Chemistry Life 2015 - Fakulta chemická VUT v Brně · PDF fileChemistry & Life 2015 ......
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Chemistry & Life 2015
Sixth Meeting on Chemistry and Life
2nd to 4th September 2015
Brno, Czech Republic
Faculty of Chemistry, Brno University of Technology
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Copyright © 2015 Brno University of Technology, Czech Republic
All rights reserved. No part of this publication or the information contained herein may be
reproduced, stored in a retrieval system, or transmitted in any form or by any means,
electronic, mechanical, by photocopying, recording or otherwise, without written prior
permission from the publisher.
Although all care is taken to ensure the integrity and quality of this publication and the
information herein, no responsibility is assumed by the publishers or the author for any
damage to property or persons as a result of operation or use of this publication and/or the
information contained herein.
Book cover design: Beata Spáčilová
Printed by: Brno University of Technology, Faculty of Chemistry, 2015
ISBN: 978‐80‐214‐5228‐2
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HISTORY OF CONFERENCE
After the reopening of the Faculty of Chemistry of Brno
University of Technology in 1992 and reaching its stability in the
area of teaching, the research activities of both academic and
scientific staff began to develop. Modest instrumentation
brought publications based on experimental work of the faculty
staff. In 1999 prof. Lubomir Lapčík – the dean of that time‐
organized the International Conference ʺThe First Meeting on
Chemistry & Lifeʺ to boost a mutual exchange of experience. It
was held on Sept. 9 ‐ 10, 1999 in the newly opened Faculty premises on Purkyňova 118, Brno.
There were 147 contributions presented by more than 230 authors, including the prominent
experts from abroad (PV Krivenko from Ukraine, M. Sprinzl from Germany, A. Korgo
Switzerland, TG Langdon from the USA). The conference was attended by the scientists and
academics from Slovak and Czech universities.
The Second Meeting on Chemistry & Life was held at Brno University of
Technology on Sept 10 – 11, 2002. The conference was organized as a part
of the events celebrating the 10th anniversary of the faculty and was held
under the auspices of the rector of Brno University of Technology, prof.
Jan Vrbka. The conference presented 54 contributions and more than 100
posters. The quality of the conference was also supported by the invited
lectures given by the prominent domestic and foreign experts (K.
Friedrich from Germany, S. Mierts from Italy, M. Kodíček of the Institute of Chemical
Technology in Prague and R. Zahradník of the Academy of Science of the Czech Republic).
The Third Meeting on Chemistry & Life was held at the Faculty of Chemistry in Brno on
Sept. 20‐ 22, 2005 under the auspices of prof. Jan Vrbka, the rector of BUT and prof. Jaroslav
Fiala, the dean of the Faculty of Chemistry. The event followed the tradition of three‐annual
meetings providing people from industry, research and academia with a forum to exchange
the ideas on recent advances in research and development in chemistry, biotechnology,
materials, science and environmental technology. There were five plenary lectures (M. Anke
from Germany, N. Inagaki from Japan, D. Klockow from Germany, and J. Hajšlová and L.
Lapčík from the Czech Republic), 93 lectures in the sections and 184 posters.
The Fourth Meeting on Chemistry & Life was held at Brno
University of Technology on September 9 ‐ 11, 2008 under the
auspices of prof. Karel Rais, the rector of BUT and prof. Jaromir
Havlica, the dean of the Faculty of Chemistry. The conference
included 8 plenary lectures, 6 of which given by prominent
foreign experts from Slovenia, Ukraine, Germany and Serbia. In
addition to Czech and Slovak scientists the conference was also
attended by the experts from other countries (France, Romania, Russia, Spain, Australia,
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Iran, Serbia, Brazil, Italy, and Borneo). The negotiations were conducted in 10 sections:
Environmental Chemistry & Technology, Food Chemistry & Biotechnology, Chemistry of
Inorganic Materials, and Chemistry of Organic materials, Photochemistry, Polymers and
Polymer Composites. There were 77 lectures and 300 posters presented in these sections
The Fifth Meeting on Chemistry & Life was held from 14 to 16
September 2011 traditionally at the Faculty of Chemistry, Brno
University of Technology under the auspices of prof. Karel Rais,
the rector. There were six plenary lectures at the conference, and
5 invited lectures by prominent Czech and foreign scientists (AJ
Lesser from the USA, M. Chaplin from the UK, T. Rustad from
Norway, TD Mark from Austria, MG Fernández from Spain, M.
Palouš and J. Híveš from Slovakia, J. Hajšlová from the Czech Republic and others). In
addition, there were 56 presentations and more than 56 posters presented by both academics
and doctoral students.
The Sixth Meeting on Chemistry and Life will take place at Brno University
of Technology, Faculty of Chemistry on Sept. 2‐4, 2015. The conference will
be held under the auspices of the rector of Brno University of Technology,
prof. Petr Štěpánek. The scientific level of the conference is guaranteed by
the dean of the Faculty of Chemistry, prof. Martin Weiter. We expect the
outstanding experts from abroad (G.H Pollack and A. Crosby from USA, K.
Kovar from Switzerland,, L.E Melymuk from Canada and J. Hofman from the Czech
Republic) to present plenary lectures and more than 200 other participants from the Czech
and Slovak Republic and abroad (Cyprus, China, Kuwait, Iran, Poland, Romania, Russia,
Turkey and Ukraine). The conference will also be attended by several companies
collaborating with the faculty in the area of contracted research and business activities.
ACKNOWLEDGEMENT
Publication of this book was financially supported by the Czech Ministry of Education,
Youth and Sports, under project No LO1211.
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CONFERENCE SPONSORS
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Committees
INTERNATONAL SCIENTIFIC COMMITTEE
Martin Weiter (Brno University of Technology, Czech Republic), chairman
Leon Govaert (Eindhoven University of Technology, Eindhoven, Netherlands)
Jaromír Havlica (Brno University of Technology, Czech Republic)
Josef Jančář (Brno University of Technology, Czech Republic)
Karin Kovar (School of Life Sciences and Facility Management, ZHAW, Wädenswil,
Switzerland)
Ivana Márová (Brno University of Technology, Czech Republic)
Miloslav Pekař (Brno University of Technology, Czech Republic)
Jan Schwarzbauer (RWTH Aachen, Germany)
Ján Šajbidor (Slovak University of Technology in Bratislava, Slovakia)
Peter Šimon (Slovak University of Technology in Bratislava, Slovakia)
Bimal Kumar Sarkar (Galgotias University, Greater Noida, India)
Milada Vávrová (Brno University of Technology, Czech Republic)
Michal Veselý (Brno University of Technology, Czech Republic)
Daniel Wagner (Weizmann Institute of Science, Rehovot, Israel)
Oldřich Zmeškal (Brno University of Technology, Czech Republic)
ORGANIZING COMMITTEE
Oldřich Zmeškal, FCH BUT, Brno, Czech Republic, chairman
Hana Alexová, FCH BUT, Brno, Czech Republic
Jan Brada, FCH BUT, Brno, Czech Republic
Petr Dzik, FCH BUT, Brno, Czech Republic
Renata Herrmannová, FCH BUT, Brno, Czech Republic
Ilona Pipková, FCH BUT, Brno, Czech Republic
Michal Veselý, FCH BUT, Brno, Czech Republic
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Invited Speaker
Professor Gerald H. Pollack
University of Washington
Seattle, USA.
http://faculty. washington. edu/ghp/
E‐mail: ghp@u. washington. edu
CV
Gerald Pollack received his PhD in biomedical engineering from the University of
Pennsylvania in 1968. He then joined the University of Washington faculty and is now
professor of Bioengineering. He is also Founding Editor‐in‐Chief of the journal, WATER,
convener of the Annual Conference on the Physics, Chemistry and Biology of Water, and
Executive Director of the Institute for Venture Science.
RESEARCH ACTIVITIES
His interests have ranged broadly, from biological motion and cell biology to the interaction
of biological surfaces with aqueous solutions. His 1990 book, Muscles and Molecules:
Uncovering the Principles of Biological Motion, won an “Excellence Award” from the
Society for Technical Communication. His 2001 book, Cells, Gels and the Engines of Life,
and his newest book, The Fourth Phase of Water: Beyond Solid, Liquid, and Vapor won that
Society’s “Distinguished Award, ” their highest distinction. The latter book went on to
receive the World Summit Excellence Award.
AWARDS
Pollack received an honorary doctorate in 2002 from Ural State University in Ekaterinburg,
Russia, and was more recently named an Honorary Professor of the Russian Academy of
Sciences and foreign member and Academician of the Srpska Academy. He received the
Biomedical Engineering Society’s Distinguished Lecturer Award in 2002. In 2008, he was the
faculty member chosen by his university colleagues to receive their highest annual
distinction: the UW Faculty Lecturer Award. Pollack is a Founding Fellow of the American
Institute of Medical and Biological Engineering and a Fellow of both the American Heart
Association and the Biomedical Engineering Society. He received an NIH Director’s
Transformative R01 Award. He was the 2012 recipient of the Prigogine Medal for
thermodynamics of dissipative systems, and in 2014 he received the Scientific Excellence
Award from the World Academy of Neural Therapy, as well as the Society for Scientific
Exploration’s Dinsdale Prize.
PAPER PRESENTED
The Fourth Phase of Water: Beyond Solid, Liquid, and Vapor
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Invited Speaker
Prof. Dr. Karin Kovar Head of the Bioprocess Technology Section
School of Life Sciences and Facility Management
SWITZERLAND
E‐mail: koka@zhaw. ch
CV
Since 1999, Professor Karin Kovar has been Head of the Bioprocess Technology Section &
Lecturer in Bioprocess Technology and Bioprocess Informatics at the Zurich University of
Applied Sciences ZHAW in Wädenswil, Switzerland. Her unique career has developed
across academic and industrial sectors, and both her research and teaching are based on
profound cross‐disciplinary knowledge. She has held industrial and academic research
appointments at F. Hoffmann‐La Roche Ltd, Vitamin Research, Basel, CH, the Swiss Federal
Institute of Environmental Science and Technology (EAWAG), Dübendorf, CH, and at the
Institute of Chemical Technology, Prague, CZ. Moreover, she accomplished internships at
the Max‐Planck‐Institute, Mülheim a. d. Ruhr, D and the University of Bayreuth, Germany.
Karin Kovar graduated (MSc. Hons.) in two fields, chemical engineering, and ecology, from
the University of Chemical Technology (UCT) in 1989 and the Charles University, Prague,
CZ in 1992 respectively. In 1996 she obtained her PhD in microbial physiology from the
Swiss Federal Institute of Technology (ETH), Zürich, CH, with special emphasis on
microbial growth kinetics.
FIELDS OF THE RESEARCH
The research focus of the Bioprocess Technology Section has yielded several industrial
applications relating to microbial biotechnology. Their approach is multidisciplinary,
drawing on microbial physiology, advanced data evaluation, computational methodology
and process engineering as well as skills and competences which are implemented in close
collaboration with teams focussed on molecular biological strain testing and metabolic
pathway engineering. The main topics of research currently include:
• kinetics of (recombinant) product formation
• analyses of culture/population heterogeneity at the single‐cell level
• recombinant protein (over‐) production with Pichia pastoris
• variations in post‐translational modifications during production processes
• heterotrophic, mixotrophic and photoautotrophic culture modes with microalgae
The overarching goal of this research is to understand and predict factors affecting
productivity in biotechnological processes and varying qualities of synthesised products.
RESEARCH ACTIVITIES
The Bioprocess Technology team at the ZHAW develops concepts and strategies for the
design and optimisation of biotechnological manufacturing processes using bacteria, fungi
(yeasts) and microalgae that are particularly selected to produce functional and structural
recombinant proteins including enzymes, growth factors, membrane transporters,
antibodies and collagen as well as pigments, vitamins, PUFAs, steroids, etc.
Professor Kovar and her team were presented with the international Bodensee Innovation
Award in both 2009 and 2012 as well as they were a finalist for the ZHAW’s Best Teaching
Award in 2013 and 2015, in respect of the unique and innovative educational programme
“New business opportunities for biotechnology in chemical manufacturing”.
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Besides her research and teaching activities, she manages the e‐learning platform
http://www. biotechLAB. net, which was initiated within the scope of the Swiss Virtual
Campus Programme, and she has developed science communication projects for primary
school pupils and their parents, supported by the Swiss National Science Foundation
(http://miwelt. net) as well as initiating and co‐organising the successful BioTech, Czech‐
Swiss Symposium and Pichia scientific series of conferences.
PUBLICATIONS
A selection of her most relevant publications are listed under:
http://ibt. zhaw. ch/fileadmin/php_includes/popup/person‐detail. php?kurzz=koka
PAPER TO BE PRESENTED
Strategies for optimum production of high‐value products using microalgae.
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Invited Speaker Professor Alfred J. Crosby
Polymer Science & Engineering Department
University of Massachusetts Amherst
USA
E‐mail: crosby@mail. pse. umass. edu
CV
Al Crosby received his B. S. degree in Civil Engineering and Applied Mechanics at the
University of Virginia in 1996 and his Ph. D. in Materials Science and Engineering at
Northwestern University in 2000, with his doctoral dissertation research entitled:
Deformation and Failure of Thin Viscoelastic Adhesives. He was awarded a National
Research Council Research Fellowship in 2000 to conduct his postdoctoral research on
Combinatorial Characterization of Polymer Thin Film Mechanics and Adhesion in the
Polymers Division at the National Institute of Standards and Technology. In 2002, he joined
the faculty at the University of Massachusetts Amherst as an Assistant Professor. He was
promoted to Associate Professor in 2008 and Full Professor in 2012. Professor Crosby’s
research group focuses on the mechanics of soft materials, especially in the context of
adhesion and bio‐inspired materials.
FIELDS OF RESEARCH
‐ Bio‐inspired materials design
‐ Polymer adhesion
‐ Mechanics of hierarchical structures
‐ Deformation and fracture of thin polymer films
‐ Polymer nanocomposites
RESEARCH ACTIVITIES
Across an extensive size scale range, we focus on gaining fundamental knowledge of
structure‐property‐performance relationships in order to create new materials that can
interface with humans on human size scales. Our materials design paradigms introduce not
only advanced functions but also routes to sustainable and robust production methods. We
organize our research along four themes: bio‐inspired adhesion; polymer surface instabilities;
polymer‐nanoparticle hybrid assemblies; and properties of gels and living tissues. Our
research has been covered extensively in the popular media, including Discovery Channel,
Bloomberg Businessweek and CNN Money/Fortune Magazine, which named the Geckskin™
project one of the Top 5 Science Breakthroughs of 2012.
PUBLICATIONS
Prof. Crosby has published more than 100 peer‐reviewed scientific publications, 4 book
chapters, 15 patents or patent applications, and his publications have been cited over 2400
times.
PAPER PRESENTED
Polymer‐Nanoparticle Mesostructures and Their Mechanics
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Invited Speaker Dr. Lisa Melymuk
Research Centre for Toxic Compounds in the Environment
Faculty of Science, Masaryk University
Czech Republic
Email: melymuk@recetox. muni. cz
CV
Lisa Melymuk received her Hon. B. Sc. in geology and physics from McMaster University,
Canada, her M. Sc. degree in geography from the University of Toronto, Canada, and her PhD in
Chemical Engineering and Applied Chemistry from the University of Toronto in 2012. Her
dissertation research was on: Semi‐volatile Organic Contaminants in the Urban Atmosphere:
Spatial and Seasonal Distributions and Implications for Contaminant Transport. In 2012, she
joined the Research Centre for Toxic Compounds in the Environment (RECETOX) at Masaryk
University, Brno, as a postdoctoral researcher.
FIELD OF RESEARCH
‐ Air sampling methods for semivolatile organic contaminants
‐ Endocrine disrupting compounds in consumer products
‐ Indoor levels of semivolatile organic contaminants and endocrine disruptors
‐ Linking consumer product use and exposure to endocrine disruptors
RESEARCH ACTIVITIES
Dr. Melymuk’s research activities broadly address semivolatile organic contaminants, with a
focus on their distribution in indoor environments. Her current research projects address
conventional and new sampling methods for organic pollutants, such as passive and active air
sampling, and aim to refine those techniques to best address the broad suite of legacy and
current use chemicals which are of concern for human and environmental health. She is also
working on identification of the pathways of chemical transport indoors from chemical use in
building materials and consumer products through to human exposure. Her research involves a
combination of environmental sampling, experimental case studies and stochastic modeling
techniques to address exposure pathways.
PAPER PRESENTED
Organic contaminants in the indoor environment: linking sources to human exposure
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Invited Speaker Assoc. Prof. Jakub Hofman
Masaryk University
Faculty of Science, RECETOX
Brno CZECH REPUBLIC
hofman@recetox. muni. cz
CV
Jakub Hofman received his MSc. degree in Environmental Protection and Management at the
Masaryk University (the Czech Republic) in 1998. He received his Ph. D. degree in
Environmental Chemistry and RNDr. degree in Ecotoxicology in 2003 and 2004 at the
Masaryk University. His doctoral research was focused on soil microbial parameters and their
use in environmental (bio) monitoring. Since 1998, he worked as researcher and then as
Assistant Professor at Masaryk University in the Research Centre for Toxic Compounds in the
Environment (RECETOX). He was promoted to Associate Professor in 2011 in Environmental
Chemistry with the habilitation thesis entitled: Contaminants in the soil environment and
their effects on biota. Today he works in RECETOX at MU and his research group focuses on
the soil ecotoxicology and environmental chemistry and on the bioavailability of
environmental contaminants.
FIELDS OF RESEARCH
‐ soil environmental chemistry and ecotoxicology
‐ soil contamination and monitoring
‐ bioavailability of contaminants in soils
‐ soil quality and degradation, soil protection, policy and legislation
‐ currently used pesticides
RESEARCH ACTIVITIES
Our main area of interest lies in understanding the interactions between pollutants and biota
in soil. In various research projects we have studied behavior and bioavailability of soil
contaminants as the key processes affecting their toxicity. In the past, we mostly focused on
persistent organic pollutants, but recently we shifted to the group of currently used
pesticides. Our topic is also the investigation of the methods suitable for bioavailability
determination. Further, we focus our attention to research of the effects of complex mixtures
on soil organisms. Dredged sediments application on soil has been studied as an example.
From the basic research issues above, the attention of our group has been always focused also
on the soil protection and soil related policy, legislation and education.
PUBLICATIONS
Dr. Hofman has published 35 peer‐reviewed IF scientific publications, 2 book chapters, 1
utility model, and his publications have been cited over 250 times.
PAPER PRESENTED
Can currently used and emerging pesticides in agriculturally used fluvisols be risky for
human and ecosystem health?
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Table of contents
Advanced Ceramics .............................................................................................................. 25
Svec, J., Bartonickova, E., Jebava, A., Masilko, J., Ptacek, P.
Synthesis of Layered Calcium Cobaltites Intended for Thermolectric Applications .......... 25
Solny, T., Ptacek, P., Bartonickova, E., Masilko, Tkacz, J., Daviðsdóttir, S., Ambat, R.
TiO2 Surface Coating of Mn‐Zn Dopped Ferrites Study .......................................................... 26
Fojt, P., Zlámalová, H., DeVaufleury, A.
Possible Use of Terrestrial Gastropod (Helix Aspersa Aspersa) and It’s Life Stages as a
Tool for Environmental Risk Assessement ................................................................................ 26
Heinrichová, P., Kovalenko, A., Dzik, P., Zhivkov, I., Honová, J., Vala, M., Weiter, M.
Development of Large Area Organic Solar Cells ...................................................................... 27
Mocan L,, Matea T.C., Iancu C., Mocan T.
Immunoglobulin G Functionalized Gold Nanoparticles for Selective Treatment of Cancer
.......................................................................................................................................................... 28
Krouská, J., Pekař, M.
Solution Calorimetry as a Tool for API Characterization ........................................................ 29
Raghvendra Singh Yadav, Jaromir Havlica
An Overview of Cation Distribution and Particle Size Dependent Properties of Ferrite
Nanoparticles ................................................................................................................................. 29
Biotechnology ....................................................................................................................... 33
Tonkopii, V.
Isolation, Purification and Kinetic Behaviour Of Fishʹs Blood Serum Cholinesterase ........ 33
Hudečková, H. Babák L.
Lactic Acid Production from Waste Bread ................................................................................ 33
Pilgrova, T., Pekar, M.
Interaction between Cationic Micelles and Hyaluronan ......................................................... 34
Bokrová, J., Matoušková, P., Pavelková, R., Márová, I.
Preparation and Stability of Liposome Particles with Encapsulated Natural UV Filters ... 35
Benesova, P., Obruca, S., Milerova, M., Marova, I.
Bioremediation of Organic Pollutants by Cupriavidus Necator ............................................ 36
Matoušková, P., Sosková, S., Krempaský, K., Vajglová, K., Márová, I.
Development of Organic Micro‐ and Nanoparticles as Delivery Systems for Antimicrobial
Agents ............................................................................................................................................. 37
Hlavacek, V., Petrik, S., Haronikova, A., Vymolova, M., Marova, I.
Utilization of Agricultural Waste Materials .............................................................................. 37
Obruca, S., Kucera, D., Dingova, T., Benesova, P., Porizka, J., Marova, I.
Biotechnological Production of Polyhydroxyalkanoates on Various Lignocellulose‐Based
Agricultural Wastes ...................................................................................................................... 38
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Obruca, S., Sedlacek, P., Mravec, F., Samek, O., Krzyzanek V., Kucera D., Benesova P., Doskocil, L.,
Marova, I.3
Polyhydroxyalkanoates in Bacterial Cells – More Than Just Storage Materials .................. 39
Obruča, S., Innemanová P.
Utilization of Petroleum Hydrocarbon Residua for Production of Polyhydroxyalkanoates
.......................................................................................................................................................... 41
Reichstädter, M., Valicová, M., Omelková, J.
Influence of Carrier Area on Properties of Immobilized Cellulase Complex ....................... 42
Sasková, D., Pořízka, J., Španová, A., Diviš, P., Kulich, P., Rittich, B.
Silver Nanoparticles Production with Probiotic Bacteria ........................................................ 42
Koudelka, S., Turanek Knotigova, P., Masek, J., Lukac, R., Prochazka, L., Neuzil, J., Miller, A. D.,
Turanek, J.
Liposomal Formulations of Hydrophobic Anticancer Drugs: Paclitaxel and Vitamin E
Analogues as Examples ................................................................................................................ 43
Čertík M., Klempová T., Slaný O.
Fungal Solid‐State Fermentation as a Useful Tool for Preparation of Functional Cereal‐
Derived Biomaterials .................................................................................................................... 44
Breierova E., Čertik M., Márova I.
The Influence Free Radicals on The Uptake of Copper (II) Ions by Exopolymers and the
Fibrillar Part Oof Cell Wall of The Red Yeast ............................................................................ 45
Kovar, K., Barmettler, M, Stadler, M., Zamora, I., and Neutsch, L.
Strategies for Optimum Production of High‐Value Products Using Microalgae ................ 46
Perútková, K., Steinová, J., Novotná, Z., Červený, J., Trtílek, M.
Growth Dynamics Characterization of Setlicola Philippina Gen. et Spec. Nov.
(Trebouxiophyceae, Chlorophyta), Performed in Two Types of Photobioreactors ............. 47
O. Samek, A. Haroniková, K. Hrubanová, I. Márová, S. Bernatová, P. Zemánek, V. Krzyžánek
Yeast Biomass Analysis for Application in Biotechnology Based on Raman and SEM
Spectroscopy .................................................................................................................................. 48
Mašek, J., Turánek Knotigová, P., Lukáč R., Křupka M., Bartheldyová E., Koudelka Š., Miller, A. D.,
Kratochvílová I., Ledvina, M., Raška, M., and Turánek, J.
Liposomal Vaccine Delivery Systems......................................................................................... 49
Environmental Chemistry and Technology .................................................................... 51
Hribova, S., Vavrova, M., Zlamalova Gargosova, H.
Are Terrestrial Organisms Able to Live in Contaminated Soil after Fire‐Fighting? ............ 51
Chytil, V., Vavrova, M.
Flame Retardants and their Occurrence in the Terrestrial Ecosystem ................................... 52
Kosárová, H., Holubová, Z., Řeháková, J., Čáslavský, J., Řehůřková, I., Ruprich, J.
Microwave Digestion Method of Biotic Samples for Elemental Analysis ............................ 53
Bukackova, M., Vitkova, L., Vavrova, M., Caslavsky, J., Rehurkova, I., Ruprich J.
Optimization of Gas Chromatography Tandem Mass Spectrometry Method for the
Determination of Bisphenols in Selected Food Samples .......................................................... 54
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Kavrik, R., Nevrla, J., Caslavsky, J., Rehurkova, I., Ruprich, J.
Monitoring of Chlorate and Perchlorate in Czech Food Basket ............................................. 55
Vitkova, L., Bukackova, M., Caslavsky, J., Rehurkova, I., Ruprich, J.
Evaluation of Occurrence of Selected Groups of Fatty Acids in Fish and Fish Products ... 57
Smutna, M., Caslavsky, J
Determination of Sildenafil, Vardenafil and Tadalafil in Wastewater by HPLC/MS .......... 58
Lastuvkova,M., Turkeova,I., Smilek,J., Sedlacek, P., Kratochvilova, R., Schmiedova, V., Klucakova, M.
Morphology of Plant Cuticles as The Limiting Barrier for the Uptake of Fertilizers .......... 59
Smilek, J., Kalina, M., Lastuvkova, M., Turkeova, I., Sedlacek, P., Klucakova, M.
Reactivity‐Mapping Tool Based on Diffusion Techniques for Characterization of
Biocolloids ...................................................................................................................................... 60
Turkeova, I., Enev, V., Klucakova, M., Krouska, J., Lastuvkova, M.
Thermodynamics of Metal Ion Interaction with Humic Acids ............................................... 60
Enev, V., Turkeova, I., Szewieczkova, J., Doskocil, L., Klucakova, M.
Fluorescence Analysis of Cu (II), Pb (II) and Hg (II) Ion Binding to Humic and Fulvic
Acids ................................................................................................................................................ 61
Vitkova, L., Bukackova, M., Caslavsky, J., Rehurkova, I., Ruprich, J.
Optimization of Method for the Determination of Fatty Acids with Regard to Their Trans
and Cis Isomers ............................................................................................................................. 62
Olejnickova, Z., Dzik, P., Vavrova, M., Vesely, M.
Degradation of Estriol by Photocatalysis ................................................................................... 63
Kratochvílová, R., Klučáková, M., Laštůvková, M., Kalina, M.
Superabsorbent Polymers and Their Effect on Soil Water Retention .................................... 64
Iman Nazari, Behrouz Shaabani, Amir Zarei
Removal of Heavy Metals from Aqueous Solutions by Low‐Cost Bio Materials ................ 65
Iman Nazari, Pegah Abbasifar, Nasim Pouya
Determination of Heavy Metals and Nitrate in Drinking Water of Capital City of Iran and
its Side Effects in Public Health ................................................................................................... 66
Komendova, R., Hajdova, J.
Lichen Hypogymnia Physodes – Bioindicator Tested for the Determination of Palladium
in Urban Air in Brno, Czech Republic ........................................................................................ 68
Hábová, M., Pospíšilová L.69
UV‐VIS Spectral Characteristics of Humic Substances in Chernozems ................................ 69
Řezáčová, V., Osinová, P.
Study of the Effect of Interferents on Spectrophotometric Determination of Anionic
Surfactants ...................................................................................................................................... 70
Johanna Rajasärkkä, Jonáš Lašňák, Luděk Bláha
Effects of Organic Lining Materials and Plastic Pipes to the Chemical Content of Drinking
Water ............................................................................................................................................... 71
Staněk, T., Sulovský, P.
Testing of Special Binders for Immobilization of Toxic Elements .......................................... 72
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Diana Yudin, Anton Yudin, Andreea Iordache, Claudia Sandru, Sonia Suvar, Monica Culea
Development and Validation of Spectrophotometric Method for Determination of
Biochemical Oxygen Demand in Wastewater ........................................................................... 73
Mikula, P., Minarikova M., Sovadinova, I., Nadres, E., Takahashi, H., Kuroda, K., Babica, P.
Activity of Biomimetic Antimicrobial Polymers Against Cyanobacteria and Green Algae74
Melymuk, L., Bohlin Nizzetto, P., Vojta, S., Klanova, J.
Organic Contaminants in the Indoor Environment: Linking Sources and Human Exposure
.......................................................................................................................................................... 75
Mihaela Vladu
Environmental Radioactivity at Tritium Removal Facility‐ ICIT ........................................... 76
Voica, C., Iordache, A. M., Suvar, S., Culea, M., Ionete, R. E.
Study on Metal Contamination in Water, Sediments and Soils Samples from N‐W
Romania, using ICP‐MS ............................................................................................................... 77
Repková M., Šípková, H.
Comparison of Separation Efficiency at Different Levels of Technological Line For
Drinking Water Treatment at Švařec .......................................................................................... 78
Tobková, L., Švestková, T., Vávrová, M.
Contamination of Environment by Musk Compounds ........................................................... 79
Vávrová, M., Dvořáková, P., Sýkora, R., Clemensová, G., Lisá, H., Olejníčková, Z.
Problems of Contamination of Wastewater Drugs ................................................................... 80
Hájek, R., Chytil, V., Vávrová, M., Lisý, M.
Occurence of Organic Compounds in Tar Produced from Biomass Combustion and
Gasification ..................................................................................................................................... 82
Čáslavský, J., Vávrová. M., Remerová, M., Jurasová, L.
Hormones in Drinking and Waste Water .................................................................................. 83
Zlámalová Gargošová, H., Milatová, M., Kučera, F.
Ecotoxicological Evaluation of Polymeric Substances ............................................................. 84
Darina Lankova, Katerina Urbancova, Jana Pulkrabova and Jana Hajslova
A Novel Strategy for The Determination of Polycyclic Aromatic Hydrocarbons (PAHs)
Metabolites in Urine ...................................................................................................................... 85
Pulkrabová J., Lanková D., Urbancová K., Švarcová A., Stupák M., Hajšlová J.
Assessment of Body Burden of Czech Population to Polycyclic Aromatic Hydrocarbons 86
Hofman, J., Šimek, Z., Bielská, L., Hvězdová, M., Sáňka, M., Scherr, K., Šmídová, K., Škulcová, L.,
Šudoma, M., Svobodová, M., Vašíčková, J.
Can Currently Used and Emerging Pesticides in Agriculturally Used Fluvisols be Risky
for Human and Ecosystem Health? ............................................................................................ 87
Tomášková, M., Chýlková, J.
The Possibilities of Voltammetric Determination of Different Antioxidants in Biodiesel .. 89
Chýlková, J., Tomášková, M., Šelešovská, R.
The Determination of Moluscocide Methiocarb using DPV – the Possibility of Monitoring
for The Supress of Zooplankton Growth ................................................................................... 90
18
Janíková, L., Šelešovská, R., Štěpánková, M., Chýlková, J.
Sensitive Determination of Anti‐Inflammatory Drug Sulfasalazine using Green
Electrochemical Sensor Based on Silver Solid Amalgam ........................................................ 91
Pryszcz, A.
Preparation of Sorbents from Tar Deposits. .............................................................................. 92
Hajslova, J., Pulkrabova, J., Lankova D.
Sources and Transfer of Emerging Halogenated Contaminants Across the Food Chain ... 93
Food Chemistry ..................................................................................................................... 95
Vítová, E., Sůkalová, K., Mahdalová, M., Butorová, L., Musilová, L., Pecinová, E95
Comparison of Sensory Quality of Model Swiss Cheese with Commercially Obtained
Corresponding Product ................................................................................................................ 95
Butorová, L., Polovka, M., Tobolková, B., Vítová, E.
Assessment of Antioxidant Properties of Different Types of Herbs by EPR and UV‐VIS
Spectroscopy .................................................................................................................................. 96
Mahdalová, M., Vítová, E., Ryglová, H., Sůkalová, K., Buňka, F.
The Development of Volatile Flavour Compounds During Ripening of Gouda Cheese ... 97
Fričová, M., Čuta, R., Křížová, J., Španová, A., Rittich, B.
Simply Method of DNA Isolation from Lactic Acid Bacteria ................................................. 98
Konecna, J., Spanova, A., Horák, D., Rittich, B.
Solid ‐ Phase DNA Extraction Using Various Types of Magnetic Microparticles ............... 99
Sůkalová, K., Vítová, E., Buňka, F., Mahdalová, M.
Influence of Vegetable Oils on Fatty Acids Composition in Processed Cheese Analogues
........................................................................................................................................................ 100
Olšovcová, Z., Vespalcová, M., Diviš, P., Matějíčková, J., Kaplan, J., Matějíček, A.
Small Berries as an Important Source of Antioxidants .......................................................... 101
Mikulíková, R., Svoboda, Z., Benešová, K., Běláková, S.
Determination of Content of Hordein Peptides in Beer ........................................................ 102
Vašíček, R, Vaňásek, J, Konečná, J, Trachtová, Š, Španová, A, Rittich, B.
Detection of Lactobacillus Acidophilus Species in the Probiotic Meat Product ................ 103
Divis, P., Christovova, S., Porizka, J., Vespalcova, M., Matejicek, A.
Determination of Total Polyphenol Content and Total Antioxidant Activity of Different
Currant and Gooseberry Cultivars Grown in the Czech Republic ...................................... 103
Svoboda, Z., Mikulíková, R., Benešová, K., Běláková, S.
Determination of Trans‐2‐nonenal in Barley Varieties Recommedned for Production of
Czech Beer .................................................................................................................................... 104
Diana Yudin, Anton Yudin, Irina Geana, Gili Saros, Iuliana Piciorea, Monica Culea
Uncertainty Characterization Procedure for Drinking Water Laboratory Analysis ......... 105
Buňka, F., Černíková, M., Pachlová, V., Salek, R. N., Stašková, I.
The Effect of Heat Treatment, Temperature of Coagulation, Calcium Chloride and
Enzyme Concentration on The Rennet Coagulation of Cow Milk ....................................... 106
19
Iordache, A. M., Voica, C., Suvar, N. S., Culea, M., Ionete, R. E.
Determination of the Metal Content in Seafood and Fish Species From the Romanian
Market ........................................................................................................................................... 107
Matoušková, P., Pražáková, J., Márová, I.
Determination of Nicotine in Different Types of Products ................................................... 108
Niculina‐Sonia Suvar, Andreea Maria Iordache, Cezara Voica, Roxana Elena Ionete, Ramona
Bleiziffer, Monica Culea
Comparison of Nutrients Composition of Some Vegetable Oils .......................................... 109
Polovka, M., Tobolková, B., Belajová, E., Durec, J.
On the Qualitative Parameters of Fruit Juices and Possibilities of their Modification via
Technological Modifications ...................................................................................................... 110
Tatiana Klempova, Janka Janstova, Sona Gavurnikova, Michaela Havrlentova, Milan Certik
Applications of New Types of Biomaterials Obtained by Fungal Solid‐State Fermentation
In Bakery Products Manufacturing .......................................................................................... 111
Krmela, A., Schulzová, V., Hajšlová, J.
Rose Hips – The Sources of Galactolipids for The Production of Food Supplements ...... 112
Hůrková, K., Rubert, J., Hajšlová, J.
HRMS Based Metabolomic Fingerprinting for Berries and Cranberries Authentication . 113
Fenclova, M., Rimpelova, S., Zachariasova, M., Hajslova, J.
The Study of Distribution of Sesquiterpene Lactones in Model Systems of Human Prostate
Cancer Cells and Macrophages ................................................................................................. 114
Stupák M., Hajšlová J.
GC‐HRTOF: A Powerful Tool for Evaluation of Whisky Quality and Authenticity ......... 115
Hradecký J. and Hajšlová J.
Why is this Product Smelling: Application of SPME Coupled with GC‐HRMS ................ 116
Kopuncová, M., Kolek, E., Sádecká, J.
Impact Of Different Processing Atmospheres on the Volatiles of Orange Juice with Pulp
........................................................................................................................................................ 116
Vítová, E., Sůkalová, K., Mahdalová, M., Butorová, L., Musilová, L., Pecinová, E.
Comparison of Sensory Quality of Commercial and Home‐Made Model Swiss Cheese . 118
Drabova, L., Pulkrabova, J., Hrbek, V., Kocourek, V., Hajslova, J.
Occurence of Organic Contaminants in Food Supplements Based on Fish Oil ................. 119
Chemistry of Silicates ........................................................................................................ 120
Pavel Šiler, Iva Kolářová, Tomáš Sehnal, Roman Snop, Tomáš Opravil, František Šoukal
The Particle Sizes Influence on The Properties of Portland Cement Pastes ........................ 121
Bednárek, J., Novotný, R., Šoukal, F., Tvrdík, L.
The Preparation of Heat Insulating Moulded Refractories ................................................... 122
Hajdúchová, M., Langová, M., Enev, V., Kalina, L. ........................................................................... 122
Possibilities of Using Plasticizers and Superplasticizers in Alkali‐Activated Systems ..... 122
20
Parizek, L., Bilek Jr., V., Brezina, M.
Chloride Resistance of Alkali Activated Slag Pastes With Fly Ash Replacement ............. 123
Bilek Jr., V., Parizek, L., Kosar P., Kratochvil, J., Kalina, L.
Strength and Porosity of Alkali Activated Materials ............................................................. 124
Jiří Kratochvíl, Hana Kalousová, Tomáš Opravil
Optimization of Alternative Aggregates Based on Fluid Combustion Fly Ashes ............. 124
Jan Koplík, Miroslava Smolková, Jakub Tkacz
The Leachability of Heavy Metals from Alkali‐Activated Fly Ash and Blast Furnace Slag
Matrices ......................................................................................................................................... 125
Kalina, L., Bílek, V., Komosná, K., Novotný, R., Tkacz, J.
Effect of Phosphates on the Hydration Process of Alkali Activated Materials .................. 126
Masilko, J., Soukal, F., Zurova, M., Havlica, J.
