3 rd International Conference on Analytical Chemistry. August 28-31, 2016 Iasi, Romania BOOK OF ABSTRACTS

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1 3 rd International Conference on Analytical Chemistry August 28-31, 2016 Iasi, Romania BOOK OF ABSTRACTS

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3 CONTENTS ORGANIZERS... 4 WELCOME... 5 CONFERENCE TOPICS... 6 SCIENTIFIC COMMITTEE... 7 ORGANIZING COMMITTEE... 8 SCIENTIFIC PROGRAM... 9 PLENARY LECTURES KEYNOTE LECTURES ORAL COMMUNICATIONS POSTER PRESENTATIONS POSTER SESSION 1 YOUNG ANALYTICAL CHEMISTS POSTER SESSION 2 PHARMACEUTICAL AND BIOMEDICAL ANALYSIS POSTER SESSION 3 ENVIRONMENTAL ANALYSIS POSTER SESSION 4 ADVANCED MATERIALS ANALYSIS ÈME ÉDITION DE L ATELIER NOUVEAUX MATÉRIAUX POUR LA RECONNAISSANCE ELECTROCHIMIQUE DES MINERAUX ET DES ESPÈCES BIOLOGIQUES NOMARES KEYNOTE LECTURES NOMARES ORAL COMMUNICATIONS NOMARES NOMARES POSTER PRESENTATIONS SPONSORS INDEX OF AUTHORS Page3

4 ORGANIZERS Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania American Chemical Society European Chemical Sciences, Division of Analytical Chemistry Romanian Chemical Society Page4

5 WELCOME Welcome to the 3 rd International Conference on Analytical Chemistry (Ro-ICAC 2016) to be held in Iasi, August 28 31, This conference is a meeting place for analytical chemists working in academia, research institutes, industry, clinical laboratories etc. The scientific program will give a broad overview of Analytical Chemistry topics that contribute to a better life. A special session will be organized for young chemists. Leading companies are invited to exhibit and present new developments in their analytical instrumentation. Do not miss the opportunity to exchange experience with analytical chemists from Romania and abroad and to show the large contribution that Analytical Chemistry has for a Better Life! We look forward to welcoming you in Iasi, Raluca-Ioana STEFAN-VAN STADEN Bogdan C. SIMIONESCU Chairpersons of Ro-ICAC 2016 Page5

6 CONFERENCE TOPICS Electroanalytical Chemistry Bioanalytical Chemistry Biomedical Analysis Enantioanalysis Spectroscopy in Analytics Chromatography Environmental Analysis Marine Geology and Geoecology Food Analysis Pharmaceutical Analysis Clinical Analysis Hyphenated techniques in Analytics Process Systems and Techniques in Analytics Chemometrics Nanoanalytics Surface Analysis for Biomedicine Advanced Materials Analysis Metrology, Reference Materials and Method Validation Education on Analytical Chemistry Page6

7 SCIENTIFIC COMMITTEE George HORVAI, Budapest University of Technology and Economics, Budapest, Hungary Rodica Mariana ION, The National Institute for Research & Development in Chemistry and Petrochemistry (ICECHIM), Bucharest, Romania ConstantinA P. KAPNISSI-CHRISTODOULOU, University of Cyprus, Nicosia, Cyprus Wolfgang LINDNER, Vienna University, Vienna, Austria Gheorghe NECHIFOR, University Politehnica of Bucharest, Bucharest, Romania Sibel A. OZKAN, Ankara University, Ankara, Turkey Mariana PINTEALA, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Gabriel Lucian RADU, University Politehnica of Bucharest, Bucharest, Romania Cristiana RADULESCU, Valahia University of Targoviste, Targoviste, Romania Sorin ROSCA, University Politehnica of Bucharest, Bucharest, Romania Luigia SABBATINI, Univerity of Bari Aldo Moro, Bari, Italy Costel SARBU, Babes-Bolyai University, Cluj-Napoca, Romania Acad. Bogdan C. SIMIONESCU, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania and Ghe. Asachi Technical University of Iasi Raluca-Ioana STEFAN-VAN STADEN, National Institute of Research for Electrochemistry and Condensed Matter, Bucharest, Romania Jacobus Frederick VAN STADEN, Process Analytical Technology Laboratory (PATLAB), Bucharest, Romania Dana VLASCICI, West University of Timisoara, Timisoara, Romania Luminita VLADESCU, University of Bucharest, Bucharest, Romania Paul WORSFOLD, Plymouth University, Plymouth, United Kingdom Page7

8 ORGANIZING COMMITTEE SCIENTIFIC SECRETARY Dr. Marcela Mihai, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania MEMBERS Daniela AILINCAI, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Andreea Irina BARZIC, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Andrei BEJAN, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Adrian BELE, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Catalin Paul CONSTANTIN, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Florica DOROFTEI, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Claudiu-Augustin GHIORGHITA, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Marinela LAZAR, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Narcisa MARANGOCI, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Stefania RACOVITA, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Daniela RUSU, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Radu-Dan RUSU, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Iuliana STOICA, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Codrin TUGUI, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Silvia VASILIU, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Mirela ZALTARIOV, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Tincuta BUNIA, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Mioara SAVA, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Liviu BUNGHEZ, Petru Poni Institute of Macromolecular Chemistry, Iasi, Romania Page8

9 Sunday, August Registration of Participants Welcome cocktail SCIENTIFIC PROGRAM Monday, August Registration of Participants Conference Opening Session 1 Conference hall Chairs: Raluca Ioana STEFAN-van STADEN and Charlotta TURNER PL1. Bogdan C. SIMIONESCU, Romanian Academy and Petru Poni Institute of Macromolecular Chemistry PL2. Ryszard LOBINSKI, CNRS and Institute of Analytical Chemistry and Physicochemistry of Materials and Environment in Pau, France Coffee Break and *Poster session Session 2 Conference hall Chair: Jacobus F. van STADEN PL3. Charlotta TURNER, Lund University, Sweden KN1. Dragos EFSTATIADE, Pro Analysis Systems, Romania Lunch Session 3 Conference hall Chair: Calin DELEANU PL4. Jacobus F. van STADEN, National Institute of Research for Electrochemistry and Condensed Matter, Bucharest, Romania Coffee Break and *Poster session Sessions 4 Special Session for Young Analytical Chemists Conference hall Chairs: Hassan Y. Aboul-ENEIN and George HORVAI Sessions 5 Workshop NOMARES Library hall Chair: Eleonora Mihaela UNGUREANU KN2. Livia GUGOASA KNN1. Eric SAINT AMAN L1. Sevinc KURBANOGLU L2. Roxana BALAHURA KNN2. Vesna MIŠKOVIĆ- STANKOVIĆ L3. Ramona GEORGESCU-STATE KNN3. Vessela TSAKOVA L4. Grigorina MITROFAN LN1. Liviu BIRZAN Coffee Break and *Poster session L5. Mihai STANESCU LN2. Tzonka GODJEVARGOVA L6. Ahmed Muklive AL-OGAIDI LN3. Yavor IVANOV L7. Mihaela BALAN-PORCARASU LN4. Anna LIELPĒTERE L8. Alina-Maria ANGHELACHE Conference Dinner Page9

10 Tuesday, August 30 Session 6 Conference hall Chairs: Małgorzata LEKKA and Rodica Mariana ION PL5. Hassan Y. ABOUL-ENEIN, National Research Center in Cairo, Egypt PL6. Sibel OZKAN, Ankara University Faculty of Pharmacy, Turkey Coffee Break and *Poster session Session 7 Conference hall Chairs: Sibel OZKAN and Livia Alexandra GUGOASA PL7. George HORVAI, Technical University of Budapest, Hungary PL8. Calin DELEANU, Costin D. Nenitescu Centre of Organic Chemistry, Bucharest, Romania Lunch Session 8 Conference hall Chairs: Alina NICOLESCU and Marcela MIHAI PL9. Małgorzata LEKKA, Institute of Nuclear Physics, Polish Academy of Science, Poland KN3. Gordon van t SLOT, Bruker Daltonik GmbH, Bremen, Germany Coffee Break and *Poster session Sessions 9 Pharmaceutical and Biomedical Analysis Conference hall Chairs: George HORVAI and Radu-Dan RUSU Sessions 10 Environmental Analysis Library hall Chairs: Eric Saint AMAN and Mirela ZALTARIOV KNN4. Eleonora Mihaela Sessions 11 Chromatography and spectroscopy Intelcentre Chairs: Vesna MIŠKOVIĆ-STANKOVIĆ and Sevinc KURBANOGLU KN4. Rodica Mariana KN8. Mariana CRISTEA ION UNGUREANU KN5. Alina NICOLESCU KN6. Mihai LOMORA KN9. Alin Constantin DARTU L9. Andrei A. BUNACIU KN7. Marcela MIHAI KN10. Laura ION L10. Raluca-Ioana STEFAN-VAN STADEN L14. Iustinian BEJAN L15. Camelia DRAGHICI L11. Ramona GEORGESCU STATE L12. Livia Alexandra GUGOASA L13. Bogdan CALENIC L16. Claudiu Augustin GHIORGHITA Conference Closing and awards for oral and poster presentations Wednesday, August Excursion Page10 *Posters will be exposed on the panels on Monday, August 29, during participants registration and will remain exhibited during the entire conference period. Discussion on posters are expected during all coffee breaks.

11 POSTERS LIST Poster Session 1 Young Analytical Chemists P1Y Ioana-Raluca SUICA-BUNGHEZ P2Y Daniela AILINCAI P3Y Leyla KARADURMUS P4Y Sevinc KURBANOGLU P5Y Ioana Lavinia ARDELEAN P6Y Ecaterina Anca SERBAN P7Y Alexandra OPRISANU P8Y Amalia Gabriela DIACONEASA P9Y Grigorina MITROFAN P10Y Ahmed Jassim Muklive AL-OGAIDI P11Y Ana Maria MACSIM P12YN Georgiana Luiza ARNOLD Poster Session 2 Pharmaceutical and Biomedical Analysis P1PBA Ioana MC IENASCU P2PBA Ioana Adina OANCEA P3PBA Gabriela STANCIU P4PBA Raluca-Ioana STEFAN-van STADEN P5PBA Raluca-Ioana STEFAN-van STADEN P6PBA Bogdan CALENIC P7PBA Malgorzata LEKKA P8PBA Alina DIMA P9PBA Camelia STANCIU-GAVAN P10PBA Marcela Corina ROSU P11PBA Mihaela (BADEA) DONI P12PBA Mihaela (BADEA) DONI Poster Session 3 Environmental Analysis P1EA Oxana SPINU P2EA Elisabeta Irina GEANA P3EA Adina CATA P4EA Tatiana CAZAC P5EA George-Octavian BUICA P6EA Iustinian BEJAN P7EA Mariana Nela STEFANUT P8EA Cristina STOIAN Poster Session 4 Advanced Materials Analysis P1AMA Marius RADA P2AMA Raluca Marinica ALBU P3AMA Andreea Irina BARZIC P4AMA Simona RADA P5AMA Mariana Nela STEFANUT P6AMA Diana SERBEZEANU P7AMA Cristiana Diana CIRSTEA P8AMA Cristina BANCIU Poster Session 5 NOMARES P1N Elena DIACU P2N Lucia MUTIHAC P3N Cecilia LETE P4N Alexandra OPRISANU P5N Catalina NEGUT P6N Laurentiu TATU P7N Cristina DUMITRIU P8N Magdalena-Rodica BUJDUVEANU P9N George-Octavian BUICA P10N Maria Daniela POP Page11

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13 PLENARY LECTURES Page13

14 PL 1. ROMANIAN ACADEMY AND THE "PETRU PONI" INSTITUTE OF MACROMOLECULAR CHEMISTRY Bogdan C. Simionescu Romanian Academy and Petru Poni Institute of Macromolecular Chemistry The Romanian Academy was founded on 1/13 April 1866 under the name of the Romanian Literary Society. The name changed in 1879 into the Romanian Academy. From the very beginning, the newly founded institution was a national, encyclopedic and active society. The 21 founding members were scholars and literati not only from Wallachia and Moldavia, but also from Transylvania, Banat, Maramures, Bukovine, Bessarabia (today the Republic of Moldavia) and the Balkan Peninsula (all these provinces hosted important Romanian communities). Since its inception 150 years ago Romanian Academy has crossed both good and somber periods, has known both success and defeat, and throughout all has enjoyed the admiration of the nation, the respect of scholarly circles worldwide, and the generosity of many donors who have thus ensured, next to government funding, the necessary resources for the activity and development of a scientific center of such breadth. During the longest part of its activity, the Academy achieved the goals set by its founders, and succeeded in being the main forum of reflection and intellectual creation, literary, artistic and scientific of the Romanian people. The Petru Poni Institute of Macromolecular Chemistry is an institute of excellence of the Romanian Academy and concentrates on basic and applied research in polymer chemistry and physics. The research topics are directed towards multifunctional polymeric materials (smart polymers, photoactive polymers, thin films, micro/nanoparticles); supramolecular chemistry (rotaxanes, self assembling systems); bioactive/biocompatible polymers based on natural and synthetic polymers (controlled drug release, tissue engineering); management of polymer wastes; polymers for environment protection (degraded soil regeneration, water purification). The main expertise of the research staff (about 130 researchers and 55 PhD students) is on organic and polymer chemistry (synthesis by conventional and unconventional methods, structural characterisation), polymer physics (solution and solid state thermal, rheological, mechanical, electrical, optical, surface properties), polymeric materials (alloys, composites, hybrids, thin films, multilayer films, micro and nanoparticles), bioactive and biocompatible polymers and supramolecular chemistry. According to recent hierarchies/evaluations ( or ISI, Scopus) the Petru Poni Institute of Macromolecular Chemistry (PPIMC) is on top of the list of research institutions from Romania, holds one of the top ten positions in "all fields", "nanosciences and nanotechnologies", "multidisciplinary chemistry", "multidisciplinary materials sciences" and holds the first position in "polymers science" and "applied chemistry". 61 of the top 100 researchers in polymer science (from overall of 940 researchers), ranked by their scientific papers, are employed in PPIMC ( According to www. scimagoir.com, Romania ranks 28th among the world countries on the basis of the number of publications in the field of chemistry. In the period, PPIMC yearly contributed with about 12-19% to these figures. Page14

15 PL 2. BIOLOGICAL TRACE ELEMENT ANALYSIS: ELEMENTS, ISOTOPES, AND SPECIES Ryszard Lobinski LCABIE, CNRS UMR 5254 IPREM, Héliooparc, Pau, France The concentration ratios of the individual elements in biological systems are controlled by the physiology and biochemistry of an organism. The metal-induced gene expression results in the synthesis of a myriad of biological ligands on the proteome and metabolome levels implied in the uptake, trafficking, accumulation and excretion of trace elements. Therefore, information on the metal speciation becomes an essential contribution to the understanding of the role and fate of metals in a biological system. Also, there appears evidence that biochemical and physiological processes can contribute to the fractionation of mineral elements on the isotopic level, as it has been already well established for oxygen, nitrogen or sulfur. The status of a mineral element in a biological sample can be defined by: (i) concentration (possibly isotopic composition), (ii) chemical speciation and (iii) localization. The control of all the three is essential for the cellular metal homeostasis. Therefore there is a need for analytical methods able to provide the necessary information for all the elements, for the maximum of species and with a maximum spatial resolution at an adequate time scale. The paper discusses the state of the art of the development of such a toolbox, its recent advances and evolution trends. Particular attention is given to global approaches aimed at a simultaneous comprehensive speciation analysis of one or several elements. The topics discussed will include largescale selenometabolomics, human selenoproteomics, and global metabolomics of metal complexes, especially in the context of the recent advances in high resolution (Fourier Transform) electrospray mass spectrometry. Trends in the other fields of analytical metallomics: multielement microanalysis, highresolution multicollector ICP MS and laser ablation and nanosims imaging will be briefly overviewed. Page15

16 PL 3. FROM SUBCRITICAL WATER TO CARBON DIOXIDE EXPANDED LIQUIDS IN SEPARATION SCIENCE Charlotta Turner Lund University, Department of Chemistry, Centre for Analysis and Synthesis (CAS), The Green Technology Group (GTG), P.O. Box 124, SE Lund, Sweden Byproducts and waste from agricultural, forestry and food industry contain high-value compounds that can be extracted prior to recovering the energy from these materials [1-2]. Examples of high-value compounds are carotenoids in microalgae [3], phenolic compounds in lignin, essential oil in tree resin and polyphenols and lipids in berry press cakes [4]. In our research, we use supercritical carbon dioxide (scco2), subcritical water (SCW) and carbon dioxide expanded liquids (CXLs) to extract and analyze a variety of compounds in complex samples [5]. scco2 has dielectric properties similar to hexane, and is a suitable solvent for e.g. oil, waxes and carotenoids. Supercritical fluid extraction (SFE) operates at moderate temperatures (ca. 40 C), however, at high pressures (ca MPa), which makes the equipment difficult to operate. In fact, we have shown the benefits of coupling an evaporative light scattering detector on-line with the SFE, which gives continuous data useful in modeling of extraction kinetics [6-7]. SCW is a solvent being appropriate for polar compounds, although its dielectric properties are tunable with temperature [8]. The higher the temperature, the less polar compounds can be extracted. However, the downside is the inherent degradation/reaction of thermally labile compounds. Therefore, the focus of our research is currently on the use of CXLs [9] solvents which are obtained by adding compressed liquid CO2 to a classical organic solvent such as ethanol, ethyl acetate, ethyl lactate or even glycerol. Dielectric properties of CXLs are tunable, depending on molar ratio of CO2, pressure and temperature. Furthermore, viscosity decreases and thereby diffusivity is increasing when adding CO2 to the liquid solvent, while density remains nearly constant [10]. In this presentation, examples will be given on the use of scco2, SCW and CXLs in extraction as well as chromatography of phenolic compounds and carotenoids in complex plant-derived samples. The impact of different compressed fluid mixtures on the solubility, desorption and diffusion in extraction will be discussed. References [1] A. Ekman, M. Campos, S. Lindahl, M. Co, P. Börjesson, E. Nordberg Karlsson, C. Turner, J. Cleaner Prod., 2013, 57, [2] H. Rohm, C. Brennan, C. Turner, E. Günther, G. Campbell, I. Hernando, S. Struck, V. Kontogiorgos, Foods, 2015, 4, [3] V. Abrahamsson, I. Rodriguez-Meizoso, C. Turner, J. Chromatogr. A., 2012, 1250, [4] F. Jumaah, M. Sandahl, C. Turner, J. Am. Oil Chem. Soc., 2015, 92, [5] F. Jumaah, S. Larsson, S. Essén, L. P. Cunico, C. Holm, C. Turner, M. Sandahl, J. Chromatogr. A, 2016, 1440, [6] V. Abrahamsson, I. Rodrigues-Meizoso, C. Turner, Anal. Chim. Acta, 2015, 853, [7] V. Abrahamsson, N. Andersson, B. Nilsson, C. Turner, J. Supercrit. Fluids, 2016, 111, [8] M. Plaza, C. Turner, TrAC Trends in Analytical Chemistry, 2015, 71, [9] C. Turner, Lipid Technol., 2015, 27, [10] P. G. Jessop, B. Subramaniam, Chem. Rev., 2007, 107, Page16

17 PL 4. SENSOR (DETECTION) DEVICES AND PROCESS CONTROLLERS IN INTEGRATED REAL-TIME PROCESS CONTROL. DO THEY FULLFIL THE ACTUAL REAL-TIME ON-SITE DOMAIN REQUIREMENTS? Jacobus (Koos) F. Van Staden Process Analytical Technology Laboratory (PATLAB), 202 Splaiul Independentei Str., Bucharest, Romania. Website: The origin of Analytical Chemistry can be found BC in Zechariah 13.9 on fire assays on gold. Peter Shaw published on Spa water analysis in Manual analysis became dominant in the Analytical World since the late 1600s, beginning of 1700, through 1800s and 1900s up to around Electroanalysis with glass membrane electrodes starts in 1906, flow analysis with chromatography in 1905 and non-segmented inventions in Many original chemo-, electrochemical and optical measuring sensing detection systems were invented and implemented in the period and even later. The modern history of the petroleum industry starts in 1846 in Canada, the first large petroleum refinery was built at Ploiesti, Romania in 1856 using abundant oil available in Romania, and SASOL in South-Africa as the world s first oil-from-gas company started producing in Automatic control systems were first invented over years ago with the first control device ancient water clock in Egypt around the third century B.C. The first industrial control computer system was built in 1959 at the Texaco Port Arthur, Texas, refinery. Sasol originally used central control rooms in the early 1960s with manual/semi-automated distributed control systems where their setpoint of control was pressure and temperature in the different plants with operators manually operating as controllers, turning valves etc. Ideas of receding horizon control and model predictive control can be traced back to the 1960s and practical implementation of real-time-optimization (RTO) in conjunction with model predictive control (MPC) with soft sensors (mainly temperature and pressure) dates back to late 1980s in refinery and chemical industries. With the arrival of more advanced computer systems in the early 1970s and internet in the a number of process control systems were developed with control theory from mathematicians. The industry of tomorrow however places a heavy demand on more efficient processes that performs in a more fluent cost-saving and sustainable way throughout the whole process production system. These industries need improvements in process monitoring and measurement that is the key for delivering better process control and therefore more sustainable processes. Innovations in process measurement are therefore needed to relate more closely to the full stream process environment to deliver better higher final quality products by allowing better process control and hence substantial cost reduction and a friendlier environment. This will need a complete new approach for the different scenarios regarding the innovation, development, design, behaviour, implementation and application of sensor (detection) devices. These type of measuring devices and probes should functioned in various temperatures and pressures on a continuous basis for extended periods. Some new modern current process analytical (micro- and nano) technological detection and diagnostic systems advanced excellently with implementation and performance of multivariate instrumentation (sensing probes, imaging systems etc.) to nano-molecular and atomic scale and are able to sense and detect very fast multicomponent substances on-site in high complex chemical processes and refinery industries. It is however extremely important to identify and implement these systems also from chemical and process engineering side with the development of extended new sophisticated innovative enhanced ultrafast powerful molecular inspired parallel tempering stochastic model-based algorithms with simulation and iteration in integrated process control in real-time. This talk will look and highlight these developments in the fulfillment of the actual real-time on-site domain requirements. Acknowledgements: Program Ideas by PN-II-ID-PCE / , financed by contract 100/ , Romania. Support received from the University of Pretoria and various industries, especially SASOL. Page17

