coruña Km 7.5; E-28040 Madrid

Over the last decade, an increasing number of

manufactured nanomaterials (MNs) have been

incorporated into new products or processes. As a

result, the risk of release of these nanomaterials to

the environment is rising. However, nowadays

there are analytical deficits that limit our

capabilities to determine actual levels of exposure

to these new substances. In addition, and although

new information about the toxicity of MNs is

released continuously, there is an important lack

of knowledge in relation to the hazard posed by

nanoparticles (NPs) to organisms. As a result the

risk assessment of these materials suffers of

important constraints. Establishing the

mechanisms of toxic action of MNs at the

organismal, tissue and cellular level is essential to

better understanding their possible long-term

effects necessary for an appropriate hazard

assessment. Taking this into account we have done

an important effort trying to unravel the

mechanisms underlying the toxicity of a number of

MNs to cells maintained in vitro. Most of our work

has been performed with fish cells cell lines, but

mammalian and human cell lines were also used as

a reference. Suspensions of MNs were obtained in

culture medium and characterized through a

variety of techniques including dynamic light

scattering (DLS; to determine frequency size

distribution), transmission and scanning electron

microscopy (TEM and SEM respectively; to

establish frequency size distribution and shape)

and inductively coupled plasma mass spectrometry

(ICP-MS; to measure actual exposure

concentrations) among others. Cytotoxicity was

assessed through a number of techniques and the

possible interference of the NPs with the readouts

was estimated. In addition, levels of glutathione

(GSH and GSST) and enzyme measurements gave

important information about oxidative stress. By

means of centrifugation or ultracentrifugation we

were able to retire NPs obtaining the ionic

fractions of the suspensions. The use of electron

microscopy allowed observing the internalization

of MNs into cells and their interaction with plasma

membrane and with cellular organelles. We have

been able to set up a methodology for observing

through three different measurements performed

simultaneously in the same plate possible

disturbances on the plasma membrane, on

lysosome functioning and on cellular metabolism.

These approaches allowed us to estimate the

contribution to the toxicity of the ionic fractions of

the suspensions and to observe, with some

exceptions, a limited toxicity of the particulated

fraction. We reported also important variations in

the toxicity of different forms of the same MN,

variations that were difficult to relate with

particular properties (as shape or size). We studied

in depth the mechanisms of internalization of

some MNs considering the possibility that they can

influence the toxicity of other substances present

in the medium or that they could have some

applications if used as carriers. Graphene

nanoplatelets exhibited a very particular behavior,

with nanoplatelets causing toxicity only at high

concentrations and being present in the cytoplasm

without surrounding membranes. Co-exposure

experiments have allowed obtaining very

important information. For instance, it has been

evidenced that graphene could facilitate the

entrance of environmental contaminants into the

cells increasing toxicity. Coincubation of CuNPs and

ZnONPs also provoked striking synergistic toxicity,

probably due to a mutual interaction of these MNs

potentiating the entrance of particles and ions into

the cells until unbearable levels. These

Jose Maria Navas

[email protected]

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experiments also permitted to establish some

limitations to the oxidative stress paradigm applied

to MNs. In this case, the simultaneous exposure to

CuNPs causing an increase in reactive oxygen

species (and therefore in oxidative stress) and of

substances triggering the cellular defenses against

oxidative stress and provoking a reduction of ROS

levels did not lead to a simultaneous decrease in

toxicity.

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C o l l o i d a l S t a b i l i t y h a s a c r u c i a l r o l e

f o r n a n o m a t e r i a l s t o x i c i t y t e s t i n g i n -

v i t r o : n Z V I - a l g a e c o l l o i d a l s y s t e m a s

c a s e s t u d y

1:Departamento de Biología, Facultad de Ciencias, Universidad Autónoma de Madrid,

Cantoblanco, E-28049 Madrid, Spain. 2:

Departamento de Ingeniería Química, Universidad de Alcalá, E-28871, Alcalá de

Henares, Madrid, Spain. 3:Department of Environmental Engineering Sciences, University of Florida, Gainesville,

Florida, USA

Aggregation is one among those parameters

focusing the attention in Nanotoxicology due to its

methodological implications [1, 2]. Aggregation is a

physical symptom of a more general

physicochemical condition of colloidal particles,

that is, colloidal stability. A destabilized colloidal

system may tend to reduce its net surface energy

by self-aggregation, but also by hetero-aggregation

which may involve biological interfaces. In this

regards, colloidal stability may have an important

role as driver of ENM bioactivity. In the present

study, a physical speciation phenomenon of nZVI

nanoparticles, we called colloidal singularity [3],

was found when generating a dose gradient of

zero-valent iron nanoparticles (nZVI) in algal

culture medium. The colloidal singularity consisted

of an exceptionally stable ENM suspension with

particles in their primary size (4 - 12 nm) occurring

within a tight dose range (0.1-0.5 mg/L). Outside

this range, nZVI suspensions aggregated.