Mechanisms of Macro‐Pores Origin in The MDF Composites Fabrication ........................ 126
Martin Boháč, Radoslav Novotný, Miroslava Hajdúchová, Jakub Tkacz, František Šoukal, Tomáš
Opravil, Martin Palou
The Role of Temperature on Binary System of Metakaolin/Portland Cement ................... 127
Zezulova, A., Stanek, T., Opravil, O.
The Influence of Barium Compounds on the Formation of Portland Cement Clinker ..... 128
Galvánková, L., Opravil, T.
Possibilities of Using Energy by‐Products as Raw Materials for Hydrothermal Reaction129
Masarova, A.
Synthetic Preparation of Thaumasite ....................................................................................... 130
Koutný, O., Opravil, T.
The Basics of Low Volume Weight Aerated Autoclaved Concrete Preparation ................ 130
Baraček, J., Palou, M., Másilko, J., Wasserbauer, J., Šoukal, F., Boháč, M.
Application of Sol‐Gel Method to Investigate the Influence of P2o5 on the Course of
Reactions in CaO‐SiO2 system ................................................................................................... 131
Organic Electronics ............................................................................................................ 133
Florian, P., Pospisil, J., Zmeskal, O.
Simple Method for Determination of Type Charge Carriers in Semiconductors .............. 133
Schmiedova V., Pospisil J., Zmeskal O., Vretenar V.
Optical Characterization of Graphene Oxide Films by Spectroscopic Ellipsometry ......... 134
Honova, J., Kovalenko, A., Vala, M., Weiter, M.
Diketopyrrolopyrrole Based Donors for Bulk Heterojunction Organic Solar Cells .......... 135
Altsmid, J., Kubersky, P., Navratil, J., Nespurek, S., Hamacek, A., Zmeskal, O.
New Ionic Liquid Based Electrolytes for Application in Electrochemical Sensors ............ 136
21
Jan Koutný, Martin Vala, Stanislav Luňák, Karel Pauk, Zdeněk Eliáš, Aleš Imramovský, Martin
Weiter
Materials with High Fluorescence in Solid State: The Influence of Chemical Structure on
Optical Properties ........................................................................................................................ 137
Hrabal, M., Omasta, L., Vala, M., Weiter, M.
Optimization of Screen Printing Process for Printed Electronic Devices ............................ 138
Stanislav Stritesky, Martin Weiter, Martin Vala, Petra Horáková, Lenka Dokládalová, Luboš Kubáč
New Diketopyrrolopyrrole Derivatives in OFET Transistors .............................................. 139
Omasta, L., Salyk, O., Hrabal, M., Weiter, M.
Preparation and optimization of printed layers for biosensing ........................................... 140
Sionová, M., Vala, M., Černý, J., Kubáč, L., Krajčovič, J., Weiter, M.
Characterization of Novel Small Molecules for Organic Electronics and Photonics ......... 141
Kubáč, L., Akrman, J., Josefík, F., Dvorský, D., Martinková, L., Marek, J.
Functionalization of Textile Materials by Conductive Polymers for Smart Textile
Applications ................................................................................................................................. 141
Krajčovič, J.
Molecular Tuning Powerful Tool at Synthesis of Smart Molecules for Organic Electronics
........................................................................................................................................................ 143
Michal Hatala, Pavol Gemeiner, Milan Mikula
Hybrid Organic‐Inorganic Perovskite Solar Cells with Printed Photo‐Anode .................. 144
Bondarev, D. Gladyš, S. Polášková, M. Huťťa M.
Fully Conjugated Alcohol ‐ and Water Soluble Metallo‐Supramolecular Polymers ......... 145
Trhlíková, O., Gladyš, S. Sedláček, J. Bondarev, D.
SEC‐DAD – Application of the Method for the Characterization of ‐conjugated polymers
........................................................................................................................................................ 146
Salyk, O., Omasta, L., Vala, M. and Weiter, M.
Printed Organic Sensor for Cardiomyocytes Research .......................................................... 147
T. Syrový, P. Kuberský, J. Řeboun, L. Syrová, A. Hamáček, J. Stejskal, S. Nešpůrek
Sensors Fabrication Using Screen Printing Technique .......................................................... 148
Vala Martin, Weiter Martin, Krajčovič Jozef, Stanislav Luňák, Jan Vyňuchal, Luboš Kubáč
Diketo‐Pyrrolo‐Pyrrole: A Versatile Chromophore for Organic Electronics and Photonics
........................................................................................................................................................ 149
Photochemistry and Photocatalysis ................................................................................ 150
Salomatova, V., Pozdnyakov, I., Sherin, P., Grivin, V., Bazhin, N., Plyusnin, V.
Aqueous Photochemistry of Bisphenols: Mechanistic Aspects ............................................ 151
Pospíšek, M., Kučera, F.
Preparation of Covalently Bonded Polyacrylic Layers onto the Polypropylene Surface . 152
Oravec, M., Gál, L., Čeppan, M.
Principal Component Analysis of NIR Spectral Data used as Forensic Method for Inkjet
Printed Document ....................................................................................................................... 153
22
Makunina, M., Pozdnyakov, I., Grivin, V., Plyusnin, V.
Direct And Fulvic Acid Assisted Photolysis Of Drug Propranolol In Aqueous Solution: the
nanosecond laser flash photolysis study ................................................................................. 154
Alexander Kovalenko, Petr Ashcheulov, Patricie Heinrichová, Ladislav Fekete, Martin Vala, Martin
Weiter, Germà Garcia Belmonte and Irena Kratochvílová
Boron‐Doped Polycrystalline Diamond layers For Organic Photovoltaic Devices ........... 156
Belovičová, M., Čeppan, M., Baráthová, A.
Spectral Analysis of Laser Prints for Forensic Investigation ................................................. 157
Michal Veselý, Petr Dzik, Mária Veselá, Ivana Uhrová, Oldřich Zmeškal
Printed UV Dosimeter ................................................................................................................ 158
Dzik, P., Veselý, M., Bednárková, J., Uhrová I.
Automated Monitoring of Self‐Cleaning Glass Photocatalytic Activity ............................. 158
Huo, P., Matějová, L., Šihor, M., Reli, M., Obalová, L., Kočí, K.
CO2 Photocatalytic Reduction in Gas Phase over Photocatalyst Based on the TiO2 .......... 159
Baudys, M., Krýsa, J.
Determination of Photocatalytic Activity of Self‐Cleaning Paints Using Smart Inks ........ 160
Paušová Š., Kment Š., Krýsa J.
TiO2 Nanostructures for Electrochemical Water Splitting..................................................... 161
Physical Chemistry & Life ................................................................................................ 162
Milan Mazur, Lucia Husáriková, Michal Kaliňák, Marián Valko
“Vinum Regnum – Rex Vinorum”. NMR Spectroscopy Study of the Slovak Tokaj Wines
........................................................................................................................................................ 163
Mondek, J., Mravec, P., Pekař, M. ...................................................................................................... 163
Binding of Surfactant to Polyelectrolyte in Non‐Standard Conditions ‐ Fluorescence Study
........................................................................................................................................................ 163
M.Kalina, J. Smilek, R.Kratochvílová, Š. Krňávková, M. Laštůvková, M.Klučáková
Study of Agarose Gelation Process by Unconventional Dynamic Light Scattering Method
........................................................................................................................................................ 165
Smilek, J., Kynclová, H., Sedláček, P., Prášek, J., Klučáková, M.
Characterization of Nanoporous Membranes with Controlled Permeability .................... 165
Kynclová, H., Smilek, J., Prášek, J., Sedláček, P., Klučáková, M.
Preparation and Utilization of Alumina Oxide Membranes for Sensor Devices ............... 166
Martin Chytil, Pavla Hájovská, Vasile Simulescu, and Alena Sereda
Overview of the Polysaccharide‐Protein Complexes ............................................................. 167
Hájovská, P., Chytil M.168
Protein‐Polysaccharide Gels ...................................................................................................... 168
Pavel Osmera, Pavel Werner, Pavel Osmera Jr.
From Atom of Hydrogen to Molecule of Water ..................................................................... 169
Klucakova M.
Thermal and Chemical Stability of Metal‐Humic Complexes .............................................. 170
23
Klucakova M., Veznikova K., Kalina M., Chytilova A.
Conformational Arrangement of Humic Particles in Aqueous Solutions .......................... 171
Klimova, E. J., Jonisova, L., Krcma, F.
Decomposition of Selected Alkaloids by Diaphragm Discharge ......................................... 171
Omelka L., Šafaříková L.
Radical Reactions of Secondary Amines in the Presence of Some H‐Abstracting Agents 172
Radkova, L., Fojtikova, P., Prikryl, R., Krcma, F.
Plasma Chemical Reduction of Model Corrosion Brass Layer Prepared in Soil ................ 173
Gece G.
Density Functional Theory Study of the Anticorrosive Properties of Two Quinoline
Chalcones ...................................................................................................................................... 174
Mańko, D., Zdziennicka, A., Jańczuk, B.
The Aggregation Properties of Triton X‐100 and Rhamnolipid Mixtures .......................... 175
Fojtikova, P., Radkova, L., Janova, D., Krcma, F.
Using of Argon‐Hydrogen Plasma as a Tool for Removing of Corrosion Layers from
Bronze Samples ............................................................................................................................ 176
Prochazka, M., Blahova, L., Horak, J., Pekarek, J., Prikryl, R., Krcma, F.
Artefact Conservation Using Thin Films Based on Parylene C and Silicone‐Acrylate Resin
........................................................................................................................................................ 177
Gerald H. Pollack
The Fourth Phase of Water: Beyond Solid, Liquid, and Vapor ............................................ 178
Polymer Composites and Nanocomposites ................................................................... 179
Bystricky, Z., Jancar, J.
Morphogenesis of Photo‐Polymerized Dimethacrylate Networks, Network Formation
Kinetics and Viscoelastic Parameters ....................................................................................... 179
Knob, A., Babik, A., Cech, V., Drzal, L. T.
Mechanical Response of Plasma Interlayers in Polymer composites .................................. 180
Kulovaná, E., Žídek, J., Jančář, J.
Role of Water in Electrically Charged Hydrogels During Deformation Molecular
Dynamics Study........................................................................................................................... 180
Postulkova, H., Vojtova, L., Jancar, J.
Natural Polysaccharide Gum Karaya as Novel Biomaterial for Medical Applications .... 181
Petrus, J., Kucera, F., Petruj, J.
Preparation of Poly (Lactic Acid) Grafted with Itaconic Anhydride via Radical Grafting in
Melt ................................................................................................................................................ 182
Švachová Veronika, Vojtová Lucy, Jurtíková Veronika, Hampl Aleš, Pavliňák David
Stable Gelatin Nanofibers Modified with Oxidized Cellulose for Soft Tissue Engineering
........................................................................................................................................................ 183
Matláková, J., Kučera, F., Jančář, J.
Radical Grafting of Maleic Anhydride onto Polypropylene via Reactive Extrusion ........ 184
24
V. Kupka, P. Benesova, S. Obruca, J. Brtnikova, L. Vojtova, I. Marova, J. Jancar
Polyurethane‐Polyhydroxybutyrate Composites: Synthesis, Biodegradation and
Morphological Evaluation ......................................................................................................... 184
Ivana Chamradová, Lucy Vojtová, Josef Jančář
Rheological Study of Core‐shell Particles in Thermosensitive Copolymer Matrix for Bone
Regeneration Utilization ............................................................................................................ 185
Zboncak, M., Ondreas, F., Jancar, J.
Force‐Assembled Fe3O4 Particle Chains in Polyurethane Matrix ......................................... 186
Lepcio, P., Jancar, J.
Rheological Behavior of Polymer Nanocomposite Suspensions .......................................... 187
Ondreas, F., Lepcio, P., Zbončák M., Jancar, J.
Thermo‐Mechanical Behavior of Polymer Glasses Probed by Nano‐Particles ................... 188
Matea T. C., Mocan T., Iancu C., Mocan L.
Bi‐Functional Silver Nanoparticle Design and Characterization for Bone Regeneration
Applications ................................................................................................................................. 189
Mocan T., Matea T. C., Orasan R., Mocan L.
Mucin‐1 Functionalized Gold Nanoparticles for Immunological Applications ................ 190
25
Advanced Ceramics
Synthesis of Layered Calcium Cobaltites Intended for Thermolectric
Applications
Svec, J., Bartonickova, E., Jebava, A., Masilko, J., Ptacek, P.
Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkynova 118,
612 00, CZECH REPUBLIC
Abstract
Layered misfit cobaltites exhibit adequate combination of electrical and thermal properties
under the high temperatures. Cobaltites are due to these properties and appropriate costs
optimal candidates for thermoelectric industrial applications [1]. Calcium cobaltites were
prepared via conventional and less conventional synthesizing methods. Wet citric and
glycine/nitrate combustion syntheses were compared with conventional solid state reaction.
Prepared powders and bulk ceramics were studied in terms of phase and chemical
composition, morphology, size of particles/agglomerates and thermoelectric properties.
Sintering behavior of synthesized powders was studied by using of heating microscope
analysis. Particle size of prepared powders was varied from nano to micro size with different
level of agglomeration. The lowest values of particle size (~ 160 nm) with low agglomeration
were obtained with citric combustion method. The influence of preparation method on the
properties of final bulk product was evaluated within this work.
Keywords
calcium cobaltites, combustion synthesis, solid state reaction, sintering, electrical
conductivity
Acknowledgements The authors gratefully acknowledge the funding provided from Materials Research Centre at
FCH BUT‐ Sustainability and Development, REG LO1211, with financial support from
National Programme for Sustainability I (Ministry of Education, Youth and Sports).
References
[1] MIN‐GYU KANG, KWANG‐HWAN CHO, JIN‐SANG KIM, SAHN NAHM, SEOK‐JIN
YOON, MIN‐GYU KANG, KWANG‐HWAN CHO, JIN‐SANG KIM, SAHN NAHM,
SEOK‐JIN YOON, Post‐calcination, a novel method to synthesize kobalt oxide‐based
thermoelectric materials, Acta Materialia 73 (2014) 251–258
26
******
TiO2 Surface Coating of Mn‐Zn Dopped Ferrites Study
Solny, T., Ptacek, P., Bartonickova, E., Masilko, Tkacz, J., Daviðsdóttir, S., Ambat, R.
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 118,
CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
This study deals with TiO2 coating of powder Mn‐Zn ferrite in order to recieve photocatalytic
layer on the top of these particles, forming core‐shell catalyst. Powder catalysts are of great
advance over the world due to the high surface area, considering the kinetics proceeds
through heterogenous phase boundary catalysis. However their withdrawal from cleaning
systems often requires energetically and economically demanding processes such as
filtration and ultrafiltration. Since the ferrite is magnetic, the advantage of such formed core‐
shell photocatalyst is easibility of removing from photocatalytic decomposition system using
external magnetic field. In this study the surface coating is performed, using Ti alkoxides
mixtures with nanosized TiO2 particles and C and Au coating to form film layer of TiO2 on
the surface. SEM, XRD and EDS analysis are employed to study surface coating.
Keywords TiO2, surface coating, ferrites, core‐shell catalyst, TiO2 alkoxides,
Acknowledgements
This work was supported by project Nr. LO1211, Materials Research Centre at FCH BUT‐
Sustainability and Development (National Programme for Sustainability I, Ministry of
Education, Youth and Sports).
******
Possible Use of Terrestrial Gastropod (Helix Aspersa Aspersa) and It’s Life
Stages as a Tool for Environmental Risk Assessement
Fojt, P., Zlámalová, H., DeVaufleury, A.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Using different organisms for prediction of negative effects of pollutants is one of the crucial
concerns in the environmental research. The main aim of this work is to establish a
laboratory breeding of the named organism Helix aspersa aspersa and to describe its
possibilities for ekotoxicity assessement. Among other species, which are commonly used for
such a purpose (earthworms, springtails, etc.), land snails are still newly and not frequently
used group of organisms, however, they seems to be a very useful as a sentinel organisms.
There are few examples from many of them why to work with them in ecotoxicological and
environmental field of study: very easy breeding under laboratory conditions, their short life
cycle, their space‐saving, cost‐effectiveness, their well‐known biology and ecology. Moreover
they are important part of the soil ecosystem and food chain. There are two exposure routes
27
we can use for an ecotoxicological experiments – oral or dermal. In the first case, the control
substance is mixed with a snail food (usually in powder form). Secondly, there could be an
artificial soil, mixed with different substances in a dry state, or it can be impregnated by a
control solution. Also a real soil or sediment, contaminated by different pollutants from the
environment, could be used. One of the advantages of this organism is the possibility to use
its different life stages (eggs, juveniles, adults). It means that we are able to observe many
effects of tested substances/matrices at different stages of development. Possible endpoints to
measure are: mortality, growth inhibition, reproduction and embryonal damage, enzymatic
activities, changes in specific organs, etc.
Keywords Gastropod, land snail, ecotoxicity, soil.
Acknowledgements
This study was supported by the grant no. FCH‐S‐15_2869 from the Ministry of Education,
Youth and Sports of theCzech Republic.
******
Development of Large Area Organic Solar Cells
Heinrichová, P., Kovalenko, A., Dzik, P., Zhivkov, I., Honová, J., Vala, M., Weiter, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract This contribution presents development of large area organic solar cells (OSC) with respect
to their main advantages: mechanical flexibility and possibility of large scale fabrication by
printing methods. One of the biggest challenges is the selection of suitable materials, which
fulfils the number of requirements on deposition of OSC by printing methods on plastic foils.
Therefore except from the choice of active materials, the attention is paid to the selection of
materials for transport layers of charge carriers, which are also the necessary components of
OSC. Nowadays the most efficient and highly stable OSC devices that exceed power
conversion efficiency of 10 %, contain metal oxide based transport layers like TiO2, ZnO,
MoOx and others [1]. However, these layers usually require preparation by the vacuum
thermal evaporation or deposition by the solgel process, during which the layers are
thermally treated at very high temperature (up to 500°C). Such conditions are not compatible
with the deposition by printing on flexible plastic foils. In this contribution, we present a
preparation of TiO2 and ZnO using low temperature methods that allow for utilization of
printing techniques. The prepared OSC devices achieved photogeneration efficiency
comparable to devices with ZnO and TiO2 prepared by traditional solgel process.
Keywords
Organic solar cells, transport layers, TiO2, ZnO, metal oxides
Acknowledgements
This work was supported by Czech Science Foundation via project No. 15‐05095S, research
infrastructures were supported by project MŠMT No. LO1211.
28
References
[1] IKERNE, E., AJURIA, J., PACIOS, R.: Solution‐processable polymeric solar cells: A
review on materials, strategies and cell architectures to overcome 10%. Organic
Electronics 19 (2015), 34‐60.
******
Immunoglobulin G Functionalized Gold Nanoparticles for Selective
Treatment of Cancer
Mocan L,, Matea T.C., Iancu C., Mocan T.
3rd Surgery Clinic, Department of Nanomedicine, “Iuliu Hatieganu” University of Medicine and
Pharmacy, Cluj‐Napoca, ROMANIA
Abstract Gold nanoparticles are easily synthetized nanostructures and present unique optical
properties. Several studies have demonstrated their potential application in bio‐imaging,
chemical sensing and drug delivery. Immunoglobulin G represents the most important type
of antibody directed against non‐self molecules. We have reasoned that binding IgG to GNP
would direct the nanoparticles towards cancerous cells, leaving the healthy cells untargeted.
Citrate stabilized gold nanoparticles were obtained by employing a modified Turkevich
method where Au3+ ions were reduced to Au0 in a aqueous solution in the presence of
citrate ions. In order to functionalize the obtained GNPs with immunoglobulin G, the protein
was first reduced with the aid of Cleland’s reagent. The obtained GNP‐IgG bio‐
nanocomposite was subjected to UV‐Vis spectroscopy in order to evaluate its stability,
dynamic light scattering for nanoparticle size measurements, ATR‐FT‐IR in order to confirm
the presence of IgG onto the GNP surface and atomic force microscopy for the determination
of nanoparticle size and shape. Also the stability of the obtained GNP‐IgG was assessed in
different biological media.
Keywords
gold nanoparticles, IgG, GNP functionalization
Acknowledgements This work was suported under the frame of European Social Found, Human Resources
Development Operational Programme, Human Resources Development Operational
Programme 2007‐2013, project no. POSDRU/159/ 1. 5/S/138776. Also, we wish to
acknowledge grant numbers PN‐II‐PT‐PCCA‐2013‐4‐1553 and PN‐II‐PT‐PCCA‐2011‐3. 1‐
1551.
29
******
Solution Calorimetry as a Tool for API Characterization
Krouská, J., Pekař, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Solution calorimetry measures the heat of solution of a material (solid, liquid) dissolving into
a solvent. Typically, there is a measurable difference in the enthalpies of solution –
dissolution of a crystalline material is an endothermic process and exothermic for an
amorphous material. Therefore it is possible to differentiate between different morphologies
of the sample – between mixtures of crystalline and amorphous material and between
mixtures and polymorphs. In addition, solution calorimetry is used not only for the detection
but also for the quantification of the composition from this point of view. This knowledge is
important, for example, for formulators of solid dosage forms for drug delivery. This work
focuses on the characterization of pharmaceuticals, especially of active pharmaceutical
ingredients (APIs). The reason for amorphous APIs production in the world is mainly their
better solubility when compared with the crystalline form. The precise amorphous phase
content in the unknown sample is determined from the method of a calibration curve when
100% amorphous and 100% crystalline material and a known mixture of thereof are
measured.
Keywords
solution calorimetry, heat of solution, amorphous, crystalline, API
Acknowledgements
This work was supported by the Centre for Materials Research at the Faculty of Chemistry,
Brno University of Technology by Project No. LO1211 from the Czech Ministry of Education,
National Program of Sustainability I.
******
An Overview of Cation Distribution and Particle Size Dependent Properties
of Ferrite Nanoparticles
Raghvendra Singh Yadav, Jaromir Havlica
Materials Research Centre, Brno University of Technology, Purkyňova 464/118, 61200 Brno,
CZECH REPUBLIC.
Abstract Now‐a‐days, magnetic nanoparticles are the focus of much research and development due to
its applications in magnetic resonance imaging (MRI) enhancement, magnetically guided
drug delivery, magnetic recording media, magnetic fluids for the storage and retrieval of
information, catalysis, sensors, etc [1]. In particular, spinel ferrite nanoparticles have been an
important subject of research as they exhibit unique properties, different from those of bulk
materials [2]. An extensive amount of research has been focused on learning how changes in
30
grain size, cation distribution, and surface properties affect the magnetic properties of a
ferrite magnetic nanoparticles [3‐4]. Magnetic properties can also be promisingly modified
for ferrites by doping the rare earth elements. Rare‐earth ions enter into the ‘B’ sites of ferrite
and by displacing a proportionate number of Fe3+ from ‘B’ to ‘A’ sites, leads to change in
magnetic properties [5‐7].
Recently, our research group has focused to investigate the change in magnetic properties
with a change in particle size and cation distribution in cobalt ferrite, zinc ferrite and nickel
ferrite nanoparticles[1‐4]. The change in cation redistribution with change of particle size was
studied by X‐ray photoelectron spectroscopy. X‐ray photoelectron spectroscopy revealed the
presence of Co2+ and Fe3+ at octahedral and tetrahedral sites in CoFe2O4 nanoparticles. From
the XPS data, the occupation formula for the CoFe2O4 nanoparticles annealed at 500 oC
sample and for CoFe2O4 nanoparticles annealed at 900 oC sample was 〖(〖Co〗_0.24^(+2)
〖Fe〗_0.48^(+3))[ 〖Co〗_0.76^(+2) 〖Fe〗_1.52^(+3)]O4 and (〖Co〗_0.36^(+2) 〖Fe〗
_0.66^(+3))[ 〖Co〗_0.64^(+2) 〖Fe〗_1.34^(+3)]O4, respectively[4]. Where brackets () and [ ]
denote tetrahedral and octahedral sites respectively. The highest value of coercivity 1091. 2
Oe and saturation magnetization 54. 76 erg/g were obtained for CoFe2O4 nanoparticles
annealed at temperature 900 oC and 1100 oC, respectively. Further, the change in Raman
modes and infrared absorption bands were also noticed with change of particle size for
NiFe2O4 and ZnFe2O4 nanoparticles. The X‐ray photoelectron spectroscopy of NiFe2O4
nanoparticles revealed the presence of Ni2+ and Fe3+ at octahedral and tetrahedral sites. The
representative sample NiFe2O4 nanoparticles annealed at 400 oC, have mixed cation
distribution (〖Ni〗_0.23^(+2) 〖Fe〗_0.52^(+3))[ 〖Ni〗_0.77^(+2) 〖Fe〗_1.48^(+3)]O4. The
highest value of coercivity 62. 35 Oe and saturation magnetization 34. 10 erg/g for NiFe2O4
nanoparticles were obtained at annealing temperature 600 oC and 1000 oC, respectively. The
significant role played by Nd3+, Pr3+, Dy3+ and Gd3+ ions added to cobalt ferrite to change
cation distribution and further to influence structural and magnetic properties, was studied
[5‐7]. The change in Raman modes in synthesized ferrite system were observed with rare‐
earth ion substitution, particle size and cation redistribution. The impact of rare‐earth ion on
cation distribution of Co2+ and Fe3+ at octahedral and tetrahedral sites in spinel ferrite cobalt
ferrite nanoparticles was investigated by X‐ray Photoelectron Spectroscopy. Room
temperature magnetization measurements showed that the saturation magnetization and
coercivity increases with addition of rare‐earth ion substitution in cobalt ferrite. To further
reduce the particle size, ferrite nanoparticles were ball‐milled. The change in Raman modes
and relative intensity were observed due to ball milling and consequently decrease of
particle size and cationic redistribution. The high strain in the lattice initiated by ball milling
has influenced the lattice to shrink. This lattice shrinkage also plugs to cation redistribution
between tetrahedral and octahedral sites in spinel ferrite nanoparticles, and it was noticed
through XPS study of sol‐gel and ball milled ferrite nanoparticles. The quantitative analysis
shows higher degree of inversion for CoZnFe2O4 Ball‐Mill sample. From the XPS data,
occupation formula for the CoZnFe2O4 Sol‐Gel sample and CoZnFe2O4 Ball‐Mill sample was (
〖Co〗_0.195^(+2) 〖Zn〗_0.255^(+2) 〖Fe〗_0.550^(+3))[ 〖Co〗_0.305^(+2) 〖Zn〗
_0.245^(+2) 〖Fe〗_1.450^(+3)] and (〖Co〗_0.195^(+2) 〖Zn〗_0.23^(+2) 〖Fe〗_0.575^(+3))[
〖Co〗_0.305^(+2) 〖Zn〗_0.27^(+2) 〖Fe〗_1.425^(+3)], respectively. Where brackets () and
[ ] denote tetrahedral and octahedral sites respectively. Furthermore, the pellet form of Co1‐
xZnxFe2O4 (x=0. 0 and 0. 5) ferrite nanoparticles were achieved by hot‐press sintering at high
temperature to study its mechanical, elastic and magnetic properties. It is well known that
31
the ferrites are very strong and cannot be deformed under normal conditions, however, their
strength‐to‐weight ratio is not outstanding and therefore, results often being brittle.
Therefore, study of mechanical and elastic properties of spinel ferrite nanoparticles in pellet
form after hot‐press sintering at high temperature, has great importance for their application
in industry.
Keywords
Spinel Ferrite, Nanoparticles, Cation Distribution, Magnetic properties
Acknowledgements
This work was supported by Project Excellent Teams ‐ CZ. 1. 07/2. 3. 00/30. 0005 at The
Materials Research Centre, Brno University of Technology and project Centre of Polymer
Systems (Reg. Number: CZ. 1. 05/2. 1. 00/03. 0111) at Tomas Bata University in Zlín, Czech
Republic. Authors also acknowledge the support obtained from Institute of Inorganic
Chemistry and Institute of Measurement Science at Slovak Academy of Sciences, Dúbravská
cesta 9, SK‐845 36 Bratislava, Slovak Republic.
References [1] R. S. YADAV, J. HAVLICA, M. HNATKO, P. ŠAJGALÍK, A. CIGÁŇ, M. PALOU, E.
BARTONÍČKOVÁ, M. BOHÁČ, F. FRAJKOROVÁ, J. MÁSILKO, M. ZMRZLÝ, L.
KALINA, M. HAJDÚCHOVÁ, V. ENEV, Magnetic properties of Co1‐xZnxFe2O4 spinel
ferrite nanoparticles synthesized by starch‐assisted sol–gel auto‐ combustion method
and its ball milling. J. Magnetism Magn. Mat., 2014, vol. 2015, no. 378, p. 190‐199. ISSN:
0304‐ 8853.
[2] R. S. YADAV, J. HAVLICA, P. PTÁČEK, I. KUŘITKA, Z. KOŽÁKOVÁ, M. PALOU, E.
BARTONÍČKOVÁ, M. BOHÁČ, F. FRAJKOROVÁ, J. MÁSILKO, M. ZMRZLÝ, M.
HAJDÚCHOVÁ, V. ENEV, Structural and Magnetic Properties of CoFe2O4
Nanoparticles Synthesized by Starch‐Assisted Sol‐Gel Auto‐Combustion Method in Air,
Argon, Nitrogen and Vacuum Atmospheres. Journal of Superconductivity and Novel
Magnetism, 2014, vol. 2015, no. 28, p. 249‐258. ISSN: 1557‐ 1947.
[3] R. S. YADAV, J. HAVLICA, I. KUŘITKA, Z. KOŽÁKOVÁ, M. PALOU, E.
BARTONÍČKOVÁ, M. BOHÁČ, F. FRAJKOROVÁ, J. MÁSILKO, M. HAJDÚCHOVÁ, V.
ENEV, J. WASSERBAUER, Magnetic Properties of ZnFe2O4 Nanoparticles Synthesized
by Starch‐Assisted Sol‐Gel Auto‐ combustion Method. Journal of Superconductivity and
Novel Magnetism, 2014, vol. 2015, no. 28, p. 1417‐1423. ISSN: 1557‐ 1947.
[4] R. S. YADAV, J. HAVLICA, J. MÁSILKO, L. KALINA, M. HAJDÚCHOVÁ, V. ENEV, J.
WASSERBAUER, I. KUŘITKA, Z. KOŽÁKOVÁ, Structural, Cation Distribution, and
Magnetic Properties of CoFe2O4 Spinel Ferrite Nanoparticles Synthesized, Using a
Starch‐Assisted Sol–Gel Auto‐ Combustion Method. Journal of Superconductivity and
Novel Magnetism, 2015, vol. 2015, ISSN: 1557‐ 1947.
[5] R. S. YADAV, J. HAVLICA, I. KUŘITKA, Z. KOŽÁKOVÁ, J. MÁSILKO, M.
HAJDÚCHOVÁ, V. ENEV, J. WASSERBAUER, Effect of Pr3+ Substitution on Structural
and Magnetic Properties of CoFe2O4 Spinel Ferrite Nanoparticles. Journal of
Superconductivity and Novel Magnetism, 2014, vol. 2015, no. 28, p. 241‐248. ISSN: 1557‐
1947.
[6] R. S. YADAV, J. HAVLICA, I. KUŘITKA, Z. KOŽÁKOVÁ, E. BARTONÍČKOVÁ, J.
MÁSILKO, L. KALINA, J. WASSERBAUER, M. HAJDÚCHOVÁ, V. ENEV, Structural
32
and Magnetic Properties of CoFe2‐xGdxO4 (0. 0<=x>=0. 1) Spinel Ferrite Nanoparticles
synthesized by Starch‐Assisted Sol‐Gel Auto‐ combustion Method. Journal of
Superconductivity and Novel Magnetism, 2015, vol. 2015, ISSN: 1557‐ 1947.
[7] R. S. YADAV, J. HAVLICA, I. KUŘITKA, Z. KOŽÁKOVÁ, M. PALOU, E.
BARTONÍČKOVÁ, M. BOHÁČ, F. FRAJKOROVÁ, J. MÁSILKO, L. KALINA, M.
HAJDÚCHOVÁ, V. ENEV, J. WASSERBAUER, Magnetic Properties of Dysprosium‐
Doped Cobalt Ferrite Nanoparticles Synthesized by Starch‐Assisted Sol‐Gel Auto‐
Combustion Method. Journal of Superconductivity and Novel Magnetism, 2015, vol.
2015, ISSN: 1557‐ 1947.
33
Biotechnology
Isolation, Purification and Kinetic Behaviour Of Fishʹs Blood Serum
Cholinesterase
Tonkopii, V.
Institute of Limnology, Rus. Acad. Sci., Sevastyanova str. 9, 196105 St. Petersburg, RUSSIA
Abstract It is well known that the cholinesterase (ChE) of fish' s brain is the typical
acetylcholinesterase (AChE) with the same substrate specificity and sensitivity to
organophosphates (OP) and carbamates as AChE from human erythrocytes. On the other
hand the ChE of some fish' s blood plasma has its own specificity. Some years ago we
discovered the earlier unstudied blood plasma of fresh water fishes ‐ blue bream (Abramis
ballerus) and roach (Rutilus rutilus) contains nonordinary ChE with unusually high
sensitivity to some OP pesticides. This observation is of scientific and practical interest and
so the fish' s blood plasma ChE was purified for study of kinetic behaviour and
sensitivity to anticholinesterase compounds. After cryoprecipitation and centrifugation the
native plasma was stabilized by addition of inhibitors of protease, diluted in start buffer,
cleaned by filtration and applied on the column with Q‐sepharose at 40 – 70 °C. Proteins were elutriated from the column with NaCl‐gradient and fractionated. Enzyme in fraction
was identified as butyrylcholinesterase (BuChE) by measuring of the specific enzyme
activity. Fractions with BuChE activity were collected and concentrated by ultrafiltration.
Concentrated samples were purified on the column with phenyl‐sepharose, pooled,
concentrated again and desalted by gel filtration and then lyophilized by lyophilic drier. We
obtained a stabilized lyophilized powder with activity of 5‐10 units per mg of protein. The
kinetics of choline and thiocholine ethers hydrolysis has been studied at various
temperatures and pH levels. The new ChE has been compared with other commercial ChE
now available in Russian and another countries. The results of experiments indicate that new
ChE can be classified as a nonordinary BuChE with the peculiarities of kinetic behaviour.
New purified ChE in their sensitivity to OP pesticides in 100‐1200 times more than the
sensitivity of all types of commercial ChE. On the other hand new enzyme has an extremely
low sensitivity to carbamates, which is particularly valuable for the separate identification of
OP compounds and carbamates.
******
Lactic Acid Production from Waste Bread
Hudečková, H. Babák L.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Lactic acid is organic acid traditionally used in food and pharmaceutical industries. It has
great potential in producing the biodegradable plastics. Polylactic acid (PLA) is alternative to
traditional plastics but its large‐scale application is limited by high price of lactic acid
34
production. Optimization of fermentation and searching of cheaper raw materials may be
useful for reducing costs of production. Food waste offers interesting composition to be a
suitable fermentation feed. Mainly bakery waste offers good composition for fermentation.
Because of it we tried to use waste bread as raw material for lactic acid production.
Traditional lactic acid producers have optimal temperatures of growing and fermenting
about 30 to 40°C. It means that raw material have to be sterilized. Therefore we tried to
fermentation with thermotolerant Bacillus coagulans. Its advantage is that grows and
ferments at temperatures from 50 to 60 °C. The other benefits are simple nutrition
requirement and production of high optical pure L‐lactic acid. In experiment we used 250
mL of 15% (w/v) bread and water suspension. It was hydrolysed by successive adding of ‐amylase (BAN 240L) and glucoamylase (AMG 300L). We chose conditions applicable for
both enzymes and optimised hydrolysis. After hydrolysis followed fermentation by Bacillus
coagulans.
Keywords Lactic acid, waste bread, ‐amylase, glucoamylase, hydrolysis
References [1] MA, K., MAEDA, T., YOU, H. & SHIRAI, Y.. 2014. Open fermentative production of l‐
lactic acid with high optical purity by thermophilic Bacillus coagulans using excess
sludge as nutrient. Bioresource Technology [online], vol. 151, pp. 28‐35. Available from:
http://linkinghub. elsevier. com/retrieve/pii/S0960852413016027
******
Interaction between Cationic Micelles and Hyaluronan
Pilgrova, T., Pekar, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Micelles are particles of colloidal dimension and it is known that in an aqueous phase can
solubilize water insoluble molecules (hydrophobic biologically active substances) in their
inner core. However surfactants may have adverse effects on biological structures.
Association of micelles with suitable bioacceptable molecules (e. g. hyaluronan) may lead to
enhance their biocompatibility, decrease the nanoparticles cytotoxicity and also to target to
the specific receptors in a human body. In this study, results of the research of electrostatic
coating of cationic micelle with hyaluronan are reported. The cationic micelle/hyaluronan
complexes were studied using turbidimetry and dynamic light scattering method and were
evaluated to determine their structure, average size and zeta potential as a function of the
amount of the both component in the system. Turbidimetric titration was chosen as indicator
of the loss of intensity of transmitted light due to the scattering effect of particles associated
from hyaluronan and surfactant in it. Dynamic light scattering measurement provided
information about size distribution and zeta potential during mixing of component. Pilot
solubilization experiments were performed to evaluation of stability and solubilization
ability of the complexes. Results of turbidimetry revealed that aggregates formation
(turbidity increasing) depends especially on hyaluronan concentration while surfactant
35
concentration (above critical micelle concentration) affects interaction insignificantly.
Dynamic light scattering experiments indicate that hyaluronan molecular weight has
insignificant effect on isoelectric point of the systems. It was found that solubilization ability
of the complexes is influenced by molecular weight of hyaluronan.
Keywords
hyaluronan, micelle, nanoparticles, turbidimetry, dynamic light scattering
Acknowledgements
This work was supported by Materials Research Centre at FCH BUT‐ Sustainability and
Development, REGLO1211, with financial support from National Programme for
Sustainability I (Ministry of Education, Youth and Sports).