18 PL 5. LIPASE-CATALYZED KINETIC RESOLUTION OF RACEMATES: A VERSATILE METHOD IN CHIRAL SEPARATION AND DRUG DEVELOPMENT Hassan Y. Aboul-Enein Pharmaceutical and Medicinal Chemistry Department, National Research Centre, Dokki, Giza 12622, Egypt hyaboulenein@yahoo.com Enzymes and especially lipases are biological catalysts of extraordinary selectivity and efficiency. They catalyze and regulate reactions of important biochemical pathways. In common with all catalysts, they accelerate the attainment of chemical equilibrium but can not mediate a thermodynamically unfavorable reaction. Since they are chiral, they are able to assert a dramatic chiral influence on the reaction due to the chiral active site they owe. The reactant molecules are bound instantaneously to the active site while the reaction takes place. Only one enantiomer of a chiral reactant fits it properly and is able to undergo the reaction while the second enantiomer is left unreacted and in enantiomerically pure form. Lipases, have been widely used in three main types of reactions yielding optically pure compounds. These are kinetic resolution of racemic carboxylic acids or alcohols, enantioselective group differentiations of meso dicarboxylic acids or meso diols and enantiotopic group differentiation of prochiral dicarboxylic acid and diol derivatives. Enantiomerically pure drugs especially those containing a secondary hydroxyl or carboxylic functional groups are preferably synthesized by enzymatic kinetic resolution of the racemates. This biochemical transformation process has become a standard reaction protocol to access to enantiomarically pure compounds. The ways in which efficiency and practicality of this procedure are defined is depending on a large numbers of factors. Among these factors are scale, reagent costs, time allotted and required, suitable equipments and reliable methods used in the determination of the enantiomeric excess of substrate and the resulting product. In this presentation, the applications of lipases to access to enantiomarically pure compounds together with the reliable methods used in chiral separation are discussed. R * OH (R/S)-alcohol + R * O Lipase R * O + O Org. Solv. OH + O Isopropenyl acetate (acyl agent) (R)-ester (S)-alcohol O Page18

19 PL 6. FROM MERCURY TO NANOSENSORS Sibel A. Ozkan Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, Ankara, Turkey Electroanalytical methods are routinely used in pharmaceutical and biomedical analysis. They are powerful and versatile analytical techniques that offer high sensitivity, accuracy, and precision as well as a large linear dynamic range, with relatively low-cost instrumentation. Polarography was the first developed automated method of voltage-controlled electrolysis with dropping mercury electrode. Then, hanging mercury drop and static mercury drop electrodes were added as an alternative indicator electrode. In this way, polarography turned formally into voltammetry with mercury electrodes in the electroreduction way. Solid electrodes such as noble metal and carbon based electrodes can be used for the investigation of the compounds for both oxidation and reduction directions, which is called voltammetry. The voltammetric and polarographic techniques are more sensitive, reproducible, and easily used electroanalytical methods that can be alternative to more frequently used separation and spectrometric methods. Furthermore, in some cases there is a relationship between voltammetry and pharmaceutical samples, and the knowledge of the mechanism of their electrode reactions can give a useful clue in elucidation of the mechanism of their interaction with living cells. The voltammetric and polarographic analysis of drugs in pharmaceutical preparations are by far the most common use of electrochemistry for analytical pharmaceutical problems. Recent trends and challenges in the electrochemical methods for the detection of DNA hybridization and pathogens are also available. Low cost, small sample requirement and possibility of miniaturization justify their increasing development [1]. References [1] S.A., Ozkan, Electroanalytical Methods in Pharmaceutical Analysis and Their Validation. HNB Publishing, New York, Page19

20 PL 7. MOLECULAR IMPRINTING WHERE ARE WE NOW? George Horvai 1 *, Zsanett Dorkó 1,2, Viola Horváth 2, Blanka Tóth 1 1 Budapest University of Technology and Economics, Department of Inorganic and Analytical Chemistry, Szt. Gellért tér 4, H-1111 Budapest, Hungary 2 MTA-BME Research Group of Technical Analytical Chemistry, Szt. Gellért tér 4, H-1111 Budapest, Hungary * george.horvai@mail.bme.hu Molecularly imprinted polymers (MIP) are polymeric solids prepared in the presence of a target compound, with the goal that after the removal of the target compound the polymer should be capable of selectively recognizing and rebinding the target. The possible and demonstrated applications of MIPs are numerous, and include chromatography, sensors, artificial enzymes and antibodies, binders of environmental and technological contaminations, slow drug release matrices, etc. For years the main targets were small molecules but recently protein targets are in the focus. The lecture will summarize recent results achieved internationally in molecular imprinting. Then it will present some results of the authors. These will include the following subjects: Novel formats of MIPs and their application for analysis Adsorption properties of MIPs Chromatography with MIPs Selectivity of MIPs. Acknowledgements The financial support of OTKA, Hungary (Grant No. K104724) is gratefully acknowledged. Z. Dorkó acknowledges the support of the Ernő Pungor Scholarship. References [1] V. Horvath, B. Lorantfy, B. Toth, J. Bognar, K. Laszlo, G. Horvai, J. Sep. Sci. 2009, 32, [2] Z. Dorko, A. Szakolczai, T. Verbic, G. Horvai, J. Sep. Sci. 2015, 38, [3] Z. Dorko, T. Verbic, G. Horvai, Talanta, 2015, 132, Page20

21 PL 8. NMR SPECTROSCOPY IN MEDICAL RESEARCH AND DIAGNOSIS Calin Deleanu Costin D. Nenitescu Centre of Organic Chemistry of the Romanian Academy, Spl. Independentei 202-B, Bucharest, Romania. Petru Poni Institute of Macromolecular Chemistry of the Romanian Academy, Aleea Grigore Ghica Voda 41A, Iasi, Romania During its rather brief history, NMR spectroscopy (discovered in 1946 by Block & Purcell) was initially used by physicists. It was only in the 1960 s when the chemical shift was discovered that the chemical community started to use it and the NMR field took off. Thus, NMR became an indispensable tool in structure elucidation of pure compounds and until late 1980 s this remained the most important type of application. Once the high field NMR spectrometers entered the chemical community the method started to be used also for complex mixture analysis, penetrating new fields like medicine or food sciences. Today we see a rather balanced use of the NMR spectroscopy between the structure elucidation of pure compounds and analysis of complex mixtures. When it comes to applications of NMR to complex systems, like biological ones, one should carefully balance between the excitement of the potential of the technique and claims of ultimate diagnosis tool capabilities. Thus, one should always be aware which techniques and protocols are valuable but restricted to advanced medical research and which ones can be already extended to clinical diagnosis. The paper presents examples of diagnosing or monitoring various diseases using NMR spectroscopy. Examples include diabetes, inborn errors of metabolism, cancer, cardiovascular diseases and transplant of organs. Experimental factors, reproducibility, and data interpretation via either biomarker identification approach or blind statistical classifier approach are also discussed. Acknowledgements Financial support from the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, through project numbers PNII-ID-PCCE and PN-II-ID-PCCE is warmly acknowledged. Page21

22 PL 9. AFM AND TOF SIMS MEASUREMENTS FOR CANCER CELL IDENTIFICATION Małgorzata Lekka*, Justyna Bobrowska The Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, Kraków, Poland * Cancer progression is a multistep process leading to alterations in cellular cytoarchitecture and biophysical properties that are associated with chemical changes observed in cell membrane [1]. Various studies on cancer progression show a wide range of changes in chemical composition leading to a conclusion that a general, single change of a specific molecular compound does not exist [2]. In our studies, biochemical changes on a surface of the cell were studied using Time-of-Flight Secondary Ion Mass Spectrometry (ToF SIMS) due to its nm depth resolution. The measurements were carried out in high vacuum conditions, thus, the elaboration of sample preparation protocol was needed to be performed. This protocol applies a chemical fixation with paraformaldehyde followed by alcohol dehydrating and drying. Subsequently, high resolution mass spectra, range up to 500 Da, were collected for single cells (human bladder and melanoma) cultured on a silicon surface. The Principal Component Analysis (PCA) enabled to differentiate between various cell types. The mechanical alterations induced by oncogenic transformation were examined using AFM-based elasticity measurements (quantified by the Young s modulus) in search of the correlation with chemical composition of cellular surface. The characterization of cancer-related changes in a quantitative manner with respect to normal, benign, and cancerous cells defines a new target area for novel diagnostic approaches. Acknowledgements The work has been financed by the NCN project no DEC-2013/11/N/ST4/ JB is grateful to Polish National Science Center (NCN) for the financial support of the ETIUDA scholarship no DEC- 2015/16/T/ST4/ References [1] E. Gazi, J. Dwyer, N. Lockyer, P. Gardner, J. C. Vickerman, J. Miyan, C. A. Hart, M. Brown, J. H. Shanks, N. Clarke, Faraday Discuss. 2004, 126, [2] K. S. Kulp, E. S. F. Berman, M. G. Knize, D. L. Shattuck, E. J. Nelson, L. Wu, J. L. Montgomery, J. S. Felton, K. J. Wu, Anal. Chem. 2006, [3] J. Gostek, K. Awsiuk, J. Pabijan, J. Rysk, A. Budkowski, M. Lekka, Anal. Chem. 2015, 87, Page22

23 KEYNOTE LECTURES Page23

24 KN 1. AN ACCURATE ANSWER FOR A CHALLENGING SCIENCE HIGH RESOLUTION AND ACCURATE MASS SPECTROMETRY Mihnea Dragos Efstatiade Pro Analysis Systems, Street, 29 Sfanta Vineri, Bucharest, Romania dragos.efstatiade@proanalysis.ro More samples per day, increased number of analytes per sample, complex and new matrices as well as the necessity of decreasing both positive and negative false results are common, every day challenges in present analytical laboratories. In this challenging environment, Thermo Fisher Scientific answered with turnkey solutions based on high resolution and ultimate accuracy in chromatography and mass spectrometry, solutions which are not only able to respond to these present requirements, but also offering an advanced platform able to withstand the dynamic increase in requirements and regulations, for which the question is not if they will come but how soon they will come. Based on novel, revolutionary concept in mass spectrometry, orbital ion trapping in pure electrostatic field, Alexander Macarov (Thermo Fisher Scientific) developed a new series of instruments providing high resolution and accurate mass measurements, overcoming the most challenging present and future requirements and surpassing all other instruments based on Time Of Flight (TOF) technology. The Orbital Ion Trap is providing the analysts with highest sensitivity and selectivity, ultimate confidence in measurements and fastest results possible today, enabled by outstanding resolving power of FWHM, extreme accurate mass measurements and sensitivity in low femtograms region, available only on this class of instruments. A new concept, QUANFIRMATION (qualitative, quantitative and confirmation of the results in a single analysis) was introduced, which, together with retrospective data analysis offers the users the ultimate tools for overcoming the present and the future analytical challenges for any application. References [1] Alexander Makarov, Anal. Chem., 2000, 72, [2] Reiner Westermeier, Tom Naven, Hans-Rudolf Hopker, Proteomics in Practice, Second Edition, Wiley-VCH Verlag GmbH & Co. KGaA, 2008 [3] Ingvar Eidhammer, Kristian Flikka, Lennart Martens, Svein-Ole Mikalsen, Computational Methods for Mass Spectrometry Proteomics, John Wiley & Sons Ltd., 2007 Page24

25 KN 2. STOCHASTIC SENSORS AS SCREENING TOOLS FOR OBESITY AND RELATED DISEASES Livia Alexandra Gugoasa Laboratory of Electrochemistry and PATLAB Bucharest, NIRDECM, Bucharest-4, , Romania In the recent years obesity was considered more than an esthetic issue, being known as a risk factor for many chronic diseases such as type II diabetes, different types of cancers, cardiovascular issues, hypertension and stroke, and also for the inset of early puberty in children. Aiming the prevention of these diseases we have developed screening methods for biomarkers specific to obesity and related diseases. Our studies proved that preventing obesity can be done earlier by (1) avoiding the use of plastics based on bisphenol A, as well as hormone injected foods, (2) conducting genetic obesity tests (leptin and PAI-1) and (3) conducting screening tests for detection of adipokines and cytokines such as: interleukin-6 (IL-6), monocyte chemoattractant protein -1 (MCP-1), peroxisome proliferator activated receptor (PPAR- ). The screening methods were based on the use of stochastic sensors for molecular recognition of these biomarkers. Stochastic sensors are designed from carbon based materials modified with electroactive compounds. The physical immobilization of these electroactive compounds makes possible the stochastic response due to the formation of stable pores which favor both qualitative and quantitative assay of specific biomarkers. Up to five markers were analyzed simultaneous in one run. This analysis of the panels of biomarkers responsible for obesity is simple, it reaches very low determination limits, very good sensitivities and it is price affordable for any patient and can it be done within minutes. Acknowledgements: The author acknowledge the funds obtained from the projects ERC-like ( ), and Ideas 123/2011. Page25

26 KN 3. SIMULTANEOUS QUANTITATION AND IDENTIFICATION OF ABOUT 500 PESTICIDE RESIDUES IN FOOD EXTRACTS BY LC-QTOF MASS SPECTROMETRY AND THE CHALLENGE OF FALSE POSITIVES Gordon van 't Slot 1*, Carsten Baessmann 1, Adrian Arsintescu 2 1 Bruker Daltonik GmbH, Fahrenheitstraße 4, Bremen, Germany 2 Mecro System, 100P Timisoara Blvd, RO Bucharest 6, Romania * Gordon.vant_Slot@bruker.com Fast and comprehensive full scan accurate mass screening and quantitation became an excellent tool in food control in particular if hundreds of pesticides have to be proved in a short time frame. Additionally to the high number of targets the technique takes advantage of unknown evaluation and retrospective analysis. We describe the development of a solution for screening and quantitation of pesticide residues in food matrices using high-resolution LC-QTOF accurate mass analysis. Central parts of the solution are TASQ, a software package for screening and quantitation and high quality databases. The software allows us to quantify hundreds of pesticide residues and securely identify them at the same time, by applying the diagnostic ion concept using qualifier ions. Our pesticide database contains about 820 pesticides; all qualifier ions in MS and broad band CID MS/MS annotated with molecular formulae. This allows us to determine the exact mass for all qualifier ions. In this study we show the simultaneous quantitation and identification of about 500 pesticides in food extracts. A great challenge in such a study is avoiding false positives. In this presentation we describe the successful application of strategies to avoid false positives by selecting the best diagnostic ions for identification and the best principle ion for quantitation. Page26

27 KN 4. ACTIVE NATURAL COMPOUNDS IN COSMETICS AND PHARMACEUTICALS ANALYTICAL ASPECTS Rodica Mariana Ion ICECHIM, 202 Splaiul Independentei, Bucharest, , Romania Valahia University of Targoviste, 13 Aleea Sinaia, , Targoviste 1. Introduction As the largest and most widespread, the natural compounds found in plant extract, display a great variety of structures, ranging from simple compounds containing a single aromatic ring to highly complex polymeric substances such as tannins and lignin [1]. These bioactive compounds have useful properties for cosmetics, functional foods and human health. The analytical techniques, suitable for rapid analysis of some phenolic acids (chlorogenic acid, ferulic acid, alpha-tocopherol, apigenine, lycopene, rutin), will be presented in this paper. Their detection in plant will be presented through advanced analytical techniques and their potential applications in cosmetics and sunscreen gels will be evaluated. 2. Experimental Relevant analytical characterization methods are presented and discussed as follows: UV-Vis, FTIR and Raman spectroscopy, dynamic light scattering (DLS), atomic-force microscopy (AFM) and scanning electron microscopy (SEM) and HPLC, with the following parameters: linearity, linear range, limit of detection (LOD), limit of quantification (LOQ). 3. Results and discussion The linearity was expressed as the regression coefficients for all compounds, the limits of quantification (LOQ) and the limits of detection (LOD) Figure 1. DLS results for lycopene extracted from tomatoes Table 1. The HPLC analyses of phenolic acids. Compound Linearity (R 2 ) LOD (μg ml -1 ) LOQ (μg ml -1 ) Chlorogenic acid Rutin Apigenine Lycopene Ferulic acid tocopherol Conclusions The conclusion was that some bioactive molecules are present in plant extracts and they are efficient for cosmetic and sunscreen gels. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research, CNDI-UEFISCDI, projects number PNII 185/2014. References [1] R. M. Ion, I. R. Bunghez, (2015). Oxidative Stress-Based Photodynamic Therapy with Synthetic Sensitizers and/or Natural Antioxidants, in: Basic Principles and Clinical Significance of Oxidative Stress, SJT Gowder (Ed.), InTech, pp Page27

28 KN 5. INBORN ERRORS OF METABOLISM. CASE STUDIES BY NMR Alina Nicolescu 1 *, Romana Vulturar 2, Natalia Usurelu 3, Bogdan C. Simionescu 1,4, Calin Deleanu 1,5 1 Petru Poni Institute of Macromolecular Chemistry of the Romanian Academy, Aleea Grigore Ghica Voda 41A, RO Iasi, Romania 2 I. Hatieganu University of Medicine and Pharmacy, Department of Cell and Molecular Biology, Str. Pasteur 6, RO Cluj-Napoca, Romania 3 The Institute of Mother and Child, Chisinau, MD-2028 Moldova 4 Gheorghe Asachi Technical University, Dept. of Natural and Synthetic Polymers, Iasi RO , Romania 5 Costin D. Nenitescu Centre of Organic Chemistry, Romanian Academy, RO Bucharest, Romania. * alina@icmpp.ro The paper deals with NMR spectra of complex body fluids, discussing some experimental factors, reproducibility, and data interpretation via either biomarker identification approach or blind statistical classifier approach. The core of this presentation focuses on successful applications of NMR spectroscopy to clinical tests for metabolic disorders. Several cases of Romanian and Moldovian children with inborn errors of metabolism (IEM) that have been diagnosed by NMR spectroscopy are discussed. Cit Cit DMA Pyr GABA Ala Lac Val Val ppm Figure 1. Water-suppression whole 1 H-NMR spectrum (400 MHz) of a urine sample (left), with examples of metabolite signal assignments in the region ppm (right). To ensure reproducibility, apart from the NMR parameters and pulse sequences, several additional technical problems have to be solved. Some technical aspects are also discussed in the paper. Acknowledgements The authors acknowledge the financial support of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PNII-ID-PCCE Page28

29 KN 6. POLYMERSOMES WITH ENGINEERED SELECTIVE MEMBRANE PERMEABILITY AS NOVEL BIOSENSING NANODEVICES Mihai Lomora 1 *, Ionel Adrian Dinu 1,2, Martina Garni 1, Tomaz Einfalt 1, Serena Rigo 1, Fabian Itel 1, Xiaoyan Zhang 1, Wolfgang Meier 1, Cornelia G. Palivan 1 1 University of Basel, Department of Chemistry, Klingelbergstrasse 80, CH-4056 Basel, Switzerland 2 Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, Iasi, Romania * mihai.lomora@unibas.ch Introduction In nature, biomolecules such as biopores, ion transporters and membrane proteins play a major role in controlling the dynamics of ions and molecules across the cellular membrane [1]. Using a bio-mimetic approach, functional membranes with selective permeability were engineered by inserting these biomolecules into the membrane of synthetic nanocompartments. The self-assembled nanostructures with smart membranes were loaded with enzymes or specific fluorescence markers and used as sensing nanodevices for selective detection of ions and molecules [2-5]. Results and discussion Here, we present combinations of biomolecules and polymer membranes, which serve for generation of selective permeability for the design of biosensing nanodevices. We used amphiphilic block copolymers, which self-assemble in aqueous solutions into vesicles and can adapt biomolecules into their membranes. Poly(2-methyl-2-oxazoline) block - poly(dimethylsiloxane) block - poly(2-methyl-2- oxazoline) triblock copolymers were chosen because the resulting synthetic membranes are mechanically stable and their properties (thickness, flexibility, and stimuli-responsiveness) can easily be adjusted [6,7]. Conclusions Using synthetic membranes with a high flexibility and fluidity, composed of amphiphilic triblock copolymers, we were able to successfully insert various biomolecules into the membranes of polymer vesicles, without affecting their architecture. In this way, the polymer membrane became selectively permeable allowing the passage of ions and molecules. These results open new borders for designing biosensors or nanoreactors with increased sensitivity and stimuli-responsiveness. Acknowledgements The authors gratefully acknowledge the financial support provided by the Swiss National Science Foundation, the National Center of Competence in Research and University of Basel. References [1] J. N. Sachs, D. M. Engelman, Ann. Rev. Biochem. 2006, 75, [2] M. Lomora, M. Garni, F. Itel, P. Tanner, M. Spulber, C. G. Palivan, Biomaterials 2015, 53, [3] M. Lomora, F. Itel, I. A. Dinu, C. G. Palivan, Phys. Chem. Chem. Phys. 2015, 17, [4] M. Lomora, I. A. Dinu, F. Itel, S. Rigo, M. Spulber, C. G. Palivan, Macromol. Rapid Commun. 2015, 36, [5] X. Zhang, M. Lomora, T. Einfalt, W. Meier, N. Klein, D. Schneider, C. G. Palivan, Biomaterials 2016, 89, [6] F. Itel, M. Chami, A. Najer, S. Lo rcher, D. Wu, I. A. Dinu, W. Meier, Macromolecules 2014, 47, [7] F. Itel, A. Najer, C. G. Palivan, W. Meier, Nano Lett. 2015, 15, Page29

