Book of Abstracts

10th International Conference on Instrumental Methods of Analysis: Modern Trends and Applications

Book of abstracts

17-21 September 2017 Heraklion, Greece

10th International Conference on Instrumental Methods of Analysis: Modern Trends and Applications

September 17-21, 2017, Heraklion - Greece

Organized by Department of Chemistry, University of Crete

School of Chemical Engineering, National Technical University of Athens

Hellenic Centre for Marine Research

Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas

Main Sponsors

3 Sponsors

Supporters

University of Crete National Technical University of Athens

Hellenic Centre for Marine Research

University of Ioannina University of Patras

National and Kapodistrian University of Athens Aristotle University of Thessaloniki

Technical University of Crete

Preface

The organizing committee of the IMA-2017 Conference would like to welcome all participants to the 10th anniversary International Conference on "Instrumental Methods of Analysis-Modern Trends and Applications", held in Heraklion, Greece, from 17-21 September. The conference is organized by the Department of Chemistry, Univ. of Crete and the Lab of Inorganic and Analytical Chemistry, School of Chemical Engineering of the National Technical University of Athens under the support of the Hellenic Centre for Marine Research and the Institute of Electronic Structure and Laser, Foundation for Research and Technology - Hellas. IMA is a biannual series of conferences that started in 1999 and covers all areas of modern trends and applications of Chemical Analysis.

During this meeting special emphasis will be given to new developments in analytical instrumentation and novel principles of analysis. New trends in single cell analysis are also hot topics to be discussed. Due to the great interest and the numerous participants from the Food Science and Technology community, this year’s conference will continue to emphasize novel aspects of food analysis research. For this reason, 3 sessions are devoted to research related to food analysis with emphasis on food safety, natural product determination, food metabolomics, packaging, and novel foods. Current analytical trends will be revealed through presentations covering a wide range of techniques in the areas of spectrometry, atomic and molecular mass spectrometry, electrochemical analysis and chromatographic separations. The trend of using hyphenated techniques has unfolded new perspectives and challenges in chemical analysis, dealing with difficult problems related to modern materials, biological systems, food and environmental micro-pollutants of (eco)toxicological interest. These are also some of the issues that will be discussed during IMA2017.

The scientific program of the Conference consists of 16 invited and plenary lectures, 18 sessions with oral presentations and close to 150 posters in 3 poster sessions. In addition, researchers from Academia, Research Institutes and the Industry will present state-of-the-art developments in analytical instrumentation as well as a wide range of applications in the physical, earth and life sciences. An exhibition of analytical and laboratory equipment will also take place parallel to the conference. At the same time a cultural program with visits to archaeological sites of Knossos Palace and Heraklion Archaeological Museum, as well as a visit to Cretaquarium will render the participants’ stay more interesting and enjoyable.

6 10th International Conference on Instrumental Methods of

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We strongly believe that the discussions and the exchange of ideas among the participants during the 5 days of the meeting will make IMA a brilliant platform to initiate new research collaborations, particularly in favor of the young scientists participating in the conference.

Novel and unpublished work presented at IMA2017 are encouraged to be submitted to either of 2 high-impact journals, namely Journal of Analytical Atomic Spectrometry (Royal Society of Chemistry) and Analytical and Bioanalytical Chemistry (Springer) depending on the topic. Accepted papers will be referenced to IMA2017 and will make up a Virtual Special Issue. We hope you all enjoy the conference and have a memorable stay in Heraklion, looking forward to meet you again at the next IMA2019.

With our best regards

The Chairpersons

Dr. Spiros A. Pergantis Dr. Maria Ochsenkühn-Petropoulou

Professor, Environmental Chemical Processes Professor, Lab of Inorganic and Analytical Lab., Dept. of Chemistry, University of Crete Chemistry, School of Chemical Engineering, National Technical University of Athens

Committees

International Scientific Committee F. Adams (Univ. Antwerp), D. Anglos (Univ. Crete-FORTH), A. Anthemidis (AUTh), O. Yavuz Ataman (METU, Ankara), M. Beazi-Katsioti (NTUA), B. Beckhoff (PTB Berlin), A. Bobrowski (AGH Krakow), A. Calokerinos (Univ. Athens), N. Chaniotakis (Univ. Crete), Th. Christopoulos (Univ. Patras), S. Chanthai (Khon Kaen Univ.), A. Detsi (NTUA), I. Dotsikas (Univ. Athens), L. Ebdon (Univ. Bedfordshire), C. Efstathiou (Univ. Athens), W. Frenzel (TU Berlin), C. Georgiou (AU Athens), C. Giaginis (Univ. Aegean), S. Hamilakis (NTUA), E.H. Hansen (TU Lyngby), G. Hieftje (Indiana Univ.), G. Kakali (NTUA), A. Isleyen (TUBITAK), N. Kallithrakas-Kontos (TU Crete), S. Kamitsos (NHRF), M. Kanakidou (Univ. Crete), J. Kapolos (TEI Peloponnese), M. Karayannis (Univ. of Ioannina), A. Kettrup (TU Munich), D. Knopp (TU Munich), A. Koliadima (Univ. Patras), K. Kollia (NTUA), M. Kompitsas (NHRF), K. Kordatos (NTUA), M. Koupparis (Univ. Athens), M. Koupparis (NTUA), M. Krokida (NTUA), R. Lobinski (Univ. Pau), M. Loizidou (NTUA), G. Lymberatos (NTUA), N. Lydakis-Simantaris (Univ. Appl. Sciences Crete), B. Michalke (Helmholtz Center Munich), M. Mitrakas (AUTh), A. Moropoulou (NTUA), A. Moutsatsou-Tsima (NTUA), R. Niessner (TU Munich), K.-M. Ochsenkühn (NTUA), M. Ochsenkühn-Petropoulou (NTUA), V. Oreopoulou (NTUA), D. Panias (NTUA), I. Panderi (Univ. Athens), I. Papadoyannis (AUTh), A. Pappa (NTUA), M. Prodromidis (Univ. Ioannina), H. Puxbaum (TU Vienna), E. Rosenberg (TU Vienna), V. Samanidou (AUTh), C. Samara (AUTh), A. Sanz-Medel (Univ. Oviedo), A. Spyros (Univ. Crete), C. Stalikas (Univ. Ioannina), M. Statheropoulos (NTUA), I. Stratis (AUTh), J. Szpunar (CRNS, Pau), P. Taoukis (NTUA), N. Thomaidis (Univ. Athens), A. Tsantili-Kakoulidou (Univ. Athens), M. Tsapakis (HMCR), F. Tsopelas (NTUA), N. Tzamtzis (NTUA), C. Tzia (NTUA), R. Tzimou-Tsitouridou (AUTh), A. Vlessidis (Univ. Ioannina), G. Zachariadis (AUTh), J. Ziomas (NTUA).

Continuation Committee M. Ochsenkühn-Petropoulou, NTUA (IMA 1999, 2009, 2013, 2015), M. Karayannis, Univ. Ioannina (IMA 2001), I. Stratis, AUTh (IMA 2003), N. Chaniotakis, Univ. Crete (IMA 2005), Th. Christopoulos, Univ. Patras (IMA 2007), A. Calokerinos, Univ. Athens (IMA 2009), N. Kallithrakas-Kontos, TU Crete (IMA 2011), R. Tzimou- Tsitouridou, AUTh (IMA 2013), J. Kapolos, TEI Peloponnese (IMA 2015).

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Local organizers

Chairpersons Prof. Dr. Spiros A. Pergantis, Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete Prof. Dr. Maria Ochsenkühn-Petropoulou, Laboratory of Inorganic and Analytical Chemistry, School of Chemical Engineering, NTUA

Members Prof. D. Anglos (Univ. Crete-IESL/FORTH), Prof. N. Chaniotakis (Univ. of Crete), Assist. Prof. A. Detsi (NTUA), Prof. M. Kanakidou (Univ. of Crete), Assoc. Prof. M. Krokida (NTUA), Prof. M. Loizidou (NTUA), Assoc. Prof. N. Lydakis-Simantiris (Technological Education Institute of Crete), Prof. N. Mihalopoulos (Univ. of Crete- National Observatory of Athens), Dr. K.-M. Ochsenkühn (NTUA), Prof. A. Pappa (NTUA), Assist. Prof. A. Spyros (Univ. of Crete), Prof. E. Stephanou (Cyprus Institute-Univ. of Crete), M. Tsapakis (HCMR), Dr. F. Tsopelas (NTUA).

Local Organizing Committee-Secretariat Th. Lymperopoulou (NTUA), L.-A. Tsakanika (NTUA), K. Simeonidis (TEI Eastern Macedonia), Ch. Stergiopoulos (NTUA), E. Mavrakis (Univ. of Crete), L. Mavroudakis (Univ. of Crete), L. Trasanidou (Univ. of Crete), A. Kouvarakis (Univ. of Crete).

Exhibition Kaiti Euklidou-Tsimpogianni Elena Ochsenkühn

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General Information

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Introduction The 10th Anniversary International Conference "IMA 2017-Instrumental Methods of Analysis-Modern Trends and Applications" 17-21 September 2017, Heraklion, Greece is a five-day scientific meeting covering all areas of modern trends and applications of Chemical Analysis. For the last 18 years IMA has provided an excellent framework for the presentation of new concepts, instruments, methods, systems, and applications in the area of modern chemical analysis. Researchers and scientists from Universities, Research Institutions, State Organizations, and the Industry come together during the meeting to present and discuss the current state of the art in the area of instrumental methods of analysis. At the same time, it provides the grounds for the graduate and post graduate students to present their projects, discuss scientific collaborations with other groups, as well as to explore employment opportunities. An exhibition of analytical instruments and accessories will be also organized in the conference place whereas a number of excursions, tours and social events are included in the program of the IMA 2017.

Topics Current trends in Spectrochemical, Electrochemical, Chromatographic, Mass Spectrometric, Microscopic and Thermal analysis methods, Proteomics, Metabolomics, Metallomics and Elemental Speciation analysis, Chemical- and biosensors, Field analysis-Mobile analytical instruments, Miniaturized analytical systems (Lab-on-a-Chip), Micro- and Nano- fluidics, Immunoassays, Electrophoretic separation techniques, Sampling techniques and strategies, Sample handling and preparation, Robotics and Automation, Quality control-quality assurance in analysis, Metrology, Environmental, Biomedical, Pharmaceutical, Food, and Materials Analysis (Nanomaterials, Smart/Advanced Materials), Archaeometry, Analytical chemistry markets and possibilities for commercialization.

Previous conferences The past conferences were held in Chalkidiki (1999), Ioannina (2001), Thessaloniki (2003), Iraklion (2005), Patras (2007), Athens (2009), Chania (2011), Thessaloniki (2013) and Kalamata (2015) with 250-300 scientific papers presented by scientists from all over the world at each one.

Location of Conference IMA-2017 will be held in Heraklion, Crete. Particularly, it will take place in the conference centre of Aquila Atlantis Hotel. The site is near the centre of Heraklion city

located close to the historic harbour. Ideally positioned in the heart of the city, it is the perfect starting point to discover Heraklion and its many historic monuments and museums, all, within easy reach of the business and commercial district. The Aquila Atlantis Hotel has the largest conference centre in Heraklion with 6 multipurpose spaces covering a surface of 1,000 m2, with a total capacity over 900 seats.

City of Heraklion Heraklion is the largest urban centre in Crete with approximately 150,000 inhabitants, the capital of the region and the economic centre of the island. The town enjoys of a dynamic and imaginative combination of natural beauty, climate, strategic positioning, cultural heritage and scientific background that has created an environment which generates added value to the broader entrepreneurial activity in the region and stimulates the local economy. Heraklion is the top choice for tourist destinations in the Mediterranean thanks to its strategic geopolitical position connecting three continents and many different cultures, furthermore the city is also the commercial and scientific centre of the island. If you begin a walk around Heraklion, starting at the fishing harbour close to the modern port, what will strike you first is the Venetian fortress at the harbour gate. The fortess was originally built by the Venetians and called Rocca al Mare or Koules. It has a mixed history; for centuries it was used as protection against invaders, as were the great city walls and ditches. These are among the longest city walls in Europe. The harbour itself is home to brightly coloured fishing boats and busy tavernas selling fresh fish. Looking back towards the city you will see the strong arches which housed boats under repair and were used as an arsenal for storing guns and gunpowder. The greatest threat to the Venetian stronghold of Heraklion, or Candia, as it was named, was thought to come from the seaward side of the city, and indeed, many naval skirmishes were fought off this coast. The view northward takes in the uninhabited island of Dia, where evidence of ancient Minoan settlement (approx 2700-1450 BC) was found by the diver, Jacques Cousteau.

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The centre of the Minoan civilisation and capital of Minoan Crete, Knossos, lay 5km south of Heraklion. Knossos flourished for approximately two thousand years. It had large palace buildings, extensive workshop installations and luxurious rock-cut cave and tholos tombs. As a major centre of trade and the economy, Knossos maintained ties with the majority of cities in the Eastern Mediterranean. Heraklion is one of the liveliest cities of Greece. You can find something for everyone. Nightclubs, bars, traditional coffee shops and modern cafeterias are located all over the center of the city. Lions Square, Freedom Square and the streets around them are full of bars, cafeterias, tavernas and restaurants. The coastal area of the city is also a place to visit with nightclubs and tavernas beside the sea. Close to the centre of the city, one in the east and the other in the west, two well organised clean long beaches offer a great experience under the Cretan sun.

Papers presentation Scientific program will include plenary and keynote lectures, which will provide an up-to-date presentation of modern trends of Instrumental Methods of Analysis as well as of related subjects of general interest. Invited and plenary speakers should plan on a 35 minute long talk followed by 5 minutes for discussion. For all other oral presentations: presenting authors should plan on a 17 minutes long talk followed by 3 minutes of discussion. Presentations should be in Microsoft PowerPoint format (ppt or pptx file) or Adobe Acrobat Reader format (pdf file). The file should be electronically handed by the speaker to the Registration Desk at least one session before his/her presentation. Contributed papers describing original research work will be also presented as posters in order to promote efficient discussion on new scientific ideas and results. The presenting authors should hang their posters in the morning of their presentation and remove them at the end of the poster session. The preferable dimensions for posters should be 100 x 120 cm (width x height). All posters are required to conform to portrait orientation. Posters should be clear and easy to read. Type size should be sufficiently large to allow people to read from 2-3 meters.

All presentations should be in English. Poster and oral presentation will be accepted if at least one of the authors is registered and present at the conference for personal communication.

Best poster award A competition for the best poster among the young scientists in each poster session will also take place. These awards will be given to recognize excellence in research and presentation. The winners will be announced during the Closing ceremony on 21st September at noon.

Journal publication Participants are invited to submit manuscripts based on their presentations in one of the following journals: Analytical and Bioanalytical Chemistry (papers related to innovative research on analytical and bioanalytical chemistry) and Journal of Analytical Atomic Spectrometry (papers related to innovative research on the fundamentals and applications of atomic spectrometric techniques).

Exhibition Suppliers of analytical instrumentation and laboratory equipment will exhibit their latest offerings in the Exhibition Hall during the Conference. Official opening of the exhibition will take place on 18th September at 20:00. The exhibition area is adjacent to the lecture area and within the poster, coffee break and lunch areas in the Conference Center of Aquila Atlantis Hotel.

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Social events

Welcome reception 17/9/2017 Aquila Atlantis Hotel 20:30

The welcome cocktail will take place after the end of the Opening session in the registration place.

Archaeological site of Knossos 19/9/2017 Departure: Aquila Atlantis Hotel 08:30 A guided tour around the complex labyrinth of Knossos Palace, the capital of the Minoan civilization dated back in 2000 B.C., and experience the Minoan grandeur. Then, back to the city of Heraklion, to visit the most important sites of both historical and cultural importance.

Cretaquarium 20/9/2017 Departure: Aquila Atlantis Hotel 11:30

Come face to face with hundreds of species and thousands of living organisms and be fascinated by their behavior as they

reveal the wide variety of shapes, colors, habits in their world. Includes transfer, English speaking guide, lunch buffet. Don’t forget casual dress, comfortable shoes, camera.

Conference dinner 20/9/2017 Restaurant Thea, Rogdia Village 21:00 Departure: Aquila Atlantis Hotel 20:30

The conference dinner will be held on September the 20th at 21.00 in a Cretan Traditional tavern located 8 km from Heraklion. The menu will include a wide variety of Cretan food, pastry and local wine. Event will start with folklore dances and will close with a mix of Greek and international party.

Post-conference excursion Elounda-Spinalonga and BBQ 22/9/2017 a minimum number of participants is required Departure: Aquila Atlantis Hotel 09:00 Return: 17:30

Elounda was once a small seaside fishing village located in the Cretan prefecture of Lassithi, lying around the coast from the large town of Aghios Nikolaos. The settlement of Elounda dates back to ancient times, the Minoan/Roman city of Olous lay only metres from the current site of the town. After stay in Elounda, we take a boat to visit Spinalonga, the small island at the entrance of Elounda bay. We finish our day with a visit to Kolokytha, a splendid area for swimming, near the ruins of the historical Church of Agios Fokas, where we have a BBQ lunch.

Conference program

10th International Conference on Instrumental Methods of

Analysis: Modern Trends and Applications

Program at a glance

Sunday 17 September 2017

1630-2030 Registration

1800-1830 Opening ceremony

1830-2030 Plenary lectures

2030 Welcome reception

Monday 18 September 2017

0815-0900 Registration

0900-0940 Plenary lecture

0945-1105 Parallel Sessions

MINOS II Hall PASIPHAE I Hall

Analytical Instrumentation and Techniques Environmental Analysis

1105-1130 Coffee break

1130-1210 Plenary lecture

1215-1335 Parallel Sessions

MINOS II Hall PASIPHAE I Hall

Developments in ICP-MS Food Analysis 1

1335-1430 Lunch

1430-1530 Poster Session 1 - Exhibition

1530-1610 Plenary lecture

1615-1715 Parallel Sessions

MINOS II Hall PASIPHAE I Hall

Spectrometric Analysis Sample Preparation

1715-1740 Coffee break

1740-1920 Advances in Bioanalytics

1930-2100 Poster Session 1

2000 Opening of Exhibition

Poster Session 1 Mass Spectrometry / Spectrometry / Sample handling / Environmental analysis

Tuesday 19 September 2017

0830-1330 Visit to archaeological site of Knossos

1330-1430 Lunch

1430-1530 Poster Session 2 - Exhibition

1530-1610 Plenary lecture

1615-1715 Parallel Sessions

MINOS II Hall PASIPHAE I Hall

Archaeometry Chromatography 1

1715-1740 Coffee break

1740-1920 Chromatography 2

1930-2100 Poster Session 2 - Exhibition

Poster Session 2 Chromatography / Archaeometry / Spectrometry

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Wednesday 20 September 2017

0830-0900 Registration

0900-1040 Parallel Sessions

MINOS II Hall PASIPHAE I Hall

Elemental speciation analysis Food Analysis 2

1040-1110 Coffee break

1130-1430 Visit to Cretaquarium and Lunch

1430-1530 Poster Session 3 - Exhibition

1530-1710 Parallel Sessions

MINOS II Hall MINOS I Hall

Materials/Spectrometry Electrochemistry

1710-1745 Coffee break

1710-1845 Poster Session 3 - Exhibition

2100 Conference Dinner

Poster Session 3 Food / Electrochemistry / Materials / Sensors

Thursday 21 September 2017

0900-1040 Food Analysis 3

1040-1110 Coffee break

1110-1150 Plenary lecture

1150-1330 Sensors

1330-1400 Closing Ceremony/Poster Awards

10th International Conference on Instrumental Methods of

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Detailed program

Sunday 17 September 2017

OPENING SESSION (MINOS II Hall, Chair: S. Pergantis, M. Ochsenkühn-Petropoulou) 1800-1830 Greetings - Addresses 1830-1910 IMA - Twenty years of symposia PL01 L. Ebdon 1910-1950 Myths, mysticism and science during the development of chemistry and analytical chemistry from the ancient times to the middle of the 20th century PL02 M.I. Karayannis 1950-2030 The study of environmental and cultural heritage via analytical chemistry combined with other scientific fields PL03 J.A. Stratis

2030 Welcome reception

Monday 18 September 2017

PLENARY LECTURE (MINOS II Hall, Chair: L. Ebdon, R. Lobinski) 900-940 A highly versatile source for elemental, speciation, and metallomic analysis PL04 G.M. Hieftje, A.J. Schwartz and J.T. Shelley

PARALLEL SESSIONS ORAL SESSION: Analytical Instrumentation and Techniques (MINOS II Hall, Chair: L. Ebdon, R. Lobinski) 945-1005 Signal reversing cavity-based polarimetry: Evanescent-wave and ambient chiral sensing MO01 D. Sofikitis, G.E. Katsoprinakis, A.K. Spiliotis, B. Loppinet, T.P. Rakitzis 1005-1025 LIBS-SSI-MS: A new technique for the characterization of metal containing biomolecules and complexes MO02 K. Marmatakis, S.A. Pergantis and D. Anglos 1025-1045 Environmental and food safety applications of tandem mass spectrometry using a novel flow-based design of ion optics MO03 A. Bisi 1045-1105 Determination of biothiols on paper-based analytical devices using the photoreduction of silver halide nanocrystals MO04 F.A. Kappi, G.Z. Tsogas, D.C. Christodouleas, A.G. Vlessidis, D.L. Giokas 1105-1130 Coffee Break

ORAL SESSION: Environmental Analysis (PASIPHAE I Hall, Chair: M. Ochsenkühn-Petropoulou, M. Tsapakis) 945-1005 Three candidate certified reference materials for environmental analysis MO05 A. Isleyen, J. Vogl, D. Nikolic, A. Jotanovic, T. Naykki, N. Perkola, M. Horvat, A. Zon, E. Bulska, M. Ochsenkühn-Petropoulou, S. Zuhtu Can, R. Jacimovic, L. Gazevic, O. Cankur, B. Ari, M. Tunc, B. Binici, T. Gokcen, Z. Cakilbahce, V. Lymperopoulou

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1005-1025 Validation of methods for determination of specific elements in environmental samples using Microwave Plasma Atomic Emission Spectrometry (MP-AES) MO06 A. Jotanovic, D. Coric

25 45 10 -10 Towards new reference methods for the accurate determination of PM2.5(10) in ambient air based on the generation of synthetic ambient aerosols MO07 K. Vasilatou 1045-1105 Particulate matter emissions from combustion of different types of biomass MO08 A. Zosima and M. Ochsenkühn-Petropoulou 1105-1130 Coffee Break

PLENARY LECTURE (MINOS II Hall, Chair: B. Michalke, S. Pergantis) 1130-1210 Method development for metal detection at cellular levels PL05 N. Jakubowski, H. Traub, A. Jutta Herrmann, K. Löhr, A. Lopez-Serrano Oliver, J. Kneipp, L. Mueller

PARALLEL SESSIONS ORAL SESSION: Developments in ICP-MS (MINOS II Hall, Chair: B. Michalke, S. Pergantis) 1215-1235 sp-ICP-MS for determining/characterizing silver nanoparticles in seafood after ultrasound assisted enzymatic hydrolysis procedures MO09 M.V. Taboada-Lopez, N. Alonso-Seijo, P. Herbello-Hermelo, P. Bermejo-Barrera, A. Moreda-Piñeiro 1235-1255 Particulate and dissolved elements in Antarctic ice cores: Detection with a new generation ICP-MS and Single Particle (SP) Software MO10 G. Baccolo, M. Clemenza, B. Delmonte, R. Magarini 1255-1315 ICPMS measurement of potassium traces in NaI for dark matter search MO11 I. Dafinei, M. L. di Vacri, S. Nisi 1315-1335 Effects of silver nanoparticle exposure at the ng L-1 level on marine microbial plankton dynamics MO12 A. Tsiola, P. Pitta, M. Kagiorgi, I. Kalantzi, K. Mylona, S. Psarra, I. Santi, C. Toncelli, S. Pergantis, M. Tsapakis 1335-1530 Lunch – Poster Session 1 - Exhibition

ORAL SESSION: Food Analysis 1 (PASIPHAE I Hall, Chair: A. Jotanovic, M. Kanakidou) 1215-1235 Development of liquid extraction surface analysis mass spectrometry for rapid screening for the presence of post-polymerization residues in food packaging materials MO13 A. Issart, S. Godin, H. Preudhomme, K. Bierla, A. Allal and J. Szpunar 1235-1255 Food quality control and authentication using NMR spectroscopy and metabolomics MO14 A. Spyros, M. Amargianitaki, E. Ralli, M. Misiak and P. Dais 1255-1315 Metabolic fingerprinting based on high-resolution orbitrap mass spectrometry for wine authentication MO15 G. Kaklamanos, A. Maquet, E. Aries, V. Exarchou and F. Ulberth 1315-1335 Voltammetric detection of virgin olive oil adulteration MO16 F. Tsopelas, D. Konstantopoulos and A. Tsantili- Kakoulidou 1335-1530 Lunch – Poster Session 1 - Exhibition

PLENARY LECTURE (MINOS II Hall, Chair: D. Anglos, N. Lydakis-Simantiris) 1530-1610 Novel femtosecond laser ablation sampling technologies in optical emission spectroscopy PL06 V. Zorba

PARALLEL SESSIONS ORAL SESSION: Spectrometric Analysis (MINOS II Hall, Chair: D. Anglos, N. Lydakis-Simantiris) 1615-1635 Laser Induced Breakdown Spectroscopy for the rapid characterization of nanometer scale thin multilayer samples MO17 P. Siozos, S.P. Banerjee, N. Giannakaris, T. Sarnet, A. Klini, M. Sentis, D. Anglos 1635-1655 Simultaneous determination of Na, K, Li, Rb and Cs in the natural objects MO18 A.A. Zak, E.V. Shabanova, I.E. Vasileva

55 15 16 -17 Use of EIS to investigate of adsorption of NaCN and Na2S2O5 on pyrite MO19 Z. Ertekin, K. Pekmez and Z. Ekmekci 1715-1740 Coffee Break

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ORAL SESSION: Sample Preparation (PASIPHAE I Hall, Chair: N. Kallithrakas-Kontos, A. Isleyen) 1615-1635 Bromate removal from water using surfactant modified red mud MO20 F.A. Megalopoulos and M.T. Ochsenkühn-Petropoulou 1635-1655 Separation and preconcentration of particles and solutes before analysis using ultrasonic standing waves MO21 V.M. Shkinev, R.Kh. Dzhenloda, T.V. Danilova and B.Ya. Spivakov 1655-1715 DNA purification with a plasma micro-nanotextured polymeric microfluidic device using micro-solid phase extraction MO22 A.S. Kastania, P.S. Petrou and E. Gogolides 1715-1740 Coffee Break

ORAL SESSION: Advances in Bioanalytics (MINOS II Hall, Chair: J. Thomas-Oates, A. Bisi) 1740-1820 Probing metal interactions with biomolecules in-vivo using electrospray high resolution mass spectrometry PL07 R. Lobinski 1820-1840 Differentiating tumor heterogeneity in FFPE colon adenocarcinoma tissues using PCA analysis of MALDI IMS spectral data MO23 I. Panderi, K. Perez, L. Noble, D. Pantazatos 1840-1900 Phosphorylated amino acids detection and extraction combining fluorogenic MIP core-shell particles and microfluidics MO24 J. Bell, W. Wan and K. Rurack 1900-1920 High sensitive multiresidue analysis of pharmaceuticals in surface water using UHPLC-LTQ/Orbitrap HRMS MO25 Ch. Nannou, Ch. Kosma, V. Boti and T. Albanis 1930-2100 Poster Session 1 – Opening of the Exhibition

POSTER SESSION 1 Mass Spectrometry / Spectrometry / Sample handling / Environmental analysis PASIPHAE II Hall P1-01 Preparative isoelectric focusing of microorganisms in cellulose-based separation medium and subsequent analysis by CIEF and MALDI-TOF MS M. Horka, K. Slais, J. Salplachta and F. Ruzicka P1-02 Characterization of changes in volatile profile of elderflowers (Sambucus nigra L.) caused by harvesting and drying processes T. Bajer, P. Bajerova, A. Eisner, M. Adam and K. Ventura P1-03 Comparison of different sample preparation methods for the multi-residue detection and quantification of pesticides in fruit juices by LC-MS/MS and GC-MS/MS B. Papaioannou, H. Botitsi, S. Antoniou, D. Tsipi and A. Economou P1-04 Single-Calibrant paper-based analytical devices for in-situ standard addition assays G. Giannoulas, G.Z. Tsogas, A.G.Vlessidis, D.L. Giokas P1-05 Dispersive suspended microextraction of silver nanoparticles from water samples with oxidative dissolution back-extraction prior to their determination by atomic absorption spectrometry T.G. Choleva, G.Z. Tsogas, A.G. Vlessidis, D.L. Giokas P1-06 High resolution mass spectrometry to investigate psychiatric drugs and their metabolites in wastewaters Ch. Kosma, Ch. Nannou, V. Boti and T. Albanis P1-07 Flow sample preparation using standing wave ultrasound and magnetic fields in the determination of nucleic acids by real-time polymerase chain reaction B.Ya. Spivakov, R.Kh. Dzhenloda, V.M. Shkinev and D.G. Petrov P1-08 Hyphenated techniques in mass spectrometry applications for assessment of metals exposure B. Janasik, M. Stanislawska, R. Kuras, W. Wasowicz P1-09 Evaluation of method based on vacuum assisted solid phase microextraction for analysis of beer volatile profiles M. Adam, K. Adámková, A. Eisner, T. Bajer and K. Ventura P1-10 Analytical determination of antibiotics in surface waters of aquacultures by LC-ORBITRAP MS V. Toli, V. Boti and T. Albanis P1-11 Determination of common pesticides used in aquacultures in mussels using

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QuEChERS in combination with LC- hybrid LTQ Orbitrap MS E. Trantopoulos, V. Boti, T. Albanis P1-12 Optimisation of experimental conditions for analysis of silver nanoparticles by single particle ICP-MS M. Loula, A. Kaňa and O. Mestek P1-13 Detection of emerging contaminants in water samples by homogeneous liquid- liquid microextraction using switchable hydrophilicity solvents as acceptor phase C. Rivera-Vera, C. Toledo-Neira, G. Lasarte-Aragones P1-14 Comparative determination of fludioxonil by GC/MS-MS and LC/MS-MS in raspberry M. Jaksic, N. Tomcic, J. Banic-Simicic, S. Cujic, B. Marosanovic P1-15 Dried blood spots and laser ablation ICP-MS for multi-element determination in whole blood from newborn J. Moreda-Piñeiro, A. Cantarero–Roldan, J.A. Cocho, P. Bermejo-Barrera and A. Moreda-Piñeiro P1-16 Assessment of titanium dioxide and silver nanoparticles in urine by single particle – ICP-MS K. Badalova, P. Herbello-Hermelo, P. Bermejo-Barrera, and A. Moreda-Piñeiro P1-17 Development of analytical methodologies for the chemical investigation of insect attractants or repellents S. Giannoukos, A. Pappa, A. Michaelakis and S. Taylor P1-18 SeaFast sample introduction system for multi-element determination in serum samples by ICP-MS M.d.P. Chantada-Vazquez, P. Herbello-Hermelo, P. Bermejo-Barrera, A. Moreda- Piñeiro P1-19 Binding kinetics of analytes in microfluidic channels: A simple model for Salmonella cells and immobilized antibodies A.S. Kastania, K. Tsougeni, V. Constantoudis and E. Gogolides P1-20 Investigating the mechanism for gas-phase ion production in Sonic-Spray Ionization (SSI) mass spectrometry L. Mavroudakis, G.R. Agnes, E.A. Kapellios, K. Kanaki, S.A. Pergantis P1-21 Characterization of gamma radiation fields emitted by 60-co sources inside of multifunctional interaction chamber C. Postolache, D. Negut, C. S. Tuta, S. Bercea, A. Celarel, C. Cenusa, V. Fugaru, M.-R. Ioan P1-22 Optimizing the delivery of phenolic compounds from Salvia triloba and Vitis vinifera

G. Asimomiti, N. Soteriou, D.Z. Lantzouraki, T. Tsiaka, P. Natskoulis, E. Spanidi, K. Gardikis, V.J. Sinanoglou and P. Zoumpoulakis P1-23 Tracking the fate of metal-based nanoparticles in environmental matrices using single particle ICP-MS R. Magarini, C. Stephen P1-24 Detection of honey adulteration with sugar syrup addition, using LC-MS/MS and ICP-OES M. Christofakis, G. Siragakis and G. Miliadis P1-25 Highly selective detection of multi-phosphorylated peptides via Zn2+-IMAC enrichment and MALDI-TOF MS analysis S. Won Bae P1-26 Method validation for the determination of aqua regia extractable trace elements in soils Th. Lymperopoulou, L.-A. Tsakanika and M. Ochsenkhuhn-Petropoulou P1-27 Microwave-driven ICP for analytical spectrometry J. Giersz, K. Jankowski, A. Ramsza and E. Reszke P1-28 Sulfonamides in wastewaters: Method development, occurrence, mass loading, removal efficiencies and environmental risk assessment M. Gougousi, Ch. Kosma, V. Boti and T. Albanis P1-29 Exploiting UV-femtosecond LIBS in single- and double-pulse modes for the analysis of aqueous aerosols K. Marmatakis and D. Anglos P1-30 UV femtosecond Laser Induced Breakdown Spectroscopy for characterization of nanometer thin multilayer samples N. Giannakaris, P. Siozos, D. Anglos P1-31 Determination of metals present in metalloproteins from athletes’ serum samples using double column affinity chromatography inductively-coupled plasma mass spectrometry (ICP-MS) L. Trasanidou, S.A. Pergantis, T. Nomikos P1-32 A porous graphitized carbon LC-ESI/MS method for the quantification of metronidazole and fluconazole in breast milk and human plasma A. Geballa-Koukoula, K. Zervas, D. Gennimata, P. Vourna, E. Panteri-Petratou and I. Panderi P1-33 Quantification of rosuvastatin and metformin in human plasma using hydrophilic interaction liquid chromatography / electrospray ionization mass spectrometry for therapeutic drug monitoring N. Antonopoulos, G. Machairas, D. Gennimata, G. Migias, E. Panteri-Petratou and I. Panderi

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P1-34 Development and validation of a HILIC-ESI/MS method for the quality control of cosmeceuticals containing oligopeptide-20 and oligopeptide-24 M. Giannakou, A. Varvaresou, A. Vonaparti, S. Papageorgiou and I. Panderi P1-35 Investigating heavy metal (Pb, Cd, Ni and arsenic species) uptake by Chlamydomonas reinhardtii cells by means of Single-Cell ICP-MS E. Mavrakis, N. Lydakis-Simantiris, C. Stephan, R. Magarini, S.A. Pergantis P1-36 Development of an extraction method to characterize silver nanoparticles from sewage sludges using SP-ICP-MS E. Andrade Carpente, E. Peña-Vazquez, M.C. Barciela Alonso and P. Bermejo- Barrera P1-37 Characterization of titanium dioxide nanoparticles from WWTP sewage sludges using SP-ICP-MS P. Costa Tome, E. Peña-Vazquez, M.C. Barciela-Alonso and P. Bermejo-Barrera P1-38 Comparative proteomic analysis of heterocysts from two hydrogenase mutants from Anabaena sp. PCC 7120 A. Kourpa, V. Strataki and G. Tsiotis P1-39 Chiral Cavity Ring-Down Polarimetry: New methods for ultrasensitive measurements of chirality A.K. Spiliotis, D. Sofikitis, G.E. Katsoprinakis, B. Loppinet, T.P. Rakitzis P1-40 Targeted protein analysis by MALDI-MS using molecularly imprinted polymers T. Vaneckova, L. Vanickova, V. Adam, M. Vaculovicova P1-41 Bioconjugation of nanoparticles with antibodies for LA-ICP-MS imaging A. Moravanska, M. Vlcnovska, K. Smerkova, M. Tvrdonova, T. Vaculovic, M. Vaculovicova and V. Adam P1-42 Rapid and Sensitive analysis of major use antibiotics by UHPLC-High Resolution Orbitrap MS M. Kalampoka, V. Boti, V. Sakkas and T. Albanis P1-43 Water soluble fine aerosol ionic composition and effects of residential wood burning, in Athens, Greece D. Paraskevopoulou, E. Liakakou and N. Mihalopoulos

P1-44 Real time measurements of water soluble phosphoric ions in PM2.5 aerosols in the eastern Mediterranean E. Tsiodra, M. Tsagkaraki, P. Zarmpas, K.Violaki, R. Weber, A. Nenes and N. Mihalopoulos P1-45 First observations of bioaerosols in the Eastern Mediterranean Ch. Almpani, A. Negron, G. Kouvarakis, I. Magiopoulos, P. Pitta, M. Kanakidou, N. Mihalopoulos and A. Nenes

P1-46 Development of magnetic nanocomposites for the removal of Sb and As below drinking water regulation limits K. Simeonidis, E. Kaprara, M. Mitrakas P1-47 Magnother: a novel nanoparticle fluid for localized cancer therapy by magnetic hyperthermia and thermally-triggered drug delivery K. Simeonidis, E. Kokkinos, A. Mitropoulos

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Tuesday 19 September 2017

0830-1330 Visit to archaeological site of Knossos

1330-1530 Lunch – Poster Session 2 – Exhibition

PLENARY LECTURE (MINOS II Hall, Chair: M.I. Karayannis, J. Stratis) 1530-1610 Palaeomics: when mass spectrometry meets archaeology PL08 J. Thomas-Oates

PARALLEL SESSIONS ORAL SESSION: Archaeometry (MINOS II Hall, Chair: M.I. Karayannis, J. Stratis) 1615-1635 Revealing fakes and forgeries of works of art using instrumental archaeometric techniques TU01 M.I. Karayannis 1635-1655 Archaeological and climatic data from elemental ratios using rapid analysis of shell carbonate with LIBS TU02 N. Hausmann, P. Siozos, A. Lemonis, K.T. Li and D. Anglos 1655-1715 Safe boundaries for analysis of heritage materials in the context of Raman microscopy TU03 A. Philippidis, P. Siozos and D. Anglos 1715-1740 Coffee Break

ORAL SESSION: Chromatography 1 (PASIPHAE I Hall, Chair: K. Valko, I. Panderi) 1615-1635 Portable capillary electrophoresis systems for rapid on-site determination of drug abuse TU04 M. Kulp, M. Kaljurand, M. Vaher, J. Mazina-Šinkar, P. Saar-Reismaa, A. Špiljova 1635-1655 Development and application of methods for the determination of pesticide residues in natural waters and sediments TU05 M. Kapsi, V. Sakkas and T. Albanis 1655-1715 Fast routine analysis of polar ionic pesticides in water and foods by suppressed ion chromatography coupled to mass spectrometry TU06 M. Godula, K. Bousova, F. Schoutsen and A. Kurz 1715-1740 Coffee Break

ORAL SESSION: Chromatography 2 (MINOS II Hall, Chair: F. Tsopelas, F. Schoutsen) 1740-1820 Biomimetic chromatography and its application in drug discovery PL09 K. Valko 1820-1840 The performance of biopartitioning micellar chromatography on a series of structurally- diverse drugs and its potential to estimate cell permeability TU07 F. Tsopelas, P. Danias, T. Sialda, C. Stergiopoulos, A. Pappa and A. Tsantili- Kakoulidou 1840-1900 The use of immobilized artificial membrane chromatography to predict ecotoxicity of pesticides in aquatic environment TU08 C. Stergiopoulos, F. Tsopelas and M. Ochsenkuehn-Petropoulou 1900-1920 Development and validation of an isotope dilution liquid chromatography- tandem mass spectrometry confirmatory method for the simultaneous determination of acidic and basic non steroidal anti-inflammatory drugs in foodstuffs of animal origin TU09 C. Arkouli, A. Economou, V. Schoina, E. Stathoudaki, Ch. Alexopoulos, E. Kakoulides 1930-2100 Poster Session 2 – Exhibition

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POSTER SESSION 2 Chromatography / Archaeometry / Spectrometry PASIPHAE II Hall P2-01 Determination of levoglucosan and its stereoisomers by ESI-LC-MS-MS as tracers for fine particle emissions from biomass burning in Luxembourg J. Ziebel, A. Krein, J. Junk and C. Guignard P2-02 A rapid method for drug testing and authenticity based on pyrogallol chemiluminescence A. Votani, S. Tzoka, G.Z. Tsogas, A.G. Vlessidis, D.L. Giokas P2-03 Utilization of preparative IEF and MALDI-TOF mass spectrometry in the identification of Escherichia coli from urine samples J. Salplachta, M. Horka, F. Ruzicka and K. Slais P2-04 Chemical composition of buckles dated from the 3rd to the 7th centuries AD found in North-Eastern Bulgaria D. Lesigyarski, B. Zlateva and L. Trajkova P2-05 qNMR spectroscopy as an innovative and powerful technique for the determination of purity of organic compounds A. Alexopoulos, E. Kakoulides, A. Panagiotopoulou P2-06 Determination of amines using HPLC with fluorescence detection A. Eisner, S. Surmova, O. Peterka, P. Bajerova, T. Bajer, K. Ventura, M. Adam P2-07 Total fluorescence spectroscopy associated to chemometrics helps to reveal the presence of defensin in honey E. Fuentes, G. Cebrero, M. Báez, C. Ley, J. Martínez and M. Báez P2-08 A portable XRF spectrometers for non-destructive analyses in the archaeometry: examples from Bulgaria B. Zlateva, D. Lesigyarski and V. Bonev P2-09 Chemical composition of fibulae, found in ancient Emporion Pistiros V. Bonev and B. Zlateva P2-10 Analysis of coarse, fine, ultrafine particles and associated metals resulted from welding using SEM-EDS technique M. Stanislawska, T. Halatek, M. Cieslak, I. Kaminska, R. Kuras, B. Janasik, W. Wasowicz P2-11 New synthetic targets for modification of DNA by oxoosmium complexes L. Havran, P. Vidláková, J. Spacek and M. Fojta

P2-12 Cholesterol determination in blood serum by means of voltammetry at chemically modified electrode E.I. Korotkova, K.V. Derina P2-13 QuEChERS methodology combined with high performance liquid chromatography-UV/DAD for the determination of common pesticides in honey products E. Gotsi, V. Boti, T. Albanis P2-14 Discrimination of prehistoric teeth by infrared spectroscopy: Comparison of four models C. Levasseur-Garcia and R. Vezian P2-15 Evaluation of second-order multivariate calibration and fluorescence spectroscopy for mercury determination in environmental samples M.A. Bravo, R. Veneciano, J. Bergmann, W. Quiroz P2-16 Evaluation of monolithic column for mercury speciation analysis in fish samples M.A. Bravo, O. Riquelme, S. Parra, W. Quiroz P2-17 Real time monitoring of laser cleaning on stone by means of photoacoustic signal detection G.J. Tserevelakis, J.S. Pozo-Antonio, P. Siozos, K. Melessanaki, T. Rivas, A. Ramil, P. Pouli, G. Zacharakis P2-18 Sulphur analysis in high lead content samples by a mobile X-Ray Fluorescence System N. Kallithrakas-Kontos and A. Fragkos P2-19 The potential of biopartitioning micellar chromatography to estimate ecotoxicity of pesticides C. Stergiopoulos, F. Tsopelas, D. Makarouni, A. Tsantili- Kakoulidou, M. Ochsenkuehn-Petropoulou P2-20 Non-linear imaging techniques as diagnostic tools for Cultural Heritage studies M. Mari, V. Tsafas, E. Gavgiotaki, K. Melessanaki and G. Filippidis P2-21 Arsenic speciation in fish from Greek coastal areas I. Kalantzi, K. Mylona, K. Sofoulaki, M. Tsapakis and S.A. Pergantis P2-22 Solid-phase spectrophotometric iodometric determination of various analytes using a polymethacrylate matrix D.A. Fedan, N.A. Gavrilenko, N.V. Saranchina and M.A. Gavrilenko P2-23 Validated HPLC-ESI/MS method for identification and quantification of 15 phenolic acids in plant extracts

38 10th International Conference on Instrumental Methods of

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N.Y. Sipkina, M.V. Baranova, Y.A. Skorik P2-24 Quantification of new antifungal drug by HPLC-ESI/MS in biological liquids N.Y. Sipkina, I.P. Yakovlev P2-25 NMR spectroscopy analysis of 19th century decorative interior paintings in Helsinki, Finland E. Ralli, H. Mannerheimo, U. Knuutinen and A. Spyros P2-26 Portable hybrid LIBS-diffuse reflectance spectrometer for spectroscopic analysis of inorganic pigments P. Siozos, D. Anglos P2-27 Analytical techniques based on mobile laser instruments, for the study of cultural heritage objects A. Philippidis, P. Siozos, Z.E. Papliaka, K. Melessanaki, M. Vakondiou, O. Gratziou and D. Anglos P2-28 Temperature-dependent photoluminescence and lasing emission of ZnO nanocomposites D. Patramanis, A. Tsoukala, A. Klini, and D. Anglos P2-29 Chemical analysis of industrial scales and real-time monitoring of their dissolution processes via laser spectroscopy O. Kokkinaki, P. Siozos, A. Philippidis, K. Marmatakis, M. Tsagkarakis, N. Koromila, M. Hadjistephanou, C. Gounarakis, D. Anglos P2-30 Remote LIBS for assessing the condition of field-aged composite HV outdoor insulators O. Kokkinaki, A. Klini, M. Polychronaki, N. Mavrikakis, K. Siderakis, E. Koudoumas, D. Pylarinos, E. Thalassinakis, C. Kalpouzos, D. Anglos P2-31 Hydrophilic interaction liquid chromatographic method coupled with PDA detection for the simultaneous determination of impurities in tablets containing rosuvastatin and metformin G. Machairas, A. Geballa-Koukoula, A. Rozou, O. Galanopoulou, P. Charitos and I. Panderi P2-32 Capillary electrophoresis with light emitting diode-induced fluorescence detection for characterization of conjugation of antibodies with nanoparticle and lathanide chelate labels L. Nejdl, M. Tvrdonova, T. Vaculovic, M. Vaculovicova and V. Adam P2-33 Chiral separation of acidic chiral compounds on a clarithromycin- zirconia hybrid monolith by capillary electrochromatography M. Yeon Kim, J. Hag Park P2-34 Determination of tritium contents in incinerable samples

C. Postolache, V. Fugaru, G. Bubueanu P2-35 Radionuclide characterization of tritiated water using NMR spectrometry C.S. Tuta, C. Postolache, V. Fugaru, G. Bubueanu P2-36 Computational Method for the Determination of Intense Gamma-Rays Sources Activity by Using GEANT4 M.-R. Ioan, C. Postolache, V. Fugaru, S. Bercea, A. Celarel, C. Cenusa P2-37 Determination of C-14 concentration in irradiate graphite samples collected from thermal column of VVR-S reactor using AMS facility based on the 9 MV accelerator V. Fugaru, C. Stan-Sion, M. Enachescu and C. Postolache

40 10th International Conference on Instrumental Methods of

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Wednesday 20 September 2017

PARALLEL SESSIONS ORAL SESSION: Elemental Speciation Analysis (MINOS II Hall, Chair: G. Hieftje, S. Pergantis) 900-940 The power of combined speciation- and metabolomics studies on transition metal and selenium compounds in brain/at neural barriers within neurodegeneration research PL10 B. Michalke 940-1000 Antimony speciation in spirits stored in pet bottles: identification of a novel antimony complex WE01 S. Carneado, J.F. López-Sánchez, A. Sahuquillo, E. Klontzas, G.E. Froudakis, S.A. Pergantis 1000-1020 Which is the best approach for on site trace metal speciation determination? WE02 C. Parat, and I. Le Hécho 1020-1040 Optimizing Sn(II) oxy-hydroxides adsorbents by increasing their reducing capacity: Application on Cr(VI), Se(VI) and Sb(V) removal from water WE03 E. Kaprara, K. Kalaitzidou, A. Kamou, K. Simeonidis, M. Mitrakas 1040-1110 Coffee Break

ORAL SESSION: Food Analysis 2 (PASIPHAE I Hall, Chair: A. Calokerinos, A. Spyros) 900-940 Applications of nuclear magnetic resonance in food science and technology PL11 J. van Duynhoven 940-1000 MCPD and glycidyl esters in food products – occurrence, methods and analytical facts WE04 G. Karanikolopoulos, D. Chrysafidis, V. Tzamtzis and D. Tsipi 1000-1020 Analytical characterization of meglumine by HPLC/MS WE05 C. Martano, F. Ferretti, F. Buonsanti, L. Lattuada

1020-1040 Honey authenticity: Evaluation of phenolic compounds as potential authenticity markers using target and non-target LC-HRMS screening WE06 G.A. Koulis, A.S. Tsagkaris, R. Aalizadeh, S. Drivelos, C. Proestos, C. Georgiou, N.S. Thomaidis 1040-1110 Coffee Break

1110-1430 Visit to Cretaquarium and Lunch

1430-1530 Poster Session 3 – Exhibition

PARALLEL SESSIONS ORAL SESSION: Materials/Spectrometry (MINOS II Hall, Chair: V. Zorba, N. Jakubowski) 1530-1610 Characterization of advanced materials and particles at the nano- and microscales by X-ray spectrometry using calibrated instrumentation PL12 B. Beckhoff 1610-1630 Determination of noble metals in geological samples by scintillation arc atomic emission spectrometry WE07 E.V. Shabanova and I.E. Vasileva 1630-1650 Analysis of mercury selective complexing membranes by X-Ray Absorption Near Edge Spectrometry (XANES) WE08 N. Kallithrakas-Kontos and R. Moschochoritou 1650-1710 Immobilization of hemin on thin mesopourous Sno2 films for the detection of organohalides in aqueous solution WE09 E. Topoglidis, A. Panagiotopoulos and C. Tiflidis 1710-1745 Coffee Break

ORAL SESSION: Electrochemistry (MINOS I Hall, Chair: N. Chaniotakis, K. Ochsenkühn) 1530-1610 Novel approach to stripping voltammetric determination of selected metals using screen-printed electrodes modified with metal films PL13 A. Bobrowski

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1610-1650 New methods of electrochemical monitoring of biologically active organic compounds in environmental and biological matrices PL14 J. Barek, J. Fischer, A. Makrlikova, T. Navratil, and B. Josipcuk 1650-1710 Electrochemical behavior study and sensitive voltammetric determination of theophylline in pharmaceutical dosages and human urine WE10 K. Cinkova, N. Zbojekova and L. Svorc 1710-1745 Coffee Break

1710-1845 Poster Session 3 –Exhibition

2100 Conference Dinner

POSTER SESSION 3 Food / Electrochemistry / Materials / Sensors PASIPHAE II Hall P3-01 Anodic stripping voltammetry detection of lead using glassy carbon electrode modified with aza-crown ether and Nafion R. Segura and J. Pizarro P3-02 An electrochemical sensor based on electrochemically reduced graphene for the simultaneous determination of Pb(II) and Cd(II) by square wave anodic stripping voltammetry (SWASV) J. Pizarro and R. Segura P3-03 Electrochemical measurements in flow systems on amalgam tubular detector combined with platinum auxiliary electrode O. Josypcuk, J. Barek and B. Josypcuk P3-04 Ferrocenil complexes functionalized with crown ether moiety. Synthesis and application for the determination of metal ions F. Godoy, N. Agurto and A. Oliver P3-05 Determination of Cu(II) using a modified electrode with ferrocenyl crown ether compound by square wave anodic stripping voltammetry E. Flores, J. Pizarro, F. Godoy, R. Segura, A. Gómez, N. Agurto, P. Sepúlveda P3-06 Colorimetric sensor for determination of thiocyanate in oilfield water T. Volgina, N. Gavrilenko and M. Gavrilenko P3-07 Time-based assay of thiols by target-mediated photoinduced modulation of gold nanoparticles growth A. Kostara, G.Z. Tsogas, T.G. Choleva, A.G. Vlessidis, D.L. Giokas P3-08 Application of electrochemically switchable DNA tags in DNA analysis P. Vidlakova, L. Havran and M. Fojta P3-09 Determination of heparin by means of voltammetry D.A. Vishenkova, E.I. Korotkova P3-10 Monitoring real-time changes in the concentration of inorganic solutions on the border of heterogeneous dielectric materials according to the parameters of electromagnetic signals A.A. Bespal`ko, L.V. Yavorovich, A.P. Surzhikov P3-11 Thermomagnetometric analysis of substituted lithium ferrites A.P. Surzhikov, E.N. Lysenko, A.L. Astafyev P3-12 Microstructure analysis of ferrite powders ball-milled in a planetary mill E.N. Lysenko, A.P. Surzhikov, E.V. Nikolaev

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P3-13 Microstructure and thermal analysis of lithium ferrite ceramics E.N. Lysenko, A.V. Malyshev, V.A. Vlasov, E.V. Nikolaev P3-14 An adsorptive stripping voltammetry procedure for simultaneous determination of trace bismuth(III) and lead(II) in natural water samples M. Grabarczyk, C. Wardak and J. Wasag P3-15 Simple and fast voltammetric procedure for direct determination of trace concentrations of Ge(IV) in environmental water samples M. Grabarczyk P3-16 Study of Greek extra virgin olive oil as far, quality control, different olive harvests and adulteration with seed oils, by spectroscopic methods A. Philippidis, D. Sygelaki, A. Velegrakis and M. Velegrakis P3-17 Assessment of phenolic content, antioxidant and antiradical activity of wood aged “tsipouro” V.J. Sinanoglou, E.-M. Manika, V. Resiti, I.F. Strati, E. Siores, M. Giannakourou and P. Zoumpoulakis P3-18 Antioxidant enrichment of fresh-cut cucumber using infusions of edible herbs M. Giannakourou, V. Mantanika, S. Poulis, I.F. Strati, P. Zoumpoulakis and V.J. Sinanoglou P3-19 Optimization of polyphenol extraction from Allium Ampeloprasum var. porrum through Response Surface Methodology I.F. Strati, G. Kostomitsopoulos, F. Lytras, P. Zoumpoulakis and V.J. Sinanoglou P3-20 Evaluation of antioxidant activity and Mid-FTIR absorbance spectra of balsamic and common vinegars V.J. Sinanoglou, I.F. Strati, D. Tangouli, N. Paloumpis, D. Cavouras, and P. Zoumpoulakis P3-21 Influence of the pasteurization and filtration on selected chemical components of beer J. Porizka, D. Vopelkova, V. Dtursa and P. Divid

P3-22 Chemical sensor for the detection of CBr4 based on modified TiO2 thin film P. Nikolaou, A. Vassilakopoulou, D. Papadatos, I. Koutselas and E. Topoglidis P3-23 Mycotoxins in Foods: Employing microorganisms in milk detoxification Κ. Lapapokonstantaki, P. Giannikopoulou, E. Kakoulides, D. Mamma, D. Kekos P3-24 Synthesis of Magnetic Ionic Liquid for the determination of pesticides in aqueous samples M. Kapsi, V. Sakkas and T. Albanis P3-25 Development of DGT technique for determination of mercury in various matrix

P. Divis and M. Reichstädter P3-26 Assessment of CdS quantum dots effect on UV-C induced DNA damage using an electrochemical biosensors V. Svitkova and J. Labuda P3-27 Multi-element method validation for rare earths, precious metals and trace elements determination through ICP-MS in meat products G.P. Danezis, A.S. Tsagkaris, A.C. Pappas, E. Zoidis, G. Papadomichelakis, I.E. Hadjigeorgiou and C.A. Georgiou P3-28 Nutritional value & safety of Greek PDO cheeses through elemental metabolomics G.P. Danezis, A.C. Pappas, E. Tsiplakou, E.C. Pappa, M. Zacharioudaki, A.S. Tsagkaris, K. Sotirakoglou, G. Zervas and C.A. Georgiou P3-29 Soft Greek PDO cheeses authentication and discrimination from possible imitations using elemental metabolomics G.P. Danezis, A.C. Pappas, E. Tsiplakou, E. C. Pappa, M. Zacharioudaki, A.S. Tsagkaris, K. Sotirakoglou, G. Zervas and C.A. Georgiou P3-30 Optimization of high energy extraction of antioxidant compounds from Lippia citriodora C. Makris, T. Tsiaka, D. Lantzouraki, C. Proestos, V.J Sinanoglou, P. Zoumpoulakis P3-31 Optimization of extraction methodology for the recovery of phenolic antioxidants from wine less D. Tagouli, D. Lantzouraki, T. Tsiaka, V.J. Sinanoglou, P. Zoumpoulakis P3-32 An exhaustive study of antioxidant related properties of Artemisia leaves N. Kalogeropoulos, V. Kafourou, A.C. Kaliora, D.P. Makris, P. Zoumpoulakis P3-33 Comparative evaluation of the antioxidant activity and phenolic profile of different extracts from industrial peach by-product H. Fragiadaki, T. Tsiaka, D.Z. Lantzouraki, V.J. Sinanoglou and P. Zoumpoulakis P3-34 Investigation of Sc leaching from bauxite residue using phosphoric acid L.-A. Tsakanika, Th. Lymperopoulou and M. Ochsenkuehn-Petropoulou P3-35 Total phenols and antioxidant capacity of koumaro distillates from five mainland areas of Greece I.A. Athanasoula, P.G. Demertzis and K. Akrida-Demertzi P3-36 The determination of some toxic elements in the surface water samples in the vicinity of Copper Mining and Smelting Complex Bor M. Steharnik, S. Stankovic, S. Serbula, T. Kalinovic, A. Ilic and J. Kalinovic P3-37 The maturation of Cretan graviera cheese as monitored by high resolution NMR spectroscopy and low field NMR relaxometry/diffusometry

46 10th International Conference on Instrumental Methods of

Analysis: Modern Trends and Applications

E. Ralli, O.V. Petrov, C. Mattea, B. Gizatullin, S. Stapf and A. Spyros P3-38 Analytical methods as a tool for the evaluation of microalgae drying process S. Papadaki, M. Stramarkou and M. Krokida P3-39 Encapsulation of β-carotene in food grade nanofibers by coaxial electrospinning C. Drosou, M. Krokida, C. Biliaderis P3-40 Optical gas sensing based on the photolumiscence of ZnO-PDMS nanohybrids A. Klini, S. Pissadakis, R.N. Das, E.P. Giannelis, S.H. Anastasiadis, and D. Anglos P3-41 Utilization of tomato by-products for the production of functional products and bioactive ingredients A. Yfanti, P. Eleni, M. Krokida and D. Bilalis P3-42 Design and synthesis of ferrocene derivatives. Determination by UV-Vis to divalent metal ions N. Agurto, C. Silva, F. Godoy and A. Oliver P3-43 Investigating the effect of Zn/Fe-LDH ratio on antimony adsorption E. Kokkinos, S. Tresintsi, E. Tsafou and M. Mitrakas P3-44 Cavity-Based methods for precise, real-time refractive index measurements A.K. Spiliotis, D. Sofikitis, G.E. Katsoprinakis and P.T. Rakitzis P3-45 Gadolinium-Schiff base complex modified CdTe quantum dots as a sensor of cell membrane damage quantified by capillary electrophoresis L. Nejdl, A. Moulick, M. Vaculovicova, T. Vaneckova, K. Smerkova, V. Adam and M. Vaculovicova P3-46 Rheological, physical and sensory characteristics of low fat and low sugar chocolates formulated with Stevia rebaudiana Bertoni extract as natural sweetener V. Oikonomopoulou, I. Argyriou, C. Drosou and M. Krokida P3-47 Synthesis and characterization of Layered Double Hydroxides for arsenic adsorption from drinking water S. Tresintsi, E. Kokkinos, K. Simeonidis, M. Mitrakas and G. Kyriakou P3-48 Optimization of Se(IV) / Se(VI) determination by GFAAS in natural waters K. Kalaitzidou, N. Tsiftsakis, Ε. Kaprara and M. Mitrakas P3-49 Phenolics profiling in extra-virgin olive oil, olive leaves, and olive mill waste water by NMR spectroscopy E. Manolopoulou, S. Tachtalidou, E. Beleli, A.M. Gómez-Caravaca, A. Segura- Carretero and A. Spyros P3-50 Studies on reproducibility of isolation of pure ashalthene fraction and its properties for separation techniques

G. Boczkaj, M. Plata-Gryl, M. Momotko P3-51 Selectivity tunning of aspalthene based sorbents by means of chemical modification M. Momotko, M. Plata-Gryl, S. Makowiec, G. Boczkaj P2-52 Synthesis of the silver nanoparticles stabilized by bovine serum albumin and investigation of their electrochemical properties Ye. Khristunova, E. Korotkova, J. Barek and B. Kratochvíl P2-53 Voltammetric determination of synthetic food dyes at modified electrodes O.I. Lipskikh, E.I. Korotkova

48 10th International Conference on Instrumental Methods of

Analysis: Modern Trends and Applications

Thursday 21 September 2017

ORAL SESSION: Food Analysis 3 (MINOS II Hall, Chair: A. Spyros, G. Koulis) 900-940 Analytical chemistry of natural products PL15 A.C. Calokerinos 940-1000 Discrimination of olive varieties based on SNP genotyping and HRM analysis TH01 G. Polychronaki, A. Sofouli, G. Stathakarou, D. P. Kalogianni, C. Bazakos, T.K. Christopoulos and P. Kalaitzis 1000-1020 Development of immunoanalytical test-systems for the determination of salbutamol in food TH02 E.A. Zvereva, A.V. Zherdev, S.A. Eremin, B.B. Dzantiev 1020-1040 Migration of phthalates and di(2-ethylhexyl)adipate in foods packed in recycled paperboard TH03 I.E. Parigoridi, M. Zikos, K. Akrida-Demertzi and P.G. Demertzis 1040-1110 Coffee Break

PLENARY LECTURE (MINOS II Hall, Chair: B. Beckhoff, A. Bobrowski) 1110-1150 Acoustic sensors for molecular diagnostics and point-of-care PL16 E. Gizeli

ORAL SESSION: Sensors (MINOS II Hall, Chair: B. Beckhoff, A. Bobrowski) 1150-1210 Fabrication of amperometric xanthine biosensor based on ZnO nanoparticles- multiwalled carbon nanotubes-1,4-benzoquinone composite TH04 B. Dalkiran, C. Kacar, P.E. Erden, E. Kilic 1210-1230 Development of a reliable electrochemical sensor for pesticide on field detection TH05 I. Mazerie, C. Parat, S. Reynaud, E. Perez, A. ter Halle and I. Le Hecho

1230-1250 Electrochemical biosensor based on CoS-CNT nanocomposites for detection of Uric acid TH06 Z.O. Erdogan, I. Akin, S. Kucukkolbasi 1250-1310 Environmental analysis by bioindicator organisms: honeybees, mussels, algae, and bioluminescent bacteria TH07 S. Girotti, L. Bolelli, E. Ferri, G. Isani, N. Barile 1310-1330 The effect of various multiwalled carbon nanotubes on the performance of xanthine biosensors TH08 C. Kacar, B. Dalkiran, P.E. Erden, E. Kilic

1330-1400 Closing ceremony – Poster awards

Sunday 17 September 2017 MINOS II Hall Chair: S. Pergantis, M. Ochsenkühn-Petropoulou

Opening Session

10th International Conference on Instrumental Methods of

Sunday 17/9 Analysis: Modern Trends and Applications

Plenary lecture IMA - Twenty years of symposia

L. Ebdon

University of Bedfordshire, University Square, Luton, LU1 3JU, UK

In Plato's time a symposium was a convivial discussion with drinking, music and perhaps dancing. The twenty years of IMA have included elements of all these but the convivial discussion has developed into expert discussion by leading analytical scientists. The author will share some memories of IMA from the very beginning and consider on how the PL01 conference has reflected the advances made in instrumental methods of analysis and responded to the challenge of the transition from the 'age of materials' to the 'age of the genome.'

Plenary lecture Myths, mysticism and science during the development of chemistry and analytical chemistry from the ancient times to the middle of the 20th century

M.I. Karayannis

Department of Chemistry, University of Ioannina, Dourouti, 45100 Ioannina, Greece

PL02 E-Mail: [email protected]

The history of chemistry and the significant steps of the evolution of analytical chemistry will be highlighted. In chronological time spans, covering the ancient world, the Hellenistic and Roman Empire ages, the middle Ages to the first decades of the 20th century, the progress of chemistry will be presented. Though modern chemistry and analytical chemistry, as we know it today, began with the Chemical Revolution of the 18th century, chemical processes were in use long before that. Already from the epoch of Homer there are references in his poems, Odyssey and Iliad, to processes nowadays closely associated with chemistry. The roots of chemistry as a science are deep starting with pre-Socratic philosophers Heraclitus and Embedocles, who established the concept of existence of the principall elements, fire, air, water, and earth, named roots («ρίζες»). Leucippus and Demokritus, proposed the first theories for the nature of matter and atomism. Aristotle added the fifth element of aether, whereas Plato gave shapes to all atoms through his platonic solids and used for the first time the word “στοιχείον” (stoicheion = element) to describe them. During the Hellenistic era and up to the 4th century AD, a great number of philosophers and experimentalists studied particular materials and processes. The Arab conquerors of Egypt (639–642 AD) made use of this ancient knowledge, and contributed greatly to the newborn “science”, the Alchemy. During the Byzantine Empire the famous ‘‘υγρόν πύρ’’ (hygron pyr = liquid fire, Greek fire) was known as the unbeatable incendiary weapon of Byzantines. The Alchemists followed the Aristotelian ideas but considered also the three primary elements of matter (tria prima): mercury, sulphur and salt. In the Middle Ages, the alchemists searched relentlessly for the philosopher's stone, but also a major component of the elixir of life (Arabic al + iksir = the stone, "stone of knowledge", Greek "ξηρίον" ). During the Renaissance time, Paracelsus (1493-1541), was the precursor of medical chemistry. The phlogiston theory, was developed by J.J. Becher (1635–1682) late in the 17th century and was extended and popularized by G.E. Stahl (1659–1734). This theory dominated for many decades until it collapsed by Antoine-Laurent Lavoisier. The excellent contributions of the scientist who worked for the development of chemistry and analytical chemistry, during the 19th to the first decades of the 20th centuries will be also highlighted.