******
Preparation and Stability of Liposome Particles with Encapsulated Natural
UV Filters
Bokrová, J., Matoušková, P., Pavelková, R., Márová, I.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Photoprotective agents are compounds that can prevent skin damage caused by exposure to
UV light. Encapsulation enables controlled released of these photoprotective compounds
from the particles applied on the skin surface as well as protection of actives against
enviromental threats. Presented work is focused on possibilities of encapsulation natural UV
filters in liposome micro‐ and nanoparticles. Beta carotene, tocopherol, vitamin C and
catechin were packed into liposomes using several types of techniques. The efficiency of
encapsulation was evaluated by HPLC/UV‐VIS and spectrophotometrical methods. Size of
prepared particles was determined by dynamic light scattering. Stability of particles was
determind using zeta potential. Long‐term stability of particles in water and oil as well as in
model cosmetic emulsion was evaluated. Moreover, sedimentation stability of emulsion
containing liposomes was studied too. To analyse sun protection factor (SPF)
spectrophotometry was used. In this work it was found that selected natural UV filters were
packed into liposomes with high encapsulation efficiency. All of tested liposomes with
actives exhibited excellent stability. Prepared particles with encapsulated UV filters could be
used as ingredients for sunscreen products and also for daily cosmetics.
Keywords
liposom, UV filter, encapsulation
Acknowledgements
This work was supported by project „Materials Research Centre – Sustainability and
Development“ No. LO1211 (Ministry of Education, Youth and Sport of the Czech Republic).
36
******
Bioremediation of Organic Pollutants by Cupriavidus Necator
Benesova, P., Obruca, S., Milerova, M., Marova, I.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Nitroaromatic compounds (NAC) are widely used in a range of industries and are generally
recalcitrant to biological treatment. p‐Nitrophenol, an important member of the NAC family,
is used for the manufacture of pesticides, dyestuffs, pharmaceuticals, and as a fungicide to
protect leather from fungal mould. Nitroaromatic pesticides, such as dinoseb, dinitrocresol,
parathion and methyl parathion, are used extensively in agriculture, leading to accumulation
of nitrophenols in the soil. Traditionally, contaminated sites are treated by physical or
chemical methods which are often difficult to execute, costly, and not environmentally
friendly. Bioremediation, an emerging alternative technology for restoration of contaminated
environments, includes bioaugmentation which involves the addition of exogenous micro‐
organisms to a contaminated site. The aim of this work was the study of bioremediation of p‐
nitrophenol by bacterial strains, Cupriavidus necator H16 and its mutant strain Cupriavidus
necator H16/PHB‐ 4 was used for the purpose of bioremediation. The bacteria strains were
cultivated in presence of various nitrophenol concentrations and viability of cells has been
monitored by flow cytometry, during the degradation process. The main changes in
nitrophenol spectra were detected, by analysis of absorption spectra in range of 280‐600 nm,
after 7 days cultivation of Cupriavidus necator H16. Moreover, the production of PHB by
Cupriavidus necator H16 during the bioremediation process was observed, hence it could be
concluded that bacteria strain is capable of PHB production in presence of p‐nitrophenol.
Keywords
Bioremediation, Cupriavidus necator, pollutants, PHA
Acknowledgements
This work was supported by the project “Materials Research Centre at FCH BUT ‐
Sustainability and Development” No. LO1211 of the Ministry of Education, Youth and Sports
of the Czech Republic, by the project ʺExcellent young researcher at BUTʺ No. CZ. 1. 07. /2. 3.
00/30. 0039 and by the project GP15‐206455 of Czech Science Foundation (GACR).
37
******
Development of Organic Micro‐ and Nanoparticles as Delivery Systems for
Antimicrobial Agents
Matoušková, P., Sosková, S., Krempaský, K., Vajglová, K., Márová, I.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
The pharmacological industries have produced a number of new antibiotics, but resistance to
these drugs by microorganisms has increased. The use of herbs extracts with known
antimicrobial properties can be of great significance to reduce this problem. For a long period
of time, plants have been a valuable source of natural products for maintaining human
health and the antimicrobial properties of herbs have been investigated by a number of
researchers worldwide. Presented work is focused on study possibilities of encapsulation
antimicrobial herbs and spices extract, as well as lysozyme and other antimicrobial
ingredients. Antimicrobial components were packaged into liposome and polysaccharide
particles (chitosan and alginate). The antimicrobial activity were tested against two Gram‐
positive (Bacillus subtilis, Micrococcus luteus), two Gram‐negative (Escherichia coli, Serratia
marcescens) bacteria and one fungal strains (Candida glabrata). Encapsulation efficiency was
measured spectrophotometrically and by HPLC/PDA. Particle size and distribution were
analyzed by dynamic light scattering and by microscopy. Stability of the particles was
measured using a zeta potential and all prepared particles exhibited good stability. Long‐
term stability of particles and amount of released component in model cosmetics conditions
was monitored too. Encapsulation was successful in all types of particles and liposome
showed a very good long‐term stability. Prepared particles with encapsulated antimicrobial
herbs and spices extract could be also used as antimicrobial wound gel formulation
containing antimicrobial nanoparticles with control release.
Keywords
encapsulation, liposomes, polysaccharide particles, antimicrobial activity
Acknowledgements
This work was supported by project “Materials Research Centre – Sustainability and
Development” No. LO1211 (Ministry of Education, Youth and Sport of the Czech Republic).
******
Utilization of Agricultural Waste Materials
Hlavacek, V., Petrik, S., Haronikova, A., Vymolova, M., Marova, I.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
The importance of reasonable reuse of industrial waste materials is becoming very important
nowadays. Mainly the lignocellulose residues produced by agriculture, which are still rich in
38
hydrocarbons, represent a suitable source for further usage. One of possible usages is
fermentation of those materials after optional physical, chemical or combined pretreatment.
Cheap ethanol can be then obtained by a biotechnological process. Two very abundant waste
agricultural materials were used for this aim of ethanol production. One of them is grape
pomace as a winemaking byproduct and the second one is rapeseed press cake from oil
refining industry. Both of these substrates are rich in hydrocarbons. The concentration of
cellulose is 17. 35% in rapeseed cake and 17. 2% in pomace. More over grape pomace is rich
in free reducing sugars 19. 7% while the press cake contains 31. 26% of hemicellulose which
can be converted to fermentable sugars as well as the cellulose. The hydrocarbons suitable
for fermentation can be released by hydrolysis. The hydrolysis can be carried out as either
chemical or enzymatic. The disadvantage of chemical hydrolysis is possible forming of
inhibitory substances and higher energy consumption. On the other hand it provides a
higher reducing sugars yield in a shorter time than enzymatic hydrolysis. The enzymatic
hydrolysis is more time consuming but doesn’t produce any by products and can be carried
out simultaneously with fermentation. The fermentation itself was performed by
Saccharomyces cerevisiae CCY 21‐4‐47 strain. The highest ethanol yield reached 32. 2 g/l,
detected by HPLC‐RI.
Keywords
bioethanol, rapeseed cake, grape pomace
Acknowledgements
This work was supported by “Materials Research Centre – Sustainability and Development”
project Nr. LO1212 of the Ministry of Education, Youth and Sports
References
[1] ZYL, W. H. van, CHIMPHANGO, A. F. A., HAAN, R. den, GORGENS, J. F., CHIRWA,
P. W. C., 2011. Next‐generation cellulosic ethanol technologies and their contribution to
a sustainable Africa. Interface Focus 1, 196‐211
[2] MODENBACH, A. A., NOKES, S. E., 2013. Enzymatic hydrolysis of biomass at high‐
solids loadings – A review. Biomass Bioenergy 56, 526‐544.
******
Biotechnological Production of Polyhydroxyalkanoates on Various
Lignocellulose‐Based Agricultural Wastes
Obruca, S.1, Kucera, D.2, Dingova, T.2, Benesova, P.1, 2, Porizka, J.1, 2, Marova, I.1, 2
1Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkynova 118,
612 00 Brno, CZECH REPUBLIC.
2Department of Food Chemistry and Biotechnology, Faculty of Chemistry, Brno University of
Technology, Purkynova 118, 612 00 Brno, CZECH REPUBLIC.
Abstract Polyhydroxyalkanoates (PHAs) are bacterial polyesters which are considered as
biodegradable and environmentally‐friendly alternative to petrochemical plastics. Their
main disadvantage – high production cost, can be significantly reduced by utilization of
inexpensive carbon source. Therefore, various agricultural and food industry related wastes
39
are considered as very attractive substrates for economically feasible biotechnological
production of polyhydroxyalkanoates. This work deals with identification of potential
strategies for biotechnological production of PHAs from various lignocellulose‐based waste
materials (such as apple fiber, corn stover, spent coffee grounds, spend malt grains and wine
pomace) employing Burkholderia cepacia and Burkholderia sacchari. Lignocellulose
materials were subjected to enzymatic and/or diluted acid hydrolysis prior to their
utilization as waste carbon substrates for cultivation. Composition of the hydrolysates was
analysed by HPLC‐RID/PDA (sugars, furfurals) and ion chromatography (organic acids).
The first cultivations were conducted in Erlenmeyer flasks, biomass concentration was
determined gravimetrically PHA content in cells was assayed by GC‐FID. The cultivations
on the most promising waste materials were also performed in laboratory bioreactor. Since
we discovered capability of B. cepacia to excrete lignocellulytic enzymes and utilize none‐
hydrolyzed lignocellulose materials, we also characterized its hydrolytic enzyme cocktail by
enzymatic assays and PAGE‐SDS. Apple fiber and corn stover seems to be the most
promising inexpensive carbon substrates for PHAs production among those tested in this
work. Further, the fact that B. cepacia is capable of producing lignocellulose hydrolysing
enzymes (in particular cellulase and xylanase and also protease and lipase) might reduce the
cost of up‐stream processing when using lignocellulose‐based substrates. Moreover, these
extracellular enzymes can be considered as valuable side products of the technology.
Keywords
polyhydroxyalkanoates, lignocellulose materials, extracellular enzymes
Acknowledgements
This work was supported by the project “Materials Research Centre at FCH BUT ‐
Sustainability and Development” No. LO1211 of the Ministry of Education, Youth and Sports
of the Czech Republic, by the project ʺExcellent young researcher at BUTʺ No. CZ. 1. 07. /2. 3.
00/30. 0039 and by also the project GP15‐206455 of the Czech Science Foundation (GACR).
******
Polyhydroxyalkanoates in Bacterial Cells – More Than Just Storage
Materials
Obruca, S.1, Sedlacek, P.1, Mravec, F.1, Samek, O.2, Krzyzanek V. 2, Kucera D.3, Benesova
P.1, 3, Doskocil, L.1, Marova, I.1, 3
1Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkynova 118,
612 00 Brno, CZECH REPUBLIC. 2Institute of Scientific Instruments of the ASCR, v. v. i., Academy of Sciences of the Czech Republic
Kralovopolska 147, 612 64 Brno, CZECH REPUBLIC. 3Department of Food Chemistry and Biotechnology, Faculty of Chemistry, Brno University of
Technology, Purkynova 118, 612 00 Brno, CZECH REPUBLIC.
Abstract Since polyhydroxyalkanoates (PHAs) belong among the most widespread storage materials
within bacteria genus, it can be assumed that the ability of PHAs accumulation represent
significant advantage in the natural environments. Of course, probably the most obvious is
40
the possibility to utilize PHAs when external carbon sources are depleted. Nevertheless, it is
likely that PHAs play much more complex role in the stress response. Therefore, the aim of
this work was to investigate possible influence of PHA accumulation in bacteria on physical
properties of the cells and their cytoplasm with respect to possible stress survival.
Furthermore, we also investigated role of PHA monomers in stress response towards
selected stress factors. In this study, selected properties of cytoplasm were compared in PHA
accumulating and none‐accumulating strains of Cupriavidus necator. Fluorescence
correlation spectroscopy and time‐resolved fluorescence spectroscopy were used to
determine viscosity of cytoplasm as well as PHA granules and also to map intracellular pH.
Sedimentation characteristics of cells with various PHA content were determined using
analytical centrifugation, which showed that sedimentation rate correlate with PHA mount
in cells. Potential cryo‐protective effects of PHA granules in bacterial cells were evaluated by
Differential Scanning Calorimetry. Further, we observed that PHA granules revealed utterly
different behavior than the rest of bacterial cells when investigated by Cryo‐SEM. Unlike the
rest of the cell, PHA granules were not simply fractured during freeze‐fracturing process but
rather underwent plastic deformation resulting in formation of pullout structures, which
indicates that PHA granules in bacterial cells possess highly plastic properties even at very
low temperatures (below ‐150°C). In addition, we investigated protective effect of PHA
monomers towards proteins as well as whole cells. According to our results, PHA monomers
can protect biological systems against various stress conditions such as heat, cold, freezing,
osmotic stress and also oxidation. Therefore, polyhydroxyalkanoates can be considered as
very important metabolites which are significantly involved in stress response of PHA
accumulating bacterial cells.
Keywords
polyhydroxyalkanoates, stress response, bacterial cell cytoplasm, stress condition
Acknowledgements
This work was supported by the project “Materials Research Centre at FCH BUT ‐
Sustainability and Development” No. LO1211 of the Ministry of Education, Youth and Sports
of the Czech Republic, by the project ʺExcellent young researcher at BUTʺ No. CZ. 1. 07. /2. 3.
00/30. 0039 and by also the project GP15‐206455 of the Czech Science Foundation (GACR).
41
******
Utilization of Petroleum Hydrocarbon Residua for Production of
Polyhydroxyalkanoates
Obruča, S., Innemanová P.
Material Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova 118,
Brno 612 00, CZECH REPUBLIC
Dekonta, a. s., Dřetovice 109, 273 42 Stehelčeves
Institute of Environmental Studies, Faculty of Science, Charles University in Prague, Benátská 2, 128
01, Prague 2, CZECH REPUBLIC
Abstract
Poly‐3‐hydroxybutyrate acid (PHB), the most common intracellular raw material
accumulated by many bacteria, has a number of interesting characteristics and can be used in
various ways similar to conventional synthetic plastics. In spite of many satisfactory
properties of PHB and poly‐3‐hydroxyalkanoates (PHA) in general, their commercial
applications have been limited by their high price. A possible approach to reduce the final
price of PHA is using of inexpensive carbon sources for their production, such as waste
frying oil1, waste glycerol2, sugar molasses3, etc. During a join project carried out by Brno
University of Technology and Dekonta, a. s. ten bacterial oil‐degraders were investigated for
their ability to accumulate PHB during the growth on diesel as the sole carbon source. All
tested strains are commercially used in bioremediation technologies provided by Dekonta, a.
s. Neither any detectable PHB, nor any PHA production was observed during the cultivation
on diesel. Thereafter six samples of soil originated from TPH contaminated sites were used
as inocula for cultivation in a mineral salt medium with diesel as the sole carbon source.
Nile‐red staining method 4 was used for identification of the potential PHA producers. Four
colonies were positively stained. Although all these isolates exibited the ability to utilize
diesel for growth and production of PHB, only two of them were able to produce PHB in a
satisfactory amount. The preliminary results show that the production of PHB on the
substrates of fossil origin (oil/petroleum hydrocarbon residua) could be a promising
production strategy especially in cases, where the substrates represent environmental
burdens. Then single/impact problems (e. g. lagoons) or permanent sources of
contaminations (e. g. oil traps or dissolving NAPL) can serve as the suitable carbon sources.
Keywords
polyhydroxyalkanoates, poly‐3‐hydroxybutyrate, petroleum hydrocarbon residua
Acknowledgements This work was supported by The South Moravian Innovation Centre (JIC).
References
[1] OBRUČA, S., ŠNAJDAR, O., SVOBODA, Z., MÁROVÁ, I. : World J Microbiol Biotechnol
(2013) 29:2417‐2428
[2] KAWATA, Y., AIBA, S. : Biosci Biotechnol Biochem (2010) 74 (1) :175‐177
[3] ALBUQUERQUE, M. G. E., TORRES, C. A. V., REIS, M. A. M. : Water Research (2010) 44
(11) : 3419‐3433
42
[4] SPIEKERMANN, P., REHM, B. H. A., KALSCHEUER, R., BAUMEISTER, D.,
STEINBÜCHEL, A. : Arch. Microbiol (1999) 171:73‐80
******
Influence of Carrier Area on Properties of Immobilized Cellulase Complex
Reichstädter, M., Valicová, M., Omelková, J.
Brno University of Technology, Faculty of Chemistry. Purkyňova 118, 61200 Brno, CZECH
REPUBLIC, omelkova@fch. vutbr. cz
Abstract
Commercial cellulase preparation Cellulast 1. 5 L was attached to the synthetic carrier from
polyethyleneterephtalate (PET) of different surface area, when applying the activation with
glutaraldehyde. It was found that all carriers used have always bound the entire amount of
the enzyme. The highest relative activity have retained the preparation bound to the carrier
with the largest particle size. During the one month storage at 4o C this preparation showed
no decrease in activity. After the immobilization no change of the pH optimum was
observed, when compared to the free enzyme. Simultaneously, any change of the
temperature optimum was not proved in comparison to the free enzyme. From experiments,
in which the decrease of viscosity of the polymeric substrate as a function of the percentage
of cleaved glycosidic linkages was observed, follows that the immobilization alone does not
substantially change the mode of action of the immobilized preparation.
Keywords
cellulase, immobilization, polyethylenterephtalate
******
Silver Nanoparticles Production with Probiotic Bacteria
Sasková, D., Pořízka, J., Španová, A., Diviš, P., Kulich, P., Rittich, B.
Brno University of Technology, Faculty of Chemistry, Institute of Food Science and Biotechnology,
Purkyňova 118, CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
Silver nanoparticles (colloidal silver) have a bactericidal effect against a variety of bacteria,
fungi and viruses. They are promising for biomedical applications due to the limited toxicity
against eukaryotic cells. Important role in the silver nanoparticles production have various
microorganisms including lactic acid bacteria of the genus Lactobacillus. Probiotic
Lactobacillus species are good candidates for nanoparticles producing in the laboratory and
in industrial scale, too. The aim of this work was to test the production of colloidal silver
nanoparticles with probiotic species Lactobacillus casei. Nanoparticles production was tested
in the reaction mixtures (phosphate buffer, glucose, bacterial cells) upon addition of varying
concentrations of AgNO3 (1 ‐ 4mM). Production of the silver nanoparticles was proven by
screening of reaction mixtures by Transmission electron microscopy. Level of Ag+ ions
utilization to nanoparticles was analysed by optical emission spectrometry. Results showed
43
high efficiency of nanosilver production with narrow size distribution of nanoparticles (12 ‐
27nm).
Keywords
Silver nanoparticles, Probiotic bacteria, Lactobacillus, bactericidal effect, TEM, ICP‐OES
******
Liposomal Formulations of Hydrophobic Anticancer Drugs: Paclitaxel and
Vitamin E Analogues as Examples
Koudelka, S.1, 2, Turanek Knotigova, P.1, Masek, J.1, Lukac, R.1, Prochazka, L.1, Neuzil, J.3, 4,
Miller, A. D.5, Turanek, J.1
1Veterinary Research Institute, Brno, Czech Republic 2International Clinical Research Center, St. Anne´s University Hospital Brno, Brno, CZECH
REPUBLIC 3School of Medical Science, Griffith University, Southport, Qld, AUSTRALIA
4Institute of Biotechnology, Academy of Sciences of the Czech Republic, Prague, CZECH REPUBLIC 5King´s College London, London, UNITED KINGDOM
Abstract
Paclitaxel (PTX) is anticancer drug approved for the treatment of ovarian and breast cancer.
However, current chemotherapy using conventional PTX formulation (Taxol®) causes
serious side effects without any premedication. Liposomes themselves represent non‐toxic
biocompatible nanoparticles approved by FDA for application in human medicine. In
general, the developed liposomal PTX formulations are troubled by low PTX encapsulation
capacity (maximal content, 3 mol%) and accompanied by PTX crystallisation. Application
of”pocket‐forming” lipids can significantly increases the encapsulation capacity of PTX in
the liposomes up to 10 mol%. Based on the pocket‐forming lipids, we have developed stable
lyophilized formulation encapsulating PTX (7 mol%) in liposomes composed of
SOPC/POPG/MOPC lipids (molar ratio, 60:20:20) and vitamin E (5 mol%). The physical
stability of PTX liposomes, morphology and original size of 180 nm as well as suppressed
PTX crystallization was preserved for 6 months at 4°C. A significant reduction of lung
metastasis was achieved by the application of liposomal PTX (100 and 50 mg/kg) in
melanoma bearing mice. The side effects of liposomal PTX were negligible in comparison
with Taxol®, whose toxic dose was about 20–25 mg PTX/kg. Besides, both single doses of 100
mg PTX/kg and a cumulative dose of 150 mg PTX/kg (3 equivalent doses, 48‐h period) were
well tolerated without any signs of toxicity.
Pro‐apoptotic vitamin E analogues (VEA) exert selective anticancer effect on various animal
cancer models. However, suitable formulation of VEA for clinical application has been
reported yet. Due to hydrophobic character of VEA, liposomes are predetermined as suitable
delivery system. VEA were formulated in PC liposomes (molar ratio, 3:17) having final size
of 130 nm. Encapsulation up to 15 mol% of VEA did not cause any phase separation. Neither
‐tocopheryl succinate (100 mg/kg) nor ‐tocopheryl maleamide (25 mg/kg) formulated in
liposomes affected the leukocyte count in peripheral blood within 3 weeks following their
administration in mice. Tumor growth inhibition was demonstrated by i. v. application of
liposomal ‐TOS (15 M) and liposomal ‐TAM (1. 5 M) in FVB/N c‐neu transgenic mice
44
with spontaneous breast carcinoma. Liposomal formulations of both VE analogues applied
by i. v. route proved the anti‐cancer efficacy while acute toxicity and immunotoxicity of ‐TAM were eliminated by the drug encapsulation.
Keywords anticancer drugs, apoptosis, drug delivery, liposomes, nanotechnology, paclitaxel, vitamin E
analogues
Acknowledgements
The following grants supported this work: GAP503/12/G147, CZ. 1. 07/2. 3. 00/20. 0164, CZ. 1.
07/2. 3. 00/30. 0043, MZE0002716202 and MSMT ‐ Project FIT (JT, ADM). Support of Global
Acorn (ADM) is kindly acknowledged.
******
Fungal Solid‐State Fermentation as a Useful Tool for Preparation of
Functional Cereal‐Derived Biomaterials
Čertík M., Klempová T., Slaný O.
Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinského 9, 812 37
Bratislava, SLOVAK REPUBLIC
Abstract Cereals as one of the main component in human diet and feed industry are important
sources of several macronutrients (proteins, carbohydrates) and micronutrients (minerals,
vitamins). However, their nutritional and functional properties and subsequent applications
could be improved significantly by solid state fermentations. During this biotechnological
process suitable lower filamentous fungi efficiently utilize cereals and convert them to new
prefermented biomaterials with a high content of valuable metabolites such as
polyunsaturated fatty acids, carotenoids, ergosterol, coenzyme Q10, dietary fibres and
various enzymes. Fungi also improved content of dry matter, proteins, detergent fibers and
ash in biomaterials. These functional biomaterials should be generally recognized as safe
(GRAS) for the production of food or feed ingredients/additives. Thus, biotechnologically
modified agromaterials may open novel prospects for the market of functional cereal‐based
food and feed supplements.
Keywords
cereals, solid state fermentations, fungi, functional biomaterials
Acknowledgements
The work was supported by grants VEGA 1/0574/15, VEGA 1/0457/14, APVV‐0662‐11 and
APVV SK‐CZ‐2013‐0167.
References
[1] M. ČERTÍK, Z. ADAMECHOVÁ, L. SLÁVIKOVÁ, Biotechnological enrichment of
cereals with polyunsaturated fatty acids, in: C. T. Hou, J. ‐F. Shaw, (Eds), Biocatalysis
and Molecular Engineering, John Wiley & Sons, Hoboken (NJ), USA, 2010, pp. 175‐193
45
[2] M. ČERTÍK, T. KLEMPOVÁ, L. GUOTHOVÁ, D. MIHÁLIK, J. KRAIC, Biotechnology
for the functional improvement of cereal‐based materials enriched with polyunsaturated
fatty acids and pigments, Eur. J. Lipid. Sci. Tech. 115 (2013) 1247‐1256
******
The Influence Free Radicals on The Uptake of Copper (II) Ions by
Exopolymers and the Fibrillar Part Oof Cell Wall of The Red Yeast
Breierova E., Čertik M., Márova I.
1Institute of Chemistry, Slovak Academy of Sciences, Dúbravská cesta 9, 845 38 Bratislava,
SLOVAKIA, 2Department of Biochemical Technology, Faculty of Chemical and Food Technology, Slovak
University of Technology, Radlinského 9, 812 37 Bratislava, SLOVAKIA, 3Department of Food Chemistry and Biotechnology, Faculty of Chemistry, University of Technology,
Purkyňova 118, 612 00 Brno, CZECH REPUBLIC
Abstract
Copper is a natural fungicide and can be found as the active component of various
pesticides. In three red yeast strains of species Rhodotorula glutinis (two strains) and
Sporobolomyces roseus (one strain) the uptake of copper ions was tested. The response to
metal stress alone and in combination with peroxide stress was studied too. The maximum
of Cu2+ sorption was observed inside the cells of Rhodotorula glutinis CCY 20‐2‐33 (25. 18
mg/g dry weight). Further, Cu2+ ions were also bound to yeast exopolymers in which high
amounts (10. 22 mg/g dry weight) were accumulated. The rest of copper was sorbed onto the
fibrillar part of cell wall (3. 75 mg/g dry weight). The presence peroxide (oxidative stress) in
cultivation medium decreased the toleration of yeasts to Cu2+ ions. The yeast cells were able
to take up less of about 17 % of Cu2+ (in range of 3 mM to 2. 5 mM), although the total
uptake was quite lower (11. 01‐ 15. 96 %). We found that both strains of Rhodotorula glutinis
are able to bound about 44 % more copper ions (25. 18 ‐24. 32 mg/g dry weight) when
compared with Sporobolomyces roseus strain (16. 92 dry weight). However, the addition of
peroxide into the cultivation medium affected trade changes by reducing the ability to
uptake Cu2+ ions. In conclusion, exopolymers and fibrous part of cell wall of some red yeasts
could be used as biopolymers with high sorption ability for metals.
Keywords
red yeast, uptake copper ions, peroxide, extracellular glycoprotein
Acknowledgements
This work was supported by the Slovak Research and Development Agency under the
contract No. APVV‐0662‐11 and VEGA agency grant No. 2/0023/14.
46
******
Strategies for Optimum Production of High‐Value Products Using
Microalgae
Kovar, K., Barmettler, M, Stadler, M., Zamora, I., and Neutsch, L.
Institute of Biotechnology, School of Life Sciences and Facility Management, Zurich University of
Applied Sciences ZHAW, Wädenswil, SWITZERLAND
Abstract
The potential versatility of microalgae for biotechnological production has only recently
begun to be explored extensively. The range of achievable product classes is constantly
expanding, and the original focus on bulk production of microalgal biomass or lipids for
biofuel use has been extended to a variety of high value‐added compounds for
pharmaceutical, food and feed, or cosmetic applications, as well as for fine chemicals and
specialities. In particular, substances produced biotechnologically may contain modifications
to their core molecules (e.g. glycosylation) that can alter their physico‐chemical properties
compared with chemically synthesised analogues.
However, one of the main obstacles to the economically feasible and routine use of
microalgae as a future biotechnological production system is the lack of robust and generic
cultivation strategies. The unique traits of microalgae (as compared to other microbial
systems), in particular their ability to cope with different trophic modes (i. e. photoauto‐,
hetero‐ and mixotrophic) and their responses to light as a factor affecting physiological state,
provide novel options for process control. The development of such biotechnological
processes is highly demanding and is therefore only justified for those product classes for
which microalgal production systems are uniquely suited.
Keywords microalgae photoauto‐, hetero‐ and mixotrophic high value‐added biotechnological product
References
[1] CCMA (Combining Competences in MicroAlgae) at the ZHAW: http://lsfm. zhaw.
ch/de/science/forschung/interdisziplinaritaet/ccma‐combining‐competences‐in‐
microalgae/aktuelles. html
[2] KOVAR, K., P. PRIBYL, and M. WYSS. 2013. Microalgae grown under heterotrophic and
mixotrophic conditions. In: Meyer, H. ‐P. and Schmidhalter, D. (Eds) Industrial Scale
Suspension Culture of Living Cells. Wiley‐VCH Verlag GmbH & Co. KGaA pp. 164‐184,
ISBN 978‐3‐527‐33547‐3.
[3] HYKA, P., S. LICKOVA, P. PRIBYL, K. MELZOCH, and K. KOVAR. 2012. Applications
of flow cytometric methods to develop biotechnological processes with microalgae.
Biotech. Adv. 31:2‐16.
[4] BUMBAK, F., S. COOK, V. ZACHLEDER, S. HAUSER, and K. KOVAR. 2011. Best
practices in high cell density microalgal processes: achievements, limitations and
potential. Appl. Microbiol. Biotechnol. 91:31‐46.
47
******
Growth Dynamics Characterization of Setlicola Philippina Gen. et Spec.
Nov. (Trebouxiophyceae, Chlorophyta), Performed in Two Types of
Photobioreactors
Perútková, K., Steinová, J., Novotná, Z., Červený, J., Trtílek, M.
Photon Systems Instruments, Drásov 470, 664 24, CZECH REPUBLIC
Charles University in Prague, Faculty of Science, Department of Botany, Benátská 2, Praha 2, 128 01,
CZECH REPUBLIC
Global Change Research Centre, Academy of Sciences of the Czech Republic, Bělidla 986/4a, Brno, 603
00, CZECH REPUBLIC
Abstract The first part of our study is focused on novel genus and species of green algae Setlicola
philippina. This strain was isolated from freshwater bentic biofilm from Taal Volcano Crater
Lake, Philippines. S. philippina is a small coccal Chlorella‐like algae 5, 5 – 11 m in size with
very simple morphological characters. Therefore, we used 18S rDNA sequence to define
differences from other related taxa. According to phylogenetic analysis S. philippina form
separate lineage within Watanabea‐clade (Trebouxiophyceae, Chlorophyta) and represent
undescribed taxon.
In the second part, preliminary results of the optimal cultivation condition were determined.
Initially growth characteristics were tested under different light intensities and temperatures
during S. philippina cultuvation in multicultivator MC1000‐OD. MC1000‐OD continuously
recorded optical density (OD) and temperature. Next growth dynamics experiments were
conducted in photobioreactor FMT 150. Except OD and temperature FMT 150 is able to
measure continuously fluorescence, pH and concentration of dissolved gases (O2, H2, CO2).
In both devices growth curve was recorded in OD680. The best growth rate was observed in
the exponential phase, which was verified by determination of doubling time. Calculated
value of shortest doubling time was 12, 22 hours for cultivation in MC 1000‐OD and 18, 5
hours for culture growing in FMT 150.
Keywords
Setlicola philippina molecular phylogeny growth dynamics photobioreactor
48
******
Yeast Biomass Analysis for Application in Biotechnology Based on Raman
and SEM Spectroscopy
O. Samek1, A. Haroniková2, K. Hrubanová1, I. Márová2, S. Bernatová1, P. Zemánek1, V.
Krzyžánek1
1Institute of Scientific Instruments of the AS CR, v. v. i., Academy of Sciences of the Czech Republic,
Královopolská 147, 61264 Brno, CZECH REPUBLIC 2Centre for Material Research, Brno University of Technology, Purkynova 118, 612 00, Brno,
CZECH REPUBLIC
Abstract
A biomass of red yeast (e. g. Rhodotorula spp., Cystofilobasidium spp. and Sporobolomyces
spp.) has been recently studied due to potential applications in the field of food industry and
biofuel generation [1]. In order to utilize biomass for efficient industrial production, the
optimal cultivation parameters have to be determined and monitored. Thus, high production
of desired substances such as carotenoids and oil in the selected cell line can be achieved.
Therefore, techniques are required allowing for rapid characterisation/identification of yeast
species, and specifically to determine the beta‐carotene and unsaturation of constituent fatty
acids in species lipid bodies. It has been shown that Raman spectroscopy can provide this
biochemical information and reveal the molecular composition of the studied
microorganisms [2]. Thus, the use of Raman spectroscopy for the monitoring, detection and
identification of important, basic molecules in biological samples will be presented.
Moreover, in order to study red yeast strains in more details a combination of scanning
electron microscopy (SEM), and Raman spectroscopy was explored. In addition we used
HPLC analysis to quantify the concentration of carotenoids in selected samples.
In our experiments we have observed different morphology when employing SEM to study
yeast cells cultivated in media with different carbon to nitrogen (C/N) ratio. Also, Raman
spectroscopy study supports findings that C/N ratio of cultivation media has an influence to
the production of yeast lipids or carotenoids. Consequently, all matrix changes within the
studied cells introduced by stress response mechanisms can be visualized (SEM) and
chemically characterize (Raman).
Keywords
red yeast, biomass, Raman spectroscopy, electron microscopy
Acknowledgements This work received support from the Ministry of Education, Youth and Sports of the Czech
Republic (LO1212) together with the European Commission and the Czech Science
Foundation (ALISI No. CZ. 1. 05/2. 1. 00/01. 0017, GA15‐20645S).
References
[1] PETRIK, S., MAROVA, I., HARONIKOVA, A., KOSTOVOVA, I., and BREIEROVA, E.
ʺProduction of biomass, carotenoid and other lipid metabolites by several red yeast
49
strains cultivated on waste glycerol from biofuel production – a comparative screening
study, ʺ Ann. Microbiol. 2013, 63, 1537–1551.
[2] SAMEK, O., BERNATOVA, S., JEZEK, J., SILER, M., SERY, M., KRZYZANEK, V.,
HRUBANOVA, K., ZEMANEK, P., HOLA, V., and RUZICKA, F. “Identification of
individual biofilm‐forming bacterial cells using Raman tweezers, ” J. Biomed. Opt. 2015,
20, 051038.
******
Liposomal Vaccine Delivery Systems
Mašek, J.1, Turánek Knotigová, P. 1, Lukáč R. 1, Křupka M. 2, Bartheldyová E. 1, Koudelka Š. 1, 6, Miller, A. D.3, Kratochvílová I. 4, Ledvina, M. 5, Raška, M. 2, and Turánek, J.
1Department of Pharmacology and Immunotherapy, Veterinary Research Institute, Brno, CZECH
REPUBLIC 2Palacky University, Faculty of Medicine and Dentistry, Department of Immunology, Olomouc,
CZECH REPUBLIC 3King' s College London, Pharmaceutical Sciences Division, London, UK 4Institute of Physics, Czech Academy of Sciences, Prague, CZECH REPUBLIC
5Institute of Organic Chemistry and Biochemistry, Czech Academy of Sciences, Prague, CZECH
REPUBLIC 6International Clinical Research Center, St. Anne´s University Hospital Brno, Brno, CZECH
REPUBLIC
Abstract Liposomes represent nanoscale‐based formulations showing a potent adjuvant activity to
protein antigens. Metallochelating liposomes were designed to attach His‐tagged protein by
non‐covalent interaction. Metallochelating liposomes were prepared from the mixture of egg
phosphatidyl choline and nickel‐chelating lipid DOGS‐NTA‐Ni. New non‐pyrogenic
hydrophobized derivatives of muramyl dipeptide were incorporated into liposomes as
molecular adjuvants. We tested several His‐tagged protein antigens for construction of
experimental recombinant vaccine formulations. As an examples, OspC antigen from
Borrelia burgdorferi and Hsp90 from Candida Albicans will be presented.
Lyme disease caused by spirochete Borrelia burgdorferi sensu lato is a tick‐born illness that
can lead to chronic complications. The immune response to Borrelia is mediated by
phagocytic cells and by Borrelia‐specific complement‐activating antibodies associated with
Th1‐cell activation. Liposomes represent almost ideal carrier system for the preparation of
synthetic vaccines due to their biodegradability and versatility as regards the incorporation
of various molecules having different physico‐chemical properties.
The structure of proteoliposomes was studied by dynamic light scattering, transmission
electron microscopy, atomic force microscopy, and gel permeation chromatography. The
liposomes with surface‐exposed hydrophobized derivatives of muramyl dipeptide were well
recognized and phagocyted by human dendritic cells in vitro. In vivo, the immune response
towards this experimental vaccine applied in mice by intradermal route demonstrated both
Th1 and Th2 response. No side effects were observed after the application of liposomes.
50
Metallochelating liposomes with lipophilic derivatives of muramyl dipeptide represent a
new biocompatible platform for the construction of experimental recombinant vaccine.
Keywords
vaccine, liposome, His‐tag, antigen, molecular adjuvant, MDP
Acknowledgements
This work was supported by the following grants: the Grant Agency of Czech Republic
GAP503/12/G147 (JT), the Ministry of Education, Youth and Sports CZ. 1. 07/2. 3. 00/20. 0164
(JT) Project FIT ‐ the Ministry of Education, Youth and Sports (JT, ADM, MR),
MZE0002716202 of the Czech Ministry of Agriculture, AZV‐ČR 15‐32198A, CZ. 1. 07/2. 3.
00/30. 0043. Support of Global Acorn (ADM) is kindly acknowledged.
51
Environmental Chemistry and Technology
Are Terrestrial Organisms Able to Live in Contaminated Soil after Fire‐
Fighting?
Hribova, S., Vavrova, M., Zlamalova Gargosova, H.
