8th Conference on Analytical Sciences Ireland 2016 14 & 15 April 2016 #dcucasi

Contents

Welcome to the 8th Conference on Analytical Sciences Ireland 2016 3

Conference Information 4

Acknowledgements

5

Conference Programme 7

Plenary Abstracts 10

Keynote Abstracts 13

Oral Abstracts 20

Flash Abstracts 38

Poster Titles 48

2

Welcome to the 8th Conference on Analytical Sciences Ireland 2016

Dear Colleagues

Welcome to DCU!

We are delighted to be hosting this 8th Conference on Analytical Science here at DCU. This is the flagship biennial conference of the Royal Society of Chemistry Analytical Division Republic of Ireland Sub-Region. The conference itself aims to showcase topics and themes in Analytical Science that are current and relevant to Irish-based analytical research. It is a great honour for us at the National Centre for Sensor Research in DCU to be hosting the showcasing of such a rich and advanced area of research in the Irish context.

We have been overwhelmed with the interest in this meeting from when we began to advertise earlier this year. Many of the main universities and research institutes on the island of Ireland are well represented, as well as several which are further afield. We also have a strong presence from State-sponsored bodies and industry which are represented right across sponsorship support, attendance and research submissions. We have exceeded our expectations in terms of interest and attendance, and would like to take from this, that Analytical Science is very much a vibrant, active topic in Ireland - it is clearly an exciting time and place to be involved in this research effort.

The programme for CASi2016 is packed full with oral, flash and poster presentations around a diverse range of topics. Given the short time we have for this meeting, we have tried to maximise the number of presentation slots, making a fairly intense and hopefully rich programme. However, as importantly, we hope that this meeting will afford you the time to get to know the great community of people you are working alongside in Ireland as well as internationally. Please make use of the times during lunch, coffees, the poster session and the conference dinner which are dedicated to networking and scientific discussion.

We would like to thank both the local organising and the scientific committees who have been particularly supportive. Ms. Claire Williams, however has really been the backbone of the organisation. She has done a spectacular job on behalf of the NCSR, and the anticipated success of this conference will be a tribute to her amazing skills at rolling out events such as this.

Finally, we’ll leave you with some relevant trivia – It is reputed to have been an Irishman to have first coined the term ‘Chemical Analysis’. Who was this? First to tweet the answer using #dcucasi will be rewarded in the next life!

Enjoy the meeting and many thanks for your support,

____________________________ __________________________

Dr. Aoife Morrin Dr. Blánaid White

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Conference Information

Campus Map

• The venue for the 8th Conference on Analytical Sciences Ireland is the Helix.

• The Conference dinner will take place at the 1838 Restaurant at 19:15 on the 14th April 2016. The 1838 restaurant is located in Albert College.

Accessibility

For bus times to and from DCU please see Dublin Bus. The nearest bus stop for DCU can be located on Ballymun Road. Buses 4, 9, 11 and 13 are serviced from this stop.

Taxis

VIP Taxis – 01 478 3333 Cabs 2000 – 01 890 0900

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Acknowledgements

The 8th Conference on Analytical Sciences Ireland 2016 is please to acknowledge generous sponsorship from:

Aquilant Services

Advion

Bards

Brennan & Co

Eurachem

I J Cambria

Lennox Laboratory Supplies Metrohm

The Merck Group

NCSR

5

Acknowledgements

PerkinElmer

The Royal Society of Chemistry

Thermo Fisher Scientific

Waters

6

Conference Programme

Day 1 – Thursday 14th April 2016

08:30 – 09:00 Coffee & Registration

09:00 – 09:10 Welcome and Opening Address – Dr. Aoife Morrin

Session 1 Session Chair: Dr. Damian Connolly

09:10 – 09:55 Plenary Speaker – Prof. Melissa Hanna-Brown – Pfizer Technology & Innovation UK Innovative Strategies to Enable Accelerated Molecule to Medicine Development

09:55 – 10:25 Keynote Speaker – Dr. Amy Managh – Loughborough University, UK New Technologies for Single Cell Detection

10:25 – 10:40 Saidhbhe O Riordan – NUI Maynooth, Ireland Electrochemical methods to investigate disorders of the brain and evaluate muscle tissue viability; Real-time monitoring of physiological biomarkers

10:40 – 10:55 Aoife Delaney – Institute of Technology Tallaght, Ireland AURO-QUANT: Design and fabrication of an electrochemical immunosensor (Immuno-CAP) for bovine progesterone assessment

10:55 – 11:20 Coffee Break

Session 2 Session Chair: Dr. Alan O’Riordan

11:20 – 11:50 Keynote Speaker - Brenda Canty – Johnson & Johnson Laboratories Pharma 2020 – trends that are shaping the industry

11:50 – 12:05 Helen Cantwell - State Laboratory, Ireland Challenges in Method Validation – A Regulatory Laboratory Perspective

12:05 – 12:20 Elizabeth Gilchrist – University College Cork, Ireland Oxyhalide determination by ion chromatography-mass spectrometry

12:20 – 12:35 Dr. Damian Connolly – Waterford Institute of Technology Characterisation of volatiles and semi-volatiles in gin using dispersive liquid-liquid microextraction with gas chromatography

Flash Presentations – Session 1 Session Chair – Dr. Lisa Jones

12:35 – 12:40 Jennifer Deignan – Dublin City University, Ireland Wearable chemical sensing – optimising fluidics for real-time sweat analysis

12:40 – 12:45 Abeer Alyami – Tyndall National Institute, Ireland Use of gold nanorods for SERS analysis of ballpoint pens and felt tip pens

12:45 – 12:50 Andrew Quigley – Waterford Institute of Technology Fatty acid profiling in bovine milk in selected breeds using dispersive liquid-liquid microextraction coupled with GC-FID

12:50 – 12:55 Keana De Guzman – Dublin City University, Ireland Physical characterisation of a silver screen-printed tattoo sensor for skin hydration monitoring

12:55 – 13:00 Patricia Vazquez – Tyndall National Institute, Ireland Smarter-Si: bringing micro and nanotechnologies to the SMEs

13:00 – 14:00 Lunch

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Conference Programme

Session 3 Session Chair – Dr. Eric Moore

14:00 - 14:45 Plenary Speaker – Prof. Dermot Diamond - Dublin City University The Evolution of Microfluidics to Bio-Inspired Systems with Revolutionary Analytical Capabilities

14:45 – 15:15 Keynote Speaker – Mr. John Clancy – Henkel Ireland Problem Solving In The Adhesive Industry

15:15 – 15:30 Ronan O’Neill – University of Southampton, UK Temporally resolving receptor activation mechanisms using inertial microfluidics

15:30 – 15:45 Rohit Mishra – Dublin City University, Ireland Lab-on-a-disc - A versatile platform for decentralised bioanalytical testing

15:45 – 16:15 Coffee Break

16:15 – 16:30 Iain Mayer - Thermo Fisher Scientific – UK Utilizing Novel technologies for the research and development in Material Science, processing and analyzing

16:30 – 16:45 Dr. Alan O Riordan – Tyndall National Institute , Ireland Electrochemical nanosensors towards point-of-care sensing devices

16:45 – 17:00 Danielle Bruen – Dublin City University, Ireland Boronic acid fluorophores for saccharide sensing

17:00 – 17:15 Shauna Scanlon – Tyndall National Institute, Ireland Comparison of a Nafion®-modified glassy carbon, screen printed carbon and screen printed gold electrode for the electrochemical detection of caffeine

17:15 - 17:30 Dr. Jonathan Bones – National Institute for Bioprocessing Research and Training, Ireland Quantitative N-Glycomics in High Definition

Flash Presentations – Session 2 Session Chair – Dr. Emer Duffy

17:30 – 17:35 Coren Pulleybank – Dublin City University, Ireland Tracking the Fate of Polycyclic Aromatic Hydrocarbons in Contaminated Soils during Windrow Bioremediation Pilot Project

17:35 – 17:40 Niamh Creedon - Tyndall National Institute, Ireland Soda can templated flexible polymer SERS substrates for multiple sensing applications

17:40 – 17:45 Barbara O’Leary – State Laboratory Eurachem Ireland

17:45 – 17:50 Alexandru Tudor - Dublin City University, Ireland Poly(ionic liquid) valves for microfluidic devices

17:50 – 17:55 Sean Jordan - Dublin City University, Ireland Mid-Holocene climate change and landscape formation in Ireland: Evidence from a geochemical investigation of a coastal ombrotrophic peat bog

18:00 – 18:45 Poster Session & Wine Reception

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Conference Programme

Day 2 – Friday 15th April 2015

Session 1 Session Chair: Dr. Mercedes Vazquez

09:00 – 09:45 Plenary Speaker – Dr. Evin McGovern – Marine Institute Chemistry all at Sea! ….. Monitoring the changing chemistry of our marine environment

09:45 – 10:15 Keynote Speaker – Dr. Paul Kavanagh – NUI Galway Integrating biological catalysts and electrodes: from biosensors to biopower

10:15 – 10:30 Brian Murphy – Dublin City University, Ireland The occurrence of PAHs and faecal sterols in Dublin Bay and their influence on sedimentary microbial communities

10:30 – 10:45 Abdunnaser Etorki – University of Tripoli, Lybia Adsorption study of mercury ions on polyaniline emeraldine salt prepared by chemical method

10:45 – 11:00 Dr. Tania Dey – Limerick Institute of Technology, Ireland Fourier transform infrared spectroscopy (FTIR): a versatile analytical tool

11:00 – 11:30 Coffee

Session 2

Session Chair: Dr. Matthew Kitching

11:30 – 12:00 Keynote speaker – Dr. Panagiotis Manesiotis – Queens University Belfast, Ireland Development of novel functional building blocks for molecular imprinting of biologically important compounds

12:00 – 12:15 Guy Wilson – Waters Limited, UK SFC Come Of Age - A Review of How SFC is Solving Chromatographic Challenges Today

12:15 – 12:30 Anna Maria Hogan – Tyndall National Institute, Ireland Capillary electrophoresis technique for rapid separation and detection of organophosphate nerve agents

12:30 – 12:45 Matthew Jacobs – University of Tasmania, Australia Evaluation of a miniaturised single-stage resistively heated modulator for comprehensive two-dimensional GC

12:45 – 13:15 Keynote Speaker - Dr. Blanaid White - Dublin City University Elucidating the mechanisms of metal induced DNA damage

13:15 – 13:30 Awards, Presentations & Closing Remarks

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Plenary Abstracts

INNOVATIVE STRATEGIES TO ENABLE ACCELERATED MOLECULE TO MEDICINE DEVELOPMENT

Professor Melissa Hanna-Brown - Pfizer Technology & Innovation UK

The pharmaceutical industry is going through a period of great change. Fewer blockbusters exist, while the emergence of precision/personalized medicines and drugs for rare/orphan diseases are driving the industry towards more products with smaller volumes. At the same time, there is unrelenting pressure on the cost of drug products. Further, despite increased portfolio complexity, pressures are mounting to achieve a local market demand-driven supply chain with reduced lead-time requirements that is more responsive to volume uncertainty. Put together, these factors are influencing significant changes in the molecule to medicine development process. This presentation will outline some of the scientific areas Pfizer are investing in to facilitate the accelerated development requirements with specific focus on predictive science.