References 1. J.A.R. Newlands, Chem. News 12 (1865) 83 2. S.A. Arrhenius, Z. Phys. Chem. I (1887) 631 3. I. M . Tsangaris: PARADOSI, A’3, July-September 1992 4. M. I. Karayannis, C. E. Efstathiou, Anal Bioanal Chem, 400:3181-3185, 2011 5. M. I. Karayannis, C. E. Efstathiou, Talanta, 102:7-15, 2012.

54 10th International Conference on Instrumental Methods of

Sunday 17/9 Analysis: Modern Trends and Applications

Plenary lecture The study of environmental and cultural heritage via analytical chemistry combined with other scientific fields

J.A. Stratis

Analytical Chemistry Laboratory, School of Chemistry, Faculty of Sciences, Aristotle University, 54124 Thessaloniki, Greece; Present Address: K.Karamanli 49, 57010 Greece

E-mail: [email protected] PL03 Cultural and Environment Heritage are connected with our everyday life. UNEP has a common emblem for Environmental and Cultural Heritage protection and actually the same methodology and techniques are used for their study. Analytical Chemistry provides several data that contribute to the creation a “fingerprint” for all archaeological findings. The more the data, the more completed the “fingerprint” is. Main and secondary constituents are associated with the production patterns and raw materials used for various artifacts, while trace elements are more closely related to the origin and the trade routes used for both raw materials and artifacts. This presentation will focus on the ability of Analytical Chemistry to investigate Archaeological issues and provide answers to both archaeologists and conservators of art objects. The combination of Analytical Chemistry with other scientific fields, such as Mathematics, Mineralogy, Physical Chemistry etc., gives a powerful tool for the holistic study to Environmental and Cultural heritage. The study of materials of which our cultural heritage is built, but also the changes that it has undergone over the centuries from the effect of environmental and anthropogenic factors, as well as the investigation of the mechanisms of deterioration and degradation of monuments, can be thoroughly researched with the contribution of Analytical chemistry in conjunction with Mathematics, Physical, mineralogy etc. The composition of construction materials, characterization of weathering products and the investigation of the deterioration mechanisms are the key pillars in the study and protection of cultural heritage. A number of examples from our work dealing with Cultural heritage studies and Environmental protection studies are given as well as the opinion about the curriculum for the corresponding studies.

References [1] Ariadne Kostomitsopoulou-Marketou et al. “A Unique Colours’ Workshop in the Ancient Aegean World: Physicochemical Characterisation of the iron-containing pigments found at the site”, Technart Conference, Bilbao 2017 [2] J.A. Stratis, G. A. Zachariadis, V. D. Simeonov, “Classification of Macedonean early bronze age ceramics using various chemical and technological feature” Fresenius J Anal. Chem (1995), 351: 697- 699. [3] J. A. Stratis et al. “Chemometrrical classification of biomonitoring Analytical Data for Heavy metals Part I Trees (leaves) as bioindicators”, Toxicological and Environmental Chemistry, 54: 29-37. [4] J. F. van Staden, Miltiades I. Karayannis, Ioannis Stratis, “3rd International Conference on Instrumental Methods of Analysis: Modern Trends and Applications, 23–27 September 2003, Thessaloniki, Greece”, Anal Bioanal Chem (2004) 379: 750–753 [5] Abu Bakr Moussa, N. Kantiranis, K. S. Voudouris, J. A. Stratis, M. F. Ali, V. Christaras “Diagnosis of weathered Coptic wall paintings in the Wadi El Natrun region, Egypt”, Journal of Cultural Heritage 10 (2009) 152e157

Monday 18 September 2017 MINOS II Hall Chair: L. Ebdon, R. Lobinski

Analytical Instrumentation and Techniques

10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Plenary lecture A highly versatile source for elemental, speciation, and metallomic analysis

G.M. Hieftje1, A.J. Schwartz1 and J.T. Shelley2

1Dept. of Chemistry, Indiana University, Bloomington, IN 47401 2Present address: Dept. of Chemistry & Chemical Biology, Rensselaer Polytechnic Institute, Troy, NY 12180

E-mail: [email protected] PL04

The solution-cathode glow discharge (SCGD) was developed as an alternative to the inductively coupled plasma (ICP) for emission-based elemental analysis. In this mode, the SCGD provided detection limits that rivalled those of the ICP. However, it operated on low dc power (~70W), required no gas supply, nebulizer, or spray chamber, and yielded simpler emission spectra, so smaller spectrometers could be employed. For some elements, particularly the alkali metals, the SCGD produced detection limits that were as much as 100- fold better than the ICP. Given this success, recent efforts have been made to explore the use of the SCGD as an ion source for mass spectrometry. Initial findings were disappointing: elemental detection limits were several orders of magnitude poorer than those from the ICP. However, it was then discovered that the “hardness” of the SCGD ion source could be tuned just be adjusting its power input, particularly the operating current. At higher currents, the SCGD caused greater fragmentation of molecules introduced into it, enabling the molecular structure or speciation to be deduced. In contrast, lower operating currents yielded the molecular ion, thereby simplifying identification. When fed with a biomolecule, specifically a polypeptide, the SCGD generated a mass spectrum from which the amino-acid sequence could be immediately deduced. Clearly, the SCGD holds significant promise as a powerful, versatile source for elemental, speciation, molecular, biomolecular and metallomic characterization. Additional recent results with the SCGD will be provided.

Signal reversing cavity-based polarimetry: Evanescent-wave and ambient chiral sensing

D. Sofikitis1,2, G.E. Katsoprinakis1,2, A.K. Spiliotis1,2, B. Loppinet1, T.P. Rakitzis1,2

1Institute of Electronic Structure and Laser, Foundation for Research and Technology - Hellas, 71110 Heraklion, Greece 2Department of Physics, University of Crete, 71003 Heraklion, Greece

E-mail: [email protected] MO01 Chirality is a fundamental property of life, and sensing and analysis is very important in various scientific fields such as biology, chemistry, and medicine, as well as in the pharmaceutical, chemical, cosmetic, and food industries. The most widely used chiral sensing techniques are optical rotary dispersion (ORD) and circular dichroism (CD). However, ORD and CD signals are typically very small and are limited by spurious birefringence and poor background subtraction procedures, which place severe constraints on detection sensitivity and time resolution. Recently, our group has introduced a new cavity-based [1,2], which overcomes all these problems. The OR signals are enhanced by a factor on the order of the number of cavity passes. The signal reversals incorporated in this method allow chiral measurements without the need for background subtraction. Additionally, the noise suppression resulting from these reversals allows the measurement of relatively small OR in the presence of large birefringence.

Fig. 1 a) Experimental set-up, showing the optical cavity, magneto-optic element (TGG) and the two counter-propagating modes b) Chiral and Faraday rotation in the light frame (up) and in the light frame (down).

The experimental set-up is similar to the one shown in Figure 1.a. The optical cavity has a bowtie configuration, which supports two distinct, counter-propagating modes. The different symmetry of the polarization rotation caused by either the chiral sample or the magneto-optic element is shown in Figure 1.b. Subtracting those angles for the two counter-propagating modes and reversing the direction of the magnetic field provides the signal reversals. This cavity-based technique improves chiral sensitivity limits while opening the way for new applications, which include measurements of human body fluids, studies of surface chirality and biomolecule interfacial processes, studies of vibrational circular dichroism (VCD) of biomolecules and more. Additionally, the ability to perform chiral detection without the need for background subtraction allows the in situ chiral measurements, such as chiral forest emissions. Finally, further improvement of the sensitivity of the technique might allow studies of parity violation of the weak force [3].

References [1] D. Sofikitis et al Nature 514 (2014) 76 [2] L. Bougas et al J. Chem. Phys. 143 (2015) 104202 [3] L. Bougas et al Phys. Rev. Lett. 108 (2012) 210801

60 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

LIBS-SSI-MS: A new technique for the characterization of metal containing biomolecules and complexes

K. Marmatakis1,2, S.A. Pergantis1 and D. Anglos1,2

1 Department of Chemistry, University of Crete, PO Box 2208, GR 710 03 Heraklion, Crete, Greece 2 Institute of Electronic Structure and Laser, Foundation for Research and Technology - Hellas (IESL- FORTH), P.O Box 1385, GR 711 10 Heraklion, Crete, Greece

E-mail: [email protected], [email protected]

The combination of laser-induced breakdown spectroscopy (LIBS) with sonic-spray ionization MO02 mass spectrometry has lead to the development a new hybrid tool for performing fast speciation analysis measurements. The hybrid technique (LIBS-SSI-MS) offers the ability to simultaneously acquire information about elemental composition, relative molecular mass and structure of the analyzed compounds. This approach have several advantages arising from the analytical figures of merit of each technique, such as short analysis times and reduced analysis cost, compared to the most used approaches that require the use of a combination of liquid chromatography with electrospray or inductively coupled plasma mass spectrometry. The combination of the LIBS and SSI-MS techniques is achieved via a single pneumatic nebulizer. The aerosol, typically produced from a water-methanol solution containing various metal complexes and metalloproteins, is fed into the inlet of the mass spectrometer at a constant flow, 15-20 μL/min, and mass spectra are collected. During this process the spray is simultaneously interrogated, at a repetition rate of 5-10 Hz, by pulses from a nanosecond laser (Nd:YAG, λ = 1064 nm) that give rise to the formation of strongly emitting plasma, off of which time-resolved LIBS spectra are recorded1. Spatial constraints are dealt with by a custom designed, compact optical setup, which enables tight focusing of the laser beam in the space between the nebulizer tip and the MS inlet along with efficient collection of the plasma plume emission. In the present study we describe the integration of the SSI-MS with LIBS into a hybrid system, its optimization and recent results from the simultaneous analysis of a several metal containing complexes and biomolecules. The effect of the ablation process on the detection of molecular ions and molecular ion clusters was also investigated and will be discussed here.

References 1. Marmatakis, K., Pergantis, S. A. & Anglos, D. Spectrochim. Acta Part B At. Spectrosc. 126, (2016) 103–109.

Environmental and food safety applications of tandem mass spectrometry using a novel flow-based design of ion optics

A. Bisi

PerkinElmer Viale dell’Innovazione 3 20126 Milano (It)

E-mail: [email protected]

The increased awareness of people of factors affecting the quality of their life is pushing the request of increased controls on environmental and food quality and safety; the number of MO03 analysis is growing year after year, more parameters must be controlled and cutoff concentration of target products is lowering. To speed-up the workflow, simplified sample preparation is preferred leading to lower cleanup and increased concentration of matrix injected with the need to increase the selectivity of analytical technique and tandem mass spectrometry can provide the required sensitivity and selectivity. In 2016 analytical instruments must provide increased sensitivity, better sample throughput and less down-time than in the past and this can be achieved through a novel ion optics design that makes the tandem mass spectrometer more sensitive and at the same time more rugged and less prone to matrix contamination. After a quick description of the novel flow-based design we’ll go through several applications on environmental and food contaminant like per-fluorinated compounds in water, pesticides and antibiotics in food.

62 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Determination of biothiols on paper-based analytical devices using the photoreduction of silver halide nanocrystals

F.A. Kappi1, G.Z. Tsogas1, D.C. Christodouleas2, A.G. Vlessidis1, D.L. Giokas1

1Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece 2Department of Chemistry, University of Massachusetts, Lowell, Massachusetts 01854, United States

E-mail: [email protected]

This study describes a new low-cost and fieldable method for the detection of the total MO04 concentration of biothiols that uses the heterogeneous reaction of silver chloride crystals with biothiols on paper-based analytical devices. The sensing method is based on the sensitizing effect of biothiols in the UV-mediated photoreduction of silver halide crystals and uses broadly-available imaging devices (e.g. smartophone cameras) or the bare eye as a detector. By appropriately regulating the experimental conditions and the properties of silver halide nanocrystals through Ostwald’s and coalescence ripening mechanisms, the devices can be tuned to exhibit high photosensitivity in the presence of biothiols and good stability under ambient working conditions (ambient light, temperature, humidity, etc). The applicability of the paper-based assay was evaluated in biological samples, such as urine and blood plasma, in two different applications: a) the determination of the total concentration of biothiols and b) determination of reduced/oxidized thiol ratios. In both applications the assay exhibited satisfactory analytical features in terms of sensitivity, selectivity, recoveries and reproducibility. The developed method uses inexpensive materials, lightweight and portable detectors and an analytical protocol that is easily executable with minimum technical expertise. Therefore, it could allow an affordable and fast screening of biothiol levels both in routine biochemical laboratories and resource-limited settings.

Monday 18 September 2017 PASIPHAE I Hall Chair: M. Ochsenkühn-Petropoulou, M. Tsapakis

Environmental Analysis

10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Three Candidate Certified Reference Materials for Environmental Analysis

A. İsleyen1, J. Vogl2, D. Nikolic3, A. Jotanovic4, T. Näykki5, N. Perkola5, M. Horvat6, A. Zoń7, E. Bulska8, M. Ochsenkuhn-Petropoulou9, S. Zühtü Can1, R. Jacimovic6, L. Gažević3, O. Cankur1, B. Arı1, M. Tunç1, B. Binici1, T. Gökçen1, Z. Çakılbahçe1, V. Lymberopoulou9

1TÜBİTAK UME-National Metrology Institute, Kocaeli, Turkey 2BAM-Federal Institute for Materials Research and Testing, Germany 3DMDM- Directorate of Measures and Precious Metals, Serbia MO05 4IMBIH- Institute of Metrology, Bosnia & Herzegovina 5SYKE-Finnish Environment Institute, Finland 6IJS-Institute Jozef Stefan, Slovenia 7GUM-Central Office of Measures, Poland 8UWAR-University of Warsaw, Poland 9NTUA-National Technical University of Athens, Greece

E-mail: [email protected]

Reliable analysis of chemical indicators in water and soil samples for the purpose of environmental pollution assessment poses one of the greatest analytical challenges, due to the complexity of sample matrix and low concentrations of pollutants. Organics (PFOS and PFOA) in ground water and heavy metals (Hg, Cd, Ni, Pb and As) in river water and soil represent main target parameters for the three candidate certified reference materials (CRMs). Laboratories performing sampling and tests in this field regulated by respective EU directives [1], need matrix CRMs enabling appropriate quality control. NMIs and DIs with proven metrological capabilities for the production and certification of such materials are necessary for the provision of quality data. Our project [2] is aiming to develop capacity to produce CRMs for environmental analysis by transferring the theoretical and practical know-how between the partners and combining their skills to focus on environmental CRM production according to ISO 17034 [3]. Raw materials were collected from locations in Turkey to ensure representation of the samples that laboratories are routinely analysing. River water was collected from a creek which is feeding a reservoir supplying water to İstanbul. Soil was collected from a coal burning power plant area at the district of Ankara. Ground water was collected from a well operating in İstanbul supplying water for the swimming pools and irrigation of gardens. After bottling, all CRM candidates were gamma sterilised to further enhance their stability and extend their shelf-lives. In this presentation, results of the homogeneity and stability tests will be shared with details of the material processing of candidate CRMs. Information about the characterization studies utilizing primary measurement techniques for the certification will also be presented.

References [1] Water Framework Directive 2008/105/EC – Annex II: Priority substances and other pollutants http://ec.europa.eu/environment/water/water-framework/priority_substances.htm [2] This project is funded by EMPIR which is co-funded by the EU’s Horizon 2020 research and innovation programme and the EMPIR Participating States. For more information please visit http://www.envcrm.com [3] International Organization for Standardization, ISO 17034, General requirements for the competence of reference material producers, ISO, Geneva (2015).

Validation of methods for determination of specific elements in environmental samples using Microwave Plasma Atomic Emission Spectrometry (MP-AES)

A. Jotanović, D. Ćorić

Institute of Metrology of Bosnia and Herzegovina

E-mail: [email protected]

MO06 In the framework of EMPIR project “14RPT03 - Matrix reference materials for environmental analysis (ENVCRM)” an inter-comparison studies between the partners will be organized in order to produce and characterise the candidate reference material for river water sample and soil sample. The analytes of interest are: As, Cd, Hg, Ni and Pb, as mandatory elements, and Se, as optional elements (for river water) and As, Cd, Co, Cr Cu, Fe, Hg, Mn, Ni, Pb Sb, V and Zn (for soil). The overall target expanded uncertainties for certified values are in the range of 10 to 15%. Production process of certified reference materials includes good manufacturing practices for processing materials, analytical method development and validation for homogeneity, stability and characterisation tests, characterisation of selected analytes together with additional information about matrix constituents, calculation of individual uncertainties (between units inhomogeneity, long term stability, characterisation) and combination of uncertainties to determine overall uncertainty of matrix reference materials. The Agilent 4200 MP-AES (Microwave Plasma – Atomic Emission Spectrometer) is one of analytical techniques used for characterisation of above mentioned metals in river water sample and soil sample. The 4200 MP-AES is a fast sequential multi-element system that uses nitrogen to sustain plasma, extracted from the ambient air (using a nitrogen generator). The addition of the MSIS (Multimode Sample Introduction System) accessory is used for production of hydride species which are separated from liquid and introduced to plasma, delivering better performance and lower detection limits than with conventional nebulization. This paper presents development and validation of methods for chemical analysis of analytes of interest.

References [1] Application of Microwave Plasma Atomic Emission Spectrometry (MP-AES) for environmental monitoring of industrially contaminated sites in Hyderabad City; C.T. Kamala, V. Balaram, V. Dharmendra, M. Satyanarayanan, K.S.V. Subramanyam, A. Krishnaiah; Springer, Environ Monit Assess, 186 (2014) 7097–7113 [2] Microwave Plasma Atomic Emission Spectrometry (MP-AES) using Hydride-generation techniques for the determination of specific elements in mineral water; I. Mikheev, T. Samarina, D. Volkov, M. Proskurnin; Russian Scientific Foundation, grant no 14-23-00012.

68 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Towards new reference methods for the accurate determination of PM2.5(10) in ambient air based on the generation of synthetic ambient aerosols

K. Vasilatou

Federal Institute of Metrology METAS, Sector of Analytical Chemistry, Lindenweg 50, 3003 Switzerland

E-mail: [email protected] MO07 Atmospheric pollution by airborne particles significantly contributes to climate change and has been linked to respiratory and cardiovascular diseases and lung cancer [1]. It has been estimated that in Europe alone more than 500,000 deaths per year can be attributed to PM (Particulate Matter) exposure, whereas pollution hot spots of PM are responsible for a loss in life expectancy of up to 12 to 36 months [1]. For EU member states, air quality monitoring - as laid down in the Air Quality Directive 2008/50/EC [2] – is mandatory and comprises quantification of airborne particles and their components. The most important metric to monitor particulate air pollution is the mass concentration, or more specifically the total mass per unit volume of air of particles with an aerodynamic diameter smaller than 10 μm or 2.5 μm, commonly referred to as PM10 and PM2.5; the ambient limit values of which are established in Europe and the USA. Ambient PM is not uniform with respect to chemical composition, particle sizes and shapes. In most cases, it does not refer to a single pollutant with a distinct chemical signature, such as carbon or nitrogen oxides, but rather to a highly variable mixture of combustion particles, salts, metal oxides, organic substances and other materials. Therefore, a suitable standard calibration aerosol does not currently exist. To date, automated PM-measuring instruments are tested for equivalence with the manual gravimetric reference method in monitoring sites using real ambient air [3]. However, this requires long and expensive testing campaigns at multiple sites during different times of the year to compensate for the variability of the meteorological conditions and the temporal and spatial variations of the ambient air composition. This presentation will outline current efforts being made within the EMPIR-Project “Aeromet” towards the generation of reference synthetic aerosols that mimic the properties of ambient air. To this end, an aerosol mixing chamber is currently being designed based on numerical simulations for the homogenisation of primary aerosol components and its operation will be validated with dedicated physicochemical analysis of the produced aerosols. The ultimate goal is to develop new highly innovative facilities for the lab-based calibration of automated PM- measuring instruments under controlled conditions and with the use of stable, well- characterised reference aerosols.

References [1] S. Fuzzi et al., Atmos. Chem. Phys, 15 (2015) 8217-8299. [2] 2008/50/EC Directive: http://ec.europa.eu/environment/air/quality/legislation/directive.htm [3] Guidance to the demonstration of equivalence of ambient air monitoring methods (January 2010) http://ec.europa.eu/environment/air/quality/legislation/assessment.htm

Particulate matter emissions from combustion of different types of biomass

A. Zosima and M. Ochsenkühn-Petropoulou

Laboratory of Inorganic and Analytical Chemistry, School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou 9, 15773, Athens, GR

E-mail: [email protected]

Biomass is considered to be a "CO2 neutral" fuel, with social-economic and environmental MO08 benefits. However, biomass and specifically wood pellets are responsible for air pollution that includes levels of particulate matter (PM), carbon monoxide (CO), volatile organic compounds (VOC) such as polycyclic aromatic hydrocarbons (PAHs), elemental carbon (ΕC), organic carbon (ΟC), and emissions of heavy metals and toxic elements that are found adsorbed to particulate matter emissions [1]. The aim of this study was to explore various factors leading to PM emissions from burning of various types of biomass used in heating devices. Eight types of biomass, commercially available the last years in Greece for domestic heating, were investigated such as: “mix pine- beech-oak”, “mix spruce-pine-oak”, “100% spruce”, “100% beech”, “olive pellets”, “pellets from the olive core”, “briquettes” and common “wood oak”. Wood fuel quality, the amount of fuel and the airflow setting are the main parameters that can influence PM emissions and which were examined. Olive pellet was discussed among other types of biomass, is a new biofuel made from natural wood raw materials without impurities and respond to the demand for cheap and clean, domestic energy. A lab-scale device was used in order to simulate the combustion process using a tube furnace providing it with different oxygen flows and a filter holder system to collect directly their PM emissions. Then, real combustion tests were carried out in domestic top-feed, pellet-fired stoves and in an open fireplace as well [2]. Determination of particle size distribution of particles with a scanning electron microscope (SEM) was followed. Measurements were made as to the various forms of carbon (TC, EC, OC, CC) as well as PAHs by gas chromatography - mass spectrometry (GC-MS). Metals adsorbed on PM particles, were determined after appropriate treatment as follows: Fe, Mg, Zn, Al, Ba, Cu, Cd by inductively coupled plasma - optical emission spectrometry (ICP-OES), Cr, Mn, Co, Ni, As, Hg, Pb by inductively coupled plasma - mass spectrometry (ICP-MS) and Ca, Na, K by atomic absorption spectrometry (AAS). Some of them such as arsenic, mercury, cadmium, nickel and lead are highly toxic and thus harmful to human health, even at trace concentrations, due to the long-term exposure of population. A statistical analysis of the database was followed that result conclusions as to the common origin of the emission of pollutants and their correlation.

[1] C. Schmidl, M. Luisser, E. Padouvas, L. Lasselsberger, M. Rzaca, C. Ramirez-Santa Cruz, M. Handler, G. Peng, H. Bauer, H. Puxbaum, Atmospheric Environment, 45 (2011) 7443-7454. [2] A. Zosima, L.A. Tsakanika and M. OchsenkühnPetropoulou, Journal of Environmental Science and Health, Part A, 52 (2017) 497-506.

Acknowledgements The work was funded by “IKY FELLOWSHIPS OF EXCELLENCE FOR POSTGRADUATE STUDIES IN GREECE – SIEMENS PROGRAM”.

Monday 18 September 2017 MINOS II Hall Chair: B. Michalke, S. Pergantis

Developments in ICP-MS

10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Plenary lecture Method development for metal detection at cellular levels

N. Jakubowski1, H. Traub1, A. Jutta Herrmann1,2, K. Löhr1, A. López-Serrano Oliver1, J. Kneipp2, L. Mueller3

1 Bundesanstalt für Materailforschung und -prüfung (BAM), Berlin, Germany 2 Humboldt University Berlin, Germany 3 Thermo Fisher Scientific, Bremen, Germany;

E-mail: [email protected] PL05

An overview about different analytical approaches will be presented for detection of metals in individual biological cells by use of ICP-MS. For this purpose, we are using different sample introduction systems for ICP-MS for detection, imaging and quantification of metals at cellular levels. By use of laser ablation, we have studied the up-take by and distribution of metallic nanoparticles (Ag, Au) in single adherent cells (fibroblast cell line) [1]. Recently, we have developed staining techniques to image the protein (by a lanthanide containing chelate) and DNA (by an Ir-containing intercalator) distribution in single cells which can be combined withnanoparticle studies [2]. Additionally, we have developed an immunoassay by use of metal-tagged antibodies to identify the cell status of individual cells [3]. Using pneumatic nebulization or microdroplet generation [4], we have also studied the up-take of nanoparticles and toxic metals as well as essential elements in single suspension cells using different ICP-MS mass spectrometric concepts (sector field instrument, triple-quad instrument, time of flight (CyTOF) instrument). For this purpose, the ICP-MS was operated in single particle mode. First results of single cell ICP-MS (scICP-MS) will be presented for uptake of metallic (Ag) nanoparticles by THP 1 and macrophage cells and the strength of the different instruments will be discussed. Finally, the weaknesses and strength of imaging and scICP-MS detection mode will be critically discussed.

References [1] L. Mueller, H. Traub, N. Jakubowski, D. Drescher, J. Kneipp, V. I. Baranov, Trends in Single Cell Analysis by ICP-MS, (2014) Anal. Bioanal. Chem. 406, 6963-6977, DOI 10.1007/s00216-014-8143-7 [2] A. J. Herrmann, S. Techritz, N. Jakubowski, A. Haase, A. Luch, U. Panne, L. Mueller, A simple metal staining procedure for identification and visualization of single cells by element microscopy based LA-ICP-MS, The Analyst, 2017 (in press) [3] L. Mueller, A. J. Herrmann, S. Techritz, U. Panne, N. Jakubowski, Quantitative characterization of single cells by use of immunocytochemistry combined with multiplex LA-ICP-MS (2017) Anal. Bioanal. Chem. 409, 3667–3676, DOI 10.1007/s00216-017-0310-1 [4] K. Shigeta, H. Traub, E. Rampler, G. Koellensperger, U. Panne, L. Rottmann, N. Jakubowski, U. Panne, Sample introduction of single selenized yeast cells (Saccharomyces cerevisiae) by micro droplet generation into ICP-Sector Field Mass Spectrometer for label free detection of trace elements, (2013) J. Anal. At. Spectrom. 28, 637-645

sp-ICP-MS for determining/characterizing silver nanoparticles in seafood after ultrasound assisted enzymatic hydrolysis procedures

M. Vanesa Taboada-López, N. Alonso-Seijo, P. Herbello-Hermelo, P. Bermejo- Barrera, A. Moreda-Piñeiro

Group of Trace Elements, Spectroscopy and Speciation (GETEE), Health Research Institute of Santiago de Compostela (IDIS). Department of Analytical Chemistry, Nutrition and Bromatology. Faculty of Chemistry. University of Santiago de Compostela. Avenida das Ciencias, s/n. 15782- Santiago de Compostela, Spain MO09 E-mail: [email protected]

The remarkable increase in the preparation and use of engineered nanomaterials implies the presence of nanomaterials in the environment [1]. Silver nanoparticles (Ag NPs) are hugely used due to their antimicrobial, antifungal and antibacterial activities. In addition, they have remarkable physico-chemical properties, such as high electrical and thermal conductivity, chemical stability, catalytic activity and non-linear optical behavior. They are used in inks, microelectronics, medical imaging and consumer products, as food and textiles [2]. The potential risks of NPs on human health and the environment is still unknown and there is a need to develop analytical methods for their determination and characterization in complex matrix [3]. Traditionally, the extraction of the nanoparticles is made by incubation with an enzyme solution at 37ºC during 12 hours. In this communication, an ultrasound assisted enzymatic hydrolysis procedure has been proposed for a fast isolation of Ag NPs from seafood before sp- ICP-MS measurements. The measurements are performed using a dwell time 50 ms. Optimum extraction conditions imply ultrasonication (80% amplitude) for 10 min with 2 mg L-1/2 mg L- 1 pancreatine: lipase. The developed method was found to be repeatable (repeatability of 7.6% for the over-all procedure). Several bivalve mollusks (clams, cockles, and razor shell) were analyzed for total silver content (ICP-MS after microwave assisted acid digestion), and for Ag NPs by the proposed method.

References [1] A. López, R. Muñoz, J. Sanz, C. Cámara. Anal Methods, 6 (2014) 38-56. [2] Q. H. Tran, V. Q. Nguyen, A-T. Le. Adv Nat Sci: Nanosci. Nanotechnol, 4 (2013) 1-20. [3] S. Arora, J. Jain, J. Rajwade, K. Paknikar. Toxicol Appl Pharmacol, 258 (2012) 151-165.

74 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Particulate and Dissolved Elements in Antarctic Ice Cores: Detection with a New Generation ICP-MS and Single Particle (SP) Software

G. Baccolo1,2,3, M. Clemenza3,4, B. Delmonte2, R. Magarini5

1Earth Science Department, University of Siena, Italy 2Environmental Sciences Department, University of Milano-Bicocca, Italy 3INFN-MIB, Italy 4Physics Department, University of Milano-Bicocca, Italy 5PerkinElmer - Milano, Italy MO10

e-mail: [email protected]

Several natural archives can be used for reconstruction of past climates and environment, among them the ice cores play a key role. The chemical and physical analyses of the ice and ice contained materials offer valuable information on several climatic and environmental parameters over the last hundreds thousands years. Elemental analysis is one of the important tools in dealing with ice cores. It provides detailed multi-elemental records that allow evaluation of past volcanic activities, changes in atmospheric circulation and biogeochemical cycles. Focusing on recent periods, elemental analysis is extremely useful for assessing the impacts of anthropic activities on remote areas such as Antarctica or Greenland. And the determination of soluble and insoluble elemental fractions is useful to distinguish the contribution due to atmospheric mineral dusts (insoluble fraction) from the soluble one, associated with snow precipitations. These soluble and insoluble elemental fractions are obtained in a single determination by using an advanced ICP-MS spectrometer and a specific Single Particle (SP) software. The combination allows to determine the particle size, size distribution and elemental content of insoluble particles, together with the concentration of concomitant dissolved fractions. A reaction cell (DRC) has also been used to eliminate /reduce spectral interferences on some isotopes, allowing to obtain better accuracy and LODs. This study presents preliminary results on the simultaneous determination of soluble and insoluble content of selected elements (Al, Si, Ca and Fe) in ice samples collected from an Antarctic ice core. The analysed samples cover different climatic periods, ranging from few thousand years ago (Holocene) to more than 20k years ago (last glacial period).

ICPMS measurement of potassium traces in NaI for dark matter search

I. Dafinei1, M. L. di Vacri2, S. Nisi2

1 INFN-Sezione di Roma 1,Piazzale Aldo Moro 2-00185-Roma, Italy 2 INFN-Laboratorio Nazionale del Gran Sasso-, Via G. Acitelli, 22-67100 Assergi, (AQ) Italy

E-mail: [email protected]

MO11 The search for a direct evidence of dark matter is among the most exciting challenges of the modern physics. Some experiments around the world are using [1][2] or developing [3][4] NaI crystal based detectors, which is a promising material for this studies. A fundamental aspect for dark matter searching experiments is the radio-purity of the materials used for the construction of the detector, since the experimental sensitivity is strongly affected by the radioactivity background. The possibility to quantify natural radionuclides (Th, U and K) with the best available sensitivity is thus a fundamental aspect for the selection of materials during the design and construction of such experiments. Due to the chemical affinity between sodium and potassium, the most critical radionuclide contaminant for NaI based detectors is potassium, whose background budget is 10-8 g/g [4]. Although the inductively coupled plasma mass spectrometry (ICP-MS) still remains the fastest and most sensitive technique for trace element analysis, the measurement of potassium by ICP- MS is strongly limited by isobaric interferences of polyatomic species formed from argon, which is the plasma gas. It is therefore difficult to reach very low detection limit for this element with ICP MS in standard conditions. Another important issue related to ICP-MS quantification of potassium traces arises from the background. This element is indeed widely present in the environment and the risk of contamination during sample preparation and measurement is quite high. In this work, an analytical method developed for quantification of potassium traces in NaI by ICP-MS will be reported. The method involves an ultra-clean sample dissolution procedure, the use of a high resolution mass spectrometer (HR ICP MS) specifically tuned for this application and a calibration method to account for high salt matrix concentrations. A detection limit of 10-9 g/g K in NaI were obtained. This result represents an important achievement for all dark matter experiments using NaI detectors, since it will allow a robust and reliable potassium assay during all stages of crystal production, ensuring the possibility to obtain detectors with the required levels of radiopurity.

Acknowledgements This work was made with the contribution of the Ministry of Education, Universities and Research of the Italian Republic, MAECI-PGR04136

References [1] J. Amaré et al, Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 742 (2014) 187-190. [2] R. Bernabei et al, Nuclear Instruments and Methods in Physics Research A, vol.592, n 3, 2008, p.297 [3] K.W. Kim et al, Astroparticle Physics, 62 (2015) 249-257. [4] E. Shields, J. Xu and F. Calaprice, Physics Procedia, 61 (2015) 169-178. .

76 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Effects of silver nanoparticle exposure at the ng L-1 level on marine microbial plankton dynamics

A. Tsiola1,2, P. Pitta2, M. Kagiorgi2, I. Kalantzi2, K. Mylona2,3, S. Psarra2, I. Santi1,2, C. Toncelli2,3, S. Pergantis3, M. Tsapakis2

1University of Crete, Department of Biology 2Hellenic Centre for Marine Research, Institute of Oceanography 3 University of Crete, Department of Chemistry

E-mail: [email protected] MO12

Natural marine planktonic communities were exposed to silver nanoparticles (AgNPs) at the ng L-1 level within the frame of 3 microcosm and 1 mesocosm experiments. Seawater was collected from a coastal site in the Eastern Mediterranean Sea and was used to fill 10-L tanks. Different coating agents (branched-polyethyleneimine: BPEI vs. poly-vinylpyrrolidone: PVP), sizes (40 vs. 60 nm) and concentrations (200, 500, 2000, 5000, 10.000 ng Ag L-1) of AgNPs were tested and the effects on bacteria and micro-plankton were evaluated at 24, 48 and 72 incubation hours. Seawater from the same site was later used to fill 1-m3 mesocosm tanks to test the potential impact of environmentally relevant AgNPs concentration (stepwise addition of 1000 ng Ag L-1 final concentration) on nano-, pico- and micro- plankton. All experiments were run in triplicates (including control incubations) and samples were analyzed with a recently developed flow injection on-line dilution single particle inductively coupled plasma mass spectrometry (ICP-MS) method [1]. The results of the microcosm experiments showed that dissolution was the predominant process of AgNP transformation, with its rate being related to the type and thickness of the nanoparticle. Indeed, PVP dissolved faster and caused higher toxicity than BPEI AgNPs, as indicated by chlorophyll a concentration. A size- dependent toxicity was seen for BPEI AgNPs, with 40 being more toxic than 60 nm. A significant and negative effect was also seen on cyanobacterial abundance, which decreased upon exposure at 200-10.000 ng Ag L-1 concentration. Moreover, the dinoflagellate community composition changed at exposure concentration of 2000 ng Ag L-1. The effects on cyanobacteria and dinoflagellates were seen again in a large-scale mesocosm experiment, confirming the sensitivity of these planktonic organisms. Viral and bacterial genomes, pico- and nano- plankton, the production of reactive oxygen species and the concentration of dissolved and particulate nutrients were also analyzed in the mesocosms but were not affected by AgNP treatment. Similarly to the microcosms, AgNP dissolution was the predominant transformation process. Formation of an extra peak at low AgNP range in size distribution profiles at higher exposure times has been indirectly confirmed by the mass balance between total dissolved silver determined by ICP-MS and the calculated dissolved silver as a result of the decreased average size at higher exposure times.

References [1] C. Toncelli, K. Mylona, M. Tsapakis, and S. A. Pergantis. J Anal At Spectrom. 31 (2016): 1430- 1439.

Monday 18 September 2017 PASIPHAE I Hall Chair: A. Jotanovic, M. Kanakidou

Food Analysis 1

10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Development of liquid extraction surface analysis mass spectrometry for rapid screening for the presence of post- polymerization residues in food packaging materials

A. Issart, S. Godin, H. Preudhomme, K. Bierla, A. Allal and J. Szpunar

IPREM- UMR 5254 CNRS- UPPA – Université de Pau et des Pays de l’Adour – Hélioparc – 2av. du president Angot 64053 Pau Cedex, France.

E-mail: [email protected] MO13 In the food industry, packaging plays a fundamental role as it protects the products from the environment and enhances its shelf life. Nevertheless, it could be harmful for the consumer; as it is processed at very high temperature severe degradations of the polymer and its additives may occur, producing molecules small enough to migrate to the food, residues, pollution and odour [1]. Analyses carried out by mass spectrometry in frame of this study confirmed that point: molecules from the plastic packaging have been found in ham fat. Hence, it is essential to find accurate, fast and easy to set up screening methods able to analyse polymer food packaging. So far, analyses have been done after multi-step batch extraction of the analytes but this process often gives incomplete recoveries, may degrade the analytes and is time consuming. A novel method based on liquid extraction surface analysis mass spectrometry (LESA- MS, Figure 1) was developed allowing the analysis of the migrating species directly from a polymer film. The proposed procedure is fast, environmentally friendly and efficient for the surface analysis of polymers. The use of different solvents has been tested in order to check the possibility of extracting specifically some species. No sample preparation is needed, the extraction of the analytes requires only a small volume of solvent and the results are reproducible. The method was validated by a comparison to “classic” in bulk mass spectrometry and an ambient ionisation DART (Direct Analysis in Real Time) MS proving its suitability for rapid screening for the presence of Figure 1. LESA-MS principle [2]. post-polymerization residues in food packaging materials.

References [1] Marcato B. et al., Migration of antioxidant additives from various polyolefinic plastics into oleaginious vehicles. International Journal of Pharmaceutics, 2003. 257(1-2) 217-225. [2] M.R.L. Paine, P.J. Barker, S.J. Blanksby, Ambiant ionisation mass spectrometry for the characterisation of polymers and polymers additives: A review. Analytica Chimica Acta, 2014, 808 70- 82

Food quality control and authentication using NMR spectroscopy and metabolomics

A. Spyros, M. Amargianitaki, E. Ralli, M. Misiak and P. Dais

NMR Laboratory, Department of Chemistry, University of Crete, 70013 Heraklion Crete, Greece

E-mail: [email protected]

During the last few decades the powerful analytical capabilities of NMR spectroscopy have transformed it to indispensable tool in modern food analysis [1]. Apart from the qualitative MO14 and quantitative chemical profiling of food ingredients, which is important from a nutritional and quality control point of view, NMR spectroscopy has found increased application by providing spectroscopic input data for multivariate statistical analysis techniques that can be employed to study a broad range of food analysis problems, including authenticity, protected denomination of origin (PDO), adulteration, sensory evaluation, etc. [2]. In this contribution we will present some applications of NMR metabolomics studies currently in progress in our laboratory, including the metabolic profiling, authentication, quality control and sensory evaluation of some foods of special importance for the local Cretan island economy (wine, graviera cheese, honey).

Authentication of Cretan PDO graviera cheese using an untargeted OPLS-DA model based on the 1H NMR spectra of polar and non-polar graviera extracts

References [1] A. Spyros, P. Dais, NMR spectroscopy in food analysis, RSC Publishing, Cambridge UK, (2013). [2] L. Mannina, A. P. Sobolev, S. Viel, Progr. NMR Spectr. 66 (2012) 1-39.

82 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Metabolic fingerprinting based on high-resolution orbitrap mass spectrometry for wine authentication

G. Kaklamanos1, A. Maquet1, E. Aries1, V. Exarchou1 and F. Ulberth1

1European Commission, Joint Research Centre, Directorate F – Health, Consumers and Reference Materials, Retieseweg 111, B-2440 Geel, Belgium

E-mail: [email protected]

Ultra high performance liquid chromatography (UHPLC) coupled to High resolution Orbitrap MO15 mass spectrometry (HRMS) was used for a non-targeted metabolomics analysis for the determination of the geographical origin and varietal composition of wines. The chromatographic separation was performed on reversed phase (RP) and hydrophilic interaction liquid chromatography (HILIC), performing separate data acquisitions in positive and negative ionization mode. The sample set included 12 red wines of 3 different varieties (Cabernet Sauvignon, Merlot and Tempranillo) from 5 different countries and 47 white wines of 7 different varieties (Chardonnay, Müller-Thurgau and Pinot Blanc, Pinot Gris, Riesling and Sauvignon Blanc) from 4 different countries. Sample preparation was the least possible, including dilution with water (1/1), filtration and injection on the UHPLC-HRMS system. Additionally, a number of red and white microvinfied wine samples were analysed to evaluate their degree of similarity to commercial wines of the same variety. For global analysis, a commercial available software package (XCMS package of R) was employed and optimized for automatic data pre-processing, filtering, grouping, retention time correction, re-grouping, filling missing data and normalisation, resulting to a matrix features data set. Further on, SIMCA-P software was used to perform multivariate statistical analysis. Principal Component Analysis (PCA) and Orthogonal or Partial Least Square Discriminant Analysis (OPLS-DA and PLS-DA) were applied to build descriptive and predictive models. Features in multivariate analysis were further investigated to obtain statistically significant variables that can highlight candidate markers responsible for class separations. A well- defined UHPLC-MS experimental design and metabolomics workflow was designed in advance before conducting the experiments. Following the data processing pipeline from the unsupervised PCA to more supervised methods PLS-DA and OPLS-DA, the analysis of the white and red wine samples showed class separation based on the country of origin and the varietal composition. Microvinified wine samples showed their potential to represent commercial wine as they clustered together. The potential of the UHPLC-HRMS (Q Exactive Quadrupole-Orbitrap) metabolomics approach in wine authenticity was demonstrated and it can be considered also as a valuable tool for identifying markers that can be used for targeted tandem mass spectrometry. However, in order to create robust models and validate them, the sample size needs to be enlarged including different varieties and locations, in order to include greater variability and achieve a global applicability. Additionally, it is of great importance to obtain authentic wine samples with well traceable information regarding the variety and country/region of origin.

References [1] R, Díaz et al., Journal of Chromatography A, 1433 (2016) 90–97.

Voltammetric detection of virgin olive oil adulteration

F. Tsopelas1, D. Konstantopoulos1 and A. Tsantili- Kakoulidou2

1Laboratory of Inorganic and Analytical Chemistry, School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou 9, 157 80 Athens, Greece. 2Laboratory of Pharmaceutical Chemistry, School of Pharmacy, University of Athens, Panepistimiopolis, Zografou, 157 71 Athens, Greece.

E-mail: [email protected]

MO16 Olive oil is obtained from the fruit of olive trees (Olea europea L.) and it is widely appreciated for its nutritional, health and sensory properties. Extra virgin oil, extracted from olive fruit by only mechanical procedure, possesses the best nutritional characteristics and reputation. As olive oil is normally sold at a higher price than other vegetable oils, is often adulterated with seed oils and olive oils of lower grade. Thus, the verification of olive oil authenticity is of paramount importance to preserve the image of olive oil, improve its competitiveness and increase the consumers’ trust. The detection of virgin olive oil adulteration can be achieved by means of spectrometric and chromatographic techniques. Among others, Fourier transform infrared spectroscopy (FT-IR), mid- infrared spectroscopy (MIR) nuclear magnetic resonance (NMR), mass spectrometry (MS) and chromatographic approaches have been employed. However, such approaches are generally suited in centralized laboratories, requiring extensive labor and analytical resources and often results in a lengthy turnaround time, as some of them require pre-processing of the samples. In recent years, substantial efforts have been oriented towards the development of simplified, fast and inexpensive approaches with the possibility to be utilized in mobile analytical devices. In this aspect, electrochemical techniques are very attractive owing to their high sensitivity, inherent simplicity, miniaturization and low cost [1]. The aim of the present study was to evaluate the potential of cyclic voltammetry to detect the adulteration of virgin olive oil with olive pomace oil as well as the most common seed oils, namely sunflower, soybean and corn oil. For this purpose, cyclic voltammogram of olive and seed oils in presence of dichloromethane and 0.1 M of LiClO4 in EtOH as electrolyte were recorded at a glassy and a platinum electrode. Cyclic voltammetry was also employed in methanol extracts of olive and seed oils. Datapoints of cyclic voltammograms was exported and submitted to Principal Component Analysis (PCA) and Partial Least Square- Discriminant Analysis (PLS-DA) and a satisfactory discrimination of oils according to their origin was obtained. This discrimination was more pronounced in the case of cyclic voltammograms of methanol extracts of oils. For the quantification of olive oil adulteration with olive pomace oil or seed oils, a model based on cyclic voltammogram of methanol extracts and Partial Least Square (PLS) analysis was developed. Detection limit of adulteration in olive oil was found to be 2% (v/v). The validation of the proposed method was achieved by analysis of oil mixtures with known adulteration level as well as the commercial oil samples.

References [1] I.M. Apetrei and C. Apetrei, Computers and Electronics in Agriculture, 108 (2014) 148-154.

84 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Monday 18 September 2017 MINOS II Hall Chair: D. Anglos, N. Lydakis-Simantiris

Spectrometric Analysis

10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Plenary lecture Novel Femtosecond Laser Ablation Sampling Technologies in Optical Emission Spectroscopy

V. Zorba

Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

Laser ablation-based optical emission spectroscopy enables in situ, near real time, spatially- and axially- resolved chemical analysis and imaging without sample preparation. The advent of ultrafast lasers and their use in plasma spectroscopy over the past few years has enabled PL06 high-resolution elemental analysis capabilities and suppressed matrix effects, which have resulted in improved analytical performance. In this talk we discuss the use of emerging femtosecond laser technologies in optical emission spectroscopy, such as femtosecond optical vortex beams, laser filamentation, ultrafast sampling in optical near-field, and sub-micron ablation for elemental and isotopic analysis with Laser Induced Breakdown Spectroscopy (LIBS) and Laser Ablation Molecular Isotopic Spectrometry (LAMIS). Specifically, we introduce ultrafast optical vortex beams carrying orbital angular momentum as sampling tools in optical emission spectroscopy, and present the influence of topological charge on the laser-induced plasma properties and LIBS emission. We also demonstrate the ability to perform standoff isotopic analysis at extended distances (85 m) through the combination of femtosecond filaments and LAMIS (F2-LAMIS). Near-field femtosecond laser sampling is studied as a way to beat the diffraction limit in laser ablation sampling, and tightly focused femtosecond beams are used in the far-field to improve spatial resolution and absolute limits of detection in LIBS down to the attogram scale. Finally, we demonstrate the use of femtosecond laser pulses and resulting separations in the laser induced plasma for high- resolution 3D elemental imaging in a variety of applications, with special emphasis on Li-ion batteries.

Laser Induced Breakdown Spectroscopy for the rapid characterization of nanometer scale thin multilayer samples

P. Siozos1, S.P. Banerjee2, N. Giannakaris3, T. Sarnet2, A. Klini1, M. Sentis2, D. Anglos1,3

1 Institute of Electronic Structure and Laser (IESL), FORTH, 71110, Heraklion, Crete, Greece; 2 Laboratoire LP3, Case 917, 163 Avenue de Luminy, Marseille, 13009, France; 3 Department of Chemistry, University of Crete, 71003 Heraklion, Crete, Greece;

E-mail: [email protected] MO17 Material distribution or compositional analysis and depth profiling of nanometer thick multilayer samples require the use of sophisticated techniques. Laser Induced Breakdown Spectroscopy (LIBS) has been demonstrated to be a promising technology for the selective detection of materials at different depths in nanometer scale multilayered samples [1]. Due to its simplicity and instrumental versatility, LIBS can be adapted for the rapid characterization of ultra-thin nanometer layers and this is of importance in particular concerning industrial applications, for example in the context of semiconductors or photovoltaics production monitoring. However, the processes that take place during laser induced plasma formation and emission from a very thin layer of material are quite complex in the spatio-temporal domain and therefore extensive research must be carried out to properly understand these phenomena and eventually optimize spatial and analytical sensitivity. In the current work results are presented from the application of LIBS in the characterization of nanometer scale thin multilayered samples investigating ultra-short laser pulses (picosecond and femtosecond). In particular, we have applied LIBS using 40 fs (Ti: Sapphire) laser pulses on an organic photovoltaic sample composed of a top electrode (opaque or transparent), organic layer, bottom electrode, barrier layer and substrate layer situated from the top consecutively. The same samples have been used for the depth profiling using a 50 ps pulsed laser source at two different wavelengths (1030 and 515 nm) with very low pulse energy (<10 μJ/pulse). Finally, 450 fs laser pulses at 248 nm have been used to record LIBS emission from Al and Indium Tin Oxide (ITO) multilayer samples on a glass substrate. The experimental results clearly point out to the critical influence of laser parameters in the formation of plasma and subsequent LIBS emission. This project is under the support of the International Associated Laboratory (LIA) MINOS between LP3 and IESL-FORTH.

References [1] S.P. Banerjee, T. Sarnet, P. Siozos, M. Loulakis, D. Anglos, M. Sentis, Appl. Surf. Sci. (2016), in press; doi: 10.1016/j.apsusc.2016.11.136

88 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Simultaneous determination of Na, K, Li, Rb and Cs in the natural objects

A.A. Zak, E.V. Shabanova, I.E. Vasil’eva

Vinogradov Institute of Geochemistry, Siberian Branch of Russian Academy of Sciences, Favorsky St., 1a, Irkutsk, Russia 664033

E-mail: [email protected], [email protected]

Determination of Na, K, Li, Rb and Cs in the natural and man-made environments is necessary for classification and dating of objects. However, the average abundances of alkali metals for MO18 natural environments differ in thousand times, and their simultaneous determination is a complex and time-consuming task. Flame atomic emission spectrometry (FAES) is widely used technique determining the whole group of alkali metals. It is mono-element method in contrast to multi-element methods such as X-ray fluorescence analysis, atomic emission and mass spectrometry with inductively coupled plasma. All alkali metals are determined by the FAES in the range from 10-4 to tens of % wt., and sometimes in during the analysis additional procedures of sample preparation are needed. There are modern spectrometers with multichannel recording of spectra and a wide dynamic range of radiation intensity measuring (e.g. spectrometer "Kolibri-2", «VMK-Optoelektronika» Ltd., Russia [1]) that are providing the simultaneous detection of analytical signals of Na, K, Li, Rb and Cs at concentrations of their natural abundance. Therefore, for using all opportunities such spectrometers the technique of simultaneous determination of Na, K, Li, Rb, and Cs in a wide range of concentrations has to be developed. Various versions of sample preparation of solutions for solid natural objects, such as rocks, minerals, sediments, soils, coal ashes were studied. The optimal conditions of atomization of element (solution injection rate and gas flow), and also the ways of recording and processing (exposure, recording time, number of multiple determinations, calculation of analytical parameters for each lines of alkali metals) of the spectra were chosen. Calibration was carried out with using certified reference materials (CRM) to minimize some matrix effects. Correlation the intensity of analytical signals between both acid concentration and mineralization of solution was studied. Analytical signals are stable during the whole period of validity of solutions (i.e. 9 months) therefore the constant calibration method is applicable. Thus, the developed technique allows to simultaneously determine Na (0.025-7.4 % wt.), K (0.085-15.0 % wt.), Li (0.00025-0.33 % wt.), Rb (0, 0005-0.15 % wt.) and Cs (0.0002-0.0070 % wt.). The accuracy and trueness of the results were tested via the CRM, such as DVM, DVG, SI-1, SNS-2, SSn-1, BIL-1, SGHM-4, SDO-9, SP-1, ZUA-1 (Russia), and by the method of standard additions. Information about the contents of Ca (1-31 % wt.), Mn (0.16-1.37 % wt.) and Sr (0.02-0.83 % wt.) were additionally obtained. As a result, the proposed flame atomic emission spectrometry technique of simultaneous determination of alkaline elements is economically benefited due to reducing of time spent for the analysis.

Reference [1] «VMK-Optoelektronika» Ltd. http://www.vmk.ru

Use of EIS to investigate of adsorption of NaCN and Na2S2O5 on Pyrite

Z. Ertekin1, K.Pekmez1 and Z. Ekmekçi2

1 Hacettepe University, Department of Chemistry, Beytepe, Ankara, Turkey 2 Hacettepe University, Department of Mining Engineering, Beytepe, Ankara, Turkey

E-mail: [email protected]

MO19 Electrochemical techniques have been used to provide valuable information about electrochemical reactions occur in the sulfide mineral flotation system. Since most of the metal sulfides are semiconductor, there is a strong correlation between flotation of the minerals and electrochemical reactions. For this purpose, commonly used electrochemical techniques include cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), open circuit potential (OCP) (also referred to as rest potential) measurement, polarization curves, potentiometry, coulometry, chronoamperometry, etc. Among these meauserement techniques, EIS is proved to be the most effective electrochemical technique for surface characterization. Especially, EIS has recently been used for in-situ investigation of solid/liquid [1,2]. Pyrite (FeS2, iron disulfide), which is the most common sulfide mineral on the Earth, is an nontoxic semiconductor and occupies an important position in studying transition metal sulfides because of its excellent properties, such as electrochemical performance degradation, optical and electronic property. Since electrochemical potential is known as the key factor in pyrite flotation process, it is important to understand what is occuring in a flotation system containing pyrite, such as changes in pyrite surface chemistry due to oxidation, the interaction of pyrite with other components, adsorption of collector and depressants on the surface [3]. The aim of this study is to provide detailed information on effects of NaCN and sodium metabisulphite (Na2S2O5)-SMBS as a depressant and Potassium Amyl Xanthate (KAX) as a collector for pyrite samples by using EIS technique. For the EIS measurements, a novel mineral electrode fabrication method was used to prepare the mineral electrodes as pyrite samples were in the form of fine partice size material [4,5]. Moreover, the effect of sequence of addition of collector and depressant were also discussed for the pyrite sample.

References [1] R.Woods, J. Miner. Process. 72 (2003) 151–162. [2]Y. Mua, L.Li, and Y.Peng, Min. Eng. 101 (2017) 10-19. [3] H. Moslemi and M. Gharabaghi, Journal of Industrial and Engineering Chemistry 47 (2017) 1–18. [4 ]Z. Ekmekçi, E. Tekes Bagci, M. Can, Ö. Bıçak, and Pekmez, K., AMIRA P9O Mineral Processing, (2011) 417–486. [5] Z. Ertekin, K. Pekmez and Z. Ekmekçi, Int. J. Miner. Process. 154 (2016) 16-23.

Monday 18 September 2017 PASIPHAE I Hall Chair: N. Kallithrakas-Kontos, A. Isleyen

Sample Preparation

10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Bromate removal from water using surfactant modified red mud

F.A. Megalopoulos and M.T. Ochsenkuehn-Petropoulou

National Technical University of Athens, School of Chemical Engineering, Laboratory of Inorganic and Analytical Chemistry, Iroon Polytechneiou 9, 15773 Athens, Greece

E-mail: [email protected]

Bromate, a known carcinogen, is often detected in intensively ozonated and chlorinated, bromide containing waters destined for human consumption as well as industrial use. In cooling water treatment, residual bromine, whose decay leads to bromate formation, can be MO20 estimated with the help of cooling circuit's basic operational parameters [1]. Many adsorption techniques have been employed to achieve bromate removal, either from drinking water as well as from other matrices [2]. Red mud is a hazardous by-product of the Bayer process, used to produce alumina from bauxite ore with proven abilities to adsorb anions after acid activation [3]. In this work, the impregnation of red mud with the cationic surfactant Cetyl-Trimethyl Ammonium Chloride (CTAC) and the subsequent bromate removal capabilities of the composite material are investigated. CTAC has successfully been used as an enhancer of granular activated carbon’s bromate adsorption effectiveness [4]. Red mud was supplied by an alumina refinery in the Greek territory. The acid activation method is described by Cengeloglu et al [3] followed by CTAC impregnation which was carried out at ambient temperature and pressure, using solutions of different CTAC concentrations. Investigation of the maximum loading of CTAC onto activated red mud and the time needed was carried out. Maximum loading capacity is 0.32g CTAC/g red mud and was achieved after 24 h contact time. pH increase was found to adversely affect bromate removal. The uptake of bromate by the CTAC impregnated red mud is fairly fast as after 10min contact time the maximum possible bromate quantity has been adsorbed. The adsorption process follows the Langmuir isotherm model. CTAC impregnated red mud, an industrial waste, has been proven that after its treatment can be an effective mean from bromate removal which is a hazardous bromine decomposition by- product. This is an important finding as red mud is redirected back into productive use which is consistent with the goal of sustainable development.

References [1] F.A. Megalopoulos, and M.T. Ochsenkuehn-Petropoulou, J. Env Sci Heal A, 50 (2015) 144-150 [2] F.A. Megalopoulos and M.T. Ochsenkuehn-Petropoulou, Desalin Water Treat, In Press DOI 10.5004 [3] Y. Cengeloglu, A. Tor, M. Ersoz and G. Arslan, Sep Purif Technol, 51 (2006) 374-378 [4] W. Chen, Z. Zhang, Q. Li and H. Wang Chem Eng 203 (2012) 319-325

Separation and preconcentration of particles and solutes before analysis using ultrasonic standing waves

V.M. Shkinev, R. Kh. Dzhenloda, T.V. Danilova and B.Ya. Spivakov

Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russian Federation

E-mail: [email protected]

Ultrasound (US) is widely used in analysis, in particular, for pretreatment in the recovery of MO21 analytes, in decomposition and partial dissolution of sample components (homogenization, leaching), in filtration, liquid-liquid and solid-phase extraction. US promotes filtration separation of liquid and solid phases using in some cases flow systems. It is also used in chromatographic systems for removal of gases and foam from test solutions and for solving other problem. US standing waves are not often applied to analytical purposes. Such waves are formed due to interference of US waves from the source and reflected from set up components. They are used, e.g. in microfluidic devices for the separation of particles and cells. As a rule, the separations are carried cut in flat devices at similar direction of US and the flow. In our works, we used an US source in the form of semisphere and cylindric chamber. US waves were bands located at a distance of half-wave, whereas the flow was perpendicular to them. Such an approach may result in better retention of particles and more effective sorption of solutes if the particles (less than 5 µm) possess adsorption properties. This can improve the separation of particles and enrichment of solutes. The theoretical analysis of the processes of particle retention and sorption of solutes on particles shows that, depending on the conditions, complete retention of particles and separation of both particles and solutes are possible. The process proposed can be used for the separation of standard micro and nano particles as well as sorbents based on silica gels bearing different function groups. Conditions have been found for preconcentration of various metals from aqueous solution, sea water, wines. Interesting results have been obtained for the enrichment and determination of nucleic acids of different microorganisms and viruses in aqueous extracts of soils.

The authors are grateful for the financial support of RFBR (No. 16-03-00106, No. 16-33- 00214) and Russian Academy Program (No. 8P).

94 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

DNA purification with a plasma micro-nanotextured polymeric microfluidic device using micro-solid phase extraction

A. S. Kastania1,2, P. S. Petrou3 and E. Gogolides 1

1Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, Aghia Paraskevi, 153 41, Greece 2Department of Chemistry, University of Athens, Athens, 157 71, Greece 3Institute of Nuclear & Radiological Sciences & Technology, Energy & Safety, NCSR “Demokritos”, Aghia Paraskevi, 15341, Greece

E-mail: [email protected] MO22

DNA purification is of high significance to molecular diagnostics and with the advent of micro-technology there has been an effort of transferring this process to microfluidics. Methods utilizing magnetic micro-particles or silica beads or other solid phase material inside micro-solid phase extraction (micro-SPE) chips [1] have been used towards this direction, over the last 15 years, and the most widespread chemistry used is based on silica. Our work focuses on a microfluidic polymeric device for DNA purification with solid phase extraction [2]. More particularly, we use oxygen plasma and nanotexturing to create both carboxyl groups on the DNA purification chip surface as well as high surface area. On these chips we are exploring two protocols for DNA purification: In the first protocol the carboxyl groups interact directly with DNA. This DNA purification protocol contains the following steps: a) DNA precipitation utilizing the high density of carboxyl groups of the chip surface together with a buffer of polyethylene glycol and ethanol, b) removal of impurities with ethanol, c) removal of ethanol and d) elution of DNA. The chip design comprises of a micromixer making it amenable to integration with other microfluidic devices in one Lab-on-a-chip (LOC) platform and the device is capable of purifying DNA within a large dynamic range (0.263 fg - 2x500 ng Salmonella DNA of MW 4857 kbp), with high efficiency and capacity and with high shelf life. The device has been tested for purifying DNA successfully from Salmonella bacteria in certain solution buffers as well as from milk spiked with Salmonella according to standard practice, within an integrated LOC platform that includes also a microfluidic device for cell capturing and lysis. We also explore a second protocol based on DNA-amine interactions. The plasma treated chip surface is first reacted with polyamines, such as histidine or polyhistidine solutions. Amine functional groups are thus bound on the surface. DNA purification can take place without using substances (which may poison subsequent DNA multiplication processes) as follows: a) DNA sample injection and DNA binding on the chip surface at pH< pka of the ionisable amine groups, b) washing step and c) elution at pH> pka. We are presently evaluating this protocol and comparing it with the one based on carboxyl groups. This device was used in the development of a Lab-on-Chip platform for food pathogen detection as described within the EU project LOVE-FOOD (http://love-food-project.eu/ ) and currently the system is being optimized for faster pathogen analysis within EU project LOVEFOOD2Market (http://lovefood2market.eu/ ).

References [1] S.J. Reinholt, A.J. Baeumner, Angew Chem Int Ed, 53(2014) 13988-4001. [2] A.S. Kastania, K. Tsougeni, G. Papadakis, E. Gizeli, G. Kokkoris, A. Tserepi and E. Gogolides, Anal Chim Acta, 942(2016) 58-67.

Monday 18 September 2017 MINOS II Hall Chair: J. Thomas-Oates, A. Bisi

Advances in Bioanalytics

98 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Plenary lecture Probing metal interactions with biomolecules in-vivo using electrospray high resolution mass spectrometry

R. Lobinski

Institute of Analytical Sciences and Physicochemistry of Environment (IPREM) UMR 5254, National Research Council of France (CNRS), Hélioparc, 64 053 Pau, France

e-mail: [email protected] PL07 The current progress in electrospray ionization Fourier transform mass spectrometry (ESI FT MS) using electrostatic orbital trap (Orbitrap) offers unparalleled resolution (up to 1 000 000), accuracy of mass measurement (sub-ppm), and intrascan dynamic range for the analysis of biomolecules. The combination of such systems with a linear ion trap allows additional experiments towards structural analysis (up to MS10) and opens more and more new possibilities for elemental speciation. So far, ESI MS has been considered as a complementary technique used for the identification of elemental species separated by HPLC and detected by ICP MS. Nowadays, the coupling of HPLC – ESI Orbitrap MS allows the detection of the heteroatom-isotopic pattern (an equivalent of the element-specific signal) in mass spectra down to the intrascan abundance of 0.001 with the low- and sub-ppm mass accuracy. A cascade of product ion mass spectra with the preservation of the isotopic pattern can be produced at the sub-ppm mass accuracy largely facilitating the analyte structure elucidation. Thus, the ESI MS has been not only complementing ICP MS, but also slowly replacing it for many speciation-related applications in the analysis of biological samples. The lecture evaluates the growing potential of "soft" ionization ESI FT-MS for the detection and identification of metal/metalloid-containing biomolecules in comparison with classical ICP MS ("hard" ionization) based methods. A hypothesis is put forward that, taking into account the rate of progress in the development of ESI MS, this technique is likely to take the place of ICP MS in speciation studies. The presentation summarizes findings of several projects focused on identification and quantification of species formed as a result of in-vivo interactions of metals with biomolecules in plants and bacteria.

Differentiating tumor heterogeneity in FFPE colon adenocarcinoma tissues using PCA analysis of MALDI IMS spectral data

I. Panderi 1,2, K. Perez1, L. Noble1, D. Pantazatos1

1Brown University, Warren Alpert Medical School, COBRE Center for Cancer Research, Rhode Island Hospital, Providence, RI, USA 2National and Kapodistrian University of Athens, Department of Pharmacy, Laboratory of Pharmaceutical Analysis, Athens, Greece

MO23 E-mail: [email protected]

Adenocarcinoma is the most common histologic type of colorectal cancer, with etiologies which include genetic factors, environmental exposures as well as inflammatory conditions of the digestive tract. Matrix-assisted laser desorption/ionization mass spectrometry imaging (MALDI-IMS) can be useful to define molecular patterns of mass ion peaks specific for tumor regions and provide further insight regarding tumor behavior, diagnosis and prognosis of this disease. Colon tissue section

MALDI-TOF IMS

Ion image PCA

2-D distribution diagrams

MALDI IMS datasets comprise huge amounts of spectra and their interpretation requires the use of multivariate statistical methods. In this study, MALDI IMS spectral data have been processed using sequential principal component analysis (PCA) and 2-D peak distribution tests so as to investigate the molecular differentiation of tumor regions in formalin-fixed paraffin- embedded (FFPE) tissue biopsies of colorectal adenocarcinoma. Multivariate analysis of spectral data revealed a specific pattern of mass ion peaks in different tumor regions that were distinguishable from the adjacent normal regions within a given specimen. These significant mass ion peaks have been used to generate ion images and visualize the difference between tumor and normal regions. This study provides evidence in support of the clinical utility of MALDI-IMS to analyze colorectal adenocarcinoma biopsies at a molecular level. The significant mass ion peaks detected in this work may serve as potential biomarkers for colorectal adenocarcinoma in FFPE and fresh frozen tissue section samples.

References [1] I. Panderi, E. Yakirevich, S. Papagerakis, L. Noble, K. Lombardo, D. Pantazatos, Differentiating tumor heterogeneity in formalin-fixed paraffin-embedded (FFPE) prostate adenocarcinoma tissues using principal component analysis of matrix-assisted laser desorption/ionization imaging mass spectral data. Rapid. Commun. Mass Spectrom, 31(2) (2017) 160-170.