30 KN 7. SORBENTS FOR IONIC MOLECULES BASED ON CaCO 3 / POLYMER COMPOSITES Marcela Mihai 1 *, Ion Bunia 1, Simona Schwarz 2 1 "Petru Poni" Institute of Macromolecular Chemistry, Grigore Ghica Voda Alley 41 A, Iasi, Romania 2 Leibniz-Institut für Polymerforschung Dresden e. V., Hohe Strasse 6, Dresden, Germany * marcelas@icmpp.ro The high porosity and specific surface area of CaCO3 materials are favorable for the adsorbent of functional molecules. The polymorph ratio on the composite structures is expecting to induce different sorption capacity. The main property relevant to the loading/sorption capacity of a particle is its exposed surface area, which is a function of its size, colloidal stability and porosity. In general, the smaller the particle radius the greater is its surface area relative to its volume. Porosity affects also the particles surface area: a porous particle provides more location for adsorption because it exposes additional surface area inside the particle. The surface reactive groups affect the specificity of the particle: highly selective separation is achieved by the adsorption of target molecules onto these groups. The interaction between trace metal ions and the widespread calcium carbonate minerals is often found in nature and influence the distribution of the ions in the aquatic environment as well as the reactivity of the minerals [1]. Last years, ion exchange resins were intensively used in the removal of inorganic matters in water and wastewater [2]. The retention of metal cations could occur by ion exchange using cation exchangers or strong base anion exchangers, if the metal cations are as complex anions or there are conditions to form these anions and chelating processes, when ion exchangers contain into their functional groups one or more electron-donor elements [3]. The interactions between trace metal ions and the calcium carbonate minerals is often meet in nature and influence the distribution of the ions in the aquatic environment and the reactivity of the minerals [1]. Therefore, some resins beads, before and after CaCO3 mineralization, were tested as sorbents for Cu(II) ions [4]. The beads were tested as sorbents for Cu(II) ions both before and after CaCO3 mineralization. The sorption capacity was shown to increase significantly after CaCO3 crystals growth on the weak anionic beads surface (up to mg Cu(II)/g sample) as compared to that of unmodified beads (491.5 mg Cu(II)/g sample). The newly formed patterns on beads surface after Cu 2+ sorption were observed by SEM and the elements distribution on the composites and the chemical structure of crystals after interaction with Cu(II) were investigated by EDAX mapping and FTIR-ATR, respectively. CaCO3/pectin samples prepared with different pectin concentrations, pectin chemical structure were tested as sorbents for Cu(II) and Ni(II) ions [5]. The maximum sorption capacity was determined taking into account the initial CuSO4 and NiSO4 concentration in aqueous solutions and the residual concentration of the supernatant after sorption. The composites characteristics (pectin concentration in anionic groups or the amide group presence, and also the calcite/vaterite ratio) influence the sorption capacity against Cu(II) and Ni(II) ions. The composites have a good sorption capacity for Ni(II) ions whereas that for Cu(II) ions is extremely high, even at the lowest tested concentration (0.01 wt%) when the sorption capacity was 2470 mg Cu(II)/g sample. The sorption capacity increased with increasing the pectin concentration up to ~3200 mg/g for 0.05 wt.% pectin content. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS UEFISCDI, project number PN-II-RU-TE Page30 References [1] J. Paquette, R. J. Reeder, Geochim. Cosmochim. Acta 1995, 59, [2] K. Mandel, F. Hutter, C. Gellermann, G. Sextl, ACS Appl. Mater. Interfaces 2012, 4, [3] Z. Hubicki, D. Kołodyńska; in A. Kilisliog lu (Ed.); Ion Exchange Technologies, Publisher InTech, 2012; Chapter 8, pp [4] M. Mihai, I. Bunia, F. Doroftei, C.-D. Varganici, B.C. Simionescu, Chem. Eur. J. 2015, 21, [5] M. Mihai, C. Steinbach, M. Aflori, S. Schwarz, Mater. Design 2015, 86,

31 KN 8. DYNAMIC MECHANICAL ANALYSIS IN POLYMERIC MATERIALS: OLD-FASHIONED OR VINTAGE INVESTIGATION? Mariana Cristea Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda, 41A, Iasi, Romania In the digital age all the instruments dedicated to the investigations of polymers, and not only, have been accordingly optimized and updated. Practically, most of them can be used on a regular basis for investigations by any committed researcher after some basic training. Often the software facilities make the result to be transferred to the manuscript without any modification. Unfortunately, not the same happens with the reading and the interpretation of the results. There are still misunderstandings in the world of polymer chemists concerning the dynamic mechanical analysis (DMA) [1,2]. The very first one is connected with name of the method: dynamic mechanical (thermal) analysis, dynamic mechanical spectroscopy or torsional braid analysis [3-5]. Then, the method is frequently the technique of choice for determining the glass transition temperature of polymers, which is very correct if some requirements concerning the sample are fulfilled. However, before being a thermal method, DMA belongs to the group of techniques that take advantage of the time-dependent properties of polymers. Briefly, it makes the difference between the elastic and the viscous characteristics of polymeric materials, that is reflected in the determination of storage modulus (E ), loss modulus (E ) and loss factor (tan ). The way these parameters vary with temperature and/or in time may offer an overview of the structure-property relationship. After a short introduction in the history of the method, the presentation aims to put forward the utility of the method as a research instrument in the field of polymers, with connections to examples encountered in every-day life. The advantages/drawbacks of DMA will be illustrated on polymers synthesized in Petru Poni Institute of Macromolecular Chemistry, Iasi, in comparison with other techniques [6-8]. The dilemma dynamic mechanical analysis/rheology will be elucidated. References [1] K. P. Menard, Dynamic mechanical analysis: A practical introduction, CRC Press, Boca Raton, FL, [2] T. G. Mezger, The rheology handbook, Vincentz Network, Hannover, Germany, [3] J. Mijovic, H. Lee, J. Kenny, J. Mays, Macromolecules 2006, 39, [4] X. Wu, Z. Zhu, J. Phys. Chem. B 2009, 113, [5] J. K. Gillham, J. Macromol. Sci. B 1974, 9, [6] M. Cristea, D. Ionita, B. C. Simionescu, Eur. Polym. J. 2010, 46, [7] M. Cristea, D. Ionita, C. Hulubei, D. Timpu, D. Popovici, B. C. Simionescu, Polymer 2011, 52, [8] M. Cristea, D. Ionita, F. Doroftei, B. C. Simionescu, J. Mech. Behav. Biomed. Mat. 2013, 17, Page31

32 KN 9. CHALLENGES IN GAS-CHROMATOGRAPHYC ANALYSIS OF THERMALLY UNSTABLE COMPOUNDS. CASE STUDY FOR BROMINATED FLAME RETARDANTS Alin Constantin Dirtu 1,2 *, Dan Maftei 1, Mihai Dumitras 1, Adrian Covaci 2 1 Alexandru Ioan Cuza University of Iasi, Department of Chemistry, Carol I Blvd. No 11, , Iasi, Romania 2 University of Antwerp, Toxicological Center, Universiteitsplein 1, 2610 Wilrijk, Belgium * alin.dirtu@chem.uaic.ro 1. Introduction Flame retardants (FRs) are materials that inhibit or resist the spread of fire that are added to polymers which are used in consumer goods. They might migrate into indoor environments generating increased human exposure to such compounds. One of the most important classes of FRs used in indoor materials are polybrominated diphenyl ethers (PBDEs). Apart of these, BDEs which contains higher than eight Br atoms in molecule and especially decabrominated diphenyl ether (BDE 209) were reported to degrade at temperatures around 300 o C affecting their gas-chromatographic (GC) quantitative analysis. Since no scientific evidence is currently available on their thermal behavior, through the following of the present study we evaluated both from theoretical point of view and also experimental the conditions to be employed in order to accurately analyze such organic contaminants through the use of GC-MS methods. 2. Experimental and Computational We have investigated the thermal degradation of BDE 209 by simultaneous TG/DTA coupled with EGA-FTIR/MS under various conditions. Kinetic analysis of nonisothermal data was performed by NPK method. Within theoretical computations at the density functional theory level, a wide range of approximate density functionals/ basis set combinations were first benchmarked against available experimental data in reproducing (aromatic) C-O and C-Br bond dissociation energies. Theoretical estimates for bond dissociation enthalpies were used to propose initial steps in thermal degradation Results and discussion We could therefore explain the thermal behavior of BDE 209 during GC-MS analysis (see Figure) with the formation of the main of its degradation products, namely nona-bdes. The most abundant degradation product observed during analysis, BDE 207 could be explained by the theoretical computations suggesting the possibility of its monitoring during BDE 209 analysis in order to have a control of the observed thermal degradation during GC elution. However, in order to increase the methods accuracy by minimizing the thermal degradation, our results evidenced that the use of low-pressure gas chromatography coupled to mass spectrometry is the technique which provides the proper conditions for the minimum degradation of the thermal unstable compounds. Acknowledgements ACD acknowledges the University of Antwerp for the financial support on the GC-MS experiments. Thermal degradation experiments were employed with an instrument acquired by a grant supported by the ANCS, Ministry of Economy, Trade and Business Environment, through the National Program Capacities, CERNESIM. This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS-UEFISCDI, project number PN-II-RU-TE Page32 Signal (counts) Degradation products in GC Retention Time (min) BDE 209

33 KN 10. LYSOSOMAL STORAGE DISEASES: MRM-MS AND FLUORIMETRIC DIAGNOSTICS Laura Ion 1,2 *, Lucian Hritcu 3, Cristina Dimitriu 4, Stefan Maeser 2, Michael Przybylski 2, Brindusa- Alina Petre 1,2 1 Al. I. Cuza University, Faculty of Chemistry, Blvd Carol I, , Iasi, Romania 2 Steinbeis Center Biopolymer Analysis and Biomedical Mass Spectrometry, Bahnhofsplatz 1, 65428, Rüsselsheim Germany 3 Al. I. Cuza University, Faculty of Biology, Blvd Carol I, , Iasi, Romania 4 Sf. Maria Hospital, Vasile Lupu, , Iasi, Romania * ion.laura26@yahoo.com 1. Introduction Lysosomal storage disorders (LSDs) are rare inherited disorders of lysosome function and are classified into more than 40 types [1]. The majority of LSDs result from defective lysosomal acid hydrolysis of endogenous macromolecules and their consequent accumulation [2] [3]. 2. Experimental In this report we describe a specific and sensitive diagnostics on dry blod spots (DBS) for single and multiplex assay of rare diseases by multiple reactions monitoring mass spectrometry (MRM-MS). Clinical diagnostics assays were developed by comparative fluorimetric and MS-MRM determinations (Bruker ion trap-ms). 3. Results and discussion We have developed a high-throughput single and multiplexing assay for rare diseases in DBS. In our studies, the enzymatic activity levels in DBSs were determinate by fluorimetry or multiple reactions monitoring mass spectrometry in the presence of an internal standard showing a good statistical correlation in singles assays. The data obtained suggest that the new mass spectrometric assay is fast, reliable and can be successfully used in clinical trials for quantification of metabolites. Figure 1. Duplex assay using a modified umbelliferone substrate Acknowledgements This work was supported by the Romanian National Authority for Scientific Research, CNCS UEFISCDI, project number PN-II-RU-TE References [1] J.J. Hopwood, C.P. Morris, Mol. Biol. Med. 1990, 7, [2] A. Vellodi, Br. J. Haematol. 2004, 128, [3] D. Marsden, H. Levy, Clin. Chem. 2010, 56, Page33

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36 L 1. A DUAL ELECTROCHEMICAL NANOBIOSENSOR FOR THE INHIBITION BASED DETECTION OF CAPTOPRIL AND CATECHOL Sevinc Kurbanoglu 1,2 *, Lourdes Rivas 2, Sibel A. Ozkan 1, Arben Merkoçi 1,3 1 Catalan Institute of Nanoscience and Nanotechnology (ICN2), CSIC and The Barcelona Institute of Science and Technology, Campus UAB, Bellaterra, Barcelona, Spain 2 Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, 06100, Tandogan, Ankara, Turkey 3 ICREA, Barcelona, Catalonia, Spain * skurbanoglu@gmail.com 1. Introduction Tyrosinase is extensively found in nature, is a multifunctional copper-containing enzyme that catalyzes two distinct reactions of melanin synthesis: a hydroxylation of monophenols to o-diphenols (monophenolase activity) and an oxidation of o-diphenols to o-quinones (diphenolase activity), both using molecular oxygen. Captopril is an angiotensin-converting enzyme inhibitor drug which is widely used to treat congestive heart failure in combination with other drugs through its inhibitory effect on the angiotensin-converting enzyme [1,2]. 2. Experimental In this study, a novel biosensor based on electrochemically reduced graphene oxide and iridium oxide nanoparticles for the detection of angiotensin-converting enzyme inhibitor drug, captopril is presented. Tyrosinase is immobilized onto screen printed electrode by using coupling reagents. Biosensor response is characterized towards catechol, which is a well-known substrate of tyrosinase. Catechol detection is optimized in terms of graphene oxide concentration, number of cycles to reduce graphene oxide, amount of iridium oxide nanoparticles and amount of tyrosinase. 3. Results and discussion The designed biosensor is used to inhibit tyrosinase activity by captopril, via chelating copper at the active site of tyrosinase and thioquinone formation. The captopril detection using both inhibition ways are very sensitive with low limit of detection µm and µm for chelating copper at the active site of tyrosinase and thioquinone formation, respectively. The proposed methods have been applied in captopril determination in spiked human serum and pharmaceutical dosage forms. 4. Conclusions A novel biosensor based on the use of a biocomposite made of electrochemically reduced graphene oxide, iridium oxide nanoparticles and tyrosinase for catechol and captopril detection is developed. Acknowledgments We acknowledge MINECO (Spain) through Project MAT S. Kurbanoglu acknowledges the support given by Ankara University BAP14L for her Ph.D. thesis project. References [1] S.A. Ozkan, Electroanalytical Methods in Pharmaceutical Analysis and Their Validation. HNB Publishing, New York, [2] S. Marn, A. Merkoçi, Electroanalysis. 2012, 24, Page36

37 L 2. NEW NANOSTRUCTURED MATERIAL DETECTS 8-HYDROXY-2 -DEOXYGUANOSINE Roxana Balahura 1, Raluca-Ioana Stefan-van Staden 1*, Livia Alexandra Gugoasa 1, Jacobus F. van Staden 1, Hassan Y Aboul-Enein 2 1 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 2 Pharmaceutical and Medicinal Chemistry Department, The Pharmaceutical and Drug Industries Research Division, National Research Centre, Dokki, Giza 12622, Egypt * ralucavanstaden@gmail.com 1. Introduction 8-hydroxy-2 -deoxyguanosine was reported as a biomarker for leukemia. Its early detection can help early diagnosis and immediate treatment. 2. Experimental A new stochastic sensor based on graphene modified with Ag nanoparticles and TiO2 was designed by physical mixture of the modified graphene powder with porphyrin solution and paraffin oil. 3. Results and discussion The high sensitivity and selectivity of the sensor when used for the assay of 8-hydroxy-2 -deoxyguanosine at two different phs 3.00, and 7.46 made possible its utilization as screening tool for leukemia. Urine samples and whole blood samples were screened using this sensor. The screening tests proved that the new material used for sensors design recognized the 8-hydroxy-2 -deoxyguanosine at both phs, and also were able to quantify reliable the biomarker. 4. Conclusions The proposed sensor can be reliably used for the screening tests of whole blood and early detection of leukemia. Acknowledgements The authors want to thank to UEFISCDI, Ideas 123/2011 for the financial support. Page37

38 L 3. DETERMINATION OF DOPAMINE USING THE ALKALINE LUMINOL-HYDROGEN PEROXIDE SYSTEM FOR SEQUENTIAL INJECTION ZONE FLUIDICS ANALYSIS Ramona Georgescu-State 1 *, Jacobus Frederick van Staden 2 1,2 National Institute of Research for Electrochemistry and Condensed Matter, Process Analytical Technology Laboratory (PATLAB), Splaiul Independentei, Bucharest, Romania * state_ramona@yahoo.ro In this work we investigate the possibilities of a luminol-hydrogen peroxide Photon Counter detector cell as chemiluminescence tubular reactor with the combination of sequential injection analysis with zonefluidics for the determination of dopamine as an alternative procedure by performing the analysis based on chemiluminescence reaction chemistry. We stack and sandwich the dopamine sample zone between alkaline luminol and hydrogen peroxide solutions zones separated further by air bubble head and tail zones inside a holding coil. These zones were reversed and rapidly dispensed into the Photon Counter tubular reactor detector with zone penetration and trapped as reaction mixture inside the tubular reactor detector cell for measurement using fluid flow-based stopped-flow manipulation technologies. The linear concentration range for dopamine was between 10-8 and 10-6 mol/l with the relative standard deviation of 3.30% and with the limit of detection of 2.60 x 10-9 mol/l. The proposed Sequential Injection Analysis - Zone Fluidics system was used reliably (the relative standard deviation is 2.57%, n = 5) for the assay of dopamine from the selected pharmaceutical ampoules with a recovery of 99.63%. This presentation will outline and highlight the investigation, observations and results obtained. Acknowledgements The authors would like to acknowledge the financial support received from project Program Ideas by PN- II-ID-PCE / , financed by contract 100/ Page38

39 L 4. MICROSENSORS BASED ON NANOSTRUCTURED MATERIALS AS NEW TOOLS FOR RECOGNITION OF INSULIN AND PROINSULIN IN BLOOD SAMPLES Grigorina Mitrofan 1*, Raluca-Ioana Stefan-van Staden 1,2, Constantin Ionescu-Targoviste 3 1 University Politehnica, Bucharest, 313 Splaiul Independentei Str, , Bucharest, Romania 2 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 3 National Institutes of Diabetes Nutrition and Metabolic Disease. N.C.Paulescu, Bucharest, Romania * mitrofan.grigorina@gmail.com 1. Introduction Determination of insulin and proinsulin at a very early stage is essential for reversal of diabetes. The main interest is to develop a method able to detect the ratio between the two markers at the stage when the diabetes can be reverse, even for children. 2. Experimental Five stochastic microsensors based on diamond and graphite paste were developed for the assay of insulin and proinsulin C-peptide in serum samples. For the design of the microsensors based on graphite paste, different electrocatalysts such as TiO2-Au and Pt modified with porphyrins (PIX and MEG 107) were used. Diamond paste based microsensors were modified with inulin TEX and with a mixture of inulin TEX and ionic liquid (L-alanine tert-butyl ester L-lactate). 3. Results and discussion The best limit of quantification for the assay of both insulin and prosinsulin C-peptide was obtained using the microsensor based on graphite, modified with Pt and porphyrin IX ( 5.28 fu/ml respectively 0.84 fmol/l). Proinsulin C-peptide can also be detected with the microsensors TiO2-Au-GR-PIX and TEX-L- Ala-C4-Lac with a low limit of quantification and a good sensitivity (1.24x109 respectively 2.25x108 mol/l). In the same time TiO2-Au-GR-PIX microsensor can detect insulin within the linear concentration range of 5.28x x10-12 U/mL. 4. Conclusions The new stochastic sensors proposed for the assay of insulin and proinsulin can be reliable used for the screening tests of whole blood samples. Acknowledgements The authors want to thank to UEFISCDI, Ideas 123/2011 for the financial support. Page39

40 L 5. THE EFFECT OF CHIRAL AMINO ACID BASED IONIC LIQUIDS ON CHIRAL DISCRIMINATION ABILITY OF HPΒCD IN CE SEPARATIONS Mihai Stanescu 1 *, Corina-Cristina Arama 1, Crina-Maria Monciu 1, Irina Doicin 2 1 University of Medicine and Pharmacy Carol Davila, Bucharest, Faculty of Pharmacy, Analytical chemistry Department 2 University of Medicine and Pharmacy Carol Davila, Bucharest, Faculty of Pharmacy * mihai.st88@yahoo.com 1. Introduction and objectives Cyclodextrins are cyclic oligosaccharidic compounds that are the commonly used as selectors in chiral separations in HPLC and electromigration techniques. HPβCD is a substituted cyclodextrin that serves as a selector in chiral electrophoretical separations of several classes of drugs. [7, 4] The aim of this study was to investigate the possibilities to enhance the efficiency of the chiral separations achieved when using HPβCD as a chiral selector in CE. Several dual selector systems amino acid ionic liquids (AAIL) and HPβCD were tested in order to establish the extent to which enantioresolution provided by the cyclodextrin may be increased [2, 3, 6]. 2. Materials and methods We have selected several racemates (ondansetron, ofloxacin, mianserin) separated with different resolutions using HPβCD as sole selector in CZE [7, 8]. Amino acid based ionic liquids (tetraalkylammonium - tetrabutylammonium and tetramethylammonium - salts of amino acids) were synthesized and characterized [1, 5] and the influence of ionic liquids on the separations enantioselectivities was tested. The BGE used all over the study was 50 mm citrate buffer, ph 3 and the analysis in CZE were performed using an Agilent G 1600 system. Several parameters (the concentration of both selectors, the applied voltage and the working temperature) were changed to highlight the effect of the AAILs. We maintained a low HPβCD concentration in the BGE (maximum 15 mm). 3. Results The dual system HPβCD-AAIL was a better choice for the separation of the racemic drugs cited above. The enantioseparation efficiency varied, depending on the side chain of the tetraalkyammonium moiety and on the amino acid anion. The enantioselectivity was better with longer side chain of the tetraalkylammonium ion. 4. Conclusion We have demonstrated that AAIL and HPβCD have a synergic effect on the chiral separations and we have selected the proper conditions for the analysis of specific racemic mixtures. References: [1] C. R. Allen, P. L. Richard, A. J. Ward, L.G. A. Van de Water, A. F. Masters, T. Maschmeyer, Tetrahedron Lett. 2006, 47, [2] J. L. Anderson, D. W. Armstrong, G.-T. Wei, Anal. Chem. 2006, 78, [3] A. Berthod, Anal. Chem. 2006, 78, [4] Y. Cui, X. Ma, M. Zhao, Z. Jiang, S. Xu, X. Guo, Chirality 2013, 25, [5] Y. Y. Jiang, G. N. Wang, Z. Zhou, Y.-T. Wu, J. Geng, Z.-B. Zhang, Chem. Commun. 2008, [6] M. Li, D. K. Bwambok, S. O. Fakayode, I. M. Warner; in Berthod, A., (Ed.); Chiral Recognition in Separation Methods, Mechanisms and Applications, Ed. Springer-Verlag Berlin, Heidelberg, 2010, p [7] F. E. O. Suliman, A. A. Elbashir, O. J. Schmitz, J. Incl. Phenom. Macrocycl. Chem. 2015, 83, [8] G. Tóth, R. Mohácsi, A. Rácz, A. Rusu, P. Horváth, L. Szente, S. Béni, B. Noszál, J. Incl. Phenom. Macrocycl. Chem. 2013, 77, [9] F. Wang, M. G. Khaledi, Anal. Chem. 1996, 68, Page40

