1 2 nd TUS International Collaboration Workshop Joint Symposium with International Industry-Academia-Government Collaboration Tokyo University of Science (TUS) Topics: Nano Materials Science Date: December 10 and 11, 2008 Place: Hotel Metropolitan Edmont, Tokyo, near TUS Kagurazaka Campus Host University: Tokyo University of Science Collaboration Universities: University of California, Davis University of California, Santa Cruz Ohio State University University of California, Santa Barbara University of California, Los Angeles Invited Universities and Institutions: Bulgarian Academy of Sciences (Bulgaria) Institute of Organic Chemistry and Biochemistry (Czech Republic) Nanjing University of Science and Technology (China) Peking University (China) Shanghai Jiao Tong University (China) University of Alicante (Spain) University of Padova (Italy) University of Science and Technology, Beijing (China) University of Toronto (Canada) University of Waterloo (Canada) Zhejiang University (China)
Transcript
1
2nd TUS International Collaboration Workshop
Joint Symposium with International Industry-Academia-Government Collaboration
Tokyo University of Science (TUS) Topics: Nano Materials Science Date: December 10 and 11, 2008 Place: Hotel Metropolitan Edmont, Tokyo, near TUS Kagurazaka Campus Host University: Tokyo University of Science Collaboration Universities:
University of California, Davis University of California, Santa Cruz Ohio State University University of California, Santa Barbara University of California, Los Angeles
Invited Universities and Institutions: Bulgarian Academy of Sciences (Bulgaria) Institute of Organic Chemistry and Biochemistry (Czech Republic) Nanjing University of Science and Technology (China) Peking University (China) Shanghai Jiao Tong University (China) University of Alicante (Spain) University of Padova (Italy) University of Science and Technology, Beijing (China) University of Toronto (Canada) University of Waterloo (Canada) Zhejiang University (China)
2
Organizing Committee: Iwao Hashimoto (Chair, Dean of Faculty of Science) Yoshihiro Maruyama (Professor, Liberal Arts Program) Shizuo Miyajima (Professor, Department of Mathematics) Hiroshi Yabe (Professor, Department of Mathematical Information Science) Yoshimi Egawa (Professor, Department of Mathematical Information Science) Kazuyuki Watanabe (Professor, Department of Physics) Yukihiro Ishii (Professor, Department of Applied Physics) Tomohiko Saitoh (Associate Professor, Department of Applied Physics) Kazuo Miyamura (Program Leader, Professor, Department of Chemistry) Takeo Furukawa (Professor, Department of Chemistry) Hirofumi Yajima (Professor, Department of Applied Chemistry) Kenso Soai (Professor, Department of Applied Chemistry) Shinichi Saito (Associate Professor, Department of Chemistry) Tadanori Mizoguchi (Deputy Director, Center for Promotion of Internationalization) Cooperated by Robert Powell (University of California, Davis) Warren Pickett (University of California, Davis) Yayoi Takamura (University of California, Davis) David Belanger (University of California, Santa Cruz) Susie Miller (University of California, Santa Cruz) Dieter Wanner (Ohio State University) Matthew Platz (Ohio State University) Loy Lytle (University of California, Santa Barbara) Matthew Tirrell (University of California, Santa Barbara) David Unruh (University of California, Los Angels) David Lundberg (University of California, Los Angels)
3
Workshop Programs (Room Banri)
December 10 (Wednesday) Opening 9:00 - 9:05 President Shin Takeuchi 9:05 - 9:10 Opening Remarks by Dean I. Hashimoto 9:10 – 9:20 International Collaboration Approach by T. Mizoguchi Session I: Materials Physics Session Chair: T. Saitoh 9:20 – 9:40 Prof. N. Hamada, Tokyo University of Science “Thermoelectric Power Calculation by the Bloch-Boltzmann Theory” 9:40 – 10:00 Prof. W. Pickett, University of California, Davis “Electron Behavior and Misbehavior at Polar interfaces and Surfaces” 10:00 – 10:20 Prof. Dave Belanger, University of California, Santa Cruz “Nanoparticle size as a length probe of order in cobaltites” 10:20 – 10:40 Prof. Kaiming Deng, Nanjing University of Science and Technology
“Could the properties of Sn12 and Pb12 be tuned with 3d transition-metal atoms?”
10:40 – 11:00 Coffee Break Session Chair: W. Pickett 11:00 – 11:20 Prof. Lian-Mao Peng, Peking University
“High Performance Carbon Nanotube Based CMOS and Optoelectronics Devices”
11:20 – 11:40 Prof. Pimo He, Zhejiang University “Controlling the Electronics Structures of Graphene”
11:40 –12:00 Assoc. Prof. Junjie Qi, University of Science and Technology, Beijing “Electrical Transport Properties of Polar-Surface Dominated Sb-doped ZnO
12:00 – 12:20 Prof. Mustafa Yavus, University of Waterloo “Nanojoining and Fabrication of Nanojunctions”
At Room Hakoh Poster Session Chair: K. Watanabe Poster Session (10:30 – 16:30) 12:20 – 14:30 Core Time for Odd Number Posters At Room Banri Ridai Scitec Industry-Academia-Government Collaboration Session I Topics on Advanced NanoTechnology Research at TUS (先端ナノテクノロジー研究紹介) 13:00 – 13:25 Takashi Yamashita (Department of Pure and Applied Chemistry)
Functionalization of Thermo-Stable Transparent Polymers (耐熱性透明樹脂の高機能化)
13:30 – 13:55 Naoki Toshima (Department of Materials and Environment Technology, Tokyo University of Science, Yamaguchi)
New Development in Technology of Metal Nanoparticles (金属ナノ粒子技術の新展開)
(Note: In Japanese, no English translation in this session. 注意：日本語での発表、
英語通訳はなし。)
Session II: Chiral Materials Research Session Organizer: Kenso Soai, Shinichi Saito 14:30 – 15:00 Prof. Carmen Najera, University of Alicante
“Enantioselective Synthesis of Proline Derivatives by Asymmetric1,3-Dipolar Cycloadditions of Azomethine Ylides and Alkenes”
Chairperson: Prof. Kenso Soai 15:00 – 15:30 Prof. Jared T. Shaw, University of California, Davis
“New multicomponent reactions (MCRs) for the rapid assembly of complex chiral molecules” Chairperson: Prof. Tadashi Nakata
15:30 – 16:00 Dr. Irena. G. Stara, Institute of Organic Chemistry and Biochemistry “From Smaller to Larger Aromatics with Helical Chirality”
Chairperson: Prof. Tsuyoshi Sato
5
16:00 – 16:20 Coffee Break 16:20 – 16:40 Prof. Shinichi Saito, Tokyo University of Science
“Spontaneous Resolution and Dynamic Chirality of Bidentate Bis(N-heterocyclic carbene)-Palladium Complexes with Xanthene Framework”
Chairperson: Prof. Takao Saito 16:40 – 17:00 Prof. Tsuneomi Kawasaki, Tokyo University of Science “Asymmetric Autocatalysis Induced by Chiral Crystals Composed of
Achiral Organic and Inorganic Compounds as the Possible Route for the Origin and Evolution of Chirality”
Chairperson: Prof. Takao Saito 17:00 – 17:30 Prof. Annaliese Franz, University of California, Davis “Design and Synthesis of Organic Silanols for Asymmetric Catalysis” Chairperson: Prof. Isamu Shiina 17:30 – 18:00 Prof. Andrei K. Yudin, University of Toronto “Amphoteric Molecules for the Synthesis of Stereochemically Complex Amines” Chairperson: Prof. Yujiro Hayashi Poster Session Close at 16:30 18:45 – 20:30 Reception at Hotel Metropolitan Edmont (Room Banri)
6
December 11 (Thursday) Session III: Soft Materials Research and Analysis Session Chair: T. Furukawa 9:00 – 9:20 Prof. K. Tsukiyama, Tokyo University of Science
“Solvation structures of excess proton in protonated methanol cluster ions studied by infrared photodissociation spectroscopy”
9:20 – 9:40 Prof. Tonya Kuhl, University of California, Davis “X-ray Reflectometry and Grazing Incidence Diffraction Studies of the Structure of Single Phospholipid Bilayers on Solid Supports”
9:40 – 10:00 Prof. Prof. Yunfeng Lu, University of California, Los Angeles “A Novel Protein Delivery Platform based on Single-Protein-Nanogels” 10:00 – 10:20 Prof. Gao-Xiang Ye, Zhejiang University
“Metallic nano-structures and thin films on liquid substrates” 10:20 – 10:40 Prof. Brian Higgins, University of California, Davis “Dynamics of Coating Flows with Chemical Reaction”
10:40 – 11:00 Coffee Break Session Chair: Brian Higgins 11:00 – 11:20 Prof. T. Furukawa, Tokyo University of Science “Hierarchical structures and functional properties of polymers” 11:20 – 11:40 Prof. Vito di Noto, University of Padova