Biography Melissa joined Pfizer in 2006 and after working as a Lead Separation Scientist she moved to an Analytical Lead role for a variety of Active Pharmaceutical Ingredient and Drug Product Pfizer projects in the late development portfolio. Melissa is now the Technology & Innovation UK/EU Lead and Analytical expert in a global Technology and Innovation Group in Pfizer. Based in the UK, she supports UK and EU colleagues facilitating business interactions with the dynamic external innovation ecosystem. Melissa chairs and manages the budget for External Collaborations with a team of some of the most senior scientists across the Pharmaceutical Sciences organization. Melissa studied for her PhD with King’s College London and SmithKline Beecham before taking a KCL EPSRC postdoctoral researcher position (separations instrumentation development). She then spent 8 years in the Pharmacy Department at King’s College London as an academic teaching Pharmaceutical Chemistry and leading a separation science research group (PhD and postdocs). During this time she won the Desty Award for Innovation in Separation Science and secured funding from UK research councils, EU Commission and pharmaceutical companies. She is currently a Visiting Full Professor in the Department of Chemistry at the University of Warwick and has authored more than 50 publications.

Melissa is the Pfizer representative on the European Federation of Pharmaceutical Industries and Associations (EFPIA) Analytical Method Lifecycle Group and the British Pharmacopeia Commission Working Party on Analytical Quality by Design. She is a Fellow of the RSC, an elected RSC council member, current President of the RSC Analytical Division, and chairs the Analytical Chemistry Trust Fund.

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Plenary Abstracts

THE EVOLUTION OF MICROFLUIDICS TO BIO-INSPIRED SYSTEMS WITH REVOLUTIONARY ANALYTICAL CAPABILITIES?

Professor Dermot Diamond – Dublin City University

Diamond, D., Florea, L., Francis, W., Dunne, A., Tudor A., BenAzouz, A., Coleman, S. and Bruen, D. Insight Centre for Data Analytics, National Centre for Sensor Research, Dublin City University

Since the initial breakthroughs in the 1960’s and 70’s that led to the development of the glucose biosensor, the oxygen electrode, ion-selective electrodes, and electrochemical/optochemical diagnostic devices, the vision of very reliable, affordable chemical sensors and bio-sensors capable of functioning autonomously for long periods of time (years) remains unrealized. This is despite massive investment in research and the publication of many thousands of papers in the literature. It is over 40 years since the first papers proposing the concept of the artificial pancreas, by combining glucose monitoring with an insulin pump. Yet even now, there is no chemical sensor/biosensor that can function reliably inside the body for more than a few days, and such is the gap in what can be delivered (days), and what is required (years) for implantable devices, it is not surprising that in health diagnostics, the overwhelmingly dominant paradigm for reliable measurements is still single use disposable sensors. Realising disruptive improvements in chem/bio-sensing platforms capable of long-term independent operation requires a step-back and rethinking of strategies, and considering solutions suggested by nature, rather than incremental improvements in available technologies.

Through recent developments in 3D fabrication technologies in recent years, we can now build and characterize much more sophisticated 3D platforms than was previously possible. We can create regions of differing polarity and hydrophobicity, mix passive and binding behaviours, and regions of differing flexibility/rigidity, hardness/softness. In addition, we can integrate materials that can switch between these characteristics, enabling the creation of biomimetic microfluidic building blocks that exhibit photoswitchable characteristics such as programmed microvehicle movement (chemotaxis), switchable binding and release, switchable actuation (e.g. valving), and photodetection. These building blocks can be in turn integrated into microfluidic systems with hitherto unsurpassed functionalities that can contribute to bridging the gap between what is required for many applications, and what we can currently deliver. For example, these disruptive advances should at last open the way to long-term implantable devices that can monitor, report and assist the management of an individual’s personal health. A key development will be the integration of biomimetic functions like self-diagnosis and self-repair capabilities to extend their useful lifetime.

Biography Dermot Diamond received his Ph.D. and D.Sc. from Queen’s University Belfast (Chemical Sensors, 1987, Internet Scale Sensing, 2002), and was Vice-President for Research at Dublin City University (2002-2004). He joined the School of Chemical Sciences at DCU in 1987, and has led a series of large-scale research initiatives since then. He has published over 300 peer-reviewed papers in international journals, is a named inventor in 18 patents, and is co-author and editor of four books. He was director and founding member of the National Centre for Sensor Research at Dublin City University, possibly the largest and most successful centres of its type worldwide, with over 250 researchers, and income in excess of €100 million. In 2002, Dermot was awarded the inaugural silver medal for Sensor Research by the Royal Society of Chemistry, London, and in 2006 he received the DCU President’s Award for research excellence. In May 2014, in recognition of his academic contributions and achievements, he was admitted to Membership of the Royal Irish Academy. Professor Diamond has recently been awarded the Boyle-Higgins Medal from the Institute of Chemistry, Ireland. He is a PI in four FP7 projects, focused on distributed environmental sensing, fundamental materials chemistry and is coordinating partner of the EU-Australia International Network ‘MASK’, funded under the Marie Curie IRSEs programme. He is also a Funded Investigator under the SFI-INSIGHT Centre initiative.

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Plenary Abstracts CHEMISTRY ALL AT SEA! ….. MONITORING THE CHANGING CHEMISTRY OF

OUR MARINE ENVIRONMENT

Dr. Evin McGovern – Marine Institute

Marine ecosystems are subject to ever increasing stresses as a result of human activities. Multiple pressures include climate change and acidification, resource extraction (including fishing) and pollution by chemical substances, litter and noise. Good data are a prerequisite for sound management and sustainable use of this shared resource and therefore, harmonised monitoring and assessment of the state of and impacts on marine ecosystem is a key aspect of European directives and intergovernmental conventions for the protection of the marine environment. This presentation will focus on approaches and challenges for measuring the changing chemistry of our seas, including nutrient inputs to coastal waters, the ubiquitous occurrence of persistent bioaccumulative and toxic substances, and ocean acidification due to uptake of anthropogenic CO2 from the atmosphere. For example, tools such as passive sampling are emerging as a complementary approach to determination of hazardous substances in water, biota and sediment although their role in regulatory monitoring has yet to be agreed. Novel technologies and monitoring platforms offer the opportunity for new paradigms for continuous long-term monitoring of physical, chemical and biological variables over wide spatial scales, although developments of robust and precise sensors is required to fully realise this.

Biography Dr. Evin McGovern heads the Marine Chemistry group at the Marine Institute. The group provides scientific advice as well implementing seafood and environmental monitoring and assessment programmes in fulfilment of the requirements of EC legislation and intergovernmental conventions. He has been a member of many national and international scientific expert groups and was Irish lead in drafting the OSPAR Convention’s 2010 Quality Status Report; a benchmark report on the state of the North-East Atlantic. He is a former chair of both the long-standing Marine Chemistry Working Group of the International Council for the Exploration of the Sea (ICES) and the Joint ICES-OSPAR Study Group on Ocean Acidification. Active research interests include marine pollution and its effects; novel techniques for environmental monitoring; chemical substances in seafood and risks to consumers; and marine biogeochemical cycling, specifically ocean acidification and its impacts.

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Keynote Abstracts

NEW TECHNOLOGIES FOR SINGLE CELL DETECTION

Dr. Amy Managh – Loughborough University

1Managh, A.J.*; 1Douglas, D.N.; 1Sharp, B.L.; 1Reid, H.J.; 2Hutchinson, J.A. and 3Bushell, A. 1 Department of Chemistry, Loughborough University, UK

2 Department of Surgery, University Hospital Regensburg, Germany 3 Nuffield Department of Surgical Sciences, University of Oxford, UK

Cell based therapy is attracting increasing attention for the treatment of conditions such as diabetes, myocardial infarction and autoimmune disease. In the field of solid organ transplantation, four distinct cell based therapies are now reaching the point of clinical application.1 The emergence of these therapies has produced a demand for highly sensitive methods to monitor individual cells in vivo. We recently demonstrated that commercially available labelling agents can be used to tag therapeutic cells, permitting their tracking using laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS).2,3 Whilst undoubtedly a valuable research tool, the lengthy analysis times associated with conventional LA-ICP-MS systems prevent its use for routine clinical monitoring. Thus, in recent years, a number of fast-washout laser ablation cells have been developed,4 which enable analysis to take place at ~50 fold faster speed and with ~6-10 fold higher sensitivity than conventional technology.5

This keynote presentation will outline recent technological developments in the fields of laser ablation and ICP-MS, their application to single cell analysis, and their potential to facilitate the development of personalised approaches to medicine.

References [1] www.onestudy.org [2] Managh, A.J. et al. Anal. Chem., 2013, 85(22), 10627. [3] Managh, A.J. et al. J. Immunol., 2014, 193(5), 2600. [4] Van Malderen, S.J.M. et. al., J. Anal. Atom. Spectrom., 2016, 31, 423. [5] Douglas, D.N. et al. Anal. Chem., 2015, 87(22), 11285.

Biography Amy obtained a BSc in Chemistry from the University of Leeds in 2009, which she followed with a move to Loughborough University, where she completed an MSc in 2010 and a PhD in February 2015. Her research focusses the on the trace analysis of metals, with an emphasis on bio-imaging and single cell detection. Amy is currently an Enterprise Fellow at Loughborough University, where she is designing prototype analytical instrumentation and collaborating with industry to bring the resulting technology to market.

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Keynote Abstracts

PHARMA 2020 – TRENDS THAT ARE SHAPING THE INDUSTRY

Brenda Canty - Johnson & Johnson Laboratories

By 2020 the pharmaceutical market is anticipated to more than double to US$1.3 trillion, with the E7 countries — Brazil, China, India, Indonesia, Mexico, Russia and Turkey — accounting around for one fifth of global pharmaceutical sales. Further, incidence of chronic conditions in the developing world will increasingly resemble those of the developed world. The current pharmaceutical industry business model is both economically unsustainable and operationally incapable of acting quickly enough to produce the types of innovative treatments demanded by global markets. In order to make the most of these future growth opportunities, the industry must fundamentally change the way it operates. By 2020 the current role of the pharmaceutical industry’s innovation, manufacturing, sales and marketing workforce will be replaced by a new model as the industry shifts from a mass-market to a target-market approach to increase revenue. This presentation will discuss the fundamental dynamics the industry faces that are reshaping the pharmaceutical and some of the major changes that are predicted for the industry over the coming years.

Biography Brenda is a Senior Manager with Johnson & Johnson labs, responsible for the development and execution of the J&J lab strategy. She has over fifteen years laboratory experience concerned with the testing and data management of clinical and commercial products. She has experience leading labs in both chemical API and biologics sectors. More recently, Brenda has also been part of a team developing the Quality strategy, including all Quality & laboratory operations, for the Janssen pharmaceutical supply chain (J&J). Prior to joining Johnson & Johnson, Brenda worked in several analytical development and Quality Control roles of increasing responsibility. Brenda has BSc in Chemistry from NUI, Galway and an MSc in Applied Science (Analytical Chemistry) from University College Cork.