41 L 6. DETERMINATION OF P53 USING GRAPHITE AND GRAPHENE BASED AMPEROMETRIC SENSORS Ahmed Jassim Muklive AL-Ogaidi 1*, Livia Alexandra Gugoasa 2, Raluca-Ioana Stefan-van Staden 1,2 1 University Politehnica, Bucharest, 313 Splaiul Independentei Str, , Bucharest, Romania 2 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania * ahmed.mukleef@yahoo.com 1. Introduction P53 it is a very important tumoral marker for colon cancer diagnosis. Its determination at a very early stage can help the doctor diagnose the patient and start to treat the patient. Therefore it is a real need to design very sensitive sensors for its detection. 2. Experimental Amperometric sensors were design in the laboratory for the assay of P53. The sensors were based on grahite and grapheme powder with modifiers such as porphyrins and oleamides. 3. Results and discussion Very low limits of determination and detection were achieved using the proposed stochastic sensors. These limits are in the range of early detection, but can also allow the assay of p53 in stages 3 or 4 of the colon cancer. The sensors exhibited high selectivity over other colon cancer biomarkers, but also over other components from whole blood such as neurotransmitters. The recovery tests performed proved the suitability of these sensors for the early detection of p53 in whole blood samples. 4. Conclusions The assay of p53 in whole blood was reliable performed using the proposed amperometric sensors bsed on physical immobilization of porphyrins and oleamides in graphite and grapheme based pastes. Acknowledgements The authors want to thank to UEFISCDI, Partnership 22/2014 for the financial support. Page41

42 L 7. NMR CHARACTERIZATION OF IMIDAZOLIUM-CYCLODEXTRINE INCLUSION COMPLEXES Mihaela Balan-Porcarasu 1*, Alina Nicolescu 1, Emilian Georgescu 2, Florentina Georgescu 3, Bogdan C. Simionescu 1,4, Calin Deleanu 1,5 1 Petru Poni Institute of Macromolecular Chemistry of the Romanian Academy, Aleea Grigore Ghica Voda 41A, RO Iasi, Romania 2 Research Center Oltchim, Str. Uzinei 1, RO Ramnicu Valcea, Romania 3 Teso Spec S.R.L., Research Dept., Str. Muncii 53, RO Fundulea, Calarasi, Romania 4 Gheorghe Asachi Technical University, Dept. of Natural and Synthetic Polymers, RO Iasi, Romania 5 Costin D. Nenitescu Centre of Organic Chemistry, Romanian Academy, RO Bucharest, Romania. * mihaela.balan@icmpp.ro Cyclodextrines are compounds which can be obtained in industrial amounts and at accessible prices. The interest for cyclodextrines comes from various scientific topics such as their structure, host-guest complexations with other compounds, catalytic properties, supramolecular architectures. They are readily available as natural products and have various applications into fields like pharmaceuticals, environment protection, food industry and others. Native cyclodextrines and their derivatives could accommodate a wide variety of inorganic, organic, and biological molecules in their hydrophobic cavity forming stable inclusion complexes in aqueous solution. Such complexes can be used to increase the bioavailability of poorly soluble compounds. There is a high interest in cyclodextrine inclusion complexes with imidazolium derivatives, studies aiming to explore changes in solubility, drug/compound delivery carriers, structural or theoretical parameters. NMR spectroscopy is one of the most important analytical methods used to follow cyclodextrines interactions. Using different 1D and 2D NMR techniques, detailed information about cyclodextrines themselves and their inclusion complexes can be obtained. The present paper discusses the NMR characterization of inclusion complexes of cyclodextrines with various imidazolium derivatives. Some experimental parameters used during routine NMR analysis which can alter the results and lead to possible misinterpretations are also discussed. Acknowledgements The authors acknowledge the financial support of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PNII-ID-PCCE Page42

43 L 8. SYNTHESIS OF A NOVEL α, ω-diepoxy-poly(2-ethyl-2- OXAZOLINE) OLIGOMER Alina-Maria Anghelache 1,2,3 *, Valentin Victor Jerca 3, Florica Adriana Jerca 3, Dumitru Mircea Vuluga 3, Mircea Teodorescu 1 1 University POLITEHNICA of Bucharest, Faculty of Applied Chemistry and Materials Science, Department of Bioresources and Polymer Science, Splaiul Independentei 313, , Bucharest, Romania 2 National Research and Development Institute for Industrial Ecology ECOIND Bucharest, Drumul Podu Dambovitei St , , Bucharest, Romania 3 Centre of Organic Chemistry Costin D. Nenitescu, Romanian Academy, Spl. Independentei, 202 B, , Bucharest, Romania * alina_anghelache1987@yahoo.com Recently, there has been an increasing interest in the development of environmentally responsive polymers as biomaterials [1]. Current research in chemistry proved that the class of 2-oxazolines is enabling the preparation of materials with tailor-made properties [2]. The living cationic ring-opening polymerization (CROP) of 2-oxazolines provides easy and direct access to a wide variety of well-defined polymers [3], in which the endgroup functionality could be controlled during the initiation and termination steps. Nowadays, the particular focus has been to apply these materials for biomedical applications [4], whereas it is essential that the temperature responsiveness to be consistently at physiologically relevant temperatures and the polymer to be biocompatible. Herein we present a detailed investigation of the modulation of the endgroup functionality for oligomeric poly(2-ethyl-2-oxazoline). The major aim of this study is to prepare prepolymers for further incorporation into tridimensional structures. α, ω-diepoxy-poly(2-ethyl-2-oxazoline) oligomers were synthesized by reacting α, ω-dihydroxy-poly(2-ethyl-2-oxazoline) oligomers with epichlorohydrin using both phase transfer catalysis and the metalation method. Figure 1. Synthesis routes for diepoxy-terminated poly(2-ethyl-2-oxazoline) oligomer (PEtOxepoxy) References [1] C. He, S. W. Kim, D. S. Lee, J. Control. Release 2008, 127, [2] E. Rossegger, V. Schenk, F. Wiesbrock, Polymers 2013, 5, [3] R. Hoogenboom, Angew. Chem. Int. Ed. 2009, 48, [4] N. Adams, U. S. Schubert, Adv. Drug Deliv. Rev. 2007, 59, Page43

44 L 9. VIBRATIONAL SPECTROSCOPY IN BODY FLUIDS ANALYSIS Andrei A. Bunaciu 1,*, Oana Mihaela Antochi 1, Serban Fleschin 2, Vu Dang Hoang 3 and Hassan Y. Aboul-Enein 4 1 SCIENT - Research Center for Instrumental Analysis, (CROMATEC_PLUS S.R.L.), , Tancabesti Snagov, Romania 2 Department of Organic Chemistry, Biochemistry and Catalysis, Faculty of Chemistry, University of Bucharest, , Bucharest, Romania 3 Department of Analytical Chemistry and Toxicology, Hanoi University of Pharmacy, Hanoi, Vietnam 4 Pharmaceutical and Medicinal Chemistry Department, Pharmaceutical and Drug Industries Research Division, National Research Centre, Cairo 12311, Egypt * aabunaciu@gmail.com Vibrational spectroscopy offers a unique opportunity to investigate the composition of unknown substances on a molecular basis. The spectroscopy of molecular vibrations using mid-infrared or Raman techniques has been applied to samples of body fluids. Vibrational spectroscopic methods such as FTIR- and Raman spectroscopy are multipurpose techniques that offer advantages in simplicity, rapidity, low-cost, and minimal sample preparation. Vibrational spectroscopic techniques have significant potential in the field of biomedical analysis, as they can give molecularly specific biochemical information without the use of extrinsic labels and without being invasive to the system studied. The greatest benefit of this techniques lies in the high molecular sensitivity combined with a spatial resolution down to a few micrometers. Another advantage is the ability to probe samples under native conditions, which allows new insights into samples without the need for fixation, stains, or an additional marker. Advances in instrumentation have made FTIR spectroscopic imaging the tool of choice for an increasing number of applications. The development of Raman spectroscopic signatures of body fluids has demonstrated the potential for routine spectroscopic examination of biological samples. FT-IR and ATR FT-IR spectroscopic techniques produce spectra containing bands, or peaks, representative of the vibrations of structural bonds and functional groups within biological samples. The positioning of the peaks are specific to particular interactions with molecular bonds and provide specific information relating to the biochemical composition. The review presents some applications related to body fluids published in the period Page44

45 L 10. NEW DEVELOPMENTS IN BIOMEDICAL ANALYSIS USING STOCHASTIC SENSORS Raluca-Ioana Stefan-van Staden Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 1. Introduction Early detection of diseases became in the past year a high request from medical doctors. Some diseases like diabetes, cancer, hepatitis, can be reversed, and cured in only one condition; to be detected at a very early stage. Different types of electrochemical sensors were developed for medical analysis to date. The only reliable class of sensors is the one of stochastic sensors. 2. Experimental Different stochastic sensors were designed, characterized and validated for the assay of biomarkers for diabetes, cancer, obesity, neurotransmitters in biological fluids. 3. Results and discussion The limits of determination obtained as well as the recovery tests performed proved that they can be reliable used for the assay of such biomarkers in biological fluids of adults and children. This is an advantage over the standard methods of analysis that cannot be always applied for analysis of certain biomarkers in biological fluids such as saliva. 4. Conclusions The utilization of stochastic sensors increased the reliability of qualitative and quantitative analysis. They can be used for early screening and detection of different diseases. Acknowledgements The authors want to thank to UEFISCDI, PNII framework programs Ideas 123/2011 and Partnership 22/2014 for the financial support. Page45

46 L 11. STUDY AND EVALUATION OF THE ENHANCEMENT OF TRYPTOPHAN- FLUORESCENCE RESPONSE WITH THE INFLUENCE AND COMPARISON WITH MODIFICATION WITH FLUORESCENT DYES AND OXIDANTS IN TRYPTOPHAN ASSAYS Jacobus (Koos) F. Van Staden*, Ramona Georgescu-State Process Analytical Technology Laboratory (PATLAB) Bucharest, Splaiul Independentei Str., 202, Bucharest, Romania, * koosvanstaden2012@yahoo.com, Website: Tryptophan is an essential amino acid for humans with a significant role in cell metabolism. Depletion of tryptophan in the human body as well as toxic products generated in the brain by improper metabolism may be contributed to diseases and disorders development in human people. Tryptophan is an important intrinsic fluorescent substance (amino acid) and this property was first used as part of the determination of tryptophan and in estimation of the nature of the microenvironment of tryptophan. We found with confirmation to previous publications that the native fluorescence of tryptophan alone was, however, not very sensitive in our studies with a limitation of reliability and sustainability of the tryptophan analysis. We proceed then with a strategic study and evaluation with an investigation to get a stable and sustainable increase in the maximum response signal of tryptophan-fluorescence for proper determination of tryptophan. Fluorescein as fluorescent dye and potassium hexacyanoferrate(iii) as oxidant successfully enhanced the tryptophan-fluorescence response signal to such an extent that a proposed enhancement tryptophan-fluorescence method with modification using these inexpensive reagents was successfully applied for the determination of tryptophan in pharmaceutical capsules and beer with very good recoveries and relative standard deviation. Fluorescein and potassium hexacyanoferrate(iii) reagents in this proposed method are commercially easy available and therefore the proposed method could be easily adopted to routine laboratories for the determination of tryptophan in pharmaceutical formulations and the beer industry. The recoveries agreed very well with the certified amount labeled for tryptophan in pharmaceutical formulations with very good recoveries between 99.9 and % and a relative standard deviation (RSD%) of less than 0.5% (n = 5). The recoveries for the determination of tryptophan in beer were between 93.7 and 95.1 % with a relative standard deviation (RSD%) of less than 0.5% (n = 5). This presentation will outline and highlight the investigation, observations and results obtained. Acknowledgements The authors would like to acknowledge the financial support received from project Program Ideas by PN- II-ID-PCE / , financed by contract 100/ Page46

47 L 12. PATTERN RECOGNITION OF COLON CANCER BIOMARKERS FROM WHOLE BLOOD SAMPLES USING STOCHASTIC SENSORS Livia Alexandra Gugoasa 1*, Raluca-Ioana Stefan-van Staden 1, Ionela Raluca Comnea-Stancu 1, Camelia Stanciu-Gavan 2 1 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 2 Department of Surgery 4, University of Medicine and Pharmacy Carol Davila, Bucharest, Romania * livia.gugoasa@yahoo.com 1. Introduction Colon cancer is the second leading cause of cancer-related deaths in the world. P53 and KRAS genes are considered to be essential in the early-stage development of colon cancer. 2. Experimental Twelve stochastic sensors based on graphite, diamond and metal nanocomposites-graphene pastes modified with different types of porphyrins and oleamides were employed for the pattern recognition of colon cancer biomarkers: tumor protein 53 (P53) and KRAS. 3. Results and discussion Whole blood samples from patients with colon cancers were analyzed using stochastic sensors to detect the levels of P53 and KRAS knowing that the levels in sick patients are high. Stochastic sensors could reach low determination limits for the detection of P53 (5.63 x 10-9 µg ml -1 ) and of KRAS (1.97 x 10-9 µg ml -1 ). 4. Conclusions Stochastic sensors are a good alternative for the assay of P53 and KRAS from biological samples because they provide both qualitative and quantitative analysis, and they could have reliable used for the determination of the proposed biomarkers in whole blood. Acknowledgements The authors want to thank to UEFISCDI, Partnership 22/2014 for the financial support. Page47

48 L 13. INTERACTION BETWEEN POLYMERIC NANOPARTICLES AND ORAL KERATINOCYTE STEM CELLS Bogdan Calenic 1,2 *, Radu Eugen 3, Cristina Sabliov 4, Maria Greabu 1, Raluca Ioana Stefan-van Staden 2 1 Department of Biochemistry, Faculty of Dental Medicine, UMF Carol Davila 2 National Institute of Research for Electrochemistry and Condensed Mater, Bucharest, Romania, 3 Department of Cell Biology, Faculty of Medicine, UMF Carol Davila 4 Department of Biological and Agricultural Engineering, College of Engineering, Louisiana State University * bcalenic@yahoo.co.uk 1. Introduction Nanoparticle (NPs) interaction with humans organ and tissues has developed into and very important research field. While the oral route is an important way of nanoparticle delivery, data on the interaction between cells of the oral mucosa and nanoparticles is to data very limited. The aim of this work is to offer a brief review on the properties of polymeric nanoparticles and to focus on the oral keratinocytes uptake of these NPs. 2. Methods Oral keratinocyte cells with different phenotypes were separated from human oral mucosa using a magnetic based method and two surface markers α6β4 and CD71. The cells were exposed to different concentrations of PLGA and PLGA-Chitosan nanoparticles and analyzed for cell cytotoxicity, uptake and proliferation. 3. Results Proliferation and viability remained the same as negative controls. At the same time no cytotoxic effects could be observed at the analyzed points in time. Significant cellular uptake (30.2 ± 4.3% vs 10.4 ± 3.2%) could be observed in stem vs. normal keratinocyte population after 24 hours of incubation with 5µg/ml of PLGA-Chitosan. 4. Conclusion Normal keratinocytes, transit amplifying cells and oral keratinocyte stem cells had different uptake times following NPs exposure. Page48

49 L 14. ATMOSPHERIC CHEMISTRY INVESTIGATIONS IN A NEWLY DESIGNED GAS PHASE SIMULATION CHAMBER (ESCQ-UAIC) Iustinian Bejan 1*, Cecilia Arsene 1,2, Romeo Iulian Olariu 1,2 1 Alexandru Ioan Cuza University of Iasi, Integrated Center of Environmental Science Studies in the North Eastern Region - CERNESIM, 11 Carol I, Iasi, Romania 2 Alexandru Ioan Cuza University of Iasi, Faculty of Chemistry, 11 Carol I, Iasi, Romania * iustinian.bejan@uaic.ro Environmental chambers play a key role in the understanding of the atmospheric chemistry and associated global problems with climate changes, pollution and greenhouse effect. These simulation platforms are used in the validation of the atmospheric chemical models as well. Recently, a new Environmental Simulation Chamber - Quartz at University Alexandru Ioan Cuza (ESCQ-UAIC), has been developed in Iasi, Romania, to study the atmospheric chemical reactions at ambient pressure and temperature. ESCQUAIC, with a volume of 760 litres, is highly equipped with a series of analytical instruments for on- and off-line measurements. For validation purposes, measurements of selected volatile organic compounds (VOCs) have been performed using long path absorption in situ Fourier Transform Infrared (FTIR) spectroscopy (492±1.2 m) and on-line Proton Transfer Reaction Time of Flight (PTR-TOF) mass spectrometry. In this study have been performed a complex gas phase investigation for selected VOCs. Infrared (IR) cross sections determinations for a series of aromatic compounds as well as kinetic and mechanistic studies have been used to validate the performance of the ESCQ-UAIC chamber facilities. The kinetic results data from mesitylene reaction with OH radicals (k=5.07± cm 3 molecule -1 s -1 ) studied by using relative method in the ESCQ-UAIC chamber (Figure 1) are in good agreement with the literature data [1]. However, there is no other relative rate kinetic study using H2O2 photolysis as OH precursor. Mechanistic investigations of the OH radical initiated gas phase degradation of p-xylene have been also performed. Ring retaining (ptolualdehyde, 2,5-dimethylphenol) and ring opening (glyoxal, methylglyoxal, 3-hexene-2,5- dione, 2-methyl-butenedial) products have been obtained by FTIR and PTR-TOF-MS analysis. This set-up has been used for first time in this study. ref. m-cresol ref. methyl-vinyl-ketone Figure 1 Kinetic data plot of the reaction of mesitylene with OH radical using two reference compounds. (insert) Gas phase mesitylene IR spectrum. The entire set of experimental data generated by using the ESCQ-UAIC chamber facility strongly confirms the suitability of the chamber for further similar studies. Investigations are in progress both on relative rate kinetic and gas phase mechanistic investigations with relevance for atmospheric chemistry. Acknowledgements This work was supported by two grants of the Romanian National Authority for Scientific Research and Innovation, CNCS UEFISCDI within the project PN-II-TE and project PN-II-PCE CERNESIM Center is gratefully acknowledged for the infrastructure used in this study. References [1] J.G. Calvert, R. Atkinson, K.H. Becker, R. Kamens, J. Seinfeld, T.J. Wallington, G. Yarwood, The Mechanisms of Atmospheric Oxidation of Aromatic Compounds, Oxford University Press, Page49

50 L 15. FUNCTIONAL SURFACES BASED ON SOLID SUPPORTED BIOMOLECULES- POLYMER MEMBRANES Camelia Draghici 1,2 *, Viktoria Mikhalevich 1, Justyna Kowal 1, Gesine Gunkel-Grabole 1, Wolfgang Meier 1, Cornelia G. Palivan 1 1 Chemistry Department, University of Basel, Klingelbergstrasse 80, 4056 Basel, Switzerland 2 Department of Product Design, Mechatronics and Environment, Transilvania University of Brasov, 29 Eroilor Blv, Brasov, Romania * c.draghici@unitbv.ro We developed functional surfaces based on solid supported mono- and bilayers of asymmetric triblock copolymers, which serve as templates for biomolecules immobilisation. A group of poly(ethylene glycol)- block-poly(γ-methyl-ε-caprolactone)-block-poly[(2-dimethylamino) ethyl methacrylate] amphiphilic copolymers, with different hydrophilic and hydrophobic domains (PEG45-PMCLX-PDMAEMAY) was selected to generate solid supported polymer membranes. The behavior of the copolymers in terms of their molecular arrangements at the air-water interface was established by a combination of Langmuir isotherms and Brewster angle microscopy (BAM) [1]. Uniform thin layers of copolymers were obtained by transferring the polymeric films onto silica solid supports, at optimal surface pressure, by Langmuir Blodgett transfer technique (Figure 1). These solid supported polymer membranes were further characterized by assessing their properties, such as monolayer thickness, hydrophilic/hydrophobic balance, topography and roughness. Laccase and tyrosinase were used as biomolecule models, to generate active surfaces by adsorption on solid supported polymeric surfaces. Both were successfully adsorbed to copolymer membranes by stable interactions as followed by quartz crystal microbalance with dissipation (QCM-D) measurements, and preserved their activity, as indicated by activity assays. The interaction between the amphiphilic triblock copolymer films and immobilized enzymes represents a straightforward approach to engineer functional surfaces, with biomolecules playing the active role by their intrinsic bioactivity. Figure 1. Principle of the Langmuir Blodgett transfer technique. [1] C. Draghici, J. Kowal, A. Darjan, W. Meier, C.G. Palivan, Langmuir, 2014, 30, Page50

51 L 16. COMPOSITE MICROPARTICLES USED IN SELECTIVE SEPARATION OF PEPSIN Claudiu-Augustin Ghiorghita*, Florin Bucatariu, Ecaterina Stela Dragan Petru Poni Institute of Macromolecular Chemistry, Grigore Ghica Voda Alley 41A, , Iasi, Romania * 1. Introduction Cross-linked thin films based on ph-responsive polymers with a specific ligand inside the organic layer, are useful materials in separation processes [1] or in fabrication of controlled delivery systems [2]. 2. Experimental Herein, we report the step-by-step deposition of polymer multilayers based on poly(ethyleneimine) (PEI), poly(acrylic acid) (PAA) and poly(sodium methacrylate) (PMAA) followed by the Congo Red (CR) immobilization onto composite Daisogel silica microparticles. After deposition of the film, the composite microparticles [Daisogel//(PEI/PAA)n and Daisogel//(PEI/PMAA)n] with CR entrapped inside the organic layer were used for PEP immobilization experiments (Figure 1). Figure 1. Schematic representation of polymer multilayers construction onto Daisogel microparticles, using PEI, PAA and PMAA followed by CR sorption in organic layer and PEP immobilization. 3. Results and discussion Using different proteins (PEP, BSA, TRY, LYS), with iep situated in the acidic and basic range of ph, it was shown that only PEP molecules are immobilized onto composites surfaces with CR inside the multilayer. This fact was attributed mainly to the β-sheet secondary structure of PEP which determines specific interactions with CR. The PEP sorbed amount depended on both the CR sorbed amount in the organic layer and the equilibrium concentration of PEP and do not depend by the number of polymer layers deposited. Acknowledgements This work was supported by CNCSIS-UEFISCSU by the project PN-II-IDPCE References [1] S. Bekri, L. Leclercq, H. Cottet, J. Chromatogr. A 2015, 1399, [2] F. Bucatariu, C.-A. Ghiorghita, E.S. Dragan, Colloids Surf. B: Biointerfaces 2015, 126, Page51

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53 POSTER PRESENTATIONS Page53