“Structure, properties and proton conductivity of Nafion/[(TiO2)·(WO3)0.148]ψTiO2 nanocomposite membranes”
11:40 – 12:00 Assoc. Prof. Roland Faller, University of California, Davis “Molecular Modeling of soft matter” 12:00 – 12:20 Prof. Shunai Che, Shanghai Jiao Tong University
“Anionic Surfactant Liquid Crystal Templating Route for Synthesizing Mesoporous Silica”
At Room Hakoh Poster Session Chair: T. Saitoh/K. Miyamura Poster Session 12:20 – 14:30 Core Time for Even Number Posters At Room Banri Ridai Scitec Industry-Academia-Government Collaboration Session II Topics on Advanced NanoTechnology Research at TUS (先端ナノテクノロジー研究紹介) 13:00 – 13:25 Prof. Yukishige Kondo, Department of Industrial Chemistry
13:30 – 13:55 Prof. Takeshi Kondo, Department of Industrial Chemistry Surface /Interface Control Of Conductive Diamond And Its
Application To Functional Electrode Material (導電性ダイヤモンドの表面・界面制御と機能性電極材料への応用)
(注意：日本語での発表、英語通訳はなし。Note: In Japanese, no English translation
in this session)
Continue Session III Soft Materials Research and Analysis (Room Banri) Session Chair: T. Furukawa 14:30 – 14:50 Prof. Shaowei Chen, University of California, Santa Cruz
“Functional Nanoparticles by Interfacial Engineering” 14:50 – 15:10 Prof. Shengfu Chen, Zhejiang University
“The Avenue to New Nonfouling Materials - a magic effect from nanometer size”
15:10 – 15:30 Coffee Break
8
Session IV Low Temperature Quantum Phenomena Session Chair: K. Watanabe 15:30 – 16:00 Prof. Takayanagi, Tokyo University of Science
“Spin-polarized Carrier Injection Effect in Ferromagnetic Semiconductor/ Diffusive Semiconductor/Superconductor Junctions”
16:00 – 16:30 Prof. Andrew Cleland, University of California, Santa Barbara ”Quantum control of photons and phonons using superconducting integrated circuits”
16:30 – 17:00 Prof. Tin-Lun Ho, Ohio State University “Grand Challenges and Opportunities in Ultra-Cold Atom Research”
17:00 – 17:30 Associate Professor Nikuni, Tokyo University of Science “Dynamics of Ultracold Quantum Gases”
Poster Session Close at 16:30 Note: Poster Session in parallel to oral sessions both December 10 and 11 Room: Hakoh Posters by Students, Post Doctoral Fellows, Young Researchers December 10 10:30 – 16:30
Core time 12:30 – 14:30 (Odd number) December 11 10:30 – 16:30
Core time 12:30 – 14:30 (Even number) Industry-Academia-Government Collaboration Booths both December 10 and 11 Room: Hakoh December 10 10:30 –16:30 December 11 10:30 – 16:30
9
December 12 (Friday) Coordination Meeting at Hotel Metropolitan Edmont, Tokyo Time: 9:00 – 12:00 Room: Bubaria Participants: TUS : I. Hashimoto (Dean, Faculty of Science, Member of Board of Director)
K. Watanabe (Professor, Department of Physics) T. Saitoh (Associate Professor, Department of Applied Physics) T. Furukawa (Professor, Department of Chemistry) Y. Egawa (Professor, Department of Mathematical Information Science) H. Yabe (Professor, Department of Mathematical Information Science)
Y. Nakatani (Associate Professor, Department of Management) T. Mizoguchi (Deputy Director, Center for Promotion of Internationalization) UCD : Warren Pickett (Chair Professor, Department of Physics)
Beth Greenwood (Director, International English & Professional Programs) Nicole Ranganath (Director, Global Study Program International Program)
UCSC : David Belanger(Chair Professor, Department of Physics) Shaowei Chen (Professor, Department of Chemistry)
Susie Miller (Director, English Language & International Program) OSU : Tin-Lun (Jason) Ho (Professor, Department of Physics) UCSB : Lili Byall (Director, University Immersion Program & Open Enrollment) UCLA : David Lundberg (Director, International Partnership of California
NanoSystems Institute) Zeta Yu-Peralta (Global Academic Program Development)
TUS : Administration Staff : M. Yoshidome, T. Watanabe, M. Kondou, T. Asakura,
M. Masuda, I. Schmidt, M. Shimamura
10
Agenda Discussion and confirmation of 2009 TUS Study Abroad schedule at UCD, UCSC
and UCSB Issues on course registration for TUS SAP students: early registration, treatment of
TUS compulsory courses, etc. Issues on changing campus from UCD to UCSC and UCSB in Fall: timing of
English skill qualification, student visa, course registration, accommodation, etc Discussion on a draft agreement of double degree program Next year (2009) planning of the lecture series in Materials Science Course aiming
opening of International Course at TUS: three 2 credits lectures in Materials Science Courses, one or two lectures in Chemical Science and Technology and Biological Science
Preparation of Nano-Bio Workshop in March 2009 Etc. For Other Participants 9:30 – 17:00 Excursion (To be planned)
11
Abstract
12
Session Ⅰ 9:20 – 9:40
THERMOELECTRIC POWER CALCULATION BY THE BLOCH-BOLTZMANN THEORY
N. Hamada,
Department of Physics, Faculty of Science and Technology, Tokyo University of Science
The first-principles calculation of the thermoelectric power receives great attention in order to design effective materials for efficient use of wasted heat. We employ the full-potential linearized augmented-plane-wave (FLAPW) method in the local density approximation (LDA). The Seebeck coefficient is estimated within the Bloch-Boltzmann theory, assuming that the relaxation time is independent of the wave vector and the energy. Applicability of the Boltzmann equation itself and its constant-relaxation- time approximation is questionable in application to actual materials. We often experience, however, that the Boltzmann theory can be applied beyond the theoretical limit, and gives us valuable information. Akasaka et al. shows that the calculation gives a quantitatively good result for the Seebeck coefficient in Mg2Si [1]. The calculation is, however, insufficient for NaxCoO2, because of the contribution of the magnetic fluctuation [2]. The calculation fails even to give a sign of the Seebeck coefficient for some metals, e.g., Mo. We review such calculations and show the problems that should be solved in the near future. [1] M. Akasaka, T. Iida, A. Matsumoto, K. Yamanaka, Y. Takanashi, T. Imai and N. Hamada, J. Appl. Phys. 104 (2008) 013703. [2] N. Hamada, T. Imai and H. Funashima, J. Phys.: Condens. Matter 19 (2007) 365221.
13
Session Ⅰ 9:40 – 10:00
ELECTRON BEHAVIOR AND MISBEHAVIOR AT POLAR INTERFACES AND SURFACES
Warren E. Pickett
Department of Physics University of California Davis
When growing layers of one ionic material on top of another with a differing type of formal charge per layer (LaAlO3 on SrTiO3, say, where layer charges are +1/-1 and 0/0 respectively), there is a local charge mismatch at the interface that has attracted great interest. As one grows such a system, and assuming the formal ionic charges persist, an increasingly large electric dipole forms. This is known as the polar catastrophe: the dipole potential grows with limit. This cannot be sustained to very many layers, and the questions is: what happens, when does it happen, and how does it happen? Density functional theory calculations reveal that strong polar ("ferroelectric") distortions screen the dipolar electric field (much more strongly than the electronic screening from LaAlO3), and sustain the formal charges (the system remains insulating) up to 5 unit cells of LaAlO3 on SrTiO3, similar to what is seen in experiment. At this point interesting metallization must occurs, although at this time of writing the process is not yet understand. "Capping" SrTiO3 layers produce unexpected changes, which will also be discussed. ** in collaboration with Rossitza Pentcheva.
14
Session I 10:00 – 10:20
Nanoparticle size as a length probe of order in cobaltites.
David Belanger
Department of Physics
University of California, Santa Cruz
We have grown nanoparticles of La1-xSrxCoO3 as small as 20nm and characterized them using neutron, x-ray, and magnetization techniques. I will describe similarities and differences between the nanoparticle properties and those of bulk particles with concentrations from zero to 0.35.
15
Session Ⅰ 10:20 – 10:40
Could the properties of Sn12 and Pb12 be tuned with 3d
transition-metal atoms?