Brno University of Technology, Faculty of Chemistry, Institute of Chemistry and Technology of
Environmental Protection, Purkyňova 118, CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
Many fire accident happend in several decades. There were several wildfires and also huge
fires of large industry areas or companies in the world. In order to put down the fire, fire‐
fighting foaming agents (FEAs) are often used. Their good properties, i. e. stability and large
active surface of foam, are the reasons of their frequent usage. In fact, these agents are
mixtures of several chemical substances as alcohols, perfluorinated hydrocarbons,
surfactants, additives and water, of course. An infiltration of FEAs solution occurs after
application during firefighting. FEAs are partly captured by the soil particles and causing
contamination of the soil environment. Consequently, the soil may be uninhabitable pro
terestrial organisms during dry seasons. On the contrary, there is known premise about rainy
seasons, when the contamination is diluted and rinsed as leachate with low ecotoxicity. The
crucial question is, whether the soil environment is suitable for life of indigenous terestrial
organisms after direct FEAs application. There were performed test of ecotoxicity with using
earthworms Eisenia Fetida as chief representative of terrestrial organisms in the study. Soil
matrix LUFA 2. 3 was selected as a model of natural soil environment. Tested FEAs were
follows: Sthamex F‐15, Moussol‐APS F‐15 and Finiflam F‐15. For experimental purposes,
laboratory installation for infiltration was designed and compiled. Infiltration of three FEAs
solutions was done before the ecotoxicity testing. Contaminated soil after infiltration was
tested for semi‐chronic ecotoxicity and reproduction ecotoxicity then. Introductory results
indicates differences between each FEA, caused by various composition. Sthamex F‐15 was
determined as the most ecotoxic agent at all. Whilst Moussol‐APS F‐15 was evaluated as the
agent with least ecotoxicity effect.
Keywords Fire‐fighting, soil, earthworms, ecotoxicity.
Acknowledgements
This study was supported by the grant no. FCH‐S‐15_2869 from the Ministry of Education,
Youth and Sports of theCzech Republic.
References [1] JOHNSON, A Field Method for Measurement of Infiltration. U. S. Geol. Survey Water‐
Supply Paper 1544‐F., 1963, p. F1–F27. ISO 15799, Soil quality ‐ Guidance on the
ecotoxicological characterization of soils and soil materials, 2003. ISO 11268‐2, Soil
quality ‐ Effects of pollutants on earthworms ‐ Part 2: Determination of effects on
reproduction of Eisenia fetida/Eisenia andrei, 2012.
52
[2] S. HRIBOVA, H. ZLAMALOVA GRAGOSOVA, M. VAVROVA, Sorption ability of the
soil and its impact on environmental contamination, Interdisciplinary Toxicology,
Bratislava, 2014, Vol. 7 (4), p. 177 ‐ 183, doi: 10. 2478/intox‐2014‐0025.
[3] M. B. KIRKHAM, Principles of Soil and Plant Water Relations, 2. Ed., Elsevier, USA,
2014, pp. 579, ISBN 978‐0‐12‐420022‐7.
[4] S. R. ELLIS, M. E. HODSON, P. WAGE, The influence of different artificial soil types on
the acute toxicity of carbendazim to the earthworm Eisenia fetida in laboratory toxicity
tests, European Journal of Soil Biology, Vol. 43, 2007, pp. 239 ‐ 245, ISSN 1164‐5563
******
Flame Retardants and their Occurrence in the Terrestrial Ecosystem
Chytil, V., Vavrova, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
This study was focused on the analysis of four compounds from a brominated flame
retardants group, namely pentabromoethylbenzene, hexabromocyclododecane,
hexabromobenzene and tetrabromobisphenol A. Matrices were represented by four soil
samples and four seats of fire samples. In addition, bisphenol A was also examined. As a first
step, the process of extraction of the analytes from matrices was optimized. Three different
extraction techniques were tested (pressurized solvent extraction, microwave‐assisted
extraction and ultrasound‐assisted extraction). The next step was to verify the stability of
target compounds in strongly acidic conditions and to optimize the clean‐up of an extract by
a column chromatography using different types of sorbents and eluting solvents. On the
basis of several experiments, the gas chromatography with electron capture detection (GC‐
ECD) was chosen as an appropriate analytical method for the determination of brominated
flame retardants. Bisphenol A was investigated by the gas chromatography with mass
spectrometric detection (GC‐MS). Phenolic analytes were derivatized before their final
analytical determination. The most abundant analyte was the hexabromocyclododecane
which was quantified in all matrices in the range of 7. 018‐81. 88 ng/g dry weight. On the
contrary, tetrabromobisphenol A was not proven in any of analyzed samples. The ash from
the Brandýs nad Labem restaurant fire contained the highest amount of all target
compounds (total 118. 2 ng/g dw). The least contaminated place was the forest burnt‐out area
near Velmovice (hexabromocyclododecane only, 7. 843 ng/g dw). As for soil samples, greater
concentrations were found in the area near the industrial site in Chropyně, where a store of
plastic materials burnt down in 2011. The analysis of the seat of fire samples showed that
compounds of interest are more abundant in ash than in a soil part (some of them were
mixtures of ash and soil). All measured concentrations fall within a range in which these
analytes are present at many other places in the world (tenths to tens ng/g dw).
Keywords
bisphenol A, brominated flame retardants, gas chromatography, hexabromobenzene,
hexabromocyclododecane, pentabromoethylbenzene, seat of fire analysis, soil analysis,
tetrabromobisphenol A
53
Acknowledgements
This study was supported by the project No. FCH‐S‐14‐2487 from the Ministry of Education,
Youth and Sports of the Czech Republic.
******
Microwave Digestion Method of Biotic Samples for Elemental Analysis
Kosárová, H., Holubová, Z., Řeháková, J., Čáslavský, J., Řehůřková, I., Ruprich, J.
Institute of Chemistry and Technology of Environmental Protection, Faculty of Chemistry, Brno
University of Technology, Purkyňova 118, 612 00 Brno, CZECH REPUBLIC
National Institute of Public Health in Prague, Centre for Health, Nutrition and Food in Brno,
Palackého 3a, Brno 612 42, CZECH REPUBLIC
Abstract This contribution deals with development, optimization and application of procedure for
preparation of biotic samples for the determination of heavy metals using microwave
system. This procedure is based on the wet mineralization at high pressure and also elevated
temperature, using microwave assisted decomposition in acidic solution in hermetically
enclosed Teflon containers. Elemental analysis of biotic matrices requires decomposition of
the sample. Advantages of microwave assisted decomposition are relatively short time
needed to perform decomposition of the sample, high efficiency of decomposition, small
quantities of the reactive substance and no contamination. The microwave program is
consisted of thirteen steps with maximum temperature of 220 °C and gradually increasing
performance from 250 W to 650 W. Decomposition process is controlled by temperature
sensor, which is set up on 240 °C, this temperature should not be exceeded during
decomposition. Different amount of samples (0. 5 – 10 g) was decomposed in the mixture
nitric acid and hydrogen peroxide, which was used as the extraction solvent. After previous
studies several variables which affect the extraction efficiency were optimized: temperature
and time of decomposition, the performance of each step and amount of samples. Other
parameters (such as volume of the solvent) were kept constant. The optimized microwave
program was established as a compromise between demands on decomposition processes
for various samples (samples with high content of fat on one side and samples with higher
content of water on the other side). F‐AAS, ET‐AAS, HG‐AAS, AES and ICP‐MS were then
used for the determination of targeted elements. The trueness and accuracy of the optimized
procedure was verified by the analysis of certified reference materials. Our laboratory is
accredited according to the standard EN ISO/IEC 17025:2005.
Keywords Microwave digestion, decomposition, elemental analysis
Acknowledgements
This project was supported by Ministry of Health, Czech Republic – conceptual development
of NIPH in Prague, (NIPH 75010330) and by the project Assessment of the entry of new
contaminants to the environment from Ministry of education, youth and sports of the Czech
Republic (FCH‐S‐15‐2869).
54
******
Optimization of Gas Chromatography Tandem Mass Spectrometry Method
for the Determination of Bisphenols in Selected Food Samples
Bukackova, M., Vitkova, L., Vavrova, M., Caslavsky, J., Rehurkova, I., Ruprich J.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
National Institute of Public Health in Prague, Centre for Health, Nutrition and Food, Palackého 3a,
Brno, CZECH REPUBLIC
Abstract Bisphenol A (BPA) was first synthesized in 1891 and nowadays is widely used in industry as
a monomer in the production of epoxy resins, polycarbonates and in the products of modern
consumer society. Polycarbonates are often used in foodstuffs packaging such as beverage
and food containers while epoxy resins are used as protective linings against direct contact of
food with metal in food and beverage cans. Unfortunately, heat or contact with basic or acid
compounds can cause acceleration of hydrolysis of the ester bond linking BPA molecules in
polycarbonate and resins, leading that small amount of BPA can leach out from food
containers into the foods. Possible risk to human health (estrogenic activity of bisphenol A)
resulted in reduction of its use in food industry, being replaced by other bisphenols such as
bisphenol F (BPF), bisphenols S (BPS), bisphenols Z (BPZ) currently, only very limited
information about their effects on human health and their migration into the foods is
available [1, 2]. Therefore the aim of this study was to develope and optimize an efficient
analytical method for determination of 4 bisphenols and their corresponding diglycidyl
ethers in various food samples, representing the average food basket of the Czech
population. The standard operating procedure, based on the solvent (L/L) and solid phase
extraction (SPE), was developed for various foodstuffs matrices and all obtained extracts
were analyzed using gas chromatography coupled to tandem mass spectrometry (CG‐
MS/MS). Using of gas chromatography requires a derivatization step due to the presence of
polar hydroxyl groups in the structure of bisphenols which can decrease peak intensity. The
derivatization step for this method is based on silylation reaction of bisphenols using N, O
Bis (trimethylsilyl) trifluoroacetamide (BSTFA). The results from this study will be used for
the assessment of total dieatary exposure of these bisphenols.
Keywords
Bisphenols, diglycidyl ethers, solid phase extraction, gas chromatography tandem mass
spectrometry
Acknowledgements This project was supported by Ministry of Health, Czech Republic – conceptual development
of NIPH in Prague, (NIPH 75010330) and project Assessment of the entry of new
contaminants to the environment from Ministry of education, youth and sports of the Czech
Republic (FCH‐S‐15‐2869).
55
References
[1] Y. DECEUNINCKA, E. BICHONA and col. : Development and validation of a specific
and sensitive gas chromatography tandem mass spectrometry method for the
determination of bisphenol A residues in a large set of food items (2014), Journal of
Chromatography A, vol. 1362, pp. 241‐249.
[2] S. C. CUNHA, J. O. FERNANDES: Assessment of bisphenol A and bisphenol B in canned
vegetables and fruits by gas chromatography–mass spectrometry after QuEChERS and
dispersive liquid–liquid microextraction (2013). In: Food Control, vol. 33, pp. 549–555.
******
Monitoring of Chlorate and Perchlorate in Czech Food Basket
Kavrik, R., Nevrla, J., Caslavsky, J., Rehurkova, I., Ruprich, J.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Perchlorate occurs naturally in the environment in deposit of nitrate and potash fertilizers. It
may be formed in atmosphere and precipitate into the soil and groundwater. The
anthropogenic way of contamination by perchlorate is fundamental. Perchlorate is used as
propellant for a rocket fuel, in a manufacturing process of explosives, fireworks and airbags.
It is a degradation product of sodium hypochlorite and may be generated from chlorine‐
based biocidal products which are used as disinfectants in water [1]. In the past perchlorate
was used as herbicide, this practise is in Europe prohibited since 2010 [2]. Impact of
perchlorate on a human health is in inhibition of the thyroxin (T3) and triiodothyronin (T4)
production in the thyroid gland by blocking of uptake of iodide from the blood [3, 4]. U. S.
National Academy of Sciences announced a perchlorate reference dose of 0. 7 μg/kg body
weight/day [5]. Joint FAO/WHO Expert Committee on Food Additives derived PTMDI value
of 0. 01 mg/kg body weight. Chlorate occurs as accompanying substance of sodium
hypochlorite. Its oxidation ability causes blood cell damage. Ministry of Health, Labour and
Welfare of Japan announced a chlorate reference dose of 30 μg/kg body weight/day. Chlorate
and perchlorate were observed in many of food matrices. The higher concentration is in
vegetables (hundred μg/kg), in fruits (dozens μg/kg), vegetable and fruits juice and in infant
formulae. The aim of this study is development of LC‐MS/MS method for determination of
these two substances in food. The pre‐treatment of samples is developed and optimized for
different matrices. These results will be used for Program of monitoring of dietary exposure
(National Institute of Public Health) and the dietary exposure will be estimated. Samples
were analyzed using method for the analysis of residues of highly polar pesticides in food of
plant origin with LC‐MS/MS detection. Method was modified and optimized for analysis of
other food matrices. In the 2015 are analyzed over 400 samples of plant and animal origin
from the Czech food basket. To the best of our knowledge it is probably one of the most
comprehensive study from the Central Europe area. In this project was tested effect of
transfer of chlorate and perchlorate from contamination water to vegetables. This transfer
may be caused by irrigation or washing by contamination water. The transfer from water to
vegetables was observed and quantified. Perchlorate in food, especially in fruits and
vegetables is very serious subject in the presence in EU. The actual situation is described in
56
Scientific Opinion by EFSA [6]. This document concluded that short period exposure to
perchlorate could induce adverse effect in groups of population such breast‐fed infants and
small children with low iodine intake. Results from this project will be used for estimation of
total dietary exposure to these contaminants and in discussion about national maximal level
of chlorate/perchlorate in food too.
Keywords
chlorate, perchlorate, dietary exposure
Acknowledgements
This project was supported by Ministry of Health, Czech Republic – conceptual development
of NIPH in Prague, (NIPH 75010330) and project Assessment of the entry of new
contaminants to the environment from Ministry of education, youth and sports of the Czech
Republic (FCH‐S‐15‐2869).
References
[1] K. KOSAKA, M. ASAMI, S. KUNIKANE: Perchlorate: origin and occurrence in drinking
water (2011). In: Encyclopedia of environmental health, Elsevier
[2] COMMISSION DECISION of 10 November 2008 concerning the non‐inclusion of
chlorate in Annex I to Council Directive 91/414/EEC and the withdrawal of
authorisations for plant protection products containing that substance (2008). In: Official
Journal of the European Union, Brussels
[3] M. A. GREER, G. GOODMAN, R. C. PLEUS, S. E. GREER: Health effects assessment for
environmental perchlorate contamination: the dose response for inhibition of thyroidal
radioiodine uptake in human (2002). In: Environ Health Perspect, vol. 110 (9), p. 927–
937.
[4] A. SRINIVASAN, T. VIRARAGHAVAN: Perchlorate health effects and technologies for
its removal from water resources (2009). In: Int J Environ Res Public Health, vol. 6 (4), p.
1418–1442
[5] National Research Council: Health implications of perchlorate ingestion (2005). In:
National Academies Press, Washington DC:
[6] EFSA Panel on Contaminants in the Food Chain (CONTAM) : Scientific Opinion on the
risks to public health related to the presence of perchlorate in food, in particular fruits
and vegetables (2014). In: EFSA Journal, vol. 12 (10), 3869
57
******
Evaluation of Occurrence of Selected Groups of Fatty Acids in Fish and Fish
Products
Vitkova, L.1, 2, Bukackova, M.1, 2, Caslavsky, J.1, 2, Rehurkova, I.1, Ruprich, J.1
1National Institute of Public Health in Prague, Centre for Health, Nutrition and Food in Brno,
Palackého 3a, CZ‐612 42 Brno, CZECH REPUBLIC 2Institute of Chemistry and Technology of Environmental Protection, Faculty of Chemistry, Brno
University of Technology, Purkyňova 118, CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
Fatty acids (FA) are a necessary part of every cell of organism and serves as a source of
energy. These compounds are divided by the saturation to saturated (SAFA), which have
adverse effects to human organism, and unsaturated. This group is then subdivided to
monounsaturated (MUFA) and polyunsaturated (PUFA). The group of unsaturated fatty
acids comprising trans configuration on the double bond in their chain is called trans‐
unsaturated fatty acids (TFA). Fatty acids are found in a wide variety of foods. Vegetable oils
and some foodstuff of animal source (e. g. meat, milk and milk products, eggs, fish oil) are
considered as their main sources. Essential fatty acids such as PUFA omega‐3 and PUFA
omega‐6 are very important for human organism but human body cannot produce these
compounds. For this reason, these fatty acids must be obtained from food [1]. For the
determination of fatty acids is at first necessary to extract the fat. Liquid–liquid extraction
belongs to the most commonly used method followed by esterification of fatty acids to
obtain fatty acid methyl esters (FAMEs). In this study the esterification with methanolic
solution of KOH was used. FAMEs were detected by gas chromatography with flame‐
ionization detector which is the most suitable due to its high sensitivity and selectivity [2].
The aim of this study was the determination of 37 fatty acids in fish and fish products. In
samples of marine fish (16 samples) were found different ratios of SAFA, MUFA and PUFA
in comparison with freshwater fish (22 samples of carp). Marine fish contained 4. 5 times
higher amount of SAFA and 3. 3 times lower amount of MUFA in comparison to freshwater
fish. Levels of FA in canned fish, smoked and marinated fish (in total 64 samples) were also
compared. It was found that canned fish show higher values of MUFA than marine fish. This
could be due to the fact that some fish were loaded in oil with higher concentration of oleic
acid.
Keywords
fatty acids, fish, fish products, FAME, SAFA, MUFA, PUFA
Acknowledgements
This project was supported by Ministry of Health, Czech Republic – conceptual development
of NIPH in Prague, (NIPH 75010330) and project Assessment of the entry of new
contaminants to the environment from Ministry of education, youth and sports of the Czech
Republic (FCH‐S‐15‐2869).
58
References
[1] AP. SIMOPOULOS, Omega‐3 fatty acids in health and disease and in growth and
development., Am J Clin Nutr. 1991 Sep 54 (3) :438‐63.
[2] K. EDER, Gas chromatographic analysis of fatty acid methyl esters. J Chromatogr B
Biomed Appl. 1995 Sep 15 671 (1‐2) :113‐31.
******
Determination of Sildenafil, Vardenafil and Tadalafil in Wastewater by
HPLC/MS
Smutna, M., Caslavsky, J
Institute of Chemistry and Technology of Environmental ProtectionBrno University of Technology
Faculty of ChemistryPurkyňova 118 CZ‐612 00 Brno CZECH REPUBLIC
Abstract
This work is focused on the determination of phosphodiesterase 5 selective inhibitors in
communal wastewater. Phosphodiesterase inhibitors are the main active ingredients of
medicaments which are used in the treatment of erectile dysfunction. The aim of this work
was determination of three phosphodiesterase inhibitors in communal wastewater
specifically it was sildenafil citrate, vardenafil hydrochloride and tadalafil. These compounds
are the main active ingredients of medicaments with trade names Viagra, Levitra and Cialis.
In this study phosphodiesterase inhibitors in municipal wastewater from three sewage
treatment plants with different numbers of equivalent inhabitants were analysed: Sewage
treatment plant in Brno – Modřice (630 000 EI), Hodonín (90 000 EI) and Luhačovice (16 200
EI). In each of the above mentioned facilities 24 ‐ hour cumulated samples of the influent and
effluent wastewater were collected. On the Brno ‐ Modřice sewage treatment plant also
weekly monitoring of the concentration of phosphodiesterase inhibitors was realized. At
first, the analytical method was optimized and then applied on real wastewater samples.
Solid phase extraction (SPE) was used for the pre‐treatment of wastewater samples. High
performance liquid chromatography‐mass spectrometry with electrospray ionization
(HPLC/ESI‐MS) was applied for the identification and quantification of the target
compounds. It was assumed that the most widely used of these drugs is Viagra (this
assumption was based on survey in pharmacies), so sildenafil would be found in the largest
quantities. In spite of this, only vardenafil was detected at concentrations exceeding the limit
of detection and quantification and only in influent wastewater its levels were between 0. 1
and 0. 6 ng/l. Due to good efficiency of the treatment process its concentrations at outflow
water were bellow limit of detection. Tadalafil had to be excluded from the measurement
because of his extremely low recovery during SPE extraction optimization.
Keywords
sildenafil, vardenafil tadalafil, wastewater, SPE extraction, HPLC/MS
Acknowledgements
This study was supported by the project FCH‐S‐15‐2869 from the Ministry of Education,
Youth and Sports of the Czech Republic.
59
References
[1] STAŇKOVÁ, M. Determination of the presence of phosphodiesterase inhibitors in
municipal wastewater. Brno University of Technology, Faculty of chemistry, 2014. 84 p.
Master‘s thesis supervisor: doc. Ing. Josef Čáslavský, CSc.
******
Morphology of Plant Cuticles as The Limiting Barrier for the Uptake of
Fertilizers
Lastuvkova, M., Turkeova, I., Smilek, J., Sedlacek, P., Kratochvilova, R., Schmiedova, V.,
Klucakova, M.
Material Research Centre, Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐
61200 Brno, CZECH REPUBLIC
Abstract
The uptake of pesticides into plant foliage varies with plants and chemicals are based on
adjuvants and environmental condition. The penetration of nutrients into plant leaves relates
to the physicochemical properties of the active ingredients (molecular size and lipophilicity).
For the penetration studies of active ingredients are usually used thin layers from the leaves
surfaces – cuticles. These barriers are isolated by specialized methods (enzymatically and
chemically) and they can be used for evaluate the leaf surface permeability. However, the
uptake rate of a compound or function can be influenced by isolation methods. During
isolation process the structure of cuticles or function of stomates of cuticles can be changed.
The cuticles were characterized by Fluorescence Lifetime Imaging Microscopy (FLIM) and
Isothermal Microcalorimetry (IMC). These methods enable to study of binding and
interaction of compounds with the cuticles surface. Optical Microscopy (OM) was used for
inner state the structure of cuticles and their changes influence effect of water, air or
potassium lignohumate (LHA). Change of inner structure were study of Fluorescence
Microscopy (FM), cuticles are enable to excitation for different wavelength. Thicknesses of
cuticles were measured by Profilometer.
The knowledge obtained from the measuring is very important for the next research of
improving foliar uptake and problem with nutrients overloading in soil and degradation not
only soil, but ground water as well.
Keywords
foliar fertilizers, cuticles, morphology
Acknowledgements This work has been supported by Materials Research Centre at Faculty of Chemistry, Brno
University of Technology – Sustainability and Development, REG Lo1211, with financial
support from National Program for SustainabilityI (Ministry of Education, Youth and
Sports).
60
******
Reactivity‐Mapping Tool Based on Diffusion Techniques for
Characterization of Biocolloids
Smilek, J., Kalina, M., Lastuvkova, M., Turkeova, I., Sedlacek, P., Klucakova, M.
Materials Research Centre, Brno University of Technology, Faculty of Chemistry, Purkyňova 118,
CZ‐612 00, Brno, CZECH REPUBLIC
Abstract
The universal reactivity‐mapping tool was developed for characterization and study on
barrier properties of selected biopolymers. The reactivity of biocolloids (humic acids) was
studied by both diffusion techniques (break‐through diffusion technique and non‐stationary
diffusion). The rate of reactivity of humic acids was compared by the interactions with basic
cationic organic dye (Methylene Blue) because of the positive interactions among anionic
supramolecular humic acids and cationic organic dyes were expected. The reactivity and
barrier properties of biocolloids were compared by determination of fundamental diffusion
parameters such as effective diffusion coefficient, sorption capacity, break‐through time (the
time needed for penetration of chosen organic dye through hydrogel porous barrier) or the
concentration of organic dye on the interface hydrogel‐solution. The original combination of
simple diffusion experiments of suitable diffusion probe (organic dye) with the advantages
of hydrogel porous media (simple preparation of hydrogels, the diffusion is undisturbed by
convection, etc.) provides very valuable information about the reactivity of chosen
biocolloids.
Keywords
diffusion, biocolloids, hydrogels, reactivity, humic acids
Acknowledgements
This work has been supported by Materials Research Centre at Faculty of Chemistry, Brno
University of Technology – Sustainability and Development, REG Lo1211, with financial
support from National Program for SustainabilityI (Ministry of Education, Youth and
Sports).
******
Thermodynamics of Metal Ion Interaction with Humic Acids
Turkeova, I., Enev, V., Klucakova, M., Krouska, J., Lastuvkova, M.
Material Research Centre, Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐
612 00 Brno, CZECH REPUBLIC
Abstract
Humic substances presented in soil are capable to bond with pollutants, water and nutrients.
Considering their bonding with pollutants it is generally observed, that humic substances are
able to bond heavy metals ions in nature. Study of thermodynamics of these reactions
significantly improves our knowledge about reactivity of humic substances. The object of our
study were two various samples of HA. HAs were isolated from two different organic origin
61
– compost and South Moravian lignite. Isolation of soil HA was performed according to the
procedure recommended by the International Humic Substances Society (IHSS). All samples
of HA were characterized by elemental analysis (EA). The reactivity (thermodynamics) of
humic acids (HAs) and metals was studied by isothermal titration calorimetry (ITC). As
model metals were chosen Cu (II) and Pb (II) ions. Reaction enthalpy of systems were
calculated and discussed as well as amount of metal binding by specific humic acid.
Keywords humic acid, heavy metals, isothermal titration calorimetry, reaction enthalpy
Acknowledgements
Acknowledgement: This work was supported by project Nr. LO1211, Materials Research
Centre at FCH BUT‐Sustainability and Development (National Programme for Sustainability
I, Ministry of Education, Youth and Sports).
******
Fluorescence Analysis of Cu (II), Pb (II) and Hg (II) Ion Binding to Humic
and Fulvic Acids
Enev, V., Turkeova, I., Szewieczkova, J., Doskocil, L., Klucakova, M.
Material Research Centre, Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐
612 00 Brno, CZECH REPUBLIC
Abstract
Various methods and techniques have been used for studying humic substances binding to
metal ions, among which steady‐state fluorescence spectroscopy has proven to be one of the
most promising and productive. The aim of this work was study molecular and quantitative
analysis of metal ion binding to humic substances (HS). The object of our study was two
standards of humic substances (Elliott Soil standard HA 1S102H and Elliott Soil standard FA
2S102F). All samples of IHSS standards HS were characterized by elemental analysis (EA),
ultraviolet‐visible spectroscopy (UV/Vis), Fourier transform infrared spectroscopy (FTIR)
and steady‐state fluorescence spectroscopy. UV/Vis spectra of aqueous solutions HS were
measured by spectrophotometer Hitachi U‐3900 in the wavelength range of 200–900 nm.
Absorption coefficients (EET/EBz and E465/E665) of HS were calculated from the absorbance
values. Infrared spectroscopy is a useful technique in characterization of structure, functional
groups and formation modes of HS. For the fluorescence experiments the final concentration
of the HS was adjusted to 15 mg.L–1. All fluorescence spectra were performed on a Horiba
Scientific Fluorolog. The fluorescence intensity (IF) values (in CPS) of samples were corrected
using method of Lakowicz. A fluorescence titration method was used for determining metal
ion complexing capacities and stability constants of metal ion complexes of standards HS.
Titration with Cu (II), Pb (II) and Hg (II) ions decreased fluorescence intensities of HS.
Chemical parameters on the complexation of Cu (II), Pb (II) and Hg (II) ions, including the
conditional stability constants and the percentage of fluorophores participating in the
complexation, were estimated by the modified Stern–Volmer equation.
62
Keywords
humic substances, titration, steady‐state fluorescence spectroscopy, Stern‐Volmer equation,
fluorescence quenching
******
Optimization of Method for the Determination of Fatty Acids with Regard
to Their Trans and Cis Isomers
Vitkova, L.1, 2, Bukackova, M.1, 2, Caslavsky, J.1, 2, Rehurkova, I.1, Ruprich, J.1
1National Institute of Public Health in Prague, Centre for Health, Nutrition and Food in Brno,
Palackého 3a, CZ‐612 42 Brno, CZECH REPUBLIC 2Institute of Chemistry and Technology of Environmental Protection, Faculty of Chemistry, Brno
University of Technology, Purkyňova 118, CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
Gas chromatography coupled to flame ionization detector is widely used method for
determination of fatty acids (FA), however for better determination they have to be
converted by esterification to more volatile compound ‐ fatty acid methyl esters.
Esterification can be acid‐catalysed or base‐catalysed, depending on the type of used reagent.
Acid‐catalysed esterification requires a higher temperature than ambient which is sufficient
for base‐catalysed esterification. The most commonly used reagents for acid‐catalysed
esterification are hydrochloric acid, sulfuric acid and boron trifluoride (BF3) in methanol,
which is suitable for all types of lipids. Potassium hydroxide (KOH) in methanol and sodium
methoxide is the most often used for base catalysed esterification. Disadvantage of sodium
methoxide is its unsuitability for esterification of free fatty acids [1, 2]. Selection of the
stationary phase for GC separation is another very important step. Capillary columns with
highly polar or polar stationary phase are preferred, e. g. HP‐88, CP‐SIL 88, SP‐2560. The aim
of this study was the optimization of the method for the determination of fatty acids in
sample with declared values of FA and comparison of separation of cis‐ and trans‐isomers of
fatty acid methyl esters on two capillary columns with highly polar stationary phases ‐ HP‐
88 and Select FAME which was chosen for optimal cis/trans separations of FAMEs. From the
obtained results follows that Select FAME column provided better resolution of targeted
FAMEs than HP‐88. Moreover, five esterification methods were assessed. Three of them were
based on base‐catalysed esterification and remaining two methods used both alkaline and
acidic reagent. Esterification with methanolic solution of KOH and BF3 provided better
results than the other methods.
Keywords acid‐catalysed esterification, base‐catalysed esterification, FAME, KOH, BF3
Acknowledgements
This project was supported by Ministry of Health, Czech Republic – conceptual development
of NIPH in Prague, (NIPH 75010330) and project Assessment of the entry of new
contaminants to the environment from Ministry of education, youth and sports of the Czech
Republic (FCH‐S‐15‐2869).
63
References
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Biomed Appl. 1995 Sep 15 671 (1‐2) :113‐31.
[2] M. C. MILINSK, M. MATSUSHITA, J. V. VISENTAINER, L. F. DIAS, M. M.
YAMAGUCHI, M. R. PEDRO, N. E. de SOUZA, Influence of the esterification method
on the quantification of olive oil fatty acids, Semina: Cincias Exatas e Tecnológicas
(Londrina) 2011, Vol. 32 No. 2, pp. 139‐150, ISSN 1676‐5451
******
Degradation of Estriol by Photocatalysis
Olejnickova, Z., Dzik, P., Vavrova, M., Vesely, M.
Brno University of Technology, Faculty of chemistry, Purkyňova 118, CZ‐612 00, Brno, CZECH
REPUBLIC
Abstract Presence of hormones in water ecosystems is a problem of great interest nowadays.
Estrogens (female sex hormones) are one of the most debated substances. These compounds
with steroid structure play an important role in medicine, they are part of oral contraceptives
and are used for hormone substitution therapy [1]. They can be difficult to remove
completely by wastewater and drinking water treatment technologies therefore they are
found in natural aquatic ecosystems and in potable water [2, 3]. This fact is associated with a
potential serious risk to the environment and human health [1]. Photocatalysis is one of
promising methods for removal of estrogens from water [4] therefore in this study we
focused on assessment of TiO2 photocatalysis to eliminate natural estrogen estriol.
Photocatalytic experiments were conducted in a glass circulated reactor with a rotary holder
of immobilised TiO2 and UV‐A LED light source (365 nm emission wavelength). Printing ink
was prepared from water dispersion Tiodispers NA‐AS (Centre for Organic Chemistry,
Czech Republic) and deposited by inject printing onto soda‐lime glass substrate [5]. Initial
concentration of estriol in ultrapure water samples was 5 mg/L. Estriol levels were measured
by liquid chromatography coupled with mass spectrometry. Four hours photocatalytic
process led to reduction in estriol concentration about 54 %. The same time of photolysis
(without TiO2) or adsorption (without light) had no effect to estriol levels.
Keywords photocatalysis, estrogens, HPLC‐MS
Acknowledgements
This study was supported by the project No. FCH‐S‐15_2869 from the Ministry of Education,
Youth and Sports of the Czech Republic.
References [1] Hazardous Substances Data Bank (HSDB) [online database]. Available at http://toxnet.
nlm. nih. gov/cgi‐bin/sis/htmlgen?HSDB.
[2] YING, Guang‐Guo, Rai S. KOOKANA, Anu KUMAR and Munro MORTIMER.
Occurrence and implications of estrogens and xenoestrogens in sewage effluents and
64
receiving waters from South East Queensland. Science of The Total Environment. 2009,
vol. 407, issue 18, p. 5147‐5155.
[3] VULLIET, Emmanuelle, Cécile CREN‐OLIVÉ and Marie‐Florence GRENIER‐
LOUSTALOT. Occurrence of pharmaceuticals and hormones in drinking water treated
from surface waters. Environmental Chemistry Letters. 2011, vol. 9, issue 1, p. 103‐114.
[4] FRONTISTIS, Zacharias, Vasileia M. DASKALAKI, Evroula HAPESHI, Catherine
DROSOU, Despo FATTA‐KASSINOS, Nikolaos P. XEKOUKOULOTAKIS and
Dionissios MANTZAVINOS. Photocatalytic (UV‐A/TiO2) degradation of 17‐
ethynylestradiol in environmental matrices: Experimental studies and artificial neural
network modeling. Journal of Photochemistry and Photobiology A: Chemistry. 2012, vol.
240, p. 33‐41.
[5] ČERNÁ, Marcela, Michal VESELÝ, Petr DZIK, Chantal GUILLARD, Eric PUZENAT and
Martina LEPIČOVÁ. Fabrication, characterization and photocatalytic activity of TiO2
layers prepared by inkjet printing of stabilized nanocrystalline suspensions. Applied
Catalysis B: Environmental. 2013, vol. 138, p. 84‐94.
******
Superabsorbent Polymers and Their Effect on Soil Water Retention
Kratochvílová, R., Klučáková, M., Laštůvková, M., Kalina, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Agricultural land is in a very bad condition in the Czech Republic nowadays. There is a
problem of pollution caused by previous synthetic fertilizing. The land lost its natural
property of water controlling. Rain has rather devastating than beneficial effect for the
ground. Artificially applied nutrients are often flushed away and only a bit of them is
transported to the targeted location. Solution of these problems can be found in application
of natural fertilizer in form of hydrogel matrix. Superabsorbent polymers were used for this
purpose in this work. The aim of this work is to develop superabsorbent polymer with
incorporated fertilizer in its structure and confirm its ability to enable controlled release of
fertilizer from hydrogel matrix. This system should also provide enhancement of natural
ground humidity. Water retention tests were then also carried out. Several different samples
of superabsorbent polymers based on acrylic acid were observed during our research. They
differed in a basic composition of superabsorbent and mainly in a type of fertilizer. Common
synthetic NPK fertilizer was used as well as natural lignohumate fertilizer. The role of
dosage of these components was also studied. This work proves that novel form of
agricultural preparation was developed. The superabsorbent polymer allows controlled
release of variety fertilizers. Its role as the water reservoir system was proved as well. The
usage of superabsorbent polymers in agriculture can have a very positive effect on crop
yield.
Keywords
superabsorbent polymers, controlled release, fertilizer
65
******
Removal of Heavy Metals from Aqueous Solutions by Low‐Cost Bio
Materials
Iman Nazari1, Behrouz Shaabani2, Amir Zarei3
1Department of Chemical Engineering, University of Tabriz, Tabriz, IRAN 2Department of Inorganic chemistry, University of Tabriz, Tabriz, IRAN 3Department of Applied Chemistry, University of Tabriz, Tabriz, IRAN
Abstract In small quantities certain heavy metals are nutritionally essential for a healthy life. The
heavy metals linked most often to human poisoning are lead, mercury, arsenic and
cadmium, other heavy metals, including copper, zinc and chromium are actually required by
the body in small quantity but can also be toxic in large doses, nowadays, we have
contamination to this heavy metals in some untreated industrial waste waters and even in
several populated cities drinking waters around the world, the contamination of ground and
underground water sources to heavy metals can be concentrated and travel up to food chain
by drinking water and agricultural products, in recent years the need for safe and
economical methods for removal of heavy metals from contaminated water has necessitated
research interest towards the finding low‐cost alternatives. Bio‐adsorbents have emerged as
low cost And efficient materials for the removal of heavy metals from waste and ground
waters. The bioadsorbents have affinity for heavy metals ions to form metal complexes or
chelates due to having functional groups including carboxyl, hydroxyl, imidazole and etc.
the objective of this study is to review researches in less expensive adsorbents and their
utilization possibilities for various low‐cost bio‐adsorbents such as coffee beans, ricehusk
and saw dust for the removal of heavy metals from contaminated waters.
Keywords
Heavy Metals, Bio Adsorbents, Public Health, Low cost material
References
[1] ALLURI, H. K., RONDA, S. R., SETTALLURI, V. S., BONDILI, V. S.,
SURYANARAYANA, V., VENKATESHWAR, P. (2007), Biosorption: An eco‐friendly
alternative for heavy metal removal. Afr. J. Biotechnol. 6, 11, 2924‐2931.
[2] BABEL S. and KURNIAWAN T. A., (2003), Low‐cost adsorbents for heavy metals uptake
from contaminated water: a review, J. of Hazard Mater, 97, 219–243.
[3] BASU, A., MUSTAFIZ, S., ISLAM, M. R., BJORNDALEN, N. RAHAMAN, M. S.,
CHAALAL, O. (2006), A Comprehensive Approach for Modeling Sorption of Lead and
Cobalt Ions through Fish Scales as an Adsorbent, Chemical Engineering
Communications, 193, 580–605
[4] CARTWRIGHT, P. S., (1985), ʺMembranes Separations Technology for Industrial
Effluent Treatment ‐ A Reviewʺ, Desalination, 56, 17.
[5] D. MOHANA and C. U. PITTMAN Jr, (2007), Arsenic Removal from Water/wastewater
using Adsorbents‐ A Critical Review, 105‐111.
[6] GHABRIS, A., ABDEL‐JAWAD, M., and ALY, G., (1989), ʺMunicipal Wastewater
Renovation by Reverse Osmosis, State of the Artʺ, Desalination, 75, 213.
66
[7] GOPALRATNAM, V. C, et al. (1988), ʺThe Simultaneous Removal of Oil and Heavy
Metals from Industrial Wastewater by Joint Precipitation and Air Flotation. ʺ Environ.
Prog., 7, 84.