54 POSTER SESSION 1 YOUNG ANALYTICAL CHEMISTS P1Y. GREEN METHOD FOR NOBLE METALLIC NANOPARTICLES PREPARATION FROM SIDERITIS SKARDICA EXTRACTS Ioana-Raluca Suica-Bunghez 1 *, Sofia Teodorescu 2, Ioan Alin Bucurica 2, Raluca Somoghi 1, Rodica Mariana Ion 1,3 1 ICECHIM, 202 Splaiul Independentei, Bucharest, , Romania 2 Multidisciplinary Science and Technology Research Institute of Valahia University of Targoviste - ICSTM-UVT, 13 Aleea Sinaia, , Targoviste 3 Valahia University of Targoviste, 13 Aleea Sinaia, , Targoviste * raluca_bunghez@yahoo.com 1. Introduction The green method for obtaining metallic nanoparticles (PtNP, AgNP, AuNP) is shown in this paper, by using Sideritis Scardica extracts. 2. Experimental Relevant analytical characterization methods are presented and discussed as follows: UV-Vis, FTIR and Raman spectroscopy, dynamic light scattering (DLS), optical microscopy (OM), atomic-force microscopy (AFM) and scanning electron microscopy (SEM), Fig Results and discussion The composition, total phenolic content, total flavonoid content, total tannins content and total monoterpenoids content in flowers and strains of Sideritis Scardica plant, have been determined and correlated with the antioxidant activity, determined by using DPPH method. 4. Conclusions The conclusion was that the noble metallic nanoparticles could be generated due to bioactive molecules present in plant extracts. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research, CNDI- UEFISCDI, projects number PNII 185/2014. Page54 References [1] I.R. Bunghez, M.E. Barbinta-Patrascu, N. Badea, S.M. Doncea, A. Popescu, R.M. Ion, J. Optoel. Adv. Mat. 2012, 14, [2] I.R. Bunghez, O. Dumitrescu, R. Somoghi, I. Ionita, R.M. Ion, Rev. Chim, 2015, 66, [3] I.R. Bunghez, R.C. Fierascu, O. Dumitrescu, I. Fierascu, R.M. Ion, Rev. Roum. Chim., 2015, 60, Figure 1. Photo of Sideritis Skardica (up) and the AFM image (down) for Pt nanoparticles

55 P2Y. INFLUENCE OF MOLECULAR WEIGHT ON ISOTROPIC-ANISOTROPIC TRANSITION IN A CELLULOSE DERIVATIVE: RHEOLOGY AND OPTICAL MICROSCOPY INVESTIGATIONS Daniela Ailincai*, Luminita Ioana Buruiana, Andreea Irina Barzic Petru Poni Institute of Macromolecular Chemistry, 41 A Grigore Ghica Voda Alley, Iasi, Romania * ailincai.daniela@icmpp.ro 1. Introduction Cellulose derivates are known to possess the ability to self-organize if they are added in an appropriate organic solvent [1]. Liquid crystalline polymers have found applications in various domains ranging from electronics to biomedicine. The transition from isotropic to anisotropic phase is affected by several factors, such as temperature, solvent type and molecular weight [2,3]. 2. Experimental The rheological investigations were performed on polymer solutions of different concentrations at room temperature. Polarized light microscopy experiments were employed to analyze the anisotropic character of the polymer films prepared from the corresponding solutions. 3. Results and discussion The studied cellulose derivative, with variable molecular weight, was added in an organic solvent. The shear viscosity tests revealed sudden changes in viscosity as the polymer concentration increases. This is indicative of the liquid crystal phase occurrence. The critical concentration that denotes orientation of the chains in the system is influenced by the molecular weight of the polymer. Optical microscopy images reveal that the film samples, obtained from solutions at concentrations above the critical one, exhibit birefringent domains as a result of liquid crystal phase formation. 4. Conclusions The prepared samples are useful in optoelectronic applications, where films substrates with orientation ability are required for nematic alignment purposes. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS UEFISCDI, project PN-II-RU-TE , no. 256/ References [1] P. Navard, J.M. Haudin, J. Polym. Sci. Part B 1986, 24, [2] M.H. Godinho, P.L. Almeida, J.L. Figueirinhas, Materials 2014, 7, [3] P. Navard, J. Polym. Sci. Part B 1986, 24, Page55

56 P3Y. ELECTROCHEMICAL DETERMINATION OF ROSUVASTATIN AND EZETIMIBE FROM HUMAN SERUM AND URINE Leyla Karadurmus 1,2 *, Sevinc Kurbanoglu 2, Bengi Uslu 2, Sibel A. Ozkan 2 1 Adıyaman University, Faculty of Pharmacy, Department of Analytical Chemistry, Adıyaman Turkey 2 Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, Ankara, Turkey * leylakrdrms@gmail.com 1. Introduction Rosuvastatin bis((e)-7-(4-(4-flurophenyl)-6-1sopropyl-2-(methyl(methylsulfonyl) amino) pyrmidin-5yl) (3R,5S) -3,5-dihydroxyhept-6-enoic acid) calcium salt, is a highly effective 3-hydroxyl-3- methylglutarylcoenzyme, is a competitive inhibitor of the enzyme HMG-CoA reductase and synthetic statin drug. Ezetimibe ((3R,4S)-1-(4-fluorophenyl)-3-[(3S)-3- (4-fluorophenyl)-3-hydroxyl propyl)] -4-(4- hydroxy phenyl)-2-azetidinone) is a drug that inhibits cholesterol absorption from the small intestine, which was approved by the US Food and Drug Administration for the treatment of primary hypercholesterolemia [1]. 2. Experimental In this study, the electrochemical behavior of Rosuvastatin and Ezetimibe were investigated using stripping differential pulse voltammetric technique at glassy carbon electrode. Stripping conditions such as deposition potential, deposition time were optimized and 0.1 M H2SO4 was used as supporting electrolyte. Dependence on ph, scan rate studies were also performed. 3. Results and discussion Under optimized conditions, linear relation was obtained between and mm for Ezetimibe, and mm for Rosuvastatin with LOD values of mm and mm, respectively. 4. Conclusions The proposed method has been extensively validated in terms of precision, accuracy, linear range, limit of detection and quantification values and discussed according to ICH Guidelines and USP criteria. The electrochemical method is also used for the determination of Ezetimibe and Rosuvastatin in spiked human serum and urine samples, and reported in terms of recovery studies. References [1] S.A., Ozkan, Electroanalytical Methods in Pharmaceutical Analysis and Their Validation. HNB Publishing, New York, Page56

57 P4Y. DETERMINATION OF DIHYDROERGOTAMINE VIA LC METHOD COUPLED WITH FLUORESCENCE DETECTION IN PHARMACEUTICAL FILM PREPARATIONS Sevinc Kurbanoglu 1 *, Ozgur Esim 2, Cansel Kose Ozkan 2, Ayhan Savaser 2, Sibel A. Ozkan 1, Yalçın Ozkan 2 1 Ankara University, Faculty of Pharmacy, Department of Analytical Chemistry, Ankara, Turkey 2 Gulhane Military Medical Academy, Department of Pharmaceutical Technology, Etlik, Ankara, Turkey * skurbanoglu@gmail.com 1. Introduction Dihydroergotamine mesylate, ergotamine derivative, is used to stop or treat symptoms of an emerging migraine. It acts as an agonist to the serotonin 5-HT(1D) receptors and causing vasoconstriction of the intracranial blood vessels. It also interacts centrally with dopamine and adrenergic receptors. It can be used to treat acute intractable headache or withdrawal from analgesics. 2. Experimental In this study, Dihydroergotamine mesylate was determined by LC coupled with fluorescence detector, using Agilent Eclipse XDB-C8 5 µm 4.6 x 150 mm column with a flow rate of 1.2 ml/min, at 25 C with mobile phase composition of 70:30 Buffer (containing 1.5% Formic Acid):ACN at an excitation wavelength of 280 nm and an emission wavelength of 350 nm. 3. Results and discussion The analysis of Dihydroergotamine mesylate was obtained within 6 min. Sensitive determination method for the dihydroergotamine mesylate with LC coupled with fluorescence detector was achieved in range of M to M. with LOD value of 5.14x10-7 M and LOQ value of 1.71x10-6 M. 4. Conclusions The proposed method has been extensively validated in terms of precision, accuracy. Linear range, limit of detection and quantification values, are also calculated and discussed according to ICH Guidelines and USP criteria [1]. The method is also used for the determination Dihydroergotamine in pharmaceutical film preparations and Dihydroergotamine was obtained from film formulations with an acceptable recovery results. References [1] M. Gumustas, S. Kurbanoglu, B. Uslu, S.A. Ozkan, Chromatographia, 2013, 76, Page57

58 P5Y. SYNTHESIS AND CHARACTERIZATION OF A NEW MAGNETITE- EDTA/POLYSULFONE MICRO- AND NANOBEADS Ioana Lavinia Ardelean*, Luric Bogdan Niculae Stoencea, Denisa Ficai, Anton Ficai, Gheorghe Nechifor, Ecaterina Andronescu University Politehnica of Bucharest, Faculty of Applied Chemistry and Material Science; 1-7 Polizu St., Bucharest, Romania * dy4_ioana@yahoo.com Due to the low chemical, mechanical and thermal stability, magnetite nanoparticles are often treated with different surface modification agents in order to increase these properties. Due to their high rigidity, creep resistance, good thermal, mechanical and chemical stability, considerable attention has been paid to polysulfone as surface modification material of MNPs [1,2]. In this work we present the synthesis of a new micro and nano-beads Fe3O4/EDTA/polysulfone by phaseinversion process starting form Fe3O4/EDTA nanoparticles (MNPs) and polysulfone, in dimethylformamide (DMF) 15 or 20 %wt. After this, the polysufone Fe3O4/EDTA suspension is sprayed in distilled water, thus micro and nano-beads are formed. The structure and morphology of these materials were characterized by X-ray diffraction (XRD); Fourier transform infrared spectroscopy (FTIR); scanning electron microscopy (SEM); chemical stability in acidic media and their capacity to remove cations from aqueon solution. References [1] G. Arthanareeswaran, D. Mohan, M. Raajenthiren, Appl. Surf. Sci. 2007, 253, [2] V. Kaiser, C. Stropnik, V. Musil, M. Brumen, Eur. Polym. J , [3] D. Ficai, A. Ficai, R. Trusca, B.S. Vasile, G. Voicu, C. Guran, E. Andronescu, Curr. Nanosci. 2013, 9, [4] C. Dizman, S. Ates, L. Torun, Y. Yagci, Beilstein J. Org. Chem. 2010, 6, DOI: /bjoc Page58

59 P6Y. BULK LIQUID MEMBRANE CONCENTRATING TECHNIQUE APPLIED FOR COMPOUND USED IN MEDICAL APPLICATIONS Ecaterina Anca Serban*, Ioana Diaconu, Eugenia Eftimie Totu, Cristina Monica Mirea, Elena Ruse, Gheorghe Nechifor University Politehnica Bucharest, Faculty of Applied Chemistry and Materials Science, Department of Analytical Chemistry and Environmental Engineering, no 1-7 Polizu Street 7000 Bucharest, Romania * Recent research put in evidence that indole-3-acetic acid plays a major part as carriers for the indol derivates within biological fluids. Although, free indole-3-acetic acid behaviour in human fluids and tissues is not enough studied yet, medical application of indole-3-acetic acid would be possible following its proved pharmacological properties, also allowing a photochemically generation of some products with antitumor activity [1]. In consequence, we consider that using indole-3-acetic acid in a complex nanocomposite material where titanium dioxide photocatalyst would be included, there will be created interesting premises for its usage in medical environment, specifically for novel dental materials applied in stomatological devices. Therefore a lot of work is directed towards the concentration of this promising product from various solutions. Compared to conventional extraction processes membrane extraction represents an attractive alternative being a highly selective process that can be applied to samples with very low concentrations. In this study we present experimental data on the use of membranes in liquid bulk concentration processes of aqueous solutions of indole 3-acetic acid analytical purposes. Thus it was studied the influence of the operating parameters on the indole-3-acetic acid permeation through a membrane of chloroform containing as a carrier tributyl phosphate. There were studied operational parameters such as: the influence of the concentration of indole-3-acetic acid on feed phase, the concentration of reactive from stripping phase, the time transport and the presence of carrier tributyl phosphate in membrane phase. The assessment of the process of transport was done by determining the concentration factor and the degree of recovery. Under optimum conditions of transport: - Feed phase: indole 3-acetic acid solution concentration 10 -⁴ mol/l -10 ³ in the presence of hydrochloric acid concentration of 10-2 mol/l, (ph = 2); - Membrane: tributyl phosphate solution concentration of 10-2 mol/l in chloroform; - Stripping phase: sodium hydroxide solution concentration of 10-2 mol/l; the stirring speed of the phase: 180 rpm. It was obtained a recovery efficiency of the indole-3-acetic acid of 100% after a time of transport of 3-4 hours. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CCCDI UEFISCDI, project number 30/2016 (ERA-NET-MANUNET II) within PNCDI III. Reference [1] Tomasic, B. Bertosa, S. Tomic, M. Soski, V. Magnusa, J. Chromatogr. A 2007, 1154, [2] E. Fahmideh-Rad, G. H. Rounaghi, M. H. Arbab-Zavar, M. Chamsaz, Der. Pharma Chemica 2010, 2, [3] E. A. Serban, I. Diaconu, C. M. Mirea, E. Ruse, G. Nechifor, Rev. Chim. 2016, 67, [4] I. Diaconu, C. M. Mirea, E. Ruse, Gh. Nechifor, Environ. Eng. Manag. J. 2015, 14, Page59

60 P7Y. ON THE ELECTROCHEMICAL BEHAVIOR OF SOME SELENINYL AZULENE COMPOUNDS Alexandra Oprisanu 1*, Georgiana Anca Inel 1, Eleonora-Mihaela Ungureanu 1, Liviu Birzan 2 1 Faculty of Applied Chemistry and Materials Science, University Politehnica Bucharest, Splaiul Independentei, 313, , Bucharest, Romania 2 Institute of Organic Chemistry C.D. Nenitzescu of Romanian Academy, Splaiul Independentei 202B, PO Box , Bucharest, Romania * oprisanualex@yahoo.com 1. Introduction This work is devoted to the electrochemical characterization of two seleninyl azulene compounds. The investigations were performed by cyclic voltammetry and differential pulse voltammetry. The redox processes for each compound were established, analyzed and assessed to the particular processes which can take place during oxidation and reduction scans. This assessment was based on the similarity of the two seleninyl compounds structure connected to the number of substituents. Due to the involvement of selenium in the metabolic cycle of living organisms and its presence in some organic molecules, the interest for the electrochemistry of organoselenium compounds is increasing, also caused by the interest from pharmaceutical point of view. The study of electrochemical behaviour of organic selenides aims to enhance the understanding of their redox processes in biological. The electrochemical study of some organoselenium compounds, such as 1-phenyl-seleninyl azulene and 1,3-bis(phenylseleninyl)azulene has shown that aromatic selenides are more stable toward electrochemical reduction, compared to alkylselenides because the aryl radicals have a higher electron density than alkyl radicals and they are generated harder from anion radicals. 2. Experimental Seleninyl azulene derivatives 1 and 2 have been prepared by chemical oxidation with sodium periodate of the corresponding selanyl derivatives. Acetonitrile and tetrabutylammonium perchlorate (TBAP) from Fluka were used as received for electrochemical study, as solvent and supporting electrolyte salt, respectively. The electrochemical experiments were carried out using a PGSTAT 12 AUTOLAB potentiostat in a threeelectrode cell. The working electrode was a Metrohm glassy carbon disk (having the diameter of 3 mm). The active surface was polished before each experiment with diamond paste (2 μm) and cleaned with solvent. Ag/10 mm AgNO3 dissolved in 0.1 M TBAP, CH3CN was used as reference electrode. The electrode potential was finally referred to the potential of the ferrocene/ferricinium redox couple (Fc/Fc+) which in our experimental conditions was +0.07V. A platinum wire was used as auxiliary electrode. The experiments were performed at the room temperature under argon atmosphere by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The CV curves were generally recorded at 0.1 Vs-1 scan rate or at various scan rates (0.1-1 Vs-1) - when studying the influence of this parameter. DPV curves were recorded at 0.01 Vs-1 with a pulse height of V and a step time of 0.2 s. Se O Se O Se O Page60 Figure 1. Structures of investigated compounds 1 and 2 References [1] A.C. Razus, L. Birzan, M. Cristea, E.A. Dragu, A. Hanganu, Monatsh. Chem. 2011, 142, [2] H.M. Priestly, Dialkyl Selenoxide Hydronitrates, US patent , [3] S.J. Kuhn, and J. C.Mcintyre, 3-(beta-aryl-beta-(arylthio) (orarylseleno)-propionyl)pyrone products, US patent , [4] G. A. Inel, M. Soare, M. Bujduveanu, S. Varga, E.M. Ungureanu, L. Birzan, U.P.B. Sci. Bull. B 2014, 76.

61 P8Y. FAST SCREENING OF TISSUE SAMPLES FOR GLYCOGEN Amalia Gabriela Diaconeasa 1, Raluca-Ioana Stefan-van Staden 1*, Camelia Stanciu-Gavan 2 1 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 2 Department of Surgery 4, University of Medicine and Pharmacy Carol Davila, Bucharest, Romania * ralucavansaden@gmail.com 1. Introduction Screening of tissue samples for glycogen is very important in assessing the ageing, but also the state of health of the tissue. 2. Experimental Two needle stochastic sensors based on maltodextrins presenting different dextrose equivalence (DE) MD-m (DE ), and MD-M (DE ) immobilized in diamond paste (obtained from synthetic diamond and paraffin oil) were designed and characterized. 3. Results and discussion The lowest limit of determination (1fmol/L) and the highest sensitivity (2.33x10 10 s -1 /mol * L -1 ) were obtained when MD-M/DP based needle stochastic sensor was used. The needle stochastic sensors showed good stability when used daily for measurements, the RSD(%) values for the sensitivities varying with less than 1.00%. 4. Conclusions These stochastic sensors were used reliable for both qualitative and quantitative analysis for the assay of glycogen in tissue samples with limits of determination as low as 1fmol/L. Acknowledgements The authors want to thank to UEFISCDI, Partnership 22/2014 for the financial support. Page61

62 P9Y. SIMULTANEOUS ASSAY OF THYROID HORMONS AND TSH IN WHOLE BLOOD SAMPLES Grigorina Mitrofan 1*, Raluca-Ioana Stefan-van Staden 1,2, Hassan Y Aboul-Enein 3 1 University Politehnica, Bucharest, 313 Splaiul Independentei Str, , Bucharest, Romania 2 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 3 Pharmaceutical and Medicinal Chemistry Department, The Pharmaceutical and Drug Industries Research Division, National Research Centre, Dokki, Giza 12622, Egypt * mitrofan.grigorina@gmail.com 1. Introduction Simultaneous assay of thyroid hormones and TSH is essential in determining the function of thyroid, and related diseases. 2. Experimental Stochastic microsensors based on immobilization of inulins and ionic liquids on diamond paste; 3. Results and discussion The proposed stochastic sensors were successful used for the analysis and enantioanalysis of thyroid hormones and TSH. They had a good sensitivity and low determination levels even for the assay of D-T4 making possible its assay in whole blood samples of cancer pacients. The enantioselectivity of the sensors made possible the discrimination between the enantiomers of thyroid hormones. The recovery tests performed shown that the thyroid hormones and TSH can be determined in whole blood samples with recoveries higher than 99.00%. 4. Conclusions The proposed stochastic sensors proved high reliability for the assay of thyroid hormones and TSH in whole blood samples. They can be also used for pharmaceutical analysis of tablets formulated with L-T4 as active compound. Acknowledgements The authors want to thank to UEFISCDI, Ideas 123/2011 for the financial support. Page62

63 P10Y. DETERMINATION OF KRAS USING GRAPHITE AND GRAPHENE BASED AMPEROMETRIC SENSORS Ahmed Jassim Muklive AL-Ogaidi 1*, Livia Alexandra Gugoasa 2, Raluca-Ioana Stefan-van Staden 1,2 1 University Politehnica, Bucharest, 313 Splaiul Independentei Str, , Bucharest, Romania 2 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania * ahmed.mukleef@yahoo.com 1. Introduction KRAS is a very important tumoral marker determined usually in tissue samples for colon cancer diagnosis. Its determinationin biological fluids such as whole blood shall decrease the risk of fast spreading of disease in the bodytherefore it is a real need to design very sensitive sensors for its detection. 2. Experimental Amperometric sensors were design in the laboratory for the assay of KRAS. The sensors were based on grahite and grapheme powder with modifiers such as porphyrins and oleamides. 3. Results and discussion Very low limits of determination and detection were achieved using the proposed stochastic sensors. These limits are in the range of early detection, but can also allow the assay of KRAS in stages 3 or 4 of the colon cancer. The sensors exhibited high selectivity over other colon cancer biomarkers, but also over other components from whole blood such as neurotransmitters. The recovery tests performed proved the suitability of these sensors for the early detection of KRAS in whole blood samples. 4. Conclusions The assay of KRAS in whole blood was reliable performed using the proposed amperometric sensors based on physical immobilization of porphyrins and oleamides in graphite and grapheme based pastes. Acknowledgements The authors want to thank to UEFISCDI, Partnership 22/2014 for the financial support. Page63

64 P11Y. NMR STRATEGIES FOR ASSIGNMENT OF METABOLITES IN PLANT JUICES Gabriela Ailiesei 1 *, Mihaela Cristea 1, Ana-Maria Macsim 1, Mihaela Balan-Porcarasu 1, Alina Nicolescu 1, Calin Deleanu 1,2 1 Petru Poni Institute of Macromolecular Chemistry of the Romanian Academy, Aleea Grigore Ghica Voda 41A, RO Iasi, Romania 2 Costin D. Nenitescu Centre of Organic Chemistry, Romanian Academy, RO Bucharest, Romania. * darvarug@yahoo.com Nuclear Magnetic Resonance (NMR) spectroscopy is one of the most versatile tools available for characterizing complex natural mixtures, providing information on both global profile of the sample and the individual metabolites. The 1 H NMR spectrum of a plant juice can be rationalized in three regions, as it can be seen in figure 1: the high field region between ppm, with various signals corresponding to aliphatic metabolites such as amino acids, carboxylic acids and alcohols, the intermediate region between ppm dominated by signals from different sugars and the low field region between ppm with signals corresponding to aromatic derivatives, heterocycles, organic acids and polyphenols. This spectral fingerprint is characteristic to different plant juices, with some variations in signals intensities, depending on metabolites concentrations in the plant. Figure 1. Main regions of the 1 H NMR spectrum for plant juice. The present paper reports on different NMR experiments used to unambiguously assign a metabolite in complex mixtures, such as plant juices. Acknowledgements The authors acknowledge the financial support of the Romanian National Authority for Scientific Research, CNCS-UEFISCDI, project number PN-II-PT-PCCA Page64