Kaiming Deng
Department of Applied Physics
Nanjing University of Science and Technology
The geometric, optical, and magnetic properties of the M@X12 clusters (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni; X = Sn, Pb) are studied using the relativistic density-functional method. The geometric optimization shows that the ground states of M@X12 clusters are probably very close to the Ih structure. Our calculations demonstrate that the optical gaps of the M@Sn12 can be tuned from infrared to green by doping transition metal atoms into Sn12 cage, suggesting that M@Sn12 could be a new class of potential nanomaterials with tunable optical properties. The magnetism calculations demonstrate that the magnetic moments of M@Sn12 (M = Ti, V, Cr, Mn, Fe, Co, Ni) vary from 2μB to 5μB, and these of M@Pb12 (M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni) vary from 1μB to 5μB by doping different transition-metal atoms into Sn12 and Pb12 cage, respectively. Therefore, they possess tunable magnetic properties. Moreover, the electronic structure calculation shows that the Mn@Pb12 has large energy gap and doping energy. Of particular interesting is that its structure and energy gap remain unchanged with a strong external electric field up to 0.1 V/ Å, thus, Mn@Pb12 would be a good candidate as the building block with high magnetic moment for cluster assembly materials.
16
Session Ⅰ 11:00 – 11:20
High Performance Carbon Nanotube Based CMOS and
Optoelectronics Devices
Lian-Mao Peng Key Laboratory for the Physics and Chemistry of Nanodevices and
Department of Electronics, Peking University, Beijing 100871, China Ballistic n-type carbon nanotube (CNT) based field-effect transistors (FETs) have been fabricated by contacting semiconducting single wall CNTs using Sc. Together with the demonstrated ballistic p-type CNT FETs using Pd contacts, this closes the gap for doping free fabrication of CNT based ballistic CMOS devices and circuits. The feasibility of this doping free CMOS technology has been demonstrated by fabricating a simple CMOS inverter on a SiO2/Si substrate using the back-gate geometry, but in principle much more complicated CMOS circuits may be integrated on a CNT on any suitable insulator substrate using the top-gate geometry and high-dielectrics. This CNT based CMOS technology only requires the patterning of arrays of parallel semiconducting CNTs with moderately narrow diameter range, e.g. 1.6-2.4nm, which is within the reach of current nanotechnology. This may lead to the integration of CNT based CMOS devices with increasing complexity and possibly find its way into the computers brain – the logic circuit. References: 1. Doping-free fabrication of carbon nanotube based ballistic CMOS devices and circuits, Z.Y. Zhang,
X.L. Liang, S. Wang, K. Yao, Y.F. Hu, Y.Z. Zhu, Q. Chen, W.W. Zhou, Y. Li, Y.G. Yao, J. Zhang, and
L.-M. Peng, Nano Letters 7(12) (2007) 3603-3607
2. High-performance n-type carbon nanotube field-effect transistors with estimated sub 10ps gate delay,
by Z. Y. Zhang, S. Wang, L. Ding, X. L. Liang, H.L. Xu, J. Shen, Q. Chen, R.L. Cui, Y. Li and L.-M.
Peng, Appl. Phys. Lett. 92 (2008) 133117
3. A doping-free carbon nanotube CMOS inverter based bipolar diode and ambipolar transistor, by S.
Wang, Z.Y. Zhang, L. Ding, X.L. Liang, J. Shen，H.L. Xu, Q. Chen, R.L. Cui, Y. Li, and L.-M. Peng,
Adv. Mater. 20 (2008) 3258
4. Self-aligned ballistic n-type single-walled carbon nanotube field effect transistors with adjustable
threshold voltage, by Z.Y. Zhang, S. Wang, L. Ding, X.L. Liang, T. Pei, J. Shen, H.L. Xu, R. Cui, Y.
Recently, the graphene layers have attracted much of interest because of its large change carrier mobility and the potential application in electronic devices. The key point is opening a energy gap in graphene layer by modifying its lattice through hetero-growth. In this talk, we will present our recent investigations on the behavior of graphene.
18
Session I 11:40 – 12:00
Electrical Transport Properties of Polar-surface Dominated
Sb-doped ZnO Nanobelts
Yue Zhang*, Ya Yang, Junjie Qi
State Key Laboratory for Advanced Metals and Materials, Department of
Materials Physics,
University of Science and Technology Beijing, Beijing 100083 China
Abstract:
We report the fabrication of the high-quality polar-surface dominated
Sb-doped ZnO nanobelts. The n-type and p-type conductions were
demonstrated in as-synthesized and annealed nanobelts, respectively. The
transverse electrical transport was dominated by two reversed potential
barriers induced by the Schottky contact and the piezoelectric effect, which
are invariable and tuned by the loading forces, respectively. An exponential
relation was found between the resistance and the loading forces, which is
suggested due to the piezoresistance effect and the piezoelectric effect.
Nano-and Micro-Systems Research Lab University of Waterloo
There is a huge growing interest in nano-particles, nanowires and
tubes-that we have named as nano-building blocks-, with functional electronic characteristics, since the assembly of these materials into nanoscale devices and circuits could enable diverse applications in nanoelectronics and photonics. Most of these applications involve the use of hetero-structures in which materials of different compositions meet at interfaces.
To fabricate the nano-devices from the “nano-building-blocks”, it is necessary to interconnect these blocks to have ohmic nano-contact. However, to realize electronic applications, such as quantum wires, ballistic conductors microchip interconnects, transistors and super energy saving light bulbs the need to reproducibly fabricate connections between individual nano-building blocks and electrodes has been identified as a major impediment. For instance, as previous studies show, making an electrically conductive connection between nanotubes is not straightforward. Instead of the desired ohmic contacts, tunnel junctions are often generated. Studies of unmodified crossed-single-walled metallic nanotube junctions show a resistance of approximately 200kΩ. Such a high resistance has to be interpreted in view of the small contact area of the order of 1 nm2, where crossing tubes touch at one point only. Improvements may be expected when a connection by a technique such as welding, soldering, or pasting can be established that joins the nanotubes and -wires and thin films with an electrically conductive material over a larger surface area.
Conventional techniques such as pasting with conductive epoxy or soldering with liquid metals (like tin) are hardly applicable due to the small dimensions of the arrangements. Until recently, although multiple-way junctions of carbon-nano-tubes have been synthesized, using a simple
20
chemical vapor deposition (CVD) method without use of any template, the formation of these different junctions is still random. In addition, several ideas for post-growth modifications have also been proposed such as welding, but it seems that they did not allow one to make a more complicated network of joint nanotubes with predetermined positions of junctions between nanotubes.
Dr. Yavuz’s and his team’s research involves growing nano-building-blocks of different natures (single- and poly-crystalline and amorphous and metallic and non-metallic) and their interconnections (hetero-junction) using in-situ growth techniques by PVD and CVD systems, and also connect nano-building-blocks by nano-welding/-brazing for nanoelectronics such as ultra-fast transistors and super energy saving bulbs [1, 2].
Bibliography 1. S. Sahin, M. Yavuz and N. Zhou, Handbook of Microjoining and
Nanojoining, “Chapter 18: Introduction to Nanojoining”, 70 pages, editor: N. Zhou, Woodhead Publishing Ltd., 2007.
2. W. Wu, A. Hu, X. Li, J.Q. Wei, K.L. Wang, M. Yavuz and N. Zhou, “Vacuum Brazing of Carbon Nano Tube Bundles”, Materials Letter (Elsevier), vol. 62, pp. 4486-4488, 2008.
3. Elbuken, M. Yavuz and M.B. Khamesee, “Development of Crystalline Magnetic Thin Films for Micro-levitation”, Journal of Applied Physics (American Institute of Physics-AIP), vol.104, no. 044905, 7 pages, 2008; selected for the September 8, 2008 issue of Virtual Journal of Nanoscale Science & Technology.
21
Session Ⅱ 14:30 – 15:00
Enantioselective Synthesis of Proline Derivatives by Asymmetric
1,3-Dipolar Cycloadditions of Azomethine Ylides and Alkenes
Carmen Nájera, M. Gracia Retamosa, José M. Sansano
Department of Organic Chemistry, Faculty of Sciences, and Institute of Organic Synthesis, University of Alicante, 03080 Alicante, Spain
The asymmetric 1,3-dipolar cycloaddition of azomethine ylides and alkenes provides a direct access to the synthesis of enantioenriched highly substituted pyrrolidine or proline derivatives in a high diastereo- and enantioselective form [1]. The most direct way for the preparation of the corresponding dipoles is to generate in situ a metallo-azomethine ylide from α-imino esters derived from amino acids. There are three main strategies for the asymmetric 1,3-dipolar cycloaddition of azomethine ylides: a) by attaching a chiral auxiliary to the imino group or to the ester in the dipole, b) by attaching the chiral auxiliary group to the dipolarophile, and c) by using a chiral catalyst. We will present our work in this field using the last two strategies.
EWGR1 N CO2R3
R2
+Ag(I) salt
base NH
R1CO2R3
R2R4EWG R4
We have found that the use of chiral acrylates 1 derived from methyl (R)- and
(S)-lactate as dipolarophiles with imino esters in the presence of AgOAc as catalyst and KOH as base at room temperature afforded the corresponding cycloadducts with high regio-, diastereo- and enantioselectivity [2]. This methodology has been applied to the synthesis of substituted prolines, which are hepatitis C virus RNA polymerase inhibitors 2 [3]. For the enantioselective version Ag(I) complexes with phosphorus ligand such as phosphines and phosphoramidites have been used as chiral catalysts. The employment of binap-AgClO4 complex has allowed to recover by simple filtration and to reuse this catalyst during 5 runs [4]. Different phosphoramidites 4 derived from binol have also been used as the first monodentate chiral ligands in this type of enantioselective 1,3-dipolar cycloaddition of azomethine ylides and alkenes [5].