100 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Phosphorylated amino acids detection and extraction combining fluorogenic MIP core-shell particles and microfluidics

J. Bell, W. Wan and K. Rurack

Chemical and Optical Sensing Division, BAM Federal Institute for Materials Research and Testing, Berlin/Germany

E-mail: [email protected]

The identification and quantification of phosphorylated amino acids, peptides and proteins is one of the key challenges in contemporary bioanalytical research, noteworthy to diagnose and MO24 treat diseases at an early stage. Small sensing devices like microfluidic chips combined with “smart” detection chemistry and simple data assessment, processing and presentation are attractive in this regard. We developed novel synthetic probes, targeting phosphorylated amino acids, based on core-shell microparticles consisting of a silica core coated with a molecularly imprinted polymer shell (MIP). These “plastic antibodies” which are extremely robust, resist denaturing solvents and high temperatures, can be reproducibly produced at low cost, can potentially overcome many of the problems in the current detection strategies. The MIP layer, containing a fluorescent probe monomer, responds to phosphorylated amino acids such as phosphorylated tyrosine (pTyr) with a significant imprinting factor, i.e. selectivity, higher than 3.5, and a “lighting-up” of its fluorescence accompanied by the development of a strongly red- shifted emission band. The bead-based ratiometric detection scheme has also been successfully transferred to a microfluidic chip format to demonstrate its applicability to rapid assays. Such a device could yield an automated pTyr measurement system in the future. The setup was built by coupling a PDMS/Teflon/glass microfluidic chip with an optical setup for fluorescence measurements able to extract and monitor pTyr concentration from 0.5–200 μM.

3 S-1 S-2-1 S-2-2

F / arb. u. 2

0 0.00 0.05 0.10 0.15 0.20 C / mM TBA2-Fmoc-P-Tyr-OEt Figure 1. (left) Molecular structures of the fluorescent probe and pTyr and MIP core-shell particles and (right) ratiometric response of the microfluidic sensor upon increasing concentration of pTyr (c = 0– 200 μM).

References [1] R. Wagner, W. Wan, M. Biyikal, E. Benito-Peña, M. C. Moreno-Bondi, I. Lazraq, K. Rurack, B. Sellergren, J. Org. Chem, 78, (2013) 1377-1389. [2] W. Wan, M. Biyikal, R. Wagner, B. Sellergren, K. Rurack, Angew. Chem. Int. Ed. 52, (2013), 7023- 7027.

101

High sensitive multiresidue analysis of pharmaceuticals in surface water using UHPLC-LTQ/Orbitrap HRMS

Ch. Nannou, Ch. Kosma, V. Boti and T. Albanis

Lab of Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina, GR45110, Greece

E-mail: [email protected]

A large number of pharmaceutical residues and metabolites can be found in wastewater, MO25 surface and ground water. Although the relevance of the presence of such substances in the environment has been intensively studied the long-term effects on human and especially on ecosystems are still unknown. There are several methods to determine pharmaceuticals in the aquatic environment. They mainly consist of solid-phase extraction (SPE) and liquid chromatography–mass spectrometry (LC–MS/MS). In the recent years, high-resolution mass spectrometry including time of flight (TOF) and Orbitrap has become a powerful tool for environmental studies. Combining the mass selection/isolation capability of the quadrupole and the high resolution of the Orbitrap, this instrument has a great potential to avoid false compliant and non-compliant results in residues testing [1]. The occurrence of 30 pharmaceutical residues was studied by using solid-phase extraction (SPE) and LC-LTQ Orbitrap high resolution MS in both full scan (FS) MS and targeted MS/MS modes. A validation procedure was carried out for the determination of 30 compounds in FSMS mode evaluating selectivity, sensitivity, linearity, precision and accuracy. The method showed satisfactory analytical performance. The evaluation of the recovery concluded that the majority of the compounds showed recoveries over 70%. The level of detection was at lower ppt levels for all compounds. The coefficients of determination were higher than 0.99 in all cases, over a linearity range of 0.1-500 ng/L. Targeted MS/MS analysis, performed in addition to the full scan acquisition was used for confirmatory purpose.

References [1] C. L. Chitescu, G. Kaklamanos, A. I. Nicolau, and A. A. M. L. Stolker, “High sensitive multiresidue analysis of pharmaceuticals and antifungals in surface water using U-HPLC-Q-Exactive Orbitrap HRMS. Application to the Danube river basin on the Romanian territory,” Sci. Total Environ., vol. 532, pp. 501–511, 2015.

Acknowledgements The research is implemented through the Operational Program "Education and Lifelong Learning" and is co-financed by the European Union (European Social Fund) and Greek national funds. The authors would like to thank the Unit of Environmental, Organic and Biochemical high resolution analysis- ORBITRAP-LC-MS of the University of Ioannina for providing access to the facilities.

102 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Monday 18 September 2017 PASIPHAE II Hall

Poster Session 1

Mass Spectrometry Spectrometry Sample handling Environmental analysis

103

10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Preparative isoelectric focusing of microorganisms in cellulose- based separation medium and subsequent analysis by CIEF and MALDI-TOF MS

M. Horká 1, K. Šlais1, J. Šalplachta1 and F. Růžička2

1 Institute of Analytical Chemistry of the CAS, v. v. i., Veveří 97, 602 00 Brno, Czech Republic -1 2 The Department of Microbiology, Faculty of Medicine, Masaryk University, Kamenice 53/5, 625 00 Brno, Czech Republic-2

E-mail: [email protected] P1-01

Pre-separation and pre-concentration of some, especially, uncultured bacteria are an important step in consequence of low microbial particle concentrations in real matrix. In this study, a preparative method based on an isoelectric focusing [1] of colored microorganisms in a cellulose-based separation medium from the high conductivity matrix, physiological saline solution, is described. The isoelectric points [2] were found for examined cells as 1.8 for Micrococcus luteus, as 3.5 for Dietzia sp., and as 4.7 for Rhodotorula mucilaginosa at capillary isoelectric focusing. In the preparative isoelectric focusing, the strains were analyzed in the concentration range 107–109 cell mL-1 both individually, and in the mixture of the cells, each of them 108 cell mL-1. Final positions of the colored zones of microbes are also indicated by the positions of focused zones of colored pI markers. Fractions, segments of the separation medium with cells, were harvested by spatula, simply purified using a centrifugation and analyzed by CIEF and MALDI-TOF MS. The determined fractionation efficiency was varied in the range from 78 to 93%. No significant differences were found between fractions within the same pH range collected from preparative isoelectric focusing of individual microbial strains and of their mixture. The viability of the cells was successfully verified by their cultivation.

Acknowledgement This work was supported by the Grant Agency of the Czech Republic (Grant No. 16-03749S), Ministry of Health of the Czech Republic (Grant No. 16-29916A), Ministry of the Interior of the Czech Republic (Grant VI20172020069) and by the Czech Academy of Sciences (Institutional Support RVO:68081715).

References [1] J. Šalplachta, M. Horká, K. Šlais, J. Sep. Sci. DOI: 10.1002/jssc.201700036. [2] J. Šalplachta, A. Kubesová, M. Horká, Proteomics 12 (2012) 2927-2936.

105

Characterization of changes in volatile profile of elderflowers (Sambucus nigra L.) caused by harvesting and drying processes

T. Bajer, P. Bajerová, A. Eisner, M. Adam and K. Ventura

University of Pardubice, Faculty of Chemical Technology, Department of Analytical Chemistry, Studentská 573, 532 10 Pardubice, Czech Republic

E-mail: [email protected]

Sambucus nigra L. is one of the most commonly used plants for medicinal purposes. P1-02 Historically, the leaves were considered to relieve pain and promote healing when applied as a poultice. Flowers and fruits of Sambucus nigra L. are used successfully for centuries for medicinal purposes, to prepare teas, wines and liquors. Traditional folk medicine uses infusion from dried flowers because of diuretic effects, reducing fever, promoting perspiration and moderating cough. Organoleptic characteristics of food and beverages are partially derived from their volatile components. In the case of elderflower the infusions are usually prepared from dried flowers. Therefore, volatile compounds emitted by elderflowers (Sambucus nigra L.) at various stages (blooming on the bush, and at different stages after harvesting) were analysed to investigate changes in composition of volatile profile induced by two drying procedures, drying in light at laboratory temperature and drying in dark at 45 °C in oven. Solid-phase microextraction and simultaneous distillation-solvent extraction were used to concentrate the volatile compounds. Analyses of extracts were performed by using gas chromatography coupled with a mass spectrometer or a flame ionization detector. On-site field sampling of volatiles followed-up by chromatographic analysis provided interesting information, when substances referred as component of sex pheromones released by some kinds of insect formed from 55 % to 79 % of the total peak area in the GC/MS chromatograms. Composition of aroma compounds of harvested elderflowers was strongly influenced by type of drying procedure, where the content of some volatiles decrease and some substances even occur due to ongoing physicochemical processes. Changes in volatile profile due to harvesting (prior to drying) were observed too.

106 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Comparison of different sample preparation methods for the multiresidue detection and quantification of pesticides in fruit juices by LC-MS/MS and GC-MS/MS

B. Papaioannou1,2, H. Botitsi2, S. Antoniou2, D. Tsipi2, and A. Economou1

1 Laboratory of Analytical Chemistry, University of Athens, Athens 157 71, Greece 2 General Chemical State Laboratory, 16 An. Tsoha, Athens 11521, Greece

E-mail: [email protected] P1-03 Monitoring of pesticide residues in food of plant and animal origin is essential for the protection of human health. EU multiannual and national control programs are performed annually to ensure compliance of food commodities with the Maximum Residue Levels (MRLs) set by EU Regulation ΕC No 396/2005 and to estimate the consumers’ persticide intake through the food chain. Currently, more than 1500 compounds of different chemical groups with different physicochemical properties, can be used as pesticides. The simultaneous analysis of a large number of pesticide residues and their transformation products in food matrices is feasible through large scale multi-residue methods based on general extraction procedures combined with hyphenated instrumental analysis techniques, such as gas chromatography (GC) and liquid chromatography (LC) coupled to mass spectrometry (MS) [1,2]. The aim of this work was the development, validation and comparison of three individual sample preparation methods for the detection and quantification of pesticide residues in fruit juices: i) Quick, Easy, Cheap, Effective, Rugged, Safe (QuEChERS) with citrate, ii) solid phase extraction (SPE) using OASIS HLB cartridges, and, iii) dilute-and-shoot. Extracts of spiked samples obtained using the different extraction techniques were analyzed with LC- MS/MS and GC-MS/MS for the detection and quantification of about 300 pesticides; 210 compounds were determined with LC-MS/MS while about 80 compounds were determined with GC-MS/MS. The three methods were validated according to the European Union guidelines for pesticide residues SANTE/11945/2015 [3]. Recovery and inter-laboratory reproducibility values derived from the validation experiments, fulfilled the method performance criteria set by the SANTE/11945/2015 for the majority of the target pesticides.

References [1] Botitsi H, Tsipi D, Economou A, “Current Legislation on Pesticides” in Applications in High Resolution Mass Spectrometry, Food Safety and Pesticide Residue Analysis, edited by Roberto Romero-González and Antonia Garrido Frenich, 2017, Elsevier Inc. [2] Tsipi D, Botitsi H, Economou A, (Eds.), “ Mass pectrometry for the analysis of pesticide residues and their metabolites”, 2015, Wiley Series on Mass Spectrometry, Wiley & Sons. [3] DG SANTE, European Commission, Document No SANTE/11945/2015: “Guidance document on analytical quality control and method validation procedures for pesticides residues analysis in food and feed”, http://www.eurl-pesticides.eu

107

Single-Calibrant paper-based analytical devices for in-situ standard addition assays

G. Giannoulas, G.Z. Tsogas, A.G.Vlessidis, D.L. Giokas

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece

E-mail: [email protected]

P1-04 This work presents a new approach towards the adaptive use of standard addition methodology in paper devices that uses single-calibrant paper-devices. Single-Calibrant- devices, have multiple sensing areas pre-loaded with an excess amount of the necessary colorimetric reagents and a standard solution of the tested analyte; thus, a colored product is developed in each sensing area before analysis. To perform the analysis, different volumes of the sample solution are added into the sensing zones. The analytical signal from each sensing area corresponds to the total concentration of the analyte, which is the sum of the concentration of the analyte in the tested sample plus the known amount of the analyte pre-stored in the device. Since a different sample volume is added in each sensing zone, the intensity of the colorimetric reaction products increases with increasing sample volume because a higher number of analyte is exposed to the sensing area. The combined signal retrieved from each sensing zone is plotted to form a multiple standard addition calibration curve that is used to calculate the concentration of the analyte in the sample. Using a series of colorimetric reactions for the determination of a variety of analytes of environmental, food and biological interest we demonstrate the utility of this modified standard addition approach as a calibration-free, sample-in result-out tool for point-of-use applications.

108 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Dispersive suspended microextraction of silver nanoparticles from water samples with oxidative dissolution back-extraction prior to their determination by atomic absorption spectrometry

T.G. Choleva, G.Z. Tsogas, A.G. Vlessidis, D.L. Giokas

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece

E-mail: [email protected] P1-05 The environmental impact of silver nanoparticles (AgNPs) has recently become a topic of wide interest, due to the fact that AgNPs are included in numerous consumer products [1]. Therefore, new analytical methods that enable their determination in environmental water samples have emerged in order to enable the monitoring of AgNP in the environment. In this work a dispersive suspended microextraction (DSME) method coupled to atomic absorption spectrometry was developed and optimized for the determination of AgNP in water samples Initially, AgNP are extracted into a dispersed octanol droplet under vigorous stirring. Then, the octanol droplet containing the extracted AgNPs, is restored under mild stirring and separated from the aqueous phase. The octanol phase is collected and mixed vigorously with a strongly oxidizing solution composed of HNO3/H2O2. During mixing, the octanol phase disperses again and AgNP at the interface of the octanol/aqueous phase come in contact with the oxidizing phase and are dissociated into their precursor Ag+ ions. These ions are transferred (back-extracted) into the aqueous phase of the oxidizing mixture which is then collected and used for analysis. The parameters that influence the extraction procedure and maximize the recovery of AgNPs such as, pH, volume of the extraction solvent (octanol), composition and volume of the dissolution medium (i.e. oxidizing mixture), ionic strength, sonication and extraction time were studied. Under the optimum experimental conditions the determination of AgNP was successfully accomplished in various natural water samples with very satisfactory reproducibility (RSD=2.64%, n=7) and good recoveries (> 85%). The detection limit, defined as 3 times the signal-to-noise ratio was 0.23 nM by extracting AgNP from 35 mL aqueous solution and back-extraction at 0.5 mL of dissolution medium. By increasing sample volume and decreasing the volume of the dissolution medium, a preconcentration factor up to 400 could be achieved, thus lowering the detection limits at the pM levels.

References [1] E. McGillicuddy, I. Murray, S. Kavanag, L. Morrison, A. Fogarty, M. Cormican, P. Dockery, M. Prendergast, N. Rowan, D. Morris, Sci. Total Environ., 575 (2017) 231-246.

109

High resolution mass spectrometry to investigate psychiatric drugs and their metabolites in wastewaters

Ch. Kosma, Ch. Nannou, V. Boti and T. Albanis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina, 45110, Greece

E-mail: [email protected]

Detection of pharmaceuticals in the environment has raised concerns in recent years. P1-06 Nowadays, the higher prevalence of psychiatric disorders led to a worldwide increased number of prescriptions for psychiatric pharmaceuticals. After intake, these highly active compounds undergo metabolic transformations, with subsequent excretion of their active metabolites to raw sewage, wastewater treatment plants (WWTPs) and consequently to surface waters [1]. Since WWTP have been pointed out as the main contamination pathway of pharmaceuticals (and consequently for phsychiatrics) into the environment, it seems that often only partial removal is achieved in biological treatment processes [2]. In the present study, the distribution of nine psychiatric drugs (fluoxetine, sertraline, venlafaxine, olanzapine, quetiapine, mirtazapine, clozapine, bupropion and paroxetine) and four of their metabolites (norfluoxetine, N-Desmethyl Sertraline, O-Desmethylvenlafaxine and N-Demethyl Olanzapine) in hospital wastewaters was determined. More specifically, an off-line solid phase extraction followed by UHPLC-LTQ-Orbitrap-MS methodology, in positive ionization mode, was applied. Isotope dilution was implemented for every analyte using labeled standards (fluoxetine D5 and olanzapine D3). A number of studies have demonstrated that isotope dilution is a preferred approach in order to alleviate matrix interferences as well as SPE losses and instrumental variability [2-3]. In order to optimize the extraction method, three different cartridges were tested, SDB-1, Oasis MCX and Oasis HLB, and the results showed that most of the compounds exhibited higher recoveries using Oasis HLB.

References [1] B. Du, P. Perez-Hurtado, B.W. Brooks and C.K. Chambliss, J Chromatogr A, 1253 (2012), 177- 183. [2] C.I. Kosma, D.A. Lambropoulou and T.A. Albanis, Sci Total Environ, 466-467 (2014), 421-438. [3] M.P. Schlüsener, P. Hardenbicker, E. Nilson, M. Schulz, C. Viergutz, T.A. Ternes, Environ Polut, 196 (2015), 247-256.

110 10th International Conference on Instrumental Methods of

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Flow sample preparation using standing wave ultrasound and magnetic fields in the determination of nucleic acids by real-time polymerase chain reaction

B.Ya. Spivakov1, R.Kh. Dzhenloda1, V.M. Shkinev1 and D.G. Petrov2

1Vernadsky Institute of Geochemistry and Analytical Chemistry, Moscow, Russian Federation 2Institute of Analytical Instrumentation, St. Petersburg, Russian Federation

E-mail: [email protected] P1-07 The effective recovery and enrichment of nucleic acids including DNA as bioindicators of causative agents of diseases and their subsequent detection is an important problem. In the analysis of waters and especially soil extracts, the determination of DNA is complicated with high amounts of organic substances, in particular, humic substances which are inhibitors of polymerase chain reaction (PCR) used for DNA identification. The known sorption and often used liquid-liquid extraction techniques, applied before real-time PCR detection, are multistage and require long time. Besides, they are batch-mode, deal with as small samples as about 200µl without preconcentration of analytes from 10-ml and larger samples. In this work, we used so-called suspension columns with a silica-coated magnetic sorbent to adsorb, rinse and elute DNA in a combined acoustic and magnetic fields. The use of suspension allows to intensify and automate the process of DNA recovery. It was possible to achieve better extraction of DNA from aqueous extracts of soil and to obtain concentrates for PCR analysis. The ultrasound field intensifies the adsorption, whereas the magnetic fields provides the retention of a greater sorbent mass than in the case of acoustic field alone. A sod-podzolic sandy loam (SPSL) and a typical black earth loam (TBEL) were taken as soil samples containing plasmid DNA of M.tuberculosis. The DNA recovery from SPSL and TBEL can reach 80 and 60% respectively that is sufficient for DNA detection. Thus, an effective flow method was proposed for the recovery of DNA from aqueous extracts and preconcentration with the subsequent elution and detection by RT-PCR.

The authors are grateful for the financial support of RFBR (No. 16-03-00106, No. 16-33-00214) and Russian Academy Program (No. 8P).

111

Hyphenated techniques in mass spectrometry applications for assessment of metals exposure

B. Janasik, M. Stanislawska, R. Kuras, W. Wasowicz

Nofer Institute of Occupational Medicine, Department of Environmental and Biological Monitoring, Lodz, Poland

e-mail: [email protected]

Toxicology of metals focus on elucidation of the mechanisms of action and development of P1-08 remedies and treatment plans for associated toxic effects. Mass spectrometry (MS) has become a powerful analytical technique with a wide range of application used in the toxicological analysis of metals and their metabolites owing to their high sensitivity and specificity. They are used for screening, distribution and quantification of metals and their metabolites. To date, MS applications have permeated all fields of metals toxicology which include; environmental, occupational, and clinical toxicology. While many different analytical applications are used in these fields, MS and its hyphenated applications such as; inductively coupled plasma mass spectrometry (ICP-MS), gas chromatography GC-ICP-MS, high pressure liquid chromatography HPLC-ICP-MS, laser ablation LA-ICP-MS have emerged as powerful tools used in metals exposure laboratories. This presentation will focus on these hyphenated MS techniques and their applications for occupational and environmental toxicology of metals.

112 10th International Conference on Instrumental Methods of

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Evaluation of method based on vacuum assisted solid phase microextraction for analysis of beer volatile profiles

M. Adam, K. Adámková, A. Eisner, T. Bajer and K. Ventura

University of Pardubice, Faculty of Chemical Technology, Department of Analytical Chemistry, Studentská 578, 532 10 Pardubice, Czech Republic

E-mail: [email protected]

Recently, a new headspace solid-phase microextraction procedure termed vacuum-assisted headspace solid-phase microextraction (Vac-HSSPME) was proposed by Psillakis et al [1]. P1-09 Non-equilibrium SPME sampling under vacuum conditions may dramatically improve extraction kinetics compared to SPME under atmospheric pressure. Although reduced pressure conditions during SPME sampling are not expected to increase the amount of analytes extracted at equilibrium, reducing the total pressure will increase evaporation rates and result in a faster overall extraction process [2]. The reduced pressure speeds partitioning of the semi- volatile compounds into the gas phase and reduces the boundary layer around the SPME fiber, which enables a fraction of the volatilized organics to partition into the SPME fiber. The main aim of this study was the evaluation of a modern sampling strategy based on the use of Vac-SPME procedure and its applicability to the analysis of volatile profile of various beer samples. The separation and identification of target compounds was performed by the of gas chromatography–mass spectrometry (GC–MS) method together with comparison of linear retention indices of individual compounds with those found in spectral libraries and/or available in on-line databases. As an analytical tool, experimental designs were used for the method optimisation. First of all, the most significant factors affecting the whole procedure were evaluated by the Plackett– Burman design. After that, the final experimental conditions were established by five-level orthogonal central composite design followed by response surface modelling. The proposed method was compared to conventional method based on the conventional SPME approach under atmospheric pressure [3]. It was confirmed that Vac-SPME approach provides a sufficient better results considering the response in terms of both the total peak areas and mainly the number of identified compounds, where more volatile components were detected together with less volatile substances. The use of Vac-SPME procedure proved to be a very good alternative for the screening of volatile compounds present in beer with a wider range of volatilities.

References [1] E. Psillakis, E. Yiantzi, L, Sanchez-Prado, N. Kalogerakis, Analytica Chimica Acta 742 (2012) 30– 36. [2] E. Yiantzi, N. Kalogerakis, E. Psillakis, Analytica Chimica Acta 927 (2016) 46-54. [3] M. Adam, A. Čížková, A. Eisner, K. Ventura, Journal of Separation Science, 36 (2013) 764–772.

113

Analytical determination of antibiotics in surface waters of aquacultures by LC-ORBITRAP MS

V. Toli, V. Boti and T. Albanis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina 45110, Greece

E-mail: [email protected]

The massive expansion of aquaculture has a great impact on water quality and aquatic life. P1-10 The widespread and unrestricted use of antibiotics in aquacultures to prevent bacterial infections, leads to significant amounts of residues in the aquatic environment [1]. As a result many of these compounds from different classes have been found in the aquatic ecosystem posing threat to wildlife and human health consequently. This study aims to the determination of 6 common antibiotics used in fish farms (oxytretracycline, florfenicol, sulfamethoxazole, oxolonic acid, trimethoprim and erythromycin). The analytes were extracted by Solid Phase Extraction (SPE) and then analyzed by ultra-high performance liquid chromatography (UHPLC) high-resolution Orbitrap mass spectrometry. Good linearity was obtained in all cases exhibiting excellent coefficients of determination (R2>0.9990). The method precision achieved in terms of repeatability and within-lab reproducibility, was low enough, expressed as relative standard deviation (R.S.D.%) Recoveries obtained were satisfactory for all analytes > 70% with the exception of sulfamethoxazole, while limits of detection found at the low ppt level. The analytical methodology for the routine monitoring of these antibiotics in aquaculture waters was proved to be fast and simple exhibiting at the same time excellent performance and precision.

References [1] FAO Fishers Technical Paper, 469, http://www.fao.org/3/a-a0282e.pdf

Acknowledgements The authors would like to thank the Unit of Environmental, Organic and Biochemical high resolution analysis-ORBITRAP-LC-MS of the University of Ioannina for providing access to the facilities.

114 10th International Conference on Instrumental Methods of

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Determination of common pesticides used in aquacultures in mussels using QuEChERS in combination with LC- hybrid LTQ Orbitrap MS

E. Trantopoulos, V. Boti, Tr. Albanis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina 45110, Greece

E-mail: [email protected] P1-11 In the present study a simple and sensitive QuEChERS methodoly for the determination of three organic micropollutants, which are commonly used in aquacultures (irgarol 1051, deltamethrin, azamethiphos) in mussels tissue has been developed and validated.Individual samples (5 g) were weighed into a 50 mL propylene centrifuge tube. Then, 1% glacial acetic acid was addedin acetonitrile, the tube was tightly capped and vigorously mixed for 1 min using a vortex mixer at maximum speed, and the samples were sonicated for 10 min. Appropriate amounts of anhydrous magnesium sulfate (MgSO4) and sodium acetate (NaOAc) were added to the tube and immediately mixed with a vortex mixer for 1 min. The sample was then centrifuged for 10 min at 4000 rpm. An aliquot of the acetonitrile upper layer was removed and transferred into a 15ml centrifuge tube containing MgSO4, PSA and C18 so as to be submitted in a clean-up step based on dispersive solid phase extraction (dSPE). The tube was vigorously mixed for 1 min and then centrifuged for 5 min at 4000 rpm. An aliquot of the final layer, being the final extract, was evaporated to dryness under a gentle stream of nitrogen and reconstituted in methanol, followed by filtration through PVDF syringe-driven membrane filters and transferred to screw cap vials for injection in the UHPLC-LTQ/Orbitrap-MS. The validation scheme followed was based on the US Food and Drug Administration FDA [1]. Good linearity was obtained in all cases exhibiting excellent coefficients of determination (R2>0.999). The method precision achieved in terms of repeatability and within-lab reproducibility, was low enough, expressed as relative standard deviation (R.S.D.%), complying with the requirements of US FDA document (<8%). Recoveries obtained were satisfactory for all analytes (>70%) while limits of quantification found at the low ppb level. The analytical methodology was successfully applied to determine the pollutant load of mussels from seawater ecosystems near aquaculture facilities in N.W. Greece.

References [1] FDA Guidance for Industry on Method Validation, 2001, www.fda.gov

115

Optimisation of experimental conditions for analysis of silver nanoparticles by single particle ICP-MS

M. Loula, A. Kaňa and O. Mestek

Department of Analytical Chemistry, University of Chemistry and Technology, Technická 5, 166 28 Prague, Czech Republic

E-mail: [email protected]

Single particle inductively coupled plasma mass spectrometry (sp-ICP-MS) is a novel P1-12 modification of well-known method ICP-MS that allows it to determine number concentration and size distribution of inorganic nanoparticles (NP) together with their chemical composition. The method is based on analysis of highly diluted solutions, so that at any moment at most one NP reaches the plasma. In comparison with conventional ICP-MS, where continuous signal is observed, in the sp-ICP-MS we obtain signal in form of peaks whose frequency is proportional to NP number concentration and area proportional to NP size. This work was focused on optimising experimental conditions for analysis of Ag NP. All measurements were performed on NexION 350d (Perkin Elmer, Concord, Canada) spectrometer equipped with high efficiency plasma torch, PTFE Meinhard nebuliser and glass cyclonic spray chamber. Standard solutions of Ag NP 10, 20, 40, 60 and 100 nm diameter (all Sigma Aldrich, St. Luis, MO, USA) were used. Effects of plasma power, nebulizer gas flow and sample uptake rate on NP signal intensity and transport efficiency were studied and optimal conditions were proposed. The transport efficiency was not affected by plasma power in wide range (1 000 – 1 500 W). On the other hand, it strongly depended on sample uptake. Very low sample uptake (below 0.05 ml min–1) ensured very high transport efficiency (up to 25 %), however the total number of analysed NP was extremely low. For practical use, a compromise between transport efficiency and number of analysed particles must be chosen. Influences of Ag NP diameter and number concentration on their signal intensity and transport efficiency were studied, too. Under optimal conditions, the transport efficiency reached 10 %. During these experiments dissolution of Ag NP was observed, therefore another part of this work studied stability of Ag NP in various chemical environments in attempt to find optimal environment for storing Ag NP calibration solutions and samples. Several possible stabilizers at various concentration levels were tested; best results were obtained for 0.05% gelatine solution. In the end, the sp-ICP-MS was used to analyse water samples taken from Vltava river at various places in Prague. Total concentration of Ag ranged from 5 to 22 ng L–1, number concentration of Ag NP of diameter 30 – 100 nm ranged from 340 to 1 700 mL–1.

Acknowledgements: The financial support of the Grant Agency of Czech Republic (project no. 17- 00291S) is gratefully acknowledged.

116 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Detection of emerging contaminants in water samples by Homogeneous Liquid-Liquid Microextraction using switchable hidrophilicity solvents as acceptor phase

C. Rivera-Vera1, Carla Toledo-Neira1, G. Lasarte-Aragonés2

1Laboratory of environmental electrochemistry, Faculty of Chemistry and Biology, University of Santiago de Chile, Santiago, Chile 2College of Science, George Mason University, Fairfax, VA and Center for Bio/Molecular Science and Engineering, Code 6900, U. S. Naval Research Laboratory, Washington, DC, United States P1-13 E-mail: [email protected]

Switchable solvents (SS) are defined as a system in two forms that can switch reversibly between one form that is miscible with water and another also can form a biphasic mixture with water by the presence of carbon dioxide. This gas is purged of the solution. The possibility of using carbon dioxide to reversibly change the polarity of a medium offers a promising tool for the design of eco-efficient methods. At the same time, the non-toxic nature and low cost of CO2 gas make it an ideal phase transition activator in extraction techniques. Jessop et al. have focused their use from a more profitable and ecological point of view [1,2]. Lasarte- Aragonés et al. using N, N-dimethylcyclohexylamine for the extraction of polycyclic aromatic contaminants in water samples of different nature with microextraction techniques. In this context, this work presents the development of an analytical method with the use of switchable hidrophilicity solvents (SHS) with homogeneous liquid phase microextraction and liquid chromatography for the determination of 5 NSAIDs, 2 steroidal hormones: 17-ß- estradiol and 17-α-ethynylestradiol and an antibacterial agent triclosan. N, N- dimethylbenzylamine, water and carbon dioxide were used for the synthesis of this switchable hidrophilicity solvent and concentrated NaOH was used to induce phase separation after extraction of the analytes. Effects such as sample volume, volume of extractant medium, volume of NaOH and stirring time were optimized. The optimized method exhibited a good level of accuracy, with values of relative standard deviation between 3% and 5%. The limit of detection obtained ranged from 41 to 170 ng mL-1 for all analytes, while recoveries are between 80% and 100% for analytes with Log p over 3.6. Finally, the proposed method could be successfully applied for the analysis of emerging contaminants with hydrophobic characteristics.

References [1] G. Lasarte-Aragonés, R. Lucena, S. Cárdenas, M. Valcárcel, Talanta 131, (2015) 645. [2] G. Lasarte-Aragonés, R. Lucena, S. Cárdenas, M. Valcárcel, J. Sep. Sci. 38, (2015) 990.

Acknowledgement: The authors thanks to FONDECYT PROJECT GRANT 11160835 and PAI79160152.

117

Comparative determination of fludioxonil by GC/MS-MS and LC/MS-MS in raspberry

M. Jaksic, N. Tomcic, J. Banic-Simicic, S. Cujic, B. Marosanovic

SP Laboratorija, Industrijska 3, 21220, Becej, Serbia

E-mail: [email protected]

Fludioxonil is a fungicide, which is one of the most used pesticide in berries treatment against P1-14 Fusarium, Rhizoctonia and Botrytis cinerea sp. In SP LABORATORIJA we performed optimizations of named analyte by two different techniques – gas and liquid chromatography, with tandem mass spectrometry detection. After optimization, we analyzed fludioxonil in non- contaminated, laboratory control sample of raspberry. In total, eleven samples were prepared, among which one sample was used as blank, while five samples were spiked at concentration level 0,01ppm and five at concentration level 0,1ppm. Sample preparation was performed in accordance to QuEChERS method by EN 15662 [1]. Optimization included acquiring peak properties in full scan (retention time, spectrum, precursor ion mass) and acquiring product ions with collision energies for each. Data obtained are presented in Table 1.

Technique GC/MS-MS LC/MS-MS Retention time 11.526 5.58 Transitions and 248→154.1 20 V 246.99→169.28 36 V collision energies 248→182.1 10 V 246.99→180.11 45V 248→127.1 30 V Ionization mode EI ESI-

During optimization, we observed slightly higher peak response by LC/MS-MS technique, which was 476307 for standard solution of fludioxonil at 100ppb concentration level, while the same value obtained by GC/MS-MS was 462684. Although peak response was at the same level (E4), in GC/MS-MS determination, we observed peak tailing, which lead to efficinecy decreasement of analysis, while in LC/MS-MS determination symmetry of the peak was satisfying. Recoveries obtained from analysis of prepared blank and spiked samples of raspberry, for fludioxonil are presented in Table 2.

GC/MS- Technique MS LC/MS-MS GC/MS-MS LC/MS-MS Spike level 0,01ppm 0,1ppm Average of Recoveries (%) 55 97 70 101

According to obtained data, we concluded that LC/MS-MS technique is more suitable for fludioxonil determination, due to higher sensitivity, and accuracy, as well.

References [1] Foods of plant origin - Determination of pesticide residues using GC-MS and/or LC-MS/MS following acetonitrile extraction/partitioning and clean-up by dispersive SPE - QuEChERS-method

118 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Dried blood spots and laser ablation ICP-MS for multi-element determination in whole blood from newborn

J. Moreda-Piñeiro1, A. Cantarero–Roldán2, J.A. Cocho3, P. Bermejo-Barrera4 and A. Moreda-Piñeiro4

1 University of A Coruña. Department of Chemistry. Faculty of Sciences. Grupo Química Analítica Aplicada (QANAP), University Institute of Research in Environmental Studies (IUMA), Centro de Investigaciones Científicas Avanzadas (CICA), Campus de A Coruña, s/n. 15071 – A Coruña. Spain 2 Scientific Research Support Services, Edificio de Servizos Centrais de Investigación. University of A Coruña. Campus de A Coruña, s/n 15071– A Coruña. Spain. 3 Laboratory of Metabolic and Nutritional Disorders, University Clinical Hospital, 15782 – Santiago de P1-15 Compostela. Spain 4 Group of Trace Elements, Spectroscopy, and Speciation (GETEE), Health Research Institute of Santiago de Compostela (IDIS), Department of Analytical Chemistry, Nutrition and Bromatology. Faculty of Chemistry. University of Santiago de Compostela. Avenida das Ciencias, s/n. 15782 Santiago de Compostela. Spain.

E-mail: [email protected]

Dried blood spot (DBS) samples have been collected for routine metabolic disease and genetic disorders screening in newborn since the early 1960s. DBS offers several advantages over other sample pre-treatment methods, including simple and inexpensive methodology, minimal sample volume requirements, great sample stability, and ease of storage and transportation [1]. In the current communication, an approach by laser ablation (LA) coupled with inductively coupled mass spectrometry (ICP-MS) for multi-element determination in whole blood has been performed. The method allows quantitative determination of several major (K, Na and S), minor (Ca, Cu, Fe, Mg, P, Rb and Zn), and trace elements (Al, As, Ba, I, Li, Pb, Sb, V and Tl) in DBS samples. Optimum conditions and validation were assessed using SeronormTM level II and SeronormTM level III certified reference materials. Laser ablation of DBS was performed using a focused Nd:YAG laser beam in lineal scan mode (wavelength 213 nm, laser fluency 3.0 J cm−2, repetition rate 20 Hz, laser spot diameter 90 µm, depth 0 µm, scanning speed 8 µm s-1,). Different quantification strategies for the LA-ICP-MS data using matrix- matched calibration or prearranged external calibration / addition set were applied. 13C and 32S were used for signal intensities normalization. Using a matrix-matched calibration curve and 13C or 32S as internal standards normalization, limits of quantification were found to be from 1.9 µg L−1 to 1094 mg L−1. Accuracy (analysis of SeronormTM level II) was satisfactory after statistical evaluation by applying a t-test at 95% confidence level. Repeatability and reproducibility of the methods were generally below 14%. The method was applied to several DBS from newborn.

References [1] E. K. Langer, K. J. Johnson, M. M. Shafer, P. Gorski, J. Overdier, J. Musselman and J. Ross, J. Expo. Sci. Environ. Epidemol., 21 (2011) 355-364.

119

Assessment of titanium dioxide and silver nanoparticles in urine by single particle – ICP-MS

K. Badalova1,2, P. Herbello-Hermelo1, P. Bermejo-Barrera1, and A. Moreda- Piñeiro1

1Group of Trace Elements, Spectroscopy, and Speciation (GETEE), Health Research Institute of Santiago de Compostela (IDIS), Department of Analytical Chemistry, Nutrition and Bromatology. Faculty of Chemistry. University of Santiago de Compostela. Avenida das Ciencias, s/n. 15782 Santiago de Compostela. Spain. 2Faculty of Pharmacy, Azerbaijan Medical University, Baku, Azerbaijan. P1-16 E-mail: [email protected]

The use of engineered nanomaterials, mainly metallic nanoparticles, implies the presence of nanomaterials in the environment and also in Humans. Titanium dioxide nanoparticles (TiO2 NPs) are commonly used as an additive (E171) in many foods, and it also used in personal care products, mainly sunscreens, because their effective capacity for UV filtering. Similarly, the powerful antimicrobial properties and relatively low cost have led to silver nanoparticles (Ag NPs) being used in several applications (food contact materials, cosmetics, wall paints, textiles, laundry detergents, biocide sprays and medical devices). However, the potential risks of NPs on human health and the environment is still unknown. In this communication, parameters affecting data acquisition in single particle – inductively coupled plasma – mass spectrometry (sp-ICP-MS) have been optimized for assessing TiO2 and Ag NPs in urine. Samples were diluted with 1%(v/v) glycerol for ensuring NPs stability. Repeatability of the method was assessed by preparing diluted urine samples eleven times, and by measuring three times each one (RSD values were 16 and 21 % for TiO2 and Ag NPs, respectively). Analytical recovery was assessed by spiking urine samples with TiO2 NPs (30, and 50 nm), and Ag NPs (40, and 60 nm). After sp-ICP-MS analysis, analytical recoveries were 90, and 87% for TiO2 NPs of 30 and 50 nm, respectively; whereas, analytical recoveries were 109, and 110% for Ag NPs (40 and 60 nm, respectively). The limit of detection (LOD) 3 3 -1 was 1.7 10 and 6.0 10 NPs mL for TiO2 NPs and Ag NPs, respectively. Regarding sizes, two different methods were used to assess LOD (blank value, and particle calibration methods) [1]. Values of 14 and 17 nm were obtained for TiO2 NPs; whereas, 20 nm was calculated as LOD for Ag NPs. The developed methods were applied for assessing TiO2 and Ag NPs in several urine samples from healthy people. Urine samples were also analysed for total Ti and Ag [an optimized procedure consisted of sample dilution with 1%(v/v) nitric acid before ICP- MS (procedure validated by analysing a Seronorm™ Trace Elements Urine L-2 certified reference material offering indicative values for Ti and Ag levels)]. TiO2 NPs concentrations were within the

References [1] M. Witzler, F. Kü llmer, A. Hirtz and K. Gü nther, J. Agric. Food Chem., 64 (2016) 416-41701.

120 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Development of analytical methodologies for the chemical investigation of insect attractants or repellents

S. Giannoukos1,2, A. Pappa2, A. Michaelakis3 and S. Taylor1

1Department of Electrical Engineering and Electronics, University of Liverpool, Brownlow Hill, Liverpool, L69 3GJ, United Kingdom 2National Technical University of Athens, School of Chemical Engineering, 157 73, Athens, Greece 3Department of Entomology and Agricultural Zoology, Benaki Phytopathological Institute, 8, S. Delta str., 14561 Kifissia, Athens - Greece

E-mail: [email protected] P1-17

This study focuses on the design, development and testing of a portable olfactometer for the chemical investigation of volatile organic compounds (VOCs) with insect attractant and repellent activity. The olfactometer has a Y-shape design and comprises of four chambers: a) for hosting the under-investigation insect population, b) for hosting the chemical analytes of interest, c) a control chamber and d) a decision chamber. A compact portable membrane inlet quadrupole mass spectrometer (MI-QMS) has been integrated within the developed olfactometer and employed for the first time to detect and monitor continually, both qualitatively and quantitatively, VOCs with mosquito repellent activity. On-line monitoring of such compounds in field conditions (i.e. out of the laboratory) is of great importance and allows the chemical comprehension of the olfactory behaviour of insects with potential negative impact on public health. MI-QMS is a powerful, simple analytical technique ideal for in-situ applications that offers high sensitivity (low limits of detection), selectivity, fast and accurate analysis (within seconds), with no sample preparation requirements. Representative compounds examined include: (-)-a-pinene, γ-terpinene, (+/-)-linalool, (-)-b-pinene, p- cymene, R-(+)-limonene, b-Myrcene, (-)-linalool, butyl hexanoate, ethyl butyrate, o-xylene. Gas phase experiments were performed at concentration levels from low ppb to low ppm using two techniques for gaseous standards generation: a) static dilution bottles and b) a built-in- house vapour generator. Results obtained showed very good linearity within the examined concentration range, ppb limits of detection and fast response times (within sec). Preliminary lab evaluation experiments with mosquitoes will also be presented.

121

SeaFast sample introduction system for multi-element determination in serum samples by ICP-MS

M.d.P. Chantada-Vázquez, P. Herbello-Hermelo, P. Bermejo-Barrera, A. Moreda-Piñeiro

Group of Trace Elements, Spectroscopy, and Speciation (GETEE). Department of Analytical Chemistry, Nutrition and Bromatology. Faculty of Chemistry. University of Santiago de Compostela. Avenida das Ciencias, s/n. 15782 – Santiago de Compostela. Spain

E-mail: [email protected] P1-18 The assessment of trace and ultra-trace elements in clinical samples is difficult because of the complexity of the sample, the low target concentrations, and also the low volumes/amount of samples typically available for analysis. Inductively coupled plasma – mass spectrometry (ICP-MS) offers excellent sensitivity for multi-element determinations, but requires a certain volume of sample, which is higher as the number of targets increases. In this communication, parameters affecting the sample introduction system when using a SeaFast autosampler have been optimized for allowing the determination of eighteen elements (internal standards included), and requiring only 2 mL (200 µL of serum sample diluted with internal standard and 1%(v/v) nitric acid up to 2 mL). Sample decomposition was avoided, fact that speeds the analytical process, and it is an appealing methodology for routine analysis. Matrix effects have been found to be important, and determinations were performed by using the standard addition technique. The limit of detection varied within the 0.09 µg L-1 (Li) – 147 µg L-1 (Fe) range. Intra-day precision and analytical recovery (n=11) was tested for three concentration levels (1.0, 10, and 100 µg L-1). Precision (RSD values) were lower than 13%; whereas, analytical recoveries were from 99 to 105%. The accuracy of the method was also evaluated by analysing Seronorm™ Trace Elements Serum L-1 and L-2 certified reference materials. Good accuracy was assessed for all elements certified by the manufacturer (Co, Cu, Fe, Mn, Ni, Se, and Zn). Finally, the method was applied to several serum samples.

Acknowledgement The authors belong to the Galician Competitive Research Group 6RC2014/2016. This program is co- funded by FEDER (UE)

122 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Binding kinetics of analytes in microfluidic channels: A simple model for Salmonella cells and immobilized antibodies

A.S. Kastania1,2, K. Tsougeni1, V. Constantoudis1 and E. Gogolides1

1Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, Aghia Paraskevi, 153 41, Greece 2Department of Chemistry, University of Athens, Athens, 157 71, Greece

E-mail: [email protected]

Affinity chromatography and detection with sensors are examples of separation and detection P1-19 techniques that are commonly used for various biological and chemical applications. These techniques utilize the interaction between an analyte molecule and its ligand (complementary molecule) and have been transferred over the past 10-15 years to microfluidics [1], exploiting the advantages micro-technology has to offer. A simple model is presented herein, regarding the kinetics of analytes passing through a microfluidic device with binding on the microchannel surface at the same time [2]. We concentrate more on analytes that are grouped as binding sites rather than being discrete units and the model is validated for analytes that are antigens grouped on Salmonella cells and ligands that are anti-Salmonella antibodies. An equation is developed for the surface bound cell concentration Bc(x) (Fig.1) with simple/known variables (e.g. flow rate, dimensions of the microchannel, concentrations etc.), which can be used by biologists, microbiologists or other non-math experts. More particularly, we compare our theoretical results with experiments using microfluidic devices [3] fabricated by lithography and oxygen plasma etching. First, we immobilize the anti-Salmonella antibodies on the surface of the chip and then, we inject Green Fluorescent Protein (GFP)- labeled Salmonella cells inside the chip under flow. The bound cells on the immobilized antibodies are counted, afterwards, in different locations by using fluorescence image processing. Making use of the theoretical fittings of the model developed, we estimate the 2 association rate constants kass for the counted bound cells (cells/mm ) in the microfluidic devices and calculate the cell binding efficiency as well. Finally, we use the equations derived from the model to predict the cell binding efficiency in microfluidic devices of different designs (different size and shape), which can be most useful when designing a microchannel.

ퟐ퐍퐀 훗퐍 퐤퐚퐬퐬퐒퐗ퟎ 퐁퐜 퐱 = 퐒퐗ퟎ ퟏ − 퐞퐱퐩 −퐤퐚퐬퐬훌퐌ퟎ 퐞퐱퐩 − 퐱 퐍 퐍퐀 퐇퐔 S : active surface enhancement ratio, X0 : initial surface ligand concentration (immobilized antibodies), kass : forward reaction rate constant, φ : fraction of the total number of antigens effectively accessible to antibodies, M0 : initial volumetric cell concentration (cells/μL), λ: pulse of time: injected volume / flow rate, x : spatial variable (the position along the length of the channel), H : microchannel height, U : average flow velocity on the cross section, N : total number of antigens on cell surface and NA : Avogadronumber Figure 1. The equation for the surface bound cell concentration vs simple variables.

References [1] D. Friedrich, C. Please and T. Melvin, Sensors Actuators B: Chem, 131(2008) 323-32. [2] A. S. Kastania, K. Tsougeni, V. Constantoudis and E. Gogolides, Sensors and Actuators: B. Chemical, (submitted, 2017). [3] K. Tsougeni, G. Papadakis, M. Gianneli, A. Grammoustianou, V. Constantoudis, B. Dupuy, P.S. Petrou, S.E. Kakabakos, A. Tserepi, E. Gizeli and E. Gogolides, Lab on a Chip, 16(2016) 120-31.

123

Investigating the mechanism for gas-phase ion production in Sonic- Spray Ionization (SSI) mass spectrometry

L.K. Mavroudakis1, G.R. Agnes2, E.A. Kapellios1, K. Kanaki1 S.A. Pergantis1

1Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Heraklion, 71003, Greece 2Department of Chemistry, Simon Fraser University, Burnaby, B.C., Canada

E-mail: [email protected], [email protected]

P1-20 In this work, possible mechanisms for gas-phase ion production in sonic-spray ionization (SSI) are described and compared to known pathways used to interpret gas-phase ion production in conventional electrospray ionization (ESI). To investigate these mechanisms, both ion mobility and mass spectrometry analyzers were used to assess bare ion and ionic cluster signal intensities. The ion mobility measurements, using a SSI source coupled to a gas-phase electrophoretic mobility macromolecular analysis (GEMMA) analyzer, clearly demonstrate that SSI generates gas-phase protein ions under atmospheric pressure without the need for vacuum conditions. The SSI-MS results indicate that ion production processes have reached maximum efficiency within 2 mm of the nozzle. The smallest droplets produced within 2 mm of the nozzle were estimated having diameter in the range of ~75 to ~400 nm. Upon comparison of SSI-MS and ESI-MS spectra of the protein cytochrome c, it was observed that less charges are present in the protein molecules under the SSI conditions, thus, the droplets produced from SSI contain fewer charges than those that arise from ESI and possibly less protein unfolding occurs in the SSI conditions. Different onset concentration-threshold for ionic cluster detection was observed for SSI and ESI during the analysis of caesium iodide solutions, with CsI ionic clusters consistently detected at lower concentrations using SSI. These differences were attributed to simple desolvation of droplets being predominant in SSI, whereas for ESI, the solute enrichment process of solvent evaporation and Coulomb explosions is prevalent and these differences were assumed responsible for the differential detection of CsI clusters.

124 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Characterization of gamma radiation fields emitted by 60-Co sources inside of multifunctional interaction chamber

C. Postolache, D. Negut, C. S. Tuta, S. Bercea, A. Celarel, C. Cenusa, V. Fugaru, M.-R. Ioan

Horia Hulubei National Institute for Physics and Nuclear Engineering, 30, Reactorului St., Magurele, Ilfov, Romania

E-mail: [email protected]

A new multifunctional interaction chamber was designed built and tested to establish the P1-21 technical solution for future experimental facilities dedicated to simulate the cosmic space environment at ELI NP /E5 Experimental Area, Bucharest-Magurele, Romania. The research team chose to simulate cosmic radiation using a 60-Co gamma radiation source, because: gamma radiation is slightly attenuated in the simulation chamber walls, absorbed dose rate is easy to determined, allows obtaining high dose rate and does not induce nuclear reactions associated with the activation of the exposed samples. The gamma radiation fields, emitted by three 60-Co sources positioned inside of the interaction chamber, were analysed in point of view of axial and transverse dose distribution and uniformity of dose rate using: electronic debit-meter UNIDOS T10021 type with Ionization Chamber TM 30013 type, alanine tablet EPR dosimeters and Gafchromic films.

References [1] A. Author, B. Author and C. Author, Journal, 50 (2011) 1-10.

125

Optimizing the delivery of phenolic compounds from Salvia triloba and Vitis vinifera

G. Asimomiti1,2, N. Soteriou1,2, D.Z. Lantzouraki3, T. Tsiaka1, P. Natskoulis3, E. Spanidi3, K. Gardikis3, V. J. Sinanoglou and P. Zoumpoulakis1

1Institute of Biology, Medicinal Chemistry and Biothechnology, National Hellenic Research Foundation. 48 Vas. Constantinou Ave. 11635, Athens, Greece 2Scientific Affairs Dept., APIVITA S.A., 19003, Markopoulo Mesogaias, Greece 3Laboratory of Chemistry, Analysis & Design of Food Processes, Department of Food Technology, Technological Educational Institute of Athens, Ag.Spyridonos 12210, Egaleo, Greece. P1-22 E-mail: pzoump@eie. gr

In the last two decades, plant nutraceutical and medicinal agents have attracted the attention of many pharmaceutical and cosmetic firms due to their proven role in pathological conditions [1]. Amongst other, plants native to Mediterranean countries, Vitis vinifera L. and Salvia triloba have been of great research interest, due to their phenolic constituents with proven antiradical, antioxidant, anti-inflammatory, antimicrobial and neuro-protective potential against peroxide damaging [1, 2]. This study aims to improve the extraction efficiency of phenolic-antioxidant components from the two plant materials with a final scope to be used for the development of new cosmetic products. Two high energy extraction methods have been applied for reducing the operational time and usage of organic solvents, ultrasound-assisted extraction (UAE) and pressurized liquid extraction (PLE). UAE’s mechanism is based on the cavitation phenomenon, while PLE is based on the use of solvents at elevated temperature and pressure to extract target components from various matrices [3]. For the UAE extracts, five different mixtures of methanol and water were evaluated, in order to obtain different extracts in a fast (15 min) procedure. Moreover, for the PLE extraction, conducted at pressure of 4-8 bars, five different solvent systems of water and glycerol mixtures were studied. For V. vinifera and S. triloba different extracts, the total phenolic and flavonoid contents were measured using the Folin- Ciocalteu assay, and an aluminium chloride colorimetric assay, respectively. The antiradical capacity was assessed with the DPPH free radical assay, while the reducing/antioxidant power was measured using the FRAP assay. The phenolic profiles of higher activity extracts were evaluated using Liquid Chromatography – Mass Spectrometry and Nuclear Magnetic Resonance Spectroscopy.

References [1] N. Jaradat, A. N. Zaid, F. Hussein and I. Ali, Marmara Pharmaceutical Journal, 21 (2017) 1–7. [2] R. Boukhary, K. Raafat, A. I. Ghoneim, M. Aboul-Ela and A. El-Lakany, Evidence-Based Complementary and Alternative Medicine, 2016 (2016) 1–6. [3] D.-P. Xu, Y. Li, X. Meng, T. Zhou, Y. Zhou, J. Zheng, J.-J. Zhang and H.-B. Li, International Journal of Molecular Sciences, 18 (2017) 1–32.

126 10th International Conference on Instrumental Methods of

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Tracking the Fate of Metal-Based Nanoparticles in Environmental Matrices using Single Particle ICP-MS

R. Magarini1, C. Stephen2

1PerkinElmer - Milano, Italy 2PerkinElmer - Shelton (CT), USA

e-mail: [email protected]

Production and use of engineered nanomaterials (ENMs) have experienced a fast increase in P1-23 the last decade. As a consequence, increasing is the risk of their possible releases into the environment, so the study of ENMs impact on the environment becomes of paramount importance. An appropriate risk assessment and management of ENMs in the environment requires quantitative measurements of both exposure and effects. Measurements should ideally be performed by in situ analysis to provide physicochemical characterization.[1] However, most analytical techniques are not suitable for environmental matrices since nanoparticle concentrations are typically very low. [2] Historically, particle size has been measured by dispersive light scatter (DLS) and tunnelling electron microscopy (TEM), while dissolved content has been determined post ultrafiltration. These techniques have known limitations for determining low concentrations in the presence of colloidal species in complex waters. As an alternative, single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) has been found a promising technique for detecting and characterizing metal containing nanoparticles at very low concentrations. SP-ICP-MS is fast, efficient, and provides more information than other currently available techniques. With SP-ICP-MS it is possible to determine particle size, size distribution, particle number concentration, and concentration of dissolved element. Moreover, it can easily distinguish among particles of different elements. Aim of this work is to investigate the efficiency of SP-ICP-MS in tracking the fate of metallic nanoparticles in various environmental matrices going through the environmental cycle, from waste water to surface water and drinking water, and to evaluate the various physicochemical processes such as dissolution and aggregation in each matrices.

References [1] CR Paresh, Y Hongtao, and PF Peter, Toxicity and Environmental Risks of Nanomaterials: Challenges and Future Needs, J Environ Sci Health C Environ Carcinog Ecotoxicol Rev. 27-1 (2009) 1-35. [2] RC Merrifield, C Stephan, JR Lead, Single-particle inductively coupled plasma mass spectroscopy analysis of size and number concentration in mixtures of monometallic and bimetallic (core-shell) nanoparticles, Talanta 162 (2017) 130-134.

127

Detection of honey adulteration with sugar syrup addition, using LC-MS/MS and ICP-OES

M. Christofakis1, G. Siragakis1 and G. Miliadis2

1Food Allergens Laboratory, Posidonos 1, 74100 Rethimno 2Food Allergens Laboratory, K,Varnali 40, 14231 N. Ionia, Athens Greece

E-mail: [email protected]

P1-24 Sugars are the main components of honey with an amount of total sugar varying from 45g to 90g/100g, depending on the botanical origin. Honey may easily be adulterated by addition inexpensive industrial sweeteners such as corn syrup, isoglucose, invert syrups or other high fructose syrups from rice or wheat, while remaining compliant with the legal criteria for sugar content of honey [1,2]. Main honey adulteration indicators include; a proline value of less than 180mg/kg and a sodium/potassium ratio (Na/K) of lower than 8. There are approximately 27 amino acids in hone including Proline , Lysine , Histidine , Arginine , Threonine , Aspartic acid , Glutamic acid , Glycine , Methionine , Isoleucine , Leucine , Tyrosine , Tryptophan , Phenylalanine and others. The main source of amino acids in honey is the pollen, therefore determining the types of amino acids present can give us details on the botanical origin as well as the production region of the honey. The amino acid content of honey, analyzed by LC- MS/MS can be used to investigate not only botanical origin of honey, but also speed of honey production/harvest, effect on dihydroxyacetone (DHA) conversion, inaccurate labelling, and of course sugar syrup addition. Premier Quatro LC-MS/MS was used with an aTRAQ™ kit which labels amino acids with a Δ8 reagent for analysis and also provides Δ0 labeled internal standards for comparison. Forty eight amino acids and internal standards can be accurately detected by MRM’s in 18 minutes. Sample preparation was optimized for honey and the method was validated. Potassium content is also an important tool for the identification of possible adulteration of the honey as it should be over 16 mg/100 g. Leeman Prodigy ICP- OES was used for the sodium/potassium ratio determination with a LoQ = 0.001 mg/kg. The combination of these two techniques could detect honey adulteration with sugar syrup even in less than 2% addition.

References [1] Codex Standard for Honey CODEX STAN 12-1981, [2] Directive 2014/63/EU of the European Parliament and the Council of 15 May 2014 amending Council Directive 2001/110/EC relating to honey

128 10th International Conference on Instrumental Methods of

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Highly Selective Detection of Multi-Phosphorylated Peptides via Zn2+-IMAC enrichment and MALDI-TOF MS analysis

S.W. Bae

Green Chemistry and Materials Group, Research Institute of Sustainable Manufacturing System, Korea Institute of Industrial Technology (KITECH), Cheonan, 31056 South Korea

E-mail: [email protected]

In this presentation, I’ll report a new phospho peptides enrichment method using bis-zinc(II)- P1-25 dipicolylamine complex immobilized on magnetic spheres. Due to the low abundance of phospho protein or peptide in the total proteome, developing the robust and selective phospho protein or peptide enrichment techniques have been actively studied. Bis-zinc(II)- dipicolylamine complex immobilized on the magnetic sphere was incubated with a mixed sample containing both non-phosphorylated peptides and phosphorylated peptides. After separation, MS analysis confirmed that multi-phosphorylated peptides were selectively bound to magnetic sphere from the mixed sample.

References [1] S. A. Johnson, T. Hunter, Nat. Biotechnol., 22 (2004) 1093-1094. [2] T. Hunter, Cell, 100 (2000) 113-127.

129

Method validation for the determination of aqua regia extractable trace elements in soils

Th. Lymperopoulou1, L.-A. Tsakanika2 and M. Ochsenkuehn-Petropoulou2

1Center of Environment and Quality of Life, 2Laboratory of Inorganic and Analytical Chemistry, School of Chemical Engineering, NTUA, Iroon Polytechniou 9, Zografou Campus, Athens, Greece

E-mail: [email protected]

P1-26 Validation of analytical methods is mandatory in order to ensure the reliability of the results obtained and produce data to be applied on the estimation of the overall accuracy and uncertainty. Uncertainty of the measurement is due to several sources such as uncertainties of equipment, reference values, measurement method and random variations [1,2]. There are several procedures to be followed for a method validation [3]. The method validated in this study refers to the microwave assisted extraction of trace elements from soils, using aqua regia (HCl/HNO3), followed by ICP-OES measurements. Aqua regia microwave acid digestion is a fast and precise analytical method applied on multi element environmental studies [4]. Two different soil certified reference materials (CCRM SO-2, IAEA SOIL-7) were analyzed by different digestion procedures. Six elements (Ni, Pb, Cr, Co, Mn, Cu) were measured by ICP-OES. Validation of the proposed procedure was based on comparison of different digestion methods. The methods used were aqua regia digestion on hot plate (equivalent to USEPA 3050b) and reversed aqua regia digestion (equivalent to USEPA 3052) in addition to the aqua regia microwave assisted. Accuracy was evaluated for all methods and the different soil matrices based on the reference values. Detection limits, repeatability in terms of standard deviation of triplicate sample and recoveries of spiked samples were determined for all methods and elements. The combined effect of all potential sources of uncertainty was estimated and standard uncertainty was calculated for the elements measured. Furthermore, expanded uncertainty was deduced from standard uncertainty by a coverage factor k=2 for a confidence level of 95%.

References [1] B.Magnusson, S.L.R.Ellison, Anal Bioanal Chem, 390 (2008) 201-213. [2] T.P.J.Linsinger, Trends Anal. Chem 27 (10) (2008). [3] S.L.R.Ellison, M.Rosslein, A.Williams, EURACHEM/CITAC Guide, 2nd Edition (2000). [4] S.Melaku, R.Dams, L.Moens, Anal Chim Acta 543 (1-2) (2005) 117-123.

130 10th International Conference on Instrumental Methods of

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Microwave-driven ICP for analytical spectrometry

J. Giersz1, K. Jankowski1, A. Ramsza2 and E. Reszke3

1Warsaw University of Technology, Faculty of Chemistry, Noakowskiego 3, 00-664 Warszawa, Poland 2Institute of Applied Optics, Kamionkowska 18, 03-805 Warszawa, Poland 3Ertec-Poland, Kłopockiej 13, 54-530 Wrocław, Poland

E-mail: [email protected]

Microwave plasma (MWP) cavities are widely used as excitation sources for emission P1-27 spectroscopy (AES) or as ionization sources for mass spectrometry (MS) [1]. Almost all of the MWP sources are based on the electrical excitation of plasma gas with an axial E field component relative to the plasma column [2]. This results in generation of plasma with hotter core at its axis which is not easily penetrable by sample material and plasma stability is usually sample sensitive. Using a short terminated standard rectangular waveguide with fundamental TE10 mode of oscillations it is possible to find a place with a well focused magnetic field lines. This was adopted by Hammer in both air and nitrogen MWP source [3] and implemented in a MP-AES Agilent instrument. In this configuration nitrogen or air plasma featuring a narrow hole along its axis enabling the introduction of samples. Recently, Microwave Inductively Coupled Atmospheric Plasma has been published along with some very promising analytical results [4]. The experiments with semi-lumped magnetic coupling led us to the general conclusion that symmetrical H-field excitation cannot be achieved using just a single inductor [5]. Special MW field-shaping inserts enabling generation of toroidal discharges are subject of patent pending (PCT) [6]. We are developing new MWP cavities which can revolutionize AES and MS spectrometers. This new Research Gate project is aimed at elaboration of MWP cavities operating with different gases such as air, nitrogen, oxygen, helium and argon which take the form of a bush with hollow center along which the sample aerosol can be fed in a very stable manner. Power level for miniature MWPs does not exceed 200 W while for regular sized torches (Fassel-type) it may reach 1500 W. One of the nice hollow argon MWP shapes is shown below. The general aim was focused on the choice of the feasible microwave coupling structures best suited to heat plasma discharges with hollow center axis which are capable to excite and ionize dry and wet analytical samples without perturbing the plasma stability. Preliminary results of evaluation of the novel MW ICP source are presented. Emission spectra provide OH rotational temperature of 4200K and electron density of 2∙1015cm-3. Detection limits data for some elements are promising as compared with those obtained using other AES systems.

References [1] K. Jankowski and E. Reszke, Microwave induced plasma analytical spectrometry, RSC, 2011. [2] K. Jankowski and E. Reszke, J. Anal. At. Spectrom., 28 (2013) 1196-1212. [3] M.R. Hammer, Spectrochim. Acta, Part B, 63 (2008) 456-464. [4] A.J. Schwartz, Y. Cheung, J. Jevtic, V. Pikelja, A. Menon, S.J. Ray and G. Hieftje, J. Anal. At. Spectrom., 31 (2016) 440-449. [5] D. Wydymus, A. Francik and E. Reszke, J. Micr. Power, 45 (2011) 205-211. [6] K. Jankowski, A. Ramsza and E. Reszke, Polish Patent Application, P. 416 758 (2016).

131

Sulfonamides in wastewaters: Method development, occurrence, mass loading, removal efficiencies and environmental risk assessment

M. Gougousi, Ch. Kosma, V. Boti and T. Albanis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina, 45110, Greece

E-mail: [email protected] P1-28 Antibiotics, which are an important group of pharmaceuticals in today’s medicine, have been used not only to prevent and treat diseases in human and animals but as growth promoters, as well. They are one of the most important xenobiotic contaminants due to their potential development of antimicrobial resistance [1]. As their consumption has been increased, they are being detected in all sectors of the environment and have attracted much public attention in the last decade. Sulfonamides (SAs) are the most highly consumed antibiotics, after tetracyclines, in the European Union (EU). They are commonly used to treat diseases as urinary tract infections, ear infections, bronchitis, bacterial meningitis, certain eye infections, Pneumocystis carinii pneumonia, traveler’s diarrhea, and a number of the other kinds of infection [2]. Furthermore, they are used in aquaculture and intensive livestock farming. The presence of SAs residues is of great public concern because some of them might be carcinogenic, promote occurrence of antibiotic resistant bacteria, and cause allergic reactions in humans. Therefore, in the European Union (EU), the total level of SA residue should not exceed 100 μkg-1 [3].The present work describes the development and application of a method for the determination of nine sulfonamides (sulfacetamide, sulfapyridine, sulfadiazine, sulfamethoxazole, sulfathiazole, sulfamethizole, sulfamethazine, sulfamethoxypyridazine, sulfaquinoxaline) in wastewaters in Greece. A pre-concentration step, based on solid phase extraction (SPE) using different types of sorbent cartridges and followed by LC-ESI-MS system, was used.

References [1] A. V. Herrera-Herrera, J. Hernández-Borges, Τ. M. Borges-Miquel, M. Á. Rodríguez-Delgado, J Pharmaceut Biomed 75, 130 (2012) [2] Ma J. García-Galán, M. S. Díaz-Cruz, D. Barceló, TrAC 27, 1008 (2008) [3] X. Xu, R. Su, X. Zhao, Z. Liu, Y. Zhang, D. Li, X. Li, H. Zhang, Z. Wang, Anal Chim Acta 707,92 (2011)

132 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Exploiting UV-femtosecond LIBS in single- and double-pulse modes for the analysis of aqueous aerosols

K. Marmatakis1,2, and D. Anglos1,2

E-mail: [email protected], [email protected]

The use of femtosecond laser-induced breakdown spectroscopy (fs-LIBS) is investigated for P1-29 the analysis of aerosols generated via pneumatic nebulization of aqueous solutions. Benefits arising from the use of femtosecond pulses in LIBS analysis are related to the mechanism of ablation, which is significantly different from that following nanosecond laser irradiation. Considering that under ultra-short laser excitation, there is no or minimal interaction of the laser pulse with the emerging plasma, fs-LIBS emissions tend to be weak, hence alternative schemes for signal enhancement have been proposed including double-pulse irradiation1,2. In the present study single and double pulse fs-LIBS measurements were performed, the latter by use of a collinear arrangement, based on a simple Michelson interferometer delay line permitting variable temporal separation between pulses in the range of 0 – 300 ps. Excitation was provided by a KrF laser emitting 450 fs pulses at 248 nm. Aerosols, produced from metal containing aqueous solutions were studied by fs-LIBS in atmospheric air, with argon as a carrier gas. The dynamics of atomic emissions from both the metal analyte and the matrix (water, air and argon) were monitored under single- or double-pulse excitation. It was found that double-pulse fs-LIBS exhibits higher sensitivity in comparison with the single-pulse approach, when the total laser pulse energy is maintained equal in both configurations. Preliminary results will be shown from the analysis of metal containing biomolecules.