Interestingly, nZVI exhibited toxicity to the algal

model organism, except in the 0.1-0.5 mg/L dose

range. Stability analyses, TEM images and FTIR

revealed that nZVI toxicity was mediated by nZVI-

alga interaction, and that the increased colloidal

stability of nZVI suspensions in the 0.1-0.5 mg/L

dose range prevented nZVI-algae interaction and

subsequent toxicity. Furthermore, in-situ

destabilization of this particular suspension using a

classical flocculating agent Al2(SO4)3 resulted in

toxicity. These observations demonstrate that

colloidal stability has a major role in nZVI toxicity

and that may be carefully taken in to account

when performing safety assessment of

nanomaterials beyond the initial considerations for

stock sample preparation.

R e f e r e n c e s

[1] Handy, R. D.; Cornelis, G.; Fernandes, T.;

Tsyusko, O.; Decho, A.; Sabo-Attwood, T.;

Metcalfe, C.; Steevens, J. A.; Klaine, S. J.;

Koelmans, A. A.; Horne, N., Environ Toxicol

Chem (2012), 31 (1), 15-31. DOI

10.1002/etc.706.

[2] Schrurs, F.; Lison, D., Nat Nanotechnol (2012),

7 (9), 546-8. DOI nnano.2012.148

[pii]10.1038/nnano.2012.148.

[3] Gonzalo, S.; Llaneza, V.; Pulido-Reyes, G.;

Fernandez-Pinas, F.; Bonzongo, J. C.; Leganes,

F.; Rosal, R.; Garcia-Calvo, E.; Rodea-

Palomares, I., PloS one (2014), 9 (10),

e109645. DOI 10.1371/journal.pone.0109645.

Rodea-Palomares, I1,2

, Pulido-Reyes,

G1. Gonzalo S.

2, Llaneza V.

1,2,3,

Fernández-Piñas F.1, Bonzongo J.C.

3,

Leganés F.1 & Rosal R.2

[email protected]

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I n t e r n a l i z a t i o n a n d t o x i c i t y o f a m i n e

a n d h y d r o x y l t e r m i n a t e d

p o l y ( a m i d o a m i n e ) d e n d r i m e r s t o

p h o t o s y n t h e t i c m i c r o o r g a n i s m s

1

Department of Chemical Engineering, University of Alcalá, E-28871, Alcalá de

Henares, Madrid, Spain 2

Advanced Study Institute of Madrid, IMDEA-Agua, Parque Científico Tecnológico, E-

28805, Alcalá de Henares, Madrid, Spain 3 Department of Biology, Universidad Autónoma de Madrid. 28049 Madrid, Spain.

Poly(amidoamine) (PAMAM) dendrimers are

hyper-branched polymers with uniform size,

defined molecular weight, large internal cavities

and a high number of surface groups that make

them particularly suitable for a number of

biomedical and technological applications [1]. It

has been found that surface functionalization is

the main factor modulating the toxicity of

dendrimers to mammalian cells lines, but their

effects for aquatic microorganisms is still largely

unknown [2]. We are presenting results on the

effect of generation G2, G3 and G4 amine-

terminated (–NH2) and hydroxyl terminated (-OH)

PAMAM dendrimers towards the green alga

Chlamydomonas reindhartii and the

cyanobacterium Anabaena PCC7120.

We studied the internalization of dendrimers using

PAMAM-Alexa Fluor 488 conjugates and their toxic

effect by tracking the inhibition of growth rate and

the formation of reactive oxygen species (ROS)

revealed by the fluorescent dyes 2',7'-

dichlorofluorescein diacetate and C4-BODIPY®.

Fluorescence studies were performed by flow

cytometry and confocal microscopy. Ultrastructure

alterations were studied by transmission electron

microscopy (TEM). We also report a

physicochemical characterization of PAMAM

dendrimers in culture media based on size

distribution obtained using dynamic light

scattering and zeta potential measured via

electrophoretic light scattering.