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Keynote Abstracts

PROBLEM SOLVING IN THE ADHESIVE INDUSTRY

John Clancy - Henkel Ireland

The analytical laboratory based in Henkel Tallaght possesses a wide range of chemical analysis techniques and experience in supporting the development of novel adhesive products and chemistry’s. However from time to time the laboratory is asked to perform a “problem solving“ function in respect to manufacturing or customer issues. In this presentation two such issues will be described along with the techniques/strategies used to bring them to a resolution.

Biography Joined Henkel 2007. Specialist in the use of atomic spectroscopy for the analysis of cyanoacrylate and anaerobic adhesive chemistry’s.

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Keynote Abstracts

INTEGRATING BIOLOGICAL CATALYSTS AND ELECTRODES: FROM BIOSENSORS TO BIOPOWER

Dr. Paul Kavanagh – NUI Galway

Mediated enzyme reactions form the basis of many applications, ranging from biosensors, through biocatalytic fuel cells, to applications in industrial electrolysis. This presentation will briefly review some of our efforts to date on redox mediation of enzyme reactions for such applications. Immobilization of the enzyme in a redox mediating hydrogel yields reagentless biosensors, as monitoring of mediated reduction currents for a range of substrates, present in solution, permits detection of any modulator of enzyme activity. Furthermore, co-immobilization of a redox mediator and an affinity recognition element, such as DNA or antibody, provides a generic platform for the amplified detection of complementary affinity partners (DNA or antigen) that are labelled with redox enzymes.

Our studies on oxygen biosensors demonstrated, also, that copper oxisases co-immobilized in redox hydrogels can reduce oxygen at relatively high potentials and current densities, suggesting possible applications as cathodes in implantable biofuel cells when combined to oxidation of a fuel, such as glucose, at the anode. Covalent coupling of enzymes and mediators on electrode surfaces, particularly structured surfaces, can appreciably improve the fuel cell stability and output. Similarly, biofilms of electro-active bacteria (EAB) in microbial fuel cells (MFCs) can facilitate proficient organic carbon removal from wastewater while producing biological renewable energy in the form of electricity. Our research examines cyclic voltammetric behaviour of EAB under various growth conditions to assess the efficiency of such films in MFCs. The approach adopted examines the role of an applied controlled-potential to enhancing biofilm electrochemical catalytic activity compared with the behavior of control biofilms using both single-culture studies (Geobacter sulfurreducens, Rhodoferax ferrireducens) and mixed-culture studies on model fuel/wastes, and on wastes sourced from municipal and slaughterhouse waste-streams, as well as fuels derived from second-generation biofuel crops.

Biography Paul Kavanagh is a lecturer in the School of Chemistry, National University of Ireland Galway. Paul received his BSc in Pure and Applied Chemistry from Dublin City University, Ireland in 2002. He obtained a PhD (2006) in chemistry NUI Galway, focusing on the synthesis and characterisation of redox polymer films for application to DNA biosensors and biofuel cells. His research activities include bioelectrochemistry, bioanalysis, microfluidics, transition metal complex syntheses and computational chemistry.

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Keynote Abstracts

DEVELOPMENT OF NOVEL FUNCTIONAL BUILDING BLOCKS FOR MOLECULAR IMPRINTING OF BIOLOGICALLY IMPORTANT COMPOUNDS

Dr. Panagiotis Manesiotis – Queens University Belfast

Over the past decade we have focused our efforts on the development of novel polymerisable receptors for use in molecular imprinting, ranging from simple (bis)acrylamido pyridines to (thio)ureas. These architectures have proven the benefits of custom functional monomer design tailored to the template of interest. Here, we wish to report on a series of recently developed receptors that further extend the tools available for the imprinting of compounds of biological interest. These include the first polymerisable squaramide receptors, as well as a series of polymerisable ionic liquids, used in the recognition of anionic species and neutral sulfonylureas, respectively.

Substituted squaramide receptors were prepared in a single-step or a two-step synthesis in high yields and their affinity towards common anions was tested by means of UV and 1H-NMR titrations.1 Binding constants in excess of 106 L mol-1 and strong colour changes upon binding were observed, both in solution and following polymerisation, in some instances associated with receptor deprotonation (Figure 1).

Figure 1. Binding induced colour change of squaramide based imprinted polymers. From left: 0, 2, 5, 10, 25, 50, 100 mmol L-1 of fluoride added.

Furthermore, inspired by our previous work on the use of the urea motif for anion recognition, we will report on a “reverse” approach and the first use of tetrabutylammonium methacrylate for stoichiometric imprinting of sulphonylurea antidiabetic drug glibenclamide and the application of the resulting polymers in the extraction of the drug from biological fluids.2

Lastly, we will discuss our ongoing efforts towards the synthesis and evaluation of a novel range of polymerisable ionic liquids, and give an insight on the challenges and opportunities these compounds present for the field of molecular imprinting.

References [1] P. Manesiotis, A. Riley and B. Bollen (2014) Polymerisable squaramide receptors for anion binding and sensing. Journal of Materials Chemistry C 2: 8990-8995. [2] A. N. Hasanah, F. Pessagno, R. E. Kartasasmita, S. Ibrahim and P. Manesiotis (2015) Tetrabutylammonium methacrylate as a novel receptor for selective extraction of sulphonylurea drugs from biological fluids using molecular imprinting. Journal of Materials Chemistry B 3: 8577-8583.

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Keynote Abstracts

Biography Dr Panagiotis Manesiotis studied Chemistry at Aristotle University of Thessaloniki. He then joined the group of B. Sellergren at the University of Dortmund as post-graduate student, working on the development of MIPs targeting compounds of biological interest. He performed post-doctoral research at the University of Strathclyde with D.C. Sherrington and P.A.G. Cormack and later at the PMBRC in Waterford Institute of Technology. He joined the School of Chemistry and Chemical Engineering of Queen's University Belfast in 2013 as Lecturer. His main research interests include development of molecularly imprinted polymers (MIPs) for separations, sensing and catalysis, supramolecular chemistry and synthetic receptors.

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Keynote Abstracts

ELUCIDATING THE MECHANISMS OF METAL INDUCED DNA DAMAGE

Dr. Blanaid White – Dublin City University

By monitoring oxidative DNA damage, the mode of action of proposed oxidants, and antioxidant therapies, can be investigated. Analytical platforms such as CE-EC, HPLC-UV-EC and HPLC-MS, in tandem with bioanalytical techniques such as flow cytometry and the Comet assay have been used to monitor oxidative DNA damage at both a molecular and cellular level. In this presentation, the mode of action of metal based oxidants is explored. A number of antioxidant therapies will also be discussed in terms of their ability to protect against oxidative DNA damage. The analytical and bioanalytical platforms utilised for their determinations evaluated in terms of the accuracy and precision of the resulting measurements.

For example, a series of novel therapeutics evaluated using evaluated using the oestrogen-positive MCF-7 breast cancer cell line. Guanine oxidation studies using HPLC-UV-EC confirmed that one derivative was capable of generating oxidative damage via a reactive oxygen species-mediated mechanism.

Selenium enriched protein digests were also explored to determine their antioxidant properties. Using a number of bioanalytical platforms, they were compared to organic and inorganic selenium sources and their antioxidant properties evaluated, for a number of different types of oxidative stress insult.

Biography Dr. Blánaid White’s research interests focus on the development of intelligent analysis tools and the application of analytical chemistry for the investigation of chemical and biochemical processes in the world around us. A primary focus of our research is the elucidation of molecular mechanisms which initiate and propagate oxidative stress, particularly that which leads to DNA damage. This type of damage has been linked to mutagenesis, neurological disease and aging, and understanding the underlying mechanisms has the potential to enable us to develop tailored therapies to combat these diseases. Metal mediated oxidative DNA damage is of particular interest, as this can be used to develop novel chemotherapeutic drugs and to elucidate the role of heavy metals in environmental contamination. We also research unique bioactive and nutrition profiles in Irish food, which can be used from substantiating health claims to proving authenticity. A second research focus is the development of chromatographic stationary phases using novel monolithic polymers to develop intelligent analytical platforms. These advanced analysis tools will be capable of resolving problematic complex mixtures, supporting the pharmaceutical, biopharma and environmental analysis industries.

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Oral Abstracts

ELECTROCHEMICAL METHODS TO INVESTIGATE DISORDERS OF THE

BRAIN AND EVALUATE MUSCLE TISSUE VIABILITY; REAL-TIME

MONITORING OF PHYSIOLOGICAL BIOMARKERS

Saidhbhe O’Riordan – NUI Maynooth

SL O’Riordan1 and JP Lowry1

1Neurochemistry Research Unit, BioAnalytics Laboratory, Department of Chemistry, Maynooth University, Maynooth, Co. Kildare, Ireland.

Oxidative stress has been widely associated with various brain disorders, however the implication of this damaging process as an initiating factor or alternatively as a downstream event in neurological dysfunction remains inconclusive. We have previously successfully demonstrated the in-vitro characterisation of a catalase-based hydrogen peroxide sensor. We now demonstrate the real-time detection of brain hydrogen peroxide using our catalase-based electrochemical sensor in the freely-moving animal. Our catalase-based sensor may be used to measure the onset and progression of oxidative stress in the brain via the real-time detection of neuronal hydrogen peroxide.

We have demonstrated the ability of our sensors and associated methodology to examine normal brain function and monitor neurological disease related biomarkers in rodents. In order to potentially implement our technology in the clinical environment, we have modified the application area of a platinum based electrochemical microsensor for the detection of brain tissue oxygen. We now aim to demonstrate the suitability of this oxygen sensor, to measure the onset and progression of ischemia in the peripheral muscle tissue.

This research was funded by the Health Research Board [RP/2004/44 and HRA-POR-2014-694].

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Oral Abstracts

AURO-QUANT: DESIGN AND FABRICATION OF AN ELECTROCHEMICAL

IMMUNOSENSOR (IMMUNO-CAP) FOR BOVINE PROGESTERONE

ASSESSMENT

Aoife Delaney – Institute of Technology Tallaght

Delaney, A., * Singh, B., Kelch, J., Seddon, B. and Dempsey, E.

Profitability in the dairy industry is heavily dependent on the accuracy of progesterone (P4) measurement, with periodic assessment of hormone levels in herds being utilised to determine the most fertile ovulation time for artificial insemination. Point of care and in-line instruments, coupling ELISA techniques with electrochemical detection have been explored in order to quantify P4 in bovine milk and serum, yet practical implementation of a sensitive, rapid, low cost test remains a technical challenge. The Immuno-CAP device proposed here may be described as a micro-capillary biosensor incorporating a thin-layer mesofluidic system involving rapid flow immunochromatography with electrochemical detection based on the redox activity of nanogold (AuNP) - the signalling element of a competitive ELISA format. Competition between P4 in the sample and AuNP labelled P4 for binding sites on the internal wall of the anti-P4 antibody coated capillary facilitates electrochemical detection of AuNP reaching the electrode which is in turn related to the free P4 concentration in the milk sample (Fig. 1).