22
O
O
CO2Me N CO2HSHO2C
O
2F3C(S)-1
P
3 [(R)-binap]AgClO4
P Ag+ ClO4-
PhPh
PhPhO
OP N
Ph
Ph
· AgClO4
4
Acknowledgments: This research has been supported by the DGES of the Spanish Ministerio de
Educación y Ciencia (Consolider INGENIO 2010 CSD2007-00006, CTQ2007-62771/BQU, and
CTQ2004-00808/BQU), the Generalitat Valenciana (GV05/144), and the University of Alicante.
References
[1] For recent reviews, see: a) G. Pandey, P. Banerjee, S. R. Gadre, Chem. Rev. 2006, 106, 4484. b) T.
M. V. D. Pinho e Melo, Eur. J. Org. Chem. 2006, 2873. c) M. Bonin, A. Chauveau, L. Micouin, Synlett
2006, 2349. d) C. Nájera, J. M. Sansano, Angew. Chem. Int. Ed. 2005, 44, 6272.
[2] a) C. Nájera, M. G. Retamosa, J. M. Sansano, Tetrahedron : Asymmetry 2006, 17, 1985. b) C.
Nájera, M. G. Retamosa, J. M. Sansano, A. de Cózar, F. P. Cossío Eur. J. Org. Chem. 2007, 5038.
[3] G. Burton, T. W. Ku, T. J. Carr, T. Kiesow, R. T. Sarisky, J.-L. Goerke, A. Baker, D. L. Earnshaw,
G. A. Hofmann, R. M. Keenan, D. Dhanak, Bioorg. Med. Chem. Lett. 2005, 15, 1553.
[4] C. Nájera, M. G. Retamosa, J. M. Sansano, Org. Lett. 2007, 9, 4025.
[5] C. Nájera, M. G. Retamosa, J. M. Sansano, Angew. Chem. Int. Ed. 2008, 47, 6055.
23
Session II 15:00 – 15:30
New multicomponent reactions (MCRs) for the rapid assembly of
complex chiral molecules
Jared T. Shaw Department of Chemistry
University of California, Davis
We have discovered a new four-component reaction (4CR) that produces
densely-functionalized gamma-lactams in a single operation. The reaction
uses amines, thiols, aldehydes and maleic anhdyrides as inputs and the only
by-product is water. We have used the reactivity paradigm to design new
reactions, explored enantioselective variants, and employed the 4CR in the
synthesis of complex natural products.
24
Session Ⅱ 15:30-16:00
From Smaller to Larger Aromatics with Helical Chirality
Irena G. Stará
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the
[2] Míšek, J.; Teplý, F.; Stará, I. G.; Tichý, M.; Šaman, D.; Císařová, I.; Vojtíšek, P.; Starý, I.
Angew. Chem. Int. Ed. 2008, 47, 3188.
26
Session Ⅱ 16:20-16:40
Spontaneous Resolution and Dynamic Chirality of Bidentate Bis(N-heterocyclic carbene)-Palladium Complexes with Xanthene
Framework
Shinichi Saito Department of Chemistry
Tokyo University of Science N-Heterocyclic carbenes (NHCs) and NHC-metal complexes have been widely utilized for organic synthesis.1 We recently reported the synthesis and catalytic activities of bidentate NHC-palladium complexes with xanthene framework.2 As an extension of our study, we synthesized new bidentate NHC-palladium complexes with bulky aromatic groups. The complexes adopted a twisted conformation, and complexes could be isolated as homochiral crystals.3 It was assumed that the steric repulsion between the bulky aromatic groups is effectively reduced by adopting the twisted conformation. Though each conformer is stable in the crystalline state at ambient temperature, fast racemization was observed in solution. The energy barriers for the racemization of the complexes were measured by VT NMR. References 1 (a) N-Heterocyclic Carbenes in Synthesis; Nolan, S. P., Ed.; Wiley-VCH: Weinheim, 2006. (b) N-Heterocyclic Carbenes in Trabsition Metal Catalysis; Glorius, F., Ed.; Springer: Berlin, 2006. (c) Kantchev, E. A. B.; O'Brien, C. J.; Organ, M. G. Angew. Chem. Int. Ed. 2007, 46, 2768-2813. 2 Saito, S.; Yamaguchi, H.; Muto, H. Makino, T. Tetrahedron Lett. 2007, 48, 7498-7501. 3 Makino, T.; Masu, H.; Katagiri, K.; Yamasaki, R.; Azumaya, I.; Saito, S. Eur. J. Inorg. Chem. 2008, 4861-4865.
27
Session Ⅱ 16:40-17:00 Asymmetric Autocatalysis Induced by Chiral Crystals Composed
of Achiral Organic and Inorganic Compounds as the Possible Route for the Origin and Evolution of Chirality
Department of Applied Chemistry, Tokyo University of Science
The homochirality of biomolecules is one of the essential features of life
and has been a puzzle for the chemical origin of life. Quartz (SiO2), which is naturally occurring inorganic enantiomorphous crystal, has been proposed as one of the origins of chirality.
We previously reported the asymmetric autocatalysis1), which enables to amplify the quantity and the quality (enantiomeric excess) of chiral product to achieve the large amount of highly enantioenriched compound.2)
In this presentation, we show that naturally occurring inorganic chiral crystal, cinnabar (HgS) acted as the chiral initiator of asymmetric autocatalysis to afford highly enantioenriched pyrimidyl alkanol whose configurations depended upon those of cinnabar. The chiral crystal of achiral nucleobase cytosine, and organic crystals of benzils could be used as the source of chirality in asymmetric autocatalysis to provide a near enantiopure pyrimidyl alkanol.3,4)
These results indicate the ability of chiral crystal formed from achiral compounds to serve as an origin of chirality in conjunction with autocatalytic amplification of ee.
28
1) Soai, K.; Kawasaki, T. Chirality 2006, 18, 469. 2) Kawasaki, T.; Jo, K.;
Igarashi, H.; Sato, I.; Nagano, M.; Koshima, H.; Soai, K. Angew. Chem. Int.
T.; Florini, N.; Palyi, G.; Soai, K. Org. Lett. 2008, 10, 4085.
29
Session Ⅱ 17:00-17:30
Design and Synthesis of Organic Silanols for Asymmetric Catalysis
Annaliese K. Franz
Department of Chemistry University of California, Davis
Although silanols are known to have an acidic SiOH group and exhibit
extensive hydrogen-bonding, organic silanols and silanediols have not been
examined as hydrogen-bonding catalysts for asymmetric synthesis.
Incorporating silanol hydroxy groups into a chiral organic scaffold provides a
unique opportunity to design new catalysts with dual hydrogen-bonding
capabilities and provide a high degree of stereochemical induction. Our
preliminary results demonstrate the first examples of simple silanediols and
disiloxanediols as catalysts for carbon-carbon bond-forming reactions, such
as the Strecker and Diels-Alder reaction. The ability to incorporate silanols
into modular chiral scaffolds provides access to a variety of chiral catalysts,
where our first generation of catalysts already provide up to 99%
enantioselectivity in the Strecker and Diels Alder reaction. Mechanistic,
computational, and structural studies will be discussed to characterize the
structure, acidity, and hydrogen-bonding properties of these organic silanols
and the catalyst-substrate interactions.
30
Session II 17:30 – 18:00
Amphoteric Molecules for the Synthesis of Stereochemically Complex Amines
Andrei K. Yudin
Department of Chemistry University of Toronto
Synthetic organic chemists depend on protecting group manipulations when faced with the challenges of chemoselectivity and functional group incompatibility. Overcoming this dependence will improve the overall efficiency of chemical synthesis. By taking advantage of orthogonally reactive functional groups, amphoteric molecules deliver more efficient syntheses and enable novel chemical transformations. The reagents developed using this idea provide a seamless bridge to atom- and step economy. This talk will present a summary of our ongoing efforts in this area.
31
Session III 9:00 –9:20
Solvation structures of excess proton in protonated methanol cluster ions studied by infrared photodissociation spectroscopy
Kensuke Tono and Koichi Tsukiyama,
Department of Chemistry and Infrared Free Electron Laser Research Center, Tokyo University of Science
Molecular clusters bound by hydrogen bonding have been studied
extensively as a model system for understanding solvation structures of protonated molecular ions, which play a crucial role in chemical reactions in the liquid phase. We have investigated the solvation structures in the protonated methanol cluster ions, H+(CH3OH)n (n = 5–8), by infrared photodissociation spectroscopy [1].