All amine-terminated and the G4 hydroxyl-

terminated dendrimers significantly inhibited the

growth of both microorganisms, the effect on the

green alga being higher. Expressing concentrations

in terms of molarity, it was observed a higher

toxicity for growing dendrimer generation. We also

detected a hormetic effect for hydroxyl-

terminated dendrimers at low concentrations.

Cationic PAMAM dendrimers were largely and

quickly internalized in both organisms showing a

diffuse distribution in cyanobacteria and affecting

mitochondria in algal cells.

All cationic dendrimers and G4-OH significantly

increased the formation of ROS in both organisms.

ROS formation was not related with the

chloroplast or photosynthetic membranes.

Significantly, photosystem II photochemistry was

not affected. ROS damage resulted in cytoplasm

disorganization and cell deformities and were

associated in the green alga to lipid peroxidation in

mitochondria. In the cyanobacterium we also

observed intense ROS formation, cell wall and

membrane disruption and loss of cytoplasmic

contents.

These results warn against the generalization of

the use of dendrimers which may pose significant

risk for the environment and particularly for

primary producers which are determinant for the

health of natural ecosystems. Hydroxyl-

functionalized molecules, still bearing a positive

charge, have also been shown toxic for

photosynthetic organisms.

R e f e r e n c e s

[1] S. Svenson, D.A. Tomalia, Dendrimers in

biomedical applications—reflections on the

field, Adv. Drug Deliv. Rev. 57 (2005) 2106-

2129.

[2] K. Jain, P. Kesharwani, U. Gupta, N.K. Jain.

Dendrimer toxicity: Let's meet the challenge.

Int J Pharm, 394 (2010) 122-142.

Roberto Rosal1,2

, Ismael Rodea-

Palomares1,3

, Soledad Gonzalo1,

Francisco Leganés3, Francisca

Fernández-Piñas3

[email protected]

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1 0 y e a r s o f n a n o t o x i c o l o g y r e s e a r c h -

w h a t h a v e w e l e a r n e d ?

CeSI, Aging Research Center, ‘‘G. d’Annunzio’’ University Foundation, Via Colle dell’Ara,

66100 Chieti, Italy;

LASA, University of Milan and INFN-Milan, via F.lli Cervi 201, 20090 Segrate,Milan, Italy

Nanotechnology, the science of a few billionths of

a meter, is today one of the fastest growing fields

in engineering. The feverish development of

engineered nanomaterials (NM) represents an

evolving revolutionary technology that has the

potential to have an impact on an incredible

number of industries, markets and areas of our

life. Unfortunately, in spite of the great excitement

about the potential benefits offered by

nanotechnology a huge health and safety

questions remain unsolved, and toxicological

evidences are emerging to fear that NM could

have undesirable health effects, leading the

scientific community to severe controversy

without reaching a consensus about the heal th

safety of NM. In this context, in 2004 a new

emerging discipline, nanotoxicology, has become a

new frontier in NM toxicology relevant to

workplace, general environment and consumer

safety [1]. However, the issue of nanotoxicology is

more complicated than previously thought and

proactive multidisciplinary research is an urgent

need for a mechanistic understanding of the

interaction of NM with biological systems.

Although in the last 10 years many positive lessons

have been learnt more gaps and uncertainties than

certainties are still existing, and few findings are

conclusive about the nature and extent of the

hazards of NM. In addition, the comparison of the

results at international level can be done only with

great difficulty and the interpretation of the

biological effects cannot be done with the

necessary severity.

This presentation highlights shadows and lights

emerged from the last 10 years of nanotoxicology

research, focusing on selected areas of emerging

toxicology-based challenges presented by NM:

physicochemical characterization (role of size,

shape, agglomeration, surface area, crystallinity,

porosity, surface modification characteristics in

understanding and assessing material toxicity);

metabolic pathways (uptake, translocation to

other tissues, intracellular trafficking in relation to

NM toxicity); biointeraction and biological

responses (corona effect, inflammation and

oxidative stress, systemic effects, genotoxicity and

carcinogenicity, interaction with the immune

system).

Although many advances have been made in

improving the design of studies carried out to

evaluate NM toxicity, and in developing suitable

testing strategies to assess NM safety the scientific

knowledge is still inadequate for a risk assessment

of NM, and at present NM can not be considered

neither “angels” nor “demons”

R e f e r e n c e s

[1] Donaldson K, Stone V, Tran CL, Kreyling W,

Borm PJ. (2004) Nanotoxicology, Occup

Environ Med 61:727–728.