65 P12YN. CHEMICALLY MODIFIED ELECTRODES BASED ON (Z)-2-THIOXO-5-((4,6,8-TRIMETHYLAZULEN-1-YL)METHYLENE)THIAZOLIDIN-4-ONE FOR HEAVY METALS IONS DETECTION Georgiana-Luiza Arnold*, Magdalena-Rodica Bujduveanu, Eleonora-Mihaela Ungureanu Faculty of Applied Chemistry and Materials Science, University Politehnica Bucharest, Romania There are numerous health problems associated with exposure to high levels of metal ions because of their tendency to be accumulated in the body, toxicity and low rate of clearance. Consequently, monitoring heavy metal ion levels is more and more necessary for human health and safety. (Z)-2-thioxo-5-((4,6,8-trimethylazulen-1-yl)methylene)thiazolidin-4-one (L) was used to obtain a modified electrode for heavy metal ions recognition, according to similar procedures [1, 2]. The electrochemical experiments were carried out by differential pulse voltammetry (DPV), cyclic voltammetry (CV), and rotating disk electrode voltammetry (RDE). The new modified electrodes have been tested for heavy metal ions detection. Good analytical signals have been obtained for Pb and Cd (detection limits of 10-7 M). Acknowledgements The authors are grateful for the financial support from: UEFISCDI project ID PN-II-RU-TE contract no. 10/2015, PN-II-ID-PCE contract no. 15/2011, and PN-II-PT-PCCA contract no. 236/2014. References [1] G.-O. Buica, E.-M. Ungureanu, L.Birzan, A.C. Razus, M-R Bujduveanu, Electrochimica Acta 2011, 56, [2] G.-O. Buica, E.-M. Ungureanu, L.Birzan, A.C. Razus, L.-R. Mandoc, J. Electroanal. Chem. 2013, 293, Page65

66 POSTER SESSION 2 PHARMACEUTICAL AND BIOMEDICAL ANALYSIS P1PBA. SYNTHESIS AND CHARACTERIZATION OF SOME NEW 5-CHLORO-2-HYDROXY-N-PHENYLBENZAMIDE DERIVATIVES Ioana M.C. Ienascu 1,2 *, Raluca O. Pop 3, Adina Cata 1, Mariana N. Stefanut 1, Iuliana M. Popescu 4 1 National Institute of Research and Development for Electrochemistry and Condensed Matter, Dr. A. P. Podeanu 144, , Timisoara, Romania 2 Vasile Goldis Western University of Arad, Faculty of Pharmacy, Department of Pharmaceutical Sciences, Liviu Rebreanu 86, , Arad, Romania 3 University of Medicine and Pharmacy Victor Babes Timisoara, Faculty of Pharmacy, Eftimie Murgu Square 2, Timisoara, Romania 4 Banat s Agricultural Science University, Faculty of Agriculture, Department of Chemistry and Biochemistry, 119 Calea Aradului, , Timisoara, Romania * imcienascu@yahoo.com 1. Introduction Therapeutic importance of the hydrazide-hydrazone compounds lies in the fact that these class of derivatives proved various biological properties like, antibacterial, antifungal, antituberculosis, antiinflammatory, anticonvulsant, anticancer and antihiv activities [1-4]. Moreover, the versatility of these compounds in organic chemistry is due to the presence of H N=CH group, the N-N linkage being used as a key structural motif in different bioactive agents. 2. Experimental With the purpose of obtaining new compounds with a wide spectrum of pharmaceutical applications, the synthesis and characterization of 5-chloro-2-hydroxy-N-phenylbenzamide methyl esters, hydrazides and hydrazones was achieved. Useful tools, FTIR, 1 H-NMR, 13 C-NMR, MS, were used to identify the synthetized compounds. OH CO NH Cl R 1 CH(Cl)COOCH 3 K 2 CO 3 /MEC R 1 O Cl CH O C OCH 3 CO NH R 1 =H, CH 3 N 2 H 4 EtOH R 1 O CH C O NH NH 2 Cl CO NH R 1 =H, CH 3 Figure 1. Synthesis of the 5-chloro-2-hydroxy-N-phenylbenzamide derivatives OHC R 2 EtOH R 3 R 4 R 1 O CH C O NH N Cl CO NH C H R 1 =H, CH 3 R 2 =H, OH R 3 = H, Br R 4 =H, N(CH 3 ) 2 3. Results and discussion The synthesized compounds are white, yellow, crystalline substances. The final purification required simple crystallization from absolute ethanol or dimethylformamide. The methyl esters were obtained in yields between 48-65%, while, for the hydrazides and hydrazones higher yields were obtained (84-96%). 4. Conclusions 6 novel 5-chloro-2-hydroxy-N-phenylbenzamide derivatives, potentially biological active compounds, were synthesized and characterized. All spectral data demonstrated the structural identity of the analyzed compounds. R 2 R 3 R 4 Page66 References [1] S. Rollas, S.G. Kucukguzel, Molecules 2007, 12, [2] Y. Ozkay, Y. Tunah, H. Karaca, I. Isikdag, Eur. J. Med. Chem. 2010, 45, [3] A.L.P. Candéa, M.L. Ferreira, K.C. Pais, L.N.F. Cardoso, C.R. Kaiser, M.G.M.O. Henriques, M.C.S. Lourenço, F.A.F.M. Bezerra, M.V.N. Souza, Bioorg. Med. Chem. Lett. 2009, 19, [4] S.D. Joshi, H.M. Vagdevi, V.P. Vaidya, G.S. Gadaginamath, Eur. J. Med. Chem. 2008, 43,

67 P2PBA. ANALYTICAL CHARACTERISATION OF SOME BUDS ETHERIC OILS USED IN COSMETICS Ioana Adina Oancea 1,3 *, Elena Oancea 1, Eleonora-Mihaela Ungureanu 2, Gabriela Stanciu 3, Elisabeta Chirila 3 1 SC.DAN-ELIS.SRL (Producer of Careless Beauty Cosmetics), 9 Dobrogei Street, Topraisar, Constanta, Romania 2 Faculty of Applied Chemistry and Materials Science, University Politehnica Bucharest, 1-7Polizu Street, Bucharest, Romania 3 Ovidius University, Department of Chemistry and Chemical Engineering, 124 Mamaia Blvd, Constanta, Romania * oancea.careless@gmail.com 1. Introduction Etheric oils, or aromatic oils as they were once called, have been used by many cultures around the world for centuries. Their uses varied between cultures from religious purposes to healing the sick. It is difficult to pinpoint exactly when essential oils gained notoriety as effective healing agents, but eventually the knowledge of essential oils spread around the globe. Today, etheric oils are used in many industries, particularly in the cosmetics and perfumes industry. 2. Experimental Given that cosmetology is closely related to dermatology and chemistry, the aim of this paper was to highlight the antioxidant related to antimicrobial activity of three etheric oils used in dermato cosmetic products, oils extracted from buds of Populus nigra (poplar), Pinus sylvestris (pine), and Abies alba (fir). The antioxidant activity was determined using Folin Ciocalteu method for polyphenolic assay, DPPH Radical Scavenging and β-carotene bleaching test. To highlight further the antimicrobial activity of the etheric oils, we followed a microbiologic study to point the behavior of MRSA (Methicillin-resistant Staphylococcus aureus - a bacterium that causes infections in different parts of the body) in contact with each of the etheric oils. References [1] M.G. Miguel, Molecules 2010, 15, [2] B.A. Green, R.J Yu, E.J. Van Scott, Clinics in Dermatology 2009, 27, Page67

68 P3PBA. THE EVALUATION OF ANTIOXIDANT CAPACITY FOR SOME WILD PLANT EXTRACTS USED IN COSMETICS Gabriela Stanciu 1 *, Adina-Ioana Oancea 2,3, Elena Oancea 3, Elisabeta Chirila 1 1 Ovidius University, 124 Mamaia Blvd., Constanta, Romania 2 University Politehnica Bucharest, 1-7 Polizu Street, Bucharest, Romania 3 SC.DAN-ELIS.SRL (Producer of Careless Beauty Cosmetics), 9 Dobrogei Street, Topraisar, Constanta, Romania * gstanciu@univ-ovidius.ro Wild plants contain natural antioxidants which could successfully replace the synthetic additives used to stabilize cosmetic products, most often harmful for the skin. Herbal cosmetics are quickly absorbed by the superficial layers of the skin and are usually hypo-allergenic [1]. The study aims to present original results concerning some characteristic parameters of wild plant extracts used in cosmetics: ph, ORP, total phenols content using an adapted Folin Ciocalteu method, related to antioxidant capacity [2]. The investigated extracts were: aqueous distillate, alcoholic macerate, etheric oils obtained by hydrodistillation and aqueous mixture remained after hydrodistillation. These extracts have been obtained using the next plants collected from Constanta and Buzau unpolluted areas: Althaea officinalis, Crataegus monogyna, Lavandula angustifolia, Melissa officinalis and Origanum vulgare. The obtained results show that the bioactive compounds from the studied plant extracts ensure optimum ph values and explain the long-term stability of cosmetic products, which do not contain synthetic chemicals. In the same time, natural extracts used to formulate cosmetic products have benefic effects on the skin like acnee healing, anti inflamatory, cell regeneration, retarding aging etc. References [1] P.K. Mukherjee, N. Maity, N.K. Nema, B.K. Sarkar, Phytomedicine 2011, 19, [2] E. Chirila, E. Oancea, I.A. Oancea, Ovidius University Annals of Chemistry 2014, 25, Page68

69 P4PBA. MOLECULAR SCREENING OF WHOLE BLOOD SAMPLES FOR THE SIMULTANEOUS DETECTION OF CEA, HER-1, NSE, CYFRA 21-1 USING STOCHASTIC SENSORS Ionela Raluca Comnea-Stancu 1, Raluca-Ioana Stefan-van Staden 1*, Camelia Stanciu-Gavan 2 1 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 2 Department of Surgery 4, University of Medicine and Pharmacy Carol Davila, Bucharest, Romania * ralucavanstaden@gmail.com 1. Introduction The aim of this study was to detect simultaneously four lung cancer biomarkers: CYFRA 21-1, CEA, NSE and HER-1, from blood samples. 2. Experimental Stochastic sensors based on diamond paste matrices modified with different electroactive materials like dextrins and porphyrins, as well as stochastic sensors based on three metals like Au, Cu and Ni were designed. 3. Results and discussion The stochastic sensors chosen for the screening tests of whole blood samples proved to determine reliable the four biomarkers, reaching low limits of determination of pg ml -1 magnitude order and high sensitivities. One main advantage of the sensors used for the simultaneous detection of the biomarkers is that the samples are analyzed as taken from the patients, without any pretreatment. 4. Conclusions The proposed sensor can be reliably used for the screening tests of whole blood and early detection of lung cancer. Acknowledgements The authors want to thank to UEFISCDI, Ideas 123/2011 for the financial support. Page69

70 P5PBA. PATTERN RECOGNITION OF CYFRA 21-1 IN WHOLE BLOOD SAMPLES Ionela Raluca Comnea-Stancu 1, Raluca-Ioana Stefan-van Staden 1*, Camelia Stanciu-Gavan 2 1 Laboratory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania 2 Department of Surgery 4, University of Medicine and Pharmacy Carol Davila, Bucharest, Romania * ralucavanstaden@gmail.com 1. Introduction CYFRA 21-1 is a new biomarker used in the diagnosis of lung cancer. Its early detection in whole blood samples can be used for early diagnosis of lung cancer. 2. Experimental New materials were proposed for the determination of CYFRA 21-1, a lung cancer biomarker, from human blood samples. The new materials are based on magnesium oxides (as new matrix for stochastic sensors design) and a new synthesized porphyrin (used as nanostructured materials as active compounds). The ceramics were immersed for a period of time in the solution of porphyrin, dried, and used as stochastic sensors. 3. Results and discussion The best response was showed by the sensor based on MgO10-MEG-107 with a linear domain from 0.20 pg/ml to 200 pg/ml, reaching a determination limit of 0.20 pg/ml. All the three sensors were stable over a period of six months, being used for measurements, proving the high stability of them. 4. Conclusions The proposed sensors can reliably be used for the screening tests of whole blood for CYFRA Acknowledgements The authors want to thank to UEFISCDI, Ideas 123/2011 for the financial support. Page70

71 P6PBA. OXIDATIVE STRESS FOLLOWING PLGA NANOPARTICLES ADMINISTRATION TO AN ANIMAL MODEL Bogdan Calenic 1,2 *, Daniela Miricescu 1, Cristina Sabliov 3, Maria Greabu 1, Raluca Ioana Stefan-van Staden 2 1 Department of Biochemistry, Faculty of Dental Medicine, UMF Carol Davila 2 National Institute of Research for Electrochemistry and Condensed Mater, Bucharest, Romania, 3 Department of Biological and Agricultural Engineering, College of Engineering, Louisiana State University * bcalenic@yahoo.co.uk 1. Introduction In the recent years, engineered nanoparticles such as PLGA or poly-lactic-co-glycolic acid, have raised a substantial interest due to their possible medical applications in vaccination, diagnostic imaging procedures, cancer therapy or sustained delivery of drugs.the main aim of the present work is to evaluate key oxidative stress parameters in several organs following NPs administration in an animal model. 2. Materials and methods Polymeric nanoparticles of PLGA were prepared by emulsion-solvent evaporation method and were a kind gift from Prof. Sabliov, Lousiana State University, USA. The animal model involved rats divided in 2 groups as follows: 5 rats were used as control group and 5 rats were administred NPs at a concentration of 50mg/kg body weight. The NPs were given orally using a feeding canula; rats were sacrificed at 6 hours and tissue samples from spleen and liver were analyzed for oxidative stress indicators such as glutathione (GSH), malondialdehyde (MDA), total antioxidant capacity (TAC) and advanced human oxidation protein products (AOPP). 3. Results A significant difference was found in GSH and TAC levels between the two groups in both analyzed organs: spleen 0.60 ± 0.18 vs ± 0.02 and liver 0.84 ± 0.04 vs ± 0.04 in PLGA group vs control group. For TAC the results showed: in spleen 92.6±3.46 vs 93.4±3.46, in liver 114±9.58 vs in the PLGA group vs control group. MDA levels between the two groups were reported as follows: spleen 0.01 ± 0.01 vs 0.09 ± 0.01 in PLGA group vs control group; liver 0.04 ± 0.01 vs ± 0.01 in PLGA group vs control group AOPR levels detected in spleen: 1.44±0.47 vs 2.06±0.46 and liver: 1.88±0.1vs 1.88±0.1, for PLGA vs control group respectively. 4. Conclusion Present data shows that acute oral administration of a high concentration of PLGA NPs induces a change in the antioxidant status in both rat liver and spleen but may not induce oxidative stress damage to cell structures such as lipid or protein oxidation. Page71

72 P7PBA. PROPERTIES OF Cu-BASED SURFACES WITH ANTIMICROBIAL CAPABILITY Małgorzata Lekka 1 *, Szymon Prauzner-Bechcicki 1, Katarzyna Bilewska 2, Marcin Lis 2, Grzegorz Więcław 3, Maciej Jaśkiewicz 4, Wojciech Kamysz 4, Paweł Pajzderski 5 and Adriana Wrona 2 1 The Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152, Kraków, Poland, 2 The Institute of Non-Ferrous Metals, Sowińskiego 5, Gliwice, Poland, 3 Certech Sp. z o.o., ul. Więźniów Oświęcimia 38, Wilamowice, Poland, 4 Lipopharm.pl,ul. Bysewska 26B, Gdańsk, Poland, 5 Alvo S. z o.o. Sp. k., ul. Południowa 21a, Śmigiel, Poland. * malgorzata.lekka@ifj.edu.pl Surfaces that contain an antimicrobial agent inhibiting or reducing the ability of bacteria to grow are of great interest, especially, in the context of antibiotic resistive bacteria detected [1]. There are various strategies used to design antibacterial surfaces that uses roughly two approaches, i.e. chemical and physical ones. The latter applies chemical modifications while the former modifies the surface structures [2]. Research carried out for many years delivered strong evidences for antimicrobial properties of copper-based surfaces. Results demonstrated that both chemical and molecular mechanisms responsible for bacteria growth inhibition are complex and occur in many ways, both inside the cells and in the intercellular spaces [3]. Currently, there is an intensive research on new Cu-based materials supplemented with various metals or oxides including nanoscale structures [2]. As an example, studies on the Cu-Ti alloy produced by powder metallurgy techniques in the form of frits showed a very good bacteriostatic properties, high strength and corrosion resistance of such surfaces [4]. In our studies, the Cu-based coatings containing Ti Sn metals were produced using various technological approaches. Surface structures were characterized using atomic force microscope by determining roughness from measurements in ambient conditions and quantification of adhesive properties through measurements of detachment force in aqueous environment. The capability of bacteria growth was verified using fluorescent microscope Acknowledgements The studies were financed by the NCBR project FUNPOWMED number PBS/B9/40/2015. References [1] B. Spellberg, R. Guidos, D. Gilbert, J. Bradley, H. W. Boucher, W. Michael Scheld, J. G. Bartlett, J. Edwards Jr., Clin. Infect. Dis. 2008, 46, [2] J. Hasan, R. J. Crawford, E. P. Ivanova, Trends Biotechnol. 2013, 31, [3] J. Konieczny, Z. Rdzawski, Arch. Mat. Sci. Eng , [4] E. Zhang, F. Li, H. Wang, J. Liu, C. Wang, M. Li, K. Yang, Mat. Sci. Eng. C, 2013, 33, Page72

73 P8PBA. SERUM AND SALIVARY INTERLEUKIN-6 IN LUPUS PATIENTS Alina Dima 1,2 *, Livia Alexandra Gugoasa 3, Cristian Baicus 1,2, Eugenia Balanescu 1,2, Maria Greabu 1, Bogdan Calenic 1, Raluca-Ioana Stefan-van Staden 3 1 Carol Davila University of Medicine and Pharmacy, Bucharest, Romania 2 Colentina Research Center, Bucharest, Romania 3 Laboratory of Electrochemistry and PATLAB, National Institute of Research for Electrochemistry and Condensed Matter, Bucharest, Romania * dr.alinadima@yahoo.com Introduction Interleukin-6 proved to be involved in inflammatory and immune pathology, systemic lupus erythematosus included. Aim To identify the serum and salivary IL-6 correlates in lupus patients. Method Patients diagnosed with systemic lupus erythematosus and control subjects were prospectively included. Serum and salivary IL-6 were assessed using two stochastic sensors based on metal nanocompositesgraphene pastes. The mean of these determinations was used in all analysis. Moreover, ELISA analysis was performed for the serum IL-6. Results 10 lupus patients, majority of feminine sex (90%) with mean age of inclusion 45.7 years and median disease duration of 12 years were prospectively included. When data of both cases and controls were analyzed, stochastic sensors and ELISA found similar serum IL-6 levels (p < 0.001; r = 0.997). Moreover, the salivary IL-6 levels proved to be correlated with the serum ones (p < 0.001; r = 0.951). In lupus patients, both serum and salivary interleukin-6 levels were found to be highest than in control subjects [med (inf; sup) 2.5 ( ) vs. 0.7 ( ) pg/ ml, p = respectively 2.7 ( ) vs. 1.1 ( ) pg/ ml, p < 0.001]. Also, interleukin-6 levels were higher in lupus patients with early disease onset (p = 0.035; r = , respectively p = 0.017; r = ). Conclusions Determination of IL-6 by stochastic sensors appears to be a reliable laboratory method. Salivary IL-6 determination, non-invasive tool, might be useful for the serum IL-6 assessment. Disclosure Parts of this project were presented in the 11 th Lupus Congress Vienna, Austria. Page73

74 P9PBA. WHOLE BLOOD TESTS VERSUS TISSUE TEST FOR FAST DIAGNOSIS OF CANCER Camelia Stanciu-Gavan 1 *, Raluca-Ioana Stefan-van Staden 2, Iuliana Ionita-Moldoveanu 2 1 Department of Surgery 4, University of Medicine and Pharmacy Carol Davila, Bucharest, Romania 2 Labortory of Electrochemistry and PATLAB Bucharest, National Institute of Research for Electrochemistry and Condensed Matter, 202 Splaiul Independentei , Bucharest, Romania * camelia_gavan@yahoo.com 1. Introduction In the past years there was a trend on finding fast screening noninvasive methods for early diagnosis of cancer. Therefore, there is a need to correlate the results obtained for the screening of whole blood with data obtained by screening of tissues. 2. Experimental Stochastic sensors were used for the analysis of specific biomarkers in whole blood and tissue samples. IHC was done for the analysis of tissue samples using standard procedures. ELISA was used as standard method to determine specific biomarkers in whole blood samples. 3. Results and discussion A good correlation was found for the results obtained using stochastic sensors and ELISA, and IHC for whole blood, and tissue analysis. Statistical evaluation of the data shown that the screening of whole blood using the stochastic sensor can replace the tissue analysis as well as the most laborious methods used for whole blood analysis. 4. Conclusions The data obtained as well as the statistics shown that the proposed method can substitute the tissue analysis, and can offer enough results for the fast diagnosis of cancer. Acknowledgements The authors want to thank to UEFISCDI, Partnership 22/2014 for the financial support. Page74

75 P10PBA. N-DOPED GRAPHENE/IRON-PORPHYRIN NANOCOMPOSITE AS EFFICIENT PEROXIDASE MIMETIC CATALYSTS Marcela-Corina Rosu, Crina Socaci*, Florina Pogacean, Maria Coros, Lidia Magerusan, Stela Pruneanu National Institute for Research and Development of Isotopic and Molecular Technologies, Donat Street, , Cluj-Napoca, Romania * 1. Introduction Natural enzymes act as efficient and highly specific catalysts in various biochemical processes. However, enzyme denaturation under chemical exposure together with the reduced operational stability, high cost in preparation, purification, and storage lead to the restriction of their application area [1]. Recently, research interest was focused on graphene-based nanomaterials as promising alternative materials for enzyme mimics [2,3]. The present work aims spectroscopic studies of N-doped graphene/iron-porphyrin (NGr-FeTPyP and FeTPyP-NGr) nanocomposites explored as promising catalysts to mimic natural peroxidases with application in degradation of bisphenol A. 2. Experimental The non-covalent functionalization of N-doped graphenes with iron-porphyrins was described. The ultraviolet visible (UV Vis) absorption spectra of NGr-based porphyrin nanomaterials were recorded and the time-dependent absorbance changes were observed. The catalytic activity of nanocomposites was quantified based on changes in optical absorbance, indicating the peroxidase-like activity. 3. Results and discussion The prepared nanocomposites possess intrinsic peroxidase-like activity that can catalyze the reaction of peroxidase substrate (3,3 -dimethylbenzidine) in the presence of hydrogen peroxide (H2O2) to produce a blue color reaction. This colorimetric method revealed a linear relationship between hydrogen peroxide concentration and optical absorbance of the NGr-based porphyrin nanomaterials in ph 4.2 acetate buffer at room temperature, indicating a first order reaction. Furthermore, the bisphenol A degradation efficiency increased up to 68% when the concentration of hydrogen peroxide decreased. 4. Conclusions A simple, efficient and highly sensitive/selective colorimetric method for degradation of bisphenol A has been developed and which may be used in wastewater treatment, avoiding the disadvantages employed by the enzymatic methods. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS UEFISCDI, project number PN-II-RU-TE References [1] B. Garg, T. Bisht, Y.C. Ling, Molecules 2015, 20, [2] C. Socaci, F. Pogacean, A.R. Biris, M. Coros, M.C. Rosu, L. Magerusan, G. Katona, S. Pruneanu, Talanta, 2016, 148, [3] F. Pogacean, C. Socaci, S. Pruneanu, A.R. Biris, M. Coros, L. Magerusan, G. Katona, R. Turcu, G. Borodi, Sensors and Actuators B, 2015, 213, Page75