Figure 1. a) Schematic representation of Immuno-CAP, illustrating the structure of a single-channel device and b) showing exploded view of detection mechanism following the competitive immunoassay protocol for progesterone. Device dimensions; 85 x 15 mm (L x W). Channel dimensions; L 74 mm, W 1 mm and D 160 µm

b)

a)

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Oral Abstracts

CHALLENGES IN METHOD VALIDATION – A REGULATORY LABORATORY

PERSPECTIVE

Helen Cantwell – State Laboratory

Cantwell, H.*1 and Hayden, R.2

1,2: Eurachem Ireland 1: The State Laboratory, Backweston Laboratory Campus, Celbridge, Co. Kildare

2: Public Analyst’s Laboratory, Sir Patrick Duns, Lower Grand Canal Street, Dublin 2

Laboratories providing an analytical service to customers both internal and external have a responsibility to ensure that the analytical work is demonstrably fit for purpose [1]. Demonstrating that an analytical method is, and remains, fit for purpose presents a number of challenges. Regulatory laboratories must, in general, be accredited and also operate in areas governed by legislation. When developing method validation procedures, Irish regulatory laboratories which are accredited by the Irish National Accreditation Board (INAB) must comply with the International Standard (ISO 17025 - General requirements for competence and testing laboratories), relevant International and EU legislation and INAB policy documents.

Other International and European Standards and Guidelines also provide approaches to method validation. The approach to method validation given in each may be different. This can result in even different departments of the same laboratory having different method validation procedures unless a central harmonised approach is agreed. Each procedure may demonstrate fitness for purpose of the analytical method but the lack of standardisation in method validation can be detrimental. For example, the European Food Safety Authority (EFSA) collates data from laboratories across Europe for the purposes of Risk Assessment [2]. The data must be comparable across laboratories meaning that the method validation should be also. Could a “none-detected” sample result from one laboratory be a “positive but compliant result” if analysed elsewhere?

Other challenges faced include how to demonstrate that analytical standards are appropriate; analytical methods which must be applied to a variety of matrices; calculation of measurement uncertainty; the lack of proficiency tests for all analytes and in all matrices; demonstrating that a method remains fit for purpose while in routine use; the situations where re-validation should be carried out.

Eurachem Ireland, via representation on the Eurachem Method Validation Working Group, aim to address the concerns of Irish Laboratories in the area of method validation.

References [1] The Fitness for Purpose of Analytical Methods, Eurachem Guide, 2014 [2] www.EFSA.europa.eu

22

Oral Abstracts

OXYHALIDE DETERMINATION BY ION CHROMATOGRAPHY-MASS

SPECTROMETRY

Elizabeth Gilchrist – University College Cork

Gilchrist, E.S.*, Healy, D.A., Morris, V.N. and Glennon, J.D.

In recent years there has been increased interest in coupling ion chromatography (IC) to mass spectrometry (MS) in order to gather structural information at high sensitivity. The combination of IC-MS offers advantages over other analytical techniques in terms of ICs ability to speciate, which can be essential in the identification of analytes, as well as offering selectivity and sensitivity over traditional, non-specific detection modes such as conductivity and UV/Vis. Oxyhalides are commonly encountered in a range of analytical applications, from environmental to forensic to food and beverage quality. There are several oxyhalides, for example perchlorate (ClO4

-) and bromate (BrO3-),

which can have an impact on health and ecosystems, meaning it is important to monitor their concentrations in sample matrices related to these areas, such as water. An overview of the practicality of IC-MS will be provided, along with the analytical considerations associated to enable sensitive analysis. Results from work comparing the use of IC-MS to typical IC with suppressed conductivity detection with a focus on common anions and oxyhalide analysis will also be presented, looking at the effect on the retention of analytes and separation selectivity.

23

Oral Abstracts

CHARACTERISATION OF VOLATILES AND SEMI-VOLATILES IN GIN USING

DISPERSIVE LIQUID-LIQUID MICROEXTRACTION WITH GAS

CHROMATOGRAPHY

Damian Connolly – Water Institute of Technology

Spoelders, S.; Quigley, A.; Cummins, W.; Breen, M.; Connolly, D*.

Gin is a widely consumed distilled beverage which includes various types and formulations. The most common type of gin is London Dry Gin, produced only by re-distillation of alcohol 96% (v/v) in the presence of juniper berries and other natural botanical ingredients including coriander seeds, cardamom seeds, orris root, angelica root, liquorice root, orange peel, lemon peel, and liquorice root. All of these ingredients are rich in essential oils, which contribute to the aroma of most gins, but the main flavour of distilled gin should come from the juniper berries. Alternative methods include vapour infusion in which the botanicals are held in a receptacle above the hot solvent during distillation. Since the presence of several volatile and semi-volatile compounds strongly contributes to gin flavour perception, detailed information about gin volatile composition is necessary for the characterization of distinct classes of products and as a basis for defining gin sensory quality.

The most common analytical method for gin analysis is headspace solid phase micro-extraction (HS-SPME) followed by gas chromatography with mass spectrometric analysis (or direct immersion HS-GC-MS) which requires expensive laboratory equipment and consumables (SPME fibers). Here we report the development of dispersive liquid-liquid microextraction (DLLME) in which extraction of analytes takes place in a dispersion of the extracting solvent (chloroform, dichloromethane) made in water, in the presence of a third, bridging “dispersing solvent”. The dispersion is removed by centrifugation and the extracting solvent containing analytes is taken for analysis with a micro-syringe. We report the optimisation of a DLLME-GC-FID protocol for the analysis of selected commercial gins as well as model gins produced in-house. Typical DLLME optimisation parameters such as solvent volume ratios, ionic strength and sample pH were studied using an internal standard to maximise extraction. Volatile and semi-volatile components were identified via Kovats Retention Indices using a mixed hydrocarbons standard, belonging mainly to the terpenoids family (monoterpenes, sesquiterpenes and their corresponding oxygenated compounds) including limonene, linalool, α-pinene, β-myrcene, γ-terpinene and verbenyl ethyl ether. The optimised DLLME protocol was used to (1): assay the batch-to-batch reproducibility of model gins, (2): to compare commercial gins and (3): to examine the influence of selected production methods on the generation of oxygenated terpenes and corresponding reduction in unwanted monoterpenes which is known to improve product stability.

24

Oral Abstracts

TEMPORALLY RESOLVING RECEPTOR ACTIVATION MECHANISMS USING

INERTIAL MICROFLUIDICS

Ronan O’Neill – University of Southampton

O’Neill, R.T.J*; Stavrou, M. and West, J.J. Membrane receptors represent the communication interface for coupling external cues (ligands) and transducing the information into the cell to govern behaviour. Receptor signal transduction occurs within sub-second timescales, yet current techniques do not have the temporal resolution to reveal the intermediates and thus mechanism of receptor activation. This understanding is of vital importance for the rational identification of therapeutic targets and the design of novel therapeutics.

Conventionally, quenched flow analysis, involving the rapid introduction of ligand, an incubation delay line and rapid reaction quenching, is used to reveal intermediates within the dynamics of molecular processes. However, this high-speed, turbulent, approach destroys cell membranes and thus the environment for receptor-mediated signal transduction. In microfluidic regimes, flows are laminar affording the capability to process intact cells, albeit with the disadvantage of diffusion-limited mixing. Cells transported in microfluidic channels can be rapidly displaced into ligand streams and subsequently quench streams. This approach has been used to resolve insulin-like growth factor receptor activation with millisecond resolution1 and used to discover a novel, biphasic mechanism underpinning epidermal growth factor receptor (EGFR) activation.2 The approach does, however, suffer from low cell throughput (3 days/experiment) and lengthy quantitative fluorescent microscopy.

In this research we have developed a novel microfluidic circuit based on inertial physics; high velocity (m/s) transport in microfluidic channels drives particles to equilibrium positions.3 Inertial focussing is used to laterally translate cells into the ligand in sub-millisecond timescales. Dean flows requiring channel curvature are used to focus the cells to a common position and thus common velocity, producing uniform incubation times (CV=1.2%). The temporal window of interest is between 10 to 1,000 ms. Lastly, a second inertial focussing element is used to laterally translate cells into a quench buffer to preserve the receptor intermediates in readiness for analysis. Flow cytometry is used for the multiplexed analysis of different phosphorylation sites involved in the activation process. Coupled with this, the flow rates required for inertial processing involve kHz cell processing, matching the performance of cytometry and overall providing a high throughput work flow (1 hour/experiment). We will use the inertial microfluidics technique to elucidate the overall mechanism of EGFR activation in health and in disease. The technique is broadly applicable to cell surface processes, providing the opportunity to gain new insights into a tremendous variety of biological systems.

References 1. Chiang Y.; Haeri S.; Gizewski C.; Stewart J.; Ehrhard P.; Shrimpton J.; Janasek D and West J. Anal Chem. 2013, 85(23),

11560. 2. Chiang Y. and West J. Lab chip. 2013, 13(6), 1031. 3. Amini H.; Lee W. and Di Carlo D. Lab Chip. 2014, 14(15), 2739.

25

Oral Abstracts

LAB-ON-A-DISC – A VERSATILE PLATFORM FOR DECENTRALISED

BIOANALYTICAL TESTING

Rohit Mishra - Dublin City University

Rohit Mishra*, David Kinahan, Damien King, Jens Ducrée

Simple, cost-efficient and user-friendly technologies form the backbone of modern biomedical point-of-care (POC) diagnostics. Over the recent past centrifugal microfluidic platforms have been increasingly leveraging biomedical POC diagnostics employing various liquid handling technologies [1]. In these systems, a disc-shaped cartridge, typically with similar dimensions as the common optical disc carriers (DVD or CD), is rotated at defined frequency curves by a robust and low-cost spindle motor. We have pioneered the flow control on such “Lab-on-a-Disc” (LoaD) systems using various centrifugo-pneumatic valving schemes using strategically placed sacrificial membranes such as lipophilic or (water) dissolvable films (DFs) [2, 3]. Recently, we cascaded these valves in a handshake-mode [4] where the release of liquid from one point is prompted by the arrival of another liquid at a distal location on the disc. This ‘event-triggered’ approach operates widely independently of the spin rate and thus does not require external instrumentation.

We have also applied the centrifugal microfluidic platform for the highly efficient manipulation and analysis of particles for applications in bead-based assays. The platform uses an array of geometrical V-cup barriers to trap microparticles using stopped-flow sedimentation under highly reproducible hydrodynamic conditions. The technology marks an essential step towards a versatile platform for the integration of bead- and cell-based biological assays [5].

References 1. Gorkin R. et al. Lab on a Chip 10.14 (2010): 1758-1773. 2. Gorkin R. et al. Lab on a Chip, 2012, 12, 2894-2902. 3. Mishra R. et al. 28th IEEE International Conference on Micro Electro Mechanical Systems (MEMS 2015, 523-

526. 4. Kinahan D. J. et al. Lab on a Chip, 2014, 14, 2249-2258. 5. Burger R. et al. Lab on a Chip, 2012, 12, 1289.