E. Sabbioni

[email protected]

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T o w a r d s a h a r m o n i z e d S a f e t y

A s s e s s m e n t o f N a n o m a t e r i a l s

GAIKER Technology Center, Parque Tecnológico de Zamudio Ed. 202

48170, Zamudio, Vizcaya, Spain

Traditional toxicology´s main concern is to study

the adverse effects of chemicals on a given set of

known cytological, physiological and

morphological parameters. However, these set of

well defined studies do not take into account the

special nature of nanomaterials, such as their small

size, aggregation capacity and reactivity. These

new properties may be able to alter the absorption

and transport capacity of nanomaterials across

membranes. There is also a potential for

nanomaterials to accumulate in organs, enter into

blood circulation or even cross the placental-foetal

barrier.

One main objective of the European Project

“NANoREG” is to produce a set of high quality

toxicity data from a selection of industrially

relevant nanomaterials with the aim to speed

nanomaterial toxicity assessment. To achieve this

aim the proposed strategy is two-fold; on one

hand a set of standard in vitro toxicity protocols

will be duly reviewed and adapted to the

particulars of nanomaterials if necessary based on

previous experiences from other initiatives and the

Pharma industry. On the other hand, in vitro

technologies will be challenged with a direct and

unique comparison to in vivo data. In this regard,

complex inhalation toxicity models have been

included as a way to simulate inhalation toxicity in

vitro. The final aim of this exercise being to assess

the potential of in vitro models to predict

nanotoxicity, speeding, in this way, nanomaterial

toxicity assessment. Currently, an initial

harmonization step has taken place focusing

mainly on cell lines, dosage, incubation times,

exposure mechanisms and detection techniques

and covering mainly intestine, liver, lung and the

immune system.

Our strategy aims at the core of engineered

nanomaterial development, assisting in

nanomaterial design by providing a fast and

reliable evaluation of nanomaterial toxicity in the

same fashion as any other conventional drugs are

assessed for toxicity at their preclinical stage.

R e f e r e n c e s

[1] Domínguez A, Suarez-Merino B, Goni-de-Cerio

F. Nanoparticles and blood-brain barrier: the

key to central nervous system diseases. J of

Nanoscience and Nanotech. 14: 766-779.

2014.

[2] Goñi-de-Cerio F, Mariani V, Cohen D, Madi L,

Thevenot J, Oliviera H, Uboldi C, Giudetti G, et

al. Biocompatibility study of two diblock

copolymeric nanoparticles for biomedical

applications by in vitro toxicity testing. J

Nanoparticle Res. 11: 1-17. 2013.

[3] Errico C, Goñi-de-Cerio F, Alderighi1 M, Ferri1

M, Suarez-Merino B, Soroka Y, Frušic-Zlotkin

M and Chiellini F. Retinyl palmitate–loaded

poly(lactide-co-glycolide) nanoparticles for the

topical treatment of skin diseases. Journal of

Bioactive and Compatible Polymers 27(6) 604-

620. 2012.

Blanca Suarez-Merino, Carol

Aristimuño, Felipe Goñi de Cerio,

Pedro Heredia

[email protected]

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S a f e m a n u f a c t u r i n g a n d o c c u p a t i o n a l

e x p o s u r e t o n a n o - T i O 2

F i r s t e x p e r i e n c e s i n f o u n d r y a n d s t e e l

m e t a l s e c t o r 1

Tecnalia, Leonardo Da Vinci, 11, Miñano, Spain 2 University of the Basque Country,Alameda de Urquijo s/n, Bilbao, Spain

3 Bostlan S.A., Mungia, Spain;

4 Gerdau I+D,Basauri, Spain

5 Tekniker, Eibar, Spain

6 Nanobaske, PT de San Sebastián, Spain

The growth of new products and industrial

processes based on nanotechnology has raised

issues about occupational exposure. This work

presents the measurements of occupational

exposure (inhalation and dermal) to nano-TiO2 that

have been done in three case studies covering the

life cycle of nano enable products for the foundry

and steel sector. It has been done inside the EHS-

Advance project funded by the Basque

Government (http://www.ehsadvance.com/).

The measurements have been done in industrial

work environments and include processes of

nanopowder manipulation, cold compressing,

development of tablets of nano-TiO2 and their final

incorporation in a steel ingot in a steel making

factory.

The exposure assessment strategy (inhalation)

followed NIOSH (Bulletin 63) (NIOSH, 2011).