76 P11PBA. FLOW INJECTION SYSTEM BASED ON A MODIFIED SCREEN PRINTED ELECTRODE FOR PEROXYINITRITE DETERMINATION IN MEAT EXTRACTS Mihaela Badea Doni 1 *, Ioana Silvia Hosu 1, Diana Constantinescu-Aruxandei 1, Melania-Liliana Arsene 1, Florin Oancea 1, Maria-Luiza Jecu 1 1 National Institute for Research & Development in Chemistry & Petrochemistry - ICECHIM, 202 Spl. Independentei, Bucharest, Romania * mihaela.badea@icechim.ro; m_badea@yahoo.it 1. Introduction Peroxynitrite (ONOO - ), named here PON, is a strong non-radical oxidant resulted from the reaction of free radical of nitric oxide and the free radical of superoxide. PON has an important role in the oxidation of oxymyoglobin, with the formation of metmyoglobin, in the raw meat giving its brown color which is associated by the consumers with the lack of freshness of the meat. Peroxynitrite ( M) cause rapid and extensive formation of metmyoglobin from oxymyoglobin with the majority of metmyoglobin formation occurring during the first 5-10 min of incubation [1]. 2. Experimental, results and discussion A screen printed carbon electrode was modified with the mediator cobalt (II) phthalocyanine which proves an electrocatalytic effect on the peroxynitrite oxidation allowing the detection of peroxynitrite at a much lower potential (+0.1 V). A single channel flow injection analysis (FIA) system and the developed PON sensor were used for PON determination in meat extracts, as well as for following the reaction between PON and oxymyoglobin. Figure 1. Calibration graph for FIA determination of PON (E=+0,1 V) 3. Conclusions A fast and selective FIA system was developed for following the PON reaction with oxymyoglobin in extracts of raw meat. The PON sensor allows the determination of PON in the range M, with no interference of ascorbic acid or nitrite. Acknowledgements The authors are grateful for the financial support from the project PN-II-ID-PCE , contract no. 184/2011. References [1] B.J. Connolly, R.G. Brannan, A.E. Decker, J. Agric. Food Chem. 2002, 50, Page76

77 P12PBA. SCREEN PRINTED CARBON ELECTRODE MODIFIED WITH COPPER OXIDE NANOPARTICLES FOR GLUCOSE DETERMINATION Mihaela Badea Doni 1 *, Gabriela Petcu 1,2, Mariana Patrascu 3, Melania-Liliana Arsene 1, Victor Fruth 4, Maria-Luiza Jecu 1 1 National Institute for Research & Development in Chemistry & Petrochemistry - ICECHIM, 202 Spl. Independentei, Bucharest, Romania 2 University of Bucharest, Faculty of Chemistry, Sos. Panduri, Bucharest, Romania 3 Chemspeed Ltd., 2 Str. Garii de Nord, Bucharest, Romania 4 Romanian Academy, Ilie Murgulescu Institute of Physical Chemistry, 202 Spl. Independentei, Bucharest, Romania * mihaela.badea@icechim.ro; m_badea@yahoo.it 1. Introduction There are two types of electrochemical glucose sensors: enzymatic and non-enzymatic sensors. Enzymatic sensors are selective, sensitive and fast, but with several drawbacks related to the enzyme nature, reasons that pushed-up the research towards the development of more robust and simple nonenzymatic sensors. Nanostructured materials such as graphene or metal oxides are able to enhance the sensitivity and selectivity of different metal electrodes. Recently a non-enzymatic glucose sensor based on CuO nanoparticles-graphen nanocomposites modified glassy carbon electrode was reported [1]. 2. Experimental, results and discussion Screen printed carbon electrodes (DropSens, Spain) were modified by drop-casting with CuO nanoparticles obtained by microwave - assisted synthesis using the MiniLabotron 200 equipment (80 0 C, 10 minutes at 200 W in the temperature mode in microwave cavity type TE). The pomegranate peel extract has been used as stabilizing and reducing agent for the nanoparticles synthesis and precursor was utilized Cu(CH3COO)2 H2O. The modified electrodes were evaluated for glucose determination in batch and flow injection analysis (FIA) systems. 30x mm 25x x mm I (A) 15x mm 10x10-6 5x Time (sec) Page mm 0.05 mm 0.25 mm 0.10 mm Figure 1. FIA amperogram for glucose determination using the SPCE/CuO sensor (E=+0.55 V) 3. Conclusions A sensitive and selective non-enzymatic sensor based on CuO nanoparticles was developed for glucose determination in the range 0.01mM 2 mm, with a detection limit of mm. Acknowledgements The authors are grateful for the financial support from the project PN-II-ID-PCE , contract no.184/2011. References [1] T. Alizadeh, S. Mirzagholipur, Sensors and Actuators B: Chemical, 2014, 198,

78 POSTER SESSION 3 ENVIRONMENTAL ANALYSIS P1EA. A NEW APPROACH FOR DEVELOPING MASS BALANCE EQUATIONS FOR COMPLEX CHEMICAL EQUILIBRIA IN HETEROGENEOUS MULTICOMPONENT SYSTEMS Igor Povar*, Oxana Spinu Institute of Chemistry of the Academy of Sciences of Moldova, 3 Academiei, MD2028 Chisinau, Republic of Moldova * ipovar@yahoo.ca A new approach for developing mass balance equations for complex chemical equilibria in heterogeneous multicomponent system containing solid-liquid [1-8] or liquid-liquid phases [9] has been developed. This approach utilizes thermodynamic relationships joined with original mass balance constraints, where all the components of both phases are explicitly expressed. For example, in aqueous media aluminium ion Al 3+ contains in a variety of soluble and insoluble species. The soluble aluminium in soil solutions is found as the Al 3+ ions along with chemical combinations with OH -, F -, SO 2-4, PO 3-4 and organic compounds. In acidic soils, the Al solubility is controlled by a variety of basic Al sulfate phases with general composition ( K, Na) n Al x ( OH) y ( SO ) z ( H O) (as alunogen, alunite, jurbanite and 4 2 m basaluminite). The mass balance conditions for the aluminium ion for this system can be formulated by the expression: 0 r 3i j 3 j C Al C Al C Al i[ Al OH AlF AlSO Al SO i j i ( ) ] [ ] [ ] [ ( ) ] 1 0 j j 1 j (1) 0 2 [ AlOrg ] [ AlHOrg ] [ AlH 2 PO ] C 4 Al where the quantities 0 C and r C Al Al residual concentrations of Al 3+ in the heterogeneous system, while in the precipitate in one liter of solution. (mol L -1 ) in the equation (1) represent respectively the analytical and C Al (mol L -1 ) symbolizes its quantity The factors influencing the distribution and concentrations of various soluble and insoluble species have been taken into account. The new type of diagrams, based on thermodynamic, graphical and computerized methods, which quantitatively describe the distribution of soluble and insoluble inorganic, and organic, monomeric and polymeric species in heterogeneous systems in a large range of ph values has been used. The obtained data regarding the factors influencing the component speciation, based on the constructed diagrams of heterogeneous chemical equilibria, are found to be in a good agreement with the current experimental and theoretical evidence for investigated real natural and synthetic systems. The proposed approach is intended to determine the dominant processes that are responsible for the component concentration levels and its speciation in studied systems. References [1] O. Spinu, I. Povar, Rev. Chim., 2016, 67(2), [2] I. Povar, O. Spinu, Can. J. Chem., 2016, 94(2), [3] I. Povar, O. Spinu, Ecol. Proc. 2015, 4(1), [4] O. Spinu, I. Povar, Chem. J. Mold., 2015, 10(2), [5] I. Povar, O. Spinu, Cent. Eur. J. Chem., 2014, 12(8), [6] I. Povar, V. Rusu, Can. J. Chem., 2012, 90(4), [7] I. Povar, V. Rusu, Can. J. Chem., 2012, 90(4), [8] I. Povar, Can. J. Chem., 2011, 79 (7), [9] I. Povar, O. Spinu, Solv. Extr. Ion Exch., 2015, 33(2), Page78

79 P2EA. ELEMENTAL COMPOSITION OF FUNCTIONAL FOODS BASED ON HONEY Elisabeta - Irina Geana 1 *, Claudia Sandru 1, Cornelia Dostetan 2 1 National R&D Institute for Cryogenics and Isotopic Technologies ICIT Rm. Valcea, 4th Uzinei Street, PO Raureni, Box 7, Rm. Valcea, Romania 2 SC APILIFE RO SRL, No 17/34 Mihai Viteazu Avenue, Sibiu, Romania * irina.geana@icsi.ro 1. Introduction Bee products are full of carbohydrates, vitamins, minerals, aminoacids and enzymes [1], being healthy and easy to digest, and for that, an increasing interest in the study of their chemical composition has been observed [2]. Macro and microelements are important in the diet of human beings, and bee products and fruits represent important sources of those. In this context, it was encouraged development of natural products with therapeutic potential beyond their nutritional roles such as functional foods [3]. 2. Experimental The aim of this work was to estimate the mineral composition (K, Na, Ca, Mg, Fe, Zn, Mn) of honeys and bee products (pollen, bee bread, royal jelly, propolis, apilarnil) and to evaluate the influence of supplementation of honey with bee products and dry fruits on the mineral content of resulted honey functional foods. The total metals contents were analyzed by Atomic Absorption Spectrometry (AAS) following microwave acid digestion of the samples with concentrated hydrogen peroxide and nitric acid. 3. Results and discussion Apiary cocktail based on honey dew shows higher content of Mg, K, Na and lower content of Ca, Mn, Fe and Zn compared with apiary cocktail based on acacia honey (Figure 1). Figure 1. Mineral content of apiary cocktail 4. Conclusions Supplementation of honey with bee products and dry fruits resulted in significant increase of macro and microelements levels in the analysed samples providing significant amounts of minerals into the human body. References [1] Z. Ajtony, L. Bencs, R. Haraszi, J. Szigeti, N. Szoboszlai, Talanta 2007, 71, [2] M. Russo, L. Rastrelli, Trends in Analytical Chemistry 2009, 28, [3] R. Socha, L. Juszczak, S. Pietrzyk, T. Fortuna, Food Chemistry 2009, 113, Page79

80 P3EA. ALKALINE HYDROLYSIS OF POLYETHYLENE TEREPHTHALATE UNDER MICROWAVE IRRADIATION Adina Cata 1 *, Mariana N. Stefanut 1, Ioana M.C. Ienascu 1,2, Cristian Tanasie 1, Marinela Miclau 1 1 National Institute of Research and Development for Electrochemistry and Condensed Matter, Dr. Aurel Paunescu Podeanu 144, Timisoara, Romania 2 Vasile Goldis Western University of Arad, Faculty of Pharmacy, Liviu Rebreanu 86, Arad, Romania * adina.cata@yahoo.com 1. Introduction Recycling of waste polyethylene terephthalate (PET) started as a consequence of environmental pressure to improve waste management, since the natural decomposition rate is very slow while the consumption increases dramatically worldwide. Polyethylene terephthalate has become one of the most valuable recyclable materials because of the wide range of applications. Among the recycling methods, chemical recycling is the only one acceptable according to the principles of sustainable development because it leads to the formation of raw materials from which the polymer is originally obtained [1,2]. 2. Experimental PET waste flakes (1 g) together with various amounts of 10% NaOH solution were charged into highpressure teflon reactors of 60 ml capacity without stirring. PET depolymerization was carried out under microwave irradiation at 220 C, reaction time ranging from 1 to 120 minutes. The reaction mixture was filtered to separate unreacted PET. The filtrate was acidified with concentrated HCl in order to precipitate terephthalic acid (TPA). White precipitate of TPA was filtered, dried and weighed. The obtained TPA was analyzed using FT-IR spectroscopy, X-ray diffraction, 1 H NMR, and 13 C NMR. Percent depolymerization of PET and recovery yields of TPA were gravimetric determined. 3. Results and discussion In this work we focus on the high-yield recovery of terephthalic acid through alkaline hydrolysis of PET waste using microwave irradiation. The main product is TPA disodium salt, which is converted to TPA by treatment with acid. The influence of reaction time and the amount of alkaline solution on the TPA yield have been determined in order to establish the optimum parameters at which the reaction is completed. The recorded FT-IR, X-ray (Figure 1) and NMR spectra confirmed that the solid product obtained by alkaline hydrolysis was terephthalic acid. Also, these analyzes proved the high purity of the obtained TPA. Figure 1. X-ray spectrum of PET hydrolysis product indexed to the reference 4. Conclusions The use of microwave irradiation for PET depolymerization by alkaline hydrolysis provides the significant reduction in reaction time (less than 30 minutes) as compared with the conventional heating methods. Depolymerization of PET waste was complete and TPA yield reached more than 98%. References [1] L. Bartolome, M. Imran, B. G. Cho, W. A. Al-Masry, D. H. Kim; in Achilias, D.S., (Ed.); Material Recycling Trends and Perspectives, Ed. InTech, Rijeka, Croatia, 2012, p. 65. [2] V. Sinha, M.R. Patel, J.V. Patel, J. Polym. Environ. 2010, 18, Page80

81 P4EA. THE APPLICATIONS OF SOME THIOSEMICARBAZIDE DERIVATIVES IN THE ADSORPTIVE STRIPPING VOLTAMMETRY Cazac Tatiana 1* 1 Institute of Chemistry, Academy of Sciences of Moldova, Academiei str. 3, MD-2028 Chisinau, Moldova * cazactatiana@gmail.com The present study was aimed at elucidation the electrochemical behavior of the Cu(II), Pb(II), and Cd(II) ions in the presence of organic reagents : thiosemicarbazides derivatives shown important effects of adsorption of the organic reagents and their metal complexes on the surface of the mercury drop electrode. An original method for evaluation of the stability constant of the adsorpted species has been proposed. It was demonstrated that the monosubstituted potassium phthalate in the system Сd(П) - 4-phenylthiosemicarbazde plays an important role not only for stabilization of ph, but it is also favorable to the formation and stabilization of the electroactive species. Introduction of the phenyl radical in the thiosemicarbazide molecule increases the sensitivity of the analytical signal, and makes possible the determination of the cadmium content up to the concentration M. Substitution of the sulfur atom by oxygen in the molecule of 8-quinolinaldehyde thiosemicarbazone changes the selectivity of the organic reagent. In the presence of 8-quinolinaldehyde semicarbazone it is possible the selective determination of the lead, reducing 2-3 times the mass of the samples. Using the adsorptive accumulation on the electrode, a number of original methods for determination of the heavy metal in different systems have been developed. The 4-phenylthiosemicarbazide has been proposed for determination of the cadmium in river waters, the thiosemicarbaziddiacetic acid and 8-quinolinaldehyde thiosemicarbazide for copper determination in the river waters, apple and tomato juices, 8-quinolinaldehyde semicarbazone - for determination of the lead in wheat flour and petrol. The metrological parameters of the proposed methods have been evaluated using standard additions, AAS spectrometry, and reference materials. Key words: adsorptive stripping cathodic voltammetry, adsorbtive accumulation on the mercury electrode, thiosemicarbazide derivatives, heavy metals. Page81

82 P5EA. VOLTAMMETRIC SENSING OF Pb(II) IONS USING MODIFIED ELECTRODES WITH POLY(HEXANOIC ACID-LIKE) FILMS George-Octavian Buica 1 *, Eric Saint-Aman 2, Eleonora-Mihaela Ungureanu 1 1 University Politehnica of Bucharest, Gheorghe Polizu 1-7, Bucharest, Romania 2 Université Grenoble Alpes-Grenoble 1, UFR de Chimie Biologie, Bâtiment C, Département de Chimie Moléculaire, UMR CNRS-5250 BP 53, Grenoble Cedex 9, France * george.buica@upb.ro 1. Introduction Chemically modified electrodes having complexing groups have proven effective for metal trace analysis by various electrochemical methods. They have the advantage to bind selectively or specifically cations or metal salts and to collect these species to the electrode surface [1, 2]. 2. Experimental The modified electrodes were prepared by electropolymerization of monomer in CH3CN mol L -1 TBAP in a cell using conventional three-electrode system (working electrode was glassy carbon disk, the counter electrode was a platinum wire and the reference electrode was Ag 10-2 mol L -1 Ag + in CH3CN mol L -1 TBAP). Accumulation of metal ions into the complexing polymeric films was carried out at open circuit by dipping the modified electrodes for a given time into 30 ml of a stirred acetate buffer solution containing Pb(II) metal cations at ph 5.5. They were subsequently transferred into an electrochemical cell containing 0.1 mol L -1 acetate buffer solutions and characterized under quiescent conditions by differential pulse voltammetry (DPV). Before recording DPV curves, the accumulated metal ions were reduced for 3 min at -1 V to ensure full reduction of the entrapped metal ions. 3. Results and discussion Here, we report the obtaining of chemically modified electrodes with poly(pyrrole-hexanoic acid) complexing films. The sensing properties of these modified electrodes towards Pb(II) cations were carefully investigated using the open circuit preconcentration-anodic stripping technique. The complexation parameters such as ph, reduction potential, and accumulation time were optimized. Thus, a detection limit of 10 pm for Pb(II) was obtained using these modified electrodes with a linear response between 30 pm and 50 nm (R 2 = 0.992). The modified electrode showed a very good answer for Pb(II) analysis in terms of reproducibility and selectivity. Acknowledgements The authors gratefully acknowledge for the financial support of the Romanian National Authority for Scientific Research, UEFISCDI, under grant PN-II-RU-TE no. 10/2015. References [1] G.-O. Buica, C. Bucher, J.-C. Moutet, G. Royal, E. Saint-Aman, E.-M. Ungureanu, Electroanalysis 2009, 21(1), [2] G.-O. Buica, E.-M. Ungureanu, L. Birzan, A. C. Razus, L.-R. Mandoc (Popescu), J. Electroanal. Chem. 2013, 693, Page82

83 P6EA. ATMOSPHERIC CHEMISTRY OF NITROAROMATICS: NEW DISCOVERIES ON THEIR PHOTOLYSIS Iustinian Bejan 1, Romeo Iulian Olariu 1, Jörg Kleffmann 2, Peter Wiesen 2 1 Alexandru Ioan Cuza University of Iasi, Faculty of Chemistry and Integrated Center of Environmental Science Studies in the North Eastern Region - CERNESIM, 11 Carol I, Iasi, Romania 2 Bergische University of Wuppertal, FB C, Physikalische und Theoretische Chemie, Wuppertal, Germany * iustinian.bejan@uaic.ro Aromatic hydrocarbons are key compounds for the composition of urban atmosphere [1]. Among the main classes of the anthropogenic volatile organic compounds (VOCs) emitted to the atmosphere, aromatic hydrocarbons are of particular interest. They are important contributor to the photooxidants and secondary organic aerosols (SOAs) formation and are associated with human health problems. From the aromatic hydrocarbons, nitroaromatics received more attention in the past decade due to their carcinogenic and phytotoxic properties. Nitroaromatics has been shown to play a role in forest decline. Photolysis of nitrophenols has been proved as one of the sources of nitrous acid (HONO) in the urban atmosphere [2]. HONO is one of the most important contributor to the formation of hydroxyl radical (OH) in the troposphere. OH radicals are the most important atmospheric oxidants in the degradation of the pollutants present in air. Also, OH radicals it is very important key intermediate in the formation of the tropospheric photochemical smog. Many field studies have investigated and demonstrated the contribution of HONO to the oxidation capacity of the atmosphere. However, this contribution has been underestimated and the existence of an unknown source of HONO has been clearly demonstrated. In this study, a new gas phase source of HONO in the atmosphere has been investigated in a flow reactor upon irradiation at nm of the methylated ortho nitrophenols and their derivatives. LOng Path Absorption Photometer (LOPAP) has been used for the detection of HONO at low concentration, while nitroaromatic precursor has been detected using Fourier Transform Infrared Spectroscopy (FTIR) technique. Formation of HONO was observed for the first time from this class of VOCs, upon precursor irradiation. Direct linear correlation with gas phase concentration of nitroaromatics was observed. Both proposed heterogeneous and homogenous formation pathways have been investigated. Our studies proved the existence of new photolytic source for the gas phase formation of HONO. Mechanistic investigations have been demonstrated the formation of HONO initiated by an intramolecular hydrogen transfer from ortho hydrogen donor to the nitro group. This research extends the knowledge on understanding of the oxidation capacity of the urban atmosphere. The new gas phase sources of HONO discovered in this study helps to explain at least in part the existing discrepancies between measured concentration of HONO in the troposphere and the values obtained from atmospheric models. Acknowledgements This work was supported by German Research Foundation project KL1392/2-1 and the Romanian National Authority for Scientific Research and Innovation, CNCS UEFISCDI within the project PN-II-TE References [1] J.G. Calvert, R. Atkinson, K.H. Becker, R. Kamens, J. Seinfeld, T.J. Wallington, G. Yarwood, The Mechanisms of Atmospheric Oxidation of Aromatic Compounds, Oxford University Press, [2] I. Bejan, Y. Abd El Aal, I. Barnes, T. Benter, B. Bohn, P. Wiesen, J. Kleffmann, Phys. Chem. Chem. Phys., 2006, 8, Page83