References [1] Y. Lu, V. Zorba, XL. Mao, R.E. Zheng, R.E. Russo, Journal Of Analytical Atomic Spectrometry, 28, (2013) 743-748. [2] Mateo, M. P., Piñon, V., Anglos, D. & Nicolas, G.. Spectrochim. Acta - Part B At. Spectrosc. 74– 75, (2012) 18–23.

133

UV femtosecond Laser Induced Breakdown Spectroscopy for characterization of nanometer thin multilayer samples

N. Giannakaris1, P. Siozos2, D. Anglos1,2

1Department of Chemistry, University of Crete, 71003 Heraklion, Crete, Greece; 2Institute of Electronic Structure and Laser (IESL), FORTH, 71110, Heraklion, Crete, Greece;

E-mail: [email protected]

P1-30 In the present work UV femtosecond laser induced breakdown spectroscopy (LIBS) was applied on nanometer thin multilayer samples in order to study the plasma emission produced from the different layers of the samples. In particular, a hybrid distributed feedback dye laser–KrF excimer laser, delivering 450-fs at 248 nm was employed to irradiate single and multilayered samples consist of 90 to 150 nm Indium Tin Oxide layer (ITO) and metal layers (Al, Zn, Cr) at various configurations. The weak plasma emission was collected using an optical fiber and delivered to Czerny–Turner spectrometer (Avantes, Avaspec-2048-USB2) with spectral range from 200 to 460 nm and resolution of 0.2 nm. The LIBS spectra recorded 0.3 J/cm2 fluence present clear peaks of In at 410.176 and 451.131 nm and Sn at 326.234 nm only at the first pulses that represents the ITO layer. Emission lines present at the substrate material started to be visible in the second pulse but they were prominent in the third to fifth pulse. These results indicate that the only the ITO layer was ablated in the first pulse. Additional work will be performed to study the effect of the laser pulses on the nanometer thin layers using SEM or Confocal microscopy.

1200 In 410nm Sn 326nm In 451nm Ca 393nm 1000

800 In

600

400

200

Intensity (Arb.Units) Ca 0 1 2 3 4 5 Pulse

Intensity of In, Sn and Ca emission lines at different laser pulses recorded from ITO thin layer (95 nm thickness) on 90% wt SiO2 and 10% CaO substrate.

References [1] S.P. Banerjee, T. Sarnet, P. Siozos, M. Loulakis, D. Anglos, M. Sentis, Appl. Surf. Sci. (2016), in press; doi: 10.1016/j.apsusc.2016.11.136

134 10th International Conference on Instrumental Methods of

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Determination of metals present in metalloproteins from athletes’ serum samples using double column affinity chromatography inductively-coupled plasma mass spectrometry (ICP-MS)

L. Trasanidou1, S.A. Pergantis1, T. Nomikos2

1Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Heraklion 71003, Greece 2Department of Nutrition and Dietetics, Harokopio University, Athens, Greece

email: [email protected] P1-31

High intensity physical activity of athletes can cause severe damages to their body. Overproduction of free radicals leading to oxidative stress, inflammation, as well as muscle damage accompanied by leakage of muscle enzymes and increase in intracellular proteins in blood are some of the consequences. Metalloproteins presented in human serum, are proteins associated with metals playing a crucial role in various cellular processes and protein functions, and their concentration level fluctuations can be used as indices of damage caused by intense exercise. The objective of the present study is to develop a high-throughput analytical method suitable for determining metals in metalloproteins present in athletes’ serum samples before and after one bout of exercise. The developed methodology includes a combination of affinity chromatography columns, coupled on-line with inductively coupled plasma - mass spectrometry (ICP-MS). This approach provides a rapid simultaneous multielemental analysis, resulting in metal quantification following metalloprotein fractionation. Chromatograms presenting metal profile for each athlete were obtained for serum samples collected at 0, 2, 24, 48 and 72 hours post-exercise. Metalloprotein concentration level fluctuation is examined and results reveal changes caused by intense exercise of the athletes. The concentration levels obtained by metal quantification could be potential markers of an athlete’s injury or muscle damage and other parameters that affects athletes performance and recovery.

135

A porous graphitized carbon LC-ESI/MS method for the quantification of metronidazole and fluconazole in breast milk and human plasma

A. Geballa-Koukoula1, K. Zervas1, D. Gennimata2, P. Vourna3, E. Panteri- Petratou4 and I. Panderi1

1 National and Kapodistrian University of Athens, Faculty of Pharmacy, Laboratory of Pharmaceutical Analysis, Panepistimiopolis, Zografou, 157 71 Athens, Greece. 2 General Hospital “Korgialenio-Benakio National Red Cross”, Erithrou Stavrou 1, 115 26 Athens, P1-32 Greece 3 General- Maternity District Hospital Elena Venizelou, Milk Bank and Maternal Breast-feeding Department, 2 Helena Venizelou Square, 115 21 Athens, Greece. 4 Sismanoglio General Hospital, Sismanogliou 39, 151 27 Melissia, Greece

E-mail: [email protected]

Drug treatment during breast feeding raises several issues including the risk of drug exposure through breast milk for the infant, as nearly all drugs cross into the breast milk to some extent. Breast milk is slightly more acidic than human plasma and contains significantly more lipids and fewer proteins. Thus, drugs with low molecular weight, low plasma protein binding and high lipophilicity tend to concentrate more into the breast milk. Information on drug transfer into the breast milk is essential to protect the infant from undesirable adverse effects of maternal consumption of drugs and to allow effective pharmacological treatment of breastfeeding mothers. Metronidazole and fluconazole are two drugs frequently used in nursing women to treat various infections, thus questioning infant's safety because of its drug exposure through breast milk. A reversed phase high performance liquid chromatography/positive ion electrospray mass spectrometric assay (RP-HPLC/ESI-MS), was developed for the detection of metronidazole and fluconazole in both human plasma and breast milk. The separation of the analytes occurred using a Porous Graphitized Carbon (Hypercarb) analytical column under isocratic elution pumped. Porous graphitized carbon columns shows a highly ordered crystalline structure with large bands of delocalized electrons, so that the retention mechanism is a mixture of hydrophobic and electronic interactions and is very different from that observed with silica- based bonded phases and nonpolar copolymers. A run time of less than 10 min for each sample made it possible to analyze a large number of biological samples per day. For the method development, the biological sample spiked with the analytes undergoes acetonitrile precipitation of proteins and filtration using regenerated cellulose filters, which enables injection into the LC-ESI/MS system. The method is the first reported application of porous graphitized carbon LC-ESI/MS method in the analysis of metronidazole and fluconazole in breast milk and human plasma and it can be used to support a wide range of clinical studies

References [1] E. Kiriazopoulos, S. Zaharaki, A. Vonaparti, P. Vourna, Ei. Panteri-Petratou, D. Gennimata, K. Lombardo, and I. Panderi, Drug Testing and Analysis, (2016), DOI: 10.1002/ dta2014.

136 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Quantification of rosuvastatin and metformin in human plasma using hydrophilic interaction liquid chromatography / electrospray ionization mass spectrometry for therapeutic drug monitoring

N. Antonopoulos1, G. Machairas1, D. Gennimata2, G. Migias3, E. Panteri- Petratou4, and I. Panderi1

1 National and Kapodistrian University of Athens, Faculty of Pharmacy, Laboratory of Pharmaceutical Analysis, Panepistimiopolis, Zografou, 157 71 Athens, Greece. 2 “Korgialenio-Benakio" Red Cross General Hospital, 2 Athanassaki st, 115 26 Athens, Greece 3 “Alexandra” General Hospital, 80 Vas. Sofias avenue, 115 28 Athens, Greece P1-33 4 “Sismanoglio” General Hospital, 39 Sismanogliou st, 151 27 Melissia, Greece

E-mail: [email protected]

The concept of personalized medicine along with the introduction of new drug combinations for therapy is related to the development of new sensitive, precise and accurate analytical methods for therapeutic drug monitoring. Hydrophilic interaction liquid chromatography (HILIC), in combination with mass spectrometry has been steadily gaining acceptance in the analysis of polar compounds in complex biological matrices [1,2]. The purpose of this study was on the development of a new method to detect and identify rosuvastatin and metformin which are commonly prescribed drugs in human plasma. Sample preparation was performed by protein precipitation with acetonitrile followed by filtration. All analytes and the internal standard, 4-[2-(propylamino) ethyl] indoline 2 one hydrochloride, were separated by hydrophilic interaction liquid chromatography using an X-Bridge-HILIC analytical column (150 x 2.1 mm i.d., particle size 3.5μm) under isocratic elution. The optimization of the HILIC mobile phase on the BEH XBridge®-HILIC column, involved the percentages of water, the concentration and the type of the aqueous buffer solution (ammonium formate or ammonium acetate) in the mobile phase, using acetonitrile as organic modifier. The optimum mobile phase was composed of a 12% 15mM ammonium formate water solution in acetonitrile and pumped at a flow rate of 0.25 mL min-1. The assay was linear over the concentration range of 2-100 ng mL-1 for rosuvastatin and 100- 5000 ng mL-1 for metformin. The method is the first reported application of HILIC in the analysis of rosuvastatin and metformin in human plasma. Validation results demonstrate that the analytes can be accurately and precisely quantified in human plasma. The simplicity of sample preparation and shorter chromatographic run time (less than 10 min) gives the method the capability for high sample throughput and can be used to support a wide range of clinical studies.

References [1] E. Kalogria, C. Pistos, I. Panderi*, Hydrophilic interaction liquid chromatography/positive ion electrospray ionization mass spectrometry method for the quantification of alprazolam and α-hydroxy- alprazolam in human plasma. J. Chromatogr. B, 942–943 (2013) 158-164. [2] S. Meimaroglou, A. Vonaparti, G. Migias, D. Gennimata, S. Poulou and I. Panderi*, Direct injection human plasma analysis for the quantification of antihypertensive drugs for therapeutic drug monitoring using hydrophilic interaction liquid chromatography / electrospray ionization mass spectrometry, J. Chromatogr B, 1004 (2015) 1-9.

137

Development and validation of a HILIC-ESI/MS method for the quality control of cosmeceuticals containing oligopeptide-20 and oligopeptide-24

M. Giannakou1, A. Varvaresou2, A. Vonaparti1, S. Papageorgiou2 and I. Panderi1

1National and Kapodistrian University of Athens, Faculty of Pharmacy, Laboratory of Pharmaceutical Analysis, Panepistimiopolis, Zografou, 157 71 Athens, Greece. 2 The School of Health and Caring Professions, Technological Education Institution of Athens, P1-34 Department of Aesthetics and Cosmetology, Ag. Spyridonos str., 122 10, Athens, Greece

E-mail: [email protected]

As life expectancy increases in developed countries, the impact of aging on the function and appearance of skin is receiving growing interest. Aging of the skin is influenced by several factors including genetics, environmental (e.g. exposure to solar UV irradiation), hormonal changes, and metabolic processes. Over the past 15 years there has been a significant increase in the incorporation of bioactive ingredients in the preparation of cosmetics (referred to as “cosmeceuticals”) for the improvement of the appearance of the photo-aged skin and the reduction of face wrinkles. Cosmeceuticals were made possible by the increased understanding of skin physiology. Peptide cosmeceuticals are one of the relatively new, popular options to treat aging skin. Peptides are important in many natural processes that are relevant to skin care, such as the modulation of cell proliferation, cell migration, inflammation, angiogenesis, melanogenesis, and protein synthesis and regulation. Quality control of cosmetic products containing peptides is of critical importance for public health and safety. In this work, a hydrophilic interaction liquid chromatography/ positive ion electrospray mass spectrometric assay (HILIC/ESI-MS) was developed and fully validated for the quantitation of oligopeptide-20 and oligopeptide-24 in cosmetic creams. Sample preparation was based on dilution of the cosmetic cream samples into the mobile phase following centrifugation and filtration prior to their injection into the LC-ESI/MS system. Chromatographic separation was achieved on a zwitterionic ZIC®pHILIC analytical column with a mobile phase that was composed of a 28 % 32.5 mM ammonium formate water solution (pH 9.5) in acetonitrile and pumped at a flow rate of 0.25 mL min-1. Running in positive electrospray ionization and selected ion monitoring (SIM) the mass spectrometer was set to analyze the protonated molecules [M+2H]2+ at m/z 739 for oligopeptide-20 and [M+H]+ at 1239,4 for oligopeptide 24. The assay was linear over the concentration range of 1.5-5 μg mL-1 for oligopeptide-20 and 1.76-5.86 μg mL-1 for oligopeptide 24. Intermediate precision was less than 3.1 % over the tested concentration ranges. The method is the first reported application of HILIC in the analysis oligopeptide-20 and oligopeptide-24 in cosmetic creams. With a small sample size (50 mg cream sample) and a run time less than 12 min for each sample the method can be used to support the quality control of these peptides in cosmetic products.

References [1] Papagianni P, Varvaresou A, Papageorgiou S, Panderi I*, Development and validation of an ion- pair RP-HPLC method for the determination of oligopeptide-20 in cosmeceuticals, J Pharm Biomed Anal. 56(3):645-649, 2011.

138 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Investigating heavy metal (Pb, Cd, Ni and arsenic species) uptake by Chlamydomonas reinhardtii cells by means of Single-Cell ICP-MS

E. Mavrakis1, N. Lydakis-Simantiris2, C. Stephan3, R. Magarini3, S.A. Pergantis1

1Department of Chemistry, University of Crete, Heraklion, Greece 2Department of Environmental and Natural Resources Engineering, University of Applied Sciences Crete 3Perkin Elmer

E-mail: [email protected] P1-35

The conventional method for quantitating the metal content of a biological sample by using ICP-MS is by digesting an ensemble of cells and analyzing the resulting digest as a single sample. However, this method can only give us part of the picture as the average metal content may not reflect a possible metal content variation among cells. Single-Cell (SC) analysis by means of single-particle inductively coupled plasma mass spectrometry (SP ICP-MS) is suitable for determining the metal distribution in a cell population. The operation of SC ICP-MS involves the introduction of dilute cell suspensions, that is 104 -105 cells/mL, via pneumatic aspiration into a high-temperature Ar plasma. Upon entering the plasma, each aerosol droplet that contains a cell is evaporated and the remaining single cell is atomized into its constituent elements. The resulting atoms and their isotopes are then ionized, separated by the mass analyzer and detected. Cell transport efficiency, fast data acquisition and rapid data processing are certain experimental points that need to be considered in a Single-Cell analysis. The ICP-MS introduction system should ensure that cells maintain their integrity during their transportation into the plasma. Each cell event produces a transient signal in the hundreds of μs scale so fast data acquisition with no detector settling time between each data acquisition is required. A software for handling and processing large data sets rapidly and efficiently is also needed. Perkin Elmer has managed to address these points by designing a sample introduction kit

accompanied by the Syngistix™ Single Cell Application Software Module for optimal cell transport to the plasma and data processing respectively [1]. In this work, the use of SC ICP-MS for the determination of metal and metalloid amounts (Pb, Cd, Ni, As) in individual Chlamydomonas reinhardtii cells, previously incubated in these metals, is demonstrated. In addition, the determined by SC -ICP-MS metal mass per cell and population is compared with corresponding values obtained by acid digestion and total metal determination by ICP-MS. These mass balance comparisons allow for assessing the SC ICP- MS technique in terms of its accuracy, precision and stability. The metal distributions may provide us with meaningful conclusions concerning the uptake of the given metals by the Chlamydomonas reinhardtii cells, which in turn may contribute to the advancement of biological applications.

References [1] Lauren Amable, Stan Smith, Chady Stefan, New Research Evaluating Cisplatin Uptake in Ovarian Cancer Cells by Single Cell ICP-MS, Application note, Perkin Elmer

139

Development of an extraction method to characterize silver nanoparticles from sewage sludges using SP-ICP-MS

E. Andrade Carpente, E. Peña-Vázquez, M.C. Barciela Alonso and P. Bermejo- Barrera

Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, Av. das Ciencias, s/n 15782, Santiago de Compostela, Spain. Health Research Institute of Santiago de Compostela (IDIS), Travesía da Choupana, s/n, 15706, Santiago de Compostela, Spain.

P1-36 E-mail: [email protected]

Nowadays there is an environmental concern due to the numerous applications of silver nanoparticles in consumer products including textiles, health care devices or container surfaces, and their potential effect on wastewater treatment processes. A method for the detection and characterization of silver nanoparticles in sewage sludges has been developed. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) was used to estimate the number of nanoparticles and calculate the particle size. The total concentration of silver was determined in the samples after a microwave assisted acid digestion using a mixture of nitric and sulfuric acid. Measurements were performed by ICP- MS operating in KED mode, and several internal standards isotopes were tested (Ge, Rh, Y, Se, Te). Sonication in an ultrasonic bath and a shaking procedure were studied to extract the nanoparticles from the sludges, and centrifugation and sedimentation to separate the extracts from the solid residues. Different extractants (milli-Q water, 1%(v/v) glycerol, tetrasodium pyrophosphate (TSPP)), and extraction times (1 h, 6h, 24 h and 48 h) were also tested. The highest percentage of extraction was achieved after shaking a portion of the sample (0.1 g) with water (30 mL) for 1 hour. After sedimentation (12 hours), the extracts were separated and the characterization of silver nanoparticles was performed using the SyngistixTM Nano software (Perkin Elmer) that allows ultrafast measurements with short dwell times (100 µs). The analytical characteristics of the method were evaluated, and it was applied to samples from a wastewater treatment plant (WWTP).

Acknowledgement This research was supported by the Spanish Government (Ministerio de Economía y Competitividad, project CTQ2015-68094-C2-2-R). The authors belong to the Galician Competitive Research Group 6RC2014/2016. These programs are co-funded by FEDER (UE).

140 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Characterization of titanium dioxide nanoparticles from WWTP sewage sludges using SP-ICP-MS

P. Costa Tomé, E. Peña-Vázquez, M.C. Barciela-Alonso and P. Bermejo- Barrera

E-mail: [email protected] P1-37

Titanium dioxide nanoparticles are used in many different applications: paints, sunscreens, biocides... After their release to the environment, they tend to accumulate in the sludges of the water treatment plants with the subsequent risk if those materials are used as soil fertilizers. A method for the detection and characterization of titanium dioxide nanoparticles in sewage sludges has been developed. Single particle inductively coupled plasma mass spectrometry (SP-ICP-MS) was used to measure the number of nanoparticles and to calculate the particle size. Total concentration of titanium dioxide was determined in the samples after a microwave assisted acid digestion using nitric and sulfuric acid. Measurements were performed by ICP- MS operating in KED mode. Different factors were taken into account to optimize the extraction of titanium dioxide nanoparticles from the sludges. Milli-Q water, 1%(v/v) glycerol and tetrasodium pyrophosphate (TSPP) were used as extractants, and the effect of several sample treatments (sonication, shaking, centrifugation and sedimentation) were evaluated. The extraction times studied ranged from 1h to 98 h. The biggest percentage of extraction was achieved after shaking a portion of the sample with 2.5 mM TSPP for 24 hours. After sedimentation (12 hours), the extracts were separated and diluted 20 times before measurements using the SyngistixTM Nano software (Perkin Elmer). In optimum conditions, standards of ionic titanium and a certified reference material of gold nanoparticles were used for calibration. The analytical characteristics of the method (limits of detection in size and concentration, reproducibility…) were evaluated, and it was applied to samples submitted to different treatments in a wastewater treatment plant (WWTP).

141

Comparative proteomic analysis of heterocysts from two hydrogenase mutants from Anabaena sp. PCC 7120

A. Kourpa, V. Strataki and G. Tsiotis

Department of Chemistry, University of Crete, GR-71003 Voutes, Greece

E-mail: [email protected]

Anabaena sp. PCC 7120 is a photoautotrophic cyanobacterium which has the ability to both executes oxygenic photosynthesis and nitrogen fixation [1]. These two different procedures P1-38 are distinguished by the differentiation of the vegetative cells to heterocysts in which nitrogen fixation and production of hydrogen as a byproduct of the nitrogenase are taking place. In order to improve the hydrogen production, mutants from Anabaena sp. PCC 7120 were constructed by inactivation of the uptake hydrogenase (ΔhupL) and the bidirectional hydrogenase (ΔhoxH) [2]. In this study, we proceed to the proteome analysis of the solubilized heterocysts, using nLC- ESI-MS/MS and the label-free quantification method. The generation of tryptic peptides from the crude lysates of wild type and two mutants was obtained using the FASP procedure [3]. We have identified 2728 proteins from at least two biological samples of each strain. The fact that more membrane than cytoplasmic proteins has been identified is an evidence of sufficient solubilization. As regards to the biological function, we have identified proteins which are involved in a variety of processes like photosynthesis/respiration, carbohydrate metabolism, nitrogen fixation and heterocyst differentiation. It has been found that the expression of proteins which seems to have a transportation role, is significantly higher in wild type and ΔhoxH mutant, but on the other hand, the expression of nitrogenase subunits is almost 50% higher in ΔhupL compared to the other mutant.

References [1] Igarashi R.Y.; Seefeldt L.C., Critical Reviews in Biochemistry and Molecular Biology, 2003, 38 (4): 351–84 [2] H.Masukawa; M.Mochimaru; H.Sakurai, Appl Microbiol Biotechnol 2002, 58: 618-624 [3] M.Hernandez-Valladares; E. Aasebø; O. Mjaavatten; M. Vaudel; Ø. Bruserud; F. Berven; F. Selheim, Biol Proced Online, 2016, 18: 13

142 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

Chiral Cavity Ring-Down Polarimetry: New methods for ultrasensitive measurements of chirality

A.K. Spiliotis, D. Sofikitis, G.E. Katsoprinakis, B. Loppinet, T.P. Rakitzis

Department of Physics, University of Crete, 71003 Heraklion-Crete, Greece, and IESL-FORTH, N. Plastira 100, 71110 Heraklion-Crete, Greece

Sensing chirality is of fundamental importance to many fields. The most widely used methods for optical chiral sensing are the traditional methods of circular dichroism and optical rotation. However, these chiral signals are typically very weak, and their measurement is limited by P1-39 larger time-dependent backgrounds (such as spurious birefringence) and by imperfect and slow subtraction procedures. We present proposals [1] and demonstrations [2] of a pulsed-laser bowtie-cavity-ringdown polarimeter with counter-propagating beams, which solves these background problems: the chiral signals are enhanced by the number of cavity passes (typically >103); the effects of linear birefringence are suppressed by a large induced intracavity Faraday rotation; and rapid signal reversals are effected by reversing the Faraday rotation and subtracting signals from the counter-propagating beams. These advantages allow measurements of absolute chiral signals in environments where background subtractions are not feasible.

Figure 1. Cavity Ring-Down Polarimetry Setup

Specifically, we measure optical rotation from of (+)--pinene and ()--pinene in open air, as well as from chiral liquids in the evanescent wave produced by total internal reflection at a prism surface. Evanescent-wave optical rotations of various (+)-maltodextrin and ()-fructose solutions confirm the Drude-Condon model for Maxwell’s equations in isotropic optically active media [2,3]. The improved sensitivity and background subtraction procedures should improve chiral sensing in many fields.

References [1] L. Bougas, G. Katsoprinakis, W. von Klitzing, J. Sapirstein, T.P Rakitzis, “Cavity-enhanced parity non-conserving optical rotation in metastable Xe and Hg”, Phys. Rev. Lett. 108, 210801 (2012). [2] D. Sofikitis, L. Bougas, A. Spiliotis, G. Katsoprinakis, B. Loppinet, T.P. Rakitzis, “Evanescent- wave and ambient chiral sensing by signal-reversing cavity-ringdown polarimetry” Nature 514, 76 (2014). [3] L. Bougas, D. Sofikitis,, G. Katsoprinakis,, A. K. Spiliotis, P. Tzallas, B. Loppinet, and T. P. Rakitzis. Chiral cavity ring down polarimetry: Chirality and magnetometry measurements using signal reversals, JCP 143, 104202 (2015)

143

Targeted protein analysis by MALDI-MS using molecularly imprinted polymers

T. Vaneckova1, L. Vanickova1, V. Adam1,2, M. Vaculovicova1,2

1Department of Chemistry and Biochemistry, Mendel University in Brno, Zemedelska 1, CZ-613 00 Brno, Czech Republic 2Central European Institute of Technology, Purkynova 123, CZ-612 00 Brno, Czech Republic

E-mail: [email protected] P1-40 Molecularly imprinted polymers (MIPs) show their capability to selectively bind target molecules. Among them, polydopamine-based molecularly imprinted polymers are attractive due to simple preparation steps and satisfactory selectivity [1]. Therefore, combination of this technology with sensitivity of matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) may lead to a progress in targeted protein analysis from complex biological samples such as blood. In the present work, we applied MALDI-TOFMS technique for analysis of metallothioneins that are potential biomarkers of cancer and may also be involved in development of neurodegenerative disorders [2]. Polydopamine imprinted polymer was prepared by dissolving dopamine hydrochloride (2.5 mg/ml) in Tris-HCl buffer (20 mM, pH 8.5) with metallothionein isoform 1 (MT1) serving as a template. Polymerization mixture was applied on the surface of MALDI target forming self-polymerizing monolayer. Polymer was then gently washed with acetic acid (3%) and water in order to remove template molecules of MT1 and create target shaped cavities. Sample, containing metalothionein, was applied on the polymer and after 60 minutes of application, nonspecifically adsorbed molecules and/or interferents were removed by washing. Binding properties of metallothionein were assessed using MALDI-TOFMS. Conditions of dopamine polymerization were optimized regarding polymerization time and temperature. The selectivity and sensitivity was tested by samples containing different concentration levels of metallothionein and also interferents, such as human serum albumin. Moreover, our preliminary analysis of blood samples spiked with metallothionein (0,025 mg/ml) demonstrated the ability of the method to detect metallothionein in a real sample.

Fig. 1. Scheme of molecular imprinting technology

References [1] Liu, Y., K. Ai, and L. Lu, Polydopamine and its derivative materials: synthesis and promising applications in energy, environmental, and biomedical fields. Chemical reviews, 2014. 114(9): p. 5057- 5115. [2] Adam, V., et al., Vertebrate metallothioneins as target molecules for analytical techniques. TrAC Trends in Analytical Chemistry, 2010. 29(5): p. 409-418.

Acknowledgement The study was financially supported by GACR 17-12774S and by Horizon 2020 programme Marie Skłodowska-Curie SoMoPro No. 665860.

144 10th International Conference on Instrumental Methods of

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Bioconjugation of nanoparticles with antibodies for LA-ICP-MS imaging

A. Moravanska1, M. Vlcnovska1, K. Smerkova1,2, M. Tvrdonova3, T. Vaculovic3, M. Vaculovicova1,2 and V. Adam1,2

1 Department of Chemistry and Biochemistry, Mendel University in Brno, Zemedelska 1, 613 00 Brno 2 Central European Institute of Technology, Brno University of Technology, Purkynova 123, 612 00 Brno 3 Department of Chemistry, Masaryk University, Kamenice 753/5, 625 00 Brno Czech Republic P1-41

E-mail: [email protected]

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a sensitive and isotopespecific, microanalytical method for analysis the metal distribution and metal content at trace and ultratrace levels [1]. The spatial resolution of this method for imaging in biological tissue sections using LA-ICP-MS can be achieved down to 1 µm [2]. Compared to matrix-assisted laser desorption/ionization mass spectrometry imaging, which is investigating the biomolecules occurring naturally in the tissue, the LA-ICP-MS either monitors the natural metal composition of the tissue or detects the signal of a metal label conjugated to the target molecule upon the labelling mediated by specific antibodies. With a current boom of nanotechnologies, the application of nanoparticles for labelling of antibodies for LA-ICP-MS imaging purposes is an obvious strategy. Especially taking into account that each nanoparticle is composed of thousands of atoms, enhancing the sensitivity enormously compared to conventional metal chelates. The aim of this study is to conjugate metal nanoparticles (NPs) with selected antibodies for mapping of the target analytes (proteins, peptides) within the tissue by LA-ICP-MS bioimaging. Whereas the antibodies provide the specificity and the combination of different NPs with different antibodies ensures the possibility of multiplexing. To monitor the interaction of the target analyte, the dot-blot immunolabeling technique was employed. NPs of various natures (material - gold NPs or CdTe quantum dots, sizes – 1, 4, 10, 60 nm, and conjugation procedures – zero-length linker, Fc fragment affinity heptapeptide) were conjugated to antibodies.

References [1] Becker, J. S., Zoriy, M., Matusch, A., Wu, B., Salber, D., Palm, C., Mass Spectrom. Rev. 2010, 29, 156-175. [2] Becker, J. S., Matusch, A., Wu, B., Anal. Chim. Acta 2014, 835, 1-18.

Acknowledgement The study was financially supported by GACR 17-12774S.

145

Rapid and Sensitive analysis of major use antibiotics by UHPLC- High Resolution Orbitrap MS

M. Kalampoka, V. Boti, V. Sakkas and T. Albanis

Department of Chemistry, Laboratory of Analytical Chemistry, Ioannnina 45 110, Greece

E-mail: [email protected]

Antibiotics constitute one of the most important emerging classes of environmental pollutants. This is due to their diverse use: in veterinary medicine to treat bacterial disease and protect the P1-42 health of livestock as well as in human medicine to ensure human health safety. They are a prominent group of emerging contaminants frequently found in wastewater effluents and wastewater-impacted aquatic environments. However, the ubiquitous presence of antibiotic residues can create antibiotic-resistant bacteria that are harmful for the aquatic environment along with the consideration to be one of the most serious global threats to human health in the upcoming decades [1, 2]. In this study, antibiotics of multiple classes (sulphonamides, quinolones, penicillins, macrolides, tetracyclines,pyrimidines) were selected to be accurately detected with modern chromatographic systems based on hybrid mass analyzers. For that purpose 13 antibiotics of major use were separated and detected with ultra-high performance liquid chromatography (UHPLC) high-resolution LTQ/Orbitrap mass spectrometry. The recent trend is focused toward the use of powerful high resolution MS detectors like Orbitrap which has become the technique of choice because of its high selectivity and sensitivity. The separation of the target analytes was achieved with a Fortis PFP Hypersil Gold (1.9μm, 50mm x 2.0 mm) analytical column, using a gradient elution system consisting of water (A) and methanol (B) both containing 0.1% formic acid at 400 μL/min flow rate. The target antibiotics were detected as [M+H]+ adduct ions under positive ion mode. Mass accuracy of measured ions was calculated below 3 ppm at 50 ppb, in all cases. The variables involved in the chromatographic process were optimized in instrument auto tune sections. The selected conditions proved to be excellent within 8 min elution with the instrument limits of quantification down to low ppb level for the majority of the analytes. Detector linearity was proved to be excellent in all cases. The excellent analytical characteristics achieved, showed that the proposed analytical protocol is a promising trend that could be fully exploited in the routine monitoring of these antibiotics in several environmental substrates.

References [1] M. Seifrtova, L. Novakovaa, C. Lino, A. Pena, P. Solich, Anal Chim Acta 649, (2009) 158-160 [2] I. Senta, I. Krizman-Matasic, S.Terzic, M. Ahel, , Journal of Chromatography A, 1509 (2017) 60– 68

146 10th International Conference on Instrumental Methods of

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Water soluble fine aerosol ionic composition and effects of residential wood burning, in Athens, Greece

D. Paraskevopoulou1, E. Liakakou1 and N. Mihalopoulos1,2

1Institute for Environmental Research and Sustainable Development, National Observatory of Athens, I. Metaxa and Vas. Pavlou, 15236, P. Penteli, Athens, Greece 2Environmental and Analytical Chemical Division, Department of Chemistry, University of Crete, P.O. Box 2208, 71003 Heraklion, Greece

E-mail: [email protected] P1-43

The concentrations of water soluble ionic components of fine particulate matter (PM) were measured from January 2016 to March 2016 and from November 2016 to June 2017, including periods of intense wood burning, at an urban site located in the center of Athens, Greece. Near- real time measurements took place, using a particle into liquid sampler (PILS) [1][2] coupled directly to ion chromatography. Mass concentrations (μg m-3) of water-soluble inorganic + + + 2+ components including ammonium NH4 , sodium (Na ), potassium (K ), calcium (Ca ) and magnesium (Mg2+) in fine particle aerosols (with diameters smaller than 1 μm) were determined at 15-min intervals. For the determination of cations, a Dionex Ion Pac AS11 4mm (10-32) column and a Dionex Ion Pac AG11 4mm (10-32) guard column were used with a suppressor, under isocratic elution of 20mM MSA (methanesulfonic acid). The PILS sample ambient air flow rate was 16.7±0.4 L min-1 and a cyclone was used to provide PM cut size of PM1 during the whole studied period. The reported ion concentrations were corrected for blanks. Wood burning black carbon (BCwb) constituted an additional measured tracer, which was recorded through a portable aethalometer (AE-42; Magee Scientific), performing black carbon (BC) measurements at 7 wavelengths (370, 470, 520, 590, 660, 880 and 950 nm), with time resolution of 5 min. BC concentrations were decomposed to BCwb and fossil fuel black [3] carbon (BCff) after applying corrections for multiple-scattering and shadowing effects . Additionally, back trajectories are used, in order to track days with dust transportation and evaluate the effect of dust on the studied data series. Hourly potassium values provide an -3 -3 average of 0.40±0.28 μg m while, the average BCwb is 0.56±0.24 μg m . The comparison of studied concentrations shows a reasonable correlation of potassium with BC (r2=0.28) that ameliorates when the correlations are studied on a seasonal basis. During spring, the hourly values of potassium and BCwb present a squared correlation coefficient of 0.54 that increases into a value of 0.67 during wintertime. The results also indicate a significant contribution of atmospheric organic compounds to the wood burning aerosol that is of great interest, since wood burning is widely used for domestic heating during wintertime in Greece, due to the economic recession.

References [1] Orsini, D.A., Ma, Y.L., Sullivan, A., Sierau, B., Baumann, K., Weber, R.J., Atmospheric Environment 37 (2003) 1243-1259. [2] Weber, R.J., Orsini, D., Daun, Y., Lee, Y.N., Klotz, P.J., Brechtel. F, Aerosol Science and Technology, 35 (2001) 718-727. [3] Sciare, J., D'Argouges, O., Sarda-Esteve, R., Gaimoz, C., Dolgorouky, C., Bonnaire, N., Favez, O., Bonsang, B., Gros, V., J. Geophys. Res. Atmos, 116 (2011) 22.

147

Real time measurements of water soluble phosphoric ions in pm 2.5 aerosols in the eastern Mediterranean

E. Tsiodra1, M. Tsagkaraki 1, P. Zarmpas 1, K.Violaki1,3, R. Weber3 A. Nenes3,4,5 and N. Mihalopoulos1,2

1 Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, P.O. Box 2208, 71003 Heraklion, Greece 2 Institute for Environmental Research and Sustainable Development, National Observatory of Athens, GR-15236 Palea, Pendeli Greece 3 School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia 30332, P1-44 United States 4 School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332, United States 5 Institute of Chemical Engineering Sciences, Foundation for Research and Technology−Hellas, GR- 26504 Patras, Greece

E-mail: N. Mihalopoulos ([email protected])

A new online method PILS – LWCC- SRP 1 was used for automated and continuous measurements of ambient PM2.5 phosphate over a period of 10 months (January−October 2016) at the Department of Chemistry of the University of Crete in Heraklion, Greece. This new method offers better detection of phosphate ions (detection limit was 0.4 nM P, equivalent to 0.03 nmol P m−3 in atmospheric particles). In order to compare the performance of the new method as well as to identify phosphate sources and the factors controlling phosphate variability, filter aerosol sampling was performed in parallel. Ion chromatography was used to identify the ionic composition of the filter samples and phosphate, sulphate, oxalate and potassium ions were detected. The concentrations of the phosphate anions measured by the PILS-LWCC-SRP method were satisfactorily compared to those measured by ion chromatography using the filter samples. In addition, correlations between the measured ions as well as back trajectory analyses were used for the identification of phosphate potential sources. The mean value of water-soluble phosphate concentrations over the studied period was 0.32 nmol.m-3. Periods with Sahara Desert dust events and biomass burning phenomena presented high water-soluble phosphorus concentrations with mean phosphate values during these events at 0.49 nmol.m-3, i.e about 50% higher than the mean of the studied period.

References [1] Violaki, Kalliopi et al. 2016. “Real-Time, Online Automated System for Measurement of Water- Soluble Reactive Phosphate Ions in Atmospheric Particles.” Analytical Chemistry 88(14): 7163–70.

148 10th International Conference on Instrumental Methods of

Monday 18/9 Analysis: Modern Trends and Applications

First observations of bioaerosols in the Eastern Mediterranean.

Ch. Almpani1,2, A. Negron3, G. Kouvarakis1, I.Magiopoulos4, P. Pitta4, M. Kanakidou1, N. Mihalopoulos1,5 and A. Nenes3,5,6,7

1Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete,Voutes Campus, P.O.Box 2208, 70013 Heraklion, Greece 2Department of Chemistry, University of Athens, University Campus Zografou, 15771 Athens, Greece 3School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA 30332 5Institute for Environmental Research and Sustainable Development, National Observatory of Athens, Athens, Greece 6School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia P1-45 30332, United States 7Foundation for Research and Technology, Hellas Patras, Greece

E-mail: [email protected]

Bioaerosols (primary biological aerosol particles) are a ubiquitous component of the atmosphere. They can act as cloud condensation nuclei or ice nuclei affecting warm and ice clouds [1, 2]. They impacts on health and are carriers of nutrients to the ocean ecosystems [3]. In order to quantify the concentration of supermicron bioaerosols at a remote marine ground site in the Eastern Mediterranean, sampling took place in the Finokalia Station and in the city of Heraklion. Eight hour samples were collected using a Spincon II wet-walled cyclone sampler every two days over a 9-month period (May, 2016 – January 2017) and were subsequently analyzed using flow cytometry and epifluorescence microscopy protocols developed by Negron et al., 2017 [4]. Preliminary results show low biomass samples over Finokalia site and large variability in the concentrations, depending on the origin of the airmass.

References [1] Jaenicke, R. Science 308, 73. [2] Morris, C. E. et al., Glob Chang Biol 20(2): 341-351. [3] Myriokefalitakis et al., Biogeosciences, 13, 6519-6543 [4] Negron, A., et al., Atmos. Chem. Phys.Discuss., submitted, 2017.

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Magnother: a novel nanoparticle fluid for localized cancer therapy by magnetic hyperthermia and thermally-triggered drug delivery

K. Simeonidis1, E. Kokkinos2, A. Mitropoulos1

1Hephaestus Advanced Laboratory, Eastern Macedonia and Thrace Institute of Technology, St. Lucas, 65404 Kavala, Greece 2Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece

E-mail: [email protected] P1-46 This study aims to develop a novel nanoparticle fluid oriented for localized cancer therapy by the combination of magnetic hyperthermia treatment and thermally-triggered drug delivery. For its realization, a facile and scalable method of preparation was designed to establish accurate control of synthetic parameters and a significant cost reduction compared to commercially available competitors. Magnetite nanoparticles were prepared by the aqueous coprecipitation of FeSO4 and Fe2(SO4)3 under alkaline conditions sequenced by the coating with a Mg-Al layered double hydroxide (LDH) which is deposited during the precipitation of 2- Mg(NO3)2 and Al(NO3)3 in the presence of CO3 ions. Then, fluorouracil, an anionic 2- anticancer agent, was loaded on the LDH phase through ion exchange replacing CO3 from the layered structure. The structure and morphology of the nanocomposite was examined by X-ray diffraction and electron microscopy techniques while the magnetic properties were determined by SQUID magnetometry. Evaluation of the particles fluid under magnetic hyperthermia conditions was performed by placing a quantity of the sample into an AC magnetic field (300 Oe and 765 kHz) and recording the heating rate. At the same time the quantity of released fluorouracil was determined for different periods and temperatures of treatment. The specific loss power of the nanoparticles was estimated to be around 900 W/gFe with the drug release rate to reach 80 % of total loading at a treatment temperature of 41 oC. The ultimate product of this methodology combines a number of advantages with significant importance in cancer research including magnetic targeting of tissues, a kW/g heating efficiency, on-site heat-assisted release of drugs, low toxicity and favorable cell internalization.

Acknowledgements The project is financially supported by Stavros Niarchos Foundation and Eastern Macedonia and Thrace Institute of Technology fellowships for assisting young scientists in prototyping innovative products by using cutting-edge technology. This project has received funding from the EU-H2020 research and innovation programme under grant agreement No 654360 having benefitted from the access provided by CSIC-ICMAB in Barcelona within the framework of the NFFA-Europe Transnational Access Activity.

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Development of magnetic nanocomposites for the removal of Sb and As below drinking water regulation limits

K. Simeonidis, E. Kaprara, M. Mitrakas

Analytical Chemistry Laboratory, Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece

E-mail: [email protected]

The development of a nanocomposite material able to provide a solution in the simultaneous removal of antimony and arsenic species from drinking water is the main objective of this P1-47 study. In addition, the possibility to feature these nanomaterials with magnetic properties allowing their easy separation after application was also examined. For this purpose, nanomaterials well-known for their good efficiency in the adsorption of arsenic (iron oxy- hydroxides, γ-Fe2O3) were combined with other phases that would expand the possibility to remove antimony species at the same time. Considering the difficulties to capture Sb(V) forms due to their high mobility, their reduction and stabilization of the Sb(III) is a favorable step. Here, Sn(II) hydroxides and iron oxy-hydroxides were combined with Fe3O4 and tested for their potential to enhance antimony adsorption capacity while preserving the high arsenic removal efficiency. The nanocomposites were synthesized by the sequential preparation of an iron oxy-hydroxide by the aqueous precipitation of FeSO4 at pH 4 under oxidizing conditions or tin hydroxide by the precipitation of SnCl2 at pH 2, followed by the formation of magnetite by the coprecipitation of FeSO4/Fe2(SO4)3 at pH 11. The produced nanocomposites were characterized by X-ray diffraction and Scanning electron microscopy to obtain information about the structural and morphological characteristics. Then, their potential to be used as adsorbent for antimony and arsenic was evaluated by batch adsorption tests at pH 7 in the concentration range below 200 μg/L. Recorded adsorption isotherms suggest that FeOOH/Fe3O4 nanocomposites show a simultaneous good efficiency to capture antimony and arsenic species reaching residual concentrations below the regulation limits for drinking water. On the opposite, the Sn(II) hydroxides/Fe3O4 system succeeds a higher reduction potential for Sb(V) but decreases efficiency for arsenic removal.

Acknowledgements This study was implemented within the frame of the action “Supporting Postdoctoral Researchers” of the Operational Program “Development of Human Resources, Education and Lifelong Learning 2014- 2020” of IKY State Scholarships Foundation and is co-financed by the European Social Fund and the Greek State. This project has received funding from the EU-H2020 research and innovation programme under grant agreement No 654360 having benefitted from the access provided by CSIC-ICMAB in Barcelona within the framework of the NFFA-Europe Transnational Access Activity.

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152

Tuesday 19 September 2017 MINOS II Hall Chair: M.I. Karayannis, J. Stratis

Archaeometry

154 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Plenary lecture

Palaeomics: when mass spectrometry meets archaeology

J. Thomas-Oates

Department of Chemistry and Centre of Excellence in Mass Spectrometry, University of York, Heslington, York, YO10 5DD, UK

E-mail: [email protected]

The persistence of biomolecules, including DNA, lipids and proteins, in the archaeological PL08 record allows mass spectrometry to contribute concrete scientific data to a very wide range of engaging and long-standing archaeological questions. The availability of convenient soft ionisation sources, and modern mass spectrometry’s excellent limits of detection and mass accuracy make it an outstanding tool for these applications. However, tailored sample handling protocols, the importance of applying normal analytical rigour in approaching such exciting projects, and the ability to apply both innovative as well as specialist approaches to data interpretation are also critical in maximizing the contribution of MS to such archaeological investigations. A wide variety of archaeological problems are turning out to be accessible to analysis by mass spectrometry. For example, fossilized bone samples may contain both protein and DNA, the sequences of which can identify the organism from which the bone came, and in the case of extinct organisms, also have the potential to reveal evolutionary links to extant species. In contrast, pottery pieces tend to trap and preserve some components of the materials with which they have been in contact, shedding light on the pottery’s use and on aspects of daily life of the original owners. The talk will present mass spectrometric data obtained during investigations of ancient proteins, lipids, and small molecules, and will illustrate the ways in which we have been using mass spectrometry to contribute to answering some challenging and interesting archaeological questions.

Acknowledgement The York Centre of Excellence in Mass Spectrometry was created thanks to a major capital investment through Science City York, supported by Yorkshire Forward with funds from the Northern Way Initiative, and subsequent support from EPSRC (EP/K039660/1; EP/M028127/1). Studentship support through the Natural Environment Research Council and the Analytical Chemistry Trust Fund (NE/I01959X/1) is gratefully acknowledged.

155

Revealing fakes and forgeries of works of art using instrumental archaeometric techniques

M.I. Karayannis

Department of Chemistry, University of Ioannina, Dourouti, 45100 Ioannina, Greece

E-Mail: [email protected]

The art of forging was practising as early as two thousand years ago, as practitioners TU01 put reed pens to papyrus to mimic the writing of Socrates and other ancient authors or imitate works of art of famous artists, whose works were highly valued. Today, the motive of most forgers remains the same—create something "priceless," then find an unintelligent or sucker willing to pay an exorbitant price for it. Cases of forgery have been known in texts, artworks and paintings and in most cases this exercise was a stock market play. The question of whether a work of art is fake or authentic may seem relatively simple but there are many factors that complicate the answer when we refer to different situations. Natural sciences can provide methods and procedures for the certification of the authenticity of works of arts. However, it should be emphasized that, while the natural sciences can produce proof of forgery, they can not always prove the authenticity of archaeological finds and works of art. For somebody to decide for a forgery, all it takes is a strong negative finding to support its judgment as a "non-authentic" object. To decide for authenticity, however, the opposite is true. This is a complex process requiring knowledge of both, historical and technical / scientific analysis. In this presentation different instrumental methods will be discussed for revealing forgeries of selected cases.

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Archaeological and climatic data from elemental ratios using rapid analysis of shell carbonate with LIBS

N. Hausmann1, P. Siozos1, A. Lemonis1, K.T. Li2 and D. Anglos1,3

1Institute of Electronic Structure and Laser, Foundation for Research and Technology – Hellas, Heraklion, Greece 2Academia Sinica, Institute of History and Philology, Taipei, Taiwan 3 Department of Chemistry, University of Crete, Heraklion, Greece.

E-mail: [email protected] TU02

The chemical composition of carbonate shell from palaeoecological and archaeological assemblages is laborious to analyse, yet the information that is locked within the tens of thousands of shell deposits worldwide contains valuable insights on past environments and human ecology. At present, studies struggle with the acquisition of sufficient amounts of data to make robust interpretations. Large amounts of information are inaccessible due to costly and time-intensive techniques, resulting in small, unrepresentative studies and a lack of comparability between them. Here we develop the technique of Laser Induced Breakdown Spectroscopy (LIBS), which will allow rapid chemical analyses of carbonates, increasing the cost efficiency by a factor of 20, resulting in more comprehensive datasets, as well as create a rapid and affordable method to advance the reconstruction of climate change, exploitation of coastal resources and human-landscape interactions [1]. We present results from samples of various freshwater and marine molluscan species from Taiwan, including Tegilla granosa (Linnaeus, 1758), Meretrix lusoria (Röding, 1798), Geloina erosa (Lightfoot, 1786), Crassostrea gigas (Thunberg, 1793) and Haliotis paua (Fleming, 1953). Samples were acquired from archaeological [2] and modern collections carried out by the Academia Sinica, Taipei, as well as by the authors in April 2017.

References [1] N. Hausmann, P. Siozos, A. Lemonis, A.C. Colonese, H.K. Robson and D. Anglos, Elemental mapping of Mg/Ca intensity ratios in marine mollusc shells using laser-induced breakdown spectroscopy. Journal of Analytical Atomic Spectrometry. (2017) DOI: 10.1039/C7JA00131B [2] C.H. Tsang, K.T. Li and C.Y. Chu, Footprints of ancestors: archaeological discoveries in Tainan Science-based Industrial Park. Tainan: Tainan County Government (2006)

157

Safe boundaries for analysis of heritage materials in the context of Raman microscopy

A. Philippidis1, P. Siozos1 and D. Anglos1,2

E-mail: [email protected] TU03 Analytical techniques based on intense radiation sources are applied to a large number of Cultural Heritage (CH) samples and artefacts. While most of these techniques are considered as non-destructive since no sampling is needed, alterations may occur, depending on the material analysed as well as on the experimental parameters. The literature considering radiation effects on CH objects is extremely limited. It is necessary to address these problems directly and systematically and to develop and implement new strategies to monitor, understand and mitigate radiation-induced alterations which may be occurring during analyses of heritage materials. [1,2] In the context of this study, a compact mobile Raman spectrometer was employed for investigating samples of pigments in powder form, employing its excitation laser source as both an irradiation and a monitoring tool. The case of the red pigment Vermillion (mercury (II) sulfide (α-HgS)) is presented as this is considered a common reference material for assessing pigment discoloration effects during laser irradiation. It is well-known that when the laser beam power density incident on, for instance, a paint sample, exceeds a certain threshold, thermally or photochemically induced alterations may take place and these depend on the pigment and its local environment. It is obviously important to understand such processes for various paint materials as this will lead to the development of proper mitigation strategies. For this reason different experimental parameters such as, laser power, excitation wavelength, exposure time to radiation was examined in this study.

Images employing by a microscope of the red pigment vermillion (HgS) collected a) under low-power and b) high-power irradiation conditions of a cw diode Raman laser. In the right photo the “darkening” of the pigment is obvious (darkened area diameter around 30μm).

References [1] L. Bertrand, S. Schoeder, D. Anglos, M.B.H. Breese, K. Janssens, M. Moini and A. Simon, Trends in Analytical Chemistry, 66 (2015) 128–145. [2] I. Osticioli, A.A. Mencaglia and S. Siano, Sensors and Actuators B, 238 (2017) 772–778.

158

Tuesday 19 September 2017 PASIPHAE I Hall Chair: K. Valko, I. Panderi

Chromatography 1

159

10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Portable capillary electrophoresis systems for rapid on-site determination of drug abuse

M. Kulp, M. Kaljurand, M. Vaher, J. Mazina-Šinkar, P. Saar-Reismaa, A. Špiljova

Akadeemia tee 15, 12618 Tallinn, Estonia

E-mail: [email protected]

Widespread illegal use of psychoactive substances is the reason for the development of fast, TU04 sensitive, accurate and non-invasive analytical methods to identify the narcotics used by drivers/criminals on-site, so that appropriate preventive measures can be taken. For such a method to be useful, several factors have to be considered, including non-invasive sampling and sample preparation time, the portability of instruments, instrument start-up time, and actual analysis time. To date, the preliminary assessment of illicit cannabis use employs on-site screening tests of oral fluid. Their main drawbacks are cross-reactivity and poor analyte recovery from the device, which leads to low diagnostic sensitivity (about 60%). Present study aims to demonstrate a potential of capillary electrophoresis (CE) method, its exceptional power of separation and resolution, short analysis time and ability for miniaturization for on-site assessment of illicit drugs use. In this project we translated the proof of the principle, demonstrated on a home-made lab scale instrument [1] onto a truly portable (30x30x18cm) instrument for on-site measurements. Developed CE system with deep-UV excitation source (λex 230 nm) allowed native fluorescence detection of twelve different amphetamines, cocaine and its derivative, and cannabinoids at their cut-off limits. The use of oral fluid (OF) for drug abuse testing is easy, sampling is non-invasive and does not require any special training. In this study we succeeded to combine saliva sample collection/preparation/pre-concentration procedure into one step using the Salivette sampling device. No separate precipitation of proteins and/or derivatisation was required. The whole procedure including saliva sample collection, clean-up and CE separation of analytes, took less than 20 minutes. Developed methodologies were thoroughly validated according to EMA Guidelines. Linearity of calibration curve, limits of detection and quantification (LOD and LOQ), selectivity against endogenous and exogenous interferences, inter-day precision, accuracy, carry-over effects, extraction recovery and matrix effect were evaluated. Due to exceptional selectivity and sensitivity of the constructed fluorescence detector and developed CE conditions the determination of narcotic substances in oral fluid was achieved with limits of quantification mostly below 20 ng/ml, which satisfies the EWDTS requirements [2]. Besides testing CE apparatus in the lab environment with real saliva samples provided by police, the portable instrument was also used for on-site analysis on the Baltic Weekend Festival held in Estonia in August 2016. Saliva samples were collected during the law enforcement officers ride.

References [1] J. Mazina, A. Spiljova, M. Vaher, M. Kaljurand, M. Kulp, Analytical Methods, 7 (2015) 7741. [2] European Workplace Drug Testing Society (EWDTS), 2015

161

Development and application of methods for the determination of pesticide residues in natural waters and sediments

M. Kapsi, V. Sakkas and T. Albanis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Panepistimioupolis, Ioannina, 45110, Greece

E-mail: [email protected]

A number of chemicals such as pesticides and other substances are used in aquaculture to treat TU05 sea lice or control weeds and algae. The determination of the residues of pesticides is one of the major challenges for the preservation and sustainability of the environment [1]. It is very important due to the risks that these compounds offer to human health, besides their persistence in the environment and their tendency to bioaccumulation. It is therefore, needed to collect data on these chemicals for a better knowledge of its fate and for the risk assessment. Pesticides that are more hydrophobic tend to be detected more frequently in sediment. Thus, measuring pesticides in sediment is important for tracking their fate in the environment and evaluating for potential toxicity [2]. The main objectives of this study were to develop rapid and accurate screening multiresidue pesticide methods on the basis of Solid Phase Extraction (SPE) technique for the determination of 10 pesticides in water samples and on the basis of QuEChERS technique for the sediments. The target compounds were determined by Gas Chromatography coupled with Mass Spectroscopy (GC-MS). The method was validated in terms of accuracy, precision, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at three different concentration levels, ranged between 73.2 to 101.2%, with relative standard deviations below 9.3%. The corresponding results from the sediment ranged betwwen 69.5 to 122.7% with relative standard deviations below 11.2%. The limits of detection for the pesticides in water and sediment were below 12 ng L-1 and 9 mg kg-1, respectively. The optimized methods were applied in Epirus region (North-Western Greece) to determine the concentration level of the target compounds in sea water and sediment samples.

References [1] F. Guardiola, A. Cuesta, J. Hernando and A. Agüera, Int. J. Mol. Sci, 13(2012), 1541-1560. [2] S. Brondi, A. Macedo, G. Vicente and A. Nogueira, Bull Environ Contam Toxicol, 86 (2011) 18– 22.

162 10th International Conference on Instrumental Methods of

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Fast routine analysis of polar ionic pesticides in water and foods by suppressed ion chromatography coupled to mass spectrometry

M. Godula1, K. Bousova1, F. Schoutsen1 and A. Kurz2

1Thermo Fisher Scientific, Special Solutions Center, Im Steingrund 4-6; Dreieich, 63303, Germany 2 Hochschule für Technik und Wirtschaft Aalen, Aalen, Germany

E-mail: [email protected]

Presence of polar pesticides and their metabolites in water and foods has become very hot TU06 topic in the past couple of years. The most famous representative of this group is a broad- spectrum systematic herbicide glyphosate and its metabolite AMPA. Because of the chemical properties especially high polarity, it is not possible to analyze these compounds with the conventional C18 reversed phase columns. Typically the laboratories use the methods that include time consuming derivatization steps or special chromatographic columns like the porous graphitic carbon (PGC) based HypercarbTM. With both approaches varying method robustness and unreliable results are often reported by routine laboratories. We do present an ion chromatography mass spectrometry (IC-MS/MS) method for direct analysis of a suite of polar ionic pesticides (e.g. Fosetyl-Al, Glufosinate, AMPA, Clopyralid, Glyphosate and others) in water and food samples. IC is the preferred separation technique for polar ionic analytes such as anions, cations or ionic metabolites and thanks to the recent development in the hyphenation of IC and MS it enables its unproblematic usage. The method is very easy and fast with no need for extensive sample preparation. For very dirty surface water samples the filtration through the membrane filters is recommended, foods are prepared by a simple methanolic extraction. The method was in-house validated for various water and food matrices covering surface, drinking, bottled water and fruits and vegetables. Analytical parameters as linearity, specificity, LOD, LOQ, precision and accuracy were evaluated using fortified blank samples at three different levels. All tested parameters showed satisfactory results with LOQs well below required legislative limits.

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Tuesday 19 September 2017 MINOS II Hall Chair: F. Tsopelas, F. Schoutsen

Chromatography 2

10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Plenary lecture Biomimetic Chromatography and Its Application in Drug Discovery

K. Valko

Bio-Mimetic Chromatography Consultancy, Unit 5B Business & Technology Centre, Stevenage, Herts SG1 2DX; UCL School of Pharmacy, London United Kingdom

Potent putative drug molecules often fail at later stages of the drug discovery process due to poor absorption, distribution, and pharmacokinetic properties. Physicochemical properties of molecules are responsible for the distribution and nonspecific binding of the molecules in vivo. PL09 The in vivo experiments are resource intensive and can be carried out only for a small number of compounds. Alternatively, biomimetic chromatographic measurements provide a platform for easy characterization of a large number of molecules by using components from the body such as proteins and phospholipids. Due to dynamic distribution processes during chromatography, the compounds have different retention times on chemically bonded protein and phospholipids (Immobilized Artificial Membrane, IAM) stationary phases. The retention behaviour of compounds can be easily studied under various conditions (for example different pHs) thus revealing the acid/base character of the compound. The structure – biomimetic retention studies revealed that compounds bearing positive or negative charges bind differently to albumin and phospholipids causing the different volume of distribution and tissue plasma partition. This phenomenon cannot be observer by traditionally applied lipophilicity measures, like octanol/water partition coefficient. From the systematically measured retention data using biomimetic stationary phases, we can estimate the in vivo distribution of the compounds, such as the volume of distribution, tissue/plasma partition, drug efficiency and the free concentration relative to a dose that is available at the site of action. The Druf Efficiency Index that combines potency and the biomimetic drug efficiency can be used for prioritizing compounds for in vivo measurements. References K. Valkó, lipophilicity and biomimetic properties measured by HPLC to support drug discovery, J Pharm. Biomed. Anal. 130 (2016) 35-54. http://dx.doi.org/10.16/j.jpba.2016.04.009 K. Valko, Physicochemical and Biomimetic Properties in Drug Discovery: Chromatographic Techniques for Lead Optimization, Wiley Hoboken NJ, 2014. K. Valko, S. Teague, C. Pidgeon, In vitro membrane binding and protein binding (IAM MB/PB technology) to estimate in vivo distribution; Applications in early drug discovery, ADMET & DMPK 5(1) (2017) 14-38; doi: 10.5599/admet.5.1.373

167

The performance of biopartitioning micellar chromatography on a series of structurally-diverse drugs and its potential to estimate cell permeability

F. Tsopelas1, P. Danias1, T. Sialda1, C. Stergiopoulos1, A. Pappa1 and A. Tsantili- Kakoulidou2

1Laboratory of Inorganic and Analytical Chemistry, School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou 9, 157 80 Athens, Greece. 2Laboratory of Pharmaceutical Chemistry, School of Pharmacy, University of Athens, TU07 Panepistimiopolis, Zografou, 157 71 Athens, Greece.

E-mail: [email protected]

Biopartitioning chromatography utilizes biomembrane- mimetic structures, such as liposomes, artificial membranes, microemulsions and micelles into a chromatographic system in order to gain insight into drug- membrane interactions, by rapid, friendly and reproducible measurements. It has been proved that the addition of a surfactant, in particular polyoxyethylene(23) lauryl ether (Brij35), in a saline mobile phase with the employment of an hydrophobic stationary phase can model drug biopartitioning process and the methodology has been widely known as biopartitioning micellar chromatography (BMC). The chromatographic column, modified by the surfactant, resembles the ordered array of the membranous hydrocarbon chains in regards to hydrophilic/hydrophobic character and the interactions of xenobiotics with the H-bonding groups of the adsorbed surfactant similar to the membrane ones. Therefore, the characteristics of the BMC are similar to biological barriers, whose interactions with drugs are governed by hydrophobic, electronic and steric properties of analytes. Up to now, BMC has been used to model toxicity (LD50), blood-brain barrier penetration, plasma clearance, volume of distribution as well as oral absorption. However, the reported studies mainly concerns to limited datasets and, therefore, further investigations are needed. The aim of the present study was the evaluation of the potential of biopartitioning micellar chromatography to estimate cell permeability. For this purpose, retention indices (logkw) of an extended set of structurally- diverse drugs were measured on a Discovery RP-18 column using as eluent Phosphate Buffered Saline in presence of Brij at a concentration of 0.04 M. Initially, retention factors were compared with octanol- water partitioning and indices of electrostatic and H- bonding interactions in order to unravel the underlying retention mechanism. Retention factors were subsequently used to model % Human Oral Absorption (%HOA) data, compiled from literature sources. Considering the pH gradient in gastrointestinal tract, the highest logkw values were considered, obtained either at pH=7.4 or at pH= 5.5. As intestinal absorption is a complicated process, additional physicochemical properties were tested in the %HOA/ logk w relationship. For reasons of comparison, the constructed models were compared with those derived by octanol- water partitioning. Retention factors were further correlated with Madin Darby Canine Kidney (MDCK) cell lines permeability data taken from literature at two pH values, 7.4 and 5.5.

References [1] Z. He, J. Sun, X. Wu, R. Lu, J. Liu amd Y. Wang. Curr. Drug Metab., 9 (2008) 152-166.

168 10th International Conference on Instrumental Methods of

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The use of immobilized artificial membrane chromatography to predict ecotoxicity of pesticides in aquatic environment

C. Stergiopoulos1, F. Tsopelas1 and M. Ochsenkuehn-Petropoulou1

1Laboratory of Inorganic and Analytical Chemistry, School of Chemical Engineering, National Technical University of Athens, IroonPolytechniou 9, 157 80 Athens, Greece

E-mail: [email protected]

During the last decade scientific interest in environmental pollution has risen, since a large number of organic contaminants have been found in the environment, some of which induce TU08 known or suspected undesirable effects on humans and ecosystems. Several classes of micropollutants have been investigated, such as pharmaceuticals, personal care products, perfluorinated compounds, disinfection byproducts and pesticides. Pesticides are a wide class of chemicals used to limit, inhibit and prevent the growth of harmful animals, insects, invasive plants, weeds and fungi. The main source of pesticides in the aquatic environment is runoff from agriculture. These substances are usually found in water at low concentrations and have potential adverse effects on aquatic organisms and public health [1]. The environmental fate of chemicals is influenced to a great extent by their lipophilicity, a physicochemical property being expressed as the logarithm of octanol-water partition (logP) or distribution coefficient (logD). Unfortunately, experimental determination of octanol-water partitioning is not only time-consuming and difficult, but it is also not applicable for compounds undergoing degradation. Liquid chromatography on the other hand offers a popular alternative for measuring lipophilicity, providing rapid measurements [2]. In the present work, the potential of immobilized artificial membrane chromatography (IAM) to predict ecotoxicity of pesticides in aquatic organisms was studied for the first time. More specifically, the retention of a set of pesticides was acquired by the IAM stationary phase, expressed as the logarithm of the retention factor measured or extrapolated to 100% aqueous phase (logkw). The results were then combined by statistical software with ecotoxicity data for aquatic organisms obtained under the same conditions from the literature in order to establish relationships. As additional physicochemical parameters affecting modeling, molecular weight, topological polar surface area, as well as positively and negatively charged molecular fractions were tested. The obtained models were then compared with those derived with octanol-water partitioning, as well as with micellar chromatography, which is proposed by the literature as another biomimetic approach towards this direction [3].

References [1] N. I. Rousis, R. Bade, L. Bijlsma, E. Zucatto, J. V. Sancho, F. Hernandez, S. Castiglioni, Environmental Research, 156 (2017) 31-38. [2]F.Tsopelas, C. Stergiopoulos, L. A. Tsakanika, M. Ochsenkühn-Petropoulouand A. Tsantili- Kakoulidou, Ecotoxicology and Environmental Safety, 139 (2017) 150-157. [3] J. M. Bermudez-Saldana, L. Escuder-Gilabert, M. J. Medina-Hernandez, R. M. Villanueva- Camanas, S. Sagrado, Journal of Chromatography A, 1063 (2005) 153-160.

Acknowledgements: Vioryl, Chemical and Agricultural industry, Research S.A. 28th klm Athens- Lamia national road , 19014, Afidnes, Greece

169

Development and validation of an isotope dilution liquid chromatography-tandem mass spectrometry confirmatory method for the simultaneous determination of acidic and basic non steroidal anti-inflammatory drugs in foodstuffs of animal origin

C. Arkouli1, A. Economou1, V. Schoina2, E. Stathoudaki2, Ch. Alexopoulos2, E. Kakoulides2

1Analytical Chemistry Laboratory, Department of Chemistry, National and Kapodistrian University of Athens, 157 84 Zografou Campus, Athens, Greece TU09 2Chemical Metrology Laboratory, General State Chemical Laboratory, 16 Tsocha Street, 115 21 Athens, Greece

E-mail: [email protected]

The presence of veterinary drug residues in foodstuffs of animal origin constitutes a serious human health risk. Non steroidal anti-inflammatory drugs (NSAIDs) are classified as group B substances by the Council of the EU [1]. Therefore, for products marketed in the EU, maximum residue limits (MRLs) have been set for some of these compounds while the rest are considered as forbidden substances [2]. These legislative limits necessitate the development of sensitive analytical methods to detect, identify, and monitor such residues in meat and milk [3-6]. The methods used in the official control of such products should follow specific validation requirements [7]. This communication describes the validation of a simple and rapid liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the simultaneous determination of both acidic and basic NSAIDs in foodstuffs of animal origin. The target NSAIDs were: aminoantipyrine, methylaminoantipyrine, phenylbutazone, oxyphenylbutazone, naproxen, mefenamic acid, flunixin, 5-hydroxyflunixin, tolfenamic acid, meloxicam, diclofenac, carprofen, and ketoprofen. Several extraction procedures were evaluated and the relevant matrix effects were considered during method development. The best results were obtained using extraction with acetonitrile, salting-out and solvent evaporation with no further purification. Chromatographic separation was performed on a C18 column and all analytes were determined using LC-MS/MS with heated electrospray ionization in the positive mode (HESI+). The method was validated in terms of linearity, accuracy, precision and the detection capabilities as well as the decision limits (CCα) were calculated. The method fulfills the legal requirements [7] and is implemented in the Greek monitoring plan for NSAIDs residue control in foodstuffs of animal origin.