26

Oral Abstracts

UTILIZING NOVEL TECHNOLOGIES FOR THE RESEARCH AND DEVELOPMENT

IN MATERIAL SCIENCE, PROCESSING AND ANALYZING

Iain Mayer – Thermo Fisher Scientific Polymer manufacturers need to create new materials and deliver high quality to meet ever changing end-use requirements. A thorough, precise testing and analysis process is mandatory to ensure quality and stay competitive in today’s environment. At any stage of the value chain, Thermo Fisher Scientific has comprehensive solutions to speed the development, production, and quality testing and analysis of polymers and advanced materials.

27

Oral Abstracts

ELECTROCHEMICAL NANOSENSORS TOWARDS POINT-OF-CARE SENSING

DEVICES

Dr. Alan O’Riordan – University College Cork

Nanomaterials for the development of electrochemical nanosensors are proving attractive for a new generation of devices, due to their remarkable characteristics and capabilities. The enhanced chemical and physical properties arising from discrete nanoelectrode devices make these devices an attractive option for the improvement of current electroanalytical applications. In particular, electrochemical nanosensors have played a significant role in the transition towards point-of-care devices.

This talk highlights the application of electrochemical nanosensors in a number of major fields, namely: animal health, environment, soil quality and food security, with a view to develop portable point-of-care devices. The innovative fabrication of these sensors is driven from a trifecta of attributes: sensitivity, stability and specificity. The sensitivity is achieved through modelling of the electrode design to allow increased mass transport to the electrode (via radial diffusion) and low background charging currents due to the reduced surface area and the introduction of a shield layer. Stability is achieved through the choice of electrode material and chemical modification of the electrode surface. Finally, the specificity is attained through chemical and biochemical functionalisation and utilising combined sensing mechanisms, e.g. electrochemistry with surface enhanced Raman spectroscopy. The combination of all three characteristics in a nanosensor creates a superior point of care platform that provides rapid, safe and cost-efficient sensing capabilities and demonstrates commercial opportunity for use in food safety, security and veterinary diagnostics.

28

Oral Abstracts

BORONIC ACID FLUOROPHORES FOR SACCHARIDE SENSING

Danielle Bruen – Dublin City University

Bruen, D.*; Florea, L. and Diamond, D.

Lewis acidic boronic acids (BAs) have been widely reported for their strong and reversible interactions with diol-containing compounds like sugars [1,2]. In many examples, fluorescent structures are incorporated into a BA derivative’s framework in order to monitor the effect of sugar concentrations by changes in fluorescence [1,2]. Due to the pKa of the BA at ~9 and the one for the sugar bound form at ~6, BA type sensors exhibit sugar sensing capabilities between a pH range of 6-9. This is advantageous for applications in sugar sensing under physiological conditions, where the pH for blood and ocular fluid is approximately 7.4.

Here, we report novel carboxylic acid BA fluorescent sensors, o-COOHBA and m-COOHBA, respectively, that have been synthesised via a one-step nucleophilic substitution reaction, and have been investigated for their glucose sensing capabilities in solution. Upon addition of glucose the electron density on the boron atom is increased, facilitating the partial neutralization of the positively charged quaternary nitrogen of the quinolinium moiety through a neutralisation-stabilisation interaction. This leads to a quenched state and hence a decrease in fluorescence of the COOHBA probe with increased glucose concentration. The sensor’s response was investigated in various pH buffer solutions, where the sensing range was determined to be between pH 6-9 [2], which correlates to the pKa of the BA and the sugar-bound form. As pH 7.4 lies within the sensing range, these sensors have been directed towards physiological monitoring of glucose for personalised sensing, where the sensors can be incorporated in to wearable platforms, such as a disposable contact lens, for continuous and non-invasive glucose monitoring.

References [1] Fang, H.; Kaur, G. and Wang, B. Journal of Fluorescence, 2004, 14(5), 481-489. [2] Badugu, R.; Lakowicz, J. R. and Geddes, C. D. Journal of Flourescence, 2004, 14(5), 617-633.

00.10.20.30.40.50.60.70.80.9

1

0 1 2 3 4 5 6 7 8 910

F/F0

Glucose Concentration (mM)

m-COOHBA

o-COOHBA

29

Oral Abstracts

COMPARISON OF A NAFION®-MODIFIED GLASSY CARBON, SCREEN PRINTED

CARBON AND SCREEN PRINTED GOLD ELECTRODE FOR THE

ELECTROCHEMICAL DETECTION OF CAFFEINE

Shauna Scanlon – University College Cork

Scanlon, S.*a; Hobbs, Elizabethb and Moore, E.J.a

a Tyndall National Institute, Lee Maltings, Dyke Parade, Cork and the Department of Chemistry, University College Cork, Cork

bPepsiCo International, Little Island, Cork

Fig. 1: Cyclic voltammograms recorded at Nafion®-modified glassy carbon (blue), screen printed carbon (red) and screen printed gold (green) electrodes in 0.1 M Phosphoric Acid containing 300 µM caffeine.

Food and beverage quality and safety have become of significant importance over the past decade and assuring the highest standards of process control is a key priority. The FDA's Process Analytical Technology (PAT) initiative emphasises that “quality cannot be tested into products; it should be built in or should be by design” [1]. This has generated a large amount of interest in new technologies for the analysis of pharmaceuticals, food, petroleum and many more. As with the pharmaceutical industry, the food industry faces high regulatory standards regarding the quality control; safety and traceability of their production processes. Advances in modern electronics and data acquisition technology have made it possible to potentially place a wide range of instrumentation at a number of sampling points in many industrial processes.

This research proposes a new system for quality control in the food and beverage industry. This involves the development of a multi-parameter sensing device for PAT application. The proposed device is an integrated sensing system, incorporating several different analytical techniques. The aim of the research is the miniaturization of the various techniques that are currently used off-line, for quality control analysis. Following development of the miniaturized detection methods, these will be integrated together onto a single device to create a multi-parameter sensing system for real-time process parameter analysis.

30

Oral Abstracts

To date, much of the research has been focused on the caffeine determination. Currently, in the food and beverage industry, caffeine analysis is carried out off-line, using High Performance Liquid Chromatography (HPLC). This, however, can be a time consuming method, with expensive instrumentation. It is the aim of this section of work to develop a sensor that makes the quantitative detection of caffeine possible, through electrochemical methods, on-line within the production process. In this work, chemical sensors for the electrochemical detection of caffeine in real samples have been developed and tested.

Three electrodes, a glassy carbon electrode (GCE), a Screen Printed Carbon Electrode (SPCE) and a Screen Printed Gold Electrode (SPGE) were evaluated and compared for their ability to detect caffeine, both in standard solutions and real soft drink concentrate samples. Modification of the electrode surfaces with a Nafion® solution was carried out and successfully increased electrode sensitivity. The effects of pH and scan rate on electrode performance were investigated, with all three electrodes giving comparable, efficient results, in caffeine standard solutions. A low cost, re-useable sensor for the determination of caffeine in soft drink concentrate has been developed using a Nafion®-modified screen printed gold electrode. This is the first time that a sensor of its kind is used for such a purpose. The modification procedure and experimental rinsing method were optimized for this sensor. The sensor showed highly reproducible results in diluted concentrate solution.

The results indicate the potential of electrochemical sensors to compare and compete with the current off-line methods of caffeine analysis, such as HPLC, allowing for both a reduction in time and cost of product quality analysis.

Future work will involve the use of similar electrodes for measuring parameters such as pH and conductivity, which will allow for efficient integration into a multi-parameter device that can be used for PAT application in the food and beverage industry.

References [1] United States Food and Drug Administration (FDA), Guidance for Industry PAT-A Framework for

Innovative Pharmaceutical Development, Manufacturing and Quality Assurance, FDA, September 2004

31

Oral Abstracts

THE OCCURRENCE OF PAHS AND FAECAL STEROLS IN DUBLIN BAY AND

THEIR INFLUENCE ON SEDIMENTARY MICROBIAL COMMUNITIES

Brian T. Murphy - Dublin City University

Brian T.Murphya, Shane S. O’Reillyaט, Xavier Monteysb, Barry F. Reida, Michal T. Szpaka, Margaret V. McCaula, Sean F. Jordana, Christopher C. R. Allenc, Brian P. Kellehera*.

a. School of Chemical Sciences, Dublin City University, Glasnevin, Dublin 9, Ireland. b. Geological Survey of Ireland, Beggars Bush, Haddington Rd, Dublin 4, Ireland.

c. School of Biological Sciences, Queens University Belfast, Medical Biology Centre, Lisburn Rd, Belfast, N.Ireland.

The source, concentration, and potential impact of sewage discharge and incomplete organic matter (OM) combustion on sedimentary microbial populations was assessed in Dublin Bay, Ireland. Polycyclic aromatic hydrocarbons (PAHs) and faecal steroids were investigated in 30 surface sediment stations in the bay. Phospholipid fatty acid (PLFA) content at each station was used to identify and quantify the broad microbial groups present and the impact of particle size, total organic carbon (%TOC), total hydrogen (%H) and total nitrogen (%N) was also considered. Faecal sterols were found to be highest in areas with historical point sources of sewage discharge. PAH distribution was more strongly associated with areas of deposition containing high % silt and % clay content, suggesting PAHs are from diffuse sources such as rainwater run-off and atmospheric deposition. The PAH’s ranged from 12 to 3072 ng/g, with 10 stations exceeding the suggested effect range low (ERL) for PAHs in marine sediments. PAH isomer pair ratios and sterol ratios were used to determine the source and extent of pollution. PLFAs were not impacted by sediment type or water depth but were strongly correlated to, and influenced by PAH and sewage levels. Certain biomarkers such as 10Me16:0, i17:0 and a17:0 were closely associated with PAH polluted sediments, while 16:1ω9, 16:1ω7c, Cy17:0, 18:1ω6, i16:0 and 15:0 all have strong positive correlations with faecal sterols. Overall, the results show that sedimentary microbial communities are impacted by anthropogenic pollution.

32

Oral Abstracts

ADSORPTION STUDY OF MERCURY IONS ON POLYANILINE EMERALDINE SALT

PREPARED BY CHEMICAL METHOD

Abdunnaser Etorki – University of Tripoli

A.M. Etorki * and S.Ali**

*Department of Chemistry, University of Tripoli, Tripoli, Libya, PO-Box-13203 ** Department of Environmental Science and Engineering, Libyan Academy, Tripoli. Libya

The synthesis of Conductive polymers from monomers containing conjugated double bonds such as aniline, pyrole, and thiophene, and their derivatives has become the subject of many recent studies. A plyaniline (PAN) prepared by chemical method using different oxidation reagents, was studied for Hg(II) removal from aqueous solutions. From the results, it was found that, PAN prepared by chemical method using K2Cr2O7, and HCl gave the best results for % removal, and emeraldine salts. Batch adsorption results showed solution pH values had a major impact on mercury adsorption by this sorbent with optimal removal observed around (pH 4 to 5). At both acidic and alkaline solutions beyond this optimal pH window, sorption capacity of PAN was substantially lowered, with the impact less pronounced at pH above 6. In the range of 0.02M – 0.2M, and 1M, the effect of ionic strength on adsorption of Hg(II) 0n PAN surface was also studied. The adsorption mechanism was proposed by analyzing the XRD, FTIR, SEM, and XPS spectra data before and after adsorption of mercury on (PAN) surface [1]. The results show that all the nitrogen matrix including imine, protonated imine and amine could be responsible for mercury adsorption.