Photodissociation action spectra of H+(CH3OH)n were measured between 900 and 2300 cm–1 by using the free electron laser at Tokyo University of Science (FEL-TUS). Figure 1 shows the photodissociation spectrum of n = 5 along with calculated infrared spectra for three isomers I–III. The experimental spectrum is well reproduced by the calculation for the cyclic isomer (I), in which the excess proton is equally shared by two methanol molecules. This solvation structure is responsible for spectral feature C centered at about 1600 cm–1. Because feature C is also found in the spectra of n = 6–8, H+(CH3OH)5–8 are indicated to have similar solvation structures of the proton. The calculation shows that feature A at about 1000 cm–1 comprises several bands which can be assigned to intramolecular vibrations; for example, CO stretching, CH3 rocking, and OH bending.
C
32
[1] K. Tono, et al., J. Chem. Phys. 129, 084304 (2008).
Fig. 1. Photodissociation action spectrum of H+(CH3OH)5 and simulated IR spectra forisomers I–III, of which the structures are shown on the right. Binding sites of the excessprotons are marked by the circles.
C
C
33
Session III 9:20 –9:40
X-ray Reflectometry and Grazing Incidence Diffraction Studies of
the Structure of Single Phospholipid Bilayers on Solid Supports
Tonya Kuhl
Department of Chemical Engineering and Materials Science and Department of Biomedical Engineering
University of California, Davis Over the past several decades, supported bilayers have been used as model systems of cellular membranes to investigate various membrane interactions and as platforms for development of bio-sensors. For both of these applications, a precise structural characterization of bilayer structure and how specific interactions perturb the structure is required. Our development of X-ray scattering techniques to study supported membrane systems allows high resolution information about the density profile normal to the surface and across the bilayer to be obtained (schematic shown). We report the structure of single supported membranes composed of lipids with different head groups and different chain lengths and compare the structure of membranes prepared by vesicle adsorption and monolayer deposition techniques. The density profiles obtained allowed for the determination of structural aspects including head group packing densities, identification of a region of depleted hydrocarbon density between the two leaflets of the bilayer, and structural changes to the bilayer upon crossing the melting transition between the gel and fluid phases. Recent work on polymer cushioned membranes will also be highlighted. Our results demonstrate the power of x-ray reflectometry to obtain precise information about elements of phospholipid bilayer structure and provide insight into the self-assembly process.
34
35
Session Ⅲ 9:40-10:00
A Novel Protein Delivery Platform based on Single-Protein-Nanogels
Yunfeng Lu
Chemical and Biomolecular Engineering,
University of California, Los Angeles, CA 90095
Bioactive proteins need to be delivered intracellularly to exert their therapeutic action.
However, the lipophilic nature of the biological membranes may restrict the direct
intracellular delivery of such compounds. Furthermore, the deliveried proteins are
subjected to degradation by proteases or may be trashed out through endosomes and
lysosomes. In this talk, a novel method of protein delivery will be reported. We
encapsulated a single protein with thin polymer layer through aqueous in-situ
polymerization. Tuning the surface charge of the polymer layer allows effective
protein delivery. In-vitro experiments show nanogels can be transduction into HeLa
cells efficiently. Unlike native protein, the nanogels show great resistance to
hydrolysis of proteases. This work provides a novel delivery platform for proteins and
other biological compounds.
36
Session III 10:00 – 10:20
Metallic Nano-structures and Thin Films on Liquid Substrates
Gao-Xiang Ye et al.
Department of Physics
Zhejiang University
We report the formation mechanism and physical properties of the metallic
nano-structures and thin films on liquid substrates. Metallic atoms (Ag, Au,
Fe, Ni, …) are deposited on silicone oil surfaces by thermal evaporation
method and then the diffusion process and the microstructure of the
aggregates and films are studied. In these new physical systems, several new
and interesting phenomena, which are related to the mechanical property,
electrical transportation and magnetic characteristics at low temperature,
have been detected. The physical explanations are also presented.
37
Session III 10:20 – 10:40
Dynamics of Coating Flows with Chemical Reaction
Brian G. Higgins
Department of Chemical Engineering & Materials Science University of California, Davis, CA95616
In this presentation we consider a class of coating flows in which coating properties can be altered by initiating suitable chemical reactions within the coating film. In particular, we consider non-isothermal photochemical reactions initiated by exposing the coating film to UV irradiation. Photochemical reactions are of scientific and technical interest because of the possibility of controlling spatiotemporal pattern formation in a thin film by modulation the light intensity. What is uncertain, however, is whether the distribution of chemical species during the photochemical reaction can drive Marangoni convection within the thin film, resulting in either unwanted imperfections, or at the other extreme creating desired patterns in the thin film for storage media products and nano imprint lithography. We consider a photpolymerization reaction that follows a free-radical mechanism. The free radicals are produced by a photoinitiator that dissociates when exposed to UV irradiation. The absorbed light intensity is given by a Beer-Lambert law. We make use of the lubrication approximation to derive an evolution equation for the thin film during reaction, which is coupled to the species balance and the thermal energy equations. We take the surface tension to be a function of temperature, as well as the reactant and product concentrations, and consider a long-wave deformation mode of the Marangoni convection. The species balances, energy, and the evolution equation for the film thickness are solved numerically. We show that an instability can be induced in the reacting film for certain ratios of diffusivities and film thicknesses and heat of reaction. Possible applications will be discussed.
38
Session Ⅲ 11:00-11:20 Hierarchical structures and functional properties of polymers
Takeo Furukawa
Department of Chemistry, Faculty of Science, Tokyo University of Science 1-3 Kagurazaka, Shinjuku, Tokyo 162-8601, Japan
Polymers exhibit a wide variety of properties closely related to their hierarchical structures
consisting of monomer, chain, crystal and bulk. In our laboratory, we focus our attention to their
functional properties related to energy storage, transport and conversion. Broadband electrical
spectroscopy covering 1mHz-10GHz is commonly used for the basic understanding of their
dynamical aspects. Extension to a nonlinear regime has proven to provide additional key information.
Scanning probe microscopy is also employed to examine the local structure and properties.
The ferroelectric copolymer of vinylidene fluoride (VDF) and trifluoroethylene (TrFE) has
attracted interest because of its unique functionalities as well as possible applications to a nonvolatile
memory. The spontaneous polarization is formed hierarchically as a result of parallel packing of
all-trans chain molecules which induces an alignment of all monomer dipoles in one direction. The
inter and intramolecular orders in the ferroelectric phase are lost successively with increasing
temperature due to transitions into antiferroelectric, paraelectric and molten phases as shown in Fig.
1.
Thickness reduction is a key technological requirement to achieve low voltage operation.
We have succeeded in fabricating VDF(75)/ TrFE(25) films thinner than 50nm and measuring
ultra-fast polarization switching as shown in Fig. 2. Note that the switching time shorter than 10nm
is obtained at an extremely high electric field of 1000MV/m without electrical breakdown.
1 Dipartimento di Scienze Chimiche,Università di Padova, Via Marzolo 1, 35131 Padova (PD) Italy.
2 Istituto di Scienze e Tecnologie Molecolari, ISTM-CNR c/o Dipartimento di Scienze Chimiche, Via
Marzolo 1, 35131 Padova (PD) Italy.
3Department of Chemistry, Faculty of Science, Tokyo University of Science 1-3, Kagurazaka, Shinjuku,
Tokyo 162-8601, Japan
Abstract
Perfluorinated ionomers such as Nafion are the most widely studied polymer
electrolytes for application in PEMFCs and DMFCs. Despite their extensive use, the
limits of these materials are the high cost and the loss of the conductivity and
mechanical properties at temperatures higher than 80 °C. To overcome these drawbacks
hybrid inorganic-organic composite membranes based on Nafion and inorganic
additives have been proposed. In this report are presented the preparation and the
characterization of six nanocomposite membranes of formula
( ) ( )[ ] 2
148.032 TiOWOTiONafion ψ⋅ with
2TiOΨ in the range 0-2.988. These materials are
based on Nafion and [(TiO2)·(WO3)0.148] nanofiller. The effect of [(TiO2)·(WO3)0.148]
nanopowders on the structural, thermal, mechanical and electrical properties of
( ) ( )[ ] 2
148.032 TiOWOTiONafion ψ⋅ membranes were studied. The water uptake (WU)
40
value of membranes was lower than that of pristine Nafion and was correlated with
2TiOΨ . The thermal transitions were investigated by modulated differential scanning
calorimetry (MDSC). The mechanical parameters and relaxation processes on
temperature were studied by dynamical mechanical analyses (DMA). The FT-IR ATR
and -Raman vibrational investigations allowed to determine that: a) the hydrophobic
polytetrafluoroethylene (PTFE) domains of Nafion consist of a blend of polymer chains
with 157 and 103 helical conformations; b) the fraction of chains with 103 helical
conformation depends on the concentration and the strength of
R–SO3H···[(TiO2)·(WO3)0.148] interactions in bulk ( ) ( )[ ] 2
148.032 TiOWOTiONafion ψ⋅
materials; c) the water molecules in bulk materials are distributed into six different
domains which are singled out as I, II, II, III, III and IV; d) the water uptake value is
correlated to the conformational transition 103→157 of fluorocarbon chains in PTFE-like
hydrophobic domains of Nafion. The analysis of complex conductivity plots permitted to
evaluate the electric response of ( ) ( )[ ] 2
148.032 TiOWOTiONafion ψ⋅ in the 10-2 Hz – 10
MHz and 5-155 °C regions. Results indicated that the conductivity of
( ) ( )[ ] 2
148.032 TiOWOTiONafion ψ⋅ nanocomposite membrane, with
2TiOΨ = 1.616, at
135 °C, is 5.0·10-2 S·cm-1, while its stability range of conductivity (SRC) extends up to
135 °C. In conclusion, the membranes doped with the TiO2-WO3 core-shell nanopowders
are very promising polymer electrolytes for application in PEMFCs and DMFCs.