Samples at the personal breathing zone have been

collected for off-line ICP-MS and SEM/EDX

analysis. Simultaneously, the aerosols released in

the activities have been characterized using on-line

devices following the tiered approach established

by Asbach et al. (2012).Occupational exposure

limit used for nano-TiO2 are 0.3 mg/cm3 (NIOSH,

2011). The method to measure dermal exposure is

inspired on ISO/TR 14294, specifically we have

used a removal technique (wipe sampling);

currently there is no limit value available for

dermal exposure to nano-objects.

The results showed that the occupational exposure

to nano-TiO2 was below the selected OEL for all

scenarios measured. On the other side, the

characterization of the aerosol released during the

different processes presented difficulties in some

scenarios due to the strong influence of

background in industrial environments (advanced

statistical analysis is currently being performed).

Finally the data on dermal exposure showed very

low concentration on the hands of the operators,

which may be due to residual contamination

during sampling.

These results contribute to the design and

adaptation of safe industrial processes developing

nanoenable products for this sector. This study

also has allowed the development of resources for

the EHS Advance initiative

R e f e r e n c e s

[1] NIOSH (2011) Occupational Exposure to

Titanium Dioxide. Current intelligence bulletin

63.

[2] Asbach C. et al. (2012) NANOGEM: Standard

Operation Procedures. Federal Ministry of

Educationand Research.

[3] ISO/TR 14294 (2011) Workplace atmospheres

— Measurement of dermal exposure —

Principlesand methods.

Vaquero C.1, López de Ipiña

JML. 1, Gutierrez-Cañas C.

2,

Arrabal M. 3, Idoyaga Z.

4,

Blanco M. 5, Martínez A.

6

[email protected]

PPM

201 5

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I n d e x P P M 2 0 1 5 C o n t r i b u t i o n s A l p h a b e t i c a l O r d e r

K : K e y n o t e / O : O r a l Page

Acuna, Guillermo (TU Braunschweig, Germany) DNA-origami structures for nanophotonics

O 295

Ahopelto, Jouni (VTT, Finland) Silicon Nanomembranes for Phononics

K 296

Banin, Uri (The Hebrew University of Jerusalem, Israel) Dimensionality Matters: Dimensionality Effects on Optoelectronic Behavior of Semiconductor Nanocrystals

K 297

Barbry, Marc (CFM-MPC, Centro Mixto CSIC-UPV/EHU , Spain) First-principles calculation of plasmonic resonances and electric field enhancement in metal-cluster dimers

O 298

Belobrov, Peter I (MOLPIT, Siberian Federal University, Russia) Experimental proofs of collective electron states and their localization into porous composites from nanodiamond and pyrocarbon

O 299

Consoli, Antonio (Instituto de Ciencia de Materiales de Madrid, Spain) Spectral characterization of mutually coupled random lasers

O 300

Cox, Joel (ICFO – The Institute of Photonic Sciences, Spain) Nonlinear Graphene Plasmonics

O 301

Cuevas, Juan Carlos (UAM, Spain) Near-field radiative heat transfer at the nanoscale

K 302

Dapuzzo, Fausto (University of Rome "Sapienza", Italy) THz and Mid-Infrared Plasmonic Excitation in 3D Nanoporous Graphene

O 303

Dekorsy, Thomas (Universitaet Konstanz, Germany) Coherent acoustic excitations in magnetic shape memory alloys

K 304

de Vega Esteban, Sandra (The Institute of Photonic Sciences (ICFO), Spain) Plasmonics in atomically flat gold structures

O 305

De Wilde, Yannick (ESPCI Paris Tech-CNRS, France) Near-field investigation of the electromagnetic local density of states

K 305A

Donadio, Davide (MPI for Polymer Research, Germany) Hierarchical nanostructured materials for phonon control and thermoelectric applications

K 306

Dorozhkin, Pavel (NT-MDT, Russia) Light Emitting Semiconductor Nanostructures Studied by SNOM

O 307

Espinha , André (Instituto de Ciencia de Materiales de Madrid, Spain) Engineering light transport in titania-doped multifunctional elastomers

O 308

Fernandez, Victor (Universidad Autónoma de Madrid, Spain) Radiative heat transfer through nanometer-size gaps

O 309

García de Abajo, Javier (ICFO, Spain) Plasmons in nanographene and other atomic scale systems

K 310

Garcia-Martin, Antonio (IMM-CNM/CSIC, Spain) Magneto-optical activity in interacting magnetoplasmonic nanodisks