References [1] Carromalino G.C and Petidomiguez.MD. Anal.Chem.Acta, 2008, (64),103 .

33

Oral Abstracts

FOURIER TRANSFORM INFRARED SPECTROSCOPY (FTIR): A VERSATILE

ANALYTICAL TOOL

Dr. Tania Dey – Limerick Institute of Technology

Fourier transform infrared spectroscopy (FTIR) is a versatile tool and can serve multiple purposes. FTIR can be used to quantitatively monitor the progress of a reaction, For example, while preparing vinyl ester resin from diglycidyl ether of bisphenol-A, the epoxide peak at 4530 cm-1 can be followed as a function of time and a disappearance of the peak will indicate completion of reaction [1]. On the other hand, FTIR acts as a finger print for the functional groups. Hence identifying the appropriate groups will lead to complete structural information of the molecule. To ensure polymer grafting on the surface of nanoparticle is just one example [2, 3]. Besides, FTIR can be used in attenuated total internal reflection (ATR) mode using parallelogram substrate, from which the adsorption profile and the secondary structure of proteins can be obtained [4]. So it all depends on what the analyst is aiming at and how appropriately the methods can be applied. [This paper presents some of my old work and has nothing to do with my current affiliation.]

References [1] Dey, T. Polym Int, 2007, 56(7), 853-859. [2] Dey, T. J Nanosci Nanotechnol, 2006, 6(8), 2479-2483. [3] Dey, T. J Sol-Gel Sci Technol, 2011, 57(2), 132-141. [4] Dey, T. ACS spring meeting, 2005.

34

Oral Abstracts

SFC COME OF AGE - A REVIEW OF HOW SFC IS SOLVING

CHROMATOGRAPHIC CHALLENGES TODAY

Guy Wilson - Waters Limited

As research developed in ultra-high pressure gas chromatography in the sixties the potential of using Supercritical Fluids as a mobile phase became apparent. The combination of viscosity and diffusivity yields a huge potential for Supercritical Fluids to be excellent solvents but their true potential was challenging to harness. Since then there have been waves of interest in this technique but it struggled to gain wide-spread support across the chromatographic community. Combining the Supercritical Fluid with a stronger organic solvent has enabled a broader range of analyte polarity to be addressed. The design and manufacture of high performance equipment, which has overcome many of the engineering challenges of this type of chromatographic system, has now seen Supercritical Fluid Chromatography take its rightful place alongside LC and GC as a routine analytical tool across a wide range of applications. This presentation will briefly introduce the technology that has facilitated the uptake of this technique and highlight the great work that is being done using SFC across a wide range of analyte polarity, from Lipidomics to polar pharmaceutical compounds.

35

Oral Abstracts

CAPILLARY ELECTROPHORESIS TECHNIQUE FOR RAPID SEPARATION AND

DETECTION OF ORGANOPHOSPHATE NERVE AGENTS

Anna Maria Hogan – University College Cork

Hogan A. *, Cao X., Messina W., Wang Y. and Moore, E.

Organophosphate (OP) compounds are among the most toxic substances used as chemical warfare agents and pesticides. The signs and symptoms of organophosphate poisoning can be divided into three broad categories: muscarinic, nicotinic and central nervous system effects.

There are urgent needs for new forensic tools for on-site environmental monitoring and rapid security warning/screening for detecting OP pesticides and chemical warfare agents.

The miniaturization of capillary electrophoresis make very attractive device for addressing these needs. The separation of organophosphate compounds was achieved in less than 3 minutes using short-end capillary electrophoresis technique. The separation time was further reduced to 45 seconds when the method was transferred to a microchip electrophoresis system.

The potential of microchip capillary electrophoresis as compact, fast and reliable forensic tool will be discussed.

36

Oral Abstracts

EVALUATION OF A MINIATURISED SINGLE-STAGE RESISTIVELY HEATED

MODULATOR FOR COMPREHENSIVE TWO-DIMENSIONAL GC

Matthew Jacobs – University of tasmania

Jacobs, M.R.1*; Edwards, M.2; Górecki T.2; Nesterenko, P.N.1 and Shellie R.A.1

1 Australian Centre for Research on Separation Science (ACROSS), University of Tasmania, Private Bag

75, 7005, Tasmania, Australia. 2 Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario,

Canada, N2L3G1.

Comprehensive two-dimensional gas chromatography (GC × GC) is a technique that can vastly increase the peak capacity of one-dimensional GC [1], while generating an additional dimension of separation information [2] that is very useful for the characterisation of complex samples such as petroleum products, aromas, fragrances and environmentally derived samples [3].

The critical component of any GC × GC system is the interface between the first- and second dimension columns, which is known as a modulator. A novel miniaturised single-stage resistively heated thermal modulator has been developed as an alternative to the cryogenic and flow-based techniques that are commonly used. The single-stage thermal modulator yielded average retention time relative standard deviations (RSD) of ≤ 0.2 % RSD (first-dimension) and ≤ 3.4 % RSD (second-dimension). The average peak widths generated by the modulator were 72 ± 3 ms, and the peak volume precision was better than 5.3 % RSD. GC × GC analysis can be performed using this modulator without the requirement for expensive cryogens, refrigerated cooling units or additional electronic pressure control units. The modulator and associated electronics are compact and amenable towards field analysis, requiring only electricity for operation.

This modulator was applied for qualitative and quantitative characterisation of petroleum-contaminated soils derived from a sub-Antarctic research station at Macquarie Island. Additionally two-dimensional separations of complex samples such as coffee and wine headspace have been developed to demonstrate the versatility of the present modulator and GC × GC technique.

References [1] M.S. Klee, J. Cochran, M. Merrick, L.M. Blumberg, Evaluation of conditions of comprehensive two-dimensional gas chromatography that yield a near-theoretical maximum in peak capacity gain, J. Chromatogr. A 1383 (2015) 151-159. [2] J.B. Phillips, J. Beens, Comprehensive two-dimensional gas chromatography: a hyphenated method with strong coupling between the two dimensions, J. Chromatogr. A 856 (1999) 331-347. [3] J.V. Seeley, S.K. Seeley, Multidimensional Gas Chromatography: Fundamental Advances and New Applications, Anal. Chem. 85 (2013) 557-578.

37

Flash Presentations

WEARABLE CHEMICAL SENSING – OPTIMIZING FLUIDICS FOR REAL-TIME

SWEAT ANALYSIS

Jennifer Deignan - Dublin City University

Deignan, J.*; Florea, L; Coyle, S; and Diamond, D

This work presents the optimization of electrical parameters and sampling platforms to maximize the sensitivity of conductivity measurements for applications in wearable sweat sensing. Conductivity in sweat is related to electrolyte content and offers valuable information for hydration, athletic performance and nutrition. The most abundant ions of sweat electrolytes are sodium and chloride, making sweat conductivity directly related to their concentration [1]. Capacitively coupled contactless conductivity detection (C4D) was used to test the response of commercial gold microelectrodes (figure A). This work was done in preparation for the development of an on-body detection system for sweat analysis. On body testing requires sample handling specific to the method of testing, which in this case is non-contact. For this type of handling, polydimethylsiloxane (PDMS) and poly(methyl methacrylate) (PMMA) microchannels of various configurations were tested for their compatibility with the system and the effect of their geometry on signal sensitivity. Figures B-D show the dimensions of one such PMMA channel from top, bottom and expanded side view, respectively.

References [1] Lezana, J. L.; Vargas, M. H.; Karam-Bechara, J.; Aldana, R. S. and Furuya, E. Y. J. Cyst. Fibros., 2003,

2(1), 1.

38

Flash Presentations

USE OF GOLD NANORODS FOR SERS ANALYSIS OF BALLPOINT PENS AND

FELT-TIP PENS

Abeer Alyami – Tyndall National Institute

Alyami, A.1* Saviello, D.1 McAuliffe, M.;2 Wolfe, R.;2 Martín, A.;1 Mirabile, A.;3 Lewis, L.;2 Iacopino, D.1

1 Tyndall National Institute, Dyke Parade, Cork, Ireland 2 Centre For Advanced Photonics and Process Analysis, Cork Institute of Technology Cork, Cork,

Ireland 3 Mirabile, 11, rue de Bellefond, 75009, Paris, France

Identification of inks’ formulations and elucidation of processes leading to colour fading are exceedingly important for dating, active conservation and long-term preservation of paper artworks.[1,2] Dyes and pigments in inks can be difficult to identify, due to the presence of other chemicals in the mixture and patent protection.[3] All these factors pose serious challenges for paper art conservators. Available characterization techniques require both the use of relatively large amount of sample (mg) and harsh destructive extraction methods, which are generally non applicable to works of art.[4-5] Recently Surface Enhanced Raman scattering (SERS) has been identified as suitable spectroscopic technique.[6-7] Blue and black inks in ballpoint pens were identified with the use of silver colloidal solutions. However, SERS spectra had to be taken within 10 min of colloid deposition due to fast silver oxidation. Additionally, chemical treatment of the colloidal solution had to be carried out. In this work we have use gold nanorods for the SERS analysis of BIC pens and felt tip pens in combination with thin layer chromatography (TLC). TLC was used to separate the dye components in the ink mixture. High concentrated nanorod solutions (nM) were used to take SERS spectra of separated components. Comparison between Normal Raman (NR) spectra and SERS spectra taken with laser excitation 785 nm showed SERS enhancements up to 2 orders of magnitude, especially evident with blue colors. The origin of the enhancement was attributed to the anisotropic shape of the particles as well as to their plasmon mode in resonance with the excitation wavelength.

References [1] Izzo, F. C. et al. Microchem.J., accepted 14 September 2015. [2] David, M.W.. et al Forensic Sci. Int., 2005, 152,241. [3] Sodo, A. et al. J. Raman Spectrosc., 2012, 43, 1781. [4] Li, Y.-Z. et al. J. Chromat. A, 2006, 1135, 57-64. [5] Chen, H.-S. et al. For. Sci. J., 2002, 1, 1. [6] Seifar, R. J. et al. Analyst, 2001, 126, 1418. [7] Geiman, I.; Leona, M., Lombardi J.R., J. Forens. Sci., 2009, 54, 947.

39

Flash Presentations

FATTY ACID PROFILING IN BOVINE MILK IN SELECTED BREEDS USING

DISPERSIVE LIQUID-LIQUID MICROEXTRACTION COUPLED WITH GC-FID

Andrew Quiqley – Waterford Institute of Technology

Quigley, A*; Flynn, M; Walsh, S; Cummins, W; Connolly, D.