[8] GOTTIPATI Ramakrishna and MISHRA Susmita, (2012), Application of respons surface
methodology for optimization of Cr (III) and Cr (VI) adsorption on commercial activated
carbons, Research Journal of Chemical Sciences, 2 (2), 40‐48.
[9] KWON J. S., YUN S. T., LEE J. H., KIM S. O., JO H. Y., (2010), Removal of divalent heavy
metals (Cd, Cu, Pb, and Zn) and arsenic (III) from aqueous solutions using scoria:
kinetics and equilibrium of sorption, J. of Hazar Mater, 174, 307–313.
[10] POLLARD S. J. T., FOWLER G. D., SOLLARS C. J. and PERRY R., (1992), Lowcost
adsorbents for waste and wastewater treatment, a review, Sci. of Total Environment,
116, 31–52.
[11] SATAPATHY D., NATARAJAN G. S., (2006), Potassium bromated modification of the
granular activated carbon and its effect on nickel adsorption, Adsorption, 12 147‐154.
[12] SLATER, C., AHLERT, R., and UCHRIN, C., (1983), ʺApplications of Revers Osmosis to
Complex Industrial Wastewater Treatmentʺ, Desalination, 48, 171.
[13] SRIVASTAVA, N. K., MAJUMDER, B. C., (2008), Novel biofiltration methods for the
treatment of heavy metals from industrial wastewater. J. Hazard. Mate 1:1‐8.
[14] SRIVASTAVA, V. C., SWAMY, M. M., MALL, I. D, PRASAD, B., MISHRA, I. M. (2006)
Adsorptive removal of phenol by bagasse fly ash and activated carbon: Equilibrium,
kinetics and thermodynamics, Colloids and Surfaces A: Physicochemical and
Engineering Aspects, 272: 89‐104..
[15] WANG S., ANG H. M. and TADE M. O., (2008), Novel applications of red mud as
coagulant, adsorbent and catalyst for environmentally benign processes, Chemosphere,
72, 1621–1635.
******
Determination of Heavy Metals and Nitrate in Drinking Water of Capital
City of Iran and its Side Effects in Public Health
Iman Nazari1, Pegah Abbasifar2, Nasim Pouya3
1 Department of Chemical Engineering, University of Tabriz, Tabriz, IRAN 2 Faculty of Pharmacy, University of Tabriz Medical Science, Tabriz, IRAN 3 Department of Analytical Chemistry, University of Tabriz, Tabriz, IRAN
Abstract Regarding to the dramatic rise of cancer prevalence of cancers in Iran and also base on the
investigations around environmental factors which causes cancer, The air and water
pollution is in high level in Iran’s capital city this issue motivated us to start an investigation
on concentration of heavy metals and nitrate in Tehran’s Tap water, additionally we
investigated the effects of this contaminations on publichealth, it is clear that heavy metals
and also nitrate are causes cancers directly and indirectly, we divided the city to four
districts (1) North, (2) East, (3) West, (4) South and totally collected over 30 samples from
noted districts, we Obvious difference in concentrations, after a study we founded the
reasons of this difference, the old distribution system, non‐standard sewage disposal system,
travel up from contaminated rains, releasing industrial wastes waters without any pre‐
67
treatment, the most important one is the old distribution system, Tehran is an old city hence
distribution system is old too we know that the old water pipes were built from alloys which
containing several of this harmful heavy metals, releasing of this heavy metals from pipes to
the tap water isone of the most Important reasons, as the result we presented the
concentrations by districts and the alternatives to decreasing the level of this contaminations.
Keywords
Drinking water, Water effect on health, Heavy metals concentration, Nitrate concentration,
Flame AAS
References
[1] L. KENNISH. Toxicity of Heavy Metals: Effects of Cr and Se on Human' s Health.
Journal of IndianPublic Health Education, India, (1992) 2:36 – 64
[2] B. S. CONNELL, M. COX, and I. SINGER. Nickel andChromium In: Brunner, F. and
Coburn, J. W. (eds) :Disorders of Minerals metabolism. Academic press, New York,
(1984) Pp. 472 – 532
[3] WHO, 1985b ECETOC, 1988
[4] X. ZHAO, W. H. HÖLL, G. YUN. Eliminationof Cadmium Trace Contaminations
fromDrinking Water. IWA., (2002) 36 (4) :851‐8
[5] O. LESMANA, N. FEBRIANA, F. E. SOETAREDJO, J. SUNARSO, S. ISMADJI. Studies
onPotential Applications of Biomass for theSeparation of Heavy Metals from Water
andWastewater. Bioch. Eng. J., (2009) 44 (1) :19‐41
[6] WHO. Nitrate and Nitrite in Drinking‐Water. World Health Organization, 2011,
WHO/SDE/WSH/07. 01/16/Rev/1
[7] H. A. ELLIOT, M. R. LIBERALI, C. P. HUANG. Competitive Adsorption of Heavy
Metals by Soil. Environ Qual. J., (1986) 15:214‐219
[8] D. W. CONNELL, G. J. MILLER. Chemistry and Ecotoxicology of pollution. John Wiley
& Sons, N. Y., (1984) P. 444‐445
[9] S. M. DAEINIAKI, A. TAKDASTAN, M. A. ZAZOULI, M. SEDDIGHMORTAZAVI.
Application of Nanofiltration Technology in Heavy Metals (Ni, Cu and Zn) Removal
from Wastewater. WWWJ. (2012) (1) :125‐131 [Persian]
[10] J. BUSCHMANN, M. BERG, C. STENGEL, L. WINKEL, M. L. SAMPSON, P. T. K.
TRANG, et al. Contamination of Drinking Water Resourcesin the Mekong Delta
Floodplains: Arsenicand other Trace Metals Pose Serious HealthRisks to Population.
Environ. Int., (2008) 34 (6) :756‐64
[11] Arch Iran Med 2010 13 (2) : 143 – 146
[12] B. V. L’VOV, Fifty Years of Atomic Absorption Spectrometry. J. Anal. Chem., (2005) 60:
382–392
68
******
Lichen Hypogymnia Physodes – Bioindicator Tested for the Determination
of Palladium in Urban Air in Brno, Czech Republic
Komendova, R., Hajdova, J.
Institute of Chemistry and Technology of Environmental Protection, Faculty of Chemistry, Brno
University of Technology, Purkyňova 118, CZ‐612 00, Brno, CZECH REPUBLIC
Abstract
Palladium is a metal with exceptional properties, whose demand for a practical use for the
past several years greatly increased. It is used in electronics, jewelry, medicine, chemical
industry, but also together with platinum and rhodium for its catalytic properties in
automotive catalysts. Now due to the ever increasing mass use of automotive catalytic
converters are becoming increasingly environmental contamination. The platinum group
metals in automotive catalytic converters eliminate toxic exhaust gases (carbon monoxide,
hydrocarbons and nitrogen oxides) generated from the combustion process at non‐toxic
(carbon dioxide, water and elemental nitrogen). Palladium releases into the environment
from automotive catalysts due to the high temperature flue gas, mechanical abrasion, riding
style in and under influence of catalyst poisons [1] in elemental form or in the form of
surface‐oxidized particles. Detectable amounts of palladium were found in all objects of the
environment ‐ in atmospheric aerosol, road and tunnel dust, soils, plants, in aquatic
ecosystems and in river sediments [2, 3]. Palladium is most soluble (compared with Pt and
Rh), mobile and bioavailable. Palladium subject to bioaccumulation and its contents were
found in the root systems of plants, in biological fluids of animals and birds feathers [4]. The
object of the study was to identify and assess the actual contamination of air by palladium in
Brno. The actual processing was preceded by finding optimal conditions for pretreatment of
real samples, SPE preconcentration and optimization of the determination conditions using
electrothermal atomic absorption spectrometry. Was applied form of active biomonitoring
called dry ʺbagʺ monitoring technique, using lichen (Hypogymnia physodes) as bioindicator.
Lichens are poikilohydric organisms that are able to withstand harsh environmental
conditions and stress factors. Their insole is covered with cuticle is no other safety features.
They have root system breathe entire body surface, which allows a large degree of
absorption of hazardous elements. Lichens were located in the immediate vicinity of the nine
roads with heavy traffic, adhering to the inside of the barriers. In order staggered exposure
time were placed in each section three ʺbagsʺ which were collected sequentially after 3, 4 and
5 months.
Keywords
palladium, autocatalyst, lichen, Hypogymnia physodes, SPE, ET‐AAS
Acknowledgements This work was supported by the institution research plan No. FCH‐S‐15‐2869 from the
Ministry of Education, Youth and Sports of the Czech Republic.
References
[1] TWIGG, M. V., Catalysis Today 163 (2011) 33‐41.
69
[2] MELBER, Ch., KELLER, D., MANGELSDORF, I., Environmental Health Criteria 226.
Palladium, World Health Organization, Geneva (2002) 1‐172.
[3] ROSNER, G., COENEN‐STASS, D., KÖNIG, H., Environmental Health Criteria 125.
Platinum, World Health Organization, Geneva (1991) 1‐139.
[4] KIELHORN, J., MELBER, Ch., KELLER, D., MANGELSDORF, I., Int. J. Hyg. Environ.
Helath 205 (2002) 417‐432.
******
UV‐VIS Spectral Characteristics of Humic Substances in Chernozems
Hábová, M., Pospíšilová L.,
Mendel University in Brno, Faculty of Agronomy, Department of Agrochemistry, Soil Science,
Microbiology and Plant Nutrition, Zemědělská 1, CZ‐61300 Brno, CZECH REPUBLIC
Abstract We aimed at evaluation of humic substances quality using visible and ultraviolet
spectroscopy. Object of our study were ten subtypes of Chernozems intensively used in
agriculture. UV‐VIS spectra were recorded within the range 200 nm to 700 nm. Absorbance
indexes were calculated at: 253/203, 253/230, 250/365, 253/410, 465/665 a 255/465 nm. Results
showed differences in absorbance and calculated indexes values between different subtypes
of Chernozems. The lowest absorbance was characteristic Arenic Chernozem and the highest
for Phaeoic Chernozem. One of the most important calculated colour index was the
A465/A665.
Keywords Keywords: Chernozems, humic substances, UV‐VIS spectroscopy
Acknowledgements
Study was supported by the projects IGA IP 29/2015: Effect of soil conditioners on quantity
and quality humic substances content in soil, and NAZV QJ 1210263.
References [1] FASUROVÁ, N. & POSPÍŠILOVÁ, L. (2010). Characterization of soil humic substances
by ultraviolet visible and synchronous fluorescence spectroscopy. Journal Central
European Agriculture Vol. 11, No 3: 351‐358.
[2] DEL VECCHIO & BLOUGH, N. V. (2004) : On the origin of the optical properties of
Humic Substances. Environ. Sci. Technol. 38: 3885‐3891.
70
******
Study of the Effect of Interferents on Spectrophotometric Determination of
Anionic Surfactants
Řezáčová, V., Osinová, P.
Brno University of Technology, Faculty of Chemistry, Institute of Chemistry and Technology of
Environmental Protection, Purkyňova 118, CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
Surfactants are widely used compounds because of their characteristic properties. They
consist of two parts, namely a hydrophilic and a hydrophobic part. They are classified by the
nature of the hydrophilic part as anionic, nonionic, cationic and amphoteric. The hydrophilic
part of anionic surfactants generally consists of either sulfonate or sulfate or carboxyl groups.
The anionic surfactants containing linear alkylbenzene sulfonates are widely used in laundry
detergents and household cleaners. Anionic surfactants are usually determined by
spectrophotometric method [1, 2] based on the association of the anionic surfactants with the
cationic methylene blue dye. The formed ionic pair is extracted into chloroform and the
absorbance of blue complex is measured at 650 nm. Methylene bleu is a heterocyclic aromatic
compound used in biology and chemistry. However, this dye may form colored complexes
together with different types of analytes, not only with anionic surfactant. In this work, the
effect of several interference substances on spectrophotometric determination of anionic
surfactants is studied. Five interferents from the variety of many possible were chosen.
Namely, diclofenac, that may be determined spectrophotometrically in blue complex with
methylene blue [3] nitrates, which may transfer methylene blue into the chloroform phase [4]
cationic surfactants, as they create more stable complex with anionic surfactants than
methylene blue [5] fenol, as the expected interferent [6] and humic acid, because of its
interesting structure and possible presence in sampling water.
Keywords anionic surfactants, methylene blue, spectrophotometry
Acknowledgements
This study was supported by the Grant No. FCH‐S‐15‐2869 from the Ministry of Education,
Youth and Sports of the Czech Republic.
References [1] ISO 7875‐1, 1996. Water quality. Determination of Surfactants. Part 1:Determination of
Anionic Surfactants by Measurement of the Methylene Blue Index (MBAS). ISO/TC 147.
[2] ČSN EN 903 (75 07534). Water quality: Determination of Anionc Surfactants by
Methylene Blue (ISO 7875‐1:1984 modified). Praha: ČNI, 1996. [in Czech]
[3] ČAPKA L., ZLÁMALOVÁ GARGOŠOVÁ H., VÁVROVÁ M., URBÁNKOVÁ L. : Chem.
Listy 107, 550 (2013). [in Czech]
[4] GEORGE A. L., WHITE G. F. : Environ. Tox. Chem. 18 (10), 2232 (1999).
[5] EATON A. D., CLESCERL L. S., GREENBERG A. E. in: Standard Methods for the
Examination of Water and Wastewater. 20th ed. American Public Health Association,
United Book Press, Inc., 1999. ISBN 0‐87553‐235‐7
71
[6] Designation: D 2330 – 02. Standard Test Method for Methylene Blue Active Substances 1.
An American National Standard, 2002. Available at: http://library. sut. ac.
th:8080/astm/cd11022005/PDF/D2330. pdf
******
Effects of Organic Lining Materials and Plastic Pipes to the Chemical
Content of Drinking Water
Johanna Rajasärkkä, Jonáš Lašňák, Luděk Bláha
Masaryk University, Research Centre fo Toxic Compounds in the Environment (RECETOX),
Kamenice 753/5 pavillion A29, 625 00 Brno, CZECH REPUBLIC
Abstract
Clean drinking water is among the most important health issues in the world. Chemical
contamination of drinking water can occur at several stages of its journey from source to tap.
Drinking water distribution system is one plausible source of contaminants. Since water can
reside in the distribution system for several days before reaching the user, the materials in
distribution system have a great impact on water chemical content (Kekki et al. 2007).
Organic materials used in distribution system include pipes made of plastics, such as
polyethylene (PE) and polyvinylchloride (PVC), as well as pipe inner surface lining
materials, for example epoxy resins. Plastic pipes are common especially in new construction
sites, whereas epoxy lining is an increasingly popular method for renovating old water
pipes. In recent years lining technique has been applied to household drinking water pipes
due to its ease and suitability for narrow pipe diameters. The inner surface of the pipes are
coated in situ using spray‐on or cured‐in‐place techniques (Ellison et al 2010). Organic pipe
materials can leach chemicals with harmful health effects or unwanted taste or odor. Epoxy
resins are known to leach bisphenol A or F among other chemicals (Bruchet et al 2014,
Satchwill 2002). The quality of lining process is important: poorly cured lining is very likely
to leach chemicals (Pelto‐Huikko&Kaunisto 2011). Plastic PE pipes leach, for example,
methyl‐tertbutyl ether (MTBE), ethyl‐tertbutyl ether (ETBE), tert‐butanol, 2, 4‐di‐tert‐butyl
phenol (DTBP), and BTEX (Lund et al. 2011, Skjevrak et al. 2003, Kowalska et al. 2011). PVC
pipes can leach vinyl cholride monomer (VCM) and organotin or lead metal stabilizers
(Kekki et al. 2007, Kowalska et al. 2011). Organic materials leach chemicals especially at the
beginning of their use. However, their ageing process and long term leaching properties are
poorly understood. In this research project chemicals in drinking water from buildings with
different age epoxy coated or PE pipes are studied. Samples from drinking water treatment
plants and municipal distribution system serve as comparisons for evaluating the effect of
pipe materials to water quality. Samples are collected in the Czech Republic and Finland.
Several organic volatile and non‐volatile chemicals are monitored. Water samples of 1 L are
extracted using Oasis HLB solid phase cartridges (method details by Bono‐Blay et al. 2012),
and analyzed with liquid chromatography for bisphenol A and F, their diglycidyl ethers,
nonyl phenol, and nonyl phenol ethoxylates. Gas chromatography is used to detect
phthalates and volatiles such as BTEX, DTBP, MTBE, ETBE, TBA, VCM. In addition, total
organic carbon and total metals are measured. The investigation covers the impact of each
pipe material and its age on water chemical burden, including assessment of possible risk of
chemicals in different materials to humans and the environment.
72
Keywords
Drinking water, distribution system, plastic pipes, epoxy resin, lining materials, bisphenol A,
volatile organic chemicals
Acknowledgements
The project is financed from the SoMoPro II programme. The research leading to these
results has acquired a financial grant from the People Programme (Marie Curie action) of the
Seventh Framework Programme of EU according to the REA Grant Agreement No. 291782.
The research is futher co‐financed by the South‐Moravian Region. The abstract reflects only
the author´s views and that the Union is not liable for any use that may be made of the
information contained therein. This work is carried out with the support of core facilities of
Research Centre for Toxic Compounds in the Environment (RECETOX) – National
Infrastructure for Research of Toxic Compounds in the Environment, project number
LM2011028, funded by the Ministry of Education, Youth and Sports of the Czech Republic
under the activity „Projects of major infrastructures for research, development and
innovations” and project LO1214.
References
[1] KEKKI T., KEINÄNEN‐TOIVOLA M., KAUNISTO T., LUNTAMO M. 2007. Report
(WANDER Nordic Water and Materials Institute). ISBN 978‐952‐99840‐1‐5 (PDF).
[2] ELLISON D., SEVER F., ORAM P., LOVINS W. et al. 2010. Report (EPA/Water Research
Foundation). ISBN 9781605730943.
[3] BRUCHET A., ELYASMINO N., DECOTTIGNIES V., NOYON N. 2014. Water Sci
Technol: Water Supply 14:383‐389.
[4] SATCHWILL, T. 2002. Report by The City of Calgary, Engineering and Environmental
Services Department, Waterworks Division.
[5] PELTO‐HUIKKO A., KAUNISTO T. 2011. Report (WANDER Nordic Water and
Materials Institute). ISBN: 978‐952‐67166‐7‐1.
[6] LUND V., ANDERSON‐GLENNA M., SKJEVRAK I. STEFFENSEN I. 2011. J Water
Health 9:438‐497.
[7] SKJEVRAK I., DUE A., GJERSTAD K., Herikstad H. 2003. Water Res 37:1912‐1920.
[8] KOWALSKA B., KOWALSKI D., ROZEJ A. 2011. J Water Supply Res T 60:137‐146.
[9] BONO‐BLAY F., GUART A., de la FUENTE B., PEDEMONTE M. et al. 2012. Environ sci
pollut r 19 (8) :3339‐49.
******
Testing of Special Binders for Immobilization of Toxic Elements
Staněk, T., Sulovský, P.
1Research Institute for Building Materials, Hněvkovského 65, 617 00 Brno, CZECH REPUBLIC 2Department of Geology, Faculty of Science, Palacký University, tř. 17. listopadu 12, 771 49
Olomouc, CZECH REPUBLIC
Abstract The paper deals with development of cementitious binders that would be able to efficiently
immobilize toxic elements contained in various types of wastes. The basic component of the
proposed binders are clinkers with phosphorus incorporated into the structure of clinker
73
silicates, mixtures of cement with ash containing hydroxylapatite, and belite‐rich clinkers
activated with sulfate anions. The prepared binders were mixed with water doped with
various toxic elements after a defined period of cement stone hydration the test beams were
subjected to long‐term testing of leachability of individual toxic elements. The research
methods involved besides leaching tests also optical and electron microscopy.
Keywords
cementitious binders, toxic elements, immobilization
Acknowledgements
This research was done within the project No. P104/12/1494 financed by the Czech Science
Foundation.
******
Development and Validation of Spectrophotometric Method for
Determination of Biochemical Oxygen Demand in Wastewater
Diana Yudin1*, Anton Yudin2, Andreea Iordache3, Claudia Sandru3, Sonia Suvar1, Monica
Culea1
1Univ. Babes‐Bolyai, Dept. of Physics, 1 Kogalniceanu Str, 400084, Cluj‐Napoca, ROMANIA E‐mail:
diana_f79@yahoo. com 2Wolf Kunststoff Gmbh, Heisenbergstr. 63‐65, 50169, Kerpen, GERMANY
3National R&D Institute for Cryogenics and Isotopic Technologies, Uzinei Str. 4, 240050, Rm.
Valcea, ROMANIA
Abstract
Water is an essential component of life on the Earth. All living organisms need water as
internally or living environment. Besides drinking water, there is another important class of
water, wastewaters, resulted from household and sanitary land or industrial uses.
Wasteaters from household are charged with organic substances, ammonia compounds,
surfactants and fats. Wastewaters from industrial use contain compounds that came from
technological processes. In Romania, requirements from quality of wastewater depend from
the place in which are discharged this waters. Romanian orders, No. 352/2005, prescribe
technical norms (regulation), by NTPA 001 wastewaters qualities that are discharge in
natural receivers (rivers, lakes) and NTPA 002 for sewage network or wastewaters treatment
plants. A valuble parameter regarding biodegradability, and who indicate the type of
treatement process is biochemical oxygen demand. To validate a method, it is basically the
process of defining an analytical requirement and confirming that the method under
consideration has capabilities consistent with what the application requires1. The method
gave good validation parameters for linearity, the correlation coefficient being 0. 99. Limit of
detection and quantification were also good. To prove that the spectrophotometric method is
proper for the determination of BOD, they were also tested precision and accuracy and that
showed valuble results. The measurement of BOD was evaluated in a range between 3÷25
ppm. The measurement of BOD for determination of wastewaters quality is accreditated by
Romanian Accreditation Association – RENAR, which recognize our laboratory competence.
74
Keywords
validation parameters, accreditation, Romanian orders, wastewater, biochemical oxygen
demand.
Acknowledgements
This work was supported by National Research and Development Institute for Cryogenics
and Isotopic Technologies – ICIT Rm. Valcea, Romania.
References
[1] Eurachem Guide ‐ The Fitness for purpose of Analytical methods, Second Edition,
(2014).
[2] FLORESCU D., IORDACHE A. M., COSTINEL D., HORJ E., IONETE R. E., CULEA M. :
Rom. Journ. Phys., 58 (1‐2), p. 211, (2013).
******
Activity of Biomimetic Antimicrobial Polymers Against Cyanobacteria and
Green Algae
Mikula, P.1, Minarikova M.1, Sovadinova, I.1, Nadres, E.2, Takahashi, H.2, Kuroda, K.2,
Babica, P.1
1Masaryk University, Research Centre for Toxic Compounds in the Environment (RECETOX),
Kamenice 753/5, CZ‐625 00 Brno, CZECH REPUBLIC 2University of Michigan, School of Dentistry, Department of Biologic and Materials Sciences, 1011
North University Avenue, Ann Arbor, MI‐48109, USA
Abstract Massive proliferations of cyanobacteria in aquatic ecosystems reduce water quality and
impair the use of water reservoirs for drinking water supply, recreational activities,
agricultural or aquacultural purposes. Most commonly used methods for control of
cyanobacterial growth include chemical treatments, such as application of aluminum or iron
salts, which might be toxic/dangerous to non‐target aquatic organisms. Other approaches
suitable for cyanobacteria management, such as biological or physical methods, are usually
less effective in comparison with the chemical treatment and often associated with higher
costs. Water‐soluble synthetic polymeric compounds represent a possible alternative to
traditional algicides. One of the most promising classes of such polymers is synthetic mimics
of naturally occuring host‐defence antimicrobial peptides found in the innate immune
system. Peptide‐mimetic antimicrobial polymers of interest are based on convential
methacrylate polymers and have been shown to elicit potent activity against heterotrophic
bacteria with minimal toxicity to mammalian cells. Preparation of these polymers is cost‐
effective and facile, allowing industrial‐scale production. Moreover, the versatility of
methacrylate polymer chemistry enables a wide exploration of the structural parameters
which can be finely tuned to optimize their molecular properties to increase activity and
selectivity against cyanobacteria over non‐target aquatic organisms. In this study, we
investigated effects of eight biomimetic methacrylate polymers on several species of
cyanobacteria (Synechococcus elongatus, Microcystis aeruginosa) and green algae
(Pseudokirchneriella subcapitata, Desmodesmus quadricauda). In algal growth inhibition
75
assays, several antimicrobial methacrylate polymers were found to be potent and highly
selective cyanocidal/cyanostatical agents with significantly lower toxicity to green algae.
Additionally, effects of these polymers on other non‐target aquatic organisms are being
investigated using ecotoxicological bioassays in order to further evaluate their potential for
cyanobacteria management in environmental and water treatment applications.
Keywords
Algicides, Antimicrobial activity, Cyanobacterial water blooms, Cyanobacteria management,
Cyanocides, Synthetic biomimetic polymers
Acknowledgements
This project was supported by the National Sustainability Programme of the Czech Ministry
of Education, Youth and Sports (LO1214), RECETOX research infrastructure (LM2011028),
and NSF CARRER Award (DMR‐0845592).
******
Organic Contaminants in the Indoor Environment: Linking Sources and
Human Exposure
Melymuk, L.1, Bohlin Nizzetto, P.2, Vojta, S.1, Klanova, J.1
1RECETOX, Faculty of Science, Masaryk University, Kamenice 5, 62500 Brno, Czech Republic[2]
Norwegian Institute for Air Research, Instituttveien 18, NO‐2027, Kjeller, NORWAY
Abstract
Elevated levels of pollutants in indoor environments are gaining recognition as important
risk factors for human health worldwide. The contribution of indoor air pollution to total
human exposure to pollutants is an important consideration, since people, particularly in
more developed countries, spend >90% of their time indoors and the indoor air
concentrations of some pollutants are orders of magnitudes higher than those outdoors.
Additionally, indoor air pollution in schools, hospitals, retirement homes and other sensitive
environments affects population groups that are particularly vulnerable due to their health
status and a large amount of time spent indoors. Despite this, the public health awareness of
indoor air pollution has, until recently, lagged behind that of outdoor air pollution. The
contaminant load in indoor environments is significant, as many pollutants of emerging
concern, such as brominated and fluorinated compounds, phthalates, organophosphate
esters, parabens and phenols, have mainly indoor sources. Many of these compounds are
used in consumer products and building materials, and thus their primary emissions are
directly to indoor environments, and a main route of human exposure is through the indoor
environment. This presentation will give an overview of the current state of the science
linking consumer and building products with indoor levels of pollutants, and ultimately
with human exposure. A particular focus will be given to the range of flame retardant
compounds that are measured indoors, and the relationship between the sources of these
compounds, their distribution in indoor media (air, dust, surface films) and human exposure
pathways. Case study examples on the spatial and seasonal variability of indoor pollutants
will demonstrate the techniques used in determining the overall picture of indoor exposure,
76
and integrated assessment of the currently available data will show the challenges and future
research directions in the field of indoor pollution.
Keywords
indoor environments, organic pollutants, human exposure
Acknowledgements
This research was supported by the European Social Fund and state budget of the Czech
Republic (project ʺEmployment of Best Young Scientists for International Cooperation
Empowerment” CZ. 1. 07/2. 3. 00/30. 0037) and the RECETOX research infrastructure was
supported by the projects of the Czech Ministry of Education (LO1214 and LM2011028).
******
Environmental Radioactivity at Tritium Removal Facility‐ ICIT
Mihaela Vladu
University of Pitesti, Faculty of Mechanics and Technology, 110040 Pitesti Str. Targul din Vale, nr.
1, Arges, ROMANIA
Abstract
Romanian national nuclear regulations require that for every new nuclear installation a
preoperational program for the monitoring of the environmental radioactivity around the
installation should start at least two years before the commissioning of the installation. The
goal of this paper is to present the results recorded in the last year on levels of the
beta/gamma radioactivity around the Pilot Plant for Tritium and Deuterium Separation at
ICIT (Institute for Cryogenic and Isotopic Technologies) Ramnicu Valcea. Hundreds of
samples of soil, sediment, water and vegetation, over a circle of 5 km radius around ICIT,
have been collected and analyzed according to the frequencies established within the
preoperational program. The results obtained for water samples are presented here.
Keywords
environmental radioactivity, gamma, beta, water.
Acknowledgements
This work was supported by : Project POSDRU/159/1. 5/S/138963– „Performanţă sustenabilă
în cercetarea doctorală şi post doctorală ‐ PERFORM”
References
[1] Fundamental Norms for Radiological Safety (NSR 01)
[2] Norms for the monitoring of environmental radioactivity in the vicinity of a nuclear or
radiological facility (NSR 22)
[3] ISO 10703:2007 – Water quality: Determination of the activity concentration of
radionuclides. Method by hight resolution gamma‐ray spectromentry
[4] ISO 9697:2008 – Water quality: Measurement of gross beta activity in non saline water.
Thick source method.
77
******
Study on Metal Contamination in Water, Sediments and Soils Samples from
N‐W Romania, using ICP‐MS
Voica, C.1, Iordache, A. M.2, Suvar, S.3, Culea, M.3, Ionete, R. E.2
1National Institute for Research and Development of Isotopic and Molecular Technologies, 67‐103
Donat, RO‐400293 Cluj‐Napoca, ROMANIA 2National Institute for Research and Development of Cryogenics and Isotopic Technologies, 4 Uzinei,
Raureni, RO‐240050 Ramnicu Valcea, ROMANIA 3Babes Bolyai University, Faculty of Physics, 1 M. Kogalniceanu, RO‐400084, Cluj‐Napoca,
ROMANIA
Abstract A study was carried out to determine the accumulation of trace metals in water, sediments
and soil from several locations in the Northwest part of Transylvania region (Cluj and Salaj
counties ‐ Romania), using a tool for rapid elemental determinations, the semi‐quantitative
analysis by inductively coupled plasma mass spectrometry (ICP‐MS). A significant number
of metals were identified in the investigated samples, part of them being recognized as
potentially toxic (e. g. Pb, Cd, As, Hg). Except for those elements considered as
micronutrients (e. g. Fe, Cu, Zn, Mn) found in water samples at concentrations that can reach
tens of μg/l, the toxic metal concentrations were found lying in the range of several μg/l in
most investigated waters, being within permissible limits. A seasonal variation of the metals
content was also observed water samples collected in the same area at different time periods
of the year registered higher concentrations of Ca and Mg in the warmer months, while in
the colder months Ca, Mn, Ti, V and Fe showed higher values. Moreover, a comparison of
the metals concentration in sediment, soil and vegetation samples coming from the
surrounding areas of the same water reservoir revealed a stronger concentration of rare and
toxic metals in sediments than in soil and vegetation.
Keywords
elemental analysis, ICP‐MS, sediment, soil, water quality
Acknowledgements
This work was possible due to the financial support of the Sectorial Operational Program for
Human Resources Development 2007‐2013, co‐financed by the European Social Fund, under
the project number POSDRU/159/1. 5/S/132400 with the title „Young successful researchers –
professional development in an international and interdisciplinary environment”.
References
[1] S. MELAKU, T. WONDIMU, R. DAMS, L. MOENS, L. (2005). Multi‐element analysis of
Tinishu Akaki River Sediment, Ethiopia, by ICP‐MS after microwave assisted digestion,
Canadian Journal of Analytical Sciences and Spectroscopy, 2005, 50 (1), pp 312.
[2] H. CHEN, E. DABEK‐ZLOTORZYNSKA, E. PAT, N. HASSAN, M. LANOUETTE,
Evaluation of semiquantitative analysis mode in ICP‐MS, Talanta, 2008, 74, pp. 1547
78
******
Comparison of Separation Efficiency at Different Levels of Technological
Line For Drinking Water Treatment at Švařec
Repková M., Šípková, H.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
In recent years the analyzes keeping us updated on the content of biodegradable organic
substances and the possibility of secondary propagation of microorganisms in drinking
water have come into the center of our attention. The drinking water that does not allow
propagation of microorganisms even at the minimum residual concentrations of
disinfectants is labeled as biologically stable water. Permanganate chemical oxygen demand
(CODMn), absorbance at 254 nm (A254) and culturable microorganisms are commonly
determined as frequently monitored parameters that indicate the presence of organic
substances[1, 2]. This work deals with comparing separation efficiency of individual degrees
of technological processes of drinking water treatment in Švařec water treatment plant and
focuses on the presence of organic substances in treated water and biological stability of this
water. The determination of assimilable organic carbon (AOC) using the reference strain of
Pseudomonas fluorescens (P17) was introduced to determine the biological stability of water.
The highest values of CODMn and A254 were measured in raw water. During the water
treatment a gradual decrease in both indicators was observed. The largest decrease was
recorded after the coagulation with sand filtration. Sanitation and alkalization did not prove
a significant impact on the values of the measured indicators of CODMn and A254. The
highest biological recovery was recorded in July. The water was dominated by the
filamentous cyanobacteria of Aphanizomenon genus that subjects to easy disintegration into
individual fibers and cell lysis. The results show a gradual reduction in the number of
individuals and cells in the water surrounding the technological line. Preozonization was
followed by a slight decrease in the numbers of organisms caused probably by the decay of
some cells due to ozone exposure. Coagulation with sand filtration resulted in the removal of
most organisms from water. Further elimination occurred at GAU. The measured AOC
concentration in raw water ranged from 33 to 58 g.l‐1. The observed changes in AOC content along the water treatment technological line corresponded with available resources. The
obtained results prove good separation efficiency of the coagulation followed by sand
filtration when a significant reduction in all monitored indicators was noticeable. The GAU
filters that reduced the values of the majority of the analyzed parameters also participated in
separation. As a part of the research biological stability of water using the AOC indicator
was monitored. This indicator evaluates water quality in the terms of the potential
development of the microorganisms with secondary reproduction.
Keywords
drinking water treatment, separation efficiency, biological stability, chemical oxygen
demand, assimilable organic carbon
79
Acknowledgements
This work was supported by the institution research plan No. FCH‐S‐15‐2869from the
Ministry of Education, Youth and Sports of the Czech Republic.
References
[1] VAN DER KOOIJ, Dirk. Assimilable Organic Carbon (AOC) in Drinking Water. In
Drinking Water Microbiology. Brock/Springer Series in Contemporary Bioscience, 1990,
pp. 57‐87. ISSN: 1432‐0061.
[2] WANG, Q. TAO, T. XIN, K. The Relationship between Water Biostability and Initial
Bacterial Growth Variations to Different Organic Carbon Concentrations. In Procedia
Engineering. Vol. 89, 2014, pp. 160‐167. [online]. [cit. 2015‐03‐28]. ISSN: 1877‐7058.
Dostupné z: http://www. sciencedirect. com/science/article/pii/S1877705814022875.
******
Contamination of Environment by Musk Compounds
Tobková, L., Švestková, T., Vávrová, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Synthetic musk compounds are artificial organic substances commonly used as fragrant
constituents of personal care products as perfumes, cosmetics, detergents, in‐house cleaning
and washing agents. Due to the large area of their applications and persistence, they have
leaked into all parts of ecosystem, especially aquatic one. Studying these compounds, their
properties and fate in the different parts of ecosystems have come into the center of attention
in the last years. The aim of this research was to determinate five representatives of
macrocyclic musk compounds (habanolide, exaltolide, ambrettolide, musk MC4 and
ethylene brassylate) in waste water samples from influent and effluent of three waste water
treatment plants (WWTP Brno‐Modřice, WWTP Lednice and WWTP Mikulov). One of the
main tasks was to optimize the method for the determination of selected musk compounds
in waste water and evaluation and interpretation of the results. Solid phase micro extraction
(SPME) technique was used for the extraction of analytes, consequently gas
chromatography‐mass spectrometry was used for analysis of the selected analytes.
Following evaluation the removal efficiency of musk compounds in the waste water
treatment plant was assessed. The concentration of selected musk compounds was
determined in the range of units to hundredths ng.ml‐1 in waste water. Habanolide,
exaltolide and ethylene brasylate were found on the influent of WWTP Brno‐Modřice. Only
habanolide was found on the influent of WWTP Mikulov and Lednice. Ambretolide and
musk MC4 were not detected anywhere. Musk compounds in very small concentrations or
under their detection limits were found on the effluent. The efficiency of cleaning process in
waste water treatment plant, calculated from experimental data ranged from 76. 03 to 88.
33 %.
Keywords
Macrocyclic musk compounds, fragrance, waste water, waste water treatment plant, solid‐
phase microextraction, gas chromatogramy‐mass spektrometry
80
Acknowledgements
This study was supported by the project FCH‐S‐15‐2869 from the Ministry of Education,
Youth and Sports of the Czech Republic.
References
[1] SOMMER, C. : The Role of Musk and Musk Compounds in the Fragrance. Syntehitic
Musk Fragrances in the Enviroment. 2004
[2] ABRAMSSON‐ZETTERBERG, L. SLANINA, P. : Macrocyclic musk compounds ‐ an
absence of genotoxicity in the Ames test and the in vivo Micronucleus assay. Toxicology
Letters. 2002, vol. 135, 1‐2, s. 155‐163. DOI: 10. 1016/s0378‐4274 (02) 00257‐6
[3] ZHANG, X. YAO, Y. ZENG, X. QIAN, G. GUO, Y. WU, M. SHENG, G. FU, J. : Synthetic
musks in the aquatic environment and personal care products in Shanghai, China.