O 311

Gnauck, Peter (Carl Zeiss Microscopy, Germany) Towards Sub-10 nm Nanofabrication of Plasmonic and Graphene Devices using Multiple Electron and Ion Beams

O 312

Jiménez-Solano, Alberto (CSIC, Spain) Fine tuning of the emission properties of nano-emitters in multilayered structures by deterministic control of their local photonic environment

O 314

Kavan, Ladislav (J. Heyrovsky Institute of Physical Chemistry, Czech Republic) Nanocrystalline Diamond Electrode for Dye-Sensitized Solar Cells

O 315

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Lodewijks, Kristof (Chalmers University of Technology, Sweden) Magnetoplasmonic design rules for active magneto-optics

O 316

López-Tejeira, Fernando (Universidad de Zaragoza, Spain) 1D Line Current Model for Plasmonic Half-Wave Antennas: From Nanorods to Nanocarrots

O 318

Maasilta, Ilari (University of Jyväskylä, Finland) Low temperature thermal properties of two-dimensional phononic crystals

K 319

Martinez, Alejandro (Universitat Politècnica de València, Spain) Synthesis and measurement of polarization states with silicon nanoantennas

O 320

Martinez Saavedra, Jose Ramon (ICFO, Spain) Probing nanographene phonons with electron energy-loss spectroscopy

O 321

Marzari, Nicola (EPFL, Switzerland) Engineering electrical wires in honeycomb lattices

K 322

Montesdeoca Cárdenes, Denise (Instituto de Ciencia de Materiales de Madrid, Spain) Fast fabrication of photonic glasses achieved by pressure

O 323

Pariente, Jose Angel (Instituto de Ciencia de Materiales de Madrid ICMM – CSIC, Spain) Fine control transition from photonic crystals to photonic glasses

O 324

Paltiel, Yossi (The Hebrew University, Israel) Chiral molecules based nano spintronics

K 325

Perros, Elodie (ESPCI - CNRS - Institut Langevin, France) Characterization of subwavelength spatial correlations in near-field speckle patterns

O 326

Pineider, Francesco (University of Florence & INSTM, Italy) Circular magnetoplasmonic modes in noble metal and hybrid nanoparticles

O 327

Rakovich, Yury (Centro de Fisica de Materiales CSIC-UPV/EHU, Spain) Upconversion of Photoluminescence in II-VI Nanocrystals:Feasibility of Anti-Stokes Cooling

K 328

Ruello, Pascal (Université du Maine, France) Ultrafast light-induced coherent phonons in condensed matter

K 329

Sarriugarte, Paulo (CIC nanoGUNE, Spain) Near-Field Mapping of Extremely Confined(λ0/310) IR Modes on FIB Fabricated Transmission Lines

O 330

Sarusi, Gabby (Ben-Gurion University, Israel) Infrared to Visible Integrated Up-Conversion Imaging Device using Nano-Plasmonic and Nano-Structures Absorber

K 331

Schliesser, Albert (Niels Bohr Inst / Copenhagen University, Denmark) Nanomechanical membranes as transducers for classical and quantum signals

K 331A

Silveiro, Iván (ICFO- Institut de Ciencies Fotoniques, Spain) Quantum nonlocal effects in individual and interacting graphene nanoribbons

O 332

Sotomayor Torres, Clivia M. (ICN2, Spain) Acoustic phonon Propagation in 1D and 2_D silicon-based Phononic Crystals

K 333

Tappura, Kirsi (VTT Technical Research Centre of Finland, Finland) Periodic plasmonic nanostructures for enhanced light absorption in silicon

O 334

Tserkezis, Christos (Donostia Internatioal Physics Center and Centro de Fisica de Materiales CSIC-UPV/EHU, Spain) Controlling the optical properties of ultranarrow plasmonic nanoparticle-on-mirror cavities

O 335

Vavassori, Paolo (CICnanoGUNE, Spain) Magneto-Plasmonic nanoantennas based metamaterials

K 336

Volz, Sebastian (Ecole Centrale Paris-CNRS, France) Phonon Mediated Heat transfer in Vacuum

K 337

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D N A - o r i g a m i s t r u c t u r e s f o r n a n o p h o t o n i c s TU Braunschweig, Institute of Physical and Theoretical Chemistry, Hans-Sommer-Str. 10, Braunschweig, Germany