Bovine milk, a complex biological fluid, is an important source of energy, high-quality protein and essential vitamins and minerals. Not only does it supply offspring with their complete nutritional requirements, it also lends itself to the manufacture of a limitless range of diverse and specialised dairy products and ingredients. Milk composition, in particular fatty acid composition, has a marked influence on the nutritional quality and processability of milk and hence subsequent technological properties of dairy products. Furthermore, some of these fatty acids have health benefits (e.g. conjugated linoleic acid [1]), while others are detrimental to human health (e.g. saturated fatty acids [2]). Intrinsic (breed, individual animal genetics, stage of lactation, health status) and extrinsic (diet, management and season) factors as well as their interactions can significantly alter fatty acid composition. For example, Holstein-Friesians, the predominant dairy cow breed in Ireland, produce milk with the lowest fat content (~3.5%), while Jerseys the highest (~6%). However, there is limited research carried out in beef cow breeds. Seasonal production systems, as operated in Ireland, has a marked effect on milk fat, which can vary from ~3 % in early lactation to >4.5 % in late lactation.

Milk samples (n=3) were collected from four different breeds (Rotbunt, Holstein Friesian, British Friesian, and Norwegian Red) in glass bottles at two different time-points during the lactation cycle and immediately frozen at -20 oC prior to analysis in order to study inter-breed and intra-breed fatty acid composition across the sampling time-frame. This current work focuses on a novel extraction and pre-concentration protocol for fatty acids from bovine milk, followed by separation and identification using GC-FID (gas chromatography-flame ionisation detection). Dispersive liquid-liquid micro-extraction (DLLME) involves the rapid injection of an immiscible extraction solvent into an aqueous sample in the presence of a third “dispersion” bridging solvent, producing a stable emulsion comprised of micro-droplets of extractant into which the analyte rapidly partitions. Centrifugation of the ternary mixture facilitates facile recovery of the sedimented extraction solvent prior to GC analysis and pre-concentration factors (up to several hundred-fold) can be optimised by fine-tuning of ternary solvent volume ratios, pH, aqueous phase ionic strength etc.) and results are presented herein.

References [1] K. Koba, T. Yanagita, Health benefits of conjugated linoleic acid (CLA), Obes. Res. Clin. Pract. 8 (2013) 1–8. [2] Y.S. Diniz, A.C. Cicogna, C.R. Padovani, L.S. Santana, L.A. Faine, E.L.B. Novelli, Diets Rich in Saturated and

Polyunsaturated Fatty Acids: Metabolic Shifting and Cardiac Health, Nutrition. 20 (2004) 230–234.

40

Flash Presentations

PHYSICAL CHARACTERISATION OF A SILVER SCREEN-PRINTED TATTOO

SENSOR FOR SKIN HYDRATION MONITORING

Keana De Guzman - Dublin City University

K. De Guzman*, A. Morrin

Wearable sensors have gained increasing interest in recent years due to its versatility and advantages in real time monitoring of human health or fitness via sweat1,2 or skin pH3. Epidermal electronics have been proven as a promising means of non-invasive monitoring but these devices can prove difficult to adhere to the changing morphology of the skin. Devices such as these require a fabrication methodology that would conform and flow with the mechanics of skin but to also deliver good electrical performance.

In this study, screen printed tattoo electrodes were fabricated comprising silver ink using a concentric electrode configuration. The sensor is being developed for application in atopic dermatitis patients where skin barrier function is impaired, which leads to chronic dehydration. The electrode is applied directly to the skin/skin mimic from a tattoo paper substrate that features a water-soluble starch dextran layer for easy release. AC impedance is used to track changes in water content of the hydrogel used as a skin mimic. Characterisation of this sensor has been conducted on a skin hydrogel mimic and was able to track changes in hydration and correlated with a commercial probe. The electrode was also characterised optically to determine its conformability and adherence to the surface morphology on porcine and human skin. Applications of the tattoo towards porcine and human tissue are currently being explored.

References (1) Guinovart, T.; Bandodkar, A. J.; Windmiller, J. R.; Andrade, F. J.; Wang, J. Analyst 2013, 138, 7031–

7038. (2) Bandodkar, A. J.; Molinnus, D.; Mirza, O.; Guinovart, T.; Windmiller, J. R.; Valdés-Ramírez, G.; Andrade,

F. J.; Schöning, M. J.; Wang, J. Biosens. Bioelectron. 2014, 54, 603–609. (3) Bandodkar, A. J.; Hung, V. W. S.; Jia, W.; Valdés-Ramírez, G.; Windmiller, J. R.; Martinez, A. G.; Ramírez,

J.; Chan, G.; Kerman, K.; Wang, J. Analyst 2013, 138, 123–128.

41

Flash Presentations

SMARTER-SI: BRINGING MICRO AND NANOTECHNOLOGIES TO THE SMES

Patricia Vazquez – Tyndall National Institute

P. Vazquez*(1), E. Moore(1), , Dag Andersson(2), Hans Grönqvist(2), Cees Lanting(3), Petra Weiler(4), Thomas Ortlepp(4), Andreas Albrecht(4), Stephan Karmann(5), Rainer Guenzler(5).

(1)Tyndall National Institute, (2) Swerea IVF, (3) Swiss Center for Electronics and Microtechnology, (4) VDI/VDE/IT, (5) Hahn-Schickard

Figure 1: microfluidic prototypes for 2 of the 4 currently running projects with SMEs for integration of Cross-cutting KETs in industrial products

As part of its action plan to cover the existing gab between basic knowledge generated at R&D institutions and the subsequent commercialization, the European Union has set as some of its priorities to strengthen Key Enable Technologies (KET) [1, 2] in the European industry. KET are a group of six technologies (micro and nanoelectronics, nanotechnology, industrial biotechnology, advanced materials, photonics, and advanced manufacturing technologies) that offer huge opportunities to small and medium-sized enterprises (SMEs) for their vast range of applications and advanced solutions for societal challenges. The combination of different KETs offer even greater possibilities to foster innovation and create new markets (this is usually referred as Cross-Cutting KETs) [3].

In this work we present the activities and outcomes of the European-funded project SMARTER-Si. The ultimate objective of the project is to provide SMEs with an easy access to advanced manufacturing capabilities of Cross-cutting KETs to be integrated across the full value chain and exploited commercially in existing and new markets. With this purpose in mind, 4 industry-led projects were developed during the first year. We will present the results obtained during these cooperation between SMEs and Research Organizations (see example in fig.1), and draw conclusions after the experience for a future Foundry model that is sustainable and effective in the landscape of the European SMEs.

References [1] Preparing for our future: Developing a common strategy for key enabling technologies in the EU, Brussels, 30.09.2009, COM

(2009) 512 final. [2] European Competitiveness Report 2010, Brussels, 28.10.2010, SEC(2010) 1276 final, Commission Staff working - document

accompanying the communication An integrated Industrial Policy for the Globalisation Era –Putting Competitiveness and Sustainability at Front Stage, Brussels, COM(2010) 614.

[3] High Level Expert Group on Key Enabling Technologies: KETs, time to act, Final Report, 2015, European Commission.

42

Flash Presentations

TRACKING THE FATE OF POLYCYCLIC AROMATIC HYDROCARBONS IN

CONTAMINATED SOILS DURING WINDROW BIOREMEDIATION PILOT

PROJECT

Coren Pulleybank - Dublin City University

Pulleyblank, C.E*.; Kelleher, B.P.

Petrochemical contamination of soils leads to adverse effects for human health and local ecology. Of particular concern are sixteen polycyclic aromatic hydrocarbons (PAHs) listed as priority pollutants by the EPA for their known toxic and carcinogenic properties (Samanta, Singh, & Jain, 2002). Bioremediation strategies including aerobic composting have shown promise for degrading PAHs; however studies of the optimal composting conditions for this purpose are limited (Antizar-Ladislao, Lopez-Real, & Beck, 2006). Moreover, few open air studies have been undertaken in conditions comparable to the Irish climate [e.g. 3]. In this study, we investigate the attenuation of PAHs in a heavily contaminated soil throughout an open air windrow composting pilot project in Ireland.

Five windrows were constructed and subjected to the following treatments: four control treatments – 1. no further treatment, 2. aeration only, 3. addition of 10% wood shavings and aeration, 4. addition of 5% green waste and aeration - and one test treatment – 5. addition of 10% wood shavings, 5% green material, and aeration. We provide preliminary data on contaminant attenuation of this soil and discuss the conditions which may favour remediation of PAHs during the composting process. In order to accurately track these processes, methods for improving the quantification of PAHs in solid phase and aqueous phase extracts via GC-MS analysis are investigated and discussed here.

References [1] Samanta, S. K., Singh, O. V, & Jain, R. K. Trends in Biotechnology, 2002 20(6), 243. [2] Antizar-Ladislao, B., Lopez-Real, J., & Beck, A. J. Journal of Hazardous Materials, 2006 137(3), 1583 [3] Van Gestel, K., Mergaert, J., Swings, J., Coosemans, J., & Ryckeboer, J. Environmental Pollution, 2003

125(3), 361

43

Flash Presentations

SODA CAN TEMPLATED FLEXIBLE POLYMER SERS SUBSTRATES FOR

MULTIPLE SENSING APPLICATIONS

Niamh Creedon – Tyndall National Institute

Creedon, N.*; Lovera, P. and O’Riordan A.

With increased food production required for the growing population, new low-cost diagnostic tools are essential to maintain current stringent levels of food safety. Surface-enhanced Raman spectroscopy (SERS) is an advanced Raman technique that enhances the vibrational spectrum of molecules adsorbed onto metal nanostructured surfaces providing both qualitative (molecular fingerprint) and quantitative detection., SERS is considered as a powerful technique with tremendous opportunity in food safety, security and clinical diagnostics, particularly due to its enhanced sensitivity and minimum sample preparation requirements. The recent and potential advances in SERS are highlighted with the detection of food contaminants and adulteration; concentrated specifically on antibiotics, drugs, melamine, and pesticides. However, a key challenge limiting the uptake of SERS for commercial sensor applications is the lack of reproducible and reliable approaches for substrate nano-patterning and fabrication.

To address this challenge, a low-cost approach for fabrication of SERS substrates was developed by templating a flexible thermoplastic polymer against an aluminium drink can, to produce a rough nanostructured surface1. When coated with an evaporated silver over-layer, localised electromagnetic “hot-spots” are formed between the metal nano-gaps. Electron microscopy and spectroscopic characterisation showed the SERS response arose at these “hot spot” regions of high electromagnetic field strength, following illumination. To determine the capability of these polymer substrates for SERS analysis, crystal violet and 4-aminothiophenol were investigated as probe molecules, with detection of these molecules demonstrated at sub-monolayer concentrations (10-10 Molar). Subsequently, these substrates were applied to the detection of melamine in milk and infant formula solutions, where low concentrations of melamine (100 ppb) were detected in 10 minutes without the need for sample pre-treatment. Finally, back excitation and collection through the SERS substrate is also demonstrated which permits coupling with photonic devices such as optical fibres required for future remote sensing applications.