References [1] Council Directive 96/23/EC, Off. J. Eur. Commun., L125 (1996), 10-32. [2] European Commission, Council Regulation 37/2010/EC, Off. J. Eur. Commun., L15 (2010), 1-72. [3] G. Dowling, P. Gallo, S. Fabbrocino, L. Serpe, Regan L., Food Add. & Contam. 25(2008) 1497– 1508. [4] P. Jedziniak, T. Szprengier-Juszkiewicz, M. Olejnik, J. Zmudzki, Anal. Chim. Acta, 672 (2010) 85- 92. [5] A. Gentili, F. Caretti, S. Bellante, L.M. Rocca, R. Curini, A. Venditti, Anal. Bioanal. Chem., 404(2012) 1375–1388. [6] C. Robert, N. Gillard, P-Y. Brasseur, G. Pierret, N.Ralet, M. Dubois, P. Delahaut, Food Add. & Contam, 30 (2013) 443-457. [7] European Commission, Council Decision 2002/657/EC, Off. J. Eur. Commun., L221 (2002), 8-36.

170

Tuesday 19 September 2017 PASIPHAE II Hall

Poster Session 2

Chromatography Archaeometry Spectrometry

10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Determination of levoglucosan and its stereoisomers by ESI-LC-MS- MS as tracers for fine particle emissions from biomass burning in Luxembourg

J. Ziebel, A. Krein, J. Junk and C. Guignard

Luxembourg Institute of Science and Technology (LIST), Department “Environmental Research and Innovation” (ERIN), 5, avenue des Hauts-Fourneaux, L-4362 Esch-sur-Alzette, Luxembourg

E-mail: [email protected] P2-01 Fine particles emissions from domestic biomass burning are identified as an important contributor to bad ambient air quality in Europe. In Luxembourg the use of wood for residential heating becomes more and more popular, but investigations concerning the contribution of biomass burning to the fine dust levels are still missing. Monosaccharide anhydrides such as levoglucosan (C6H10O5) and its stereoisomers mannosan and galactosan can be used as tracers for fine particle emissions from biomass burning. The aim of the study was to correlate the amount of levoglucosan in fine particle emissions to PM10 (particulate matter with an aerodynamic diameter ≤10 µm) mass levels due to biomass burning [1]. The levoglucosan/mannosan (L/M) ratio was also considered as an indicator of the type of biomass and wood burnt. Ratios between 3 and 7 are typical for the burning of soft woods. Higher ratios larger than 13 indicate the burning of harder wood types [1, 2]. Samples were collected from February to September 2016 with a low volume sampler (Comde-Derenda, 2.3 m3/h) at a typical urban background site in Dudelange, Luxembourg. In total 17 PTFE filters have been collected. They were extracted with methanol using ultrasonication [3]. The extracts were evaporated under vacuum until dryness. The samples were reconstituted with ultra-pure water, homogenized in ultrasonic bath and filtered on 0.2 µm. Analyses were performed in ESI-LC-MS/MS in negative mode with an Agilent 1260 coupled to a QTRAP 4500 (Sciex). The analytes were separated using two columns Zorbax 13 C18 Eclipse Plus (Agilent) series-connected [4]. Levoglucosan- C6 was added as internal standard just before the analysis. The linear range of the method extended from 0.05 µg/mL (limit of quantification) to 10 µg/mL for levoglucosan, mannosan and galactosan, corresponding to 0.05 and 10 µg per filter, respectively. For our sampling site, the estimated percentage of biomass burning ranged between 1.2% and 7.0%. The L/M ratios ranged from 3.8 to 8.9.

Acknowledgements: This study was supported by the luxembourgish “Ministère du Développement Durable et des Infrastructures”.

References [1] C. Schmidl, I.L. Marr, A. Caseiro, P. Kotianovà, A. Berner, H. Bauer, A. Kasper-Giebl, H. Puxbaum, Atmospheric Environment, 42 (2008) 126-141. [2] http://airuse.eu/wp-content/uploads/2013/11/B4-2MILESTONE-tracers-biomass.pdf [3] K.E. Yttri et al, Atmos. Meas. Tech., 8 (2015) 125-147. [4] C. Dye and K.E. Yttri, Anal. Chem., 77 (2005) 1853-1858.

173

A rapid method for drug testing and authenticity based on pyrogallol chemiluminescence

A. Votani, S. Tzoka, G.Z. Tsogas, A.G. Vlessidis, D.L. Giokas

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece

E-mail: [email protected]

This work reports a rapid method for the indirect CL detection of pharmaceutically active P2-02 compounds in commercial formulations. The method relies on the initial oxidation of pharmaceutical compounds by periodate or hypochlorite in aqueous solutions. The excess amount of oxidant is then injected into a FIA stream to oxidize pyrogallol towards the generation of an intense CL emission signal. The experimental conditions such as pH, temperature incubation time, reagent concentrations and FIA configuration, were optimized in order to enable the analysis of a wide range of pharmaceutical compounds under the same experimental conditions. Three categories of pharmaceutically active compounds namely nonsteroidal anti-inflammatory drugs (ibuprofen, naproxen, indomethacin), antibiotics (amoxicillin, trimethoprim, nalidixic acid) and potassium-sparing diuretics (amiloride, furosemide, clopamide) were examined for that purpose. Under the optimum conditions linear calibration curves were obtained over a wide concentration range with excellent sensitivity at the low μg L-1 levels. The reproducibility of the method, expressed as the relative standard deviation (R.S.D.), of five replicate measurements was satisfactory and ranged between 1.3- 8.5% for periodate and 1.0-9.4% for hypochlorite for all compounds.

174 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Utilization of preparative IEF and MALDI-TOF mass spectrometry in the identification of Escherichia coli from urine samples

J. Šalplachta1, M. Horká1, F. Růžička2 and K. Šlais1

1Institute of Analytical Chemistry of the ASCR, v. v. i., Veveří 97, 60200 Brno, Czech Republic 2Department of Microbiology, Faculty of Medicine, Masaryk University and St. Anne's University Hospital, Brno, Pekařská 53, 65691 Brno, Czech Republic

E-mail: [email protected] P2-03 Urinary tract infections (UTIs) are one of the most common infections in humans and are caused by a range of bacterial or fungal pathogens [1]. Escherichia coli is the most prevalent uropathogen accounting for about 80% of all infections [2]. UTI can be either asymptomatic or symptomatic and the symptoms can vary from bacteriuria with limited clinical symptoms to severe sepsis or septic shock. Therefore, fast and accurate identification of uropathogen is crucial for timely and appropriate treatment of infection. Bacteriological urine culture, the gold standard for the microbiological conﬁrmation of UTIs, is time-consuming and expensive method [3]. In recent years, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been introduced as a fast and reliable method for identification of pathogens in urine samples [4]. However, current MALDI-based methods require laborious sample treatment before MALDI-TOF MS analysis. In this study, a new approach utilizing recently developed preparative isoelectric focusing (IEF) in cellulose-based separation medium [5] with subsequent MALDI-TOF MS analysis is described. Preparative IEF was successfully used for both purification and concentration of E. coli in urine samples, E. coli was then simply collected from the separation medium and identified by MALDI-TOF MS. The proposed method enables identification of E. coli in urine specimens with bacterial colony count of ≥ 104 CFU/ml.

Acknowledgements This work was supported by the Ministry of the Interior of the Czech Republic (Grant VI20172020069) and by the Czech Academy of Sciences (Institutional Support RVO:68081715).

References [1] B. Foxman, Nat. Rev. Urol., 7 (2010) 653-660. [2] A. L. Flores-Mireles, J. N. Walker, M. Caparon, S. J. Hultgren, Nat. Rev. Microbiol., 13 (2015) 269-284. [3] E. M. Burd, K. S. Kehl., J. Clin. Microbiol., 49 (2011) S34-S38. [4] M. Íñigo, A. Coello, G. Fernández-Rivas, B. Rivaya, J. Hidalgo, M. D. Quesada, V. Ausina, J. Clin. Microbiol., 54:988–993. [5] J. Šalplachta, M. Horká, K. Šlais, J. Sep. Sci. DOI: 10.1002/jssc.201700036.

175

Chemical composition of buckles dated from the 3rd to the 7th centuries AD found in North-Eastern Bulgaria

D. Lesigyarski1, B. Zlateva2 and L. Trajkova3

1National Institute of Geophysics, Geodesy and Geography – BAS, “Acad. G. Bonchev” Str., bl. 3, 1113 Sofia, Bulgaria 2Faculty of Chemistry and Pharmacy, Sofia University, 1 “James Bourchier” Blvd., 1264 Sofia, Bulgaria 3National Archaeological Institute and Museum – BAS, 2 “Syborna” Str., 1000 Sofia, Bulgaria P2-04 E-mail: [email protected]

A set of 55 copper alloy buckles found during archaeological excavations at different sites in North-Eastern Bulgaria is analyzed by Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES). The buckles are dated to the 3rd-7th centuries AD and form several groups according to their shape and decoration. Using the ICP-AES technique the contents of 12 elements in the investigated artifacts are measured: As, Bi, Co, Cu, Fe, Mn, Ni, Pb, Sb, Se, Sn and Zn. Results show that the majority of the samples are made of bronze alloy, however some buckles consist of brass. Taking into account statistical data processing and cluster analysis performed the analyzed specimens can be divided in three clusters which overlap very good with the typological groups based on the external features observed. It can be concluded, regarding the elemental composition of the samples, that different materials or technologies were applied for the production of the buckles that form the separate clusters. On the other hand, the outliers were most probably prepared by reuse of older objects made of bronze or brass alloy which hinders their characterization and classification with respect to the chemical composition.

176 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

qNMR spectroscopy as an innovative and powerful technique for the determination of purity of organic compounds

A. Alexopoulos1, E. Kakoulides1, A. Panagiotopoulou2

1Chemical Metrology Laboratory, General State Chemical Laboratory, 16 Tsocha Street, 11521 Athens, Greece 2NMR Spectroscopy Laboratory, NCSR «Demokritos», 15310 Athens, Greece

E-mail: [email protected] P2-05 Nuclear Magnetic Resonance (NMR) is a powerful spectroscopic tool that is widely used in structural analysis. While the majority of NMR applications is focused on chemical structure elucidation (qualitative NMR), quantitative NMR spectroscopy (qNMR) represents a metrological method of analysis with unique capabilities [1]. Thus, the particular power of quantitative NMR arises from several properties: qNMR offers a unique physicochemical view of the analyte based on nuclear magnetism; qNMR constitutes a primary analytical method and could yield qualitative and quantitative information simultaneously. The more important basis of quantitative NMR spectroscopy is the direct proportionality of the signal intensity to the number of nuclei contributing to the resonance line. In this respect, qNMR could be used as a powerful tool in the determination of the purity of organic compounds [2]. The combination of 1H qNMR with metrological weighing can lead to measurement uncertainties below 0.1% when highly pure substances are used. The present communication is discussing a series of application of 1H qNMR on a variety of organic molecules, ranging from simple ones to more complex structures. The experiment preparation, the experimental conditions of the 1H qNMR measurements, the mathematical model of the determination are well presented and the pertinent uncertainty budget is also considered [3]. The application of the bottom-up approach described in JCGM 100:2008, allows for the contribution of the individual parameters underlying the analytical processes to be revealed and discussed.

References [1] S.K. Bharti, R. Roy, Trends Anal. Chem. 35 (2012) 5-26. [2] S. Westwood, T. Choteau, A. Daireaux, R.D. Josephs, R.I. Wielgosz, Anal. Chem. 85 (2013) 3118- 3127. [3] T. Yamazaki, S. Nakamura, T. Saito, Metrologia 54 (2017) 224-228.

177

Determination of amines using HPLC with fluorescence detection

A. Eisner, S. Surmová, O. Peterka, P. Bajerová, T. Bajer, K. Ventura, M. Adam

University of Pardubice, Department of analytical chemistry, Pardubice (CZ)

E-mail: [email protected]

A simple and sensitive method for the determination of free aliphatic and aromatic amines using derivatives agents (dansyl chloride, 9-fluorenylmethyl chloroformate and 4-Chloro-7- nitrobenzofurazan) as a labelling reagent by high-performance liquid chromatography with P2-06 fluorescence detection (HPLC-FLD) has been developed. Derivatization conditions including reagent concentration, buffer pH, reaction time and temperature were optimized. A fluorescence derivatization - high-performance liquid chromatography (HPLC) method, which enables the femtomole-level detection of analytes, is a powerful tool for the analysis with high sensitivity and selectivity. In recent decades, improvised explosive devices (IEDs) have become an increasing topic of public concern, with high-profile incidents such as the Bali (2002), London transport (2005), Boston Marathon (2013) and Brussels (2016) bombings garnering mass international attention.[1] Although the majority of media coverage has focused on large-scale incidents, there has also been a rise in explosive incidents involving smaller devices such as pipe bombs. This is particularly the case in the United States, where pipe bombs are considered to make up the vast majority of IED encounter. These devices can be easily constructed from everyday materials.[2] The mixture nitromethane with amines is applicable for this. Determination of residues after an explosion is important. This method (HPLC-FLD) could be useful for their determination. The proposed method is sensitive and reproducible for the determination of aliphatic and aromatic amines.

Acknowledgments The authors would like to thank the Ministry of the Interior of the Czech Republic for financial support (grant number VI20152020004).

References E.C. Bender, A.D. Beveridge, Investigation of pipe bombs, Forensic Investigation of Explosions, (2011) 429–492 G. Sauzier, D. Bors, J. Ash, J.V. Goodpaster, S.W. Lewis, Talanta, 158 (2016) 368–374

178 10th International Conference on Instrumental Methods of

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Total fluorescence spectroscopy associated to chemometrics helps to reveal the presence of defensin in honey

E. Fuentes 1, G. Cebrero 1, M. Báez1, C. Ley1, J. Martínez 2 and M. Báez 3

1Departamento de Química Inorgánica y Analítica, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Casilla 233, Chile. 2Instituto de Ciencias, Facultad de Medicina Clínica Alemana, Universidad del Desarrollo, Santiago, Chile. 3 Departamento de Bioquímica y Biología Molecular, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile, Santiago, Casilla 233, Chile. P2-07

E-mail: [email protected]

Honey is produced by bees using the nectar from the flowers enriched with some compounds that they themselves produce. As a result, honey is a concentrated aqueous solution of sugar that also contains enzymes, proteins, amino acids, volatile compounds, pigments and pollen which give its nutritional and antiseptic properties [1]. These properties are valued by the consumers and have begun to be a relevant factor on the quality of honey. Several mechanisms are involved in the antibacterial properties of honey including their osmolarity, acid pH, hydrogen peroxide production, phytochemical factors and antimicrobial peptides; specifically defensin-1 [2]. The usual way of detection of defensin-1 is through immunochemical assay with polyclonal anti-bee defensin-1 antibody. Although this method is specific and quite sensitive, its implementation is expensive and requires experience in its management. On the other hand, due to the presence of tryptophan in the defensin-1 structure the use of total fluorescence spectroscopy (TFS) is expected to be an alternative for its detection in honey. Thus, the aim of this work was to evaluate the use of TFS associated to multivariate curve resolution (MCR) as screening tool to elucidate the presence of defensin-1 in honey samples.

The fraction between 3 and 10 kDa of different honeys was obtained and analyzed by TFS- MCR. Three fluorescent components and their relative concentration were retrieved by MCR- ALS corresponding to tryptophan, room temperature phosphorescence of tryptophan (RTPT) and tyrosine; the first two related to the presence of the single tryptophan residue in defensin- 1. Similar results were observed for the analysis of a recombinant defensin-1 obtained from E. coli. Furthermore, a significant correlation was observed between the relative concentration of tryptophan as fluorescent or phosphorescent component and the content of cysteine determined as disulfide bridges in fractionated honey, both associable to defensin-1 structure. Thus, the presence of defensin-1 in the honey can be revealed in a simple way by TFS coupled to MCR becoming a useful screening tool for detecting the peptide in this appreciated bee product.

References [1] Couquet Y., Desmouliere A., Rigal M.L. Les propriétés antibactériennes et cicatrisantes du miel. Actualités pharmaceutiques, 531 (2013) 22-25. [2] Kwakman, P.H.S., te Velde, A.A., de Boer, L., Speijer, D., Vandenbroucke-Grauls, C.M.J.E., Zaat, S.A.J. How Honey Kills Bacteria. The FASEB J., 24 (2010) 2576-2582.

179

A portable XRF spectrometers for non-destructive analyses in the archaeometry: examples from Bulgaria

B. Zlateva1, D. Lesigyarski2 and V. Bonev3

1Faculty of Chemistry and Pharmacy, University of Sofia, Bul. James Bouchier 1, BG-1164, Sofia, Bulgaria 2National Institute of Geophysics, Geodesy, and Geography – Bulgarian Academy of Sciences, Department of Earth Magnetismddress 3Faculty of History, University of Sofia P2-08 E-mail: [email protected]

The XRF (X-ray Fluorescence) spectroscopy is a non-destructive technique of analysis widely used in archaeometry for the identification of chemical elements in pigments, glass, metal alloys, and other materials. The subject in this study are glass samples and copper alloy from different archaeological sites in Bulgaria. About 50 fragments of glass artefacts chronologically dated to the III c. BC to VI c. AD. The glass samples were collected from different archaeological sites in Bulgaria. The samples from copper alloy are colected from metal belts and beloning accessoaries, from NE Bulgaria also, and dated in Late Antiqiutes. Using three different p-XRF instruments (Bruker Tracer III-V, Bruker S1 Titan and Thermo Niton XL3T-900 GOLDD models) chemical composition of the artefacts and different standards are obtained. The results for the standard materials (glass 600 NIST and copper alloys BAM 211 and 213) are in very good coincidense with the certificated value for all type instruments, despite the results for archaeological objects, where there are significant differences in the chemical compositions obatined from the different models of p- XRF. The main difference is obtained for the level of As and Pb in copper alloy which can be explained by overlaping of the lines of the elements, where the best results are done by Bruker S1 Titan model. This XRF spectrometer is based on a new kind of energy dispersive device, the Silicon Drift Detector (SDD). The SDD, cooled by a Peltier element, can reach a resolution of the order of 160 eV FWHM at 6 keV. This feature makes this device ideal for portable high- resolution XRF spectrometers in the field of the Archaeometry.

180 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Chemical composition of fibulae, found in ancient Emporion Pistiros

V. Bonev1 and B. Zlateva2

1Faculty of History, University of Sofia, 15 “Tzar Osvoboditel” str, 1504 Sofia, Bulgaria 2Faculty of Chemistry and Pharmacy, University of Sofia, Bul. James Bouchier 1, 1164, Sofia, Bulgaria

E-mail: [email protected]

This study presents the results of the chemical analysis of large number of artifacts, chronologically dated between the second half of 5th century BC and the beginning of the 2nd P2-09 century BC. All of them were found in Emporion Pistiros archaeological site. It is supposed that Pistiros was an ancient Greek emporion with particular importance as trade center. The study focuses on the chemical composition of the findings and provides important information about the technology of ore processing and production of artifacts. In the initial stage of this study the concentrations of fifteen elements was determinate (Al, As, Bi, Co, Cr, Cu, Fe, Mn, Ni, P, Pb, Sb, Se, Sn, and Zn). The analytical techniques used were ICP-AES (inductively- coupled plasma atomic-emission spectroscopy, Perkin-Elmer Optima 7000 DV) and p-XRF (Bruker S1 Titan). An external calibration strategy with well characterized matrix-matched standards and different standard reference materials with similar chemical and physical properties (i.e. BAM 211) were chosen for the analysis. Multivariate statistical interpretation of the analytical data (statistical program SPSS 16.0 for Windows) reveals the types of alloy and their connection to topological characterization of the metal objects.

181

Analysis of coarse, fine, ultrafine particles and associated metals resulted from welding using SEM-EDS technique

M. Stanislawska1, T. Halatek1, M. Cieslak2, I. Kaminska2, R. Kuras1, B. Janasik1, W. Wasowicz1

1 Department of Environmental and Biological Monitoring, Nofer Institute of Occupational Medicine, Lodz, Poland 2 Scientific Department of Unconventional Technologies and Textiles, Textile Research Institute, Lodz, Poland P2-10 E-mail: [email protected]

Analysis of occupational exposure to welding fumes is based on determination of inhalable and respirable fractions of dust and its chemical components. Such measurement does not reflect the actual exposure because it does not include significant parameters related to particle sizes, especially the ultrafine ones, below 100 nm, which more and more often are a subject of discussions and research. The study was aimed at investigating of exposure to welding fumes containing metals, their compounds, and fine and ultrafine particles during of stainless steel and mild steel welding. The studies were carried out at two metal industry plants welding by the Metal Inert Gas (MIG) method in a shield of gases, stainless steel and mild steel. Stationary samples of welding fumes were collected for evaluation of morphology and structure of fluids, using the scanning electron microscope (SEM) and energy dispersive spectrometry (EDS) technique. Individual samples in welders inhalable breathing zone for assessment of the concentrations of iron (Fe), manganese (Mn), nickel (Ni), chromium (Cr +6 and Cr +3) and their compounds in inhalable and respirable fractions, using flame absorption atomic spectrometry (FAAS) and inductively coupled plasma mass spectrometry (ICP-MS) techniques. The results indicate that stainless steel welders were exposed to effects of carcinogenic and neurotoxic metals with concentrations exceeding admissible values. On the other hand the welders of low- alloy steel were exposed to smaller particles, i.e. the particles of potentially higher toxic effects. The studies demonstrate that the size and structure of particles occurring in welding fumes depend on their chemical composition.

Funding This work was supported by the National Center of Sciences in Poland [Grant numbers 2013/09/B/NZ7/04092]; and the Nofer Institute of Occupational Medicine in Lodz, Poland [internal grant numbers IMP 1.27].

182 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

New synthetic targets for modification of DNA by oxoosmium complexes

L. Havran, P. Vidláková, J. Špaček, and M. Fojta

Institute of Biophysics of the CAS, v.v.i., Královopolská 135, 612 65 Brno, Czech Republic

E-mail: [email protected]

DNA is electroactive molecule producing analytically useful intrinsic voltammetric signals at different types of working electrodes [1]. For some applications is a useful use redox active P2-11 tag to improve specificity and sensitivity of the analysis. One from approaches how to prepare DNA bearing redox label is its modification by complexes of osmium tetroxide with nitrogen ligands (Os,L). These complexes preferentially react with pyrimidines in single strand DNA producing electroactive adducts. Primary reaction site for Os,L is C=C double bond in pyrimidine nucleobases. This approach find wide used in highly sensitive DNA detection and in development of electrochemical DNA hybridization sensors [2]. Os,L formed with DNA covalent adducts, which are electroactive. These adduct produce at mercury and carbon electrodes set of voltammetric signals due to successive reduction/oxidation of Os atom. Moreover at mercury based electrodes is last Os reduction step couplet with catalytic hydrogen evolution. This signal can serve for high sensitive determination of such modified DNA. Working electrode from pyrolytic graphite (PGE) was utilized for direct analysis of reaction mixtures. Excess of unbound Os,L can be removed directly from electrode surface by extraction with organic solvent [3]. In this contribution will be presented results of reactivity study of DNA containing 7-deaza analogs of purine nucleobases and DNA with chemically modified nucleobase bearing aliphatic side chain. Both types of DNA containing C=C double bond which can serve as a targets for modification by Os,L.

References [1] Paleček E., Bartošík M., Chemical Reviews 112, (2012) 3427 - 3481. [2] Fojta M., Kostečka P., Pivoňková H., Horáková P., Havran L., Curr. Anal. Chem. 7, (2011) 35 - 50. [3] Fojta M., Havran L., Kizek R., Billova S., Talanta, 56, (2002) 867 - 874.

Acknowledgments: The research was supported by GACR (project No. 15-08434S).

183

Cholesterol determination in blood serum by means of voltammetry at chemically modified electrode

E.I. Korotkova1, K.V. Derina1

1Institute of Natural Resources, Tomsk Polytechnic University, Tomsk 634050, Russia

E-mail: [email protected]

Cholesterol is known to form plaques and cause vascular embolism. As a result, cholesterol P2-12 provokes the broad spectrum of cardiovascular diseases, such as, myocardial infarction, blood- stroke, cardiomyopathy, atherosclerosis hypertensive heart disease [1]. Therefore, cholesterol blood control plays an important role in clinical practice. Electrochemical methods are attractive for such purposes due to their simplicity, low costs and high accuracy [2]. Cholesterol chemical oxidation is possible under overvoltage. Chemically modified electrode was used for the decreasing of cholesterol oxidation potential. 2,6- diacetylglycouril was used as modifier. This compound has similar structure to flavin adenine dinucleotide (FAD), which is an active center of cholesterol reductase. Experimental studies were perfomed on voltammetric analyzer TA-Lab (Tomskanalyt, Russia). A carbon-containing electrode modified with 2,6 - diacetylglycouril was used as a working electrode. Silver chloride electrodes were used as auxiliary and reference electrode. The voltammograms were recorded using cyclic voltammetry and anodic square-wave voltammetry. The background electrolyte was phosphate buffer with pH = 6.86. Cholesterol oxidation peak was obtained at E = +0.9 V. Cholesterol reduction peak was not obtained. Certified reference materials (CRM) of Cholesterol NIST SRM 911 C was used in the recovery test to develop the method. The amount of cholesterol in SRM 911 was 99,2±1,2 mg/100 g. The results of the recovery test were satisfactory and comprised within the range of the certificated value of CRM. In the spiking test, the values ranged from 97.17% to 101.42% and the RSD values ranged from 2.16% to 3.56%. The LOD and LOQ values were 0.13 and 0.25 mg/100 g, respectively. The calibration curve of cholesterol were plotted. The linear range of the detected concentrations is observed from 0.3 to 15.6 mg/100 g (y = 6.15x + 0.02: R² = 0.99). Also, the blind tests were provided for blood serum samples received from the Cardiology Research Institute (Tomsk, Russia).

The research is supported by the Ministry of Science and Education of the Russian Federation (project «Science») and the Russian Foundation for Basic Research (project №16-33-00319).

References Ch. Liu, Yu. Zhang, D. Ding, X. Li, Yu. Yang, Yu. Zheng, D. Wang, W. Ling Atherosclerosis, 249 (2016) 116-124. A. de Barros, C.J.L. Constsantino, N.C. da Cruz, J.R. Ribeiro Bertoleto, M. Ferreira, Electrochimica Acta, 235 (2017) 700–708.

184 10th International Conference on Instrumental Methods of

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QuEChERS methodology combined with high performance liquid chromatography-UV/DAD for the determination of common pesticides in honey products

E. Gotsi, V. Boti, T. Albanis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Ioannina 45110, Greece

E-mail: [email protected] P2-13

The acaricide/insecticide use is a common worldwide practice in honey cultivation to protect the production. Nevertheless, their presence decreases honey safety and quality and affects the human health. The present study focuses on four active ingredients mainly used worldwide against varroosis: amitraz, bromopropylate, coumaphos and τ-fluvalinate. Therefore, it is important to set up an easy, reliable and rapid analytical method for determining such compounds in honey. A modified extraction procedure, based on the QuEChERS method (quick, easy, cheap, effective, rugged and safe) was employed. The insecticides were extracted and the extracts were purified with appropriate mixtures of salts adapted to the matrix and the substances to be extracted. Analyses were performed by high performance liquid chromatography on a C18 reversed-phase column with UV/ diode array detection (HPLC- UV/DAD). Isocratic elution system was used with acetonitrile-water (80:20 v/v) containing 0,01M Acetic acid as mobile phase while the selected compounds (amitraz, bromopropylate, coumaphos and τ-fluvalinate) were detected at 249, 233, 313 and 254 nm, respectively. This method, combined with accurate and sensitive detection, allowed quantification and confirmation at the low level of 50 μg/kg, with recoveries ranging between 78 and 103%. The analytical method was optimized and validated with a view to be succesfully applied to commercial honey products.

References [1] D. Paradis, G. Bérail, J-M. Bonmatin, Luc P. Belzunces, Anal Bioanal Chem, 406 (2014) 621-633. [2] A. H. Shendy, M. A. Al-Ghobashy, M. N. Mohammed, S. A. Gad Alla, H. M. Lotfy, J. Chromatogr. A, 1427 (2016) 142-160.

185

Discrimination of prehistoric teeth by infrared spectroscopy: Comparison of four models

C. Levasseur-Garcia1 and R. Vézian2

1Laboratoire de Chimie Agro-industrielle (LCA), Université de Toulouse, INRA, INPT, INP-Purpan, Toulouse, France 2Université de Toulouse, INP-Purpan, Département Sciences Agronomiques et Agroalimentaires, Toulouse, France

E-mail: [email protected] P2-14 The aim of this study is to use near infrared spectroscopy to discriminate between prehistoric teeth. NIR spectral data were collected in reflectance with an FT-NIR spectrometer (MPA, Bruker Optics, Ettlingen, Germany). Data were collected over the range 12,500–4500cm−1 at room temperature. Instrument control and initial data processing were performed using Matlab. Infrared spectra were collected on the four faces of each teeth (internal or external faces, dental neck, root of tooth and top of tooth). Discrimination models were developed after mathematical preprocessing and the performances of those models are compared in this study.

References [1] Daher C., Bellot-Gurlet L., Le Hô A.-S., Paris C., Regert M. 2013. “Advanced discriminating criteria for natural organic substances of Cultural Heritage interest: Spectral decomposition and multivariate analyses of FT-Raman and FT-IR signatures”, Talanta, 115: 540-547. [2] Daher C., Pimenta V., Bellot-Gurlet L. 2014. “Towards a non-invasive quantitative analysis of the organic components in museum objects varnishes by vibrational spectroscopies: methodological approach”, Talanta, 129: 336-345. [3] Manzano E., Navas N., Checa-Moreno R., Rodriguez-Simón L., Capitán-Vallvey L. F. 2009. “Preliminary study of UV ageing process of proteinaceous paint binder by FT-IR and principal component analysis”, Talanta, 77: 1724-1731.

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Evaluation of second-order multivariate calibration and fluorescence spectroscopy for mercury determination in environmental samples

M.A. Bravo, R. Veneciano, J. Bergmann, W. Quiroz

Laboratorio de quimica analitica y ambiental, Pontificia Universidad catolica de Valparaiso, Avenida Universidad 330, Valparaiso, Chile

E-mail: [email protected] P2-15 Mercury has been declared a contaminant of global interest due to its high degree of persistence in the environment and its toxicity to different biological species [1]. Exposure of humans to mercury and its compounds can lead to ataxia, loss of sensitivity in the hands and feet, weakness and, in extreme cases, paralysis and death. Several studies have showed that the toxicity of mercury depends on the concentration of its different chemical forms. In order to assess the exposition risk, it is extremely important have quantitative knowledge about mercury in environmental samples. For mercury determination, elemental techniques such as Atomic Absorption (AAS), Atomic Fluorescence (AFS) and inductively coupled plasma-mass spectrometry has been used. In this work, a method based on fluorescent spectroscopy and second order multivariate calibration is evaluated for determination of inorganic mercury (Hg2+) and methylmercury + (CH3Hg ) in synthetic and real aqueous samples. A chemosensor based in a selenolactone [2] and a chemodosimeter based on 2,1,3-benzothiadiazole [3] were used to quantify mercury species by fluorescence-induced. The experimental conditions are optimized in order to improve the analytical figures of merit of the proposed methodology. Two strategies for second order data generation were evaluated: A) Excitation-emission matrices (EEM); and B) Emission spectra-reaction time. The three-way data obtained were analyzed using Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS) and Unfolding Partial Least Squares-Residual Bi-linearization (UPLS-RBL). Finally, the proposed methodology was 2+ + applied to quantify Hg and CH3Hg in synthetic and real samples, in presence of uncalibrated interferences.

References [1] ENVIRONMENTAL CHEMISTRY AND TOXICOLOGY OF MERCURY, John Wiley & Sons, New Jersey, 2012, pp. 501-516. [2] X. Q. Chen, K. H. Baek, Y. Kim, S. J. Kim, I. Shin, J. Yoon, Tetrahedron, 66, (2010), 4016-4021. [3] Q. Zuo, H. Tian. Sensors and Actuators B, 149 (2010) 20-27.

Acknowledgments The authors gratefully acknowledge the FONDECYT program (Project1150950) and VRIEA-PUCV (Proyecto DI 125.701) for their financial support.

187

Evaluation of monolithic column for mercury speciation analysis in fish samples

M.A. Bravo, O. Riquelme, S. Parra, W. Quiroz

Laboratorio de quimica analitica y ambiental, Pontificia Universidad catolica de Valparaiso, Avenida Universidad 330, Valparaiso, Chile

E-mail: [email protected]

P2-16 Mercury (Hg) is a contaminant widely distributed in the environment and it is considered as one of the most toxic metals for mammals and human. In general, the toxicity of mercury is extensively documented and it depends of chemical forms, where organic compounds such as methylmercury (MeHg), are more toxic [1]. General population can be exposed to mercury species for several ways; especially, for ingestion of seafood (i.e. Fish containing MeHg) or inhalation of mercury vapor from dental amalgam restorations. For these reasons, several analytical methods have been proposed for mercury speciation analysis based on a chromatographic separation (e.g. GC or HPLC) hyphenated to selective detectors systems. In this work, we propose the evaluation of monolithic C18 column for separation of 2+ + inorganic mercury (Hg ) and methylmercury (CH3Hg ) during the analysis of real sediment samples. Firstly, the separation conditions were optimized and the figures of merit was evaluated. Then, several extraction methods form fish tissue were evaluated and their compatibility with the separation method was studied. The accuracy was assessed for the analysis of certified tuna fish sample (ERM-CE 464). Finally, the validated methodology was applied to analysis of freezed, canned and fresh fish samples in order to evaluate the potential exposition of Chilean population to mercury species.

References [1] ENVIRONMENTAL CHEMISTRY AND TOXICOLOGY OF MERCURY, John Wiley & Sons, New Jersey, 2012, pp. 501-516.

Acknowledgments The authors gratefully acknowledge the FONDECYT program (Project1150950) and VRIEA-PUCV (Proyecto DI 125.701) for their financial support.

188 10th International Conference on Instrumental Methods of

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Real time monitoring of laser cleaning on stone by means of photoacoustic signal detection

G.J. Tserevelakis1, J.S. Pozo-Antonio1,2, P. Siozos1, K. Melessanaki1, T. Rivas2, A. Ramil3, P. Pouli1, G. Zacharakis1

1Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL- FORTH) 2Dept. de Enxeñaría de Recursos Naturais e Medioambiente. Universidade de Vigo, Vigo, Spain 3Laboratorio de Aplicacións Industriais do Laser, EPS, Universidade da Coruña, Ferrol, Spain

P2-17 E-mail: [email protected]

This research paper demonstrates the suitability of photoacoustic signal detection for real-time monitoring of laser assisted removal of encrustation from stone. Photoacoustic effect is the generation of acoustic waves following the absorption of intensity-modulated optical radiation in a material, typically emitted by pulsed lasers, and has been recently introduced as a non- destructive monitoring process in laser-assisted removal of unwanted layers with encouraging results1. In this study, the specific conditions that rule the cleaning of graffiti from stone is approached with emphasis on the determination of the critical thresholds, namely the onset for material removal and the threshold for damage to the substrate upon intentional over-cleaning conditions. In this context, the exploitation of the intrinsic photoacoustic signals generated upon pulsed laser ablation of materials has been shown to enhance the non-destructive diagnosis and monitoring of laser cleaning interventions. A simple and straightforward case application of laser cleaning has been investigated, involving the removal of black graffiti from medium coarse white marble. A Q-switched Nd:YAG laser (λ=1064 nm, 8 ns FWHM) was employed for irradiating the sample at several fluence values ranging from 0.6 to 3.5 J cm-2. The photoacoustic detection setup employed a 5 MHz ultrasonic transducer, a RF amplifier and an oscilloscope, which was used for the recording of the generated photoacoustic waves. In order to validate the results provided by the proposed approach, state of the art techniques were additionally applied. Graffiti extraction was evaluated by means of stereo and electron microscopy, while the respective substrate micro-damage assessment was achieved through electron and confocal microscopy.

References [1] AE Villarreal-Villela, L. Ponce Cabrera. Open Journal of Applied Sciences 6, 2016, 626-635

Acknowledgements This work was partially supported by the BIA2014-54186-R project. J.S.P.A. was supported by a postdoctoral contract within the framework of the I2C Galicia Plan for 2014

189

Sulphur Analysis in High Lead Content Samples by a Mobile X-Ray Fluorescence System

N. Kallithrakas-Kontos1 and A. Fragkos2

1Analytical and Environmental Chemistry Laboratory, University Campus, Technical University of Crete, GR-73100 Chania, Greece 2AMEKON S.A., Industrial Zone, 35th Block, GR-25200 Patras, Greece

E-mail: [email protected]

P2-18 Analysis of high Lead (Pb) samples is of considerable interest in some industrial applications, such as recycling, metal production, etc. Mobile (portable), energy dispersive X-Ray Fluorescence (XRF) spectroscopy is a relative new technique that combines the advantages of solid sample analysis (thus avoiding solubility process with all the associated difficulties) as well as the possibility of online applications [1].

Sulphur (S) is an element that usually included in Lead compounds (e.g. PbSO4, PbS etc.). Although Pb produces its characteristic Lα and Lβ lines at medium X-ray energies (10.5 and 12.6 keV) that usually can be easy discriminated, Sulphur can be detected only by its Kα peak (2.308 and 2.306 keV) that strongly interferes with the Pb Mα1 x-ray line (2.346). The problem of Sulphur analysis becomes even more difficult as Pb concentrations often are quite higher than Sulphur ones and the mass absorption coefficient of S-line absorbance by a Pb-matrix, is extremely high. On the other hand the S Kα and the Pb Mα1 x-ray lines have similar mass absorption coefficients due to their energy close vicinity.

In the present work S was determined in high Pb content samples (of the order of 90% or even higher), that produced during battery recycling process. A series of powder standards were produced with various S and Pb concentrations and they were irradiated by an AMPTEK Mini- X-Ray tube and they were analyzed by an AMPTEK Peltier cooled Si-Pin detector with a resolution of 130 eV@S Kα. The S-Pb double peak was integrated as “one peak” fit and its centroid was calculated with a similar procedure that described in a previous works (concerning element speciation) [2, 3]. The calculated peak centroid was fitted as a function of S/Pb ratio. Results showed that a significant centroid shift takes place as S/Pb content changes, and this calibration procedure was used for Sulphur analysis in various samples.

References [1] Margaret West, Andrew T. Ellis, Philip J. Potts, Christina Streli Christine Vanhoof and Peter Wobrauschek, Atomic Spectrometry Update – a review of advances in X-ray fluorescence spectrometry and its applications, J. Anal. At. Spectrom., 31 (2016), 1706–1755. [2] N. Kallithrakas-Kontos, X-Ray chemical shift determination by energy dispersive X-Ray detection, Spectrochimica Acta B 51 (1996) 1655-1659. [3] A.G. Karydas, S Galanopoulos, Ch. Zarkadas, T. Paradellis and N. Kallithrakas-Kontos, Chemical state speciation by resonant Raman scattering, J. Phys.: Condens. Matter 14 (2002) 12367–12381.

190 10th International Conference on Instrumental Methods of

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The potential of biopartitioning micellar chromatography to estimate ecotoxicity of pesticides

C. Stergiopoulos1, F. Tsopelas1, D. Makarouni2, A. Tsantili- Kakoulidou3, M. Ochsenkuehn-Petropoulou1

1Laboratory of Inorganic and Analytical Chemistry, School of Chemical Engineering, National Technical University of Athens, Iroon Polytechniou 9, 157 80 Athens, Greece 2Vioryl, Chemical and Agricultural industry, Research S.A., 28th klm Athens-Lamia national road, 19014, Afidnes, Greece. 3Laboratory of Pharmaceutical Chemistry, School of Pharmacy, University of Athens, Panepistimiopolis, Zografou, 157 71 Athens, Greece. P2-19

E-mail: [email protected]

Biopartitioning micellar chromatography (BMC) uses reversed-phase stationary phases in combination with micellar mobile phases prepared by the addition of surfactants above their critical micelle concentration [1]. BMC acts as an in vitro system to mimic partitioning processes of xenobiotics into biological systems. The chromatographic column, modified by the surfactant, resembles the ordered array of the membranous hydrocarbon chains regarding the hydrophilic/hydrophobic character, while the interactions of xenobiotics with the H- bonding groups of the adsorbed surfactant simulate the membrane ones, found in humans, marine and terrestrial organisms. Therefore, the characteristics of BMC are suitable to estimate ecotoxicity of xenobiotics. Among others, pesticides constitute an important class of pollutants, widely used in various crop and health protection programs to control the pests and disease vectors. Therefore, the estimation of aquatic toxicity of existing and new chemical pesticides yet to enter the market would be essentially required for their safety/risk assessment process [2]. Up to now, there is a number of studies concerning the application of BMC to model ecotoxicity. However, as the reported studies mainly concern limited datasets, further investigations are needed in order to improve the predictive performance of the developed models and gain insight into the appropriate surfactant imitating ecotoxicological factors. Numerous correlations have also been developed between ecotoxicity and n-octanol–water partition coefficient (logP), however they are not always characterized by satisfactory statistics [3], apart from the laborious and time consuming nature of partitioning experiments. In the present study, the retention behavior of a set of pesticides was studied by BMC, using polyoxyethylene(23) lauryl ether (Brij35) and sodium dodecyl sulfate (SDS) as surfactants on a Discovery RP-18 column at pH=7.4. In all cases, extrapolated to pure aqueous phase retention factors (logkw) were determined. The underlying retention mechanism was scrutinized by considering the relationship of logkw with octanol-water partitioning with other physicochemical descriptors expressing electrostatic interactions and hydrogen bonding. Finally, BMC retention factors were correlated with lethal concentration levels (LC50) of marine organisms and the predictive performance of BMC was compared with the one of octanol-water partitioning.

References [1] K.E. Stepnik, I. Malinowska, Journal of Chromatography A, 1286 (2013) 127-136. [2] N. Basant, S. Gupta, K. P. Singh, Chemosphere, 139 (2015) 246-255. [3] J. M. Bermudez-Saldana, L. Escuder-Gilabert, M. J. Medina-Hernandez, R. M. Villanueva- Camanas, S. Sagrado, Journal of Chromatography A, 1063 (2005) 153-160.

191

Non-linear imaging techniques as diagnostic tools for Cultural Heritage studies

M. Mari1, V. Tsafas1,2, E. Gavgiotaki1, K. Melessanaki1 and G. Filippidis1

1Institute of Electronic Structure and Laser, Foundation for Research and Technology Hellas, P.O. Box 1527, 71110, Heraklion, Crete, Greece 2Department of Physics, University of Crete, 71003, Heraklion, Crete, Greece

E-mail: [email protected]

P2-20 Non-linear image contrast modalities (multi-photon excitation fluorescence (MPEF), second harmonic generation (SHG) third harmonic generation (THG)) have been proved to be powerful diagnostic tools for Cultural Heritage (CH) studies [1,2]. In the current study, it is shown that MPEF and THG can provide new information on the exact thickness determination and composition identification, as a function of depth of varnish protective layers and model painted artworks. Furthermore, structural information from glues used for conservation or restoration of painted artworks or papers and books of cultural heritage is obtained through the performance of polarization sensitive SHG measurements. Figure 1 presents SHG signals collected from a starch based glue (flour paste). The high intensity SHG signals mainly originate from the starch granules. Amylopectin is considered as the main molecular source of SHG in starch.

Figure 1. SHG image from a fresh flour paste.

We anticipate that, the non-linear optical imaging techniques can be extensively used as novel, minimally invasive, high resolution diagnostic tools for in situ analysis of various CH objects.

References [1] G. Filippidis, G.J. Tserevelakis, A. Selimis, C. Fotakis, Applied Physics A: Materials Science & Processing, 118 (2015) 417-423 [2] S. Psilodimitrakopoulos, E. Gavgiotaki, K. Melessanaki, V. Tsafas, G. Filippidis, Microscopy and Microanalysis, 22 (2016) 1072-1083

Acknowledgments: We acknowledge financial support from IPERION CH-H2020-INFRAIA-654028 project.

192 10th International Conference on Instrumental Methods of

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Arsenic speciation in fish from Greek coastal areas

I. Kalantzi1, K. Mylona1, K. Sofoulaki1,2, M. Tsapakis1 and S.A. Pergantis2

1Institute of Oceanography, Hellenic Centre for Marine Science (HCMR), PO Box 2214, Heraklion 71003, Crete, Greece 2Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Heraklion 71003, Crete, Greece

E-mail: [email protected]

Detection of As contamination in seafood and other marine organisms is critical both because P2-21 of health risk and environmental issues. This is because different As species exhibit different physicochemical properties and toxicities [1], [2]. However, detecting As contamination in fish present in the natural environment is particularly difficult, mainly because fish bioaccumulate As naturally. Therefore, even when marginally elevated As concentrations are found in marine biota, it is extremely difficult to associate these levels directly to anthropogenic contamination or even naturally occurring elevated As levels. So far only a limited number of As speciation studies in fish collected from Greek coastal areas have been conducted, especially for fish species that are of high consumption such as the sardines and anchovies analyzed here [3]. Also, limited reports for As speciation in these fish species, from other areas around the world, have been made so far [4]. In the present study, arsenic speciation analysis was conducted on fish samples (sardine and anchovy) collected from six areas along the Greek coastline, i.e. Artemisium Straits, Thermaikos Gulf, Amvrakikos Gulf, Strymonian Gulf, Thracian Sea, and Elefsina Gulf. Total arsenic levels ranging from 11.8 to 62.6 mg As kg-1 dry weight were determined. Arsenobetaine, a non-toxic form of arsenic, was found to be the main arsenic species, present at 8.6 to 58.8 mg As kg-1, accounting for 67-95 % of the total arsenic. Also detected in all fish samples was dimethylarsinic acid, although at considerably lower concentrations, ranging from 0.072-0.956 mg As kg-1. Monomethylarsonic acid was detected at low levels in all anchovy samples, and only in sardines from one area. Finally, inorganic arsenic in the form of arsenate was detected only in fish at one area, indicating the possible effect of an environmental parameter on its presence at detectable amounts. Statistical analysis revealed the environmental variables, such as salinity, total organic carbon and nitrogen, ammonium, phosphate, total phosphorus, dissolved oxygen and pressure index, that are potentially correlated to As species concentrations. Furthermore, based on factor analysis, biological parameters, such as fish weight, lipids, protein and ash content, that are correlated to As species concentrations of fish were also identified. The interrelationship of arsenobetaine and dimethylarsinic acid concentrations within each fish species was evaluated.

References [1] W. R. Cullen and K. J. Reimer, Chemical Reviews, 89 (1989), 713–764. [2] B. Moe, H. Peng, X. Lu, B. Chen, L. W. L. Chen, S. Gabos, X. Li, and X. C. Le, Journal of Environmental Sciences, 49 (2016), 1–12. [3] R. Schaeffer, C. Soeroes, I. Ipolyi, P. Fodor, and N. S. Thomaidis, Analytica Chimica Acta, 547 (2005), 109–118. [4] I. Kalantzi, K. Mylona, K. Sofoulaki, M. Tsapakis, and S. A. Pergantis, Journal of Environmental Sciences, (accepted 2017).

193

Solid-Phase spectrophotometric iodometric determination of various analytes using a polymethacrylate matrix

D.A. Fedan1, N.A. Gavrilenko1, N.V. Saranchina2 and M.A. Gavrilenko1

1Faculty of Chemistry, Tomsk State University, Tomsk, 634050 Russia 2Tomsk Polytechnic University, Tomsk, 634050 Russia

E-mail:[email protected]

Iodometry is widely used in chemical analysis. The concentration of an analyte is calculated P2-22 from the amount of iodine released as a result of reaction between iodide ions and an analyte in an acidic medium. The simplest and less sensitive method for the determination of iodine is based on measurements of color intensity of an aqueous triiodide solution and an iodine solution in an organic solvent after extraction. One of methods for improving sensitivity is the preconcentration of an analyte by solid-phase extraction followed by determination by solid- phase spectrophotometry. It is important that the use of solid-phase extraction is in agreement with the principles of green analytical chemistry. In our opinion, polymethacrylate may be used as a solid-phase extractant. The optical and processable properties of polymethacrylate favor the preparation of optically transparent thin plates with high transmission, which, in turn, considerably facilitates measurements of the analytical signal by spectrophotometric methods. This work is aimed at the development of simple procedures for the determination of analytes based on the application of solid-phase spectrophotometry to the determination of polymethacrylate-extracted iodine resulting from redox reactions between the analytes and iodide. The analyte reactions in an acidic medium resulted in the formation of free iodine in amounts equivalent to those of analytes, followed by the formation of a triiodide complex, which was extracted from the solution with the polymethacrylate matrix. The extraction of iodine was accompanied by a change in matrix color from pale-yellow to yellow brown. The color of the plates remained unchanged for a long time. The absorption spectrum of iodine in the polymethacrylate matrix contained only one absorption band at 370 nm, which corresponded to the absorption of the triiodide complex. Procedures for the iodometric solid-phase spectrophotometric determination of nitrite and selenium(IV) using a polymethacrylate matrix are proposed. The developed procedures ensure the determination of 0.01–0.12 mg/L of nitrite and 0.05–0.40 mg/L of selenium(IV) with limits of detection of 0.005 and 0.03 mg/L, respectively. It was shown that the proposed procedures can be applied to the determination of selenium(IV) in mineral water and nitrites in vegetables and soil. The data for the determination of selenium(IV) and nitrite suggest satisfactory accuracy and reproducibility. The developed procedures are simple in implementation, do not require toxic reagents and solvents, and are carried out on standard spectrophotometric equipment.

Acknowledgments. This research was supported by “The Tomsk State University competitiveness improvement programme”.

194 10th International Conference on Instrumental Methods of

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Validated HPLC-ESI/MS method for identification and quantification of 15 phenolic acids in plant extracts

N.Y. Sipkina1, M.V. Baranova2, Y.A. Skorik2,3

1St. Petersburg State Chemical-Pharmaceutical Academy, ul. Prof. Popova 14, St. Petersburg, Russia 2Federal Almazov Medical Research Centre, ul. Akkuratova 2, St. Petersburg, Russia 3Institute of Macromolecular Compounds of the RAS, Bolshoi pr. VO 31, St. Petersburg, Russia

E-mail: [email protected]

In this work, we propose an improved HPLC-ESI/MS method for identification and P2-23 determination of 15 phenolic acids in plant extracts. This method is based on our previous studies using UV detection [1]. C18 reversed-phase HPLC with gradient elution (0.1% formic acid/acetonitrile, flow rate 0.2 mL/min) shows an excellent selectivity for the separation of 15 fenolic acids (Fig. 1). Mass chromatograms were obtained by electrospray for negative ions. The most intense ions for each analyte were collected in a SIM experiment with span 0.6 m/z for both identification and quantification. ESI parameters: a gas (N2) flow of 15 L/min, drying gas temperature of 300°C, nebulizer of 80 psi, a capillary voltage for each analyte was in the range of -75…-120 V. The method was validated for simultaneous analysis of 15 phenolic acids regarding linearity, limit of detection, limit of quantification, precision and accuracy. Several plant dry extracts (Echinacea, Astragalus, Comarum, Aronia, Melissa, Scutellaria) were analyzed using the proposed method.

Fig. 1. The chromatogram of the standard solution of 15 phenolic acids, UV detection at 276 nm and MS detection in SIM mode.

References [1] N.Y. Sipkina, Y.A. Skorik, Journal of Analytical Chemistry, 70 (2015) 1406–1411.

195

Quantification of new antifungal drug by HPLC-ESI/MS in biological liquids

N.Y. Sipkina, I.P. Yakovlev

St. Petersburg State Chemical Pharmaceutical Academy, ul. Prof. Popova 14, St. Petersburg, Russia

E-mail: [email protected]

The highly sensitive HPLC-ESI/MS method for quantitative determination of new antifungal P2-24 drug – 2-[(1Z)-1-(3,5-diphenyl-1,3,4-thiadiazol-2(3Н)-ylidene)methyl]-3,5-diphenyl-1,3,4- thiadiazol-3-ium chloride (TDZ) [1] – was developed and validated. The reversed-phase HPLC of TDZ in isocratic elution mode using 0.03% TFA and acetonitrile at a flow rate of 0.2 mL/min was performed (Fig. 1). Determination of TDZ was carried out in a positive electrospray ionization in a SIM mode for [M+]=489 m/z.

Cl-

N+ N

N N S S

Fig. 1. Chromatograms of the reference solution of TDZ (left) and the sample solutions (right).

The method of absolute calibration was used for quantification of TDZ in two concentrations ranges: 50–2500 pg/mL and 2500–30000 pg/mL. The established method showed a good linearity (R=0.999 for both ranges), the LQD was 50 pg/mL. The fully validated method was applied for quantification of TDZ in urine and plasma of rats and rabbits during pharmacokinetics study.

References [1] Patent N2014140482/04, Yuskovets V.N., Коshevenko А.S., Yakovlev I.P., Ananieva E.P., Semakova T.L. Substituted chlorides 2-[(1Z)-1-(3,5-diaryl-1,3,4-thiadiazol-2(3Н)-ylidene)methyl]- 3,5-diaryl-1,3,4-thiadiazol-3-ium and the way of their production// Patent RU N2571102.2015.№ 35.

196 10th International Conference on Instrumental Methods of

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NMR spectroscopy analysis of 19th century decorative interior paintings in Helsinki, Finland

E. Ralli1, H. Mannerheimo2, U. Knuutinen2,3 and A. Spyros1

1NMR Laboratory, Department of Chemistry, University of Crete, 70013 Heraklion Crete, Greece 2Department of Art and Culture Studies/Museology, University of Jyväskylä, FIN-40014 Jyväskylä, Finland 3Department of Chemistry, Faculty of Science, University of Helsinki, FI-00014 Helsinki, Finland

E-mail: [email protected] P2-25 Liquid state NMR spectroscopy is a powerful analytical methodology for the characterization of organic materials in cultural heritage science, such as paint binders, waxes, resins and consolidants used in art conservation [1]. The compositional NMR analysis of cultural heritage materials can additionally provide information on their structural integrity and the effect of various aging factors, such as oxidation, hydrolysis, UV radiation, etc. [2]. In this case study, we present the NMR spectroscopy analysis of the deterioration state of decorative interior paintings of two public buildings located in Helsinki, Finland. Samples were obtained from Arppeanum’s staircase walls and the ceiling paintings of the House of the Estates. Both buildings were painted in the late 19th century by the well-known Finnish decorative painter Salomo Wuorio. Hydrolysis and oxidation markers derived from the glyceride analysis of the paint samples showed that the House of the Estates paint samples were homogeneously clustered and more aged than the Arppenaum samples (Figure 1).

The deterioration state of Arppenaum’s wall paint samples was successfully correlated with UV aging due to their position on the staircase, while for the House of the Estates paintings a correlation between oxidation state and Zn content was observed, indicating that zinc plays a synergetic role in the oxidative deterioration of the binder drying oils. Furthermore, NMR spectroscopy was used to identify the remains of various Figure 1. Oxidation/Hydrolysis (X/Y axes) marker plot modern polymeric consolidants for the paintings samples obtained from Arppeanum and utilized during previous the House of the Estates. Less aged samples are positioned restoration of the Arppenaum’s closer to the top left, more aged to bottom right. wall paints.

References [1] A. Spyros, Modern Magnetic Resonance, Webb GA (Ed.), Springer International Publishing (2016) 1-12. [2] G. Stamatakis, U. Knuutinen, K. Laitinen, A. Spyros, Anal. Bioanal. Chem., 398 (2010) 3203-3214.

197

Portable hybrid LIBS-diffuse reflectance spectrometer for spectroscopic analysis of inorganic pigments

P. Siozos1, D. Anglos1,2

1Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL- FORTH), PO Box 1385, GR 71110, Heraklion, Crete, Greece 2Department of Chemistry, University of Crete, P.O. Box 2208, GR 710 03 Heraklion, Crete, Greece

E-mail: [email protected] P2-26 A novel portable instrument, combining two spectroscopic techniques, laser induced breakdown spectroscopy (LIBS) and diffuse reflectance spectroscopy is presented and its use for the analysis of pigment materials is demonstrated. LIBS and diffuse reflectance spectra of several model samples of inorganic pigments were recorded and the complimentary information was used to effectively distinguish different types of pigments even if they had the same colour and similar elemental composition. Finally, pigment analysis was performed on an archaeological artefact demonstrating the capabilities of the proposed hybrid diagnostic approach.

Mars Black Red Ochre Yellow Ochre

Green Earth

Intensity (a.u.) Intensity

a) 360 370 380 Wavelength (nm)

100 Iron based pigments 80 Red Ochre Green Earth Yellow Ochre Mars Black

Reflectance % 20

0 b) 400 500 600 700 800 900 Wavelength (nm) a) LIBS spectrum of red ochre (red line), yellow ochre (yellow line), mars black (black line) and green earth (green line) pigment powders and b) diffuse reflectance spectra of the same pigment powders.

References [1] A. Author, B. Author and C. Author, Journal, 50 (2011) 1-10.

198 10th International Conference on Instrumental Methods of

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Analytical techniques based on mobile laser instruments, for the study of cultural heritage objects

A. Philippidis1, P. Siozos1, Z.E. Papliaka1, K. Melessanaki1, M. Vakondiou2, O. Gratziou2,3 and D. Anglos1,4

1Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL- FORTH), P.O. Box 1385, GR 711 10 Heraklion, Crete, Greece 2Institute for Mediterranean Studies, Foundation for Research and Technology- Hellas (IMS-FORTH), P.O. Box 119, GR 74100 Rethymnon, Crete, Greece 3Department of History and Archaeology, University of Crete, GR 74100 Rethymnon, Crete, Greece P2-27 4Department of Chemistry, University of Crete, P.O. Box 2208, 710 03 Heraklion, Crete, Greece

E-mail: [email protected]

In the context of this study, a multi-technique approach was employed that combined the use of Raman microscopy and laser-induced breakdown spectroscopy (LIBS), based on mobile instrumentation, appropriate for rapid analysis of materials in historical and archaeological objects and monuments. The two techniques were used in situ, directly on the objects and provide complementary compositional information, elemental the LIBS and molecular the Raman spectroscopy [1, 2]. In this versatile analytical approach, the monitoring of pigments used in stone sculpture, were investigated by performing campaigns in a museum, in a conservation laboratory and outdoors (churches), all situated in the island of Crete. From paint analysis for Venetian sculpture (13th-17th) carbon black identified by Raman and presence of manganese black suggested by LIBS analysis. In the Ottoman sculpture (17th-19th) ultramarine, red lead and chrome yellow were identified by Raman and LIBS measurements. Furthermore, LIBS analysis, imply the presence of Cu-based green pigment and gold foil, in green and “metallic” areas, respectively.

Optical probes of Raman and LIBS mobile instruments over the surface of stone inscription, during the analysis.

References [1] P. Westlake, P. Siozos, A. Philippidis, C. Apostolaki, B. Derham, A. Terlixi, V. Perdikatsis, R. Jones and D. Anglos, Anal. Bioanal. Chem. 402 (2012) 1413-1432. [2] Z. E. Papliaka, A. Philippidis, P. Siozos, M. Vakondiou, K. Melessanaki and D. Anglos, Herit Sci 4 (2016) 15.

199

Temperature-dependent photoluminescence and lasing emission of ZnO nanocomposites

D. Patramanis1,2, A. Tsoukala1,2, A. Klini2, and D. Anglos1,2

1Department of Chemistry, University of Crete, P.O. Box 2208, GR 71003 Heraklion, Crete, Greece 2Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, (IESL- FORTH) P.O. Box 1385, GR 71110 Heraklion, Crete, Greece

E-mail: [email protected]

P2-28 The dependence of the UV exciton photoluminescence (PL) of zinc oxide (ZnO) was investigated as a function of temperature (T) in a series of nano-hybrids containing ZnO nanoparticles, dispersed in organic (polydimethylsiloxane-PDMS) [1] or inorganic (silica) matrices, exploring both weak and strong laser excitation conditions that gave rise to near band-edge photoluminescence emission and random lasing respectively [2]. Low energy nanosecond laser pulses at λ = 355 nm (3rd harmonic of Nd:YAG laser), and λ = 248 nm (KrF excimer laser) were used for weak pumping while sub-picosecond pulses at λ = 248 nm were employed for the random laser emission measurement. All experimental measurements reveal that the PL emission of ZnO is quite sensitive to temperature variations in the range investigated (290 – 340 K). Increase of temperature results in a decrease of the photoluminescence emission yield along with a significant spectral broadening, whereas the emission peak position exhibits a profound red shift (from 385 nm at 290 K to 395 nm at 340 K). These spectral indicators, follow smoothly the temperature increase of the hybrids and in fact appear to be rather insensitive to the nature of the matrix, organic or inorganic. At the high intensity excitation regime, achieved through sub-picosecond optical pumping, the nano-hybrid emission shows the well-known spectral narrowing that results from the strong scattering of light by the nanoparticles. This behavior is termed random lasing. Surprisingly, a very small increase of temperature by a few degrees over room temperature results in an abrupt transition from the narrowband random lasing emission to a broad spectral profile more typical to regular PL emission. This work demonstrates the ability of luminescent ZnO nanoparticles, embedded in various matrices, to act as an optical thermometer monitoring temperature in their gaseous or liquid environment or in contact with solid substrates. The variability of different indicators, such as spectral intensity, width or maximum offers a more systematic way to monitor temperature changes in a reliable manner, opening the path for exploiting ZnO-based materials as optical sensors even at remote distances or hostile environments.

References Klini, A., Pissadakis, S., Das, R. N., Giannelis, E. P., Anastasiadis, S. H., & Anglos, D. (2015), ZnO– PDMS Nanohybrids: A Novel Optical Sensing Platform for Ethanol Vapor Detection at Room Temperature, J. Phys. Chem. C, 119(1), 623–631. Anglos, D., Stassinopoulos, A., Das, R. N., Zacharakis, G., Psyllaki, M., Jakubiak, R., Anastasiadis, S. H. (2004), Random laser action in organic inorganic nanocomposites, J. Opt. Soc. Am. B, 21(1), 208.

200 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Chemical analysis of industrial scales and real-time monitoring of their dissolution processes via laser spectroscopy

O. Kokkinaki1, P. Siozos1, A. Philippidis1, C. Marmatakis1,2, M. Tsagkarakis1, N. Koromila1, M. Hadjistephanou3, C. Gounarakis3, D. Anglos1,2

1Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL- FORTH), P.O. Box 1385, GR 711 10 Heraklion, Crete, Greece 2Department of Chemistry, University of Crete, P.O. Box 2208, GR 710 03 Heraklion Crete, Greece 3Corpex Solutions, 34 A, Diakou St., 14671 N. Erythrea, Athens, Greece P2-29 E-mail: [email protected]

The accumulation of deposits on the interior surface of process industrial equipment, known as scaling, may lead to significant production loss. Therefore, advanced dissolution protocols are employed for scales removal. Optimization of the chemical cleaning methods requires knowledge of the chemical composition of the scales [1] and on-line monitoring of the applied dissolution processes. To this end, in this work, Raman and ATR-FTIR spectroscopic analytical techniques are employed for the identification and classification of a series of samples of industrial scales. The examined samples are identified to be either organic or inorganic. The inorganic scales are further categorized in the following groups, namely calcium carbonates, calcium sulphates (hydrates and anhydrous), barium sulphates and iron oxides. As far as monitoring of the dissolution process is concerned, two separate LIBS methodologies are investigated for the determination of the total Ca concentration of aqueous solutions resulting from test dissolution procedures of Ca-rich scale materials. The first mode of analysis involves direct ablation of the solution surface (Liquid-LIBS), while the second one concerns irradiation of cellulose papers, following their drop-wise wetting with the solution (Dry- LIBS). Both modes of analysis yield fairly accurate results with LIBS on water affording higher precision, in part due to significant averaging. However, Dry-LIBS remains an attractive choice, particularly considering field applications, and, in this respect, an automated prototype system, based on Dry-LIBS methodology, is implemented and a specific protocol is developed. The system is suitable to be used by inexperienced personnel, with limited training, in order to determine the total metal (Ca, Fe and Ba) content in the solutions as a measure of the dissolution process. The software automatically calculates the Ca/CN, Fe/CN and Ba/CN intensity ratios from the stored spectra and derives the Ca, Fe and Ba concentration content in the solution, based on predefined calibration curves. The performance of the prototype LIBS system is extensively evaluated, presenting good accuracy and reliability in the measurement of the concentration of the specific elements in the water solution. However, the accuracy of the system has to be improved for applications in the field.

References [1] P. Siozos, A. Philippidis, M. Hadjistefanou, C. Gounarakis, D. Anglos, Spectrochimica Acta Part B, 87 (2013) 86-91.