41
Session III 11:40 – 12:00
Molecular Modelling of soft matter
Roland Faller Department of Chemical Engineering & Materials
University of California at Davis Soft matter including polymers, biomembranes, or glasses have a variety of length scales with need to be addressed in order to characterize the system. In recent years we have developed a variety of techniques to this end and a few examples will be presented. Coarse-graining, the systematic mapping from the atomistic to meso-scale has made significant progress in polymers over recent years. A general overview will be given and then the focus shifts to building a multiscale model of Polyisoprene (PI) and Polystyrene (PS) mixtures. We apply the “Inverted Boltzmann Method” to derive numerical potentials from atomistic models where the interaction potential is iteratively optimized against the atomistic structure using potentials of mean force. We optimize the iteration process and analyze the concentration and temperature dependencies of the evolving potential, investigating further what parameters induce the phase separation in longer chains and miscibility in shorter chains. All the work eventually leads to a better understanding of the mechanisms governing material properties. An outlook towards polymer brushes and lubrication will be given. With the advent of bionanotechnology the structure and phase behavior of lipid membranes as models for cellular membranes at the nano scale length is of importance due to implications in understanding the role of the lipids in biochemical membrane processes. Our simulations demonstrate that various coarse grained simulation models can predict different aspects of lipid phase separation and describe the change of the system under the influences of hydrophilic and hydrophobic support. We study domain formation in a two-component lipid bilayer by mesoscale Molecular Dynamics simulations in large time and length scale systems in order to capture lipid phase separation. A range of systems at different temperatures were simulated and the characterization of the phase behavior was performed by analysis of parameters such as diffusion coefficients and rotation correlation functions.
42
As simulations allow studying these properties for individual lipids the dynamical heterogeneity of the systems can be elucidated as well. The formation of gel phase apparently obeys a classical nucleation and growth mechanisms.
43
Session III 12:00 – 12:20
Anionic Surfactant Liquid Crystal Templating Route for Synthesizing Mesoporous Silica
Shunai Che
School of Chemistry and Chemical Technology Shanghai Jiao Tong University
A novel liquid crystal templating route for preparing mesoporous silicas
has been demonstrated based on the self-assembly between anionic surfactants and inorganic precursors by using aminosilane or quaternized aminosilane as co-structure-directing agent (CSDA), which is different from the previous pathways. The alkoxysilane site of CSDA is co-condensed with inorganic precursors; the ammonium site of CSDA, attached to silicon atoms incorporated into the wall, electrostatically interacts with the anionic surfactants to produce well-ordered anionic surfactant templated mesoporous silicas (AMS).1
This templating route has given rise to a variety of mesostructures such as tetragonal (P42/mnm), hexagonal (P63/mmc, p6mm), cubic (dis-continuous Pm-3m, Fd-3m, Fm-3m; bi-continuous Ia-3d and Pn-3m, etc.), and lamellar mesophases. In particular, a chiral ordered mesoporous crystal was synthesized using the anionic chiral surfactant. The material has a twisted hexagonal rod-like morphology. Transmission electron microscopy combined with computer simulations confirm the presence of hexagonally ordered chiral channels winding around the central axis of the rods.2 The helicity and the morphology of the mesoporous silica are controlled by the stirring rate during the chiral surfactant self-assembly. The enantiomeric excess (ee) of the CMS obtained was a critical function of both the substituent’s steric bulk and the temperature, and eventually exceeded 90% ee by performing the CMS synthesis at 288 K with amphiphilic N-palmitoyl-Phe or Met. Right- and left-handed excess chiral mesoporous silica nanotubes with helical channel in the wall have been formed by self-assembly of achiral surfactant SDS in the presence of chiral molecules. Conducting polymers nanofibers with controllable chiral mesopores in the size, the shape, and handedness
44
have been synthesized by chiral lipid ribbon templating and “seeding” route. AMS, the interaction between the surfactant and the CSDA produces a
uniform distribution of the organic groups, and a regular array of the group will be formed following the arrangement of the surfactant. This enables the functional groups condensed onto the pore surface in the expected ratios based on both a stoichiometry of the molecule and the geometric arrangement of the surfactant. Therefore, the study on the formation of AMS has great significance in theory and practice.
(1). Che, S.; Terasaki, O.; Tatsumi, T. et al. Nature Materials, 2003, 2, 801-805. (2). Che, S.; Liu, Z.; Ohsuna, T.; Sakamoto, K.; Terasaki,O.; Tatsumi, T. Nature 2004, 429, 281-284.
45
Session III 14:30 – 14:50
Functional Nanoparticles By Interfacial Engineering
Shaowei Chen
Department of Chemistry and Biochemistry
University of California, Santa Cruz
Janus nanoparticles represent a unique class of nanomaterials where the amphiphilic surface structure renders them ideal building blocks in the controlled assembly of nanoparticles into functional nanostructures. In this presentation, two experimental approaches will be detailed in the preparation of Janus nanoparticles. We use alkanethiolate-protected gold nanoparticles as the illustrating example by taking advantage of the interfacial ligand exchange reactions of the hydrophobic nanoparticles with hydrophilic thiol derivatives, e.g., 1,2-mercaptopropandiol (MPD) and 2-(2-mercaptoethoxy)ethanol (MEA). In the first approach, nanosized Janus particles were prepared by ligand exchange reactions of a Langmuir monolayer of hydrophobic hexanethiolate-passivated gold nanoparticles at relatively high surface pressures with hydrophilic thiol derivatives (MPD) injected into the water subphase. The ligand intercalation between adjacent particles led to impeded interfacial mobility of the particles. Consequently, ligand place-exchange reactions was limited only to the side of the particles facing the water phase, leading to the formation of amphiphilic nanoparticles which exhibited hydrophobic characters on one side and hydrophilic on the other, analogous to the dual-face Roman god, Janus. The unique amphiphilic characters of the Janus particles were confirmed by a variety of experimental measurements, including contact angle measurements, FTIR, UV-visible, and NMR spectroscopies, as well as adhesion force measurements of individual nanoparticles. Interestingly, the Janus particles might be suspended in water, forming micelle-like aggregates, as revealed in AFM measurements. In the second approach, a monolayer of the hexanethiolate-protected gold particles was first formed at the air|water interface by the Langmuir technique and then deposited onto a substrate surface by the Langmuir-Blodgett method. The particle monolayer was then
46
immersed into an aqueous solution of MEA for different periods of time. It was found that the exchange reactions occurred but were limited only to the top face of the nanoparticles and the reaction reached equilibrium in about 8 hours. The resulting particles exhibited amphiphilic characters as confirmed by contact angle and UV-visible, FTIR and NMR spectroscopic measurements. Of these, the structural discrepancy between the Janus nanoparticles and bulk-exchanged particles was clearly manifested, in particular, by NOESY NMR measurements. Acknowledgment This work is supported by the National Science Foundation (DMR-0804049)
47
Session III 14:50 – 15:10
The Avenue to New Nonfouling Materials -- a magic effect from nanometer size
Shengfu Chen
Institute of Pharmaceutical Engineering, College of Materials Science and Chemical Engineering,
Zhejiang University, Hangzhou, Zhejiang 310027
Noufouling materials were acclaimed as a new generation of biomaterials to overcome nonspecific protein adsorption. However, the advance to meet the challenge as implantable materials is stopped due to only limited materials available, such as, polyethylene glycol (PEG) and poly 2-methacryloyloxyethyl phosphorylcholine (MPC). Therefore, it is urgent to develop a design principle to meet requirements in both resistance to protein adsorption and biocompatibility. Based on all results along with the studies of the molecular-level nonfouling mechanism in last five years, it is suggested that a nonfouling surface be achieved when the surface can tightly bonded with water molecules in nanometer scale. PEG /or OEG, which classified as hydration by hydrogen bond, shows flexibility requirement in nanometer scale for more efficient water bonding; On the other hand, PC/ or other mixed charge systems, which classified as hydration by ionic solvation, show excellent nonfouling properties even in crystalline condition. However, it is preferred for mixed charge systems to be in homogenous distribution, which could lead mixed charge systems to be fully ionized in solution and enhanced their hydration to prevent protein adsorption. With the understanding of the mechanism of nonfouling properties, new nonfouling materials developed and new design principles for nonfouling materials will have strong impacts on a broad range of applications from biomedical to marine coatings.