In this presentation, we will show how the DNA-Origami technique [1] can be introduced for plasmonic and photonic applications. Firstly, we employ DNA-Origami as a platform where metallic nanoparticles as well as single organic fluorophores can be organized with nanometer precision in three dimensions. With these hybrid structures we initially study the nanoparticle-fluorophore interaction in terms of the distance-dependent fluorescence quenching [2] and angular dependence around the nanoparticle [3]. Based on these findings, we build highly efficient nano-antennas (figure a) based on 100 nm gold dimers which are able to strongly focus light into the sub-wavelength region where the fluorophore is positioned and produce a fluorescence enhancement of more than two orders of magnitude [4]. Using this highly confined excitation field we were able to perform single molecule measurements in solution at concentrations as high as 500 nM [5] close to the biologically relevant range (>1μM). Additionally, we report on a controlled increment of the radiative rate of organic dyes in the vicinity of gold nanoparticles with the consequent increment in the number of total emitted photons [6,7]. Finally we will discuss how DNA-Origami can also improve the occupation of other photonic structures, the zeromode waveguides (ZMWs). These structures, which consist of small holes in aluminum films can serve as ultra-small observation volumes for single-molecule spectroscopy at high, biologically relevant concentrations and are commercially used for real-time DNA sequencing [8]. To benefit from the single-molecule approach, each ZMW should be filled with one target molecule which is not possible with stochastic immobilization schemes by adapting the concentration and incubation time. We present DNA origami nano-adapters that by size exclusion allow placing of exactly one molecule per ZMW (figure b). The DNA origami nano-adapters thus overcome Poissonian statistics of molecule positioning [9] and furthermore improve the photophysical homogeneity of the immobilized fluorescent dyes [10].

R e f e r e n c e s

[1] P. W. Rothemund, Nature 440, (2006) 297. [2] G. P. Acuna et al., ACS Nano 6, (2012) 3189. [3] F. Möller, P. Holzmeister, T. Sen, G. P. Acuna

and P. Tinnefeld, Nanophotonics 2, (2013) 167.

[4] G. P. Acuna et al., Science 338, (2012) 506. [5] G. P. Acuna et al., Journal of Biomedical Optics

18, (2013) 065001. [6] J. Pellegrotti et al., Nano Letters 14, (2014)

2831. [7] P. Holzmeister, E. Pibiri, J.J. Schmied, T. Sen, G.

P. Acuna and P. Tinnefeld, Nat. Comm. 5, (2014) 5356.

[8] Eid J et al., Science 323, (2009) 133. [9] E. Pibiri, P. Holzmeister, B. Lalkens, G.P. Acuna

and P. Tinnefeld, Nano Letters 14, (2014) 3499.

[10] Heucke S et al., Nano Letters. 14, ( 2014) 391. F i g u r e s

Guillermo Acuna, Enrico Pibiri, Anastasiya Puchkova, Phil Holzmeister, Birka Lalkens and Philip Tinnefeld

[email protected]

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S i l i c o n N a n o m e m b r a n e s f o r P h o n o n i c s 1 VTT Technical Research Centre of Finland Ltd, Tietotie 3, Espoo, Finland 2 ICN2 – Catalan Institute of Nanoscience and Nanotechnology, Campus UAB, 08193 Bellaterra, Spain

Heat dissipation in nanoelectronics devices, optimization of thermoelectric generators and development of optomechanical couplers, among others, call for understanding the behaviour of phonons in low dimensional structures. Silicon nanomembranes provide a tool to investigate experimentally the confinement of acoustic phonons and the effects on phonon dispersion and phonon propagation. [1-5] Microelectronics fabrication processes enable realisation of large area ultra-thin membranes with thickness down to a few nanometres and with well controlled strain and doping. In this talk we will discuss the challenges in the fabrication of the silicon membranes and show results of the effects arising from the acoustic phonon confinement.

R e f e r e n c e s

[1] C. M. Sotomayor Torres, A. Zwick, F. Poinsotte, J.

Groenen, M. Prunnila, J. Ahopelto, A. Mlayah and V. Paillard, physica status solidi (c) 1 (2004) 2609.

[2] A. Shchepetov, M. Prunnila F. Alzina, L. Schneider, J. Cuffe, H. Jiang, E-I Kauppinen, C.M Sotomayor Torres, J. Ahopelto, Ultra-thin free-standing single crystalline silicon membranes with strain control, Appl. Phys. Lett. 102 (2013) 192108.