Chemosphere. 2008, vol. 72, issue 10, s. 142‐155. DOI: 10. 1021/bk‐2001‐0791. ch008
[4] VALLECILLOS, L. POCURULL, E. BORRULL, F. : An automated headspace solid‐phase
microextraction followed by gas chromatography–mass spectrometry method to
determine macrocyclic musk fragrances in wastewater samples. Analytical and
Bioanalytical Chemistry. 2013, vol. 405, issue 29, s. 9547‐9554. DOI: 10. 1007/s00216‐013‐
7375‐2
******
Problems of Contamination of Wastewater Drugs
Vávrová, M., Dvořáková, P., Sýkora, R., Clemensová, G., Lisá, H., Olejníčková, Z.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
This work focuses on the occurrence of drug residues in the environment. Non‐steroidal anti‐
inflammatory substances represent a group of pharmaceuticals that undergoes progressive
development and finds its frequent and constant applications, particularly in human
medicine. The risk of their penetration into the environment, especially its water
compartment, is rising during recent years. This work concentrates on these non‐steroidal
anti‐inflammatory drugs (salicylic acid, ibuprofen, caffeine, naproxen, ketoprofen,
diclofenac) in waste water. The aqueous environment contaminated with pharmaceutical
residues has become the most affected environmental compartment. These harmful
substances leak into water mainly from sewage treatment plants, which are able to eliminate
them only partially. The work also deals with the determination of sulfonamides and
tetracyclines in waste waters. Sulphonamides and tetracyclines are widely used in human
and veterinary medicine. This thesis sheds light on the determination of macrolide
antibiotics – with the strong accent on erythromycin, clarithromycin and roxithromycin in
wastewater. Recently these drugs rank among frequently prescribed pharmaceuticals. We
focused mainly on two estrogenic hormones – estradiol and ethinylestradiol. Sulphonamides
and tetracyclines are biologically active compounds which block biological processes in
waste water treatment plants. These substances can influence microorganisms in the
environment. They penetrate into the environment from industrial production, households,
hospitals, veterinary clinics and fish farms. Sulfonamide antibiotics, which are used in the
81
treatment of urinary and respiratory tract infections as well as in the treatment of other
infectious diseases, were chosen as target compounds. The method was optimized and
elaborated using model water samples. This method was used for the determination of the
analytes contained in real water samples. Waste water samples were collected from the
large‐scale wastewater treatment plant (WWTP) in Brno‐Modřice and WWTP in Podivín,
Pohořelice, Hustopeče, Valtice, Lednice and Mikulov. Solid phase extraction (SPE) was used
for the real sample treatment and their pre‐concentration. The determination itself was
performed using high performance liquid chromatography withmass spectroscopy method
(LC‐MS) or gas chromatography with mass spectroscopy method (GC‐MS) after
derivatization. These optimized methods were applied for the analysis of real samples.
Keywords
drugs, nonsteroidal antiinflammatory substances, hormones, antibiotics, gas
chromatography, liquid chromatography, mass spectrometry
Acknowledgements
This study was supported by the project FCH‐S‐15‐2869 from the Ministry of Education,
Youth and Sports of the Czech Republic.
References
[1] HERNANDO, M. D. et al. : Environmental risk assessment of pharmaceutical residues in
wastewater effluents, surface waters and sediments. Science Direct. 2005, vol. 69, s. 334‐
342.
[2] MICHAEL, I. et al. : Urban wastewater treatment plants as hotspots for the release of
antibiotics in the environment: A review. Water Research. 2013, vol. 47, s. 957 – 995.
HIRSCH, R., et al. Occurrence of antibiotics in the aquatic environment. The Science of
the Total Environment. 1999, no. 225, s. 109‐118.
[3] DÍAZ‐CRUZ, M. S. LÓPEZ DE ALDA, M. J. BARCELÓ, D. Environmental behavior and
analysis of veterinary and human drugs in soils, sediments and sludge. Trends in
Analytical Chemistry. 2003, vol. 22, no. 6, s. 340‐351.
[4] KOSJEK, Tina a Ester HEATH. Applications of mass spectrometry to identifying
pharmaceutical transformation products in water treatment. TrAC Trends in Analytical
Chemistry. 2008, vol. 27, issue 10, s. 807‐820. DOI: 10. 1016/j. trac. 2008. 08. 014.
[5] IRMAK, Sibel, Oktay ERBATUR a Aydin AKGERMAN. Degradation of 17‐estradiol and
bisphenol A in aqueous medium by using ozone and ozone/UV techniques. Journal of
Hazardous Materials. 2005, vol. 126, issue 1‐3, s. 54‐62. DOI: 10. 1016/j. jhazmat. 2005. 05.
045.
[6] ZHAO, Yaping, Jiangyong HU a Wei JIN. Transformation of Oxidation Products and
Reduction of Estrogenic Activity of 17‐Estradiol by a Heterogeneous Photo‐Fenton
Reaction. Environmental Science. 2008, vol. 42, issue 14, s. 5277‐5284. DOI: 10.
1021/es703253q.
82
******
Occurence of Organic Compounds in Tar Produced from Biomass
Combustion and Gasification
Hájek, R., Chytil, V., Vávrová, M., Lisý, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC)
Abstract
In recent times the global effort is made to find such a source of energy which would replace
the use of fossil fuels for another, possibly renewable technology. Biomass is the most
common form of renewable energy. Biomass combustion counts among basic technological
procedures. Another way of biomass processing comprises of gasification techniques, which
leads to production of combustible gas mixture usable in cogeneration devices. These
thermo‐chemical conversion processes contribute no ʺnewʺ carbon dioxide to the atmosphere
and therefore can be considered as a realtively pure way of energy generation. However,
there are still some potentially harmful substances formed as for example fine dust particles,
inorganic nitrogen and sulphur compounds. Also residual amounts of organic compounds,
especially phenols, volatile compounds (BTEX), organic acids, alcohols, esters and polycyclic
aromatic hydrocarbons (PAH), cause difficulties both in combustion and gasification
facilities and in the environment. These substances condense as a complex mixture known as
tar. Tar composition depends on many conditions, particularly on the fuel type, its humidity
and the operating temperature. From this reasons it is essential to develop preparation and
analytical methods for tar analysis in order to optimize tar production processes and increase
the economical and ecological potential of this technology. Within the scope of this work the
analysis of tar samples from different materials was performed. As an appropriate analytical
method the gas chromatography combined with flame ionization detection (GC‐FID) and
time‐of‐flight mass spectrometry (GC‐TOF‐MS) was chosen. The concentrations of volatile
organic compounds known as BTEX, polycyclic aromatic hydrocarbons (PAH) and phenolic
compounds were assessed.
Keywords
biomass combustion, biomass gasification, tar, BTEX, polycyclic aromatic hydrocarbons,
phenols, gas chromatography, mass spectrometry
References
[1] MCKENDRY, P. Energy production from biomass (part 2) : conversion technologies.
Bioresource Technology. 2002, vol. 83, issue 1, pp. 47‐54. DOI: 10. 1016/s0960‐8524 (01)
00119‐5.
[2] LI, Ch., SUZUKI, K. Tar property, analysis, reforming mechanism and model for
biomass gasification ‐ An overview. Renewable and Sustainable Energy Reviews. 2009,
vol. 13, issue 3, s. 594‐604. DOI: 10. 1016/j. rser. 2008. 01. 009.
[3] DEMIRBAŞ, A. Biomass resource facilities and biomass conversion processing for fuels
and chemicals. Energy Conversion and Management. 2001, vol. 42, issue 11, s. 445‐494.
DOI: 10. 1016/b978‐012410950‐6/50014‐3.
83
[4] NOLLET, L. M. Chromatographic analysis of the environment. 3rd ed. /. Boca Raton:
CRC/Taylor, 2006, xx, 1297 p. Chromatographic science, v. 93. ISBN 08‐247‐2629‐4.
******
Hormones in Drinking and Waste Water
Čáslavský, J., Vávrová. M., Remerová, M., Jurasová, L.
Institute of Chemistry and Technology of Environmental Protection, Faculty of Chemistry, Brno
University of Technology, Purkyňova 118, CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
Hormones in organisms of mammals play important role of chemical signalling necessary for
keeping of the homeostasis and guiding for the proper growth and development. Many of
compounds present in the environment as contaminants could after entering the living body
negatively influence the hormonal system by interfering with the hormones present in the
organism – they can turn on, shut off or modify response to signals that hormones carry. The
resulting effects could be very diverse: abnormal function and appearance of the thyroid
gland, decreased fertility, quality and quantity of sperm, feminization of males,
masculinization of females, decreased pup survival, changes in the immune system function,
behaviour changes, malformations of the sexual organs, altered sex ratio and in the worst
case even disappearance of populations. Compounds showing these effects include
industrial chemicals (e. g. polychlorinated biphenyls, polychlorinated diphenylethers,
polybrominated diphenylethers) and byproducts (polychlorinated dibenzo‐p‐dioxins and
furans), pesticides and insecticides (DDT, permethrin), plastic softeners (phthalates),
phytoestrogens (genistein, daidzein), pharmaceuticals (mainly contraceptives), compounds
contained in detergents, cleaning agents, cosmetics, compounds produced during cooking,
heavy metals and their derivatives (tin and tributyltin in harbours) and some others. Our
study was focused on the occurrence of contraceptives in waste water and also in drinking
water. Samples of waste water were collected at the WWTP in the town of Břeclav with
capacity of cca 50 thousands of EI. 24‐hour mixed samples were taken at inflow and outflow
of the WWTP in duration of one week. Hormones estriol, estradiol, ethinylestradiol, estron
and diethylstilbestrol were found to be present at levels above the LOQ values. Removal
efficiency of the cleaning process for these compounds varied between 75 – 85 %. Samples of
drinking water were collected at the treatment plan of Mostiště, where raw water from
valley reservoir is used for preparation of drinking water. At this place both active sampling
and passive sampling by POCIS type samplers were applied. At collected samples estriol,
estron and alpha‐estradiol were identified and quantified, whilst beta‐estradiol,
diethylstilbestrol, progesteron and norethindron were only identified, because their
concentrations were below their LOQ values.
Keywords
waste water, drinking water, hormones, passive sampling, liquid chromatography, mass
spectrometry
84
Acknowledgements
This work was supported by the project No. FCH‐S‐15‐2869 “Assessment of the entry of new
contaminants to the environment” from Ministry of education, youth and sports of the Czech
Republic.
******
Ecotoxicological Evaluation of Polymeric Substances
Zlámalová Gargošová, H., Milatová, M., Kučera, F.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Polymers or their additives may become parts of a wide range of products. After the end of
life cycle useful parts of the products are recycled but significant part becomes communal
waste. According to of European directive REACH it is therefore necessary to evaluate not
only chemicals, but also additives and products in terms of their impact on the environment.
For these purposes ecotoxicity test are used, which allow prediction of effects of tested
compounds on the environment. Via ecotoxicity tests the effects of polypropylene grafted by
itaconic anhydride and maleic anhydride on the environment were assessed, as well as that
of their additives ‐ maleic anhydride and itaconic anhydride. Polymer additives were tested
in aquatic arrangement via animal and plant testing organisms. Plant organisms were used
in the following tests: the root elongation inhibition test on Sinapis alba, the root elongation
inhibition test on Allium cepa L. and the semi‐chronic toxicity test on Lemna minor L.
Aquatic animal organisms were used for the tests of acute toxicity THAMNOTOXKIT FTM
on the Thamnocephalus platyurus and acute DAPHTOXKIT FTM on Daphnia magna. The
tests on seawater organisms Artemia salina was also used. Grafted polypropylene substances
are poorly water soluble and, therefore, were tested in a contact arrangement, via
phytotoxicity test on lettuce Lactuca sativa. The representative animal soil organism was
springtails Folsomia candida and enchytraeid Enchytraeus crypticus. Based on the test
results values of IC50, LC50, EC50 for the tested substances were determined and compared
to their toxicity. Additives of grafted polypropylene showed mild toxic effects on the test
organisms (values of above mentioned criteria were within the range of tens or hundreds of
mg/L) maleic anhydride exhibited a higher toxic effect than itaconic anhydride (e. g. values
168hIC50 for maleic anhydride and itaconic anhydride on L. minor were 48. 65 mg/l and 132.
42 mg/l, respectively 24hLC50 for these compounds on T. platyurus were 44. 65 mg/l and 84.
55 mg/L, respectively). Grafted polypropylenes contain very low amount of additives (e. g. in
PP‐g‐IAH the amount of itaconic anhydride is 0. 35 %) and polypropylene itself is
environmentally inert. Test in contact arrangement proved that there is no release of the
bound monomer into the environment and these specially modified compounds should not
pose any environmental risk.
Keywords
Polymers, monomers, ecotoxicity tests
85
Acknowledgements
This project was supported by the project No. FCH‐S‐15‐2869 “Assessment of the entry of
new contaminants to the environment” from Ministry of education, youth and sports of the
Czech Republic.
******
A Novel Strategy for The Determination of Polycyclic Aromatic
Hydrocarbons (PAHs) Metabolites in Urine
Darina Lankova, Katerina Urbancova, Jana Pulkrabova and Jana Hajslova
University of Chemistry and Technology, Prague, Faculty of Food and Biochemical Technology,
Department of Food Analysis and Nutrition, Technicka 3, 166 28 Prague, CZECH REPUBLIC
Abstract Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental pollutants. Chronic
exposure to certain PAHs is associated with a variety of adverse health effects (carcinogenity,
mutagenicity, teratogenicity). In the exposed organisms these compounds are rapidly
hydroxylated in the liver and then undergo conjugation, typically to the glucuronides and
sulfates, which are excreted in urine. Biomonitoring of PAH metabolites is an important
approach for the evaluation of body burden of these pollutants. The most frequently
measured biomarker for PAHs inhalation exposure is pyren‐1‐ol (1‐OH‐Pyr). However, 1‐
OH‐Pyr does not provide a complete assessment of human exposure to PAH mixtures due to
the different molecular sizes, shapes, and metabolism rates of various PAHs. More
importantly, pyrene itself is not carcinogenic and does not possess a bay region, a feature
closely associated with carcinogenicity. Therefore, it seems more appropriate to monitor
biomarkers of carcinogenic benzo[a]pyrene. However due to its trace levels in air compared
to pyrene and predominantly elimination of its metabolites in feces, recently hydroxylated
metabolites (OH‐PAHs) of abundant gas‐phase PAHs such as naphtalene and phenanthrene
have gained attention as biomarkers of PAH exposure. The main aim of our study was to
implement the method for the ultratrace analysis of 11 OH‐PAHs in urine using ultra‐high
performance liquid chromatography tandem mass spectrometry (UHPLC–MS/MS). The
spectrum of analytes included major 2‐, 3‐ and 4‐rings metabolites, namely naphtalen‐1‐ol,
naphtalen‐2‐ol fluoren‐2‐ol five isomers of phenanthrenol 1‐OH‐Pyr 3‐benzo[a]pyren‐3‐ol
and chrysen‐6‐ol. Since these compounds are excreted from organism as conjugates, the
conditions of enzymatic hydrolysis were also optimized. For the isolation of OH‐PAHs,
commonly used solid phase extraction (sorbent C18) was tested, but several difficulties were
observed during optimization experiments. The most significant problem was the
insufficient extract purity, which resulted in high matrix effects (signal suppression up to
90%) and increment of limits of quantification (LOQs). From these reasons, the simplified,
rapid and very easy sample preparation procedure based on the isolation of OH‐PAHs with
ethylacetate was newly developed. The organic extract was purified using dispersive SPE (d‐
SPE) with sorbent Z‐Sep, which is suitable for the removal of pigments in biological samples.
Finally, the method was successfully validated: the recoveries for all target compounds
ranged from 75 to 121% with relative standard deviations lower than 16% and the LOQs
were in the range of 0. 01–0. 8 ng/ml of urine. Within our study, also the stability of target
OH‐PAHs including their deuterated analogues, which were used as internal standards, was
86
monitored. In the next phase of our pilot study, the newly developed method will be used
for the analysis of urine samples obtained within the project Impact of air pollution to
genome of newborns (No. 13‐13458S).
Keywords PAHs, hydroxylated metabolites of PAHs, urine, UHPLC‐MS/MS
Acknowledgements
This study was funded by the Czech Science Foundation Project No. 13‐13458S.
******
Assessment of Body Burden of Czech Population to Polycyclic Aromatic
Hydrocarbons
Pulkrabová J., Lanková D., Urbancová K., Švarcová A., Stupák M., Hajšlová J.
Department of Food Analysis and Nutrition, University of Chemistry and Technology, Prague,
Technická 3, 166 28 Prague, CZECH REPUBLIC
Abstract The aim of this contribution is to summarize the main results obtained within the assessment
of body burden of Czech population from two region of the Czech Republic (České
Budějovice and Karviná) differing in atmospheric contamination by polycyclic aromatic
hydrocarbons (PAHs). This particular study is a part of the project concerned with the
impact of atmospheric carcinogens / mutagens on the genetic damage of newborns. To
characterize all the conceivable mothers´ and their newborns´ exposure pathways to PAHs i.
e. through inhalation and /or diet, we analyzed not only air (sampled by HiVol samplers of
PM2. 5), but also one week diet of pregnant women and their breast milk. A complementary
information was obtained also by determination of PAHs hydroxy metabolites (OH‐PAHs)
in urine. The samples were collected during two periods (i) summer/autumn 2013 and (ii)
winter 2013/2014. The newly optimized and validated analytical procedures for the
determination of parent PAHs (n=24) using gas chromatography in combination with
tandem mass spectrometry (GC–MS/MS) were applied for their analysis. In case of hydroxy
metabolites of PAHs (n=11) in urine, a novel sample preparation procedure with ultra‐high
performance liquid chromatography (UHPLC) hyphenated to MS/MS was employed. The
levels of all targeted PAHs in s both diet and breast milk samples were very low, in most
cases below 0. 01 ng/g. No significant differences between the sampling localities were
identified. Regarding the atmospheric contamination in the highly industrialized locality
Karviná, more than 5× higher concentrations were determined and also significant
differences during the monitored periods were found. The contribution of the diet to the
total PAHs exposure is around 30% in Karviná and 80% in České Budějovice. Regarding
urine samples, the most abundant representatives of OH‐PAHs were naphthalen‐2‐ol and
phenanthren‐1‐ol (quantified in all samples). Other analyzed compounds were found in
more than 70 % of samples with exception of chrysene‐6‐ol and benzo[a]pyren‐3‐ol, which
were not detected in any of the tested urine extracts. In general, the concentrations of OH‐
PAHs in children urine (median 7. 0 g/g of creatinine) was 1. 5× lower compared to their
mothers (median 11 g/g of creatinine).
87
Keywords
PAHs, OH‐PAHs, human exposure, diet, air, urine
Acknowledgements This study was funded by the Czech Science Foundation Project No. 13‐13458S.
******
Can Currently Used and Emerging Pesticides in Agriculturally Used
Fluvisols be Risky for Human and Ecosystem Health?
Hofman, J., Šimek, Z., Bielská, L., Hvězdová, M., Sáňka, M., Scherr, K., Šmídová, K.,
Škulcová, L., Šudoma, M., Svobodová, M., Vašíčková, J.
Research Centre for Toxic Compounds in the Environment, Masaryk University, Faculty of Science,
Kamenice 753/5, Brno, CZ‐62500, CZECH REPUBLIC hofman@recetox. muni. cz
Abstract
Fluvisols are soils developing in vicinity of rivers by periodic settling of alluvial sediments at
floodplains and periodic interruptions to pedogenesis by flooding. They are known to be
significant for agricultural production: although they cover only 6 % of agricultural land in
the Czech Republic, their relevance for crop production is much higher due to their high
fertility. On the other hand, they are known to be stressed both naturally (floods, dynamic
pedogenesis, groundwater level...) and by human activities (lowlands and river basins as
areas of intensive industry and agriculture and of high population density...). Fluvisols have
been many times reported to be seriously contaminated by both heavy metals and persistent
organic pollutants mainly coming with settled sediments during floods (Vácha et al. 2013
Hilscherová et al. 2007 Schwartz et al. 2006). Recently, the research focus has extended also to
other types of pollutants such as pharmaceuticals, endocrine disruptors and others (Yun 2008
Woelz 2012 Liu et al. 2010). There is important question if current praxis of the agriculture –
using of high amounts of pesticides (currently used pesticides – CUP) – brings additional
stress for fluvisols and increases the risks for human health and ecosystem quality. To
discuss this question will be the main goal of the lecture. In the recent decades, there has
been significant effort to replace persistent and bioaccumulative pesticides (mostly
organochlorine ones) by compounds which are less persistent and more biodegradable to
reduce pesticides hazards to ecosystems and humans. However, this is difficult to achieve as
these properties are often related to bioaccumulative and toxic properties which make
pesticides efficient towards pests. Thus, despite the fact that there are currently many non‐
bioaccumulative (logKow < 0), non‐persistent, quickly degradable CUP (e. g. MCPA, 2, 4‐D,
glyphosate, chlormequat), there are also CUP for which high bioaccumulation and
persistency in soils can be expected, based on their logKow, logKoc, and DT50 (e. g.
cypermethrin, pendimethalin, chlorpyrifos, acetochlor, azole fungicides). Many of CUP have
also been repeatedly found accumulated in agricultural soils (Gamon et al. 2003 Park et al.
2013 Yang et al. 2010 Vega et al. 2005) and/or in adjacent ground‐ or surface‐water (Kodeš et
al. 2011 Senseman et al. 1997 Vega et al. 2005 Yang et al. 2010), most likely as a result of the
high volume usage in agriculture. Although, pesticides cannot be introduced into the
environment unless they are authorized in strict registration processes (e. g. European
regulation 1107/2009), it is practically impossible to foresee all the possible risks at site
88
specific scenarios. Therefore even authorized pesticides deserve full attention and intensive
research because they are applied in huge amounts and may have significant side effects for
the ecosystem and human health. Exposure to increased levels of pesticides is known to
cause serious health effects including liver damage, immune‐suppression, endocrine and
reproductive disorders, and cancer (Hester et al. 2012 Bassil et al. 2007 Sanborn et al. 2007).
Pesticides can also seriously affect not‐target soil species (Hussain et al. 2009 Frampton et al.
2006 Strandberg et al. 2012) and decrease soil quality, fertility and productivity. New Czech
project has been started in 2015 with the goal to elucidate the mechanisms, principles and
factors of behaviour and bioavailability of CUP and emerging pesticides (nanopesticides) in
agriculturally used fluvisols. Studies will employ number of different soils, different CUPs,
several chemical methods, including novel passive samplers, and different biological
receptors (earthworms and plants) to address aspects of crop quality linked to human health
and soil quality linked to ecosystem health. Pilot results from the first phase of the project
will be presented and discussed in the lecture ‐ levels of CUP in the agriculturally used
fluvisols of the Czech Republic.
Keywords pesticides, soil quality, fluvisols, agriculture, ecotoxicology, human health, food quality, crop
protection, bioavailability
Acknowledgements
Financial support was obtained from GACR project 15‐20065S.
References [1] VÁCHA R, SÁŇKA M, SÁŇKA O, SKÁLA J, ČECHMÁNKOVÁ J. 2013. The Fluvisol
and sediment trace element contamination level as related to their geogenic and
anthropogenic source. Plant Soil Environ 59: 136‐42
[2] HILSCHEROVA K, DUŠEK L, KUBÍK V, ČUPR P, HOFMAN J, KLANOVA J,
HOLOUBEK I. 2007. Redistribution of organic pollutants in river sediments and alluvial
soils related to major floods. J Soil Sedim 7:167‐177
[3] SCHWARTZ R, GERTH J, NEUMANN‐HENSEL H, BLEY S, FORSTNER U. 2006.
Assessment of highly polluted fluvisol in the Spittelwasser floodplain ‐ Based on
national guideline values and MNA‐Criteria. J Soil Sedim 6:145‐155
[4] YUN SH, ADDINK R, McCABE JM, OSTASZEWSKI A, MACKENZIE‐TAYLOR D,
TAYLOR AB, KANNAN K. 2008. Polybrominated diphenyl ethers and polybrominated
biphenyls in sediment and floodplain soils of the Saginaw River watershed, Michigan,
USA. Arch Env Contam Tox 55:1‐10
[5] WOELZ J, GROSSHANS K, STRECK G, SCHULZE T, RASTALL A, ERDINGER L,
BRACK W, FLEIG M, KUEHLERS D, BRAUNBECK T. 2012. Estrogen receptor mediated
activity in bankside groundwater, with flood suspended particulate matter and
floodplain soil ‐ An approach combining tracer substance, bioassay and target analysis.
Chemosphere 85: 717‐723
[6] LIU H, LIANG H, LIANG Y, ZHANG D, WANG C, CAI H, SHVARTSEV SL. 2010.
Distribution of phthalate esters in alluvial sediment: A case study at JiangHan Plain,
Central China. Chemosphere 78: 382‐388
[7] KODEŠ V., VEJVODOVÁ J., ACKERMANOVÁ M. 2011. Results of national pesticide
screening in the Czech Republic. Geophysical Research Abstracts 13Senseman SA, Lavy
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TL, Daniel TC. 1997. Monitoring groundwater for pesticides at selected mixing/loading
sites in Arkansas. Environmental Science & Technology 31 (1) :283‐288.
[8] VEGA AB, FRENICH AG, VIDAL JLM. 2005. Monitoring of pesticides in agricultural
water and soil samples from Andalusia by liquid chromatography coupled to mass
spectrometry. Analytica Chimica Acta 538 (1‐2) :117‐127.
[9] YANG XB, YING GG, KOOKANA RS. 2010. Rapid multiresidue determination for
currently used pesticides in agricultural drainage waters and soils using gas
chromatography‐mass spectrometry. Journal of Environmental Science and Health Part
B‐Pesticides Food Contaminants and Agricultural Wastes 45 (2) :152‐161.
[10] PARK B‐J, LEE B‐M, KIM C‐S, PARK K‐H, KIM J‐H, KWON H, PARK S‐W, CHOI G‐H,
LIM S‐J. 2013. Long‐term Monitoring of Pesticide Residues in Arable Soils in Korea. The
Korean Journal of Pesticide Science 17 (4) :283‐292.
[11] GAMON M, SAEZ E, GIL J, BOLUDA R. 2003. Direct and indirect exogenous
contamination by pesticides of rice‐farming soils in a Mediterranean wetland. Arch
Environ Cont Tox 44: 141‐51
[12] HUSSAIN S, SIDDIQUE T, SALEEM M, ARSHAD M, KHALID A. 2009. Impact of
Pesticides on Soil Microbial Diversity, Enzymes, and Biochemical Reactions. Adv Agron
102: 159‐200
[13] FRAMPTON GK, JANSCH S, SCOTT‐FORDSMAND JJ, ROMBKE J, Van den BRINK PJ.
2006. Effects of pesticides on soil invertebrates in laboratory studies: A review and
analysis using species sensitivity distributions. Environ Toxicol Chem 25: 2480‐9
[14] STRANDBERG B, MATHIASSEN SK, BRUUS M, KJAER C, DAMGAARD C, et al. 2012.
Effects of herbicides on non‐target plants: How do effects in standard plant test relate to
effects in natural habitats? Pest Res 137
[15] HESTER S, MOORE T, PADGETT WT, MURPHY L, WOOD CE, NESNOW S. 2012. The
Hepatocarcinogenic Conazoles: Cyproconazole, Epoxiconazole, and Propiconazole
Induce a Common Set of Toxicological and Transcriptional Responses. Toxicol Sci 127:
54‐65
[16] BASSIL KL, VAKIL C, SANBORN M, COLE DC, KAUR JS, KERR KJ. 2007. Cancer
health effects of pesticides ‐ Systematic review. Canadian Family Physician 53: 1705‐
1711.
[17] SANBORN M, KERR KJ, SANIN LH, COLE DC, BASSIL KL, VAKIL C. 2007. Non‐
cancer health effects of pesticides ‐ Systematic review and implications for family
doctors. Canadian Family Physician 53: 1713‐1720.
******
The Possibilities of Voltammetric Determination of Different Antioxidants
in Biodiesel
Tomášková, M., Chýlková, J.
University of Pardubice, Faculty Chemical Technology, Institute of Environmental and Chemical
Engineering, Studentská 95, 53210 Pardubice, CZECH REPUBLIC
Abstract Biodiesels are commercial products and, as with any other product with a potential impact
on the environment, detailed analysis is necessary. As a material, biodiesel is not toxic and
90
undergoes biodegradability. Furthermore, addition of biodiesel into the diesel is now
obligatory according to the EU rules, therefore, motor vehicles with diesel engine have to use
such mixed diesel fuel [1]. On the contrary, one of the disadvantages of biodiesel is its low
oxidation stability in comparison with diesel oil [2, 3]. Resistance to oxidation is increased by
addition of various synthetic antioxidants [4]. Antioxidants are used to retard the process of
oxidative degradation of food products, polymers like rubber and plastics, fats and oils and
others such as elastomers, fibers, fuels and lubricating oils [5]. The most commonly used
synthetic antioxidants are: butylated hydroxytoluene (BHT, butylated hydroxyanisol (BHA),
tert‐butylhydroquinone (TBHQ), and N‐phenyl‐1‐naphtylamine (PNA) [6]. The present
paper describes the newest results obtained from the experimental studies of antioxidants
determination. The aim of the research was to reduce the negative impacts from industry
and transport upon the environment: in particular to reduce the production of wastes, to
minimize pollution of soil and water, to increase the operational safety. Also discussed are
the problems of biodiesel storage and the therewith connected experimental conditions of
voltammetric determination of different synthetic antioxidants.
Keywords antioxidant, voltammetry, biodiesel
References
[1] Council Directive 2009/28/EC of the European Parliament and of the Council Official J.
Eur. Union 52, 2009, pp. 16–62.
[2] A. MONYEM, J. H. VAN GERPEN, The effect of biodiesel oxidation on engine
performance and emissions, Biomass Bioenergy 20, 2001, p. 317.
[3] L. M. DUPLESSIS, J. B. M. DEVILLIERS, W. H. VANDERWALT, Stability studies on
methyl and ethyl fatty‐acid esters on sunflowerseed oil, J. Am. Oil Chem. Soc. 62, 1985,
p. 748.
[4] F. VLK, Alternative drive of motor vehicles (In Czech). Vlk publishing, Brno Czech
republic, 2006, ISBN 80‐239‐6461‐5.
[5] A. K. MUKHOPADHYAY, Antioxidants – Natural and synthetic. Amani International
Publishers, Kiel Germany, 2006, ISBN 978‐3‐938054‐05‐5.
[6] G. KARAVALAKIS, D. HILARI, L. GIVALOU, D. KARONIS, S. STOURNAS, Storage
stability and ageing effect of biodiesel blends treated with different antioxidants. Energy
36 (1), 2011, p. 369‐374.
******
The Determination of Moluscocide Methiocarb using DPV – the Possibility
of Monitoring for The Supress of Zooplankton Growth
Chýlková, J., Tomášková, M., Šelešovská, R.
University of Pardubice, Faculty Chemical Technology, Institute of Environmental and Chemical
Engineering, Studentská 95, 53210 Pardubice, CZECH REPUBLIC
Abstract
The most commonly used pesticide with insecticidal and molluscicidal activity is Methiocarb
(MTC 3, 5‐dimethyl‐4‐ (methylthio) phenyl methylcarbamate). Methiocarb belongs to a
91
group of carbamates. Carbamates are one of the major classes of synthetic pesticides and due
to their broad biological activities, these compounds are used on large scale around the
world [1]. The example being its use for reducing the overgrowth of zooplankton [2‐4]. In
this paper was tested the newly proposed method during solubility of methiocarb in water.
The aim was to determine the ability of Methiocarb to suppress the undesirable growth of
some zooplankton (during its gradual release from the preparation). This assay has been
made with Mesurol® product which, in Czech Republic, is the only available source of MTC
added into natural water collected in a pond. This work reports on the electrochemistry and
voltammetric determination of Methiocarb at such a BDDE. It was proposed a simple and
quickly‐to‐use process to determine Methiocarb in samples of environmetal character – in a
commercial product and pond water.
Keywords
moluscocide, pesticide, voltammetry, methiocarb
References
[1] H. P. LI, J. H. LI, G. C LI, J. F. JEN, Simultaneous Determination of airborne carbamates
in workplace by high performance liquid chromatography with fluorescence detection,
Talanta 63, 2004, p. 547‐553.
[2] V. VLČEK, M. POHANKA, Environmental aspects of organophosphorus and carbamate
pesticides approved for use in the Czech Republic, Chem. Listy 105, 2011, p. 908‐912.
[3] M. POHANKA, K. MUSÍLEK, K. KUCA, Progress of biosensors based on cholinesterase
inhibition, Current Medicinal Chemistry 16, 2009, p. 1790‐1798.
[4] R. FAINA, J. MÁCHOVÁ, Z. SVOBODOVÁ, H. KROUPOVÁ, O. VALENTOVÁ, Použití
přípravku Diazinon 60 EC v rybníkářské praxi k tlumení nadměrného rozvoje hrubého
dafniového zooplanktonu, Jihočeská univerzita v Českých Budějovicích, Výzkumný
ústav rybářský a hydrobiologický ve Vodňanech, 2007, pp. 18‐19.
******
Sensitive Determination of Anti‐Inflammatory Drug Sulfasalazine using
Green Electrochemical Sensor Based on Silver Solid Amalgam
Janíková, L., Šelešovská, R., Štěpánková, M., Chýlková, J.
University of Pardubice, Faculty of Chemical Technology, Institute of Environmental and Chemical
Engineering, Studentská 537, CZ‐532 10 Pardubice, CZECH REPUBLIC
Abstract Sulfasalazine (SSZ) belongs to the aminosalycilate group of pharmaceuticals and is primarily
applied for treatment of inflammatory bowel diseases, rheumatoid arthritis, ankylosing
spondylitis, psoriatic arthritis, and juvenile rheumatoid arthritis [1]. Electrochemical
methods represent very good alternative to time and money consuming analytical
techniques like liquid chromatography, which are commonly used for sensitive
determination of pharmaceuticals [2]. The presented voltammetric method, which employed
non‐toxic silver solid amalgam [3, 4] as a material of working electrode, citrate buffer of pH 5
as a supporting electrolyte, and adsorptive stripping square wave voltammetry (AdS SWV)
as a measuring technique, proved excellent results like high repeatability (RSD of 15
92
repeated measurements of 2. 50×10‐7 mol L‐1 was 2. 79 %), good repeatability of repeated
determination of various SSZ concentration levels (RSD (5) <= 5. 33 %), wide linear dynamic
range (5×10‐9 ‐ 4×10‐6 mol L‐1) and low limit of detection (LOD = 3. 24×10‐9 mol L‐1), which
confirms high sensitivity of the proposed method. Moreover, the proposed method was
successfully applied for voltammetric determination of SSZ in the sample of pharmaceutical
preparation. Finally, it can be concluded, that silver solid amalgam electrode in combination
with AdS SWV represents sensitive tool for determination of SSZ.
Keywords
Sulfasalazine, Silver solid amalgam electrode, Voltammetry, Pharmaceuticals,
Determination.
Acknowledgements
This work was supported by The Ministry of Education, Youth and Sports of the Czech
Republic (project No. CZ. 1. 07/2. 3. 00/30. 0021 “Strengthening of R&D Teams at the
University of Pardubice”) and by the University of Pardubice (project No.
SGSFChT_2015006).
References
[1] www. sulfasalazine. com, downloaded on 25th May 2015.
[2] S. A. ÖZKANA, B. USLUA, H. Y. ABOUL‐ENEIN, Analysis of Pharmaceuticals and
Biological Fluids Using Modern Electroanalytical Techniques, Critical Reviews in
Analytical Chemistry 33 (2003), 155‐181.
[3] L. NOVOTNÝ, B. YOSYPCHUK, Solid Silver Amalgam Electrode, Chemické Listy 94
(2000) 1118‐1120.
[4] B. YOSYPCHUK, J. BAREK, Analytical Applications of Solid and Paste Amalgam
Electrodes, Critical Reviews in Analytical Chemistry 39 (2009) 189‐203.
******
Preparation of Sorbents from Tar Deposits.
Pryszcz, A.
VŠB ‐ TU Ostrava, Institute of Environmental Technologies
Abstract
Tar is produced from the thermochemical processes, and is disposed as an dangerous waste,
leading to environmental pollution. Removal or conversion of tar is considered to be a
technologically very challenging problem. Tars can condense or polymerize into more
complex structures, which may lead to clogging of pipes and heat exchangers. The main goal
of this paper was to find a useful solution for decomposition of tar deposits. Extraction of tar
deposits and afterwards activation for preparing of sorbents seems to be a promising way.
The tar deposits from tar storage tanks were chosen for the experimental part. Tar deposits
were extracted by acetone, toluene, pyridine and quinoline. Next step was in activation of
these extraction products with potassium hydroxide and finally surface characterization of
these prepared carbon sorbents were made.
93
Keywords
Key words: Tar, Active carbon, Tar deposits, Extraction, Activation
Acknowledgements This article was created with the financial support of the Ministry of Education, Youth and
Sports within targeted support program „Národní program udržitelnosti I“, projekt LO1208
„TEWEP“
******
Sources and Transfer of Emerging Halogenated Contaminants Across the
Food Chain
Hajslova, J., Pulkrabova, J., Lankova D.
University of Chemistry and Technology, Institute of Chemical Technology, Technická 3, CZ‐16 628
Prague, CZECH REPUBLIC
Abstract Continuous industrial development has resulted in an increasing production of various
types of chemicals and their subsequent release into the environment. While most of the
earlier monitoring studies focused on various chlorinated persistent organic pollutants
(POPs), in the recent decades, toxicological concerns emerged on the ubiquitous occurrence
of fluorine and bromine containing com pounds that may also accumulate in food chains.
The high volume production of perfluoro alkylsubstances (PFASs) and brominated flame
retardants (BFRs), the latter represented mainly by polybrominated diphenylethers (PBDEs),
hexabromo cyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA), have led to their
widespread distribution in the environment. As regards to PFASs, due to their unique
characteristics such as chemical inertness, stability, hydrophobicity and lipophobicity, they
are used in a variety of industrial and consumer applications while BFRs are used to reduce
the flammability of treated materials. Non‐occupational human exposure to PFASs and
BFRs, that may occur through a variety of pathways including inhalation of contaminated
dust particles or food drinking water ingestion, has been clearly documented by findings of
these chemicals and their (bio) transformation products in human tissues and fluids
including plasma and breast milk. The latter matrix is a widely used bioindicator that can be
used to assess the body burden of these environmental pollutants especially with regard to
its importance as the first food for the new born. To enable assessment of the health risks for
humans, European Food Safety Authority (EFSA) launched at the end of last decade the call
for providing more information on these ´emerging´ contaminants.