201

Remote LIBS for assessing the condition of field-aged composite HV outdoor insulators

O. Kokkinaki1, A. Klini1, M. Polychronaki1,2, N. Mavrikakis3, K. Siderakis3, E. Koudoumas3, D. Pylarinos4, E. Thalassinakis4, C. Kalpouzos1, D. Anglos1,2

1Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL- FORTH), P.O. Box 1385, GR 711 10 Heraklion, Crete, Greece 2Department of Chemistry, University of Crete, P. O. Box 2208, GR 710 03 Heraklion Crete, Greece 3Technological and Educational Institute (TEI) of Crete, School of Engineering, Department of P2-30 Electrical Engineering, P.O. Box 1939, GR 710 04 Heraklion, Crete, Greece 4Islands Network Operation Dept., Hellenic Electricity Distribution Network Operator S. A., Heraklion, Crete, Greece

E-mail: [email protected]

The use of composite insulators in overhead transmission lines and in substations has been rapidly increasing in the last two decades, mainly due to their excellent performance even under pollution conditions, where the conventional ceramic insulators commonly fail [1]. However, their insulation performance can be deteriorated in service conditions as a result of ageing, caused by the interactive effects of the environmental, electrical and mechanical stresses. Therefore, condition assessment of the insulators in service is necessary in order to ensure high reliability of power systems. Several diagnostic techniques have been proposed [2] for this purpose, but the problem is that their implementation assumes disconnection of the insulators from the lines, sampling of the polymeric housing and measurement in the laboratory. This means that the insulators are destroyed and cannot be reinstalled in the lines, resulting in high financial costs. Hence, the development of non-destructive diagnostic techniques for real-time, on-site inspection of the insulators condition is required. To this end, Laser-Induced Breakdown Spectroscopy (LIBS) was found to be an efficient and reliable technique for assessing the state of polymer-based HV outdoor insulators in service. In this work, a number of insulators are examined, which had been installed in the electrical transmission network of Crete for a time period of ten years or longer. Diagnosis of the insulators state is achieved by calculation of specific spectral indicators, which reflect the extent of chemical modifications induced to the insulators surface as a result of their longtime presence in the field. Standard and remote LIBS measurements have been performed successfully both in the laboratory and on-site, respectively. A remote LIBS proof-of-principle diagnostic model is presented, which is based on measurements via off-axis Newtonian collection optics, thus indicating that LIBS can indeed become a field deployable technique for the efficient and reliable assessment of the condition of HV outdoor insulators in service.

References [1] H. Hillborg, U. W. Gedde, IEEE Trans. Dielectr. Electr. Insul., 6 (1999) 703-717. [2] S. M. Gubanski, A. Dernfalk, J. Andersson, H. Hillborg, IEEE Trans. Dielectr. Electr. Ins. 14 (2007) 1065-1080.

202 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Hydrophilic interaction liquid chromatographic method coupled with PDA detection for the simultaneous determination of impurities in tablets containing rosuvastatin and metformin

G. Machairas1, A. Geballa-Koukoula1, A. Rozou2, O. Galanopoulou2, P. Charitos2 and I. Panderi1

1National and Kapodistrian University of Athens, Faculty of Pharmacy, Laboratory of Pharmaceutical Analysis, Panepistimiopolis, Zografou, 157 71 Athens, Greece. 2ELPEN Pharmaceutical Co. Inc., 95 Marathonos Ave., 19009, Pikermi, Attica, Greece. P2-31 E-mail: [email protected]

HILIC chromatography is an alternative chromatographic technique using polar stationary phases and low aqueous/high organic mobile phases in order to achieve effective retention for polar analytes. It appears to be complementary to reversed-phase LC as the order of elution is reversed to reversed-phase LC and thus it provides reasonable retention and selectivity for polar compounds. In this work a hydrophilic interaction liquid chromatography method coupled with PDA detection has been developed and fully validated for the simultaneous determination of impurities in tablets containing rosuvastatin and metformin in a ratio 1:100. All analytes were separated by using an XBridge®-HILIC analytical column under isocratic elution. The BEH XBridge®-HILIC column that was used consists of BEH particles that are prepared from tetraethoxysilane (TEOS) monomer and bis-triethoxysilylethane (BTTE) monomer, which incorporates the preformed ethylene bridges, ensuring excellent mechanical strength in relation to the bare silica columns. According to the structure of the BEH particles substrate nearly one third of the surface silanols are removed due to the bridging ethylene groups that are embedded into the silica matrix, yet a sufficient number of accessible silanols remains on the surface. To get a better insight into the chromatography of the compounds on the BEH XBridge®-HILIC column, experimental data were compared with the physicochemical characteristics of the analytes (pka values, degree of ionization). The optimization of the HILIC mobile phase on the BEH XBridge®-HILIC column, involved the percentages of water, diethylamine, the concentration and the type of the aqueous buffer solution (ammonium formate or ammonium acetate) in the mobile phase, using acetonitrile as organic modifier.

References [1] A. Kakouris, V. Samara, A. Kalaskani, I. Panderi*, Simultaneous Determination of Impurities in Ropinirole Tablets by an Improved HPLC Method Coupled with Diode Array Detection, Chromatographia, 77(5-6): 447-457, 2014.

203

Capillary electrophoresis with light emitting diode-induced fluorescence detection for characterization of conjugation of antibodies with nanoparticle and lathanide chelate labels

L. Nejdl1,2, M. Tvrdonova3, T. Vaculovic3, M. Vaculovicova1,2 and V. Adam1,2

1Department of Chemistry and Biochemistry, Mendel University in Brno, Zemedelska 1, 613 00 Brno 2Central European Institute of Technology, Brno University of Technology, Purkynova 123, 612 00 Brno 3Department of Chemistry, Masaryk University, Kamenice 753/5, 625 00 Brno P2-32 Czech Republic

E-mail: [email protected]

The fluorescent labelling of antibodies is either done by organic fluorescent dyes (e.g., fluorescein, rhodamine, etc.), lanthanide fluorescent probes and/or fluorescent nanoparticles (NPs). Conjugation with NPs can be carried out either by nonspecific adsorption, by direct covalent coupling, or by using high affinity molecules i.e. streptavidin and biotin. The spatial orientation of the antibody is a key subject to be addressed during the conjugation procedure. The covalent conjugation is commonly mediated by the zero-length linkers (1-ethyl- 3-(3-dimethylaminopropyl) carbodiimide with N-hydroxysuccinimide, N,N'- Carbonyldiimidazole, or N,N'-dicyclohexylcarbodiimide), to link molecules bearing - NH2 and -SH groups with -COOH,-NH2 and -OH groups on the nanoparticle surface. However, this method is not assuring the correct geometrical orientation of the antibody. To guarantee the correct geometry, the attachment of the antibody through its Fc region to the nanoparticle is fairly easy, without modifying the antibody activity, stable in a media with high ionic concentration, and allowing a high load of antibody per nanoparticle. The comparison of antibody labelling effectivity by lanthanide chelates (Lu, Tb; obtained by MeCAT strategy) and nanoparticles (CdTe quantum dots) conjugated by zero-length linkers and affinity approach using HWRGWVC heptapeptide was carried out in this study by light emitting diode-induced fluorescence detection (λex = 400 nm, 230 nm).

Acknowledgement The study was financially supported by Grant agency of Czech Republic No.16-23647Y.

204 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Chiral separation of acidic chiral compounds on a clarithromycin- zirconia hybrid monolith by capillary electrochromatography

Mi Yeon Kim, Jung Hag Park

Department of Chemistry, Yeungnam University, Gyeongsan 38541, South Korea

E-mail: [email protected]

CEC and CE are increasingly employed in chiral separation due to their qualities of being cost- effective (smaller amounts of chiral selector (CS), samples and solvents are consumed) and P2-33 more efficient (reduced plate heights due to plug-like electroosmotic flow) in comparison of HPLC [1-2]. Several CS-zirconia hybrid monoliths (ZHMs) have been prepared by a single- step in-situ sol-gel approach and employed for enantioseparation of chiral drugs in our laboratory [3-6]. Clarithromycin (CLA) and CLA lactobionate have been used for enantioseparation of basic chiral drugs in capillary electrophoresis [7,8]. However, their potential as the CS for the enantioseparation of acidic chiral analytes has not been evaluated in either CE or CEC. In continuation of our work on preparation and application of CS- incorporated ZHMs for enantioseparation, we have prepared a CLA-incorporated zirconia hybrid monolithic (CLA-ZHM) capillary column by sol-gel process. A sol solution consisting of 5.5 mM of polyethylene glycol, 1 mM of water, 3 mM of acetic acid, 2 mM of formamide, and 0.04/0.96 ratio of CLA-TEOSPC/Zr-Bu resulted in a homogeneous monolith having well defined through-pores and tightly anchored to the capillary wall (Fig. 1).

Fig. 1. SEM images of the CLA-ZHM at different magnifications.

The CLA-ZHM column was employed for capillary electrochromatographic enantioseparation of ten acidic chiral drugs in mobile phases consisting of acetonitrile (ACN), methanol (MeOH) and triethylamine (TEA)-acetic acid (AcOH) buffer. Effects of ACN/MeOH ratio, AcOH/TEA ratio and their concentrations, and applied voltage on chiral separation were investigated. Baseline resolutions of all the compounds were achieved with a mobile phase of 70:30 (v/v) ACN/MeOH containing 255 mM AcOH and 17.4 mM TEA under the applied voltage of −10 kV at 25 oC (Fig. 2).

205

Fig. 2. Electrochromatograms showing baseline resolution of ten acidic chiral analytes on CLA-ZHM. Chromatographic conditions: CLA-ZHM, 75 μm I.D., 33 cm length (monolith bed, 25 cm); mobile phase, 70/30 (v/v) ACN/MeOH + AcOH (255 mM) + TEA (17.4 mM); applied voltage, 10 kV; injection, -10 kV, 3 s; capillary temperature, 25ºC; detection, 214 nm.

References [1] P. Jac, G. K. E. Scriba, J. Sep. Sci. 36 (2013) 52-74. [2] G. Gübitz, M. G. Schmid, J. Chromatogr. A 1204 (2008) 140-156. [3] S. Dixit, J. H. Park, J. Chromatogr. A 1416 (2015) 129-136. [4] L. N. Tran, S. Dixit, J. H. Park, J. Chromatogr. A 1356 (2014) 289-293. [5] L. N. Tran, J. H. Park, J. Chromatogr. A 1396 (2015) 140-147. [6] S. Dixit, I. S. Lee, J. H. Park, J. Chromatogr. A 1507(2017)132-140. [7] G. Xu, Y. Du, B. Chen, J. Chen, Chromatographia 72 (2010) 289-295. [8] M.V. Lebedeva, A.F. Prokhorova, E.N. Shapovalova, O.A. Shpigun, Electrophoresis 35 (2014) 2759–2764.

206 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Determination of Tritium Contents in Incinerable Samples

C. Postolache, V. Fugaru, G. Bubueanu

“Horia Hulubei” National Institute for Physics and Nuclear Engineering IFIN HH, Magurele, Ilfov, Romania

E-mail: [email protected]

In this study, a new facility for determination of tritium (T) in incinerable solid wastes are described. The protocol consists of oxidation in two steps of the samples in oxygen atmosphere, HTO kept and determined of T activities at Liquid Scintillation Counting. P2-34 Equipment used in experiment is constituted from:  Pressure oxygen tub with pressure regulator and flow control Rota meter  2 tube furnace with temperature controller (RT 50-250/11 Nabertherm type), one for sample oxidation (at 2000 C/4000 C/8000 C temperatures) and secondary for catalytic oxidation of resulted gases at water and carbon dioxide (700-8000 C in presence of CuO wires)  HTO collector  Trapping unit for retention of tritiated water over siccative CaCl2  Radioactive gas monitor (RGM) with Ionizing Chamber Overhoff type

Figure 1. Schematic view of the oxidizer with retention of resulted HTO. QS- Oxygen supply; FM- Flow-meter; TF (D/I)- Tube furnace (Degassing/incineration); TF (CO)-Tube Furnace (catalytic oxidation); TQ- Quartz tube; S- Sample; CuO - CuO wire oxidation bed; HTO Colector- Collector with 4 HTO retention vials; CaClV- retention cartridge with CaCl2 sic., RGM- Radioactive gas monitor, NPB- ventilated enclosure

207

Radionuclide characterization of tritiated water Using NMR Spectrometry

C.S. Tuta, C. Postolache, V. Fugaru, G Bubueanu

Horia Hulubei National Institute for R&D in Physics and Nuclear Engineering, IFIN-HH Bucharest, 30 Reactorului Street, Magurele, Ilfov county, PO Box MG-6, RO-077125, Romania

E-mail: [email protected]

This paper presents the preliminary results on determination of nuclidic purity and radioactive P2-35 concentration of tritiated water (HTO and DTO) using NMR spectrometry. The tritiated water and heavy water samples were obtained by heterogeneous isotopic exchange technique using recovery tritium from expired sources. The obtained samples were characterized in point of view of radioactive concentration: using a TRICARB TR 2800 LSC type (dilution factor of the samples between 400.000 and 800.000). The H and T nuclides in the samples were analysed using FT NMR Spectrometer AVANCE 400 MHz Micro-bay Bruker Biospin type. The H-NMR and T-NMR spectra of HTO/DTO were accumulated and chemical shift were determined (1H: 4.703 ppm; 3H: 4.718 ppm). The ratio between the T-NMR amplitude signal and the radioactive concentration of HTO/DTO is linear on the analysed range of the radioactive concentrations. Also, the ratio between signals amplitude of the T signal and nuclide content of samples is linear. In conclusion, the preliminary obtained results sustain the possibility of the use of NMR spectrometry in determination of nuclide composition and radioactive concentration for high activity tritiated water samples.

References [1] E. A. Evans, J.A. Elvidge, J.R. Jones, D.C. Warrell, 1985, Handbook of Tritium Nuclear Magnetic Resonance Spectroscopy and Applications, UK: J. Wiley and Sons [2] L. Matei, C. Postolache, G. Bubueanu, C. Podina, Fusion Sci. Technol, 54 (2008) 643-646 [3] C. Postolache., R. Georgescu, L Matei, Fusion Sci. Technol, 60, (2011) 990-993

208 10th International Conference on Instrumental Methods of

Tuesday 19/9 Analysis: Modern Trends and Applications

Computational Method for the Determination of Intense Gamma- Rays Sources Activity by Using GEANT4

M.-R. Ioan, C. Postolache, V. Fugaru, S. Bercea, A. Celarel, C. Cenusa

Horia Hulubei National Institute for R&D in Physics and Nuclear Engineering, IFIN-HH Bucharest, 30 Reactorului Street, Magurele, Ilfov county, PO Box MG-6, RO-077125, Romania

E-mail: [email protected]

In this paper, a method for the determination of intense gamma-rays sources activity by using GEANT4 (Geometry And Tracking) is proposed. The method is recommended mainly for the P2-36 cases when the activity of an intense gamma-rays source is unknown and there are no other classical activity determination methods available, or the existing ones are affected by higher uncertainties. The method is based on the fact that by starting from an experimental determination of the absorbed dose rate value (well-knowing of all the exposure conditions), the activity of the involved gamma-rays source can be determined. The experimental absorbed dose rate determination can be performed by using of a high performance calibrated dosimeter, in order to assure the traceability of the result.

209

Determination of C-14 concentration in irradiate graphite samples collected from thermal column of VVR-S reactor using AMS facility based on the 9 MV accelerator

V. Fugaru, C. Stan-Sion, M. Enachescu and C. Postolache

Horia Hulubei National Institute for Physics and Nuclear Engineering, Magurele, Romania

E-mail: [email protected]

P2-37 Carbon-14 is a pure beta emitter with a half-life of 5700 ± 30 years and is mainly produced through neutron-induced reactions with the nuclides 14 N, 13C and 17O. They are present in the fuel, fuel cladding, coolant, moderator, structural materials and mainly thermal graphite column of a nuclear reactor. The goal of these experiments was to determine 14C accumulation in the thermal column of VVR-S Reactor during a functioning time of about 50 years. Samples for the AMS were collected after the final shot down and fuel removal of the reactor core. Figure 1 presents the layout of the thermal column inside the reactor. Samples collected from locations corresponding to the 6 discs of the thermal column were finally cut in small squared slices 7 x 7 x 3 mm. Since the measurement of high concentrations of radiocarbon samples is requiring a specialized ion source and special prepared acquisition we took advantage of the upgraded work performed at this AMS machinery. A detailed description is given in [C. Stan-Sion et al., 2015]. Fig. 2 shows the results of measurements performed in this AMS experiment. Four sectors from the Disc 6, Disc 5 and one from Disc 4 were measured. Disk 6 is located close to the reactor core.

Fig. 1. Vertical movable thermal column reactor Fig. 2. AMS measurement of 14C concentration in cut-view through the VVR-S the graphite discs of the thermal column

References [1] C. Stan-Sion, M. Enachescu, A.R. Petre, C.A. Simion, C.I. Calinescu, and D.G. Ghita, Nucl. Instr. Meth.B (2015), doi.org/10.1016/j.nimb.2015.02.059

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Wednesday 20 September 2017 MINOS II Hall Chair: G. Hieftje, S. Pergantis

Elemental Speciation Analysis

10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Plenary lecture The power of combined speciation- and metabolomics studies on transition metal and selenium compounds in brain/at neural barriers within neurodegeneration research

B. Michalke

Helmholtz-Zentrum München - German Research Center for Environmental Health GmbH, Research Unit Analytical BioGeoChemistry, Ingolstädter Landstr. 1, 85764 Neuherberg, Germany

E-mail: [email protected] PL10

Background: Transition metals play a crucial role in proper brain function. Misbalances are known to affect brain, resulting in neurodegeneration. Chronic Manganese exposure leads to degeneration of dopaminergic neurons inducing a Parkinson-like complaint. Deciphering uncontrolled transport across neural barriers (NB) and the neurodegenerative mechanisms in the affected brains is still a major task for understanding the complex modes of action. Mn-dependent Parkinsonism (Mn-PD): We analyzed relevant Mn species being responsible for an uncontrolled transport across NB: Mn speciation in paired serum/cerebrospinal fluid (CSF) samples was performed two-dimensionally by SEC-ICP-DRC-MS and CZE-ICP-DRC- MS. The most important Mn-carrier, Mn-citrate, was identified by ESI-FT-ICR-MS. Elevated Mn-citrate concentration in serum act as marker for increased Mn concentration in human CSF or rat brain. A change from Mn-transferrin (Mn-Tf) to Mn-citrate was observed which was not caused by saturation of Tf, as proven by Fe-speciation. For clarification of molecular mechanisms of Mn-neurotoxicity we applied SEC-ICP-DRC- MS, ESI-FT-ICR-MS and IC-ICP-OES to rat brain extracts after low-dose Mn-feeding. ESI- FT-ICR-MS-analysis revealed a cascade of increases in oxidative stress-, inflammation- and lipid peroxidation markers. AchE-activity and glutamate concentrations were also increased in brain samples, indicating oxidative stress in brain and causing PD symptoms. Neuronal Fe(II)/(III) ratio was shifted, promoting Fenton reaction and formation of chemical radicals. Altered Fe-species distribution is related to Mn-induced neuroinflammation and several hundred metabolites are shifted under Mn exposure. Metabolites correlated either positively and others negatively to specific Mn-species. The combination of various speciation- and different mass spectrometry techniques provided information on uncontrolled Mn entry to brain and provided substantial evidence that Mn-induced neuroinflammation leads to oxidative stress triggered by multifactorial pathophysiological processes. Idiopathic Parkinsonism (i-PD): Symptomatic similarities between i-PD and Mn-PD initiated speciation research in CSF of i-PD patients: There cross correlations of transition element species showed significant differences between PD-cases and controls. Cu-amino- acid fraction was involved in each of correlations. Amyotrophic lateral sclerosis: As an additional example, Se-speciation in paired serum/CSF samples from amyotrophic lateral sclerosis (ALS) patients shows correlations between distinct Se-species (in contrast to total Se) and ALS prevalence.

213

Antimony speciation in spirits stored in pet bottles: identification of a novel antimony complex

S. Carneado1, J.F. López-Sánchez1, A. Sahuquillo1, E. Klontzas2, G.E. Froudakis2, S.A. Pergantis2,3

1 Section of Analytical Chemistry, University of Barcelona, Martí i Franqués, 1-11, 08028 Barcelona, Spain 2 Department of Chemistry, University of Crete, Voutes, 71003 Heraklion, Greece 3 Environmental Chemical Processes Laboratory. WE01 E-mail: [email protected]

Total antimony and its +V and +III oxidation state species were determined in twelve spirit samples (Greek raki and tsipouro) stored in polyethylene terephthalate bottles. Reliable and reproducible results were obtained following direct analysis by using ICP-MS providing total Sb concentrations between 0.4 – 4 µg L-1. Antimony speciation analysis by LC-ICP-MS was also assessed, showing the presence of both inorganic Sb species along with an unknown Sb complex, which was the predominant species in all samples analysed. The structure of this complex was investigated by using liquid chromatography with high-resolution tandem mass spectrometry. The analysis gave evidence for an acetaldehyde-bisulphite pyruvate Sb complex with the formula: C7H14O12S2Sb. The proposed ligands are organic substances expected to be present in the raki matrix (see Figure) [1]. In addition, the influence of high temperature storage conditions and extended exposure times up to two weeks, on Sb migration from PET bottles into raki samples was investigated. Total Sb and Sb species content was determined by ICP-MS and LC-ICP-MS, respectively. The concentrations determined were in the range of 5.6 to 28 μg Sb L-1 spirit after a week of storage at 60 ºC. In which case, inorganic Sb(V) and Sb(III) became the predominant species in comparison to the “novel” organic Sb complex.

References [1] J. C. Danielwicz, Am. J. Enol. Vitic., 58 (2007), 53–60.

214 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Which is the best approach for on site trace metal speciation determination?

C. Parat, and I. Le Hécho

CNRS / Univ Pau & Pays Adour, IPREM – UMR 5254, 64000 Pau, France

E-mail: [email protected]

Knowledge of the speciation of metals, especially of the free metal ion concentration, is essential to understand the fate of these elements in rivers and their effects on living organisms. The analytical challenge is to develop a reliable technique for on site determination of trace WE02 metal speciation in natural waters. In this context, electrochemical devices have the advantage of being easily available in small sizes and being battery operated. Consequently, two approaches based on electrochemical sensors have been carried out. The first one is a direct on site electrochemical stripping speciation method called AGNES (Absence Gradient Nernstian equilibrium stripping), developed and optimised for trace metal speciation analysis in natural freshwater [1]. The second method, called ISIDORE, consists in an in situ probe (Figure 1), based on the hyphenation of a passive sensor, the Donnan Membrane Technique device (DMT) with an electrochemical sensor, a screen-printed electrode [2].

0.08 11/04/2014

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0.06

0.10

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Peristaltic Screen-printed electrode pump in a flow-cell Figure 2. ISIDORE Probe

For each method, the effects of environmental conditions (ionic strength, O2) and the required parameters have been studied in synthetic solutions before being tested in natural freshwaters. Results appeared in good agreement with theoretical estimations computed from Visual Minteq. The ionic strength has emerged as the most important parameter to take into account for on site analyses by means of AGNES method. ISIDORE probe appeared more robust but requires a much longer conditioning and analysis time.

References [1] C. Parat, L. Authier, A. Castetbon, D. Aguilar, E. Companys, J. Puy, J. Galceran, M. Potin-Gautier, Free Zn2+ determination in natural freshwater of the Pyrenees: towards on-site measurements with AGNES, Environmental Chemistry, 12 (2015) 329-337. [2] C. Parat, J.P. Pinheiro, ISIDORE, a probe for in situ trace metal speciation based on Donnan membrane technique with related electrochemical detection part 1: Equilibrium measurements, Analytica Chimica Acta, 896 (2015) 1-10.

215

Optimizing Sn(II) oxy-hydroxides adsorbents by increasing their reducing capacity. Application on Cr(VI), Se(VI) and Sb(V) removal from water

E. Kaprara1, K. Kalaitzidou1, A. Kamou2, K. Simeonidis1, M. Mitrakas1

1Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124, Thessaloniki Greece 2Department of Physics, Aristotle University of Thessaloniki, 54124, Thessaloniki Greece

WE03 The presence of toxic metals and metalloids in water has long been recognized as a severe environmental and human health issue, especially when water is designated for human consumption. Chrome, selenium and antimony classified as toxic and carcinogenic pollutants present, in addition, a very challenging to research characteristic: they occur in natural waters, -2 -2 mainly in their higher oxidation state, namely as Cr(VI) [CrO4 ], Se(VI) [SeO4 ] and Sb(V) - [Sb(OH)6 ] that is also the most difficult form to be removed. Sn(II) oxy-hydroxides have already proven to efficiently remove Cr(VI) from natural water via a mechanism that includes the reduction of Cr(VI) to Cr(III) and the chemisorption of the latter to materials’ surface [1]. It becomes evident that the reducing efficiency of Sn(II) oxy-hydroxides plays a key role to their removal capacity. The aim of this research is to examine how the reducing efficiency of Sn(II) oxy-hydroxides, expressed as the percentage of Sn(II) content, influence their ability to remove Cr(VI), Se(VI) and Sb(V). Sn(II) oxy-hydroxides were synthesized by hydrolysis of Sn(II) salts (SnCl2 or SnSO4), using a two-stage continuous flow reactor at room temperature and pH range of 2-9. The addition of a reducing agent (H2NNH2, Na2S2O4, Na2S) to the synthesis procedure was also examined. Adsorption isotherms were recorded by batch mode experiments in natural-like water matrix to estimate Cr(VI), Se(VI) and Sb(V) uptake of the produced adsorbents. Experimental results revealed that Sn6(OH)4O4 produced by SnCl2 hydrolysis at pH 2 presents the highest reducing capacity, with Sn(II) percentage reaching 60%, while its effectiveness towards Cr(VI) removal exceeds 18.5 mg Cr(VI)/g at 10 μg Cr(VI)/L residual concentration (q10). The addition of 2, 3 and 5 g of (NH2)2 per 100g of Sn(II) precursor during synthesis increased Sn(II) percentage in the final product by 9, 16 and 22% respectively, without altering its morphology and crystal structure. This improvement in material’s reducing efficiency resulted in a corresponding raise of its removal capacity (Table 1). Despite the promising results for Cr(VI) removal, the application of Sn(II) oxy-hydroxides in Se(VI) and Sb(V) remediation proved unsatisfying, with the removal capacity of the best performing material to not exceed 0.1 mg/g.

Table 1. Influence of reducing agent addition during Sn(II) oxy-hydroxides synthesis in Sn(II) content and removal capacity. H2NNH2·H2O(g added) Sn(II)(% content) q10(mg Cr(VI)/g) - 60 18.9 2 69 20.9 3 76 26.2 5 82 31.3

E. Kaprara acknowledges financial support from IKY Fellowships of Excellence for Postgraduate Studies in Greece – Siemens Program.

References [1] F. Pinakidou, E. Kaprara, M. Katsikini, E.C. Paloura, K. Simeonidis, M. Mitrakas, Sci. Total Environ., 551–552 (2016) 246–253.

216

Wednesday 20 September 2017 PASIPHAE I Hall Chair: A. Calokerinos, A. Spyros

Food Analysis 2

10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Plenary lecture Applications of nuclear magnetic resonance in food science and technology

J. van Duynhoven

1Unilever R&D, Vlaardingen, The Netherlands 2Wageningen University, Wageningen, The Netherlands

E-mail: [email protected] PL11

Within food science and nutrition, nuclear magnetic resonance (NMR) techniques take a unique and strong position since they can deployed in widely diverse applications areas. The quantitative and unbiased nature of NMR make it a strong tool for holistic assessment of complex food mixtures. The use of selective excitation methods in combination with cryo- probes has lowered detection limits to levels that rival currently established techniques. The aforementioned advantages can also be exploited for assessment of dietary exposure and effect. For these applications the robustness of NMR is particular advantage since it allows for profiling of large number of samples with minor experimental variation (time, operator, location). The sensitivity of NMR for molecular organisation and dynamics over multiple length scales has also made it widely applied tool for food structural assessment, both in spectroscopy as well as magnetic resonance imaging (MRI) mode. Recent developments range from the quantification of nanoscale domains with crystalline order by NMR to assessment of complex flow behaviour of thixotropic food dispersions by RheoMRI. The aforementioned developments in NMR and MRI techniques for assessment of food composition, food structure and metabolic impact of nutrition will be illustrated with recent applications from the food industrial practice.

References [1] J.P.M. van Duynhoven, D.M. Jacobs, Assessment of dietary exposure and effect in humans: the role of NMR, Progress NMR Spectroscopy 96 (2016) 58-72. [2] H. Van As, J. van Duynhoven, MRI of plants and foods, Journal of Magnetic Resonance 229 (2013) 25-34.

219

MCPD and Glycidyl Esters in Food Products – Occurrence, Methods and Analytical Facts

G. Karanikolopoulos, D. Chrysafidis, V. Tzamtzis and D. Tsipi

A Chemical Division, General Chemical State Laboratory (GCSL), Athens, Greece

e-mail: [email protected]

To improve consumer acceptance, edible vegetable oils are industrially processed by removing or modifying components that can negatively impact appearance, taste, odour and self-life of WE04 the final consumer product. Nonetheless, undesirable chemical side reactions can take place during the refining process which result in the presence of potentially hazardous chemical compounds in thus produced fats and oils. Fatty acid esters of 3-Monochloropropane-1,2-diol (3-MCPDEs), 2-Monochloropropane-1,3-diol (2-MCPDEs) and 2,3-Epoxy-1-propanol (GEs), are contaminants generated in the above processes. The non-esterified 3-Monochloropropane- 1,2-diol (3-MCPD) was classified as a possible human carcinogen with a tolerable daily intake (TDI) of 2 μg/kg b.w. (currently modified to 0.8. μg/kg b.w). Accordingly, EU legislation has been enacted, specifying maximum levels for 3-MCPD in hydrolysed vegetable proteins (HVP) and soya sauce [1]. Moreover, it has been demonstrated that the toxicity of 3-MCPDEs should be considered equivalent (on a molar basis) to that of the parent compound. GEs have been assessed to be carcinogenic/genotoxic. For the 2-MCPDEs no toxicological effects could be concluded due to lack of data, but they are still under scrutiny [2]. In recent years, these categories of contaminants have been identified in various food items [3]. Setting maximum permitted levels in food for 3-MCPDEs and GEs seems to be of high priority for the European Commission. On analytical stand point the determination of MCPDEs and GEs presents several hurdles, concerning both the isolation of the analytes from different food matrices (extraction procedure) as well as the analytical process itself (i.e. challenging separation, risk of isomerisation or transformation of the analytes). In this aspect concerns have been raised regarding the reliability of results obtained from currently available analytical methods applied in various food matrices. In the present work an optimised indirect analytical protocol for the simultaneous determination of 3-MCPDEs, 2-MCPDEs and GEs by an isotope dilution gas chromatography mass-spectrometry (GC-MS) technique has been developed and tested in different food samples. The current protocol includes liquid-liquid extraction of the fat phase from the initial food matrix, formation of 3-Monobromopropane-1,2-diol (3-MBPD) esters from GEs, and finally acid transesterification and derivatisation of the released free form in ethyl acetate with phenylboronic acid (PBA). The PBA derivatives are consecutively measured by GC-MS with electron ionisation (EI) in SIM mode. The adopted method was in compliance with internationally accepted criteria (in terms of trueness and precision) and was validated for the scopes of the study. Furthermore, the applied analytical protocol was utilised for the analysis of food samples derived from the local market and results are presented and discussed.

References [1] EU Commission Regulations N° 466/2001and N° 1881/2006 [2] EU Recommandations 2014/661; EFSA CONTAM Panel, Scientific Opinion, EFSA Journal, 2016, 14(5):4426 [3] Z. Zelinková et al., Food Addit. Contam., 23(2006), 1290–1298; V. G. Samaras et al., J. Chromatogr. A, 1466(2016), 136–147

220 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Analytical characterization of meglumine by HPLC/MS

C. Martano, F. Ferretti, F. Buonsanti, L. Lattuada

Bracco Imaging SpA, Bracco Research Center, via Ribes 5, Colleretto Giacosa (TO), Italy

E-mail: [email protected]

A quali-quantitative analytical method, based on a HPLC/MS, to identify and quantify any potential by-product in meglumine 2 [1] is described. Meglumine (N-methyl-glucidylamine) is a commercial product used as counter-ion in several pharmaceutical products and it is obtained from the direct reaction between glucose and methylamine. In order to recognize and WE05 quantify the presence of glucose in meglumine, a derivatization with 1-(4-aminobenzyl)-1,2,4- triazole 3 and sodium cyanoborohydride is required before the HPLC/MS run. The following HPLC analysis was performed on a SCX column, employing isoserinol as internal standard.All possible by-products, such as sorbitol, N,N-dimethyl-glucamine, glucamine, di-glucamine, N- methyl-diglucamine and derivatized glucose are separated from meglumine itself in a single run (see 1). Some compounds are commercially available, except for N,N-dimetil- glucidylamine and derivatized glucose that were synthesized and characterized. The unavailable compounds were quantified adopting the same response factor of the most similar by-product, at comparable abundance. The derivatization step of glucose was optimized to maximize the yield. Since pure meglumine is not available from the market, a blank run is unobtainable and the calibration curves were run in matrix by the standard addition method. R2 were >0.99, DIFF%<15%, BIAS and RDS%, related to LLOQ, were <10% and recovery, at the LLOQ, between 80 and 110%.

RT: 0,00 - 60,05 SM: 7G OH OH OH 22,88 NL: 1,15E8 100 TIC F: + c ESI NH Q1MS 50 [195,60-196,60] a MS BG_4 OH OH 21,69 NL: 7,00E5 100 O H TIC F: + c ESI Q1MS 50 [91,90-92,90] MS H 2N O H b BG_4

6,62 OH OH OH NL: 5,09E5 100 TIC F: + c ESI HO Q1MS 50 [182,65-183,65] MS BG_4 OH OH c OH OH OH 19,04 NL: 9,82E5 100 TIC F: + c ESI Q1MS H2N 50 [181,60-182,60] d MS BG_4 OH OH O H O H O H H O H O H O H 17,27 NL: 9,46E5 100 TIC F: + c ESI N Q1MS 50 [345,50-346,50] MS BG_4 O H O H O H O H e 19,73 NL: 9,37E5 100 O H O H O H C H 3 O H O H O H TIC F: + c ESI N Q1MS 50 [359,50-360,50] f MS BG_4 O H O H O H O H 32,10 NL: 4,98E6 100 OH OH OH TIC F: + c ESI N Q1MS 50 [209,50-210,50] g MS BG_4 OH OH N 44,04 NL: 7,23E5 100 N TIC F: + c ESI N O H O H Q1MS 50 [269,50-270,50] N H h MS BG_4 O H O H O H 0 0 5 10 15 20 25 30 35 40 45 50 55 60 Time (min) 1 N NH2 H O H O H N N N O H 2 O H O H 3 References [1] Merck Index, 15th Edition (2013) 6150.

221

Honey authenticity: Evaluation of phenolic compounds as potential authenticity markers using target and non-target LC-HRMS screening

G.A. Koulis1,2, A.S. Tsagkaris1, R. Aalizadeh1, S. Drivelos3, C. Proestos2, C. Georgiou,3 N.S. Thomaidis1

1 Laboratory of Analytical Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis Zographou, 15771 Athens, Greece 2 Laboratory of Food Chemistry, Department of Chemistry, National and Kapodistrian University of WE06 Athens, Panepistimiopolis Zographou, 15771 Athens, Greece 3 Chemistry Laboratory, Department of Food Science and Human Nutrition, Agricultural University of Athens, Iera Odos 75, 118 55 Athens, Greece

E-mail address: [email protected]

Honey is a foodstuff which is subjected to various deceitful techniques like addition of syrups or mislabelling due to its high price in the market. Many honeys in market, sold as unifloral, are often adulterated with others, inferior in quality, on account of great demand and high production cost. It is widely known that honey obtained from specific plants is strictly associated with unique organoleptic and/or health beneficial properties [1]. Another important factor influencing the quality of the product is the geographical origin. Hence, the evaluation and verification of honey authenticity is a task of paramount importance for the producers, consumers and regulatory bodies. Phenolic compounds are the major contributors to honey antioxidant capacity and are greatly affected by botanical and geographical origin. In most cases, samples derived from the same geographical and botanical origin shared common phenolic pattern. Thus, the phenolic profile can be used for honey authenticity evaluation. To this end, a UPLC-ESI-QTOF MS method for the determination of phenolic compounds in honey has been developed, optimized and validated according to Eurachem guidelines. The method was applied to 86 honey samples of different botanical origin from Greece and Poland. A target list including 20 phenolic compounds was compiled. The detected compounds were quantified and authenticity markers were revealed. Notably, high quercetin concentration has been measured (> 3 mg/Kg) in fir honey comparing to other botanical types, while p- coumaric concentration level was proved to distinguish Polish from Greek honey samples. Furthermore, differentiation among samples of different botanical and geographical origin was accomplished using the non-target screening approach [2]. Advanced chemometrics tools were used for peak picking and extraction of the masses of interest which discriminate the samples. For the selected peaks, the identification process referred to P. Gago-Ferrero et al. was followed [2]. New compounds-markers which differentiate the samples according to botanical and geographical origin were finally identified. In conclusion, authenticity markers and discrimination patterns were emerged using target and non-target workflows.

References [1] M. Ciulu, N. Spano, M. Pilo, G. Sanna, Molecules, 21 (2016) 451-482. [2] P. Gago-Ferrero, E. Schymanski, A. Bletsou, R. Aalizadeh, J. Hollender, N. Thomaidis, Environmental Science & Technology, 49 (2015) 12333-12341.

222

Wednesday 20 September 2017 MINOS II Hall Chair: V. Zorba, N. Jakubowski

Materials / Spectrometry

10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Plenary lecture Characterization of advanced materials and particles at the nano- and microscales by X-ray spectrometry using calibrated instrumentation

B. Beckhoff

Physikalisch-Technische Bundesanstalt (PTB), Abbestraße 2-12, 10587 Berlin, Germany

The development of new materials and the assessment of nanomaterials require the correlation PL12 of the materials’ functionality or toxicity with their chemical and physical properties. To probe these properties, analytical methods that are both sensitive and selective at the nano- and microscales are required. The reliability of most analytical methods is based on the availability of reference materials or calibration samples, the spatial elemental composition of which is as similar as possible to the matrix of the specimens of interest. However, there is a drastic lack of reference materials in particular at the nanoscale. PTB addresses this challenge by means of a bottom-up X-ray analytical method where all instrumental and experimental parameters are determined with known contributions to the uncertainty of the analytical results. This first- principle based approach does not require any reference materials but a complete characterization of the analytical instruments’ characteristics and, in addition, of the X-ray fundamental parameters related to the elements composing the sample. X-ray spectrometric methods allow for the variation of the analytical sensitivity, selectivity, and information depth needed to effectively reveal the spatial, elemental, and chemical specimen parameters of interest. Exam- ples of particle characterization, interfacial speciation, elemental depth profiling, as well as layer composition and thickness characterizations in advanced materials will be given. Recent instrumental achievements provide access to liquid-solid interfaces as well as towards the in- situ speciation of nanoscaled battery materials. X-ray spectrometry under grazing incidence is capable to reveal analytical and dimensional information from layered systems and particles deposited on surfaces.

[1] B. Beckhoff, R. Fliegauf, M. Kolbe, M. Müller, J. Weser, G. Ulm, Anal. Chem. 79 (2007) 7873 [2] A. Owens, B. Beckhoff, G. Fraser, M. Kolbe, M. Krumrey, A. Mantero, M. Mantler, A. Peacock, M.-G. Pia, D. Pullan, U.G. Schneider, G. Ulm, Anal. Chem. 80 (2008) 8398 [3] F. Reinhardt, B. Beckhoff, H. Eba, B. Kanngießer, M. Kolbe, M. Mizusawa, M. Müller, B. Pollakowski, K. Sakurai, G. Ulm, Anal. Chem. 81 (2009) 1770 [4] R. Unterumsberger, B. Pollakowski, M. Müller, and B. Beckhoff, Anal. Chem. 83 (2011) 8623 [5] B. Pollakowski, P. Hoffmann, M. Kosinova, O. Baake, V. Trunova, R. Unterumsberger, W. Ensinger, and B. Beckhoff, Anal. Chem. 85 (2013) 193 [6] C. Streeck, S. Brunken, M. Gerlach, C. Herzog, P. Hönicke, C.A. Kaufmann, J. Lubeck, B. Pollakowski, R. Unterumsberger, A. Weber, B. Beckhoff, B. Kanngießer, H.-W. Schock and R. Mainz, Appl. Phys. Lett. 103 (2013) 113904 [7] P. Hönicke, M. Kolbe, M. Müller, M. Mantler, M. Krämer, and B. Beckhoff, Phys. Rev. Lett. 113 (2014) 163001 [8] M. Müller, S. Choudhury, K. Gruber, V.B. Cruz, B. Fuchsbichler, T. Jacob, St. Koller, M. Stamm, L. Ionov, and B. Beckhoff, Spectrochim. Acta B 94-95 (2014) 22 [9] T. Fischer, P.M. Dietrich, C. Streeck, S. Ray, A. Nutsch, A.G Shard, B. Beckhoff, W.E.S. Unger, K. Rurack, Anal. Chem. 87 (2015) 2685 [10] B. Pollakowski, B. Beckhoff, Anal. Chem. 87 (2015) 7705 [11] P.M. Dietrich, C. Streeck, S. Glamsch, C. Ehlert, A. Lippitz, A. Nutsch, N. Kulak, B. Beckhoff, W.E.S. Unger, Anal. Chem. 87 (2015) 10117

225

Determination of noble metals in geological samples by scintillation arc atomic emission spectrometry

E.V. Shabanova and I.E. Vasil'eva

Vinogradov Institute of Geochemistry, Siberian Branch of Russian Academy of Sciences, Favorsky St., 1a, Irkutsk, Russia 664033

E-mail: [email protected]

WE07 The total contents of noble metals (NM – Au, Ag, Pt, Pd, Ir, Os, Rh and Ru); element composition and particle size of the mineral phases containing NM; their particle-size distribution in powder samples of well-known gold ore deposits of North-East of Russia such as Natalka, Pavlik, Vetrenskoye and Degdekan; as well as certified reference materials SChS- 1 and SLg-1 [1] made from the black shale of the deposit Sukhoi Log (Irkutsk Region, Russia) were determined by atomic emission spectrometry with arc discharge and scintillation recording of spectra (SAES) [2]. Hundreds of particles-carriers of NM, including native metals, intermetallic phases and solid solutions, arsenides, antimonides, sulfoarsenides, tellurides, selenides and etc. were found by the SAES in each sample. The number and variety of found elemental associations containing NM significantly exceed the list of their minerals established previously by scanning electron microscopy and X-Ray microanalysis (SEM-X-Ray). The number of particles registered by the SAES reflects the ratio of the average abundances of NM in the Earth's crust. The total number of mineral phases containing gold, silver and platinum metals increases from rocks to ore. The sizes of the found particles were confirmed by the results of the SEM-X-Ray. It is shown that the additional study; certification of species of NM occurrence and sizes of these particles in the substance of certified reference materials of natural gold objects (for example, SChS-1 and SLg-1) by using the SAES allows developing the multifactor reference samples for the calibration and verification of analytical results of instrumental methods [3].

References [1] COMAR international database for certified reference materials. http://www.comar.bam.de/en/ (10.03.2017). [2] I.E. Vasil'eva and E.V Shabanova. Comparison of analytical possibilities of scintillation atomic emission spectrometry and automated mineralogy for studying of gold-bearing samples. Chapter 8.In "Advantage in Materials Science Research". New-York, Nova Science Publishers Inc. (2016) 255-271. [3] I. E. Vasil’eva and E. V. Shabanova. Certified reference materials of geological and environmental objects: problems and solutions. Journal of Analytical Chemistry, 72 (2017), 129-146.

226 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Analysis of mercury selective complexing membranes by X-Ray Absorption Near Edge Spectrometry (XANES)

N. Kallithrakas-Kontos and R. Moschochoritou

Analytical and Environmental Chemistry Laboratory, University Campus, Technical University of Crete, GR-73100 Chania, Greece

E-mail: [email protected]

New, mercury selective complexing membranes have been prepared last years in order to improve x-ray analysis minimum detection limits and to achieve mercury speciation. Total WE08 reflection X-Ray Fluorescence (TXRF) as well as Energy dispersive X-Ray Fluorescence (EDXRF) have been used as membrane analytical techniques. Sub ppb minimum detection limits have been achieved in drinking and seawater samples [1, 2]. Deeper understanding of the selective process will give the opportunity for more efficient membranes preparation. X-Ray absorption near- edge spectrometry (XANES) is an very sensitive technique for a chemical element structure /speciation determination directly in the solid phase. Various membrane compositions (with and without complexing etc.) were prepared in Technical University of Crete and they were analysed by XANES, in Elettra Synchrotron (Basovizza, Trieste). Selected experimental conditions were 12240-12400 eV energy range and 0.5 eV energy step. Results (Fig. 1) proved that a complexing reaction can take place inside the PVC membrane matrix.

Acknowledgment Thanks are expressed to the International Atomic Energy Agency for the financial support of this research (Research Contract No 18262/R0).

References [1] V. Hatzistavros and N. Kallithrakas-Kontos, X-ray fluorescence mercury determination using cation selective membranes at sub-ppb levels, Analytica Chimica Acta, 809 (2014) 25-29. [2] P. Koulouridakis and N. Kallithrakas-Kontos, Selective Mercury Determination after Membrane Complexation and Total Reflection X-Ray Fluorescence Analysis, Analytical Chemistry, 76 (2004) 4315-4319.

227

Immobilization of hemin on thin mesopourous SnO2 Films for the detection of organohalides in aqueous solution

E. Topoglidis, A Panagiotopoulos and C. Tiflidis

Univesrity of Patras, Department of Materials Science, Rion 26504, Greece

E-mail: [email protected]

Organohallides are widespread environmental pollutants and groundwater contaminants, resistant to natural degradation. Their detection and quantification in water resources is, WE09 therefore, of outmost importance. One of the most common methods for the selective dehalogenation of organohalides, is the use of reduced iron porphyrins. In this study we are developing a new solid state catalytic sensor consisting of a molecular catalyst such as iron (III) photoporphyrin chloride (hemin) immobilized on a heterogeneous catalyst solid material support such as SnO2 films. Nanocrystalline, mesoporous SnO2 films are a novel substrate for hemin immobilization as they allow not only high hemin loading but also both electrochemical and spectroelectrochemical studies of the immobilized hemin redox function. Previous studies have largely focused on the use of nanocrystalline TiO2 electrodes (1). We extend these studies to SnO2 films as they are a material demonstrated to be preferable to the TiO2 electrode for electrochemical studies of redox molecules, as the potential window over which the SnO2 film is conducting is shifted to more positive potentials by 500 mV (2). Cyclic voltammetry and spectroelectrochemistry are employed to demonstrate that this shift allows the observation of reversible oxidation and reduction of hemin on the SnO2 electrodes in aqueous solutions without the use of any electron-transfer promoters or mediators. Electron-transfer rate constant -1 of 1s is determined for the hemin/SnO2 electrodes. Finally, we demonstrate that the high hemin loading and electrical conductivity of hemin/SnO2 films allow the fast electrochemical sensing of organohalides in water based on their electrocatalytic reduction with the immobilized metalloporphyrin catalyst.

Figure 1. Hemin/SnO2 film used as the working electrode in a 3-electrode electrochemical cell and its CVs at different scan rates exhibiting nearly reversible, well-defined reduction and oxidation peaks.

References [1] T. Ito and G.J.Meyer, Environ. Eng. Sci., 24 (2007) 31-44. [2] E. Topoglidis, Y. Astuti, F. Duriaux, M. Gratzel and J. R. Durrant, Langmuir, 19 (2003) 6894-6900.

228

Wednesday 20 September 2017 MINOS I Hall Chair: N. Chaniotakis, K. Ochsenkühn

Electrochemistry

10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Plenary lecture Novel approach to stripping voltammetric determination of selected metals using screen-printed electrodes modified with metal films

A. Bobrowski

AGH – University of Science and Technology, Department of Building Materials Technology, Faculty of Materials Science and Ceramics, Kraków, POLAND

E-mail: [email protected] PL13 Screen-printed electrodes (SPEs) have become increasingly popular electrochemical sensors. The application of SPEs in the stripping voltammetry of metal ions usually requires the modification of their surface with a thin metal film consisting predominantly of mercury, gold, silver and bismuth. This can improve the selectivity and sensitivity of anodic stripping voltammetric (ASV) determination. The simplest modifications include in-situ and ex-situ electrochemical deposition of the metal film on the carbon SPE support. One of the aims of the presented study was to show that modification with a Pb film allows the SPE can successfully be utilized in adsorptive stripping voltammetry (AdSV). The paper presents the first attempt at the preparation of an in-situ plated lead film screen-printed electrode (PbF-SPE) and its application for the AdSV determination of Ni and Co in the form of the complexes with dimethylglyoxime or nioxime. The designed AdSV procedures of Co determination by means of PbF-SPE are among the most sensitive methods utilizing metal films deposited on a screen- printed support. Moreover, the electrochemical behavior of a tellurium film and its application for the electrochemical detection of Cu using SPEs are also reported for the first time. Finally, the amplification of ASV signals recorded using metal film screen-printed electrodes in weak magnetic fields is discussed. It is shown that the application of two bismuth precursors – Bi2O3 dispersed in the electrode body and Bi(III) ions spiked into the tested solution – combined with a favorable location of the modified SPE with respect to the magnetic stirrer makes it possible to significantly amplify the ASV signal of lead, cadmium and indium.

Acknowledgements: The author would like to express his warm thanks to the IMA 2017 Conference Organizers for the invitation. Financial support from the Polish National Science Centre (Project 2014/15/B/ST8/03921) is gratefully acknowledged.

231

Plenary lecture New methods of electrochemical monitoring of biologically active organic compounds in environmental and biological matrices

J. Barek1, J. Fischer1 , A. Makrlikova1,2, T. Navratil2, and B. Josipcuk2

1 Charles University, Faculty of Science, Department of Analytical Chemistry, UNESCO Laboratory of Environmental Electrochemistry, Albertov 6, CZ-12843 Prague 2, Czech Republic 2 J. Heyrovský Institute of Physical Chemistry of the AS CR, v.v.i., Dolejškova 3, CZ-18223 Prague 8, Czech Republic PL14 E-mail: [email protected]

The contribution will focus on development and applications of new electrode materials and arrangements suitable for large scale monitoring of electrochemically active (oxidisable or reducible) pollutants, chemical carcinogens (e.g. nitrated polycyclic aromatic hydrocarbons), phenols and nitrophenols, pesticides, dyes, drugs, and biomarkers of illness, exposure, and treatment. Possibilities and limitations of various types of amalgam electrodes (solid, paste, and porous), bismuth film and bismuth bulk electrodes, antimony, carbon film, and boron doped diamond electrodes will be discussed both for voltammetric determinations in batch arrangements and for amperometric detection in flowing systems (HPLC-ED and FIA-ED). Attention will be paid to their miniaturization and portability, to elimination of problems connected with their passivation by mechanical, chemical or electrochemical means, to their compatibility with measurements in flow systems and with the concept of green analytical chemistry. Moreover, their combination with a preliminary separation and/or preconcentration using solvent extraction, solid phase extraction, membrane separation and/or hollow fiber separation will be discussed. Advantages and limitations of newly developed carbon film embedded electrodes, and nanostructured metal electrodes sputtered on either conductive or nonconductive substrate will be presented together with the use of new types of electrodes (porous, enzyme modified, etc.) for amperometric detection of various environmental pollutants in flow systems.

Ackowledgement The research was financially supported by the Czech Science Foundation (project 17-03868S).

232 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Electrochemical behavior study and sensitive voltammetric determination of theophylline in pharmaceutical dosages and human urine

K. Cinková, N. Zbojeková and Ľ. Švorc

Institute of Analytical Chemistry, Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava, Radlinského 9, Bratislava, SK-812 37, Slovak Republic

E-mail: [email protected] WE10 Theophylline is a type of 1,3-dimethylxanthine-based alkaloid that is present in some soft drinks and food stuffs as well as natural products. It may cause various physiological effects such as relaxation of bronchial muscle, gastric acid secretion and stimulation of the central nervous system [1]. Higher levels of theophylline can give rise to arrhythmia, fever, dehydration, insomnia, anorexia, tachycardia and coma [2]. Because of the serious side effects, toxicity and even death of patients, the development of simple, rapid and sensitive analytical methods for the continuous monitoring of theophylline is of high importance. In this study, a boron-doped diamond electrode in combination with differential pulse (DPV) and square-wave voltammetric (SWV) modes was applied to the electrochemical behavior study and determination of theophylline. A well-defined oxidation peak was observed by cyclic voltammetry at a potential of +1.63 V vs. Ag/AgCl in the presence of 1 mol L-1 sulphuric acid. Under optimal experimental conditions, the current response of theophylline was proportionally linear from 2 to 380 µmol L-1 using both pulse techniques. The developed electroanalytical method yielded low detection limits of 0.91 and 1.45 µmol L-1 associated with good intra-day repeatability (relative standard deviation of 3.2 and 2.5%) using DPV and SWV, respectively. The practical applicability of the proposed method was demonstrated by the analysis of pharmaceutical dosages and human urine samples with satisfactory recoveries (varied from 93.2 to 102.5%). The results of analysis of pharmaceuticals were also in close agreement at a 95% confidence level with those obtained using reference method. To sum up, herein developed method is simple and rapid with the utilization of a modification-free electrochemical sensor providing a convenient technique for theophylline quantification in pharmaceutical products. Taking these attributes into consideration, the proposed sensor may be employed as a simple and effective analytical tool in drug control analysis and analysis of biological samples as well as a useful alternative to previously utilized modified electrodes in this field.

Acknowledgement This work has been supported by the Grant Agency of the Slovak Republic grant No. 1/0489/16 and Grant scheme for Support of Young Researchers and Excellent Teams of Young Researchers.

References [1] H. Yin, X. Meng, H. Su, M. Xu and S. Ai, Food Chem., 134 (2012) 1225-1230. [2] S. Tajik, M. A. Taher and H. Beitollahi, Sens. Actuators B, 197 (2014) 228-236.

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Poster Session 3

Food Electrochemistry Materials Sensors

10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Anodic stripping voltammetry detection of lead using glassy carbon electrode modified with aza-crown ether and Nafion

R. Segura and J. Pizarro

Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile (USACH), Santiago 3363, Chile

E-mail: [email protected]

Lead is a non-essential heavy metal of high toxicity. It is present naturally in the earth's crust, however, anthropogenic activities associated with mining and agriculture have contributed P3-01 significantly to the pollution of aquatic systems (lakes, rivers, oceans, etc.), producing harmful effects on animals, plants and humans. Prolonged exposure, even at low concentrations of this element, can affect the liver, kidneys and nervous system. Due to this, it is necessary to develop new analytical methodologies for the detection and quantification of Pb(II) at trace and ultra- trace levels. In this work, an electrochemical sensor based on a glassy carbon electrode modified with DBDA18C6 (7,16-Dibenzyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane) and Nafion has been developed for the determination of Pb(II) using square wave anodic stripping voltammetry (SWASV). The optimum conditions for the prepared electrode were as follows: Acetate buffer pH = 4.5, accumulation potential (Eacc) = -0.8 V, accumulation time (tacc) = 110 s and a frequency = 15 Hz. A linear range was observed from 5-30 µg L-1 with a limit of detection (LOD) and quantification (LOQ) of 0.177 µg L-1 and 0.5928 µg g L-1, respectively.

References [1] Zhang, L., Yao, Y., Shan, J., Haibing, Li., Nanotechnology, 22, (2011). [2] Ijeri, VS., Srivastava, AK., J. Anal. Chem. 367, 373 (2000). [3] Ghanei-Motlagh, M., Karami, C, Taher, M.A., Hosseini-Nasab, S.J. RSC Advances 6(92), 89167 (2016)

237

An electrochemical sensor based on electrochemically reduced graphene for the simultaneous determination of Pb(II) and Cd(II) by square wave anodic stripping voltammetry (SWASV)

J. Pizarro and R. Segura

Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile (USACH), Santiago 3363, Chile.

E-mail: [email protected] P3-02 Graphene, a two-dimensional honeycomb lattice of sp2 carbon atoms has generated great interest from a theoretical and experimental point of view due to its diverse physicochemical properties, such as: great surface area (2630 m2/g), high mechanical resistance, ease of functionalization and high electrical conductivity [1-2]. This nanomaterial has been applied in in the development of new electrochemical sensors for trace metal detection. In this work, an electrochemical sensor based on a glassy carbon electrode modified with electrochemically reduced graphene (ErGO/GC) has been developed for the determination of Pb(II) and Cd(II) using square wave anodic stripping voltammetry (SWASV). The modified electrode was characterized by scanning electronic microscopy (SEM), scanning electrochemical microscopy (SECM) and Raman spectroscopy. The optimum conditions for ErGO/GC were as follows: Acetate buffer with pH = 4.5, accumulation potential (Eacc) = -1.2 -1 V and accumulation time (tacc) = 90 s. A linear range was observed from 15-105 g L with a limit of detection (LOD) of 6.86 g L-1 for Pb(II) and 5.71 g L-1 for Cd(II). The methodology was applied in the simultaneous determination of Pb(II) and Cd(II) in bivalve molluscs with satisfactory results.

References [1] A.C. Neto, et al., Reviews of modern physics, 81 (2009) 109. [2] M.S. Fuhrer, C.N. Lau and A.H. MacDonald. MRS bulletin, 35 (2010) 289-295.

238 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Electrochemical measurements in flow systems on amalgam tubular detector combined with platinum auxiliary electrode

O. Josypčuk1, J. Barek2 and B. Josypčuk1

1 J. Heyrovský Institute of Physical Chemistry of AS CR, v.v.i., Dolejskova 3, 18223 Prague, Czech Republic 2 Charles University, Department of Analytical Chemistry, UNESCO Laboratory of Environmental Electrochemistry, Hlavova 2030/8, 128 43 Prague 2, Czech Republic

E-mail: [email protected] P3-03 Electrochemical detection in flow systems is mostly carried out using one of the three possible detector arrangements: i) wall-jet; ii) thin-layer iii) flow-through (tubular). Each type of the cell has own advantages and drawbacks. Tubular detector (TD) is a continuation of an outlet capillary and for minimization of its influence on a flowing mobile phase it should have the same inner diameter as connecting capillaries. A current response of TD is strongly dependent on a length of a shielding sleeve which separates an electroactive part of TD (silver amalgam tube in our case) and a solution with the auxiliary electrode [1,2]. Electrical field rapidly increases in a relatively narrow inner space of the capillaries, and hence the electroactive part of TD is only about 2 mm long part of the tubular electrode when shielding sleeve is 2 mm long [2]. The aim of this work was to design, fabricate and test such construction of the TD when its current response is not overly dependent on its position in the cell. The TD with platinum auxiliary electrode inside the silver amalgam tube (ATD+AuxE) was fabricated for the first time in this work and it was confirmed that it has the above mentioned desirable property. Moreover, it is possible to connect other detector (e.g., optical) serially right after this ATD+AuxE thus enabling simultaneous measurements using two independent detection methods (e.g. electrochemical and spectrometric). Another possibility is to employ the ATD+AuxE as an electrochemical generator in which analysed compound would be firstly reduced/oxidized and a product of this process would be then detected downstream by a suitable method (including an electrochemical one). The newly developed ATD+AuxE was tested and compared with classical amalgam TD using non-stop-flow differential pulse voltammetry [3] in its anodic stripping mode (AS-DPV) and as the amperometric detector in a glucose oxidase biosensor. The ATD+AuxE was applied for AS-DPV detection in the flow system for the first time. Solutions of Zn2+ and Cd2+ were used as the testing species for voltammetry, and detection of changes of oxygen concentration for amperometry. All these experiments require application of highly negative potentials, which is possible to realize with the detector/working electrode made of silver solid amalgam. All relevant parameters (potentials of accumulation or detection, flow rate, analyte concentrations, shielding sleeve length, etc.) were optimized for the newly developed ADT+AuxE.

References [1] J. Cvacka, F. Opekar, J. Barek, J. Zima, Electroanalysis 12 (2000) 39-43. [2] O. Yosypchuk, J. Barek, B. Yosypchuk, Electroanalysis 24 (2012) 2230-2234. [3] O. Josypčuk, J. Barek, B. Josypčuk, Electroanalysis 26 (2014) 306-311.

Acknowledgements: This work was financially supported by Grant Agency of the Czech Republic (Project no. 17-03868S).

239

Ferrocenil complexes functionalized with crown ether moiety. Synthesis and application for the determination of metal ions

F. Godoy1, N. Agurto1 and A. Oliver2

1Facultad de Química y Biología, Universidad de Santiago de Chile 2 University of Notre Dame, United States

E-mail: [email protected]

Organometallic complexes functionalized with macrocycles (crown ether, calix-arene, aza P3-04 macrocycles) linked by an organic moiety. These species have found applications in the field of optical and electrochemical sensors for the determination of alkali, alkaline-earth, and heavy metal ions [1]. Formyl derivative 2-E and 2-Z were isolated as a pure sample, both isomers react with 4’- amino-benzo-15-crown-5 to yield corresponding metalloligands 3-E-E and 3-Z-E. All compounds were obtained in moderated to high yields (50 – 90 %) and were characterized by 1H, 13C NMR, IR, MS and elemental analysis. Also, 3-E-E was studied by X-ray.

The capability of metalloligands 3, to bind divalent metal ions was determinate by UV-Vis titration using perclorate salts in acetonitrile Fig 1a. First, the stoichiometry was determined using the method of continuous variation (Job’s Method) and the Ka were determined using Benesi-Hildebran method for host-guest molecular complexation. [2,3]

2+ 2+ 2+ 3-E-E Ca Cu Cd Mix

5 5 Figure 1. a) UV-Vis spectrum of 3-E-E-(η -C5H4CH=CH-C6H4CH=N-benzo-15-Corona-5)Fe(η - -5 -1 C5H5) b) Titration curve (2,7 x 10 molL ). c) Reaction of 3-E-E and one equivalent of some metal ions.

References [1] N. Agurto, T. Maldonado, F. Godoy, A. Gómez, C. Silva, J. Pavez, G. Ferraudi, A. Oliver, A. Lappin, J. Organomet. Chem. 827 (2017) 32-40. [2] A. Sarigüney, A. Saf, A. Coşkun, Spectrochim. Acta Mol. Biomol. Spectrosc. 128 (2014) 575-582. 38.[3] L. Fielding, Tetrahedron. 56 (2000) 6151- 6170.

Acknowledgement: Project Fondecyt Nº 1151156, Dicyt-Usach.

240 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Determination of Cu(II) using a modified electrode with ferrocenyl crown ether compound by square wave anodic stripping voltammetry

E. Flores1, J. Pizarro1, F. Godoy1, R. Segura1, A. Gómez1, N. Agurto1, P. Sepúlveda2.

1Departamento de Química de los Materiales, Facultad de Química y Biología, Universidad de Santiago de Chile (USACH), Santiago 3363, Chile. 2CEDENNA, Facultad de Química y Biología, Universidad de Santiago de Chile (USACH), Santiago 3363, Chile. P3-05

E-mail: [email protected]

Heavy metals, some of which are highly toxic, bio-accumulative, and not degradable, are widely distributed on the Earth's crust [1]. Particularly, copper is an essential trace element for human beings that plays an important role in several metabolic processes [2]. However, this metal ion could be toxic at high concentrations [3]. Due to the importance of copper ions at trace levels, analytical methodologies are required for their detection and quantification. In this work, we present an electrochemical sensor based on a glassy carbon electrode modified 5 5 with ferrocenyl imine [( -C5H4CH=N-4’-benzo-15-crown-5)Fe( -C5H5)] (FcIB15C5) has been developed for the determination of Cu(II) using square wave anodic stripping voltammetry (SWASV) (Fig 1). The metalloligand FcIB15C5 was characterized by FT-IR, 1H and 13C NMR spectroscopies and mass spectrometry. The optimum conditions for the prepared electrode were as follows: Britton-Robinson buffer with pH = 6.0, FcIB15C5 concentration = 0.3 mM, accumulation potential (Eacc) = -0.8 V and accumulation time (tacc) = 90 s. A linear range was observed from 10-70 gL-1 with a limit of detection (LOD) of 0.11 gL-1. The proposed procedure was validated with TMDA-64.2 and CRM-TMDW certified reference materials, and it showed good accuracy and precision. The methodology was applied for the determination of copper in real samples of urine and a mining effluent obtaining good results.

Fig 1. Representation of Synthesis, characterization and electroanalytical determination of Cu(II).

References [1] J. Duruibe, M. Ogwuegbu, J. Egwurugwu, International Journal of Physical Sciences, 2(2007) 112- 8. [2] D. Strausak, J.F. Mercer, H.H. Dieter, W. Stremmel, G. Multhaup, Brain research bulletin, 55(2001) 175-85. [3] V. A. Lemos, M.S. Santos, M.J. dos Santos, D.R. Vieira, C.G. Novaes, Microchimica Acta, 157(2007) 215-22.

241

Colorimetric sensor for determination of thiocyanate in oilfield water

T. Volgina1, N. Gavrilenko2 and M. Gavrilenko1,2

1 The department of organic substances and polymer material, Tomsk Polytechnic University, Tomsk, Russia 2 The department of analytical chemistry, Tomsk State University, Tomsk, Russia

E-mail: [email protected] P3-06 The development of simple, cheap optical analytical systems represents an exciting area of research where everyday information technology and communications devices play an important role. The possibility of developing transparent polymer based analytical devices, often demonstrated and has received an increasing attention for a wide variety of analytical applications. Thiocyanate is an important tracker for oil reservoir monitoring also its anion can be found at different concentration levels in natural objects. Several analytical techniques have been proposed for the detection of thiocyanate in oilfield water, including UV–vis spectrophotometry and chromatographic methods. However, most of the reported methodologies are time consuming, costly, hardly portable, and involve the use of large amounts of reagents. The work describes an assay for in situ detection of thiocyanate in oilfield water with new colorimetric sensor combined both solid phase extraction and spectrophotometric/visual indication. The assay is based on the formation of an iron(III)- thiocyanate colored complex into a transparent polymer matrix. Under optimal conditions, the detection limit was less 1 mg·L-1 of thiocyanate. A colorimetric sensor is a plate the size of 6.0 x 8.0 mm and weight of about 0.05 g, based on the polymethacrylate matrix (PMM) with immobilized Fe(III). The PMM as a transparent plate was obtained by radical block polymerization. Immobilization of the Fe(III) into the PMM was performed by sorption from the solution in a static mode in water solution of Fe(NO3)3 having 0.01 M concentration for 2 min. As a result, we obtained a sensing element for determining of thiocyanate, colored light yellow with absorption peak at 490 nm. In the presence of thiocyanate, depending on its concentration, the sensor changes to red color because of the formation of the complex of Fe(III)-thiocyanate (Fig.).