References 1. P. Lovera, N. Creedon, H. Alatawi, M. Mitchell, M. Burke, A. J. Quinn and A. O’Riordan,

Nanotechnology, 2014, 25, 175502.

44

Flash Presentations

EURACHEM IRELAND

Barbara O’Leary – Eurachem Ireland/State Laboratory

Eurachem Ireland (www.statelab.ie/eurachem.html) is an organisation for people working in chemistry in Ireland, with a focus on analytical chemistry. Chemistry students are welcome too. Eurachem Ireland promotes the objectives of Eurachem (www.eurachem.org) in Ireland including good quality practices.

45

Flash Presentations

POLY(IONIC LIQUID) VALVES FOR MICROFLUIDIC DEVICES

Alexandru Tudor - Dublin City University

Tudor, A.*; Saez, J., Benito-Lopez, F., Florea, L., Diamond, D.

Insight Centre for Data Analytics, National Centre for Sensor Research,

School of Chemical Sciences, Dublin City University, Dublin, Ireland

Several phosphonium ionic liquid polymers have been shown to exhibit a lower critical solution temperature behaviour [1, 2]. This property was maintained in the case of both linear and crosslinked polymers, thus making these materials suitable for the synthesis of thermo-responsive poly(ionic liquid)s (PILs) gels [2]. Herein, we present the synthesis of a thermo-responsive tributylhexyl phosphonium 3-sulfopropyl acrylate (PSPA) crosslinked PIL hydrogel, followed by its inclusion in a microfluidic device to be used as a temperature controlled valve. The hydrated p(PSPA) hydrogels had their temperature-induced shrinking characterised using digital microscopy from 20 °C to 70 °C, in 10 °C steps. Measurements indicate a relative surface contraction of the hydrogels, in deionized water, of 34.04% ± 4.62% (n = 3) at 50 °C, and 53.37% ± 12.55% (n = 3) at 70 °C when compared to the fully hydrated gel at RT. Following this, hydrogels were polymerized in a microfluidic chip that contained a heating element and the flow though the microfluidic channel was characterised under different conditions using a flow microsensor. When the p(PSPA) hydrogel valve was heated to 50 °C, deionized water flowed through the channel at ~140 nL·min-1 compared to ~ 15 nL·min-1 at 25 °C. The required time for the PIL valve to open was ~6s, while the time required for it to close was ~8s. The PIL valves demonstrated very reproducible opening and closing over six repeat cycles. In conclusion, the results suggest that these p(PSPA) hydrogels may be attractive materials for creating thermally controlled valves in microfluidic devices. Future study will focus on the optimization of the valve geometry to optimise flow rate control and characterising the operational lifetime of the valve.

References [1] Kohno, Y. & Ohno, H., Aust. J. Chem., 2011, 65, 91. [2] Ziółkowski, B. & Diamond, D., Chem. Comm., 2013, 49, 10308.

46

Flash Presentations

MID-HOLOCENE CLIMATE CHANGE AND LANDSCAPE FORMATION IN

IRELAND: EVIDENCE FROM A GEOCHEMICAL INVESTIGATION OF A COASTAL

OMBROTROPHIC PEAT BOG Sean Jordan - Dublin City University

Jordan, S.F.a; Murphy, B.T.a; O’Reilly, S.S.b; Doyle, K.P.a; Williams, M.D.c; Grey, A.a; Lee, S.a; McCaul, M.V.d; Kelleher, B.P.a*

a School of Chemical Sciences, Dublin City University, Dublin 9, Ireland

b Department of Earth, Atmospheric, and Planetary Sciences, Massachussetts Institute of Technology, Cambridge, MA, USA

c Earth and Ocean Sciences, School of Natural Sciences, National University of Ireland, Galway, University Road, Galway, Ireland

d CLARITY: Centre for Sensor Web Technologies, National Centre for Sensor Research, School of Chemical Sciences, Dublin City University, Dublin 9, Ireland

Following a period of unusually strong winds and high seas in the spring of 2014, a blanket peat bog formerly covered by a beach comprised of fine sand and large rocks was uncovered at a coastal site in Spiddal, Co. Galway, Ireland. The surface of the bog was littered with standing tree stumps, the remnants of a Holocene forest that had succumbed to a relatively sudden drowning. A combination of inorganic and organic geochemical techniques was applied to determine the cause of this rapid submersion and to glean palaeoclimatic information from the preserved record within the peat. The study represents the first use of a multiproxy lipid biomarker approach to investigate palaeoclimate conditions from a peat bog in Ireland.The results provide evidence of climatic variation throughout a ca. 3500 yr timeframe during the mid-Holocene. The data correlate with described events, including the 4.2 ka event and the Subboreal-Subatlantic transition and show the benefit of a lipid biomarker method for investigating Ireland’s peatland resources. In particular, the indication of colder/wetter conditions coinciding with the 4.2 ka event implies the possibility that its effects were felt in Ireland, contrary to some reports. The results suggest that a combination of warm and dry conditions followed by a rapid rise in sea level led to the growth and subsequent drowning of the ancient forest landscape.

47

Poster Titles

Title Author

1 Towards functional surfaces for selective cell recognition and capture A.L. Boal

2 LSER Investigation of Achiral Retention on a Quinine Carbamate Chiral Stationary Phase Aaron Sherwin

3 Use of gold nanorods for SERS analysis of ballpoint pens and felt-tip pens Abeer Alyami

4

Environmental mapping of Dublin Bay: new diagnostic tools to assess organic pollution and its fate Aishling Cunningham

5 Photo-acid generator comonomer turns pH-responsive into photo-responsive hydrogels Aishling Dunne

6 Poly(ionic liquid) Valves for Microfluidic Devices Alexandru Tudor

7

Towards the automation of a biochip for monitoring anti-platelet therapies in a near patient setting Amy Hall

8

Counterfeit Product Identification using Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS) Anas Alfarsi

9

Fatty acid profiling in bovine milk in selected breeds using dispersive liquid-liquid microextraction coupled with GC-FID Andrew Quigley

10 Electrochemical investigation of the interactions between bioinorganic compounds and DNA Anna Banasiak

11

Optimisation of sample preparation/ preconcentration and chemical detection system for heavy metal monitoring in drinking water Anna Bednarek-Karabin

12 Investigating the autotrophic sequestration of carbon in soil organic matter: Soil as a carbon sink Anthony Grey

13 MYCOTOXIN ANALYSIS IN THE STATE LABORATORY Audrey Nugent

14 Eurachem Ireland Barbara O'Leary

15 Correcting for Unwanted Capacitance at Nanowire Electrode Benjamin O'Sullivan

16 Phone operated electronic tuberculosis diagnostics Brian Murphy

17 Microneedle Electrodes for Nitrate Detection in Water Caoimhe Robinson

18 Bulk Tank Milk Quality Screening – Electronic profiling of thermoduric bacteria and their spores Carmen Negredo

48

Poster Titles

19

DIOXIN/PCB ANALYSIS BY HIGH RESOLUTION GAS CHROMATOGRAPHY MASS SPECTROMETRY (HRGCMS) Claire Timbs

20

Tracking the Fate of Polycyclic Aromatic Hydrocarbons in Contaminated Soils during Windrow Bioremediation Pilot Project Coren Pulleybank

21

Determination of NO2/NO3 in contaminated groundwater and digestate/soil samples using ion chromatography Damian Connolly

22 Accutrace S10, a new fiscal fuel marker for Ireland David Canny

23

Raman and FTIR spectroscopy for the detection and diagnosis of prostate cancer using blood plasma and lymphocytes Dinesh Medipally

24

The Veterinary Toxicology Section in the State Laboratory: An Overview of National Reference Laboratory Duties Edward Malone

25 Phosphate responsive electrochemical sensor based on a novel copper phthalocyanine derivative Eithne Dempsey

26

Detection of Prostate specific Antigen Based on Electrocatalytic Platinum Nanoparticles Conjugated to a Recombinant scFv Antibody Elaine Spain

27

Direct, non-amplified electrochemical based detection of microRNA, MiR-134, a brain-specific, activity-regulated microRNA that is a key marker of epilepsy in real patient serum Elaine Spain

28 Analysing the human skin volatile signature Emer Duffy

29 Developing a portable Ion Chromatography System for Freshwater Analysis Eoin Murray

30 Novel polymerisable receptors for the selective recognition of sulfonylurea drugs F. Pessagno

31 A microfluidic lab-on-a-disc device for in situ measurement of phosphate in water Gillian Duffy

32 Wearable Chemical Sensing – Optimizing Fluidics for Real-Time Sweat Analysis Jennifer Deignan

33 Physical characterisation of a Silver Screen-Printed Tattoo Sensor for Skin Hydration Monitoring Keana De Guzman

49

Poster Titles

34 A ‘Smart’ Needle For Objective Nerve Localisation During Ultrasound Guided Peripheral Nerve Block Lisa Helen

35 Passive Sampling in Monitoring of New and Emerging Compounds – An Irish Perspective Lisa Jones

36

Developing Analytical Methods for the Determination of PAH in Soil to Assist Remediate Processes Marleen Vetter

37 Cell Based Biosensors for the Investigation of the Negative Impact of Nicotine in Pregnancy Michelle Fitzgerald

38

Nanowire-based, Label-free Electrochemical Detection of Bovine Respiratory Disease Pathogens in Serum Niamh Creedon

39 Soda Can Templated Flexible Polymer SERS Substrates for multiple sensing applications Niamh Creedon

40 Potentiostatic enrichment of electrochemically active bacteria from PAH polluted sediments P. Brennan

41 Smarter-Si: bringing micro and nanotechnologies to the SMEs Patricia Vazquez

42 PATsule: Process Analytical sensor technology for monitoring cell health in a bioreactor Paul O'Mara

43

Electrochemical Surface Enhanced Raman Scattering sensors for detection of macrolide antibiotics Pierre Lovera

44

Cancer biomarker detection using mediated electron transfer between enzyme-label and electrode Richard Bennett

45

Sound Bending Chemical Reactions: Non-Titrimetric Determinationof Acid-Base Reactions using BARDS. Rizwan Ahmed

46

An analysis of the protective effects of selenium on porcine jejunal epithelial cells following Cadmium-induced oxidative DNA damage Sarah Lynch

47

Mid-Holocene climate change and landscape formation in Ireland: Evidence from a geochemical investigation of a coastal ombrotrophic peat bog Sean Jordan

48

Development of a lab-on-chip electrochemical immunosensor array for detection of hydrocarbons in the environmental Shifa Felemban

50

Poster Titles

49 Development of sensor arrays to monitor alkaline phosphatase released from cells Thanih Balbaied

50 SWEATCH': Wearable, Real-Time Biological of Electrolyte Levels in Sweat Tom Glennon

51 A novel miniaturized biosensor for hydrogen peroxide sensing for use in agri-food applications Vuslat Buk

52

Fabrication, characterisation and biocompatibility testing of gold microelectrodes for the screening and detection of breast cancer Walter Messina

53 Signaller and Seeker Droplets Wayne Francis

54

Separation of Organophosphate Nerve Agents by Capillary electrophoresis and Microchip Capillary Electrophoresis Xi Cao

51