Selected publication 1. Chen SF, Jiang S. A New Avenue to Nonfouling Materials, Adv. Mater. 20，（3）335 (2008) 2. He Y., Hower J., Chen SF ., Bernards MT., Chang Y., Jiang S. Molecular simulation studies of
protein interactions with zwitterionic phosphorylcholine self-assembled monolayers in the
48
presence of water Langmuir 24(18) 10358-10364, (2008) 3. Chen SF, Yu FC, Yu QM, He Y, and Jiang S. Strong Resistance of a Thin Crystalline Layer of
Balanced Charged Groups to Protein Adsorption, Langmuir, 22: 8186 – 8191 (2006) 4. Chen SF, Liu LY, Jiang SY, Strong resistance of Oligo(phosphorylcholine) self-assemblys to protein
adsorption, Langmuir, 22: 2418-2421 (2006) 5. Chen SF, Zheng J, Li LY, Jiang SY; Strong resistance of phosphorylcholine self-assembled
monolayers to protein adsorption: Insights into nonfouling properties of zwitterionic materials, J. Am. Chem. Soc. 127 (41): 14473-14478 (2005)
6. Zheng J, Li LY, Tsao HK, Sheng YJ, Chen SF, Jiang SY; Strong repulsive forces between protein and oligo (ethylene glycol) self-assembled monolayers: A molecular simulation study, Biophys. J. 89 (1): 158-166 JUL (2005)
49
Session IV 15:30 – 16:00
Spin-polarized Carrier Injection Effect in Ferromagnetic Semiconductor/
Diffusive Semiconductor/Superconductor Junctions Hideaki Takayanagi Research Institute for Science and Technology, Tokyo University of Science,
and International Center for Materials Nanoarchitectonics, NIMS, Tsukuba
T. Akazakia, Y. Sawab, T. Yokoyamab, Y. Tanakab, A.A. Golubovc,
H. Munekatad
a NTT Basic Research Laboratories, NTT Corporation, Atsugi, Japan b Department of Applied Physics, Nagoya University, Nagoya, Japan c Faculty of Science and Technology, University of Twente, Enschede, The Netherlands d Imaging Science and Engineering Laboratory, Tokyo Institute of Technology, Yokohama, Japan In this paper, we report on the transport properties in a p-In0.94Mn0.06As/n-InAs/Nb junction where a p-In0.94Mn0.06As can be regarded as a spin injector. We discuss both experimentally and theoretically the way in which the competition between the spin polarization and superconducting proximity effect modifies the transport in our systems. We measured the bias voltage V dependence of the differential conductance of the n-InAs channel as a function of injection current from p-In0.94Mn0.06As at 0.7 K. We obtained conductance minima within | V |< 2 mV without current injection. As the injection current from p-In0.94Mn0.06As increased, the conductance minima gradually disappeared. By contrast, as the injection current from Nb increased, the conductance minima split and then shifted toward a high bias. In the calculation of the conductance in the n-InAs channel we solved both the Usadel equation and the gap equation self-consistently by taking account of the exchange field in the InAs channel that was induced by InMnAs
50
ferromagnetic electrode. The difference between the dependences of the conductance on injection current can be explained by the inverse proximity effect that the exchange field is also induced in the superconducting electrode by spin-polarized current injection from the InMnAs electrode.
51
Session IV 16:00 – 16:30
Quantum control of photons and phonons using superconducting integrated circuits
Andrew Cleland
University of California, Santa Barbara
Nanomechanical resonant devices have been under study for about the past 10 years, due to their ability to achieve very high operating frequencies (approaching 10 GHz), their extremely small mass (approaching tens of femtograms), and their very high sensitivity to changes in parameters, local forces, and their potential for achieving quantum limited motion. Performing quantum limited measurements, ultimately at the level of single phonons (the quantum of acoustic vibrations), would provide a new test of quantum mechanics for macroscopic systems. I will outline the history of some ultimate measurements in mechanical systems, described how recently we have been able to demonstrate control of electromagnetic harmonic oscillators at the level of single microwave photons (Nature 2008),
and outline how we hope to do the same with a mechanical system.
52
Session Ⅳ 16:30-17:00
Grand Challenges and Opportunities in Ultra-Cold Atom
Research
Tin-Lun (Jason) Ho
Department of Physics Ohio State University
I shall give a review on some of the major directions of the field, and the
ideas that continue to drive the field of cold atom into more and more
ambitious efforts. All these directions involve achieving various types of
strongly correlated or highly unusual ground states. The success of these
efforts will require invention of new detection schemes that will further
integrate atomic physics and condensed matter physics.
53
Session IV 17:00 – 17:30
Dynamics of Ultracold Quantum Gases
Tetsuro Nikuni
Department of Physics Tokyo University of Science
Since the first achievement of Bose-Einstein condensation trapped atomic gases in 1995, there has been an explosion of theoretical and experimental research on ultracold atomic gases. I give a broad overview of the development of the field, and discuss the dynamical properties, such as collective oscillations and sound propagations, in various types of quantum gases.
54
Poster Session
At Room Hakoh
Posters
55
1. E. Magome, N. Minoura, K. Sawada and M. Komukae Department of Applied Physics, Tokyo University of Science “Structural Study of Ferroelastic Phase Transition in Rb3H(SeO4)2”
2. H. Liu, D. Takagi, S. Chiashi, T. Chokan and Y. Homma
Department of Physics, Tokyo University of Science “Growth of Single-Walled Carbon Nanotubes from Non-Metal Materials”
3. K. Nakata[1], E. Tokunaga[1] and T. Kobayashi[2]
[1] Department of Physics, Tokyo University of Science [2] University of Electro-Communications ”Electric-Field Effects on the Aggregation State of Porphyrin J-Aggregates in Aqueous Solution”
4. K. Yamaguchi, T. Koyama, F. Sano, J. Niwa, A. Hirako and K. Ohkawa
Department of Applied Physics, Tokyo University of Science “Nitirde Photocatalyst to Produce H2 Gas from Water”
5. K. Taguchi, J. Haruyama, S. Konabe, K. Watanabe
Department of Physics, Tokyo University of Science “Time-Dependent Density Functional Calculations of Laser-Driven Molecular Dissociation Dynamics”
6. K. Ozawa[1], T. Yamamoto[2], K. Watanabe[1] and S. Watanabe[2]
[1] Department of Physics, Tokyo University of Science [2] Department of Materials Engineering, The University of Tokyo “Tight-Binding Calculations of AC Response of Nano-Bridges”
7. K. Kinjo, S. Ishiwata, H. Watanabe, S. Harako and X. Zhao
Department of Physics, Tokyo University of Science “Domain Formation of Micro-Transition Metals Patterns”
8. T. Numao, K. Kamiya, S. Yamaguchi, S. Harako and X. Zhao
Department of Physics, Tokyo University of Science “Photo-Catalytic Reaction of Nanocrystalline ZnO Thin Films Formed on Si Substrates”
56
9. M. Kagawa and Y. Ishii Department of Applied Physics, Tokyo University of Science “Holographic Recording in a Doubly Doped Lithium Niobate Crystal with Two Wavelengths; A Blue Laser Diode and A Green Laser”
10. K. Kurahashi[1], H. Iwasawa[1,2], S. Kaneyoshi[1], T. Saitoh[1],
T. Katsufuji[3], I. Hase[2], Y. Miura[4], M. Higashiguchi[4], K. Shimada[5] [1] Dept. of Applied Phys., Tokyo Univ. of Science, [2] AIST, [3] Waseda University, [4] Hiroshima University, [5] Hiroshima Synchrotron Radiation Center “Electronic Structure of Spin- and Carrier-Doped SrTiO3”
11. H. Usui[1], H. Iwasawa[1,2], M. Hirose[1], T. Saitoh[1], Y. Aiura[2], K. Sato[2,3], H. Nagata[4], and T. Kyomen[4] [1]Dept. of Applied Phys., Tokyo Univ. of Science, [2]AIST, [3]Ibaraki University, [4]Gumma University “Electronic Structure of K0.5CoO2 by ARPES”
12. T. Kato[1], T. Machida[1,2], T. Noguchi[1], R. Miyashita[1] and T. Sakuyama[1], and
H. Sakata[1] [1]Department of Physics, Tokyo University of Science [2]Superconducting Materials Center, NIMS “Research of High-Tc Superconductivity Using Low-Temperature Scanning Tunneling Microscopy/Spectroscopy”