1 2 3 Figure. Photos of initial PMM (1); PMM modified Fe3+ as colorimetric sensor (2); colorimetric sensors after contact with thiocyanate solution with different concentrations (3).

The proposed method is advantageous for on-site monitoring of oilfield water thiocyanate even by non-trained personnel. The PMM can be easily prepared with a consumption of less than 1 mg of reagents per sample. The relation between absorbance and potassium thiocyanate was linear when concentration of potassium thiocyanate was 1–30 mgL-1 and detection limit was 0.8 mgL-1. The proposed method characterized by its simplicity, portability and low sample consumption of thiocyanate in oilfield water.

This research was supported by the Russian Foundation for Basic Research project 16-43-700353.

242 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Time-based assay of thiols by target-mediated photoinduced modulation of gold nanoparticles growth

A. Kostara, G.Z. Tsogas, T.G. Choleva, A.G. Vlessidis, D.L. Giokas

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, 45110, Ioannina, Greece

E-mail: [email protected]

This work presents a new assay for the determination of thiols that relies on the ability of thiols to inhibit the photoinduced reduction of auric ions to gold nanoparticles (AuNP). Under the P3-07 appropriate experimental conditions, exposure of Au(III) ions to light, triggered their reduction to Au(0) followed by the formation and growth of AuNP. The formation of AuNP was evidenced by the appearance of a red coloration in the solution for which a surface plasmon resonance (SPR) peak could be detected at ca. 520-530 nm. In the presence of thiols, the reduction of Au(III) ions was inhibited (delayed) as a function of thiol concentration. On the basis of this finding, a time-based assay was developed that enables the determination of thiols using time as a metering unit and needless of instrumental detectors. The kinetics of Au(III) photo-reduction was also found to depend on the chemical structure of the thiol species thus imbuing the procedure with some degree of selectivity among various thiols. The method was applied to the determination of thiols in environmental, biological and pharmaceutical samples.

243

Application of electrochemically switchable DNA tags in DNA analysis

P. Vidláková1, L. Havran1 and M. Fojta1,2

1Institute of Biophysics of the Academy of Sciences of the Czech Republic v.v.i., Kralovopolska 135, CZ-61265 Brno, Czech Republic 2CEITEC-Central European Institute of Technology, Masaryk University, Kamenice 5, CZ-62500, Brno, Czech Republic

P3-08 E-mail: [email protected]

Electroanalytical methods are powerful tools for studying structure, interactions and damage of nucleic acids [1]. At mercury electrodes, adenine and cytosine in DNA produce a cathodic peak CA (due to its reduction). Guanine gives anodic signal G, which is obtained in cyclic voltammetry (CV) or in anodic stripping modes (due to oxidation of reduction product of guanine that is reduced at very negative potentials). At carbon electrodes guanine and adenine in NAs undergo oxidation at positive potentials and produce oxidation signals Aox and Gox [1]. DNA labelling is used for improvement of sensitivity of electrochemical detection of nucleic acids. Attachment of a new electroactive group into DNA strand can give rise to a new signal. The main benefit of these signals is differentiation of specific DNA strand. For analysis of labeled DNA is often advantageous to use redox tags giving reversible redox signal because of the possibility of performing several repeated measurements with one sample. Some redox tags give reversible redox signal directly. Reduction/oxidation of another redox tags is irreversible but reduction/oxidation of these groups gives rise to new groups that gives reversible electrochemistry. For application of electroanalytical techniques in analysis of DNA sequences or DNA interactions it is convenient to use DNA probes containing chemically modified nucleosides [2]. One option of DNA labeling is incorporation of chemically modified dNTPs into DNA molecules with using primer extension (PEX). PEX is technique using different DNA polymerase for extension of DNA strand from 5´end to 3´end in accordance with template. As substrate for DNA polymerase are useful both natural dNTP and chemically modified dNTP and/or their combinations. In our studies was tested a possibility of application of methoxyphenol and nitrogroup as electrochemically switchable DNA tags in voltammetric DNA analysis. We observed these tags give a well developed characteristic signal suitable for electrochemical analysis of labelled DNA.

References [1] E. Palecek, F. Scheller and J. Wang, Eds. Electrochemistry of nucleic acids and proteins Towards electrochemical sensors for genomics and proteomics, Elsevier, Amsterdam, 2005 [2] M. Fojta, L. Havran, H. Pivoňková, P. Horáková and M. Hocek, Current Organic Chemistry, 15 (2011), 2936-2949

Acknowledgments: The research was supported by GACR (project No. 15-08434S).

244 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Determination of Heparin by Means of Voltammetry

D.A. Vishenkova, E.I. Korotkova

National Research Tomsk Polytechnic University, Lenin avenue, 30, Tomsk, 634050, Russia

E-mail: [email protected]

Heparin is a highly sulfated polysaccharide that is used clinically as an anticoagulant [1]. Also it was found that it slows down tumor progression in some types of cancer and that it has an anti – inflammatory effect [2]. Chemically, heparin macromolecule is a linear unbranched chain of a heteropolysaccharide, consisting of sulfated heptasaccharide fragments linked by α- P3-09 1-4-glycosidic bonds [3]. The quantitative determination of heparin is a complex problem because of the variability of the biopolymer molecule size and charge distribution within it. Therefore, there is a need in the development of specific methods for the qualitative and quantitative determination of heparin both in pharmaceuticals, and biological fluids. The purpose of this study is to develop a voltammetric technique for heparin determination in pharmaceuticals. Electrochemical method of analysis (voltammetry) was chosen due following advantages: it is characterized by high sensitivity and selectivity, rapid response to changes in the composition of the analyzed sample, ease of automation and, finally, low cost of analytical equipment. Also, in this work for determination of heparin in pharmaceuticals by constant-current sweep voltammetry was used cationic basic dye of indamine series which is capable of forming a complex with heparin. The electrochemical studies were carried out on the voltammetric analyzer Ta-Lab ("Tomanalyt", Tomsk production) with a three-electrode system. First, the electrochemical properties of heparin were investigated by constant-current sweep voltammetry depending on influence of various factors, such as the nature of background solution, pH, an electrode material, potentials and accumulation time on an electrode. Taking into consideration all above factors, analytical signal of heparin was not detected. In connection with this, further researches for the electrochemical determination of heparin were made in complex with cationic basic dye of indamine series. According to the research by means of constant-current sweep voltammetry in Britton- Robinson buffer solution (pH 1.89) on carbon-contained electrode modified by carbon ink in anodic area from – 0.55 V to 0.55 V with scan rate 60 mV/sec at -0.25 V was found an analytical signal for heparin determination. Electrooxidation currents of complex Hep:Dye at -0.25 V increase linearly with concentration of heparin in the range of 10-20 mg/L.

This work was financially supported by the Ministry of Education and Science of the Russian Federation (the project “Science”)

References [1] H.E. Conrad, Academic Press, (1998) 527 p. [2] D.E. Piyathilake, R. Liang, Nova Biomedical Books, (2012) 332 p. [3] A.F Alekperov, A.M. Aliev, Farmatsiya, 36 (1987), p. 80 (In Russian).

245

Monitoring real-time changes in the concentration of inorganic solutions on the border of heterogeneous dielectric materials according to the parameters of electromagnetic signals

A.A. Bespal`ko, L.V. Yavorovich, A.P. Surzhikov

Tomsk, Russia, Lenin Ave. 30, National Research Tomsk Polytechnic University

E-mail: [email protected]

P3-10 To determine the content of inorganic substances in aqueous solutions, including the content of therapeutic salts in lakes, the content of harmful soluble substances in water bodies, it is necessary to carry out testing and monitoring in a continuous mode of time. There are various chemical methods of control [1], which are of a one-off (discrete) nature. We have made an attempt to develop a continuous electromagnetic monitoring of aqueous solutions of salts in the frequency range up to 1 MHz, which can later be extended to other impurities in water and liquids of a different chemical composition. The basis is taken, the method developed by the authors for monitoring electromagnetic emission of heterogeneous materials during their acoustic excitation [2]. Since in natural conditions water contacts the stones, samples of sandstone were taken as objects of investigation, which are dielectrics. The main soluble minerals, which are mainly determined by the chemical composition of the water, are: KCl, NaCl, CaSO4, CaCO3, CaMg (CO3)2. Consequently, the physical properties of sandstones under natural conditions will be determined not only by moisture, but also by the mineral composition of the water in contact with them. Thus, it is necessary to determine the main regularities of the change in the parameters of the electromagnetic signal (EMS) upon contact of sandstone with mineralized water. It is established [3] that as the degree of mineralization of water saturating the rock increases, the electrical resistance decreases, and the amplitude of the EMS increases. This is due to the fact that the ions of the dissolved chemical elements in the water have a certain charge, which, on contact with the sandstone, creates double electrical layers. Oscillations of double electrical layers by an external acoustic action lead to a change in the dipole moment and, accordingly, to a change in the parameters of the EMS. As a result of such oscillations, an alternating electric field appears in the external environment, which can be registered with special equipment. Studies have shown that when the concentration of NaCl in distilled water increases, its specific electric resistance decreases according to a law close to exponential. The most significant changes (from 600 Ω / cm3 to 100 Ω / cm3) are observed at a NaCl concentration in water of 0.3%. With a further increase in the NaCl concentration, the decrease in the resistivity of the solution and the increase in the EMS amplitude occur more slowly.

References [1] Nebel B, Wright R. Environmental Science. The Way the World Works. New Jersey: Prentice Hall, 1993. [2] Bespal`ko A.A., Gol`d R.M., Yavorovich L.V., Datsko D.I. Excitation of electromagnetic radiation in laminated rocks under acoustic influence, Journal of Mining Science, Vol. 39, No 2 (2003). [3] Bespal`ko A.A., Yavorovich L.V. Investigation of the influence of the concentration of an aqueous solution of NaCl on the parameters of the electromagnetic signal of sandstones, Russian Physics Journal, 11/2 (2008).

246 10th International Conference on Instrumental Methods of

Wednesday 20/9 Analysis: Modern Trends and Applications

Thermomagnetometric analysis of substituted lithium ferrites

A.P. Surzhikov, E.N. Lysenko, A.L. Astafyev

Tomsk Polytechnic University, Lenina Avenue 30, 634050 Tomsk, Russia

E-mail: [email protected]

Substituted lithium ferrites in which Fe3+ ions are substituted by ions of zinc and/or titanium are widely used in microwave technology. These ferrites are characterized by low values of dielectric losses and high temperature stability. X-ray powder diffraction (XRD) analysis is traditional method for phase composition control and microstructure analysis for ferrite P3-11 materials. However, for substituted lithium ferrites, it is difficult to examined by XRD the different spinel phases that can be formed in Li0.5(1x)Fe2.50.5xZnxO4 (LiZn) and Li0.5(1+х)Fe2.51.5xTixO4 (LiTi) systems as intermediate phases with identical types of the crystal lattices and close values of the lattice parameters. As was shown in [1, 2], thermomagnetometry method, which is thermogravimetric analysis of the samples in magnetic field, can be used to control magnetic-phase transformations in the synthesized lithium ferrites. In the present work, the method of ferrite phase control, which is based on thermomagnetometric analysis, was developed by solving technical problems and creating software. The sensitivity of thermomagnetometric method for determination of phase composition in a complex components mixture that is included non-magnetic and poor magnetic phases, was estimated. In addition, the magneto-phase transitions in LiZn and LiTi ferrites with different saturation magnetization have been investigated. Thermomagnetometric analysis was performed in air atmosphere using thermal analyzer STA 449C Jupiter (Netzsch, Germany). The permanent magnets creating a field of ~5 Oe were attached on the outer side of measurement cell for control of the samples magnetic state. It was shown that the method of thermomagnetometric analysis allows to examine the magnetic phase composition of ferrites more precisely. However, a complex analysis using of both X-ray and termomagnitometric methods will be the most optimal in case of the formation of non-magnetic and poor magnetic phases. It was established that the method of thermomagnetometric analysis allows to detect each ferrite phase with a content of not less than 0.5% in substituted lithium ferrites.

References [1] A.P. Surzhikov, A.M. Pritulov, E.N. Lysenko, V.A. Vlasov, E.A. Vasendina, A.V. Malyshev, J. Therm. Anal. Calorim. 112 (2013) 739–745. [2] P.K. Gallagher J. Therm. Anal. Calorim. 49 (1997) 33–44.

247

Microstructure analysis of ferrite powders ball-milled in a planetary mill

E.N. Lysenko, A.P. Surzhikov, E.V. Nikolaev

Tomsk Polytechnic University, Lenina Avenue 30, 634050 Tomsk, Russia

E-mail: [email protected]

Lithium-zinc ferrites are widely used in microwave technique. Usually, such ferrites are P3-12 prepared by the conventional ceramic double sintering method in which solid state reactions between oxides and/or carbonates are carried out in the first stage. The particle size of the initial reagents mixture has a significant effect on the properties of ferrite powders obtained as a result of solid phase synthesis. In order to achieve the necessary microstructure properties of powder reagents, additional technological operations are used, for example, a mechanical activation in a planetary mill. This type of treatment allows homogenizing, grinding and mechanically activating the initial powder reactants, which leads to a stimulation of physic- chemical processes during synthesis of ferrites [1-2]. However, the information on the effect of ball milling on the microstructure of ferrite powders is very limited [3-5]. In this work, using the Brüner, Emmett, Teller (BET) and laser diffraction methods, as well as XRD and SEM analysis, the microstructure of ball-milled initial reagents for the lithium-zinc ferrites production was studied. The initial reagents were iron oxide, Fe2O3, lithium carbonate, Li2CO3, and zinc oxide, ZnO, which are pre-dried and weighed in molar ratios of corresponding Li0.4Fe2.4Zn0.2O4 ferrite. The mixture was mechanically activated using AGO- 2S high energy planetary ball mill for 15, 30 or 60 min. The steel vial and steel grinding balls were used, and the weights of the material and balls were in the ratio 1:10. The milling was performed at 2220 rpm in the dry state at room temperature. According to the BET data, by increasing ball milling time, the average particle size of mixture, which was calculated using the specific surface area and density values, decreases. For non-milled lithium-zinc ferrite mixture, the results of the analysis by laser diffraction method showed that the particle size is characterized by bimodal distribution and is determined mainly by the size of the iron oxide powder because of its predominant content in the mixture. In this case, half of the volume of the whole mixture is occupied by agglomerates. For the ball- milled mixture, an increasing of large size agglomerates in the mixture is observed. Thus, a ball milling in a planetary mill of lithium-zinc ferrite initial reagents mixture decreases the average size of the powder and simultaneously increases the free energy of the system, due to which agglomerates are formed.

References [1] V. Berbenni, A. Marini, P. Matteazzi, R. Ricceri, N.J. Welham, J. Europ. Ceram., 23 (2003) 527536. [2] A.P. Surzhikov, E.N. Lysenko, V.A. Vlasov, A.V. Malyshev, E.V. Nikolaev, J. Therm. Anal. Calorim., 122 (2015) 1347–1353.

248 10th International Conference on Instrumental Methods of

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Microstructure and thermal analysis of lithium ferrite ceramics

E.N. Lysenko, A.V. Malyshev, V.A. Vlasov, E.V. Nikolaev

Tomsk Polytechnic University, Lenina Avenue 30, 634050 Tomsk, Russia

E-mail: [email protected]

Lithium ferrites are widely used in microwave technique. Usually, such ferrites are prepared by the conventional ceramic double sintering method in which solid state reactions between oxides and/or carbonates are carried out in the first stage. The microstructure of synthesized ferrite powders has a significant effect on the properties of ferrite ceramics obtained as a result P3-13 of sintering in the second stage. In order to achieve the necessary microstructure properties of ferrites, additional technological operations are used, for example, a mechanical milling in a planetary mill. This type of treatment allows homogenizing, grinding and mechanically activating the initial powder reactants, which leads to a stimulation of physic-chemical processes during synthesis of ferrites [1-2]. In this work, the effect of ball milling of synthesized LiFe5O8 ferrite powders on the microstructure of ferrite ceramics was studied by laser diffraction (Fritsch Analysette 22 MicroTec Plus), XRD (ARL X’TRA) and SEM (Hitachi TM-3000) analysis. The mechanical milling of LiFe5O8 was carried out in a Fritsch Pulverisette 7 or AGO planetary mills at room temperature using the zirconium or steel grinding bowls and balls. The process of ferrite sintering was investigated using dilatometric analysis (DIL 402 C, Netzsch). The structural disordering was estimated by TG/DSC analysis (STA 449 C Jupiter, Netzsch). The results showed a strong difference in the structure of ferrite ceramics obtained from ferrite powder pre-milled by dry and wet milling. Thus, dry milling via steel balls results in slight decrease in particle size of the ferrite powder, which has a narrow monomodal particle distribution. The ferrite ceramics, obtained from this powder, is characterized by the presence of an ordered -LiFe5O8 phase. On the contrary, wet milling in isopropyl alcohol leads to a formation of ultrafine ferrite powder, from which the ceramics was obtained that is characterized by a well-developed fine-grained polycrystalline structure and the main presence of a disordered -LiFe5O8 phase. It was shown that a relatively high density and low porosity were observed for such ceramics, which is practically impossible to obtain for pure lithium ferrite without the use of impurities that affect the ferrite sintering processes. It was established that during mechanical milling in a planetary mill with zirconium balls, a ferrite powder is strongly contaminated with a zirconia material, resulting in formation of LiFe5O8/ZrO2 composite ceramic.

249

An adsorptive stripping voltammetry procedure for simultaneous determination of trace bismuth(III) and lead(II) in natural water samples

M. Grabarczyk, C. Wardak and J. Wasąg

Faculty of Chemistry, Maria Curie-Sklodowska University, M.C. Sklodowska sq.3, 20-031 Lublin, Poland

E-mail: [email protected] P3-14 Bismuth and lead are among the most interesting metals which have received extensive attention in trace metal analysis. These heavy metals are introduced into the environment from a variety of human activities, so for this reason they are considered to be anthropogenic pollutants of the environment, and thus the monitoring of these elements is a very important issue. The work describes a simple, fast and inexpensive sensitive procedure for the simultaneous determination of bismuth and lead in environmental water samples. Total measurement time is about 30 s and the analyzed sample does not require any pretreatment and is added directly in its original form to the measurement cell. The method is based on the adsorptive accumulation of Bi(III)-cupferron and Pb(II)-cupferron complexes and following its reduction via the use of an appropriate variation of potential. Preliminary works showed that cupferron was a suitable complexing agent for the determination of Bi(III) [1] and Pb(II) [2] when an acetate buffer was used as a supporting electrolyte. A single potential scan allowed us to obtain qualitative and quantitative information about the trace bismuth and lead levels. This work was optimized by a selection of optimum conditions including the selection of the supporting electrolyte, its pH, concentration of the cupferron and accumulation potential and time. An important advantage of the proposed procedure is the fact that no deaeration of the solution is necessary, which makes it easy to use under laboratory and field conditions. The validity of the method was very successful, as it was shown by the analysis of waste water certified reference material SPS-WW1. Additional in order to demonstrate the applicability and reliability of the presented procedure for real water samples, Lake Zemborzyce (eastern areas of Poland) water was analysed.

References [1] A. Koper, M. Grabarczyk, J. Electroanal. Chem., 663 (2011) 67-71. [2] M. Grabarczyk, Int. J. Environ. Anal. Chem., 93 (2013) 100-1018.

250 10th International Conference on Instrumental Methods of

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Simple and fast voltammetric procedure for direct determination of trace concentrations of Ge(IV) in environmental water samples

M. Grabarczyk

Faculty of Chemistry, Maria Curie-Sklodowska University, M.C. Sklodowska sq.3, 20-031 Lublin, Poland

E-mail: [email protected]

Germanium is a relatively rare element, but one with great technological importance, and is used as an intermetallic compound in the manufacture of semiconductors, lasers, and special P3-15 optical glasses in the electronic industry [1,2]. Since the application of germanium has been growing steadily, the probability of its increased concentration in environmental water samples has risen. The need for a simple, cheap and sensitive procedure of germanium determination in environmental water samples has thus also become more pronounced. This communication provides a simple and fast procedure for Ge (IV) determination, which allows the analysis of natural samples with complicated matrices containing high concentrations of surfactants and humic substances. The proposed procedure is based on the stripping voltammetric method of germanium determination in the presence of acetic buffer as a supporting electrolyte. The interferences from the matrix of natural water samples were decreased considerably by adding the Amberlite XAD-7 resin to the sample. To obtain the optimal conditions for the removal of organic matter by adsorption on the Amberlite XAD-7 resin, the composition and concentrations of the supporting electrolyte, the amount of the resin and the time of sample contact with the resin were studied. The experiments were performed for synthetic samples containing surface-active compounds such as Triton X-100, SDS and CTAB (non-ionic, anionic and cationic surfactant, respectively) and humic substances such as humic and fulvic acids. The presented method was successfully applied in the ultra-trace determination of Ge(IV) in natural water samples. The attractive parameters and the successful application of the elaborated procedure holds great promise for its utilisation in the environmental and industrial monitoring of germanium levels.

References [1] E. Rosenberg, Rev. Environ. Sci. Biotechnol., 8 (2009) 29–57. [2] E.E. Haller, Mater. Sci. Semicond. Process, 9 (2006) 408–422.

251

Study of Greek extra virgin olive oil as far, quality control, different olive harvests and adulteration with seed oils, by spectroscopic methods

A. Philippidis1, D. Sygelaki2, A. Velegrakis3 and M. Velegrakis1

1 Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas (IESL- FORTH), GR-700 13 Heraklion, Crete, Greece 2 Department of Chemistry, University of Crete, GR 700 13 Heraklion, Crete, Greece 3 Department of Materials Science and Technology, University of Crete, GR 700 13 Heraklion, Crete, P3-16 Greece

E-mail: [email protected]

Extra virgin olive oil (evoo) is a natural product with superior quality compared to other edible oils. EVOO is more appropriate for human nutritional needs because of the moderate levels of unsaturated fatty acids and the rich presence of vitamin E. For these reasons it is very important the quality control of evoo, their classification concerning geographical, botanical and harvest- based parameters and moreover the evoo adulteration with seed oils or low quality olive oils. Different analytical techniques, that offer qualitative and quantitative information, were used in the specific fields. [1-3] In the context of this study, a series of analytical techniques such as UV-Vis, Fluorescence spectroscopy and laser based method as Raman were employed for the study of Creek extra virgin olive oil. In particular, quality controls of evoo and correlation of tasting with spectroscopic results was carried out. EVOO from the same geographical region (Crete) obtained from different harvests periods/years was studied and differences between samples was revealed. Furthermore, mixtures of evoo with different types of seed oils (soybean oil, corn oil) and pomace oil were prepared and adulteration detection were accomplished, presenting low detection limits.

References [1] E.C.L.-Diez, G. Bianchi and R. Goodacre, J. Agric. Food Chem., 51 (2003) 6145-6150. [2] K.I. Poulli, G.A. Mousdis and C.A. Georgiou, Analytica Chimica Acta, 542 (2005) 151-156. [3] A. Philippidis, E. Poulakis, A. Papadaki and M. Velegrakis, Analytical Letters, 50 (2017) 1-14.

252 10th International Conference on Instrumental Methods of

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Assessment of phenolic content, antioxidant and antiradical activity of wood aged “tsipouro”

V.J. Sinanoglou1, E.-M. Manika1, V. Resiti1, I.F. Strati1, E. Siores2, M. Giannakourou1 and P. Zoumpoulakis3

1Laboratory of Chemistry, Analysis & Design of Food Processes, Instrumental Food Analysis, Department of Food Technology, Technological Educational Institute of Athens, Ag. Spyridonos 12210, Egaleo, Greece. 2University of Bolton, UK. 3Institute of Biology, Medicinal Chemistry & Biotechnology, National Hellenic Research Foundation, 48, Vas. Constantinou Ave., 11635, Athens, Greece. P3-17

E-mail: [email protected]

The purpose of this study was to evaluate the effect of the addition of oak chips or sticks on the total phenolic content and biological activity in tsipouro. Wood ageing of wines, vinegars and distillates improves their organoleptic characteristics by giving a specific taste, flavor, aroma and color. This technique can promote the migration of numerous aromatic and phenolic compounds from the wood into the beverage, which could possess health beneficial effects. Therefore, different experimental conditions were applied to induce rapid ageing of tsipouro. Five days after immersing the oak chips in the tsipouro, the total phenolic content reached its highest value. Furthermore, the results exhibited that the infusion of the phenolic components from the wood to the tsipouro significantly increased with the increase of the temperature during ageing and of the oak chips/tsipouro ratio (w/v). Moreover, stirring during the ageing process did not affect the total phenolic content of the final product. French oak (Quercus robur) and French and American oak mix (Quercus robur- Quercus alba) sticks (nine different types) were used to examine the influence of the wood material on the final product quality. The amount of phenolic compounds released from the different oak wood types to the tsipouro, during the process, has been shown to vary considerably. High positive correlation among total phenolic content, antiradical and antioxidant activity was found for all the extracts studied.

Pearson's Folin-Ciocalteu ABTS•+ FRAP (Ferric Reducing Correlations (Total Phenolic (Antiradical Power / Antioxidant Content) Activity) Activity) Folin-Ciocalteu (Total 0.928 0.954 Phenolic Content) ABTS•+ (Antiradical 0.979 Activity)

15000 Folin ABTS FRAP 10000 5000

HVP

CNo2

HS CNo3

253

Antioxidant enrichment of fresh-cut cucumber using infusions of edible herbs

M. Giannakourou1, V. Mantanika1, S. Poulis1, I.F. Strati1, P. Zoumpoulakis2 and V.J. Sinanoglou1*

1Laboratory of Chemistry, Analysis & Design of Food Processes, Department of Food Technology, Technological Educational Institute of Athens, Ag.Spyridonos 12210, Egaleo, Greece. 2Institute of Biology, Medicinal Chemistry & Biotechnology, National Hellenic Research Foundation, 48, Vas.Constantinou Ave., 11635, Athens, Greece.

P3-18 E-mail: [email protected]

Recently, there is an increasing interest in exploiting herbs to obtain potentially bioactive phenolic compounds. The present study evaluated the oxidative stability and the potential health benefits of Cucumber (Cucumissativus) after being enriched with natural compounds. Therefore, fresh-cut cucumber slices were immersed into the infusions of twenty plant species in order to enrich them with bioactive compounds. The herbal infusion/fresh-cut cucumber slices ratio (w/w) was higher than 10:1 and the samples were processed for 2.5 h. The temperature was maintained at 70 and 80 oC, respectively for each herbal infusion treatment. All experiments were performed under atmospheric pressure. The total phenolic content (TPC) of the infusions and the post-treatment cucumber extracts was determined by the Folin- Ciocalteu assay, to define the extent of phenolic impregnation. Furthermore, the antiradical capacity of the post-treatment cucumber extracts was measured by the ABTS radical scavenging assay via the Trolox-Equivalent Antioxidant Capacity and their antioxidant activity by the ferric reducing antioxidant power (FRAP) assay. During the treatment, total phenolic content, antioxidant activity and antiradical scavenging capacity of cucumber was significantly increased, irrespective of the type of the herbal infusion and the temperature. The content of total phenols, expressed as mg of gallic acid equivalents (GAE)/kg, varied greatly, ranging from 1.41 to 781.14 mg GAE/kg of cucumber. The highest total phenolics were found in cucumber treated with Origanum vulgare infusion, followed by Jasminum officinale and Mentha spicata infusions, while the lowest in Hippophae rhamnoides infusion. The infusion of herbal phenolics into the porous structure of cucumber was confirmed by the results, leading to the increase of their stability and a significant improvement of their functional properties.

6000 Folin ABTS FRAP 4000 2000 0

254 10th International Conference on Instrumental Methods of

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Optimization of polyphenol extraction from Allium Ampeloprasum var. porrum through Response Surface Methodology

I.F. Strati1, G. Kostomitsopoulos1, F. Lytras1, P. Zoumpoulakis2 and V.J. Sinanoglou1

1Laboratory of Chemistry, Analysis & Design of Food Processes, Department of Food Technology, Technological Educational Institute of Athens, Ag. Spyridonos 12210, Egaleo, Greece. 2Institute of Biology, Medicinal Chemistry & Biotechnology, National Hellenic Research Foundation, 48, Vas. Constantinou Ave., 11635, Athens, Greece.

E-mail: [email protected] P3-19

Allium species, including leek (Allium ampeloprasum var. porrum), have been recognized as rich sources of secondary metabolites, such as polyphenolic compounds, including phenolic acids and their derivatives, flavonoids and flavonoid polymers (proanthocyanidins or condensed tannins), with related health benefits [1]. Moreover, its organosulphur compounds, responsible for the characteristic organoleptic parameters, are implicated as contributing in part to its health-promoting properties. The white bulb and the pseudostem formed by the overlapping leaves of Allium ampeloprasum var. porrum are traditionally consumed either as a vegetable or as a condiment in many Mediterranean countries. The objective of the present study was to optimize the extraction conditions of polyphenols from white bulb and green leaves of leek by implementing a central composite design (CCD). The optimization took into consideration basic factors affecting the extraction efficiency, including extraction time, liquid-to-solid ratio and solvent mixture. Maximum polyphenol yield was achieved at extraction time 60 min, liquid-to-solid ratio 5:1 (v/w) and methanol to water ratio 70:30 (v/v), for both white bulb and green leek leaves extracts. High correlation values were also observed between total phenolic content and antioxidant-antiradical activity of white bulb and green leaves optimized extracts.

Fig. 1. Response surface plot for total polyphenol content as a function of time and liquid to solid ratio (Methanol:Water =70:30, v/v)

References [1] Lanzotti, V., The analysis of onion and garlic, Journal of Chromatography A, 1112 (2006) 3–22.

255

Evaluation of antioxidant activity and Mid-FTIR absorbance spectra of balsamic and common vinegars

V.J. Sinanoglou1, I.F. Strati1, D. Tangouli2, N. Paloumpis2, D. Cavouras3, and P. Zoumpoulakis2

E-mail: [email protected]

1Laboratory of Chemistry, Analysis & Design of Food Processes, Instrumental Food Analysis, Department of Food Technology, Technological Educational Institute of Athens, Ag. Spyridonos 12210, Egaleo, Greece. P3-20 2Institute of Biology, Medicinal Chemistry & Biotechnology, National Hellenic Research Foundation, 48, Vas. Constantinou Ave., 11635, Athens, Greece. 3Medical Image and Signal Processing Laboratory, Department of Biomedical Engineering, Technological Education Institution of Athens, Ag. Spyridonos 12210 Egaleo, Greece.

E-mail: [email protected]

Vinegar, a widely consumed fermented food, has great prospects for a healthy diet, as it showed antioxidant, antiglycemic, anti-hypertensive and antitumor effects. In the present study, forty four commercially available samples of balsamic and common vinegars were examined spectroscopically and were subjected to Fourier transform mid-infrared (Mid-FTIR) spectroscopy, in order to be evaluated in terms of their total phenolic content, antioxidant activity, antiradical capacity and FTIR absorbance spectra. Statistical calculations including discriminant analysis and partial correlations were performed on the above results. Among the forty four samples of vinegars, balsamic vinegars exhibited the strongest antioxidant and antiradical capacity which correlated to the highest level of total phenolic content. A linear correlation between total phenolic content and antioxidant-antiradical activity values was found in all the samples studied, with correlation coefficient of 0.911 (P = 0.01) for ABTS assay and correlation coefficient of 0.810 (P = 0.01) for FRAP assay, indicating that both balsamic and common vinegars’ total phenols were major contributors to the high antioxidant and antiradical activity of vinegars. A principal component analysis (PCA) was implemented in order to analyse FTIR spectral data and to establish characteristic spectral bands referring to the different vinegar samples. The examination of the bands between the wavenumbers of 2600–350 cm-1 and the two-dimensional PCA plot resulted in great variation between balsamic and common vinegars probably due to the differentiation of the phenolic compounds and carbohydrate moieties, contained in the vinegars.

1b 2b 0.25 3b 4b 0.2 5b 6b 7b 8b 0.15 9b 10b 0.1 11b 12b 0.05 0 4000 3000 2000 1000 0 -0.05 Fig. 1. FTIR absorbance spectra of vinegars Fig. 2. PCA of the FTIR spectra of vinegars

256 10th International Conference on Instrumental Methods of

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Influence of the pasteurization and filtration on selected chemical components of beer

J. Pořízka, D. Vopelková, V. Štursa and P. Diviš

Brno University of Technology, Faculty of Chemistry, Institute of Food science and Biotechnology, Purkyňova 464/118, Brno, Czech Republic

E-mail: [email protected]

The aim of this work was to study the influence of the pasteurization and filtration on selected chemical compounds in beer. Specifically, the influence on elemental composition, content P3-21 of organic acids, carbohydrates and phenolic substances was studied. Effects of the post fermentation procedures were studied on 4 groups of Czech lager beers (filtrated unpasteurized, filtrated pasteurized, nonfiltrated pasteurized and nonfiltrated unpasteurized). Optical emission spectrometry with inductively coupled plasma (ICP-OES) was used for elemental analysis of beer. Organic acids in beer were analyzed by Ion chromatography. For determination of carbohydrates High performance liquid chromatography with ELSD detector (HPLC-ELSD) was used and phenolic compounds were determined by HPLC with diode array detector (HPLC-DAD). Analysis of dataset was performed by usage of univariate and multivariate statistical methods (analysis of variance and principal component analysis). Parameters that showed the most significant differences between individual groups of beers were obtained. Also correlations between the variables (chemical composition) and the technological beer processing operations were found. 12 chemical parameters of beer from total of 23 were significantly (significance level 0.05) affected by the post fermentation treatment. The effect of filtration and pasteurization was observed in content of the iron, silicon, potassium and magnesium, malic acid, monosaccharides glucose and fructose and phenolic compounds.

257

Chemical sensor for the detection of CBr4 based on modified TiO2 thin film

P. Nikolaou, A. Vassilakopoulou, D. Papadatos, I. Koutselas and E. Topoglidis

Materials Science Dept., University of Patras, Patras, 26504, Greece

E-mail: [email protected]

Mesoporous TiO2 films have been used for many applications ranging from dye-sensitized P3-22 solar cells, chemical and biochemical sensors, electrochromic windows and energy storage devices such as batteries and supercapacitors. Most of these applications rely on electro or photo induced electron transfer reactions of redox-active molecules immobilized within the mesoporous network of the TiO2 films, which are deposited on conductive active substrates such as ITO and FTO glass. The TiO2 film turns into a conductive substrate when a sufficient amount of electrons is injected into the film (e.g. by applying a cathodic potential) and to an insulator under reverse bias. In this study the Cyclic voltammetry technique is used in order to acquire a comprehensive understanding of the dynamics of electron transfer/charge transport within a standard, mesoporous, transparent semi-conductive TiO2 film loaded with perovskite and redox-active molecules. The electrochemical behavior of the adsorbed perovskites and redox species was studied as a function of the potential applied to the composite semi-conductive film. The electron transfer process is predominantly governed by the localized traps in the bandgap of the semi-conductive film. It has been observed that it is possible to detect variations in the cathodic and anodic peaks due to the presence of CBr4 on the composite films, which allow the detectability of CBr4 as low as 30 ppb.

References [1] Tzu-Sen Su, Tsung-Yu Hsieh, Cheng-You Hong and Tzu-Chien Wei, Scientific reports, 5 (2015) 1-8. [2] E. Topoglidis, T. Lutz, R. L. Willis, C. J. Barnett, A. E. G. Cass, J. R. Durrant, Farraday Discuss. 116 (2000) 35-46. [3] H. Kim, C. M Gilmore, A. Piqué, J. Horwitz, S. H. Mattoussi, H. Murata, Z. H. Kafafi and D. B. Chrisey Journal of Applied Physics, 86 (1999) 6451-6461.

258 10th International Conference on Instrumental Methods of

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Mycotoxins in Foods: Employing microorganisms in milk detoxification

Κ. Lapapokonstantaki1, P. Giannikopoulou2, E. Kakoulides2, D. Mamma1, D. Kekos1

1Biotechnology Laboratory, School of Chemical Engineering, NTUA, 151 80 Athens, Greece 2Chemical Metrology Laboratory, General State Chemical Laboratory, 16 Tsocha Street, 11521 Athens, Greece

E-mail: [email protected] P3-23

Mycotoxins are toxic secondary metabolites produced by filamentous fungi, most commonly of the genera Aspergillus, Fusarium and Penicillium [1]. Due to the high toxicity of mycotoxins, maximum levels have been established in foodstuffs. Mycotoxin consumption has serious effects on both humans and animals, especially when people suffer from liver diseases [2]. The best way to prevent mycotoxin contamination in the food chain is to improve agricultural practices and control the storage conditions of products [3,4]. Particular emphasis is given to aflatoxins which have the highest toxicity among mycotoxins because of their toxigenic, mutagenic and carcinogenic properties. In the case of contaminated products, microorganisms can be employed in the detoxification process. Saccharomyces cerevisiae and different strains of lactic acid bacteria strains have the efficiency to bind aflatoxins M1 and B1. There are indications that the process of binding is extracellular and noncovalent and is carried out by components of the cell wall of yeast and bacteria [5]. In the present experiments the ability of toxin production by the fungus Fusarium oxysmporum F3, using rice, barley, wheat, corn and cumin as carbon sources, was examined [6]. In particular, it was found that the fungus F. oxysporum F3 was not able to produce aflatoxins B1, B2, G1, G2 or DON, NIV and ZEA, at 29 ºC, after 30 days of culture, in the absence of light. The only toxin that may be produced, is fusaric acid in wheat, barley, corn, and cumin. Furthermore, the ability of S. cerevisiae to bind aflatoxin M1 was also evaluated. For this purpose, semi skimmed milk (4 % fat) was tested using three different cell concentrations (1.6 x 109, 1.6 x1010, 1.6 x1011 cells mL-1 milk) at three toxin levels (0.25, 0.5, 0.75 μgL-1). Sample analysis was carried out by liquid chromatography coupled to tandem mass spectrometry (LC-MS / MS). Both the kinetics and the percentage of binding were followed. It was shown that the binding rate of toxin from milk increases with increasing cell concentration. The percentage of binding is also stronger at higher initial concentrations of the toxin in milk.

References [1] J. W. Bennett and M. Klich, Clin Microbiol Rev, 16 (2003) 497-516. [2] J. H. Williams, T. D. Phillips, P.E. Jolly, J.K. Stiles, C.M. Jolly and D. Aggarwal, Am J Clin Nutr 80 (2004) 1106-1122 [3] J. T. Oatley, M. D. Rarick, G. E. Ji and J. E. Linz, J Food Prot., 63 (2000) 1133-1136. [4] B. L. Gonçalves, R. E. Rosim, C. A. F. de Oliveira and C. H. Corassin, Food Control, 47 (2015) 298-300. [5] C.H. Corassin, F. Bovo, R. E. Rosim and C.A.F. Oliveira, Food Control, 31(2013)80-83. [6] K. Mbae, C. Kiiyukia and G. M. Kenji, African Journal of Food, 5 (2012) 6490-6502.

259

Synthesis of Magnetic Ionic Liquid for the determination of pesticides in aqueous samples

M. Kapsi, V. Sakkas and T. Albanis

Laboratory of Analytical Chemistry, Department of Chemistry, University of Ioannina, Panepistimioupolis, Ioannina, 45110, Greece

E-mail: [email protected]

Trends in sample preparation are focused on the development of non-conventional solvents as P3-24 well as novel solid materials in extraction and preconcentration schemes to improve limitations and toxicity issues of current organic solvents and common sorbents. Within non-conventional solvents, ionic liquids (ILs) have been widely studied in recent years due to their interesting structures and unusual properties. Magnetic ionic liquids (MILs) are a subclass of ionic liquids (ILs) containing paramagnetic components and are readily manipulated by an external magnetic field [1]. In this study a dicationic class of hydrophobic MIL was synthesized and characterized for the analytical determination of a group of pesticides occurred in aquacultures. The synthetic strategy employed in this study, was based in an unsymmetrical dicationic MIL with heteroanions. Specifically, an ionic liquid with the benzimidazolium cation was first synthesized and then heteroanions were incorporated according to the following schematic procedure to the initial ionic liquid [2].

The performance of the synthesized MIL, [1, 12-di(3-Benzylbenzimidazolium) dodecane bis [(trifluomethyl) sulfonyl)] imide bromothrichloroferrate (III)] was studied for the extraction of hydrophobic analytes, such as pesticides from aqueous samples. Analytes were enriched in MIL and were further separated from the remaining components of the sample with the aid of a strong magnet. Pesticides are finally eluted from the material and subjected in Gas Chromatography coupled with Mass Spectrometry (GC-MS).

References [1] M. Rodríguez, O. Nacham, K. Clark, V. Pino, J. Anderson, J. Ayala and A. Afonso, Analytica Chima Acta, 934 (2016) 106-113. [2] O. Nacham, K. Clark, H. Yu, and J. Anderson, Chemistry of Materials, 27 (2015) 923-931.

260 10th International Conference on Instrumental Methods of

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Development of DGT technique for determination of mercury in various matrix

P. Diviš1 and M. Reichstädter

Brno University of Technology, Faculty of Chemistry, Purkyňova 118, Brno 612 00-CZ

E-mail: [email protected]

Diffusive gradient in thin films technique (DGT) has become a routine tool for determination of labile metal species or other metal species. Since the introduction of DGT technique in 1995 P3-25 [1], more applications possibilities of this technique appeared. Because the concentration of mercury in analysed samples is usually very low and the matrix of the analysed sample is often very complex, the preconcentration capability and capability of analyte separation from sample matrix are the major advantages of DGT technique. However, the application of DGT technique for determination of mercury requires special types of sorption gels, because the commercially available sorbents commonly used in DGT technique are not able to effectively bind mercury associated with some natural ligands such as chlorides, humic acids etc [2]. Some of applicable sorbents cannot be used because of their high cost or inconvenient particle size. In the presented work new sorption gel for DGT technique with thiol functional groups was prepared by immobilization of L-cysteine on amino-modified silica via reaction of glutaraldehyde. The prepared sorbent was characterized by FTIR-DRIFT technique and the presence of immobilized cysteine molecules was confirmed by characteristic bands in obtained spectra. In the further synthesis of new resin different concentrations of L-cystein were used resulting into different load of thiol groups on sorbents. Sorbents prepared from different L- cystein concentrations were characterized by CS elemental analysis. Finally, sorbent containing the highest concentration of thiol functional groups was incorporated into the polyacrylamide gel from which the sorption gel discs for DGT technique were cut and performance of DGT sampling units with new sorption gel was tested in the laboratory.

References [1] Zhang, Hao. And William. Davison. Analytical Chemistry. 1995, vol. 67, no. 19, p. 3391-3400. [2] Diviš, Pavel, Roman Szkandera And Hana Dočekalová. Central European Journal of Chemistry. 2010, vol. 8, no. 5, p. 1105-1109.

261

Assessment of CdS quantum dots effect on UV-C induced DNA damage using an electrochemical biosensors

V. Svitková and J. Labuda

Slovak University of Technology in Bratislava, Faculty of Chemical and Food Technology, Institute of Analytical Chemistry, Bratislava, Slovakia

E-mail: [email protected]

Structural damage to salmon sperm double stranded DNA at its exposure to UV-C radiation P3-26 (254 nm) in the presence of thiol-capped CdS quantum dots has been investigated using an electrochemical DNA-based biosensor composed of a glassy carbon electrode with a layered structure of chemical modifiers dsDNA and CdS quantum dots and voltammetric and impedimetric measurements. CdS quantum dots of three different sizes (from app. 4.0 to 10.5 nm) and various fluorescence intensity stabilized with mercaptosuccinic acid have been characterized by AFM and zeta sizer, absorption and fluorescence spectra and an ability to generate ROS under UV-C irradiation. Cyclic voltammetry, electrochemical impedance spectroscopy and square-wave voltammetry of the guanine moiety were utilized together with gel electrophoresis. Two experimental approaches for DNA irradiation have been used as (i) the investigation of damage to a surface attached DNA using the DNA-based electrochemical biosensor composed of a layer dsDNA and a layer of CdS QDs and (ii) the investigation of dsDNA damage in solution phase of CdS QDs followed by electrochemical and electrophoretic determination of survived DNA. The UV-C enhanced degradation of dsDNA in the presence of CdS quantum dots has been found depending on their fluorescence ability. This study presents the DNA-based biosensor as an effective analytical tool for evaluation of the UV-C degradation of dsDNA structure, i.e. risk effect of nanoparticles such as the quantum dots [1].

Acknowledgement This work was supported by the Scientific Grant Agency VEGA of the Slovak Republic (Projects No. 1/0489/16), and by the Competence Center for SMART Technologies for Electronics and Informatics Systems and Services, ITMS 26240220072, funded by the Research&Development Operational Programme from the ERDF.

References [1] V. Svitková, J. Blaškovičová, M. Tekeľová, B. M. Kallai, T. Ignat, P. Skládal, V. Horňáková, P. Kopel, V. Adam, D. Farkašová and J. Labuda, Sensor Actuat B-Chem, 243 (2017), 435-444.

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Multi-element method validation for rare earths, precious metals and trace elements determination through ICP-MS in meat products

G.P. Danezis1, A.S. Tsagkaris1, A.C. Pappas2, E. Zoidis2, G. Papadomichelakis2, I.E. Hadjigeorgiou2 and C.A. Georgiou1

1Chemistry Laboratory, Department of Food Science and Human Nutrition, 2Department of Nutritional Physiology and Feeding, Faculty of Animal Science and Aquaculture, Agricultural University of Athens, 75 Iera Odos, 11855 Athens, Greece

E-mail: [email protected], [email protected] P3-27 Elemental profile is under thorough discussion as a food quality and safety parameter [1]. In addition, rare earths have recently proved to be reliable authenticity markers, especially for geographical and genetic origin identification [2, 3]. Therefore, there is a need for robust and reliable analytical methods to assess the toxic and nutritive elemental content of food and to assure authenticity that is especially important due to recent safety issues and food scandals. The aim of this study was to validate a multi-element method for rare earths, actinides, precious metals, trace and macro elements (64 elements in total) determination in meat products by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). ICP-MS technique is an ideal and almost unique technique for rare earth analysis, enabling rapid multi-element analysis with extremely low detection limits (ng Kg-1) [1]. This is the first effort to validate an ICP-MS method for rare earth elements, actinides and precious metals determination in meat products, according to the best of our knowledge. Validation of the method was carried out on commercial rabbit samples, including muscle and liver tissues. All samples (blank, spiked, etc.) were subjected to the same sample preparation procedure (microwave assisted acid digestion). The obtained data show that the method for most elements has acceptable linearity with r2 ≥ 0.99, acceptable accuracy with recovery rates

of 70-120% and precision with SDR ≤ 20%. Quantification limits for the method are very low at 10 ng kg-1for rare earths and at 100 ng kg-1 for the majority of trace elements. An estimation of uncertainty was also performed in accordance with EURACHEM's instructions, along with matrix effect determination. The method is quick, simple and it is characterized by very good sensitivity, therefore it is suitable for routine analyses aimed either in identifying toxic elements or essential trace elements or in assessing the authenticity of meat products.

References [1] C.A. Georgiou, G.P. Danezis. Elemental & Isotopic Mass Spectrometry, in Y. Pico (Ed.) Advanced Mass Spectrometry for Food Safety and Quality, Comprehensive Analytical Chemistry, Elsevier: 68 (2015) 131–243. [2] G.P. Danezis, A.S. Tsagkaris, V. Brusic, C. A. Georgiou. Food Authentication: State of the Art and Prospects, Current Opinion in Food Science, invited opinion article, 10 (2016) 22-31. [3] S.A. Drivelos, G.P. Danezis, S.A. Haroutounian, C.A. Georgiou. Rare earth elements minimal harvest year variation facilitates robust geographical origin discrimination: The case of PDO “Fava Santorinis”. Food Chemistry, 213 (2016) 238-245.

263

Nutritional value and safety of Greek PDO cheeses through elemental metabolomics

G.P. Danezis1, A.C. Pappas2, E. Tsiplakou2, E.C. Pappa3, M. Zacharioudaki2, A.S. Tsagkaris1, K. Sotirakoglou4, G. Zervas2 and C.A. Georgiou1

1Chemistry Laboratory, Department of Food Science and Human Nutrition 2Department of Nutritional Physiology and Feeding, Faculty of Animal Science and Aquaculture, Agricultural University of Athens, 75 Iera Odos, 11855 Athens, Greece 3Hellenic Agricultural Organization—DEMETER, General Directorate of Agricultural Research, Institute of Technology of Agricultural Products, Dairy Research Department, Katsikas, 45221 P3-28 Ioannina, Greece 4Department of Plant Breeding and Biometry, Faculty of Crop Science, Agricultural University of Athens, 75 Iera Odos, 11855 Athens, Greece

E-mail: [email protected]

Food market globalization, along with the industrialization of production has led the consumers to an increasing uncertainty concerning food’s nutritional value and safety [1]. Milk and dairy products are important in a nutritional balanced diet. Their consumption has been associated with several health benefits due to their high content in proteins, fats and minerals. Milk and dairy products quality is affected by animal nutrition status, processing, and the environment. Greece is well-known for the production of many PDO (Protected Destination of Origin) cheeses, which are of high quality, nutrition value and show unique organoleptic features. Elemental metabolomics is emerging as a new technology with applications in various fields such as nutrition, agriculture and links food science to health. This study, is an implementation of elemental metabolomics Standard Operation Principles (SOPs), described along the minimal information reporting standards (MIRSs) in [2]. One hundred three samples from the 21 Greek PDO cheeses and one potential PDO cheese (Mastelo Xiou) were assessed for sixty-five elements through ICP-MS. This is the very first study to obtain comprehensive elemental signatures of chesses. Results show that Greek PDO chesses have comparable ranges of toxic elements Cd and Pb to Spanish cheese’s [3]. We have found high content of nutritive elements showing that Greek PDO cheeses are good source of trace and macro elements, having significant contribution to the Recommended Dietary Allowance (RDA). In case of a Greek man 31-50 years old, considering that cheese intake in Greece was 94.7 g/day in 2015, contribution of Feta cheese to the total calcium intake is estimated 50% according to National Institutes of Health (USA) Dietary Reference Intakes (DRI). Greek PDO chesses contribute to the RDA of other elements to different levels: phosphorous 50%, iron 23%, zinc 20% and selenium 17%.

References [1] G.P. Danezis, A.S. Tsagkaris, V. Brusic, C. A. Georgiou, Food Authentication: State of the Art and Prospects, Current Opinion in Food Science, invited opinion article, 10 (2016) 22-31. [2] P. Zhang, C.A. Georgiou, V. Brusic, Elemental Metabolomics, Briefings in Bioinformatics, (2017) 1-13. [3] R. Moreno-Rojas, P.J. Sánchez-Segarra, F. Cámara-Martos, M.A. Amaro-Lópezet, Heavy metal levels in Spanish cheeses: Influence of manufacturing conditions. Food Additives and Contaminants: Part B Surveillance, 23, 2 (2010) 90-100.

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Soft Greek PDO cheeses authentication and discrimination from possible imitations using elemental metabolomics

G.P. Danezis1, A.C. Pappas2, E. Tsiplakou2, E.C. Pappa3, M. Zacharioudaki2, A.S. Tsagkaris1, K. Sotirakoglou4, G. Zervas2 and C.A. Georgiou1

1Chemistry Laboratory, Department of Food Science and Human Nutrition 2Department of Nutritional Physiology and Feeding, Faculty of Animal Science and Aquaculture, Agricultural University of Athens, 75 Iera Odos, 11855 Athens, Greece 3Hellenic Agricultural Organization—DEMETER, General Directorate of Agricultural Research, Institute of Technology of Agricultural Products, Dairy Research Department, Katsikas, 45221 Ioannina, Greece P3-29 4Department of Plant Breeding and Biometry, Faculty of Crop Science, Agricultural University of Athens, 75 Iera Odos, 11855 Athens, Greece

E-mail: [email protected]

Authenticity of dairy products is a necessity since many consumers address their choice of purchase according the geographic or genetic origin, animal welfare and other attributes [1]. Greece is famous for its soft cheeses. Four of them are registered as PDO (Protected Designation of Origin) products, including Feta, Kalathaki Limnou, Anevato and Kopanisti. Almost in their entirety, they are made from sheep's and goat's milk. Cheese, after olive oil, is the major exported agricultural product of Greece [2]. Thus, efficient and reliable methods based on analytical chemistry to assess cheese authenticity are important. Elemental profile of cheeses is associated with the raw milk source, which, at the same time, is influenced by several factors including vegetation, drinking water, animal species and environmental conditions. Most of these factors depend or are related to geographic origin. This work tests and makes recommendations on the validity of the hypothesis that rare earth elements (REEs), actinides (Ac) and precious metals could be reliable markers of geographic and genetic origin. The study is based on principles of elemental metabolomics [3] assessing 65 elements. Elemental fingerprints of 26 authentic Greek soft PDO cheeses (Feta, Kalathaki Limnou, Anevato and Kopanisti) and 9 white cheeses (possible imitations) were obtained through ICP- MS. Discriminant Analysis (DA) was found more appropriate than artificial neural networks (ANN) and Cluster Analysis (CA) for sample classification. In more details, utilizing the total fingerprint, classification was 100% correct. By using only REEs, Ac or REEs, Ac and precious metals, the classification was 83.78% and 97.30% correct, respectively. Use of trace and macro elements only, did not provide acceptable classification. By using only the best markers (Er, Ηo, Lu, Sm, Tb, Tm, Yb, Au, Ir, Pt, Rh, Ru, Ag, Ta, Tl, W) correct classification reached 97.30 %. It is noticeable that 12 of these 16 elements belong to REEs, Ac and precious metals groups. The results demonstrate that the basic principles of elemental metabolomics can be successfully applied for cheese authentication.

References [1] G.P. Danezis, A.S. Tsagkaris, F. Camin, V. Brusic, & C.A. Georgiou, Food authentication: Techniques, trends & emerging approaches, TrAC Trends in Analytical Chemistry, 85 (2016) 123-132. [2] https://www.export.gov/article?id=Greece-Agricultural-Sector [3] P. Zhang, C.A. Georgiou, V. Brusic, Elemental Metabolomics, Briefings in Bioinformatics, (2017) 1-13.

265

Optimization of high energy extraction of antioxidant compounds from Lippia citriodora

C. Makris1,3, T. Tsiaka1,2, D. Lantzouraki1,2, C. Proestos3, V.J Sinanoglou2, P. Zoumpoulakis1

1Institute of Biology, Medicinal Chemistry and Biotechnology, National Hellenic Research Foundation, 48 Vas. Constantinou Ave., 11635, Athens, Greece. 2 Department of Chemistry, National and Kapodistrian University of Athens, Athens 15771, Greece 3Instrumental Food Analysis Laboratory, Department of Food Technology, Technological Educational P3-30 Institution of Athens, Ag. Spyridonos Street, Aigaleo, GR-12210 Athens, Greece

e-mail: [email protected]

The aim of this study was the optimization of the recovery of phenolic constituents of lemon verbena, Lippia citriodora using high energy techniques and design of experiment. More specifically, Ultrasound Assisted Extraction (UAE) was used while the design of experiment was implemented using the statistical method of Screening Values and Box – Behnken Design and the interpretation of the experimental responses was achieved with the use of Response Surface Μethodology. For comparison reasons, classical extractions were performed according to the optimized variables of UAE and in two different time durations of 20 min and 24 h. Finally, three different methods of determination of the extracts’ antioxidant profile were implemented including the Folin – Ciocalteu method for the total phenolic content, the ABTS method for the antiradical effect and the FRAP method measuring the antioxidant effect of extracts. Optimized UAE parameters leaded to extracts with high antioxidant and andiradical properties.

266 10th International Conference on Instrumental Methods of

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Optimization of extraction methodology for the recovery of phenolic antioxidants from wine less

D. Tagouli1,2, D. Lantzouraki1,2, T. Tsiaka1,2, V.J Sinanoglou2, P. Zoumpoulakis1

1Institute of Biology, Medicinal Chemistry and Biotechnology, National Hellenic Research Foundation, 48 Vas. Constantinou Ave., 11635, Athens, Greece. 2Instrumental Food Analysis Laboratory, Department of Food Technology, Technological Educational Institution of Athens, Ag. Spyridonos Street, Aigaleo, GR-12210 Athens, Greece

e-mail: [email protected] P3-31 The optimization of the extraction of phenolic compounds from wine less of white and red varieties was examined. More specifically, the wine lees supernatant, as well as its solid residue were the extraction matrices for Microwave – Assisted Extraction. For the extracts of the solid residue the optimization of the extraction of total phenolics was performed with the application of Experimental Design using Response Surface Methodology and the Box- Behnken Design. The optimal values of extraction parameters were applied to the rest of the wine lees samples. The total phenolic content, the antioxidant and antiradical capacity, of both the supernatants and the extracts, were estimated by Folin-Ciocalteu, ABTS•+ and FRAP assays. Differences between wine varieties were observed with less from red grapes exhibiting the higher values in antioxidant and antiradical activities as well as the phenolic content. From the studied wine less, those from Agiorgitiko were the most promising ones. Moreover, the extracts from the solid residues were richer in total phenolic content compared to wine lees supernatants.

267

An exhaustive study of antioxidant related properties of Artemisia leaves

N. Kalogeropoulos1, V. Kafourou1,2, A.C. Kaliora1, D.P. Makris2, P. Zoumpoulakis3

1 Department of Nutrition & Dietetics, School of Health Science and Education, Harokopio University, El. Venizelou 70, 17671 Athens, Greece 2 Department of Food Science & Nutrition, University of the Aegean, Myrina 81400, Lemnos, Greece 3Institute of Biology, Medicinal Chemistry and Biotechnology, National Hellenic Research Foundation, 48 Vas. Constantinou Ave., 11635, Athens, Greece. P3-32 e-mail: [email protected]

In the present study decoctions, as well as methanolic and aqueous glycerol extracts from the leaves of two Artemisia species, namely A. inculta Delile and A. arborescens from Greece (Gavdos island and Chania Crete, correspondingly) were evaluated. Total phenolics, flavonoids, anthocyanins, flavonols, hydroxycinnamates and terpenics contents were determined by spectrophotometric assays. The antioxidant potential of the extracts was evaluated by assessing (a) the DPPH radical scavenging capacity, (b) the ferric reducing antioxidant potential (FRAP), and (c) the inhibition of Cu2+ induced serum lipoproteins oxidation. The phenolic profile of the samples was evaluated using LC-MS, while individual polyphenols were quantitated by GC-MS. Results indicate that decoctions of the two Artemisia species did not vary significantly. Among the three types of extracts, the aqueous glycerol extracts presented the higher values per gram of plant material for all studied parameters.

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Comparative evaluation of the antioxidant activity and phenolic profile of different extracts from industrial peach by-product

H. Fragiadaki1, T. Tsiaka2, D.Z. Lantzouraki1, V.J. Sinanoglou1 and P.s Zoumpoulakis2

1Laboratory of Chemistry, Analysis & Design of Food Processes, Department of Food Technology, Technological Educational Institution of Athens, Ag. Spyridonos 12210 Egaleo, Greece 2Laboratory of Molecular Analysis. Institute of Biology, Medicinal Chemistry and Biothechnology, National Hellenic Research Foundation. 48 Vas. Constantinou Ave. 11635, Athens, Greece

E-mail: pzoump@eie. gr P3-33

Peach (Prunus persica L.) fruits have been historically cultivated in the Mediterranean countries, such as Italy, Spain, and Greece [1]. Alongside the fresh consumption, peaches are processed into puree, concentrates, juices, jams, and canned peaches, ending up to a great amount of waste material. These by-products are usually disposed to landfills or incinerated [2]. Discarding peach wastes consist a loss of a valuable material, which could be reused in other production systems. The contained phytochemicals can be isolated and be further used for applications in nutraceutical supplements, food additives, new foodstuffs or pharmaceuticals products. Peach by-products are rich in phenolic compounds that possess well-established biological activities, such as antioxidant and anti-inflammatory [1, 3]. The aim of this study was to recover and study the phenolic compounds from the residues of processed peaches. Therefore, peach by-products from the processing of fresh peaches were obtained from a Greek fruit processing industry (Danais s.a, Skidra-Aridaia, region of Macedonia, Greece). The sample consisted mainly of pulp, and it was dehydrated in a drying oven to obtain a final product with a residual water content of approximately 4% w/w. The dried product was treated with different solvent systems (methanol, methanol-water 1:4 and 4:1 v/v) in order to extract the phenolic compounds. The three different extracts were then comparatively studied. The total phenolic content (TPC) was determined by the Folin- Ciocalteu assay. The antiradical activity was measured by the ABTS radical scavenging assay, while the reducing/antioxidant power was studied by the FRAP method. The MeOH-H2O extracts, resulted to a higher extraction yield, higher TPC and exhibited higher antiradical and antioxidant activities than the MeOH extract. To a step further, an LC-MSn method was applied for the characterization of the phenolic profile of the extracts. Several phenolic and polyphenolic compounds were identified including cyanidin, caffeic acid, chlorogenic acid, epicatechin-3-O-gallate, gallic acid derivatives, glucosides of kaempferol and quercetin, naringin and naringenin. Based on the analyses' results, it is concluded that the phenolic compounds of peach by-products could be potentially recovered and utilized as natural antioxidants.

References [1] M. Siddiq, A. Liavoga and I. Greiby, Peaches and Nectarines in Handbook of Fruits and Fruit Processing, Second Edition (2012). [2] R. Vásquez-Villanueva, M. Luisa Marina and M. Concepción García, Journal of Functional Foods, 18 (2015) 137–146. [3] E. F. d. Vargas, A. Jablonski, S. H. Flôres and A. d. O. Rios, International Journal of Food Science & Technology, 52 (2017) 757–762.

269

Investigation of Sc leaching from bauxite residue using phosphoric acid

L.-A. Tsakanika1, Th. Lymperopoulou2 and M. Ochsenkuehn-Petropoulou1

1Laboratory of Inorganic and Analytical Chemistry 2Center of Environment and Quality of Life School of Chemical Engineering, NTUA, Iroon Polytechniou 9, Zografou Campus, Athens, Greece

E-mail: [email protected], [email protected], [email protected]

P3-34 Bauxite residue (BR), is the insoluble, high alkaline and very fine grained by-product of the alumina production after Bayer process. Its global production is ~120 million tons/year, while in Greece “Aluminium of Greece” produces annually 750.000 tons. The residue is rich in main and trace critical elements such as REEs (Sc, Y and Lns). The total content of REEs is about -1 -1 1kg·tn dry BR while Sc concentration ~120g·tn (0.02% Sc2O3), is close to the content in its main resources [1,2,3]. Among all the REEs, scandium is exceptionally rare and expensive with increasing demand especially in high technologies. Use of BR as secondary raw material for Sc recovery is of great interest due to Sc concentration in combination to residue availability and problematic disposal. Hydrometallurgical treatment is the most commonly used technique for REEs and Sc recovery from BR [4]. The present work is a continuation of an over 20 year research for the recovery of REEs from BR having resulted to the development of an innovative method for the selective separation and purification of REEs and especially Sc, including nitric acid leaching, ion exchange, selective extraction-backstripping and HPLC processes [1,2,3]. The whole procedure had been performed in lab scale and partially scaled up to a pilot plant with comparable results [3,5]. In this study phosphoric acid was selected as leaching agent due to phosphorus species selectivity for Sc [6] and the lack of enough relevant data in the literature. Phosphoric acid was combined with other mineral acids and compared with previous studies. Several variables were tested and evaluated focusing on high recoveries of Sc and its selective separation, especially in respect to iron. The effect of leaching conditions such as solid to liquid ratio, acid concentration, leaching time, temperature, pressure and subsequent leaching stages were investigated. Determination of Sc and Fe concentrations in the leachates, was performed using ICP-OES. Mineralogical and chemical composition was evaluated by XRD and SEM-EDX techniques.

References [1] M. Ochsenkühn-Petropulu, Th. Lyberopulu, G. Parissakis, Anal. Chim. Acta 296 (1994) 305-313. [2] Th. Lymperopoulou PhD thesis, School of Chemical Engineering, NTUA, Greece (1996). [3] L.A. Tsakanika, PhD thesis, School of Chemical Engineering, NTUA, Greece (2013). [4] Z. Liu, H. Li, Hydrometallurgy 155 (2015) 29-43. [5] M. Ochsenkühn-Petropoulou, K. Hatzilyberis, L. Mendrinos, C. Salmas, Ind. Eng. Chem. Res. 41 (2002) 5794-5801. [6] W. Zhang, R. Koivula, E. Wiikinkoski, J. Xu, S. Hietala, J. Lehto, R. Harjula, ACS Sustainable Chem. Eng., 5 (4) (2017) 3103–3114.

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Total phenols and antioxidant capacity of koumaro distillates from five mainland areas of Greece

I. A. Athanasoula, P. G. Demertzis and K. Akrida-Demertzi

University of Ioannina, Department of Chemistry, Laboratory of Food Chemistry, P.O. Box 1186, GR- 45500, Ioannina, Greece

E-mail:[email protected]

Koumaria is the common name of the bushy shrub Arbutus unedo L., also known as the P3-35 strawberry tree. Koumaro fruit is considered to be an organic product because it is widely grown without any agrochemical substances [1, 2]. It is a good source of antioxidants, such as flavonoids, vitamins C and E, carotenoids and polyphenols, which help fight chronic disease and cancer [3, 4]. Koumaro fruits are mainly used for the production of an aromatic traditional distillate. The aim of the present study was to estimate total phenols and antioxidant capacity of Koumaro distillates from five mainland areas of Greece (Preveza, Ioannina, Pieria, Thesprotia and Aitoloakarnania). 25 different samples of Koumaro distillates were used (5 samples from each of the above mentioned areas). Total phenols were determined by the Folin- Ciocalteu method and the antioxidant capacity was determined by the 2,2-diphenyl-1- picrylhydrazyl (DPPH) radical scavenging assay. The antioxidant capacity for all samples was ranging between 48.41% and 58.84% (between 49.03% and 53.93% in the samples from Preveza, between 53.36% and 58.84% in the samples from Ioannina, between 48.41% and 51.93% in the samples from Pieria, between 51.52% and 53.15% in the samples from Thesprotia and between 53.52% and 55.28% in the samples from Aitoloakarnania). Moreover, total phenols in all samples were ranging between 5.97 mg/L and 9.99 mg/L expressed as gallic acid (between 6.32 and 6.35 mg/L in Preveza samples, between 5.97 and 6.61 mg/L in Ioannina samples, between 6.87 and 7.48 mg/L in Pieria samples, between 8.29 and 9.99 mg/L in Thesprotia samples and between 7.41 and 8.33 mg/L in Aitoloakarnania samples). In conclusion, koumaro distillates exhibited a remarkable antioxidant capacity, which could possibly be increased by the addition of various kinds of berries during the distillation process.