[3] J. Cuffe, E. Chavez, A. Shchepetov, P.-O. Chapuis, E. H. El Boudouti, F. Alzina, T. Kehoe, J. Gomis-Bresco, D. Dudek, Y. Pennec, B. Djafari-Rouhani, M. Prunnila, J. Ahopelto and C. M. Sotomayor Torres, Nano Letters 12 (2012) 3569.

[4] E. Chávez-Ángel, J. S. Reparaz, J. Gomis-Bresco, M. R. Wagner, J. Cuffe, B. Graczykowski, A. Shchepetov, H. Jiang, M. Prunnila, J. Ahopelto, F. Alzina, and C. M. Sotomayor Torres, APL Materials 2 (2014) 012113.

[5] B. Graczykowski, J. Gomis-Bresco, F. Alzina, J. S. Reparaz, A. Shchepetov, M. Prunnila, J. Ahopelto and C. M. Sotomayor Torres, New Journal of Physics 16 (2014) 073024.

F i g u r e s

Figure 1: Schematics of a free-standing silicon membrane fabricated from a SOI wafer. The silicon nitride layer on top of the Si membrane is used to tune the strain in the membrane.

Figure 2: Top view optical image of a 6 nm thick membrane with 0.3 % tensile strain. The cross-sectional structure is shown in Fig. 1.

A. Shchepetov1, B. Graczykowski2, F. Alzina2, J. S. Reparaz2, C.M Sotomayor Torres2, M. Prunnila1, J. Ahopelto

1

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D i m e n s i o n a l i t y M a t t e r s : D i m e n s i o n a l i t y E f f e c t s o n O p t o e l e c t r o n i c B e h a v i o r o f S e m i c o n d u c t o r N a n o c r y s t a l s Institute of Chemistry and the Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 91904, Israel Studying the transition of properties of nanostructures as they develop from the zero-dimensional to the one-dimensional regime is significant for unravelling the modifications that occur in the electronic structure of the particle as its length to width aspect ratio is increased. Such understanding can lead to better design and control of the particle properties, with relevance for a wide range of technological applications. The ongoing improvements in the control of shape and morphology of nanoparticles in colloidal synthesis, which allows forming structures of similar composition but of different dimensionalities and shapes, open the way for probing such dimensionality effects. We will present several effects involving the 0D to 1D transition in colloidal nano heterostructures of different morphologies including “sphere in a sphere”, “sphere in a rod” and “rod in a rod”. In addition, a recently discovered new architecture of “nanorod couples” will be introduced.

Both ensemble and single particle based measurements were used to decipher these effects providing complementary viewpoints. The first dimensionality related aspect involves the modification of emission and absorption polarizations, as the dimensionality of the particles and of their cores changes. The second aspect relates to the function of these nanocrystals as donors in energy transfer processes to multiple dye molecules bound on their surfaces and functioning as acceptors (see schematic of the FRET process in the figure below). We will show how the dimensionality of the particles’ core and shell affects the donor’s time dependent survival probability, as well as the behavior of FRET to multiple acceptors on single particle level. The opportunity to tailor the systems dimensionality with multiple acceptors on the surface results in enhanced FRET efficiencies with relevance for optical, sensing and energy funneling applications.

F i g u r e s

Figure 1: Schematic representation of energy transfer processes between different core/shell semiconductor nanocrystals and multiple dye acceptors on their surface.

Uri Banin

[email protected]

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F i r s t - p r i n c i p l e s c a l c u l a t i o n o f p l a s m o n i c r e s o n a n c e s a n d e l e c t r i c f i e l d e n h a n c e m e n t i n m e t a l - c l u s t e r d i m e r s 1 CFM-MPC, Centro Mixto CSIC-UPV/EHU, Paseo Manuel de Lardizabal 5, San Sebastian, Spain 2 Donostia International Physics Center (DIPC), Paseo Manuel de Lardizabal 4, San Sebastian, Spain 3 Collisions Atomiques et Moleculaires, UMR CNRS-Université Paris-Sud 8625, Bt. 351 Université Paris-Sud, 91405 Orsay Cedex, France

Recent progress in fabrication of nanodevices has made possible the production of nanoobjects of controlled composition and shape down to atomic precision. Metallic clusters of Ag, Cu, Au have been used to amplify Raman spectroscopy signal [1]. One of the mechanism that leads to amplification of Raman signal is the enhancement of the electromagnetic field in the nanoscale [2]. Namely, if a metal cluster locates in the vicinity of a molecule, then the electromagnetic field induced by the c