13. N. Umeyama[1,2], S. Ikeda[1], N. Miyakawa[2], A. Tominaga[3], S. Horiguchi[3], H.
Sato[3] and K. Takase[4] [1] AIST, [2]Tokyo University of Science, [3]Chuo University, [4]Nihon University “Synthesis and Superconductivity on FeSex”
57
14. M. Minematsu[1], M. Fujita[2], K. Yamada[2] and N. Miyakawa[1] [1] Department of Applied Physics, Tokyo University of Science [2] Institute for Materials Research, Tohoku University
“Characteristic Features of Tunneling Conductance on Electron-Doped Cuprates, Pr1-xLaCexCuO4”
15. K. Ogata[1], P. M. Shirage[2], A. Iyo[2] and N. Miyakawa[1] [1]Department of Applied Physics, Tokyo University of Science
[2]National Institute of Advanced Industrial Science and Technology “Two-Gaps of Trilayered High-TC Cuprates, Ba2Ca2Cu3O6(O1-xFx)2”
16. S. Kawashima[1], S. Mikusu[2], K. Tokiwa[2], T. Watanabe[2] and N. Miyakawa[1]
[1]Department of Applied Physics, Tokyo University of Science [2]Department of Applied Electronics, Tokyo University of Science “Doping Dependence of Tunneling Conductances on Bi-Layered Cuprates, TlBa2CaCu2Oy”
17. E. Arahata and Tetsuro Nikuni
Department of Physics, Tokyo University of Science “Hydrodynamic Sound Propagation in Superfluid Fermi Gases”
18. T. Ozaki and T. Nikuni
Department of Physics, Tokyo University of Science “Quantum Phase Structure of Bose‐Bose Mixtures in Optical Lattices”
19. Chiaki Ishioka, Tsubasa Itoh, Takashiro Akitsu* Department of Chemistry Division II, Tokyo University of Science ”Polarized spectroscopy of hybrid materials of Mn12 single-molecule magnet and azobenzene in PMMA”
20. Ryu Yamasaki, Minami Nakagawa, Takuya Kitamura, Koreto Kato, Shinichi Saito* Department of Chemistry, Tokyo University of Science “Ni Catalyzed [4 + 3 + 2] Cocyclization Reaction between Dienyne and Methylenecyclopropane”
58
21. Hiroki Fukui, Keisuke Tsuji, Yuma Umezaki, Prof. Isamu Shiina*
Department of Applied Chemistry, Tokyo University of Science ”First Total Synthesis of Botcinins and Botcinic Acids: Identification of the True Structures of Botcinolides”
22. Yuji Miyazato, Tohru Wada, Masahiro Yamanaka, Koji Tanaka, Makoto Tadokoro* Department of Chemistry, Tokyo University of Science “Reactivity and Characterization of a Novel Oxidation Catalysis bearing Two Redox Centers.”
23. Kiyomi Sasaki, Nobuyuki Nagasawa, Hidetaka Torigoe* Department of Applied Chemistry, Tokyo University of Science “Stabilization of triplex nucleic acid under physiological condition for the application to artificial gene regulation”
24. Kaoru Kaneda, Nobuyuki Nagasawa, Hidetaka Torigoe* Department of Applied Chemistry, Tokyo University of Science “Unfolding of tetraplex nucleic acid structure by the interaction with telomeric DNA binding proteins: Possible novel mechanism of telomere length regulation in cellular cancer”
25. Kenta Suzuki, Kunihiko Hatase, Daisuke, Nishiyama, Sayaka Kamimura, Tsuneomi Kawasaki and Kenso Soai Department of Applied Chemistry, Tokyo University of Science “Spontaneous Absolute Asymmetric Synthesis in the Achiral Amine Catalyzed Addition of diisopropylzinc to Pyrimidine-5-carbaldehyde in Conjunction with Asymmetric Autocatalysis”
26. Kotaro Dai, Satoe Kusunoki, Mami Hirota, Kazuaki Tomono, Kazuo Miyamura* Department of Chemistry, Tokyo University of Science “Turning point in the crystal structure of alkylammonium salts of [Ni(dmit)2] with different alkyl chain length”
Department of Chemistry, Tokyo University of Science “Turning point of the stable adsorption of [Cu(salten)] introduced with different alkyl chain length”
28. Isamu Tajima, Katsumi Uchida, Tadahiro Ishii and Hirofumi Yajima Department of Applied Chemistry, Tokyo University of Science “Selective Separation Methods for Metallic and Semiconducting Single-walled Carbon Nanotube in Aqueous Solution with High-fluence Pulsed OPO Laser”
29. S.Miura [1], N.Kato [1], A. Hokura [1], I.Nakai [1], and Y.Shindo [2], [1] Department of Applied Chemistry, Tokyo University of Science, [2] The Middle Eastern Culture Center in Japan “X-ray characterization of luster decoration on the early-Islamic pottery”
30. Qinghui Li [1], Yuki Ono [1], Yoshikazu Homma [2], Izumi Nakai [1], Katsutoshi
Fukuda [3], Takayoshi Sasaki [3], Keiichi Tanaka [4], Satoshi Nakayama [4] [1] Department of Applied Chemistry, Tokyo University of Science, [2] Department of Physics, Tokyo University of Science, [3] Shinshu University, [4] SII NanoTechnology “Characterization of the nanomaterials using a field-emission scanning electron microscope system equipped with a transition edge sensor X-ray detector”
31. Satoru Murayama, Hiroharu Yui* Department of Chemistry, Tokyo University of Science “Analysis of Local Environment of Water Molecules/ Surfactant Interfaces in Soap Films Using Polarization Modulation Infrared-Reflection Absorption Spectroscopy”
32. Keita Takahashi, Satoru Murayama, Hiroharu Yui* Department of Chemistry, Tokyo University of Science “Analysis of OH Groups on TiO2 Single-crystal Surface Using Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) ”
60
33. Junya Ueda, Yuji Minami, Yoshiyuki Takahashi, Takeo Furukawa Department of Chemistry, Tokyo University of Science “Control of Crystalline Polymorphs and Ferroelectric Properties in Polyvinylidene Fluoride Films”
34. Masanori Kitamura [1,2], Hiroyuki Nishimoto [1], Keita Aoki [1], Shin Aoki [1,2] [1] Faculty of Pharmaceutical Sciences, Tokyo University of Science [2] Center for Drug Delivery Research, Tokyo University of Science “Selective Molecular Recognition of Anionic Guests in Aqueous Solution by Chiral Zinc(II) Complexes”
35. Satoshi Suzuki [1], Masanori Kitamura [1,2], Takeharu Haino [3], Shin Aoki [1,2] [1] Faculty of Pharmaceutical Sciences, Tokyo University of Science [2] Center for Drug Delivery Research, Tokyo University of Science [3] Graduate School of Science, Hiroshima University “Mechanistic Study on Guest Encapsulation in Aqueous Solution by Cuboctahedral Supramolecular Cages Formed by Self-assembly of Trimeric Metal Complexes”
36. Susumu Itoh [1], Masanori Kitamura [1,2], Shin Aoki [1,2] [1] Faculty of Pharmaceutical Sciences, Tokyo University of Science [2] Center for Drug Delivery Research, Tokyo University of Science “Enantioselective Aldol Reactions in Aqueous Media Catalyzed by Chiral Zinc(II) Complexes”
37. Mayumi Kishi [1], Masanori Kitamura [1,2], Shin Aoki [1,2] [1] Faculty of Pharmaceutical Sciences, Tokyo University of Science [2] Center for Drug Delivery Research, Tokyo University of Science “Synthesis of Heteronuclear Supramolecular Complexes by Self-Assembly of Zinc-Cyclen Complex with Transition Metals in Aqueous Solution”
38. TBD
61
39-40 Takashi Yamashita Department of Pure and Applied Chemistry, Tokyo University of Science
“Functionalization of Thermo-Stable Transparent Polymers” (耐熱性透明樹脂の高機能化)
41-42 Naoki Toshima Department of Materials and Environment Technology, Tokyo University of Science, Yamaguchi “New Development in Technology of Metal Nanoparticles” (金属ナノ粒子技術の新展開)
43-44. Yukishige Kondo Department of Industrial Chemistry, Tokyo University of Science “Gold-lustrous Organic Low-molecular Crystal” （金色光沢を有する有機低分子結晶）
45-46. Takeshi Kondo Department of Industrial Chemistry, Tokyo University of Science “Surface /Interface Control Of Conductive Diamond And Its Application To Functional Electrode Material” （導電性ダイヤモンドの表面・界面制御と機能性電極材料への応用）
47. Masahiro Motosuke Department of Engineering, Mechanical Engineering, Tokyo University of Science “Noncontact and Selective Manipulation of Microbubble” （微小気泡の非接触かつ選択的な輸送・除去）
48. Koichi Tsukiyama
Department of Applied Chemistry, Tokyo University of Science “Shared Use Project Of IR FEL Research Center” （赤外自由電子レーザー施設の共用利用事業について）