In the first part of this presentation, the overview of advanced analytical strategies (mainly
based on hybride high resolution mass spectrometry, HRMS/MS) applicable for multi‐
analyte/ multi‐matrix analyses will be provided. In the next phase, a number of case studies
focused on the transport of a wide range of PFASs, BFRs and their metabolites across food
chain will be presented. Worth to notice that dietary intake has been documented to be the
major source of humans´ exposure to these hazardous chemicals regarding the
contamination level in the analyzed food commodities following order decreasing was
94
observed within EU PERFOOD project (http://www. perfood. eu) : seafood > pig/bovine liver
>> freshwater/marine fish > hen egg > meat >> butter.
Keywords
halogenated contaminants, analytical strategies, food chain
95
Food Chemistry
Comparison of Sensory Quality of Model Swiss Cheese with Commercially
Obtained Corresponding Product
Vítová, E., Sůkalová, K., Mahdalová, M., Butorová, L., Musilová, L., Pecinová, E.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, 612 00 Brno, CZECH
REPUBLIC
Abstract Swiss cheese is a generic name for several related varieties of cheese resembling the true
Emmental. Swiss cheese types have ivory to light yellow colour, firm, slightly elastic texture,
characteristic mild, nutty, sweetish flavour and a distinctive appearance some cheeses have
round regular holes known as ʺeyesʺ, while some do not (known as ʺblindʺ). Three types of
bacteria are typically used to make Swiss cheese (these can vary slightly depending on the
manufacturer) : Streptococcus salivarius subsp. thermophilus, Lactobacillus spp. and
Propionibacterium freudenreichii subsp. shermanii). Propionic acid fermentation is essential
to obtain characteristic eyes and the nutty flavour. Today Swiss cheeses are produced in
many countries and a great variety is available on the world market. The aim of this work
was to produce new type of Swiss cheese with the comparable or even better sensory quality
than commercially available corresponding products. The model samples were produced in
pilot plant using standard technology procedure fresh milk in “bio” quality was used as a
basic raw material. The sensory quality of model samples was compared with standard
Swiss cheese purchased on the Czech market. The sensory analyses were carried out in a
sensory laboratory (ISO 8589:2008). Twenty‐three assessors were selected from students of
the faculty and used for evaluation of the samples. Five main sensory attributes (appearance,
colour, odour, flavour and texture) were evaluated using five point ordinal hedonic scale (1‐
excellent to 5 ‐ unsatisfactory). Paired comparison test (ISO 5495:2005) was used to
investigate preference of assessors/consumers. The significant differences (P < 0. 05) in odour,
flavour and texture were found between samples. Odour and flavour of model samples were
quite strong and piquant, which is probably the reason why they were less preferred by
conservative Czech consumers/assessors, however, prospectively they could be offered at the
Czech market as a new nontraditional cheese product.
Keywords Swiss cheese, sensory quality, sensory analysis
Acknowledgements
This work was supported by a Standard project of specific research No. FCH‐S‐15‐2827.
References
[1] FOX, P. F., GUINEE, T. P., COGAN, T. M., MCSWEENEY, P. L. H. Fundamentals of
Cheese Science. 1st. ed. Gauthersburg (Maryland, USA) : Aspen Publication, 2000, 638 p.
ISBN 0‐8342‐1260‐9.
[2] ROGINSKI, H., FUQUAY, J. W., FOX, P. F. : Encyclopedia of Dairy Science. London:
Academic Press, 2002, pp. 363–371. ISBN 0‐12‐227235‐8.
96
[3] KOCAOGLU‐VURMA, N. A., ELIARDI, A., DRAKE, M. A., RODRIGUEZ‐SAONA, L.
E., HARPER, W. J. Rapid Profiling of Swiss Cheese by Attenuated Total Reflectance
(ATR) Infrared Spectroscopy and Descriptive Sensory Analysis. Journal of Food Science,
2009, Vol. 74, No. 6, pp. S232‐S239. ISSN 0022‐1147.
[4] KOCAOGLU‐VURMA, N. A., HARPER, W. J., DRAKE, M. A., COURTNEY, P. D.
Microbiological, chemical, and sensory characteristics of Swiss cheese manufactured
with adjunct Lactobacillus strains using a low cooking temperature. Journal of Dairy
Science, 2008, Vol. 91, No. 8, pp. 2947‐2959. ISSN 0022‐0302.
******
Assessment of Antioxidant Properties of Different Types of Herbs by EPR
and UV‐VIS Spectroscopy
Butorová, L., Polovka, M., Tobolková, B., Vítová, E.
Department of Food Chemistry and Biotechnology, Faculty of Chemistry, Brno University of
Technology, Purkyňova 118, CZ‐612 00 Brno, CZECH REPUBLIC
Department of Chemistry and Food Analysis, National Agricultural and Food Centre, VÚP Food
Research Institute, Priemyselná 4, P. O. Box 25, SK‐824 75 Bratislava, SLOVAK REPUBLIC
xcbutorova@fch. vutbr. cz
Abstract There is an increasing interest in complex characterization of medical herbs and herb
products and isolation of their main active components including antioxidants. The first step
of effective isolation of antioxidants from herbs is the extraction, which must be fast, simple
and inexpensive, but also sensitive to respective bioactive components, environmental
friendly and easy to automate. The aim of this contribution was to perform the assessment of
antioxidant properties of various types of herbs commonly available in this territory in
different extraction media by using modern spectroscopic techniques. Selected herbs were
extracted in four different solvents, i. e., distilled water, 50% ethanol, 50% acetone and
dimethylsulfoxide and subsequently analysed by EPR and UV‐VIS NIR spectroscopy
involving several assays. Total content of polyphenols (TPC), total content of flavonoids
(TFC) and color characteristic using the CIE L*a*b* system were determined using the UV‐
VIS‐NIR spectroscopy. Antioxidant activity of extracts was tested by 2, 2´‐azino‐bis (3‐ethyl‐
benzothiazoline‐6‐sulphonic acid cation radical (ABTS•+) assay. The capability of extracts
components to terminate the hydroxyl radicals (•OH) generated by chemical reaction
directly in the experimental system via thermal decomposition of potassium persulfate
(K2S2O8) radical initiator in the presence of 5, 5‐dimethyl‐1‐pyrroline‐N‐oxide (DMPO) as
spin trap was also investigated. Obtained results clearly proved the solvent‐dependent
isolation of antioxidants, mainly influenced by the solvent polarity and the character of
isolated compounds. Additional experiments are in progress in order to correlate the results
of antioxidant activity assays with the composition of the investigated medical herbs
determined by LC and mineral content, evaluated by ICP‐OES.
Keywords
medical herbs, antioxidant properties, EPR, UV‐VIS
97
******
The Development of Volatile Flavour Compounds During Ripening of
Gouda Cheese
Mahdalová, M., Vítová, E., Ryglová, H., Sůkalová, K., Buňka, F.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLICTomas Bata University in Zlín, Faculty of Technology, Nám. T. G. Masaryka 275, CZ‐
762 72 Zlín, CZECH REPUBLIC
Abstract Cheese belongs to the group of fermented dairy products. Its flavour profile depends on
many factors, e.g. milk type, milk heat treatment, starter cultures, the maturation period etc.
Gouda cheese belongs to the Dutch type cheeses which are known for their characteristic and
unique aroma. In general, cheese undergoes the most significant changes during its ripening.
Proteins, saccharides and fat are important for flavour formation. Biochemical changes in
cheese may be grouped into primary (lipolysis, proteolysis and metabolism of residual
lactose, lactate and citrate) or secondary (metabolism of fatty acids and amino acids) events.
The flavour of cheese is a result of the interaction of starter bacteria, enzymes from milk,
rennet, native lipases and secondary microflora. Fatty acids arise during lipolysis they may
be the precursors of the other compounds such as esters, lactones, ketones and aldehydes.
More than 600 volatile compounds have been identified in cheese so far, but only a small
fraction of these compounds are responsible for cheese flavour. Except flavour, also cheese
texture, rheology and pH change during production and ripening. The aim of this study was
to characterize flavour development the ripening of Gouda cheeses. Most of published works
is focused on flavour changes in Gouda cheese during ripening, but there are not many
papers which investigates also raw materials and/or by‐products from cheese making.
Several authors analyzed changes in flavour of whole pasteurized milk as affected by storage
time and/or packaging material. The raw cheese and ripe cheese were analyzed for content of
volatile flavour compounds. These were extracted by solid phase microextraction and
assessed by gas chromatography with flame ionization detector.
Keywords
Gouda cheese, ripening, volatile flavour compounds, SPME‐GC‐FID
Acknowledgements This work was kindly supported by a Standard project of specific research No. FCH‐S‐15‐
2827.
References
[1] FATMA A. M. HASSAN, MONA A M. ABD EL‐ GAWAD, A. K. ENAB, Flavour
Compounds in Cheese (Review), Research on Precision Instrument and Machinery Vol.
2, Iss. 2, 2013, pp 15‐29.
[2] MCSWEENEY, PAUL L. H., Biochemistry of Cheese Ripening, International Journal of
Dairy Technology, Vol. 57, Issue 2/3, 2004, pp 127‐144.
98
[3] ALEWIJN, M., SLIWINSKI, E. L., WOUTERS, J. M. T., Production of fat‐derived
(flavour) compounds during the ripening of Gouda cheese, International Dairy Journal,
Vol. 15, Iss. 6‐9, 2005, pp 733‐740.
[4] CURIONI, P. M. G., BOSSET, J. O., Key odorants in various cheese types as determined
by gas chromatography‐olfactometry, International Dairy Journal, Vol. 12, Iss. 12, 2002,
pp 959‐984.
[5] VAN LEUVE, I., VAN CAELENBERG, T., DIRINCK, P., Aroma characterisation of
Gouda‐type cheeses, International Dairy Journal, Vol. 18, Iss. 8, Gent, 2008, pp 790‐800.
[6] KARATAPANIS, A. E., BADEKA, A. V., RIGANAKOS, K. A., SAVVAIDIS, I. N.,
KONTOMINAS, M. G., Changes in flavour volatiles of whole pasteurized milk as
affected by packaging material and storage time. International Dairy Journal, 2006, Vol.
16, Iss. 7, pp 750‐761.
******
Simply Method of DNA Isolation from Lactic Acid Bacteria
Fričová, M., Čuta, R., Křížová, J., Španová, A., Rittich, B.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLICMasaryk University, Faculty of Science, Institute of Experimental Biology, Kotlářská
2CZ‐611 37 Brno, CZECH REPUBLIC
Abstract
Identification of bacterial DNA consists of several steps: cell lysis, extraction and purification
of DNA followed by the identification of the bacterial species using polymerase chain
reaction (PCR). Genomic DNA was isolated from Lactobacillus plantarum CCM 7039,
Lactobacillus fermentum CCM 7192, Lactobacillus rhamnosus CCM 1825, Lactobacillus casei
subsp. casei CCM 7088, and Bifidobacterium bifidum CCM 3762 by fenol extraction
procedure and by the salting out with NaCl solution. Crude cell lysates were prepared using
standard procedure and using of laundry powder. The quality of isolated DNA was verified
by UV spectrophotometry and by agarose gel electrophoresis. Isolated DNA was used as a
template for PCR.
Keywords
Lactobacillus Bifidobacterium cell lysates DNA isolation NaCl PCR rep‐PCR
Acknowledgements
The financial support of internal grant FCH‐S‐13‐1912 is gratefully acknowledged.
References
[1] BERNARDEAU M., VERNOUX, V. S., DUBERNET H., GUÉGEN M. Safety assessment
ofdairy microorganisms: the Lactobacillus genus. Int. J. Food Microbiol. 2008, vol. 126,
issue 3, s. 278‐285.
[2] WALTER J. Ecological Role of Lactobacilli in the Gastrointestinal Tract: Implications for
Fundamental and Biomedical Research. Appl. Environ. Microbiol. 2008, vol. 74, issue 16,
s. 4985–499674.
99
[3] DUBERNET S., N DESMASURES N., M GUÉGUEN M. A PCR‐based method for
identification of lactobacilli at the genus level. FEMS Microbiol. Lett., 2002, vol. 214,
issue 2, s. 271‐275.
[4] WALTER J., TANNOCK G. W., TILSALA‐TIMISJÄRVI A., RODTONG S., LOACH D.
M., MUNRO K., ALATOSSAVA T. Detection and identification of gastrointestinal
Lactobacillus species by using denaturing gradient gel electrophoresis and species‐
specific PCR primers. Appl. Environ. Microbiol., 2000, vol. 66, issue 1, s. 297‐303.
[5] SAMBROOK J., RUSSEL D. W. L. Molecular cloning: a laboratory manual. 3rd. ed. New
York: Cold Spring Laboratory Harbor Press, 2001.
[6] GIRAFFA G., ROSSETI L., NEVIANI E. An evaluation of chelex‐based DNA purification
protocols for the typing of lactic acid bacteria. J. Microbiol. Methods, 2000, vol. 42, s. 175‐
184.
[7] RITTICH, B., ŠPANOVÁ, A., 2013. SPE and purification of DNA using magnetic
particles. J. Sep. Sci., 2013, vol. 36, issue 15, s. 2472‐2485.
******
Solid ‐ Phase DNA Extraction Using Various Types of Magnetic
Microparticles
Konecna, J., Spanova, A., Horák, D., Rittich, B.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovský Sq. 2,
CZ‐162 06 Prague, CZECH REPUBLIC
Abstract
Isolation of DNA is an important step in the molecular diagnostics of microorganisms. A
high quality of isolated DNA is necessary for DNA amplification by the polymerase chain
reaction. The conventional DNA isolation using phenol‐chloroform extraction and DNA
precipitation in ethanol is time‐consuming and requires the use of toxic phenol. Magnetic
separation techniques using magnetic solid particles are one of modern methods to speed up
the nucleic acids isolation. The aim of of this work was to use 3 different types of magnetic
microparticles, prepared by Horák, for solid ‐ phase DNA extraction. The amounts of DNA
in separation mixtures were measured by using UV‐VIS spectrophotometry. The first
experimental conditions were tested on chicken erythrocytes DNA. Phosphate buffer (pH 7,
7. 6 and 8) was used for adsorption of magnetic particles. It was shown that approximately
one half of DNA was adsorbed to the particles. The elution conditions of DNA were also
optimized. Secondly bacterial DNA was tested. This DNA eluted from the particles was in
PCR – ready quality.
Keywords
DNA isolation, magnetic particles, PCR
100
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Influence of Vegetable Oils on Fatty Acids Composition in Processed
Cheese Analogues
Sůkalová, K., Vítová, E., Buňka, F., Mahdalová, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Bata University in Zlín, Faculty of Technology, Nám. T. G. Masaryka 275, CZ‐762 72 Zlín, CZECH
REPUBLIC
Abstract
Knowledge of the individual fatty acid composition of neutral lipids in dairy products,
especially processed cheese and processed cheese analogues is important in terms of health
aspect as well as consumer acceptance. Fatty acids (FA), especially polyunsaturated fatty
acids originating from vegetable oils, added to the processed cheese, may offer benefit to the
final consumer in the form of higher nutritive value of products. The important index of
sensory quality and durability could be free fatty acids (FFA), their content and composition.
FFA, produced during lipolysis and also during technology procedure, contribute directly to
cheese flavour, especially short‐ and medium‐chain FFA. In addition, they also act as
substrates for further reactions producing highly flavoured catabolic end products. The aim
of this work was to assess the total FA and FFA content in the model samples of processed
cheese analogues produced with addition of different vegetable oils (apricot kernel,
blackcurrant, flaxseed and grape seed oils). The FA composition was then compared with
standard processed cheese (without addition of vegetable oil). The lipids from cheese
samples were extracted using ISO 1735, FA were esterified by methanolic KOH according to
ISO 5509 and determined by gas chromatography with flame‐ionization detection. For
obtaining FFA the lipid extracts were fractionated using Solid Phase Extraction method
before esterification process. The total content of lipids, FA and FFA content and
composition were then compared and differences between samples were evaluated.
Processed cheese analogues are known to be characteristic by a relatively high content of
monounsaturated (MUFA) and polyunsaturated fatty acids (PUFA) and by a favourable ratio
of n‐6 to n‐3 fatty acids. Following FA were present in samples in highest quantity: oleic,
palmitic, myristic, stearic and linoleic acid. When comparing the SFA: MUFA: PUFA no
significant differences between samples were found.
Keywords
Processed cheese analogue, fatty acid, free fatty acid
Acknowledgements
This work was supported by a Standard project of specific research No. FCH‐S‐15‐2827 and
by “Materials Research Centre – Sustainability and Development” project Nr. LO1212 of the
Ministry of Education, Youth and Sports
101
******
Small Berries as an Important Source of Antioxidants
Olšovcová, Z.1, Vespalcová, M.1, Diviš, P.1, Matějíčková, J.2, Kaplan, J.2, Matějíček, A.2
1Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC 2Research and Breeding Institute of Pomology Holovousy Ltd., Holovousy 1, CZ‐508 01 Horice,
CZECH REPUBLIC
Abstract Moderate clima provides a number of berry fruit, which have a high content of biologically
active substances, which are important for human health. Especially small dark berries, fruits
like elderberry, black currant, aronia, honeysuckle, mulberry and jostaberry contain
significant amounts of antioxidants, substances which belong to polyphenols, anthocyanins
and vitamin C. These small fruits have two very interesting aspects for food industry. First,
enhance the market by the new products, and second, production red colour natural origin.
The aim of this work was determination of selected of chemical substances small fruits,
which are important for the assessment of health benefits (content of total phenolics
compounds, anthocyanins and vitamin C). Then were determined parameters important for
the industrial processing of food products (pH of juice, yield of juice, titratable acids, etc.).
For the determination of selected substances were used instrumental methods (HPLC, UV‐
VIS spectrophotometer) and manual laboratory procedures by the CSN.
Fruit comes from the Research and Breeding Institute of pomology Holovousy. The content
of total polyphenols in black currants was determined in the range from 396, 0 to 551, 1 mg,
for jocheline it was 288, 4 mg, for josta it was 379, 1 mg and for Black Negus was value to 263,
2 mg per 100 g of fruit. The content of anthocyanins pigments is highly influenced
differences between fruit. For blackcurrants was ranges from 123, 7 to 232, 0 mg, for
elderberries from 0, 0 to 297, 8 mg, for jocheline value was determined to 43, 3 mg, 106, 9 mg
for josta and for Black Negus 93, 7 mg per 100 g of fruits. And very important vitamin C was
determined for black currants ranges from 132, 3 to 299, 7 mg, in elderberries fruits was from
7, 0 to 12, 7 mg, jocheline and jost was determined the content to 82, 0 mg resp. 91, 3 mg and
for black negus the value was measured to 34, 4mg per 100 g of fruits.
Keywords
jostaberry, jocheline, elderberry, black currant, elderberry, anthocyanins, phenolics, vitamin
C, HPLC
Acknowledgements
The study was financially supported by the project no. QI111141 MA.
102
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Determination of Content of Hordein Peptides in Beer
Mikulíková, R., Svoboda, Z., Benešová, K., Běláková, S.
Research Institute of Brewing and Malting, Plc., Malting Institute Brno Mostecká 7, 614 00 Brno,
CZECH REPUBLIC
Abstract
Celiac disease is a lifelong condition caused by gluten intolerance. The only therapy is a
gluten‐free diet, i. e. a complete exclusion of wheat, rye, barley, oats and products made from
them. In the effort to improve the quality of life for celiac people, the assortment of food
products suitable for gluten‐free diet has been extended recently. Gluten‐free beer belongs to
new drinks suitable for people with celiac disease. Since January 1, 2012, the amendment of
the Commission Regulation (EC) No 41/2009 concerning labelling the gluten‐free food
products has been in force. The Regulation defines a single limit for gluten‐free food
products regardless raw materials used for their production in the amount of 20 mg
gluten/kg of food ready for consumption. To be able to get in this category, a producer must
guarantee the fulfillment of the Regulation (the product must be laboratory tested and have a
label on the product packaging indicating its gluten‐free content). Hordein peptides in beer
were determined by a competitive immunoenzymatic method recommended for the
determination of peptide fragments in beers and other food products containing hydrolyzed
proteins. The used monoclonal antibody R5 recognizes among others toxic sequence QQPFP,
which occurs repeatedly in prolamin molecules. To assess the suitability of beers for celiac
people, beers from retail shops were analyzed using the competitive immunoenzymatic
assay. In fifty five samples of Czech and foreign beers analyzed, gliadin contents varied from
5. 0 to 1690 mg/l. Only 7 % of samples did not exceed the limit set up by the Commission
Regulation.
Keywords
Celiac disease, gliadin, ELISA, beer
Acknowledgements This study was funded by the institutional support of the Ministry of Agriculture of the
Czech Republic (No. RO1915)
References
[1] MOLINA‐DELGADO, M. A., AGUILAR‐CABALLOS, M. P., GÓMEZ‐HENS, A., 2011:
Usefulness of gold nanoparticles as labels for the determination of gliadins by
immunoaffinity chromatography with light scattering detection. Talanta. 85: 2391‐2396
[2] GUERDRUM, L. J., BAMFORTH, C. W., 2011: Levels of gliadin in commercial beers.
Food Chemistry. 129: 1783‐1784
[3] PICARIELLO, G., BONOMI, F., IAMETTI, S., RASMUSSEN, P., PEPE, C., LILLA, S.,
FERRANTI, P., 2011: Proteomic and peptidomic characterisation of beer: Immunological
and technological implications. Food Chemistry. 124: 1718‐1726
[4] HULÍN, P., DOSTÁLEK, P., HOCHEL, I., 2008: Methods for determination of gluten
proteins in foods. Chem. Listy. 102: 327‐337.
103
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Detection of Lactobacillus Acidophilus Species in the Probiotic Meat
Product
Vašíček, R, Vaňásek, J, Konečná, J, Trachtová, Š, Španová, A, Rittich, B,
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Probiotic bacteria have beneficial effects on human health. They positively influence the host
immune system and the composition of intestinal microflora. They can reach the
gastrointestinal tract with food. Probiotic bacteria are found in dairy products and food
supplements most often. They can be used in other matrices including meat products. The
aim of this study was to detect Lactobacillus acidophilus cells in probiotic fermented meat
product “Ovčácká klobása” using the PCR method. Attention was paid to the preparation of
the sample (homogenization, lysis of cells) and optimization of methods for the isolation of
DNA in quality suitable for PCR using magnetic microparticles. The use of magnetic
particles with immobilized antibody antiLactobacillus was also tested for Lactobacillius
acidophilus bacterial cells isolation from homogenized product. Bacterial cells bound on the
magnetic particles were identified using PCR. Specific PCR products for the species
Lactobacillus acidophilus were detected in both cases. In the control fermented meat product
“Orlík”, which had not been declared to contain L. acidophilus, the species was not detected.
It was demonstrated that immunomagnetic separation can be used for the isolation and
concentration of cells.
Keywords Probiotic bacteria, PCR, fermented meat product
******
Determination of Total Polyphenol Content and Total Antioxidant Activity
of Different Currant and Gooseberry Cultivars Grown in the Czech
Republic
Divis, P., Christovova, S., Porizka, J., Vespalcova, M., Matejicek, A.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Currants and gooseberries have been known in Europe since the 14th century. They are
consumed either fresh or as juices and jams or as a fermented fruit beverages. Currant is a
small shrub belonging to the family of Grossulariaceae of the genus Ribes. The currant bush
grows up to a height of 1–1, 5 meters. Its leaves are yellowish‐green in color and are
arranged spirally on the stems in bunches of five. During each season the shrub bears
pendulous chain of small berries. Depending on the berries colour, red, white and black
currants varieties can be distinguished. Gooseberries are deciduous, fast growing shrubs
104
reaching 1 m in height and 1, 5 m in width under optimum conditions. The leaves are
alternate, single, deeply lobed, and glossy dark green. The fruit, borne singly or in pairs at
the axils, is a berry with many miniature seeds at the center. A gooseberry may be green,
white, yellow, or in shades of red from pink to purple to almost black. Currants and
gooseberries are important source of biologically active substances and have essential
importance for humans. In this work the antioxidant activity of different cultivars of currants
and gooseberries grown in the Czech Republic was determined using DPPH and ABTS
antioxidant assays. UV‐VIS spectrophotometry was applied to gooseberry samples, electron
paramagnetic resonance (EPR) spectrometry was used for black currants. The antioxidant
activity of analysed fruits was compared with the content of polyfenolic compounds
determined by Folin‐Ciocalteu method.
Keywords
ABTS assay, DPPH assay, EPR, antioxidants, fruit
Acknowledgements
This work was supported by Ministry of Agriculture of the Czech Republic, project No:
QI111A141
******
Determination of Trans‐2‐nonenal in Barley Varieties Recommedned for
Production of Czech Beer
Svoboda, Z., Mikulíková, R., Benešová, K., Běláková, S.
Research Institute of Brewing and Malting, Plc., Malting Institute Brno Mostecká 7, 614 00 Brno,
CZECH REPUBLIC
Abstract Fatty acids contained in barley caryopses and subsequently in malt can be one of sources of
flavor‐active substances in beer. Enzymatic hydrolysis of triglycerides and following
oxidation of released unsaturated fatty acids produce substances in malt that can
unfavorably affect the taste and aroma of the produced beer. Trans‐2‐nonenal, the aldehyde
derived from the oxidation of free fatty acids, is a basic component contributing to rancid
beer taste. The threshold concentration for perception of trans‐2‐nonenal in beer is 0. 1g. l‐1
The headspace solid‐phase microextraction (SPME) was used for the extraction and
following concentration of trans‐2‐nonenal. Trans‐2‐nonenal was analyzed using gas
chromatography with a flame ionization detector and the capillary column Supelcowax.
Trans‐2‐nonenal content was analyzed in ten barley varieties recommended for production
of beer with the protected geographical indication (PGI) České pivo (Czech Beer) and malts
produced from them.
Content of trans‐2‐nonenal in barleys and malts varied from 0. 28 – 3. 06 g. kg‐1 and 8. 90 – 38. 54 g. kg‐1, respectively. Multiply higher content of trans‐2‐nonenal in malt compared to
barley grain is caused by an increased enzymatic activity at malting. Further, ten beers with
the PGI České pivo bought in retail shops were analyzed. In these beers, trans‐2‐nonenal
content moved from 1. 06 – 4. 02 g. l‐1 and 1. 06 – 4. 02 g. l‐1.
105
Keywords
Trans‐2‐nonenal, barely, malt, czech beer, SPME‐GC‐FID
Acknowledgements This study was funded by the institutional support of the Ministry of Agriculture of the
Czech Republic (No. RO1915)
References
[1] SVOBODA Z., MIKULÍKOVÁ R., BĚLÁKOVÁ S., BENEŠOVÁ K., NESVADBA Z. :
Determination of lipid content and fatty acid representation in barley caryopses and
malt, Kvasný průmysl 11‐12, 2009, roč. 55, s. 315 ‐320.
[2] SKADHAUGE, B., KNUDSEN S., LOK, F., OLSEN, O.: Barley for production of flavour‐
stable beer, Proceedings of 30th Congress of the European Brewery Convention, Prague,
2005, p. 676 ‐ 678.
[3] SCHERER R. WAGNER R. HOFFMANN KOWALSKI C. TEIXEIRA GODOY H. : (E) ‐2‐
Nonenal determination in Brazilian beers using headspace solid‐phase microextraction
and gas chromatographic coupled mass spectrometry (HS‐SPME‐GC‐MS), Ci‐nc. Tecnol.
Aliment. vol. 30 supl. 1 Campinas, 2010, p. 161‐165.
[4] VESELY, P. et al. Analysis of aldehydes in beer using solid‐phase microextraction with
on‐fiber derivatization and gas chromatography/mass spectrometry. Journal
Agricultural Food Chemistry, v. 51, n. 24, 2003, p. 6941‐6944.
******
Uncertainty Characterization Procedure for Drinking Water Laboratory
Analysis
Diana Yudin1*, Anton Yudin2, Irina Geana3, Gili Saros3, Iuliana Piciorea3, Monica Culea1
1Univ. Babes‐Bolyai, Dept. of Physics, 1 Kogalniceanu Str, 400084, Cluj‐Napoca, ROMANIA e‐mail:
[email protected] 2Wolf Kunststoff Gmbh, Heisenbergstr. 63‐65, 50169, Kerpen, GERMANY
3National R&D Institute for Cryogenics and Isotopic Technologies, Uzinei Str. 4, 240050, Rm.
Valcea, ROMANIA
Abstract
Uncertainty can give the information about quality of result providing the dispersion of
values which can be attributed to the analyte. The term of uncertainty relates estimation
based on uncertainty budget including all known uncertainty contribution1. Several sources
contribute to the deviation of an individual result from an unknown ‘true’ value2.
Conductivity is the numerical expression of the ability of water to carry an electrical current
and a measure of free ion content in the water. An increased conductivity can be the result of
released heavy metals ions from water pollutants. A higher conductivity reflects higher
water pollution3. Determinations of electrical conductivity for water quality were made with
a complex system monitoring Horiba U‐23, in which 8 sensors are conected simultaneously.
For conductivity, the instrument can measure between 0. 00‐9. 99 S/m. To estimate the
uncertainty of conductivity, we had to quantify the possible sources of uncertainty which can
be counted as follow repeatability, instrument etalonation and resolution, certification of
106
reference material, bias and purity of work solution (substance). The extended relative
uncertainty of calculated value was determinated. To every result obtained with this method,
an extended uncertainty will be calculated and associated with that result. Validation
parameters were also determinated as precision, accurancy and detection limit. Romanian
Order, No. 311/2004 for drinking water, requests that validation parameter for electrical
conductivity has to be 10% from MCA (maximum admissible concentration). From
experimental data, detection limit, accuracy and precission are in conformity with Romanian
regulation and we consider that potentiometric method to determin electrical conductivity is
liniar, exactly and precise.
Keywords Romanian Orders, detection limit, accuracy, precision, liniarity, uncertainty, electrical
conductivity, drinking water.
Acknowledgements
This work was supported by National Research and Development Institute for Cryogenics
and Isotopic Technologies – ICIT Rm. Valcea, Romania.
References
[1] PICIOREA I., OUBRAHAM A., STEFANESCU A., MLADIN C. : Proceedings of the 16th
International ICIT Conference Progress in Cryogenics and Isotopes Separation, p. 147,
42, (2010).
[2] PICIOREA I. : The Second International Proficiency Testing Conference, p. 123, (2009).
[3] FLORESCU D., IONETE R. E., SANDRU C., IORDACHE A., GEANA E. I., SAROS G. :
Asian Journal of Chemistry, 23 (12), 5209, (2011).
******
The Effect of Heat Treatment, Temperature of Coagulation, Calcium
Chloride and Enzyme Concentration on The Rennet Coagulation of Cow
Milk
Buňka, F., Černíková, M., Pachlová, V., Salek, R. N., Stašková, I.
Tomas Bata University in Zlín, Faculty of Technology, nám. T. G. Masaryka 5555, CZ‐760 01 Zlín,
CZECH REPUBLIC
Abstract
Gelation of milk proteins is the crucial first step in cheese manufacture. Rennet coagulation
of milk may be divided into primary (enzymatic hydrolysis) and secondary (aggregation)
stages, although these stages normally overlap to some extent during cheese making. During
the primary stage, kappa‐casein is cleaved by rennet at phenylalanine‐methionine bond
(Lucey, 2002). During ageing of casein, structural changes take place that affect gel
parameters such as storage modulus (G´) and hardness of gel (Mellema et al., 2002).
Nowadays, cheese manufacturers have developed new approaches that could contribute to
improve of yield during renneting. A possible approach could lie in increasing of heat
treatment – from temperatures approximately 72 – 75 °C for 15 – 20 s to heat regimes in
range of 75 – 85 °C for 30 – 40 s. The changes of heat treatment crucially influence the
properties of curd. Therefore, additional technological procedures should be included for
107
achieving of curd of appropriate properties. Temperature of coagulation, calcium chloride
concentration and/or enzyme concentration could be studied to adjust of curd properties
(Awad, 2007 Nájera et al., 2003). Dynamic oscillation rheometry (especially storage
modulus), texture analysis (especially hardness of gel) and yield markers has been used in
the study.
Keywords
Milk Rennet Heat treatment Storage modulus Hardness.
Acknowledgements
The financial support from the Tomas Bata University in Zlin, Internal Grant Agencies
(projects IGA/FT/2015/004) is gratefully acknowledged.
References
[1] S. AWAD (2007). Effect of sodium chloride and pH on the rennet coagulation and gel
firmness. LWT, 40, 220 – 224.
[2] J. A. LUCEY (2002). Formation and physical properties of milk protein gels. Journal of
Dairy Science, 85, 281 – 294.
[3] M. MELLEMA, P. WALSTRA, J. H. J. van OPHEUSDEN, T. van VLIET (2002). Effects of
structural rearrangements on the rheology of rennet‐induced casein particle gels.
Advanced in Colloid and Interface Science, 98, 25 – 50.
[4] A. I. NÁJERA, M. DE RENOBALES, L. J. R. BARRON (2003). Effects of pH, temperature,
CaCl2 and enzyme concentration on the rennet‐clotting properties of milk: a
multifactorial study. Food Chemistry, 80, 345 – 352.
******
Determination of the Metal Content in Seafood and Fish Species From the
Romanian Market
Iordache, A. M.1, Voica, C.2, Suvar, N. S.3, Culea, M.3, Ionete, R. E.2
1National Institute for Research and Development of Cryogenics and Isotopic Technologies, 4 Uzinei,
Raureni, RO‐240050 Ramnicu Valcea, ROMANIA 2National Institute for Research and Development of Isotopic and Molecular Technologies, 67‐103
Donat, RO‐400293 Cluj‐Napoca, ROMANIA 3Babes Bolyai University, Faculty of Physics, 1 M. Kogalniceanu, RO‐400084 Cluj‐Napoca,
ROMANIA
Abstract Food is the primary source of essential elements for humans but it is also an important path
of exposure to toxic elements. Particularly, fish is an important part of the human diet and a
good indicator of pollution with trace metals in the aquatic ecosystem. The metals high
toxicity, bioaccumulation and persistence in the environment make them to present health
risk for organism. Therefore, routinely investigation of food is a prerequisite in knowledge
the level of essential and toxic elements. In this work, the levels of several trace metals (As,
Cd, Cu, Mn, Pb, Zn, Ni, Co, Al) in 10 seafood and 10 fish feed samples, collected from
markets in Romania, were determined by inductively coupled plasma mass spectrometry
(ICP‐MS), after microwave digestion. A Perkin Elmer ELAN DRC (e) instrument was used.
108
Recoveries were quantitative for all studied elements (over 80 %). The relative standard
deviation was less than 10 %. In order to assess the suitability of the analysed fish species for
human consumption in respect to concentrations of some heavy metals found in edible
muscle tissue, was observed that the contents of Cd, Pb and As in fish feed samples were
lower than the maximum permissible values, as described by the Directive 2002/32/EC
concerning the undesirable substances in animal feeds.
Keywords metal content, ICP‐MS, fish, seafood
Acknowledgements
ʺThis work was possible due to the financial support of the Sectorial Operational Program
for Human Resources Development 2007‐2013, co‐financed by the European Social Fund,
under the project number POSDRU/159/1. 5/S/132400 with the title „Young successful
researchers – professional development in an international and interdisciplinary
environment”. ʺ
References [1] W. de VRIES, P. F. ROMKENS, G. SCHUTZE, Critical soil concentrations of cadmium,
lead, and mercury in view of health effects on humans and animals, Reviews of
Environmental Contamination and Toxicology, 2007, 191, pp 91.
******
Determination of Nicotine in Different Types of Products
Matoušková, P., Pražáková, J., Márová, I.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Tobacco is a plant grown for its leaves, which are smoked, chewed, or sniffed. Tobacco
contains the alkaloid nicotine, a drug classified as a stimulant. Pure nicotine is a hygroscopic,
colorless oily liquid and it is a poisonous alkaloid. Nicotine effects on the body are complex.
The drug affects the brain and central nervous system as well as the hypothalamus and
pituitary glands of the endocrine system. Nicotine improves memory and concentration, and
also increases the sensation of wakefulness. These beneficial effects may play a role in the
initiation and maintenance of tobacco dependence. Withdrawal symptoms are a sense of
emptiness, anxiety, depression, moodiness, irritability, and inattentiveness. This work was
focused on optimization of methods for the determination of nicotine in different kinds of
products. Nicotine was determined by HPLC/PDA. Quantitative analysis of nicotine
concentration was performed in cartridges for electronic cigarettes, nicotine gums, nicotine
spray, nicotine lozenges, nicotine or dispersible films and classic cigarettes. For each type of
product the most appropriate nicotine extraction method was tested too. Finally, the
encapsulation of nicotine was tested. As a material for particles preparation were used
alginate, chitosan and alginate‐starch. The particles were prepared by the method based on
the principle of gelation and cross‐linking polymers using the Büchi Encapsulator B‐395 Pro.
The particles were exposed to model gastrointestinal conditions. After exposition, particles
109
stability and amount of released nicotine was monitored. The stability of particles in the
model food was studied too.
Keywords
nicotine, HPLC/PDA, tobacco, encapsulation
Acknowledgements
This work was supported by project “Materials Research Centre – Sustainability and
Development” No. LO1211 (Ministry of Education, Youth and Sport of the Czech Republic).