References [1] E. H. Soufleros, A. S. Mygdalia and P. Natskoulis, Characterization and safety evaluation of the traditional Greek fruit distillate ‘‘Mouro’’ by flavor compounds and mineral analysis. Food Chemistry, 86 (2004) 625–636. [2] E. H. Soufleros, A. S. Mygdalia and P. Natskoulis, Production process and characterization of the traditional Greek fruit distillate ‘‘Koumaro’’ by aromatic and mineral composition. Journal of Food Composition and Analysis, 18 (2005) 699–716. [3] M. L. C. M. M. Alarcão-E-Silva, A. E. B. Leitão, H. G. Azinheira and M. C. A. Leitão, The Arbutus berry: studies on its color and chemical characteristics at two mature stages. Journal of Food Composition and Analysis, 14 (2001) 27–35. [4] E. A. González, A. T. Agrasar, L. M. Pastrana- Castro, I.O. Fernández and N. P. Guerra, Solid-state fermentation of red raspberry (Rubus ideaus L.) and arbutus berry (Arbutus unedo, L.) and characterization of their distillates. Food Research International 44 (2011) 1419–1426.

271

The determination of some toxic elements in the surface water samples in the vicinity of Copper Mining and Smelting Complex Bor

M. Steharnik1, S. Stankovic1, S. Serbula2, T. Kalinovic2, A. Ilic2 and J. Kalinovic2

1Mining and Metallurgy Institute of Bor, Department of Chemical Investigations, 19210 Bor, Serbia 2Technical Faculty Bor, University of Belgrade, V.J. 12, 19210 Bor, Serbia

E-mail: [email protected] P3-36 This paper presents the results of chemical analysis of the following toxic elements Fe, Cu, Cd, Cr, Ni, Pb, Zn, As and Se in surface water samples. The water samples were taken in the vicinity of Copper Mining and Smelting Complex Bor. After identifying and locating the critical flows in the vicinity of the Copper Mining and Smelting Complex Bor, which represent the main source of water pollution in this area, the representative samples of about 1 L of surface water were taken in cleane plastic bottles. In accordance with ISO 5667 standards for water sampling, surface water samples were collected four times from the following locations: underground mining water near Zmajevo, Valja Lutarica River, Bor River, Bor River and Krivelj River together and Ravna River. All the samples were collected at considerable distances from the outlets of the industries after waste water had mixed with contaminated or less contaminated surface water. All determinations were performed by simultaneous inductively coupled plasma atomic emission spectrometer produced by Spectro model Ciros Vision (Germany) and an appropriate Smart Analyser Vision software package were used for controlling of all measurements and investigations. In present investigations the most sensitive and recommended wavelengths [1] for all analysed elements were selected. The optimal experimental parameters were applied as compromise for multi-element analysis. The results of chemical analysis are indicated that contents of copper, zinc, iron and nickel are significantly higher compared to permissible limits for water of class IV quality for the underground mining water near Zmajevo, Bor River and Bor River and Krivelj River together. Thus, the surface water from these locations cannot be classified neither as class IV quality and presents the water with high levels of potentially toxic elements, while all of the investigated parameters are within maximum permissible limits for the surface water of class IV quality from the locations of Valja Lutarica and Ravna River. According to presented results, it can be concluded that the influence of activity of Copper Mining and Smelting Complex Bor on surface water in the vicinity of Bor town on selected locations is great, especially on Bor River.

References [1] R. K. Winge, V. A. Fassel, V. J. Peterson, M. A. Floyd, Inductively coupled plasma atomic emission spectroscopy-An atlas of spectral information, Prominent lines emitted by AES-ICP, Appendix B, Elsevier science publishers B. V. 1985.

Acknowledgements This research was supported by the project No. 46010 funded by the Ministry of Science and Technological Development of the Republic of Serbia.

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The maturation of Cretan graviera cheese as monitored by high resolution NMR spectroscopy and low field NMR relaxometry/diffusometry

E. Ralli1, O.V. Petrov2, C. Mattea2, B. Gizatullin2, S. Stapf2 and A. Spyros1

1NMR Laboratory, Department of Chemistry, University of Crete, 70013 Heraklion Crete, Greece 2FG Technische Physik II/Polymerphysik, Technische Universität Ilmenau, D-98684 Ilmenau, Germany

E-mail: [email protected], [email protected] P3-37

High resolution NMR spectroscopy is an important analytical methodology for the metabolite and lipid profiling of cheese, while low field NMR relaxometry and diffusometry, including fast field cycling (FFC) relaxometry, represent a powerful set of tools that provides information on the fat/water distribution and diffusion dynamics of different components of cheese [1]. In the present report, we provide the initial results of an ongoing project that involves the detailed study of Cretan graviera maturation for two years, using NMR spectroscopy and relaxometry. The metabolite and lipid profile changes during maturation are monitored by analytical NMR spectroscopy, while the evolution of the T1, T2 relaxation times and the diffusion coefficients D for the water and fat components of the cheese by NMR relaxometry will also be reported. Possible correlations between chemical composition and the distribution/diffusion dynamics of different cheese components as the process of maturation transforms the raw graviera cheese into a finished, ready to consume product will be highlighted. Tyramine Tyramine

t=1.7 months

t=0.7 months

Phenylalanine Tyrosine Tyrosine

t=0 months

1H NMR spectra of the aromatic region of polar extracts of graviera cheese during the initial stages of maturation. A representative 2D T1/T2 relaxation time map is presented as an inset.

References [1] A. Spyros, P. Dais, NMR spectroscopy in food analysis, RSC Publishing, Cambridge UK, Chapter 10 (2013) 280-294.

273

Analytical methods as a tool for the evaluation of microalgae drying process

S. Papadaki, M. Stramarkou and M. Krokida

School of Chemical Engineering, National Technical University of Athens, Greece

E-mail: [email protected]

Commercially cultivated microalgae represent a mature and sophisticated industry. Their P3-38 efficacy in utilizing sunlight and nutrients, their adaptability to non-arable lands, as well as their high content in high-value compounds, favor the cultivation of microalgae for both food and non-food based applications [1]. Food, chemical and pharmaceutical industries investigate their potential [2]. Among the different microalgae strains, the diatom Phaeodactylum tricornutum (PT) is a very interesting and has high commercial potential. It exhibits a high content in natural bioactive compounds, such as carotenoids and chlorophylls, which show a considerable antioxidant activity [3]. When the use of Phaeodactylum tricornutum is destined for food or pharmaceutical purposes, the preservation of the alga is needed. The most obvious solution hereto is the drying of the PT biomass, which ensures not only the reduction of its weight and volume, but also the minimization of microorganisms [3]. Drying affects drastically the qualitative characteristics of the dried biomass, and more specifically its antioxidant activity and bioactive content. Therefore, the evaluation of these characteristics using analytical methods is crucial. In the present Work, three widely used drying techniques were implemented in PT biomass: freeze drying, vacuum drying and solar drying. HPLC (high-pressure liquid chromatography) protocols were developed for qualitative and quantitative evaluation of PT bioactive content, focusing on pigments such as carotenoids and chlorophylls, as a decision making tool for the selection of the optimum drying procedure. In addition, the antioxidant activity was determined using phasmatophotometric techniques, and especially the DPPH method. According to the obtained results, vacuum drying at 50oC showed the best performance and a kinetic model of the bioactive content was developed using analytical techniques.

Acknowledgments This research was financially supported by the ΙΚΥ FELLOWSHIPS OF EXCELLENCE FOR POSTGRADUATE STUDIES IN GREECE – SIEMENS PROGRAM 2016-2017.

References [1] C. E. C. C. Ejike, S. A. Collins, N. Balasuriya, A. K. Swanson, B. Mason, and C. C. Udenigwe, “Prospects of microalgae proteins in producing peptide-based functional foods for promoting cardiovascular health,” Trends in Food Science and Technology, vol. 59. pp. 30–36, 2017. [2] M. Vigani, C. Parisi, E. Rodríguez-Cerezo, M. J. Barbosa, L. Sijtsma, M. Ploeg, and C. Enzing, “Food and feed products from micro-algae: Market opportunities and challenges for the EU,” Trends Food Sci. Technol., vol. 42, no. 1, pp. 81–92, 2015. [3] E. Ryckebosch, K. Muylaert, M. Eeckhout, T. Ruyssen, and I. Foubert, “Influence of drying and storage on lipid and carotenoid stability of the Microalga Phaeodactylum tricornutum,” J. Agric. Food Chem., vol. 59, no. 20, pp. 11063–11069, 2011.

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Encapsulation of β-carotene in food grade nanofibers by coaxial electrospinning

C. Drosou1, M. Krokida1, C. Biliaderis2

1Laboratory of Process Analysis and Design, School of Chemical Engineering, National Technical University of Athens, 9 Iroon Polytechneiou St. Zografou Campus, Athens, 15780, Greece. Tel.:+30 210 772 3149 2Laboratoty of Food Chemistry and Biochemistry, Department of Food Science and Technology, School of Agriculture, Aristotle University of Thessaloniki, P.O. Box 235, Thessaloniki, 541 24, Greece

E-mail: [email protected] P3-39

Electrospinning process is an emerging encapsulation technique, which has been used to obtain submicron encapsulates for both hydrophilic and hydrophobic bioactive compounds. Electrospinning process makes use of high voltage electric fields to produce electrically charged jets from viscoelastic polymer solutions which on drying, by evaporation of the solvent, produce ultrathin polymeric fibers [1]. Alternatively to the most common microencapsulation technique (spray- drying), electrospinning process do not require the use of a heated air stream, which avoids the deterioration of thermo- and oxygen-sensitive bioactive compound [2]. Moreover, in the coaxial methodology, the polymer and the core material are introduced into the electrospinning equipment from separated solutions; thus, the component immiscibility problem is alleviated [3]. In this work, novel ultrathin electrospun fibers from different blends of whey protein isolate (WPI) and the carbohydrate polymer pullulan have been developed and characterized. The polymers were blended at different proportions (30:70, 50:50, and 70:30 w/w) of WPI and pullulan in order to study the effect of different blends in fiber diameter and morphology. The presence of pullulan in the blends resulted in increased viscosity and lower conductivity of the solutions, related to a better chain entanglement, a factor needed for fiber formation. The blends with greater pullulan content result in defect-free smooth electrospun fibers and were selected for the encapsulation of b- carotene through coaxial electrospinning. The effect of processing parameters, such as flow rate of core and wall material, applied voltage and tip-to- collector distance, on the encapsulation efficiency of b- carotene was investigated. The results showed that the flow rate of b- carotene solution has much greater impact on the encapsulation efficiency compared to the other processing parameters (ranging from 71.95% ± 3.84 to 89.92% ± 0.93). Furthermore, the diameter and morphology, changes in molecular order and thermal stability of electrospun fibers were tested by SEM, ATR-FTIR and DSC, respectively.

References [1] C. Drosou, M. Krokida and C. Biliaderis, Drying Technology, 35(2) (2017), 139-162. [2] R. Pérez-Masiá, J.M. Lagaron, A. Lopez-Rubio, Food and Bioprocess Technology, 8(2) (2014), 459–470. [3] Z.C. Yao, M.W. Chang, Z. Ahmad and Li J.S., Journal of Food Engineering, 191 (2016), 115-123.

275

Optical gas sensing based on the photolumiscence of ZnO-PDMS nanohybrids

A. Klini1, S. Pissadakis1, R.N. Das2,3, E.P. Giannelis3, S.H. Anastasiadis1,4, and D. Anglos1,4

1Institute of Electronic Structure and Laser, Foundation for Research and Technology-Hellas, (IESL- FORTH) P.O. Box 1385, GR 71110 Heraklion, Crete, Greece 2Massachusetts Institute of Technology, Lincoln Lab. 244 Wood Street, Lexington, MA, USA 02421, USA 3Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, USA P3-40 4Department of Chemistry, University of Crete, P.O. Box 2208, GR 71003 Heraklion, Crete, Greece

Email: [email protected]

ZnO-PDMS nanohybrids, composed of luminescent ZnO nanoparticles dispersed in an inert polydimethylsiloxane (PDMS) matrix, exhibit an excellent ability to follow changes of their surrounding atmosphere (e.g. Ethanol, oxygen), through monitoring the modifications of their UV photoluminenscence (PL) emission at room temperature [1]. The performance of this new optical sensing platform as regards its sensitivity, repeatability and response at different excitation parameters (e.g. intensity, wavelength) has been systematically examined and discussed.

Air Ethanol

380 400 420 440 460 480 Wavelength (nm) 500 nm

[1] A. Klini, S. Pissadakis, R.N. Das, E.P. Giannelis, S.H. Anastasiadis, D. Anglos, J. Phys. Chem. C 119 (2015), 623-631.

276 10th International Conference on Instrumental Methods of

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Utilization of tomato by-products for the production of functional products and bioactive ingredients

A. Yfanti 1, P. Eleni1, M. Krokida1 and D. Bilalis2

1School of Chemical Engineering, National Technical University of Athens, Athens, Greece 2Agricultural University of Athens, Athens, Greece

E-mail: [email protected]

Large amount of processed and fresh tomatoes is widely consumed all over the world. Thus, P3-41 significant quantities of tomato processing by – products are produced every year. Industrial tomato processing by-products are mainly consisting of pulp, skins, seeds and matured tomatoes [1]. These by - products have been proven as rich sources of important nutrients containing several phytochemicals, such as lycopene, carotenoids and polyphenol compounds, which may have beneficial health effects [1, 2]. The goal of this study was the holistic approach for the valorisation of tomato by – products. Specifically, lycopene was recovered from tomato peels and seeds and pulp was fermented for the production of tomato origin vinegar. For the recovery of lycopene, microwave and ultrasound assisted extraction was applied using different solvents. Since vinegar production is a two-step process, the remaining pulp was at first fermented by yeast Saccharomyces cerevisiae and then fermented by acetic acid bacteria in various concentrations. HPLC-DAD analysis at 476 nm, was applied in order to quantitatively and qualitatively characterize the lycopene in the extracts and the produced vinegar. To access the biochemical composition of the produced vinegar, samples were subjected to analyse for pH, total soluble solids and total acidity. Microwave and ultrasound assisted extraction methods present high yields of lycopene content as indicated from HPLC graphs. Moreover, high amounts of lycopene were also determined in tomato vinegar.

References [1] J. Lee, H. Cho, J. Jeong, M. Lee, Y. Jeong, K. Shim and K. Seo, Food Chemistry, 141 (2013), 3241 – 3249. [2] A. Stewart, S. Bozonnet, W Mullen, G. Jenkins, M. Lean and A. Crozier, J. Agric. Food Chem., 48 (2000), 2663–2669.

277

Design and synthesis of ferrocene derivatives. Determination by UV- Vis to divalent metal ions.

N. Agurto1, C. Silva1, F. Godoy1 and A. Oliver2

1Facultad de Química y Biología, Universidad de Santiago de Chile. 2University of Notre Dame, United States

E-mail: [email protected]

P3-42 Cyclopentadienyl functionalized metal complexes substituted with a crown ether moiety, have been of great interest due to their applications as redox- responsive chemosensors. It has been demonstrated that this kind of complexes can be used in molecular recognition and host-guest interaction processes.[1] 5 5 5 The complexes (η -C5H4COCH=CH-C6H4CH=N-benzo-15-Crown-5)Fe(η -C5H5) (2) and (η - 5 C5H4CH=CH-C6H4CH=N-benzo-15-Crown-5)Fe(η -C5H5) (3) were synthesized and characterized by FT-IR, 1H and 13C NMR spectroscopies, and mass spectrometry. Furthermore, the stereochemistry for olefin and imine groups were confirmed by coupling 3 constant value ( JHH) and 2D NMR (HMBC and HSQC), which indicated that these both complexes have the E,E configuration.

The systems were studied by UV-Vis using perchlorate of copper and calcium determining stoichiometry and thermodynamic Parameters (Ka). The results obtained evidenced the importance in the synthetic design, which affect the affinity for the cations studied.

References [1] N. Agurto, T. Maldonado, F. Godoy, A. Gómez, C. Silva, J. Pavez, G. Ferraudi, A. Oliver, A. Lappin, Journal of Organometallic Chemistry, 827 (2017) 32-40.

278 10th International Conference on Instrumental Methods of

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Investigating the effect of Zn/Fe-LDH ratio on antimony adsorption

E. Kokkinos, S. Tresintsi, E. Tsafou and M. Mitrakas

Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124, Thessaloniki, Greece

E-mail: [email protected]

Considering antimony as a priority pollutant of drinking water, due to its high toxicity, it has been given one of the lowest regulation limits (5 μg Sb/L), according to international organizations [1]. In natural waters coexists in two forms, the pentavalent and the ten times P3-43 more toxic trivalent. However, it is essential to be established a technology that can remove both Sb(III) and Sb(V). The methods, able to provide residual concentrations below this limit, are ion exchange and adsorption. Layered double hydroxides (LDH) are composed of positively charged sheets and negatively charged anions in the hydrated interlayer regions which can operate both removal mechanisms. Their general formula is II III x+ n- . II III n- [M 1-xM x(OH)2] (A )x/n mH2O, where M is a divalent and M is a trivalent cation. A denotes exchangeable interlayer anion with negative charge n, m is the number of interlayer water and x is defined as the MIII/(MII+MIII) ratio [2]. The aim of this study is the synthesis of ZnII/FeIII LDH adsorbents, using different x ratio (0.2 and 0.4). As an interlayer anion is applied carbonate since it is proved to show higher performance compared with other such as chloride and nitrate [3]. The adsorbents were synthesized at a continuous flow two stage reactor for better parameters monitoring (pH 9.5 and 50 oC). Primary nucleus were left under stirring and heating for 24 h, benefiting from growth. Collected nanoparticles dried under malt temperature and sieved (<63nm) in order to be tested for antimony adsorption. Evaluation was made according to their capacity at regulation limit (Q5) using a natural like water (NSF). Isotherms’ initial antimony concentration was 1 mg Sb(III)/L and 0.5 mg Sb(V)/L, while adsorbent dosage in the range 100-400 mg/L.

Table1. Physicochemical characteristics and capacities of Zn/Fe LDH at different x ratio. Positive charge Q Sb(III) Q Sb(V) x % Zn % Fe % CO -2 BET (m2/g) pH 5 5 3 pzc (mmol OH-/g) (mg/g) (mg/g) 0.2 48.5 12.3 11.4 124.8 7.5 1.95 0.94 0.83 0.4 51.8 8 8.6 134.7 7.3 1.34 0.70 0.50

Appling isotherms data to Freundlich’s model, the calculated capacities were higher for the LDH with the lower x ratio (Table 1). This was attributed to the increase of % Fe content against Zn which results higher positive surface charge density, while surface area remains almost stable. Their Q5 values showed variations according to the different Sb(III) and Sb(V) molecule size. Especially, in natural water, Sb(V) is more likely to interact with the positive - surface, since it forms the negative charged complexes Sb(OH)6 instead of Sb(III) which forms the stable Sb(OH)3.

References [1] SAC, Standards for Drinking Water Quality, 2006. [2] H. Lu, Z. Zhu, H. Zhang, J. Zhu and Y. Qiu, Chemical Engineering Journal 276 (2015) 365-375. [3] K.M. Parida and L. Mohapatra, Chemical Engineering Journal 179 (2012) 131-139.

279

Cavity-Based methods for precise, real-time refractive index measurements

A.K. Spiliotis1,2, D. Sofikitis1, G.E. Katsoprinakis1 and P.T.Rakitzis1,2

1IESL-FORTH, N. Plastira 100, 71110, Heraklion, Crete, Greece 2Department of Physics, University of Crete, 71003, Heraklion, Crete, Greece

Email: [email protected]

Measuring the index of refraction of liquid, gas and solid substances is important for various P3-44 scientific and industrial fields, including semiconductors science, analytical chemistry and medicine. Ellipsometry is the most widely used technique for the measurement of the refractive index. However, this 100-year old technique has severe limitations related to time resolution (close to 1 s for high accuracy measurements (10−3°) and can reach the millisecond range with reduced accuracy. The combination of ellipsometry with cavity techniques, demonstrated in [1] allows much higher sensitivity and/or time resolution. The ellipsometric phase shift is enhanced by the number of passes and is imprinted in the frequency of a beating superimposed on a normal CRD signal. This phase shift is directly related to the refractive index of the sample. Eversince, Cavity Ring-Down Ellipsometry (CRDE) has been used to measure the adsorption of gases [1], and liquids and surfaces [2], probing via the evanescent wave formed at the interface between the sample and a total internal reflection (TIR) prism.

Figure 3 a) Detection of nm-sized dielectric layers b) Real-time monitoring of droplet spreading.

An example of the sensitivity achieved (~6*10-3 o) with CRDE is shown in Fig.1.a, where we see the real-time observation of the creation of nm-sized dielectric layers [3] created by layer- by-layer deposition. In the inlet we see the modification of the beating frequency each time a different electrolyte or brine is inserted on the interface. After such a succession the beating frequency reduces by a certain amount, indicating the creation of a new dielectric layer. An example of the time resolution accessible with CRDE is given via a wetting experiment [4] which results are shown in Fig.1.b. In the upper part we see the CRDE signals, as well as their corresponding Fourier transforms before, during and after wetting the upper surface of the TIR prism. In the lower part we see the evolution of the beating frequency during the wetting process. Note that the time resolution is 2 μs for a sensitivity of ~2.6*10-2 o. These are, to our knowledge, the fastest running ellipsometric measurements to date. Coupling this technique to monitoring techniques such as HPLC can produce fast and accurate instruments for the measurement of liquid samples.

References [1] Karaiskou et al., The Journal of Chemical Physics 131, 121101 (2009); doi: 10.1063/1.3236819 [2] Everest et al., Evanescent-Wave Cavity Ring-Down Ellipsometry, J. Phys. Chem. Lett. 2011, 2, 1324–1327 [3] Sofikitis et al., Sensitivity enhancement for evanescent-wave sensing using cavity-ring-down ellipsometry, Opt. Let., Vol. 38, No. 8, 2013 [4] Sofikitis et al., Microsecond-resolved SDR-based cavity ring down ellipsometry, Appl. Opt., Vol. 54, No. 18, 2015

280 10th International Conference on Instrumental Methods of

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Gadolinium-Schiff base complex modified CdTe quantum dots as a sensor of cell membrane damage quantified by capillary electrophoresis

L. Nejdl1,2, A. Moulick1,2, M. Vaculovicova1,2, T. Vaneckova1, K. Smerkova1, V. Adam1 and M. Vaculovicova1,2

1Department of Chemistry and Biochemistry, Mendel University in Brno, Zemedelska 1, CZ-613 00 Brno, Czech Republic 2Central European Institute of Technology, Brno University of Technology, Purkynova 123, CZ-612 00 Brno, Czech Republic P3-45

E-mail: [email protected]

Biological membranes play a pivotal role in various cellular processes as they control the flux of metabolites between the cytoplasm and cellular organelles, and mitochondrial and chloroplast thylakoid membranes are indispensable for the energy supply of most cells [1]. Despite their indispensability, there is still a lack of methods that allow simple real-time visualization of cellular membrane damage. Gadolinium-Schiff base complex modified CdTe quantum dots (GdQDs) are hybrid nanostructures possessing a diameter of 11±2 nm with good colloidal stability (zeta potential = -43.6±0.13 mV) and bright red fluorescence (λem = 630 nm) with quantum yield of 40.5%. Here, we show that these GdQDs can be used as fluorescence sensor of cellular membrane damage. The GdQDs preferentially interacted with Na(+)/H(+) exchange regulatory cofactors localized on endomembrane systems and nuclear membranes. These specific binding properties of GdQDs can be used for quantification of total cell membrane damage. This work describes ShortSweepCE method with laser-induced fluorescence detection using the GdQDs for this purpose. Our capillary electrophoretic (CE) method can monitor and evaluate the cell damage caused by variety of factors (mechanic, physical and chemical). Prostate cancer cell cells (PC3) in comparison with healthy prostate cells (PNT1) were used for testing of the developed CE method.

References 1. Licausi F, Kosmacz M, Weits DA, Giuntoli B, Giorgi FM, et al. (2011) Oxygen sensing in plants is mediated by an N-end rule pathway for protein destabilization. Nature 479: 419-422.

Acknowledgement The study was financially supported by Grant agency of Czech Republic No.16-23647Y.

281

Rheological, physical and sensory characteristics of low fat and low sugar chocolates formulated with Stevia rebaudiana Bertoni extract as natural sweetener

V. Oikonomopoulou, I. Argyriou, C. Drosou and M. Krokida

School of Chemical Engineering, National Technical University of Athens, 9 Iroon Polytechneiou St., 15780, Zografou Campus, Athens, Greece

E-mail: [email protected] P3-46 Obesity and various health problems associated with the metabolic syndrome (diabetes, cardiovascular disease, blood pressure) turn consumers to alternative healthy dietary choices characterized by reduced sugar and fat content. In addition, the increased consumer demand for functional foods leads food industry to the development of products with high nutritional value and multiple benefits to the human body. Chocolate is a high energy product and is one of the most popular snacks. The replacement of sucrose with low calorie sweeteners is a new trend in the chocolate industry while a major challenge is the reduction of fat due to its contribution to mouthfeel and melting properties of chocolate. The objective of this work was the development of low-fat, low-sugar functional milk chocolate products containing bioactive substances (β-carotene). β-carotene was encapsulated in natural matrices using spray drying technique and was mixed with cocoa. Cocoa butter (CB) in milk chocolate was substituted to an extent of 40% with whey protein (WP) and inulin (IN) mixture at a ratio of 50:50. Sucrose was substituted with steviol glucosides at a proportion of 50 and 100%. Standard reference chocolate without fat and sugar substitution was developed and the effects of steviol ingredients and WP/IN addition on the rheological, physical and sensory properties were investigated. Structure of spray dried formulations was evaluated with Scanning Electron Microscopy (SEM), while antioxidant activity was measured with DPPH method. Moisture content of chocolate samples was determined in vacuum oven, whereas protein and fat content was determined using the Kjeldahl method and gravimetrically with microwave assisted extraction, respectively. Rheological properties, hardness and colour were also evaluated. The acceptance of chocolate formulations was estimated by sensory evaluation. Low-sugar chocolates presented similar rheological behaviour compared to the reference chocolate. Fat replacement with WP/IN led to increased Casson viscosity. Formulated chocolates containing steviol glucosides and bioactive compounds exhibited high antioxidant activity. In addition, they presented good sensory properties (mouthfeel, sweetness), that coincide with the experimental conclusions. These data indicate that it is possible to formulate low sugar and low fat chocolate products containing bioactive compounds, using steviol glucosides as natural sweeteners, without affecting their physicochemical and sensory properties.

Acknowledgements The work was funded by “IKY FELLOWSHIPS OF EXCELLENCE FOR POSTGRADUATE STUDIES IN GREECE – SIEMENS PROGRAM”.

282 10th International Conference on Instrumental Methods of

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Synthesis and characterization of Layered Double Hydroxides for arsenic adsorption from drinking water

S. Tresintsi1, E. Kokkinos1, K. Simeonidis2, M. Mitrakas1 and G. Kyriakou1

1Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124 Greece 2Department of Physics, Aristotle University of Thessaloniki, 54124 Greece

E-mail: [email protected]

In the recent years new nanomaterials called Layered Double Hydroxides (LDHs) are used in a big range of applications such as adsorbents [1], catalysis [2] and drug delivery [3]. The P3-47 formation of LDH occurs when some of M+2 cations are substituted by M+3 cations causing a positive charge excess which favors building up of the LDH structure. The release of such positive charge is the key factor that makes the LDH able to intercalate and exchange the different organic and inorganic anions. LDHs can be described by the general formula: [M1- 2+ 3+ x+ n- x Mx (OH)2] [A ]x/n∙mH2O. This study examines the preparation and characterization of LDH adsorbents as well as their ability to remove As(V) and As(III) from drinking water, below the regulation limit of 10 μg/L. Various LDH adsorbents were synthesized using the co-precipitation method from Mg, Zn, Fe, Al, and Cu salts. The composition, crystal structure and surface properties of the samples were determined by a number of characterization techniques. Chemical analysis on the produced LDHs, focused on the determination of metal percentages, was carried out after dissolving the samples in HCl, by flame atomic absorption. The crystalline structure of the prepared LDHs was identified by X-ray diffractometry (XRD) using a water-cooled Rigaku Ultima diffractometer with CuKa radiation. Surface area and porosity of the adsorbents were estimated by nitrogen gas adsorption at liquid N2 temperature (77 K) using a micropore surface area analyzer according to Brunauer-Emmett-Teller (BET) model. The isoelectric point (IEP), the point of zero charge (PZC) and the surface charge density were determined in water dispersions of LDH solid by the zeta potential curve at 20 oC and the potentiometric mass titration method. To evaluate the adsorption efficiency of the produced LDHs, arsenic adsorption experiments were carried out in batch systems to obtain adsorption isotherms. The evaluation of the produced LDHs as arsenic adsorbents was focused on their ability to decrease residual arsenic concentration below the regulation limit of 10 mg/L. As(III) and As(V) test solutions were prepared in NSF water in order to study the actual adsorption capacity in the presence of ions in concentrations usually met in natural waters. The maximum Q10 (18 μg/mg for equilibrium pH 7.5) for As(V) was observed for the adsorbent synthesized using Zn(NO3)2∙6H2O and +2 +3 Fe(NO3)3∙9H2O with M / M ratio 5/1.

S. Tresintsi acknowledges financial support from IKY Fellowships of Excellence for Postgraduate Studies in Greece - Siemens Program.

References [1] H. Lu, Z. Zhu, H. Zhang, J. Zhu and Y. Qiu, Chemical Engineering Journal, 276 (2015) 365-375. [2] A. Ryzhikova, V. Huleaa, D. Tichit, C. Leroib, D. Anglerotb, B. Coqa and Ph. Trens, Applied Catalysis A, 397(2011) 218-224. [3] Y. Wong, K. Markham, Z.P. Xu, M. Chen, G.Q.M. Lu, P.F. Bartlett and H.M. Cooper, Biomaterials, 31 (2010) 8770-8779.

283

Optimization of Se(IV) / Se(VI) determination by GFAAS in natural waters

K. Kalaitzidou, N. Tsiftsakis, E. Kaprara and M. Mitrakas

Department of Chemical Engineering, Aristotle University of Thessaloniki, 54124, Thessaloniki Greece

E-mail: [email protected]

Drinking water regulation limit for total selenium is currently 10μg/L (ppb), with a significant P3-48 potential to get lower in the near future. Selenium is commonly present in natural waters as Se(IV) or Se(VI), thus it is highly important that its determination method to be accurate and precise independently of selenium speciation in water. Graphite furnace atomic absorption spectroscopy (GFAAS) is a friendly method for total selenium determination providing, in addition, a detection limit close to 1 μg/L. However, due to its low analytical wavelength (196.0 nm) selenium analysis by GFAAS is particularly susceptible to interferences [1]. Moreover, selenium is volatile in most of its forms, causing losses during the “preparation step” before atomization. The aforementioned reasons indicate a necessity to eliminate the background influence by palladium matrix modifier addition during selenium determination by GFAAS. The effect of ashing and atomizing temperatures, hold time, sample and diluent volume, as well as the nature and concentration of chemical modifier were investigated using a Perkin Elmer AAnalyst 800 instrument, in order to estimate the optimized conditions required for Se (IV) and Se (VI) determination in water samples. The optimal ashing and atomizing temperatures were 950 oC at hold time 20 sec and 2100 oC at 3 sec respectively, while sample and diluent volume were 30 μL and 5 μL. The examination of Ca(NO3)2 and Mg(NO3)2 influence as chemical modifiers, showed that the optimum selenium determination was achieved by adding 3 μL of palladium (1000 mg/L) and 3 μL of a mixture of Ca(NO3)2 and (Mg(NO3)2 solution of concentrations of 600 mg/L and 400 mg/L, respectively. Standard solutions 1000 mg/L Se (IV) and Se (VI) were prepared by dilution of the appropriate quantities of Na2SeO3 and Na2SeO4, respectively, while natural test (NSF) water matrix was used for all selenium samples. For the GFAAS measurements, working standards of 20, 50 and 100 μg/L Se (IV) and Se (VI) were prepared by dilution of standard solutions. The optimized equation of calibration curve for selenium species were as follows: Yabs=0.0023XSe(IV)+0.0026 and Yabs=0.0025XSe(VI)+0.0039. This result reveals a “mild” influence of valence on total selenium determination (Figure 1).

Figure 1. Calibration curves for Se(IV) and Se(VI) using the GFAAS in natural water matrix.

References [1] U.S. EPA. Selected Analytical Methods for Environmental Remediation and Recovery (SAM), (1998).

284 10th International Conference on Instrumental Methods of

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Phenolics profiling in extra-virgin olive oil, olive leaves, and olive mill waste water by NMR spectroscopy

E. Manolopoulou1, S. Tachtalidou1, E. Beleli1, A.M. Gómez-Caravaca2,3, A. Segura-Carretero2,3 and A. Spyros1

1NMR Laboratory, Department of Chemistry, University of Crete, 70013 Heraklion Crete, Greece 2Department of Analytical Chemistry, Faculty of Sciences, University of Granada, Granada, Spain 3 Research and Development Centre for Functional Food (CIDAF), Health-Science Technological Park, Granada, Spain P3-49 E-mail: [email protected]

The olive tree is of great economic and social importance in the Mediterranean, and for countries such as Italy, Greece and Spain its cultivation constitutes one of the main agricultural activities and revenue sources. Extra virgin olive oil is known for its excellent organoleptic properties and health benefits as a source of natural antioxidants present in its phenolic fraction [1]. Phenolics and other bioactive compounds are also present in high amounts in olive leaves and other by-products of the olive oil production, such as olive mill waste water (OMWW). Phenolics extracted from such sources could be used in food fortification, functional food products, medicine and cosmetics. In this report we present the development and application of analytical methodologies for the profiling and the determination of phenolic compounds in a variety of matrices, including olive oil, olive leaf extracts and OMWW using high resolution 1H NMR spectroscopy.

Oleuropein Olive leaf

Tyrosol

Olive mill waste water

Oleacein & Tyrosol Olive oil Oleocanthal Hydroxytyrosol

Aromatic region of the 1H NMR spectra in MeOD of olive oil, olive mill waste water and olive leaf extracts, indicating the main phenolic components identified.

References [1] A. Bendini, L. Cerretani, A. Carrasco-Pancorbo, A.M. Gó mez-Caravaca, A. Segura-Carretero, A. Fernández-Gutiérrez, G. Lercker, Molecules. 12 (2007) 1679−1719.

285

Studies on reproducibility of isolation of pure ashalthene fraction and its properties for separation techniques

G. Boczkaj, M. Plata-Gryl, M. Momotko

Gdansk University of Technology, Chemical Faculty, Department of Chemical and Process Engineering, Gdansk, Poland

E-mail: [email protected]

Asphaltenes are a group of substances occurring in petroleum products and characterized by P3-50 their physicochemical properties. They are an interesting group of chemical species, which can be used as stationary phases for gas chromatography [1]. The unique properties of asphaltenes can be useful also for other separation techniques. Due to their origin, a crucial stage of their production is the isolation from the primary material. This paper presents a results of studies on development of procedure allowing to obtain a high purity asphaltenes having reproducible sorptive properties. The new procedure uses 1:40 feedstock to solvent (n-heptane) ratio, filtration through cellulosic thimble and extensive washing in a Soxhlet type extractor. Group type composition and purity of the asphaltene fractions have been examined using thin-layer chromatography with flame-ionization detection. This study revealed that the new procedure provides a higher purity of asphaltene fraction but also allowing to more accurate determine their content in bitumens when comparing to the standard test method. Moreover, an attempt of evaluation of the scale-up possibility of the proposed and standard test methods was made, revealing that new procedure is more scalable than standard test methods. It is possible to obtain large quantities of a high purity asphaltene fraction even on a process scale, having reproducible sorptive properties. This feature is crucial for technical analytics, researchers studying asphaltenes characteristic as well as for other novel applications of asphaltenes such as its use as sorbents in separation techniques.

Acknowledgements The authors gratefully acknowledge the financial support from the National Center for Research and Development, Warsaw, Poland – Project LIDER, no. LIDER/036/573/L-5/13/NCBR/2014.

References [1] G. Boczkaj, M. Momotko, D. Chruszczyk, A. Przyjazny, M. Kamiński, J. Sep. Sci. 39 (2016), 2527- 2536

286 10th International Conference on Instrumental Methods of

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Selectivity tunning of aspalthene based sorbents by means of chemical modification

M. Momotko1, M. Plata-Gryl1, S. Makowiec2, G. Boczkaj1

1Gdansk University of Technology, Faculty of Chemistry, Department of Chemical and Process Engineering, Gdansk, Poland 2Gdansk University of Technology, Faculty of Chemistry, Department of Organic Chemistry, Gdansk, Poland

E-mail: [email protected] P3-51

This paper concerns research on the use of asphaltene fraction isolated from vacuum distillation residuum and bitumen as sorbents for separation techniques, especially as stationary phases for gas chromatography [1]. We compared the selectivity of the sorbents produced using a developed in our research group standardized method of isolation of pure asphaltenes fraction as well as asphaltenes modified by chemical reactions. The selectivity of obtained sorbents was evaluated using more than 50 volatile organic compounds. Retention indices were compared for the analyzed standards of studied stationary phases with the retention indices obtained for commercial stationary phases, which allowed to determine the McReynolds'a constants and to position the developed stationary phase in a series of selectivity of the current production phases. These studies revealed a high potential of developed sorbents which exhibit very high selectivity for selected groups of VOC - in particular pyridine and its derivatives.

Acknowledgements The authors gratefully acknowledge the financial support from the National Center for Research and Development, Warsaw, Poland – Project LIDER, no. LIDER/036/573/L-5/13/NCBR/2014.

References [1] G. Boczkaj, M. Momotko, D. Chruszczyk, A. Przyjazny, M. Kamiński, J. Sep. Sci. 39 (2016), 2527- 2536

287

Synthesis of the silver nanoparticles stabilized by bovine serum albumin and investigation of their electrochemical properties

Ye. Khristunova1,3, E. Korotkova1, J. Barek2 and B. Kratochvíl3

1National Research Tomsk Polytechnic University, Institute of Natural Resources, Lenina avenue, 30, 634050, Tomsk, Russia 2Charles University in Prague, Faculty of Science, Department of Analytical Chemistry, UNESCO Laboratory of Environmental Electrochemistry, Albertov 6, CZ-12843 Prague 2, Czech Republic 3Department of Solid State Chemistry, Institute of Chemical Technology Prague, Technická 5, 166 28 Prague 6, Czech Republic P3-52 E-mail: [email protected]

The main idea of this work is create the electrochemical immunosensor where silver nanoparticles (SNP’s) will be as labels that specifically bind to, and enable identification of, target biological material. Bovine serum albumin (BSA) was used to provide for additional SNP’s stabilization and to block excess SNP’s that may potentially take part in non-specific bindings with non-target proteins. In the initial research stage, spherically shaped SNP’s were synthesized [1]. After synthesis absorption spectra were recorded with the maximum at 395- 400nm which is in accordance with the average SNP’s size of 15±2 nm and the TEM analysis data. The obtained SNP’s stabilized by BSA (16 µg/ml) were researched by TEM and UV/VIS analysis, the average size was 25±2 nm and was observed the shifting of the absorption maximum into a longer-wave range (400–405 nm). The NP’s size is increased and the protein is acting as a stabilizer (a semi-transparent "coat"). Specific attention in the work was paid to making the calibration dependence from silver ions in AgNO3 and then determination of the silver ions in SNP’s solution. Anodic stripping voltammetry was used to study the electrochemical properties of silver nanoparticles (SNP’s) stabilized by BSA in buffered solution. The big advantages of this method are sensitivity, simplicity, quickness, availability of the equipment. All measurements were conducted in three-electrode cell system equipped with glassy carbon electrode (GCE) as a working electrode, silver/silver chloride (Ag|AgCl|KCl(sat.)) as a reference and platinum wire as an auxiliary electrode. The optimal conditions for quantitative determination were obtained in Britton–Robinson buffer at pH 4.1 with the scan rate 0.05 V s-1.The calibration curves of silver nitrate are linear within the range of concentration: 0.054 − 0.48 μg mL-1 for Ag+. Good linear behavior over the investigated concentration ranges were observed with the values of r2 higher than 0.983 for the silver ions. According to these calibration dependence were determined the concentration of Ag+ in silver nanoparticles (SNP’s) stabilized by BSA in buffered solution. Thus, BSA can be recommended as a stabilizer in the subsequent preparation of electrochemical immunosensor. Anodic stripping voltammetry can be recommended as a technic for detecting Ag+ in silver nanoparticles (SNP’s) stabilized by BSA in buffered solution.

Reference [1] Solomon S.D., Bahadory M., Jeyarajasingam A.V., Rutkowsky S.A., Charles Boritz., // Journal of Chemical Education, 84 (2007) 322–325.

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Voltammetric determination of synthetic food dyes at modified electrodes

O.I. Lipskikh, E.I. Korotkova

Institute of Natural Resources, Tomsk Polytechnic University, Tomsk 634050, Russia

E-mail: [email protected]

Synthetic dyes are widely used for coloring of various food products, making them more attractive to consumers. However, most of them are rather dangerous for human health [1]. P3-53 Strict quality control of foodstuffs makes it necessary to search for new, express, inexpensive techniques of synthetic dyes determining. Electrochemical methods are actively used for these purposes [2]. The aim of this work is simultaneous determination of two synthetic dyes Ponceau 4R and Tartrazine by voltammetry. Experimental studies were carried out on voltammetric analyzer TA-2 (Tomskanalyt, Russia). A carbon-containing electrode modified with carbon ink was used as an indicator electrode. Silver chloride electrodes were used as auxiliary and reference electrode. The voltammograms were recorded using cathodic voltammetry in the first- derivative mode. The background electrolyte was Britton-Robinson buffer with pH 2.0. As can be seen from Fig. 1, both dyes exhibit electrochemical activity in the cathode potential region at E = -0.05V for Ponseau 4R and E = -0.23V for Tartrazine.

Fig. 1. - Voltammograms of Ponso 4R and Tartrazine electroreduction on modified electrode in Britton- Robinson buffer (pH 2.0), depending on the concentration: C = 0.2-0.6 mg/L, W = 100 mV / s.

The calibration curves of each dye in the presence of each other were plotted. The linear range of the detected concentrations is observed from 0.02 to 0.91 mg/L for Ponseau 4R (y = 3.688x + 0.034; R² = 0.9958) and from 0.02 to 0.57 mg/L for Tartrazine (y = 3.9411x + 0.0396: R² = 0.9986). The detection limits were found to be 0.011 and 0.013 mg/L, respectively. Three kinds of marmalade containing both dyes were analyzed. In all three samples, the content of synthetic dyes does not exceed the allowable level according to SanPiN 2.3.2 1293- 03.

References K.T. Chung, J. Environ. Sci. and Health. Part C, 34, No 4 (2016) 233-261. Y. Zhang, L. Hu, X. Liu, Food Chem, 166 (2015) 352–357.

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290

Thursday 21 September 2017 MINOS II Hall Chair: A. Spyros, G. Koulis

Food Analysis 3

10th International Conference on Instrumental Methods of

Thursday 21/9 Analysis: Modern Trends and Applications

Plenary lecture Analytical chemistry of natural products

A.C. Calokerinos

National and Kapodistrian University of Athens, School of Sciences, Department of Chemistry, Laboratory of Analytical Chemistry, Panepistimiopolis, 15771 Athens, Greece

E-mail: [email protected]

During the last decade, analytical research is focused to the development of methods for PL15 sample preparation, preconcentration of analyte and sensitive and selective measurement. Method validation is now part of our everyday life and results should be presented for limit of detection, limit of quantitation, ruggedness, within day and between day repeatability, etc. Natural products such as olive oil, wine and honey are typical samples where Analytical Chemistry can be applied. Quality characteristics such as antioxidant activity and peroxide value can be easily measured by a variety of analytical techniques. Typical examples which will be presented and discussed are the measurement of antioxidant activity of edible oils, wines, date pits and pomegranate juice by chemiluminescence, fluorescence and absorption spectrophotometry, the effect of thermal treatment on quality characteristics of honey, the effect of herb infusion on quality parameters of olive oil, etc.

293

Discrimination of olive varieties based on SNP genotyping and HRM analysis

G. Polychronaki1, A. Sofouli1, G. Stathakarou1, D. P. Kalogianni1, C. Bazakos2, T. K. Christopoulos1 and P. Kalaitzis2

1Department of Chemistry, University of Patras, Patras, Greece 26504 2Department of Horticultural Genetics and Biotechnology, Mediterranean Agronomic Institute, Chania (MAICh), Chania, Crete, Greece 73100

TH01 E-mail: [email protected]

The rapid increase of the overconsumption of food stuff, along with the globalization of the market has led the consumers to concern for the food origin and quality. The authenticity, the traceability and the labeling of raw and processed food are of major demand. Many products with a high purchasing value are particularly vulnerable to fraud due to adulteration with similar products with much lower price and nutrition value. Olive oil is recognized worldwide for its nutritional benefits making it an attractive target to fraud. Single nucleotide polymorphisms (SNPs) are recognized as excellent DNA markers for authenticity tests. In this project, SNP genotyping based on real-time allele-specific PCR and subsequent HRM analysis has been used for olive oil cultivar identification. The method was developed for the screening of three SNPs (6 alleles). DNA was isolated from olive oil samples and subjected to multiplex PCR for the simultaneous amplification of 3 DNA sequences that contain the 3 SNPs. The amplicons, were then exposed to real-time allele-specific PCR using fluorescent DNA intercalating dye for detection and allele discrimination. Subsequent HRM analysis was also performed to confirm the presence of the allele-specific amplicons in the samples. The method was successfully applied for the identification of five common Greek olive cultivars (Adramytini, Chondrolia Chalkidikis, Kalamon, Koroneiki and Valanolia).

294 10th International Conference on Instrumental Methods of

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Development of immunoanalytical test-systems for the determination of salbutamol in food

E.A. Zvereva1, A.V. Zherdev1, S.A. Eremin1,2, B.B. Dzantiev1

1A.N. Bach Institute of Biochemistry, Research Center of Biotechnology of the Russian Academy of Sciences, Leninsky prospect 33, 119071 Moscow, Russia 2Chemical Department, M.V. Lomonosov Moscow State University, Moscow, Russia

E-mail: [email protected]

Salbutamol belongs to the group of beta-adrenoreceptor agonists (beta-agonists) and is widely TH02 used as growth promoter in livestock and poultry. However, its uncontrolled flow in the human body with meat products can lead to metabolic disorders and risks of cardiovascular diseases. In this connection methods of food control for the presence of beta-agonists are demanded. Test systems for controlling the content of salbutamol in food products based on enzyme linked immunosorbent assay (ELISA), fluorescence polarization immunoassay (PFIA) and lateral flow immunoassay (LFIA) are developed. The limit of salbutamol detection by ELISA is 0.07 ng/mL and the range of detectable concentrations is 0.1-1.2 ng/mL. The possibility of reducing the stage of competitive interaction to 15 min and analyzing at room temperature is shown. The advantage of the developed PFIA (using fluorescein as a label) is a homogeneous format of immune interactions that allows realizing the assay during 10 min. The reached limit of salbutamol detection is 2 ng/mL, detectable concentrations ranged from 5 to 177 ng/mL. Duration of the assay – 10 min. The third realized approach is LFIA based on the use of gold nanoparticles as labels. Its limit of visual detection is 1 ng/mL, the working range of quantitative assay – 0.2-0.7 ng/mL. Duration of the LFIA – 15 min. The applicability of the developed methods for testing meat products is shown. A comparative evaluation of the efficiency of different sample preparation protocols for meat-based food is implemented. The obtained results indicate the prospects of the developed methods for provision of food safety.

This investigation was financially supported by Russian Science Foundation (grant number 14-16- 00149).

295

Migration of phthalates and di(2-ethylhexyl)adipate in foods packed in recycled paperboard.

I.E. Parigoridi, M. Zikos, K. Akrida-Demertzi and P.G. Demertzis

University of Ioannina, Department of Chemistry, Laboratory of Food Chemistry, P.O. Box 1186, GR- 45500, Ioannina, Greece

*E-mail: [email protected]

TH03 In recent years, recycled paperboard is used as packaging material in direct contact with foodstuffs. Paperboard because of its previous use it is exposed in numerous surrogates, which are difficult to remove during the recycling process [1-3]. How safe is therefore to use recycled paper as packaging material in direct contact with foodstuffs? This study focuses on the migration potential of 7 surrogates [6 phthalates and di(2- ethylhexyl)adipate], hazardous contaminants to health, into foods packaged in recycled paperboard materials. Three commercially available paperboards were tested and were found to be contaminated with the above surrogates. Semolina (representing foods with low fat content), whole milk powder (representing foods with high fat content) and Tenax (polyphenyleneoxide- a typical dry food simulant) were used for the migration experiments. The analytical methodology applied includes the extraction of surrogates with the assistance of ultrasound waves (ultrasound assisted extraction, UAE) and their determination by gas chromatography-mass spectrometry (GC-MS) analysis. Higher migration tendency was observed in semolina and Tenax. On the contrary, much lower migration tendency was observed in whole milk powder. This can be explained by the different chemical affinities of the foods tested to the paperboard. Based on the above results, it is assessed that recycled paperboard materials could be safely used to package dry foods with high fat content.

References [1] M. Biedermann and Grob K, Journal of Chromatography A, 1272 (2013) 106-115 [2] G Rysstad., A. Ebbesen, and J. Eggestad, Food Additives and Contaminants, 15 (1998) 112-122 [3] B.D. Page and G.M. Lacroix, Food Additives and Contaminants, 9 (1992)197-212

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Thursday 21 September 2017 MINOS II Hall Chair: B. Beckhoff, A. Bobrowski

Sensors

10th International Conference on Instrumental Methods of

Thursday 21/9 Analysis: Modern Trends and Applications

Plenary lecture

Acoustic sensors for molecular diagnostics and point-of-care

E. Gizeli

Dept. of Biology, University of Crete, Vassilika Vouton, 71110, Crete, Greece and Institute of Molecular Biology and Biotechnology, Foundation for Research and Technology-Hellas, 100 N. Plastira str., 70013, Crete, Greece

E-mail: [email protected] PL16

Acoustic wave sensors are becoming increasingly popular due to the wide range of sensing capabilities they can provide. Devices based on both the quartz crystal microbalance (QCM) and surface acoustic wave (SAW) geometry are implemented in the life sciences for basic research as well as in the more applied areas of chemical, environmental and clinical analysis. The classical use of acoustic devices as a mass sensor has recently been expanded to the study and characterization of the conformation of biomolecules. As a result, acoustic sensors can now provide structural information by correlating the two signals obtained during acoustic monitoring (i.e., the energy and frequency of the wave) to the hydrodynamic properties of the attached biomolecule or bio-entity. This novel approach, developed in our lab during the last few years, has been shown both theoretically and experimentally to be able to provide quantitative information on the size and shape of biomolecules1-4. In addition, the ability to integrate SAW devices with microfluidics has opened up the possibility to develop even more integrated platforms, in the form of a Lab-on-Chip5. The concept of conformation sensing combined with microfluidics was exploited towards the development of integrated platforms for food and clinical testing. Specifically, a micro-nano-bio system was developed for foodborne pathogen (Salmonella) detection while a simple hand-held device was demonstrated to be able to perform DNA detection from as little as 5 cells in whole blood and without the need for sample purification6,7.

References 1A. Tsortos, G. Papadakis, E. Gizeli, On the hydrodynamic nature of DNA acoustic sensing, Anal. Chem. (2016) 88: 6472 2G. Papadakis A. Tsortos, E. Gizeli, Acoustic characterization of nanoswitch structures; application to the DNA Holliday Junction, Nano Lett. (2010), 10: 5093 3A. Tsortos, G. Papadakis, E. Gizeli, Shear acoustic wave biosensor for detecting DNA intrinsic viscosity and conformation: A study with QCM-D; Biosens. Bioelectron. (2008), 24: 836 4G. Papadakis et al., Direct detection of DNA conformation in hybridization processes, Anal. Chem. (2012) 84: 1854; A. Tsortos et al., The detection of multiple DNA targets with a single probe using a conformation-sensitive acoustic sensor; Chem. Comm. (2015), 51: 11504 5K. Mitsakakis, A. Tserepi, E. Gizeli, Integration of microfluidics with a Love wave sensor for the fabrication of a multisample analytical microdevice; Journal of Microelectromechanical Systems 2008, 17, 1010-1019 6G. Papadakis, P. Palladino, D. Chronaki, A. Tsortos, E. Gizeli, Sample-to-answer acoustic detection of DNA in complex samples; Chem. Comm., 2017, 53, 8058-8061 7G. Papadakis, JM. Friedt, M. Eck, D. Rabuc, G. Jobst, E. Gizeli, Optimized acoustic biochip integrated with microfluidics for biomarkers detection in molecular diagnostics; Biomedical Microdevices, 2017, 19, 16

299

Fabrication of amperometric xanthine biosensor based on ZnO nanoparticles-multiwalled carbon nanotubes-1,4-benzoquinone composite

B. Dalkıran, C. Kaçar, P. Esra Erden, E. Kılıç

Ankara University, Faculty of Science, Department of Chemistry, 06560, Tandoğan, Ankara, TURKEY

E-mail: [email protected]

TH04 Evaluation of meat freshness is significant in the food industries to manufacture safe and high quality products. The monitoring of xanthine concentration can be used as an indicant for estimating the degree of meat freshness or spoilage [1, 2]. Therefore, rapid, accurate, sensitive and selective determination of xanthine is of great significance in food quality control [3]. Nowadays, electrochemical biosensors have become a encouraging alternative of the conventional analytical methods because a low detection limit, simple usage, high sensitivity, short response time and continuous monitoring can be overcome with this technique [4]. In the present work, we report the fabrication of a xanthine biosensor based on zinc oxide nanoparticles (ZnONPs), multiwalled carbon nanotubes (MWCNTs) and 1,4-benzoquinone (BQ) dispersed in chitosan (CS) nanocomposite mediator film. Xanthine oxidase (XO) was immobilized onto BQ-MWCNTs-ZnO–CS composite modified glassy carbon electrode (GCE) using glutaraldehyde as the crosslinking agent. The construction process and the experimental variables for the biosensor were optimized. The modified electrode was characterized by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. Optimum applied potential and pH were found to be +0.25 V and 7.5, respectively. The response time of xanthine biosensor had approximately 10 s, and its sensitivity, linear working range and detection limit, 39.4 μA/mMcm2, 9.0×10−71.1×10−4 M and 2.1×10-7 M, respectively. The biosensor exhibited good long term stability and reproducibility. Moreover, the biosensor showed good selectivity due to the low operating potential. In conclusion, the presented biosensor can be applied for monitoring chicken and beef samples for the determination of meat freshness.

References [1] J.H.T. Luong, K.B. Male, A.L. Nguyen, Enzyme Microb. Technol. 11 (1989) 277–282. [2] R. Devi, B. Batra, S. Lata, S. Yadav, C.H. Pundir, Process Biochem. 48 (2013) 242–249. [3] B. Dalkiran, C. Kacar, P. Erden, E. Kilic, Sens. and Act. B, 200 (2014) 83-91. [4] S. Sadeghi, E. Fooladi, M. Malekaneh, Anal. Biochem. 464 (2014) 51–59.

300 10th International Conference on Instrumental Methods of

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Development of a reliable electrochemical sensor for pesticide on field detection

I. Mazerie1, C. Parat1, S. Reynaud1, E. Perez2, A. ter Halle2 and I. Le Hécho1

1CNRS / Univ Pau & Pays Adour, IPREM – UMR 5254, 64000 Pau, France 2CNRS/Univ Paul Sabatier, IMRCP – UMR 5623, 31062 Toulouse, France

E-mail: [email protected]

As in many fields, safety is primarily based on the development of reliable and highly sensitive sensor to detect hazardous molecules like pesticides. Therefore, there is a need for developing TH05 a simple technic for a rapid on field diagnosis of harmful molecules in our environment. In this context, electrochemical detection systems such as screen printed electrodes seem very promising because they are economic to produce, highly sensitive with a short analysis time, and easy to implement on-site [1,2]. The present work presents the development of a reliable sensor for in situ detection of three pesticides frequently detected in waters: diuron, isoproturon and glyphosate. Because of the numerous pesticide molecules able to be found in waters at very low concentrations, this sensor needs to be sensitive and selective. For that purpose, three ways were studied: the transducer, the substrate and the surface functionalization of the working electrode (Figure 1A).

Figure 4. A. On field detection principle and B. calibration curves of diuron and isoprotuon obtained with a carbon-based screen-printed electrode by differential pulse adsorption stripping voltammetry, tpulse = 0.05 s, τ = 0.5 s, ΔEpulse = 0.05 V/Ag/AgCl, ∆푬풔풕풆풑⁄흉 = 2.14 mV/s in Britton-Robinson buffer pH =1.69.

First results showed that diuron and isoproturon could be easily detected by means of a simple carbon-based screen-printed electrode, without any modification (Figure 1B). The electrochemical detection of glyphosate appeared more difficult and needed to functionalize the working surface electrode. Two kinds of polymer were tested: an hydrophobic organogel and a more hydrophilic polymer [3,4]. Investigations were carried out to immobilize the polymers on the surface of the working electrode. The sensitivity, the selectivity and the robustness of the obtained sensor were compared in order to select the most appropriate for on-site pesticide monitoring.

References [1] S. Betelu, C. Parat, N. Petrucciani and M. Potin-Gautier, Electroanalysis, 19 (2007) N°2-3, 399- 402. [2] C. Parat, L. Authier, S. Betelu, N. Petrucciani, M. Potin-Gautier, Electroanalysis, 19 (2007), 403- 406. [3] A. ter Halle, C. Claparols, J.-C. Garrigues, S. Franceschi-Messant, E. Perez, Journal of Chromatography A, 1414 (2015) 1-9. [4] C. Thévenot, A. Khoukh, S. Reynaud, J. Desbrières and B. Grassl, Soft Matter, 3 (2007), 437-447.

301

Electrochemical biosensor based on CoS-CNT nanocomposites for detection of Uric acid

Z. Özden Erdoğan, İ. Akin, S. Küçükkolbaşi

Selcuk University, Faculty of Science, Department of Cehmistry, 42075 Konya, Turkey

email:[email protected]

The accurate,sensitive, reliable and rapid detection of uric acid in biological fluids is very important in laboratory medicine and the diagnosis of several disorders such as gout, renal TH06 disease, hyperuricemia, diabetes and Lesh-Nyhan syndrome [1,2]. Among various methods, including spectrophotometry, enzymatic test kits, high-performance liquid chromatography, capillary electrophoresis, chemiluminescence,electrochemical techniques, used to detection of uric acid, biosensors based on electrochemical detection techniques are more popular due to provide advantages such as low detection limit, rapid response, high sensitivity and selectivity [3]. In this study, uric acid biosensor based on CoS-CNT nanocomposites for uric acid determination was prepared. Uricase (UOx) was immobilized on the modified electrode surface by crosslinking with glutaraldehyde. Electrochemical properties of UOx/CoS- CNT/GC electrode surface was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that CoS-CNT modified GC electrode provides good electron transmission pathway than bare GC electrode. .Optimum working conditions such as pH, enzyme unite, working potential were investigated and performance factors of uric acid biosensor were study. The working range of the biosensor was 0.415- 1788.25 µM. The results revealed that the proposed biosensor offers a good promise for practical applications in real samples.

References [1] Erden PE, Kaçar C, Öztürk F, Kılıç E (2015) Talanta 134:488-495. [2]Chauhan N, Pundir CS (2011) Analytical Biochemistry 413:97-103. [3] Jindal K, Tomar M, Gupta V (2012) Biosensors and Bioelectronics 38:11-18.

302 10th International Conference on Instrumental Methods of

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Environmental analysis by bioindicator organisms: honeybees, mussels, algae, and bioluminescent bacteria.

S. Girotti1, L. Bolelli1, E. Ferri1, G. Isani2, N. Barile3

1Dept. of Pharmacy and Biotechnology, Via S. Donato, 15 – 40127 Bologna, Italy 2Dept. of Veterinary Medicine, Via Tolara di Sopra 50, 40064 Ozzano Emilia, Bologna, Italy 3Center of Water Biology, Institute of Experimental Zooprophylaxis of Abruzzo and Molise “G. Caporale” Viale Marinai d’Italia 20, 86039 Termoli, Italy

E-mail: [email protected] TH07 The early detection of toxic pollutants in environmental compartments is of primary importance to control the consequences on the biota. The use of appropriate bioindicator organisms can solve quite easily this problem. Honeybees collect and concentrate, on or inside their bodies, all residues encountered in air, water, on flowers and vegetables performing an effective sampling. Bees can be used for the monitoring of pesticides, heavy metals, and for the detection of radionuclides for several purposes [1]. Moreover, the bees can reveal the presence of phytopatogens. The bacterium Erwinia amylovora has been identified before symptoms by analyzing the pollen with a PCR- ELISA technique based on the immunoenzymatic determination of PCR products [2]. To perform these analyses is necessary to install at least one monitoring station, i.e. two beehives equipped with collection cages for the dead bees named “underbasket”. Law provisions in both European and international policies have introduced the application of luminescent bacteria tests in environmental monitoring for sediment and water analysis. In vivo luminescence is a sensitive indicator of biotoxicity: if noxious substances are present, the luminescence decreases proportionally to their concentration. This performance find a new application when coupled to other biosensors, like mussels and algae. Acting as intensive filtrating organisms the mussels concentrate any residue present in seawater. The toxic consequences can be evaluated by a specific instrument, the Mosselmonitor™ [3] but more sensitive information on toxicants content are obtained by mixing the luminescent bacteria with the extract of Mussels grown in polluted water. This association therefore represent an effective bioindicators system to monitor coastal pollution. Bioluminescent bacteria assay can be also combined with marine or freshwater microalgae. These organisms can be directly observed to reveal the noxious effects of pollutant presence, but they are also able to bioaccumulate them. By coupling luminescent bacteria to microalgae in the same polluted sample is possible to evaluate the bioremediation capability of the microalgae simply by observing the changes in the light emission intensities.

References [1] C.Porrini, S.Ghini, S.Girotti, A.G.Sabatini, E.Gattavecchia, G.Celli. In: “Estimating the Environmental Impact of Chemicals to Honey Bees” J.Devillers and M.H.Pham-Delègue, Eds, Taylors & Francis Inc., London,(2002) pp. 186-247. [2] M.Merighi, A.Sandrini, S.Landini, S.Ghini, S.Girotti, S.Malaguti, C.Bazzi. Plant Disease, 84 (2000) 49-54. [3] N. Barile, M. Scopa, S. Recchi, E. Nerone. Ovidius University Annals of Chemistry, 27 (2016) 81- 86

303

The Effect of Various Multiwalled Carbon Nanotubes on the Performance of Xanthine Biosensors

C. Kaçar, B. Dalkıran, P.E. Erden, E. Kılıç

Ankara University, Faculty of Science, Department of Chemistry, Ankara, Turkey

E-mail: [email protected]

Carbon nanotubes (CNTs) have attracted a great deal of attention due to their TH08 extraordinary properties such as functional surface, good conductivity, biocompatibility, high reactivity, fast electron transfer and high surface area. Recently, there has been an attraction in exploring some of their novel properties, and availability of chemical functionalization for biological applications [1]. The important properties and possible potential applications of CNTs have been reviewed in recent years [2-3]. Of the applications, the development of CNT-based biosensors is one of most interesting areas [4]. In this study effects of multi-walled carbon nanotubes (MWCNTs), and multi-walled carbon nanotubes with carboxyl (COOH-MWCNTs), hydroxyl (OH-MWCNTs) and amino (NH2-MWCNTs) functional groups on the response of amperometric xanthine biosensors were investigated. For this purpose, various MWCNTs were dispersed in gelatin solution and aliquots of each suspention was drop casted onto the surface of glassy carbon electrodes (GCE). Then, xanthine oxidase (XO) was immobilized onto the surface of modified glassy carbon electrodes in order to prepare the xanthine biosensors. The morphology of the modified electrodes has been examined by scanning electron microscopy (SEM), and the electrochemical performance of the electrode has been researched by amperometric method. Electron transfer properties of the modified electrode was investigated in 0.1 M KCl support electrolyte containing 3-/4- Fe(CN)6 as redox probe by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) methods. Working conditions such as optimum pH and enzyme amount of these biosensors were determined and analytical performances of the biosensors were studied under this optimum conditions. The biosensor prepared with NH2-MWCNT exhibited a xanthine response with the highest sensitivity. The response time, linear working range, detection limit and sensitivity of this biosensor was <15 s; 9.9×10-7 M – 9.4×10-4 M; 8.7×10-7 M; 23.36 µA mM-1 respectively.

References [1] H. Hu, Y. Ni, V. Montana, R. C. Haddon and V. Parpura, Nano Letters, 4 (2004) 507-511. [2] J. Wang, Electroanalysis, 17 (2005) 7-14. [3] M. Trojanowicz, Trends in Analytical Chemistry, 25 (2006) 480–489. [4] J. Wang and Y. Lin, Trends in Analytical Chemistry, 27 (2008) 619-626.

304 10th International Conference on Instrumental Methods of

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305 Sponsors