84 P7EA. COMPARATIVE GC-MS AND HPLC METHODS FOR MONITORING OF SOME PESTICIDES RESIDUES IN MAIZE AND WHEAT CULTIVATED IN BANAT COUNTY Mariana N. Stefanut 1 *, Marius Dobrescu 1, Cristian Vaszilcsin 1, Adina Cata 1, Ioana M.C. Ienascu 1,2, 1 National Institute of Research and Development for Electrochemistry and Condensed Matter, Department of Chemical and Electrochemical Synthesis, Dr. A. P. Podeanu 144, Timisoara, Romania, 2 Vasile Goldis University of Arad, Faculty of Medicine, Pharmacy and Dentistry, 86 Liviu Rebreanu , Arad, Romania * mariana.stefanut@gmail.com 1. Introduction Nowadays, the chain: soil-plants-pesticides-environment-human and animals health is very strictly controlled [1-3]. The aim of this work was to develop some high sensitive modern analytical methods, GC- MS and HPLC, in order to monitoring some pesticides from maize and wheat cultivated in Banat County. 2. Experimental Different samples of maize and wheat cultivated in Banat County, Carpinis-Jimbolia area were taken and and were ground to less than 1 mm diameter. Then, they were extracted by ultrasound technique [4], at 59 khz and 30 o C, during min., using acetonitrile and methanol as solvents, in different ratios. The extracts were evaporated under vacuum. Finally, they were spiked with standards solution in order to identify and quantify the residues of pesticides. 3. Results and discussion The analyses were made on an Agilent Technologies GC 7890A coupled with MSD 5975C and on a HPLC-PDA, Ultimate 3000, Dionex (USA). 4. Conclusions Some chromatographic specific methods were developed. References [1] Directiva Consiliului de stabilire a continuturilor maxime de reziduuri din si de pe cereale 86/362/CEE, J. Oficial Com. Eur. L 221/37, 1986, p.195 [2] J.M. Bonmatin, P.A. Marchand, R. Charvet, I. Moineau, E.R. Bengsch, M.E. Colin, J. Agric. Food Chem. 2005, 53, [3] D.I. Kolberg, O.D. Prestes, M.B. Adaime, R. Zanella, Food Chem. 2011, 125, [4] P. Samnani, K. Vishwakarma, B.B. Saha, SOJ Chromatographic Science, linepublishing.com, Page84

85 P8EA. STUDY OF THE PIGMENTS CONTENT FROM SOME OF GREEN PLANTS SPECIFIC TO ROMANIA Cristina Stoian "Dunarea de Jos" University of Galati, Faculty of Sciences and Environment, Department of Chemistry, Physics and Environment 111 Domneasca street, Galati, Romania, Ph: Introduction Green plant pigments are of particular importance in terms of nutrition. Carotene is provitamin A, and chlorophyll contains magnesium in the coordinated form. For this reason, green plants are an excellent source of nutrients in early spring. 2. Experimental It was studied plants from the Romania flora pentru where no data on magnesium and carotene content in leaves, although they are widely used in food and even particular medicinal properties. These plants are part of spontaneous, either regular culture, namely: wild garlic (Allium ursinum), garlic (Allium sativum), onion (Allium cepa), garden sorrel (Rumex patientia) and spinach (Spinacia oleracea). Plant very studied due to its nutritional qualities, spinach was used as comparator. 3. Results and discussion For each plant was determined carotene and chlorophyll as fresh as such, and after heat treatment. Measurements were made by a spectrophotometric method on the acetone extract [1]. It was found that garden sorrel has a magnesium content much higher than spinach, and wild garlic it is comparable with spinach. Even garlic, which has the lowest magnesium content, it contains approximately one third of the magnesium content of the spinach. At thermal treatment, the carotene and chlorophyll loss follows the same kinetic (Fig. 1). Figure 1. Loss of pigments content at thermal treatment 4. Conclusions The plants described can be used as nutritional supplements in early spring, can replace spinach. References [1] Mitić, V., Jovanović, V. S., Dimitrijević, M., Cvetković, J., Petrović, G., Stojanović, G., Biologica Nyssana, 2013, 4, Page85

86 POSTER SESSION 4 ADVANCED MATERIALS ANALYSIS P1AMA. XAS, RAMAN AND SANS STUDIES ON LITHIUM-LEAD-GERMANATE GLASSES AND CERAMICS GLASS Marius Rada 1 *, Nicolae Aldea 1, Raul Erhan 3,4, Simona Rada 2, Ramona-Crina Suciu 1, Adrian Bot 1, Mioara Zagrai 2, Eugen Culea 2 1 National Institute for Research and Development for Isotopic and Molecular Technologies, Cluj-Napoca, Romania 2 Department of Physics & Chemistry, Technical University of Cluj-Napoca, Cluj-Napoca, Romania 3 Horia Hulubei National Institute for R&D in Physics and Nuclear Engineering, 30 Reactorului Street, P.O. BOX MG- 6, Bucharest Magurele, Romania 4 Joint Institute for Nuclear Research, Frank Laboratory of Neutron Physics, Dubna, 6 Joliot-Curie Street, Russia * marius.rada@itim-cj.ro 1. Introduction Lithium lead germanate glasses in the xli2o (100-x)[7GeO2 3PbO] system, where 0 x 40 mol% Li2CO3 exhibit a germanate anomaly, which is a maximum in their density profiles with the addition of Li2CO3 up to 20 mol%. 2. Experimental The structural characterization of the samples was performed by investigations of Raman spectroscopy and X-ray scattering analysis [1]. We report here small neutron scattering investigations using scattering neutrons (SANS) on these glasses and ceramics glass samples. An EXAFS analysis of the spectra collected at the germanium K-edge for series of lithium lead germanate glasses is also presented. With the EXAFS-extracted structural parameters were reconstructed to the local neighborhood of Ge atoms and were verified current opinions on the germanate anomaly in the considered glasses [3]. 3. Results and discussion The formation of higher-coordinated Ge species in the glassy network can be correlated with the density anomaly. Several structural mechanisms can be summarized by increasing of lithium carbonate in the lead germanate glassy: i) depolymerization of germanate network; ii) conversion of 3- to 4-membered [GeO4] rings; iii) transfor-mation of connected [GeO6] structural units into isolated [GeO6] structural units and a conversion part of higher to lower coordination number of germanium atoms[2]. Page86 Fig. 1. Curve XANES of investigated xli2o (100-x)[7GeO2 3PbO] glassy samples Fig.2. Experimental EXAFS functions χ1(k) of the first shell for the investigated samples Acknowledgements This work is supported by Romania-JINR-Dubna 2015 Projects, protocol no /2017. The financial support is gratefully acknowledged by the authors. References [1] G.S. Henderson, J. Non-Cryst. Solids 2007, 353, [2] M. Rada, E. Culea, S. Rada, A. Bot, N. Aldea, V. Rednic, J. Non-Cryst. Solids 2012, 358, [3] B. Ravel, M. Newville, J. Synchrotron Radiat. 2005, 12,

87 P2AMA. EVALUATION OF STRUCTURE IMPLICATIONS ON OPTICAL AND ELECTRICAL PROPERTIES OF IMIDIC COMPOUNDS Raluca Marinica Albu*, Andreea Irina Barzic Petru Poni Institute of Macromolecular Chemistry, 41 A Grigore Ghica Voda Alley, Iasi, Romania * alburaluca@yahoo.com 1. Introduction Macromolecular compounds containing imidic groups have been widely investigated because of their outstanding key properties, such as thermoxidative stability, mechanical performance and excellent electrical properties [1-3]. These polymeric materials are used as interlayer dielectrics in integrated circuit fabrication. For this practical purpose there is a great need to reduce the dielectric constant. 2. Theoretical background Evaluation of the physical properties was made starting from the assumptions of the group contribution theory. 3. Results and discussion Some imidic compounds derived from different types of dianhydrides or diamines were investigated in regard with some basic physical properties. Calculation of molar volume and molar refraction allowed determining the refractive index. The latter was further used to evaluate the dielectric constant, molar polarization, electrical volume resistivity and effective dipole moment. The results were discussed in correlation with the chemical structure of the samples highlighting the implications of the typical monomer moieties on studied physical characteristics. 4. Conclusions The obtained data show that there is a synergism between the polarizability and polymer chain packing that must be considered when designing new imidic polymers for microelectronics. Also, the results are useful in pre-establishing some features of the polymers (before starting the synthesis reactions) that are essential for pursued applications. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS UEFISCDI, project PN-II-RU-TE , no. 256/ References [1] A.S. Mathews, Y. Jung, T. Lee, S.S. Park, I. Kim, C.-S. Ha, M. Selvaraj, M. Han, Macromol. Res. 2009, 17, [2] A.I. Cosutchi, C. Hulubei, M. Buda, T. Botila, S. Ioan, Rev. Roum. Chim. 2007, 57, [3] E. Hamciuc, R. Lungu, C. Hulubei, M. Bruma, J. Macromol. Sci. Part A 2006, 43, Page87

88 P3AMA. IMPACT OF SOLVENT TYPE ON OPTICAL PROPERTIES AND BIOCOMPATIBILITY OF A CELLULOSIC POLYMER Andreea Irina Barzic*, Luminita Ioana Buruiana Petru Poni Institute of Macromolecular Chemistry, 41 A Grigore Ghica Voda Alley, Iasi, Romania * irina_cosutchi@yahoo.com 1. Introduction Modification of cellulose opened multiple perspectives in microelectronics and biomedical fields, where self-ordering, transparent and biocompatible materials are demanded. Particularly, hydroxypropyl methylcellulose (HPMC) is a semisynthetic, inert, viscoelastic macromolecular compound, which results from methoxy substitution on the cellulose chain [1]. For most applications, the finite product results from processing the corresponding polymer solution [2]. 2. Experimental The optical properties are determined from UV-VIS measurements of polymer films prepared from solutions in different organic solvents. The biocompatibility of the samples was assessed from surface properties data derived from contact angle experiments. 3. Results and discussion The properties of HPMC polymer are very interesting and they are greatly influenced by several factors, such as temperature, time and solvent type. The aim of this work is to investigate the manner, in which the solvent nature affects some optical features, namely transmittance, Tauc and Urbach energies. The solvent type also affects chain conformation and implicitly the compatibility degree of the studied polymer with cellular media as determined from surface energy concepts. 4. Conclusions The transparency in visible domain is useful in observation of biological media brought in contact with studied sample. The evaluated adhesion work values show that HPMC is suited for biomedical purposes. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research and Innovation, CNCS UEFISCDI, project PN-II-RU-TE , no. 256/ References [1] G. Sertsou, J. Butler, J. Hempenstall, T. Rades, J. Pharm. Pharmacol. 2003, 55, [2] G. Sertsou, J. Butler, J. Hempenstall, T. Rades, J. Pharm. Pharmacol. 2002, 54, Page88

89 P4AMA. EFFECT OF METALLIC PALLADIUM ON STRUCTURE AND SPECTROSCOPIC PROPERTIES OF LEAD-BORATE GLASSES AND VITROCERAMICS Stanca Mitrici 1, Leontin David 1, Simona Rada 2 *, Eugen Culea 2 1 Faculty of Physics, Babes-Bolyai University from Cluj-Napoca, , Cluj-Napoca, Romania 2 Department of Physics & Chemistry, Technical University of Cluj-Napoca, , Cluj-Napoca, Romania * radasimona@yahoo.com 1. Introduction New different series of xpd (100-x)[3B2O3 PbO2] glasses and vitroceramics where x = 0-40mol% Pd were prepared by melt-quenching method. 2. Experimental These samples were characterized by investigations on XRD, FTIR and UV-VIS spectroscopies and molecular modeling calculations. For sample with x=40mol% Pd, X-ray diffraction pattern shows the apparition of metallic palladium crystalline phase in the face-centered cubic system [1]. 3. Result and discussion Our spectroscopic data show that the incorporation of metallic Pd into lead-borate matrix causes the bending modes of the Pb-O-Pb linkages. The accommodation of the network with the excess of metallic palladium contents can be associated with a change of boron coordination, from [BO3] to [BO4] structural units and with the formation of Pd-O-Pb as well as Pd-O-B chains. The values of the band gap energy modify gradually with increasing the Pd content up to 40 mol % [2]. The DFT calculations were employed to explore the role of Pd content on the structure of the lead-borate glass network [3]. References [1] D. Orosel, P. Balog, H. Liu, J. Qian, M. Jansen, J. Solid State Chem. 2005, [2] S. Rada, E. Culea, M. Rada, Mater. Chem. Phys. 2011, 128, [3] L. Dua, P. K. Biswas, Chem. Phys. Lett. 2013, 572, Page89

90 P5AMA. NANO-HYDROXYAPATITE COMPOSITES FOR STOMATOLOGICAL USE Mariana N. Stefanut 1 *, Adina Cata 1, Ioana M.C. Ienascu 1,2, Paula Sfirloaga 1, Marius Dobrescu 1, Dan Rosu 1 1 National Institute of Research and Development for Electrochemistry and Condensed Matter, Department of Chemical and Electrochemical Synthesis, Dr. A. P. Podeanu 144, Timisoara, Romania, 2 Vasile Goldis University of Arad, Faculty of Medicine, Pharmacy and Dentistry, 86 Liviu Rebreanu , Arad, Romania * mariana.stefanut@gmail.com 1. Introduction Nowadays, many people manifest more attention for health, a perfect teeth and a beautiful smile. In dentistry, there are many possibilities to correct some natural mistakes or to repair the defects arising after accidents. Many research efforts were carried out in order to find substitutes for teeth and bones [1]. Hydroxyapatite, Ca10(PO4)6(OH)2 is an excellent material for his biocompatibility, bioactivity and osteoconductivity and is widely used as powders, particulate or porous, and solid scaffold forms. 2. Experimental The work proposes the obtaining the nano-hydroxyapatite by different methods: extraction from byproducts of food industry (Figure 1) and chemical synthesis [2, 3]. Mixtures with collagen or chitosan were made for the obtaining of some synthetic membranes with specific use in dentistry. a. b. c. d. Figure 1. Nano-hydroxyapatite from bovine bone: a- TEM image; b-distance between crystalline planes; c- STEM image; d- EDX spectrum (Ca /P ratio is 2.18) 3. Results and discussion Materials were characterized using TEM-EDX and SEM-EDAX microscopy, FT-IR and X-ray diffraction techniques. 4. Conclusions Materials with excellent properties for stomatological use were obtained. References [1] V. Uskokovič, D.P. Uskokovič, J. Biomed. Mat. Res. Part B: Applied Biomaterials. 2011, 96B (1), [2] N.A.M. Barakat, M.S. KHil, A.M. Omran, F.A. Seikh, H.Y. Kim, J. Mat. Proc. Tech. 2009, 209, [3] D.A. Wahl, J.T. Czernuca, Eur. Cells Mat. 2006, 11, Page90

91 P6AMA. CHANGES INDUCED BY LIGHT AND PROTONATION/DEPROTONATION ON THE ABSORPTION AND FLUORESCENCE SPECTRA OF NEW STIMULI-RESPONSIVE BISAZOBENZENE DERIVATIVES Mihaela Homocianu*, Diana Serbezeanu, Ionela-Daniela Carja, Ana Maria Macsim, Tachita Vlad- Bubulac, Anton Airinei Petru Poni Institute of Macromolecular Chemistry, Aleea Grigore Ghica Voda 41A, Iasi, , Romania * The smart materials used in development of technology required high sensitivity to external stimuli, such as ph, light, temperature, and/or to other multiple stimuli. In this paper we describe the synthesis and characterization of three novel dual-stimuli-responsive bisazobenzene derivatives capable of changing their properties upon treatment with light and chemical stimuli (ph). These new compounds were synthesized by solution polycondensation of 4,4 -bis(4-hydroxyphenyldiazenyl-4-phenoxy)biphenyl (BAPB-Azo) and phenylphosphonic dichloride or phenyl dichlorophosphate. The obtained oligomers were characterized by FTIR, NMR, thermal stability and optical properties. The effect of trans-cis-trans isomerization of the oligomers, induced by light, on absorption spectra was presented (see Figure 1a). Optical response to light and ph (addition of a base or an acid) were examined using the absorption and fluorescence spectroscopy. The presence of base (deprotonation) can induce a significant changes on the optical spectra (absorption and emission spectra, see Figure 1b) of these compounds. The changes induced on the absorption spectra were studied by addition of diluted NaOH solutions in polymer solutions. With increasing of the concentration of NaOH, the absorption maxima (initially at 366 nm) gradually decreases in intensity and at the same time a new strong absorption band appears in the visible region with the maximum at 490 nm (see Figure 1b). Instead, the fluorescence signal at high ph was significantly enhanced. The deprotonation/reprotonation processes (base-acid treatments) were reversible and induced the absorption turn-on/off behavior of these compounds. Such dual-stimuli-responsive polymers have certain potential for various applications (e.g. scanning probe writing, switchable wettability, sensors and actuators). Fig. 1 Changes in the absorption spectra of the BAPB-Azo in a DMSO solution, recorded for various irradiation times (at the room temperature) (a) and before (initial) and after titration with a dilute solution of NaOH (c =1 N). Arrows indicate changes in UV-Vis spectra (b) Acknowledgements The authors acknowledge the financial support of CNCSIS UEFISCSU, Project Number PN-II-RU-TE nr. 28/ References [1] J. Lu, E. Choi, F. Tamanoi, J. I. Zink, Small, 2008, 4, [2] J. E. Green, J. Wook Choi, A. Boukai, Y. Bunimovich, E. Johnston-Halperin, E. DeIonno, Y. Luo, B. A. Sheriff, K. Xu, Y. S. Shin, H. R. Tseng, J. F. Stoddart, J. R. Heath, Nature, 2007, 445, Page91

92 P7AMA. PHASE RELATIONS IN THE NiTiCu SHAPE MEMORY MATERIALS USED IN MEDICINE APPLICATION Cristiana Diana Cirstea 1 *, Marcela Mihai 2, Vasile Cirstea 3, Delia Patroi 1, Florina Radulescu 1, Virgil Marinescu 1, Magdalena Lungu 1 1 National Institute for Research and Development in Electrical Engineering INCDIE ICPE-CA, Splaiul Unirii nr. 313, , Bucuresti, Romania 2 Petru Poni Institute of Macromolecular Chemistry of Romanian Academy, Aleea Grigore Ghica Voda nr. 41A, , Iasi, Romania 3 Military Equipments and Technologies Research Agency, Strada Aeroportului nr. 16, , Clinceni, Romania * diana_cirstea@yahoo.com 1. Introduction Due to their unique combination of mechanical properties, shape memory materials possess great promise as biomaterials for medicine application. Some studies [1-3] have shown that materials like NiTiCu improve the corrosion resistance. The paper presents the phase transformation and the effect of copper addition in an amount of up to 10at% in the structure of ternary Ni50-xTi50Cu x materials (0 Cu 10%) obtained by spark plasma sintering with and without mechanical alloying. 2. Experimental The samples used in this study were made from elemental powder without and with mechanical alloying (up to 15 hours) by Spark Plasma Sintering (SPS) method with nominal composition of Ni 50 xti 50Cu x (x = 5, 10at.%). The cylindrical samples with diameter of 20 mm and height of 4-5 mm were realized in vacuum by uniaxial pressing with 50 MPa at a sintering temperature of 900ºC and holding time of 5 minutes. In order to increase the alloy homogeneity, the NiTiCu samples were subjected to a heat treatment (HT) in two steps as follows: temperature increasing with C/min until C, holding for 1 hour, cooling with C/min until C, holding for 30 min and cooling again at room temperature with C/min in argon atmosphere. After and below heat treatment, the samples were investigated by X-ray diffraction (XRD), scanning electronic microscopy together with energy dispersive X-ray spectroscopy (SEM/EDAX) and nanoindentation measurements. Also the quality of the materials was characterized by porosity and density. 3. Results and discussion Some of the results from the investigations applied to NiTiCu samples are presented in next table. 4. Conclusions The NiTiCu materials density is higher when copper content increases from 5 to 10 at%, while porosity is less than 5%, except the P1 sample where porosity was 10. After applying HT, the density decreased for HT-P0 and HT-P1, which led to increased porosity. In case of HT-S0 and HT-S1, the applied HT led to increased density. The hardness of P0 and P1 samples increases after applying HT, while the hardness of S0 and S1 samples declines after application of HT. From the viewpoint of modulus of elasticity the materials are of austenitic type. Acknowledgements Research supported by the Bilateral Collaboration Romania-Russia under the Projects No. 62/2016. Page92 References [1] B. O Brien and M. Bruzzi, Shape memory alloys for use in medicine, 2011 Elsevier Ltd. [2] F.J. Gil, J.A. Planell, Effect of copper addition on the superelastic behavior of Ni-Ti shape memory alloys for orthodontic applications, J Biomed Mater Res. 1999;48(5): [3] M. J. Yaszemski et al., Biomaterials in Orthopedics, 2003, Taylor & Francis Group, LLC

93 P8AMA. GRAPHENE NETWORK INVESTIGATION BY RAMAN SPECTROSCOPY Cristina Banciu*, Adela Bara, Marius Lungulescu, Lucia Leonat National Institute for Research and Development in Electrical Engineering INCDIE ICPE-CA, 313 Splaiul Unirii, , Bucharest, Romania * 1. Introduction Graphene is a carbon material with unique properties, of interest for various practical applications, with a hexagonal structure, in the state of sp 2 hybridized carbon, in which strong covalent bonds are formed between the carbon atoms. In general, a characterization technique of materials must meet several conditions such as: to be quick and nondestructive, providing high resolution, to give structural and electronic information and to be applicable at both laboratory and industrial level. Raman spectroscopy is a technique that meets all these requirements and has become one of the most popular methods for characterizing amorphous carbon materials and with a certain degree of structural disorder, fullerenes, carbon nanotubes, chains of carbon, poly-conjugated molecules, etc. In particular, Raman spectroscopy is used for graphene [1] because the absence of the band gap makes all incidents wavelengths to be resonant, so Raman spectra contain information both the atomic structure and the electronic properties. Raman spectra have a simple structure characterized by the presence of two major bands known as a "G band" and "2D band". If the graphene network presents structural defects, then the Raman spectrum contains a third band "D band". Chemical vapor deposition (CVD) is an alternative method to produce graphene with high conductivity. The CVD synthesized graphene is commonly grown on a flat metal foil or thin film. In this paper, we prepare the graphene network by using Ni foam as template in a CVD process with methane as the carbon source. The obtained graphene network on Ni foam were investigated by Raman spectroscopy. 2. Experimental Graphene was synthesized on a commercial nickel foam by a CVD process with methane as carbon source at 1000 C under ambient pressure, which copied the structure of the nickel foam and formed a network. Figure 1. SEM image of a graphene network synthesized on a nickel foam References [1] A.C. Ferrari, Solid State Comm., 2007, 143, Page93

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