******
Comparison of Nutrients Composition of Some Vegetable Oils
Niculina‐Sonia Suvar1, Andreea Maria Iordache2, Cezara Voica3, Roxana Elena Ionete2,
Ramona Bleiziffer1, Monica Culea1
1”Babes‐Bolyai“ University, Biomolecular Physics Department, M Kogalniceanu Str, Cluj‐Napoca,
ROMANIA 2National R&D Institute for Cryogenics and Isotopic Technologies ‐ICIT, 4 Uzinei Str, ROMANIA 3National Institute for Research and Development of Isotopic and Molecular Technologies, 67‐103
Donat Str, Cluj‐Napoca, ROMANIA
Abstract Some vegetal oils used as food supplements from Romanian organic market were compared
with regard of fatty acids and some metal ions contets: hemp seeds, poppy seeds, pumpkin
seeds, grape seeds and olive oils. Fatty acids were determined by capillary gas
chromatography‐mass spectrometry (GC/MS). The oils were from Romanian producers and
the last two were from Italy. A Trace DSQ ThermoFinnigan quadrupole mass spectrometer
coupled with a Trace GC was used. The oil samples were derivatized as fatty acid methyl
esters (FAME) and separated on a Rtx‐5MS capillary column, 30 m x 0. 25 mm, 0. 25μm film
thickness, using a temperature program from 50oC, 2 min, 8oC/min at 310oC (10 min) the
carrier gas was helium 6. 0 at a flow rate of 1ml/min. The following conditions were
followed: transfer line temperature 250oC, injector temperature 250oC ion source
temperature 250oC Splitter: 10:1. Electron energy was 70eV and the emission current, 100μA.
The identification of fatty acids was obtained by comparison of fatty acids methyl esters
mass spectra with the mass spectra of FAME standards of NIST library. The vegetal oils were
found with high amounts of polyunsaturated fatty acids (PUFAs) ranging from 68. 53%
(olive) to 88. 54% (poppy seed) as follows: olive oil
Keywords
GC/MS, FATTY ACIDS, METALS, ICP‐MS.
Acknowledgements
This work was possible due to the financial support of the Sectorial Operational Program for
Human Resources Development 2007‐2013, co‐financed by the European Social Fund, under
the project number POSDRU/159/1. 5/S/132400 with the title „Young successful researchers –
professional development in an international and interdisciplinary environment”.
110
References
[1] A. FREIJE, J. Oleo Sci., 58, 379 (2009)
[2] N. SHAPIRA, P. WEILL, O. SHARON, R. LOEWENBACH, O. J. BERZAK, Agric. Food
Chem., 57, 2249 (2009)
[3] F. V. DULF, I. OROIAN, D. C. VODNAR, C. SOCACIU, A. PINTEA, Molecules, 18,
11768 (2003)
[4] M. MIHOC, G. POP, E. ALEXA, I. RADULOV, Chem. Central J. 6, 122 (2012)
******
On the Qualitative Parameters of Fruit Juices and Possibilities of their
Modification via Technological Modifications
Polovka, M., Tobolková, B., Belajová, E., Durec, J.
National Agricultural and Food Centre, VUP Food Research Institute, Department of Chemistry and
Food Analysis, Priemyselná 4, SK‐824 75 Bratislava, SLOVAK REPUBLIC
McCarter, Ltd., Bajkalská 25, SK‐821 01 Bratislava, SLOVAK REPUBLIC production premises:
Budovateľská 1247/7, SK‐929 01 Dunajská Streda, SLOVAK REPUBLIC
Abstract
Fruit juices belong to the most popular drinks worldwide. Besides vitamins and minerals
they represent rich source of phenolic compounds recognized for their antioxidant activity.
Increasing consumer’s demands towards high quality and safe food products push their
producers to increase the production and qualitative standards of the products. Recent
innovations in juices production resulted in modification of production conditions,
comprising the modification of composition (e. g., via the addition of fruit pulp and/or small
fruit pieces) innovations in packaging materials, as well as the production atmosphere
modification. The effects of production conditions of fresh orange juices with pulp and
pineapple juices and their modification, as well as the effect of conditions of their long‐term
storage on selected qualitative characteristics (antioxidant activity, color changes and
concentration of selected phytochemicals) are assessed, dominantly by EPR and UV‐VIS
spectroscopy was evaluated. Results obtained were processed by multivariate statistics in
order to evaluate the effects of sample origin and season or production technology on the
monitored characteristics and overall quality of fruit juices. Results obtained clearly
indicated that pasteurization influence the quality of the product, although the slight
pasteurization was applied, as in comparison to the fresh – non‐pasteurized samples, slight
decrease of values of practically all the monitored parameters was observed. However, as
regards the post‐pasteurization changes, significant influence of the production atmosphere
on the monitored qualitative parameters of juices was noticed, proving that replacement of
oxygen by inert gases prolongs significantly the juices shelf live. Kinetic study of the changes
of the monitored parameters upon the storage period indicate that in majority of cases,
gradual worsening of all the monitored parameters was observed, without respect on
technology of juice processing. In the samples processed under the modified atmosphere,
generally the retardation of the decrease as a result of inert atmosphere application in
dependence on type of production gas was noticed. This trend was particularly obvious for
longer storage periods, whereas in the beginning of storage (6 ‐ 7 weeks after the respective
111
juice production), the observed trends were unambiguous. Thus, it can be supposed that this
“protecting” effect of inert atmosphere is influenced by the physico‐chemical properties of
individual gases, mostly by their solubility in the liquid juice medium, apparent particularly
for CO2 application. It was also proved, that the properties of juices without respect on type
of fruit, are significantly affected by the effects of season and raw juice origin. As follows
from the results of statistical analysis, the year of production is strong discriminant factor as
on the basis of all the monitored characteristics, absolute discrimination of the samples by
canonical discrimination analysis was achieved. As regards raw material origin, only partial
differentiation, although with high classification score was obtained. Problematic was
particularly the differentiation of the blend sample from that originating from Costa Rica. As
regards the effect of production technology, the partially successful differentiation of
samples according to the inert gas applied was obtained, both for orange and pineapple
juices. The obtained results will help the juice producer in optimization of the juice
production conditions in order to obtain the product with maximum beneficial properties
kept during the whole expiration period. Its length can also be optimized on the basis of the
presented results.
Keywords
Fruit juices, modified atmosphere, stability, antioxidant activity, color changes, seasoning
effect, statistics
Acknowledgements
This contribution is the results of the project “Improvement of nutritional and sensorial
parameters of fruity and vegetable drinks via an inert gases application – ITMS 26220220175”
implementation, supported by the Research and Development Operational Programme
funded by the European Regional Development Fund.
******
Applications of New Types of Biomaterials Obtained by Fungal Solid‐State
Fermentation In Bakery Products Manufacturing
Tatiana Klempova1, Janka Janstova1, Sona Gavurnikova2, Michaela Havrlentova2, Milan
Certik1
1Faculty of Chemical and Food Technology, Slovak University of Technology, Radlinskeho 9, 812 37
Bratislava, SLOVAK REPUBLIC
2National Agricultural and Food Center, Plant Production Research Institute, Bratislavska cesta 122,
921 68 Piestany, SLOVAK REPUBLIC
Abstract Cereals (maize, rice, wheat) serve as major food supply with world production of over 2. 5
billion metric tons (FAOSTAT, 2013). The cereals are rich source of carbohydrates and some
proteins, but they are limited in various biologically active compounds such as
polyunsaturated fatty acids, carotenoid pigments, coenzyme Q10, etc. If cereals are
considered for preparation of functional bakery products, their nutritional properties should
be naturally modified to enrich them with these compounds. Therefore, biotechnological
technique based on solid state fermentation (SSF) has been developed. During the process,
112
Zygomycetous fungi (Thamnidium sp., Cunninghamella sp., Mucor sp., Mortierella sp.)
utilize cereals and convert them to new value‐added cereal‐derived biomaterials that could
be used in food/feed industry. The work is focused on characterization of flours and breads
prepared with addition of different types of fermented cereals (wheat, oat, buckwheat).
Application of these biomaterials does not only enrich the final products with new
compound (PUFA, ergosterol, etc), but very significantly change the nutritional and
functional properties of cereals such as content of starch, glucans, dietary fibre, etc.
Fermented cereals also change rheological properties of the dough (increased water
absorption, reduction of dough‐rise, prolonged dough development time, higher softening
degree of dough) and sensorial properties of the final cereal goods (brownish color,
crackness, accepted fungal flavour). Thus, biotechnologically prepared PUFA‐enriched
cereals may open novel prospects for the market of functional cereal food.
Keywords solid‐state fermentation, biomaterial, fungi, bakery applications
Acknowledgements
This work was supported by grant VEGA 1/0574/15 from Ministry of Education, by grant
APVV‐0662‐11 from the Slovak Research and Development Agency and by grant
DOMAPLUS from Ministry of Agriculture, Slovak Republic.
******
Rose Hips – The Sources of Galactolipids for The Production of Food
Supplements
Krmela, A., Schulzová, V., Hajšlová, J.
University of Chemistry and Technology, Faculty of Food and Biochemical Technology, Department
of Food analysis and Nutrition, Technická 5, CZ‐166 28 Praha, CZECH REPUBLIC
Abstract
Traditionally rose hips have been known for its beneficial biological effects on the human
body. Rose hips are already used in food supplement production as a remedy for
inflammatory joint diseases such as osteoarthritis. Clinical studies have suggested that
galactolipids are the group of compounds that are responsible for this beneficial biological
effect on patients suffering from osteoarthritis. Galactolipids are polar lipids, basically a
diacylglycerols with one or two bonded galactose molecules. According to the number of
bound molecules of galactose, they can be divided into monogalactosyldiacylglycerols
(MGDG) and digalactosyldiacylglycerols (DGDG). The method of extraction have been
developed and identification of galactolipids have been performed on UPLC‐MS/MS. This
method was applied to samples of six varieties of rose hips, in which the profile of present
galactolipids was observed. Each variety was analyzed in fresh and dried form for the
content and stability comparison. Samples of food supplements made from dog rose (Rosa
canina) were also analyzed. Up to 13 galactolipids were identified, 6 MGDG and 7 DGDG.
An MGDG with two bonded 18:3 fatty acids was identified as a major MGDG and DGDG
with the same fatty acids composition was identified as a major DGDG. Together they
represent more than 50 percent of identified galactolipids.
113
Keywords
rose hips biologically active compounds galactolipids LC‐MS/MS
Acknowledgements This research was carried out within the project MSMT COST LD14092 and specific
university research MSMT no. 20/2015 (supported by the Ministry of Education of the Czech
Republic)
******
HRMS Based Metabolomic Fingerprinting for Berries and Cranberries
Authentication
Hůrková, K., Rubert, J., Hajšlová, J.
University of Chemistry and Technology, Prague, Department of Food Analysis and Nutrition,
Technická 3, CZ‐166 28, Praha‐Dejvice, CZECH REPUBLIC
Abstract Berry crops belonging to the Vaccinium genus represent a popular source of bioactive
compounds, mainly plyphenols. The phytochemicals contained in cranberries have been
shown to have a positive effect on cardiovascular and immune systems, some in vitro
experiments have also documented anticancer activity. Another well‐known effect of these
red berries is prevention of urinary tract infections (UTI) Recently, fraud suspicion on
cranberries‐based products has been reported Vaccinium vitis‐idaea are partly or evevn
totally replaced by cheaper Vaccinium macrocarpon berries. Although PCR methods may
provide solution, these are not available in routine laboratories focused on food analysis. On
this account, alternative analytical strategies have to be searched. In this study, metabolomic
fingerprinting employing instrumental platform consisting of ultra‐high performance liquid
chromatography coupled to high resolution tandem mass spectrometry (HPLC‐HRMS/MS)
has to be investigated. For this purpose, polar and non‐polar extracts of Vaccinium vitis‐
idaea and Vaccinium macrocarpon together with their admixtures were prepared and
analyzed by HPLC‐HRMS/MS. Subsequently, chemometric evaluation was performed to
assess the differences between the samples and to identify significant markers, which are
present exclusively or more significantly present in one of the fruit species. In parallel,
accurate mass of MS and MS/MS spectra, different software packages and different online
libraries were tentatively employed for marker identification. More pronounced clustering
and significant differences between samples were found for polar extract in both positive
and negative ionization modes. Especially, polyphenols (catechin, epicatechin, procianidins)
and glycosides (Myricetin 3‐glucoside, peonidin pentose) were identified as markers
responsible for berries and cranberries differentiation.
Keywords
Cranberries, authenticity, metabolic fingerprinting, HRMS
Acknowledgements
This work was supported by the Czech Republic National Agency for Agricultural Research
(Project no. QJ1530272)
114
******
The Study of Distribution of Sesquiterpene Lactones in Model Systems of
Human Prostate Cancer Cells and Macrophages
Fenclova, M., Rimpelova, S., Zachariasova, M., Hajslova, J.
University of Chemistry and Technology, Prague, Department of Food Analysis and Nutrition,
Technicka 3, 166 28 Prague 6, CZECH REPUBLIC
Abstract
Higher plants are known to be a source of numerous substances with various positive, health
promoting biological effects, from which the substance with potential anticancer effect are
currently of a high interest. In fact, almost 70 % of anticancer drugs are based on natural
products or their derivatives. One of the representatives of such biologically active
substances are sesquiterpene lactones, secondary metabolites of plants related mainly to the
Asteraceae and Apiaceae family. This study is focused on three structurally (and thus also
biologically) related sesquiterpene lactones, namely thapsigagrin, trilobolide and
archangelolide. The latter two of them can be isolated also from the plants occurring in the
Czech ecosystems. All of these substances pose the cytotoxic effect related to their ability to
target the sarco/endoplasmic reticulum (ER) calcium ATPase (SERCA) pump and inhibit it
from transporting the Ca2+ from the cytosol into the ER. The high cytosolic Ca2+
concentrations lead to the generation of reactive oxygen species, ER stress and subsequent
cell death. Regarding this effect, the mentioned sesquiterpene lactones have a potential to be
used as anticancer drugs (the most extensively studied thapsigargin is already in cancer
clinical trials). Additionally, thapsigargin and trilobolide are also potent immunostimulatory
agents, as they are able to induce the cytokine interferon‐? secretion and nitric oxide
production (both of which playing key roles in anti‐infectious immune defense mechanisms)
in rodent and human macrophages. The aim of the study was to evaluate and compare the
real ability of thapsigargin, trilobolide and archangelolide to cross the cell membrane and
enter the intracellular compartment of the model systems of human prostate cancer cells and
also macrophages. For this purpose, a sensitive and high throughput analytical method for
the quantitative determination of the three mentioned sesquiterpene lactones in the cell
cultures and culture media was developed using reverse‐phase ultra‐performance liquid
chromatography coupled to tandem mass spectrometry (RP‐UPLC‐QtrapMS/MS). The
method was applied for the quantification of the target analytes in the samples of cell
cultures and related culture media from the model systems of two human prostate cancer
cell lines (LNCaP and PC‐3) and one macrophages (RAW 264. 7) treated with particular
sesquiterpene lactones in vitro.
Keywords
Sesquiterpene lactones, cancer cells, macrophages, UPLC‐MS/MS
Acknowledgements
Financial support from specific university research (MSMT No 20/2015) and from Czech
Science Foundation (GAČR) Grant 303/14/04329‐S.
115
References
[1] GHANTOUS, A. GALI‐MUHTASIB, H. VUORELA, H. SALIBA, N. DARWICHE, N.
What made sesquiterpene lactones reach cancer clinical trials?. Drug Discovery Today
2010, 15, 668–678.
[2] HARMATHA, J. BUDĚŠÍNSKÝ, M. VOKÁČ, K. KOSTECKÁ, P. KMONÍČKOVÁ, E.
ZÍDEK, Z. Trilobolide and related sesquiterpene lactones from Laser trilobum
possessing immunobiological properties. Fitoterapia 2013, 89, 157–166.
[3] KMONÍČKOVÁ, E. HARMATHA, J. VOKÁČ, K. KOSTECKÁ, P. FARGHALI, H.
ZÍDEK, Z. Sesquiterpene lactone trilobolide activates production of interferon‐ and nitric oxide. Fitoterapia 2010, 81, 1213–1219.
******
GC‐HRTOF: A Powerful Tool for Evaluation of Whisky Quality and
Authenticity
Stupák M., Hajšlová J.
University of Chemistry and Technology, Faculty of Food and Biochemical Technology, Prague,
Technická 5 166 28 Praha 6 CZECH REPUBLIC
Abstract Whisky is one of the most popular spirits in the word. Since the most famous whisky is
originally from Scotland, the Scotch whisky is very often the subject of adulteration. For this
reason both consumer protection agencies and producers require analytical laboratories to
support their consumer and brand protection programmes with effective brand authenticity
analyses. Plenty of methods have been developed for quality and authenticity of whisky, e.
g. UV/VIS spectroscopy for evaluation of compounds formed during the maturation process,
near red spectroscopy or capillary electrophoresis. Furthermore, gas chromatography (GC)
coupled to flame ionization detector or mass spectrometry (MS) has been applied for the
quality assessment and in some studies for analysis of volatiles compounds also solid phase
microextraction coupled to GC‐MS was used. To the best of our knowledge, GC hyphenated
with high resolution mass spectrometry (HRMS) has never been used for the evaluation of
whisky adulteration. Therefore, we developed a new approach for authenticity assessment of
whisky based on GC‐HRMS. During the development of this method, several analytical GC
columns (both polar and non‐polar stationary phases) and different type of inlets (splitless
and split) were tested. With this new procedure, more than 140 authentic whisky samples
(mainly single malt and blended) from different regions provided by The Scotch Whisky
Research Institute were analyzed. For the chemometric evaluation of the data, principal
component analysis (PCA), partial least squares discriminant analysis (PLS‐DA) and
orthogonal PLS‐DA were applied. Using these statistical methods, we achieved adequate
distribution of samples according to the type of whisky and the region based on specific
markers.
Keywords
whisky, authenticity, adulteration, GC‐HRMS
116
******
Why is this Product Smelling: Application of SPME Coupled with GC‐
HRMS
Hradecký J. and Hajšlová J.
University of Chemistry and Technology, Department of Food Analysis and Nutrition, Prague,
Technická 5 166 28 Praha 6 CZECH REPUBLIC
Abstract
Odor emissions of plastic materials employed for production of various articles of daily use
may represent a serious problem which may result in customers’´ complaints and,
consequently producers´ losses of market position. The identification of such ´smelly´
compounds and explanation of their release is a real laboratory challenge since in many
cases, they are present at (ultra) trace level, nevertheless have a very low odor threshold.
Non target screening of headspace volatiles employing solid phase microextraction coupled
to gas chromatography / mass spectrometry (SPME‐GC/MS) is e technique of choice. For this
purpose, instrument equipped with high resolution time of flight mass analyzer (HR TOF) is
the most suitable for tracing ´unknowns´ since it provides full spectral information,
deconvolution of components occurring in complex mixtures, and their identification /
confirmation based on accurate masses of detected ions and their isotopic pattern. In a
particular, two case studies will be presented. In the first one, ´chemical´ odor was emitted
by plastic kettle, in the latter case, the distributor complained on ´strange´ smell of plastic
inhalator. The analytical strategy aimed at characterization of the problem will be presented.
Worth to notice, that In general terms, recycling of raw materials might be associated with
such type of problems, moreover, health risks due to consumers´ exposure to various
contaminants has to be taken into consideration.
Keywords
solid phase microextraction, non‐target screening, gas chromatography ‐ hight resolution
time of flight mass spectrometry
******
Impact Of Different Processing Atmospheres on the Volatiles of Orange
Juice with Pulp
Kopuncová, M., Kolek, E., Sádecká, J.
National Agricultural and Food Centre, Food Research Institute, Department of Chemistry and Food
Analysis, Priemyselná 4, SK‐824 75 Bratislava, SLOVAK REPUBLIC
Comenius University, Faculty of Natural Science, Chemical Institute, Mlynská dolina, Ilkovičova 6,
SK‐842 15, Bratislava, SLOVAK REPUBLIC
Abstract The effectiveness of three different processing atmospheres to preserve the volatiles of
orange juice with pulp during storage was investigated over two years. Application of
117
conventional “air”, and nitrogen atmosphere was evaluated in 2014 use of two inert gases,
nitrogen and carbon dioxide, was monitored in 2015.
Headspace‐solid phase microextraction (HS‐SPME), gas chromatography‐mass spectrometry
(GC‐MS) and gas chromatography coupled to flame ionisation detection and olfactometry
(GC/FID‐O) were used for extraction, and subsequently for analysis of the volatile fraction
composition. Individual compounds were identified on the basis of comparison of their mass
spectra, linear retention indices, GC analysis of standards, and by comparison of data on
occurrence and odour description with literature.
Statistical processing of GC‐MS data proved that use of nitrogen atmosphere in the
production of orange juice had different effect on the composition of its volatile fraction
during 4‐month storage than technological processing of the identical juice in the
conventional atmosphere. Effectiveness of the application of carbon dioxide as inert
atmosphere was comparable with nitrogen but its acceptability by consumers have to be
considered because of the sparkling character of final products.
None of investigated inert atmospheres was able to avoid all changes in the composition of
volatiles during 4‐month storage. However, parallel GC/FID‐O analyses proved that these
changes were not sensorially significant and they did not lead to the worsening of
organoleptic properties of juices. On the contrary, negative sensory changes in flavour,
mainly increase of bitter and astringent taste along with certain loss of freshness and fruity
sweetness, were observed for juices processed in conventional “air” atmosphere. GC/FID‐O
analyses revealed that generation of some aldehydes could be responsible for this off‐flavour
phenomenon occurred during storage.
Keywords
gas chromatography, inert atmosphere, orange juice, storage, volatiles
Acknowledgements
This work is a partial study of the research project “Improvement of nutritional and sensorial
parameters of fruity and vegetable drinks via an inert gas application” – ITMS26220220175
supported by the Research and Development Operational Programme funded by the ERDF.
McCarter Ltd., Bratislava (production premises Dunajská Streda), Slovakia, is gratefully
acknowledged for player friendly cooperation and samples provision.
118
******
Comparison of Sensory Quality of Commercial and Home‐Made Model
Swiss Cheese
Vítová, E., Sůkalová, K., Mahdalová, M., Butorová, L., Musilová, L., Pecinová, E.
Department of Food Chemistry and Biotechnology, Faculty of Chemistry, Brno University of
Technology, Purkyňova 118, 612 00, Brno, CZECH REPUBLIC
Abstract
Swiss cheese is a generic name for several related varieties of cheese resembling the true
Emmental whose name comes from the location where it supposedly originated, Emme
valley in the canton of Bern in Switzerland.
Swiss cheese types have ivory to light yellow colour, firm, slightly elastic texture,
characteristic mild, nutty, sweetish flavour and a distinctive appearance some cheeses have
round regular holes known as ʺeyesʺ, while some do not (known as ʺblindʺ). Three types of
bacteria are typically used to make Swiss cheese (these can vary slightly depending on the
manufacturer) : Streptococcus salivarius subsp. thermophilus, Lactobacillus spp. and
Propionibacterium freudenreichii subsp. shermanii). Propionic acid fermentation is essential
to obtain characteristic eyes and the nutty flavour.
Today Swiss cheeses are produced in many countries and a great variety is available on the
world market. The aim of this work was to produce new type of Swiss cheese with the
comparable or even better sensory quality than commercially available corresponding
products. The model samples were produced in pilot plant using standard technology
procedure fresh milk in “bio” quality was used as a basic raw material. The sensory quality
of model samples was compared with standard Swiss cheese purchased on the Czech
market.
The sensory analyses were carried out in a sensory laboratory (ISO 8589:2008). Twenty‐three
assessors were selected from students of the faculty and used for evaluation of the samples.
Five main sensory attributes (appearance, colour, odour, flavour and texture) were evaluated
using five point ordinal hedonic scale (1‐ excellent to 5 ‐ unsatisfactory). Paired comparison
test (ISO 5495:2005) was used to investigate preference of assessors/consumers. The
significant differences (P < 0. 05) in odour, flavour and texture were found between samples.
Odour and flavour of model samples were quite strong and piquant, which is probably the
reason why they were less preferred by conservative Czech consumers/assessors, however,
prospectively they could be offered at the Czech market as a new nontraditional cheese
product.
Keywords
Swiss cheese, sensory quality, sensory analysis
Acknowledgements This work was supported by a Standard project of specific research No. FCH‐S‐15‐2827.
119
References
[1] FOX, P. F., GUINEE, T. P., COGAN, T. M., MCSWEENEY, P. L. H., 2000:
Fundamentals of Cheese Science. 1st. ed. Gauthersburg (Maryland, USA) : Aspen
Publication, 638 p. ISBN 0‐8342‐1260‐9.
[2] ROGINSKI, H., FUQUAY, J. W., FOX, P. F. : Encyclopedia of Dairy Science. London:
Academic Press, 2002. pp. 363–371. ISBN 0‐12‐227235‐8.
[3] KOCAOGLU‐VURMA, N. A., ELIARDI, A., DRAKE, M. A., RODRIGUEZ‐SAONA,
L. E., HARPER, W. J. Rapid Profiling of Swiss Cheese by Attenuated Total
Reflectance (ATR) Infrared Spectroscopy and Descriptive Sensory Analysis. Journal
of Food Science, 2009, Vol. 74, No. 6, pp. S232‐S239. ISSN 0022‐1147.
[4] KOCAOGLU‐VURMA, N. A., HARPER, W. J., DRAKE, M. A., COURTNEY, P. D.
Microbiological, chemical, and sensory characteristics of Swiss cheese manufactured
with adjunct Lactobacillus strains using a low cooking temperature. Journal of Dairy
Science, 2008, Vol. 91, No. 8, pp. 2947‐2959. ISSN 0022‐0302.
******
Occurence of Organic Contaminants in Food Supplements Based on Fish
Oil
Drabova, L., Pulkrabova, J., Hrbek, V., Kocourek, V., Hajslova, J.
University of Chemistry and Technology Prague, Department of Food Analysis and Nutrition,
Technická 3, CZ‐16628 Prague 6, CZECH REPUBLIC
Abstract
In the last decade, a consumption of fish oil supplements has increased worldwide. They are
recommended as an additional diet source of omega‐3, omega‐6 fatty acids, minerals and
vitamins. However, fish oil may contain relatively high concentrations of organic pollutants,
especially halogenated, such as polychlorinated biphenyls (PCBs), various organochlorine
pesticides (OCPs), polybrominated diphenyl ethers (PBDEs) and also polycyclic aromatic
hydrocarbons (PAHs). Therefore, the consumption of nutritional supplements with oil
components may increase a dietary intake of various POPs and PAHs. During the recent
years several RASFF notifications on PAHs, in fish oil supplements were released. The
maximum limit set by the Regulation No. 1881/2006/EC on PAH 4 (sum of
benz[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, and chrysene) for oils and fats
intended for direct human consumption is 10 g/kg.
The main aim of this study was to analyse altogether 44 dietary supplement products based
on fish oil available at the Czech market and to assess levels of halogenated POPs and PAHs.
The rapid and simple sample preparation procedure for the simultaneous isolation of the
above mentioned target contaminants from fish oil supplements is based on a
extraction/clean‐up step employing solid‐phase extraction (SPE) on silicagel minicolumn
followed by two‐dimensional gas chromatography coupled with time‐of‐flight mass
spectrometry (GCxGC TOFMS) was used. Needed to emphasize that this procedure enables
simultaneous determination of PAHs, PCBs, PBDE and OCPs, thus in this way significant
increase of laboratory throughput is achieved.
120
The levels of PAHs and POPs in analyzed samples (0. 35‐53. 73 μg. kg‐1 for 8 PAHs, 0. 2‐55.
7 μg. kg‐1 for 7PCBs and 0. 2‐10. 3 μg. kg‐1 for PBDEs) were comparable with those
reported in literature. Three of the analyzed samples exceed the maximum limit set by the
Reg. 1881/2006/EC for PAH 4.
Keywords
food supplements, contaminants, PAHs, POPs, fish oil
Acknowledgements
The financial support by the “Operational Program Prague – Competitiveness“ (CZ. 2. 16/3.
1. 00/22197) and “National Program of Sustainability“ (NPU I (LO) MSMT ‐ 34870/2013) is
gratefully acknowledged
121
Chemistry of Silicates
The Particle Sizes Influence on The Properties of Portland Cement Pastes
Pavel Šiler, Iva Kolářová, Tomáš Sehnal, Roman Snop, Tomáš Opravil, František Šoukal
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova
464/118, Brno, CZ‐612 00, CZECH REPUBLIC
Abstract
The consumption of concrete as a building material is still increasing over the world.
Concrete production is closely associated with CO2 and other greenhouse gases emissions.
The reduction of these emissions can be achieved by a higher utilization of secondary raw
materials in cement mixtures. Particle size is an important factor for more effective use of
these materials. This work is focused on the calorimetric determination of the effect of
particle size of cement, finely ground granulated blast furnace slag (GBFS), high‐temperature
fly ash (FA) and fluidized fly ash (FFA) on the Portland cement hydration. Effect of particle
size on the hydration of pure cement pastes and pastes with the addition of secondary raw
materials is monitored by isoperibolic calorimetry. Other part of this work is aimed on the
mechanical properties of resulting materials. The flexural strength and compressive strength
were observed after 1, 7 and 28 days of curing.
Keywords
Portland cement, isoperibolic calorimetry, ground blasted furnace slag, fly ash, mechanical
properties
Acknowledgements
This work was financially supported by the project Materials Research Centre at FCH BUT‐
Sustainability and Development. REG LO1211 with financial support from National Program
for Sustainability I (Ministry of Education Youth and Sports) and Czech Scientific
Foundation number: GA13‐41018S.
References
[1] S. WILD. S. J. M. KHATIB: Cem Concr Res Vol. 27 (1997). p. 137–146
[2] J. DUCHESNE. E. J. REARDON: Cem Concr Res Vol. 25 (1995). p. 1043–1053.
[3] F. P. GLASSER. J. MARCHAND E. SAMSON, E. Cem Concr Res Vol. 38 (2008). P. 226–
246.
[4] P. ŠILER. T. BAYER. T. SEHNAL. I. KOLÁŘOVÁ. T. OPRAVIL. F. ŠOUKAL: Cons Build
Mat Vol. 78 (2015). p. 181–188.
[5] P. ŠILER. J. KRÁTKÝ. I. KOLÁŘOVÁ. J. HAVLICA and J. BRANDŠTETR: Chem pap
Vol. 67 (2013). p. 213–220.
[6] P. ŠILER. I. KOLÁŘOVÁ. J. KRÁTKÝ. J. HAVLICA. J. BRANDŠTETR: Chem pap Vol. 68
(2014). p. 90–97.
[7] V. RAHHAL. R. TALERO: J Therm Anal Calorim Vol. 78 (2004). p. 191 – 205.
122
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The Preparation of Heat Insulating Moulded Refractories
Bednárek, J., Novotný, R., Šoukal, F., Tvrdík, L.
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 118,
CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
The thesis deals with the study of influence of the foaming agent Schäumungsmittel W 53
addition on the specific weight and mechanical characteristics of mullite‐based heat
insulating refractory castables. The effect of dosing and mixing time was observed in this
work. The influence of partial substitution of mullite matrix by kaolin on specific weight and
mechanical characteristics was also studied. Kaolin was added in dry matter or in the
foamed state. Optimal dosage of the agent was 0. 25 % and the optimal mixing time was 10
min. The addition of kaolin was the most effective in the foamed state.
Keywords refractory castable, foaming agent, water foam, mullite, kaolin
Acknowledgements
The paper was prepared with financial support of TAČR through project no. TA02010995
andwith support of project Materials Research Centre at FCH BUT‐ Sustainability and
Development, REG LO1211, with financial support from National Programme for
Sustainability I (Ministry ofEducation, Youth and Sports).
References
[1] SCHACHT, C. A. 2004. Refractories Handbook. Boca Raton: CRC Press. ISBN 0‐8247‐
5654‐1.
******
Possibilities of Using Plasticizers and Superplasticizers in Alkali‐Activated
Systems
Hajdúchová, M., Langová, M., Enev, V., Kalina, L.
Brno University of TechnologyFaculty of Chemistry, Materials Research CentrePurkyňova 118CZ‐
612 00 Brno CZECH REPUBLIC
Abstract
The study deals with the preparation process and properties of alkali‐activated blast furnace
slag with different addition of plasticizers and superplasticizers. The goal of this study is to
find the suitable plasticizer or superplasticizer, which improve the workability and
mechanical properties of alkali‐activated slag. The behavior of plasticizing admixture in
alkali environment was studied by infrared spectroscopy (FT‐IR).
Keywords
blast furnance slag, alkali‐activation, plasticizing admixture
123
Acknowledgements
This work was financially supported by the project: Materials Research Centre at FCH BUT‐
Sustainability and Development, REG LO1211, with financial support from National
Programme for Sustainability I (Ministry of Education, Youth and Sports).
References
[1] AÏTCIN, Pierre‐Claude. Vysokohodnotný beton. 1. české vyd. Praha: Pro Českou
komoru autorizovaných inženýrů a techniků činných ve výstavbě (ČKAIT) a Českou
betonářskou společnost vydalo Informační centrum ČKAIT, 2005, 320 s. Betonové
stavitelství. ISBN 80‐86769‐39‐9.
[2] PROVIS, John. Alkali activated materials: state‐of‐the‐art report, RILEM TC 224‐AAM.
pages cm. ISBN 9789400776715.
[3] COLLEPARDI, Mario. Moderní beton. 1. vyd. Praha: Pro Českou komoru
autorizovaných inženýrů a techniků činných ve výstavbě (ČKAIT) vydalo Informační
centrum ČKAIT, 2009, 342 s. Betonové stavitelství. ISBN 978‐80‐87093‐75‐7.
[4] SHI, Caijun, P KRIVENKO a D ROY. Alkali‐activated cements and concretes. New York:
Taylor & Francis, 2006, ix, 376 p. ISBN 0415700043.
******
Chloride Resistance of Alkali Activated Slag Pastes With Fly Ash
Replacement
Parizek, L., Bilek Jr., V., Brezina, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
High energy requirements due to producing of Portland cement leads to a tendency to use
secondary raw materials or completely new kind of materials. One of the possibilities is
using the materials based on alkali activated slag (AAS). In this paper the influence of partial
replacement of ground granulated blast furnace slag by fly ash in AAS pastes on mechanical
properties and porosity of was investigated. For practical applications it is also necessary to
know their resistance to environment such as salty water. Chloride resistance was
investigated by setting the experiment as external chloride attack and measuring the changes
of mechanical properties, porosity and composition of the pastes.
Keywords
Alkali activated slag, chloride resistance, fly ash, Mercury intrusion porosimetry
Acknowledgements
This work was financially supported by the project ʺMaterials Research Centre at FCH BUTʺ‐
Sustainability and Development, REG LO1211, with financial support from National
Program forSustainability I (Ministry of Education, Youth and Sports)
124
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Strength and Porosity of Alkali Activated Materials
Bilek Jr., V., Parizek, L., Kosar P., Kratochvil, J., Kalina, L.
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 118,
CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
This study investigates the effect of different admixtures on strength and porosity
development of mortars and pastes based on alkali activated slag (AAS). Fluidized bed
combustion fly ash and by‐pass cement kiln dust were used to replace slag in the binder by
5%wt. and 10%wt., respectively. Pure slag mortar was also modified by a shrinkage reducing
admixture. The use of all the admixtures resulted in a reduction in early age strength, while
only shrinkage reducing admixture had significant impact on pore size distribution.
Properties of AAS based specimens were compared to those of specimens based on ordinary
Portland cement (OPC).
Keywords
alkali activated slag, FBC fly ash, by‐pass cement kiln dust, Portland cement, strength,
porosity
Acknowledgements
This work was financially supported by the project: Materials Research Centre at FCH BUT‐
Sustainability and Development, REG LO1211, with financial support from National
Programme for Sustainability I (Ministry of Education, Youth and Sports).
******
Optimization of Alternative Aggregates Based on Fluid Combustion Fly
Ashes
Jiří Kratochvíl, Hana Kalousová, Tomáš Opravil
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Effective usage of fluidized bed combustion fly ash is very low. These valuable resources are
mostly deposited or in the best case used as a filler in excavated areas. Only very small
amount is used differently. This paper presents one of the possibilities of usage of these
interesting secondary resources. The goal of this paper is to investigate possibilities of
preparation of alternative aggregate based on fluid combustion fly ashes. The work is
focused on the study of mechanical properties of prepared aggregates. Monitoring of other
properties including impact of the quality of fly ash in time, which has been stabilized as far
as possible in recent years, will be addressed in the following work.
125
Keywords
Power industry, fly ash, flue – gas desulfurization products, aggregates, artificial aggregates,
lightweight aggregates
Acknowledgements
This work was financially supported by Materials Research Centre at FCH BUT ‐
Sustainability and Development, REG LO1211, with financial support from National
Programme for Sustainability I (Ministry of Education, Youth and Sports).).
References [1] AHMARUZZAMAN, M. A review on the utilization of fly ash. Progress in Energy and
Combustion Science. 2010, vol. 36, issue 3, s. 327‐363. DOI: 10. 1016/j. pecs. 2009. 11. 003.
[2] GEETHA, S. a K. RAMAMURTHY. Environmental friendly technology of cold‐bonded
bottom ash aggregate manufacture through chemical activation. Journal of Cleaner
Production. 2010, vol. 18, issue 15, s. 1563‐1569. DOI: 10. 1016/j. jclepro. 2010. 06. 006.
******
The Leachability of Heavy Metals from Alkali‐Activated Fly Ash and Blast
Furnace Slag Matrices
Jan Koplík, Miroslava Smolková, Jakub Tkacz
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
The ability of alkali‐activated materials to fix and immobilize heavy metals was investigated.
Two raw materials were used to prepare alkali‐activated matrices – high‐temperature fly ash
and blast furnace slag (BFS). NaOH served as alkaline activator. Two heavy metals (Mn, Ni)
were added in various amounts into the matrices to find out the influence of dosage of heavy
metal on the leachability and mechanical properties of matrices. Leachability was measured
as concentration of heavy metals in leachates (ČSN EN 12457‐4) by inductively coupled
plasma/optical emission spectrometry (ICP/OES). Structure of prepared matrices was
characterized by scanning electron microscopy. Increasing of dosage of heavy metals added
to the matrices led to decrease of mechanical properties. The leaching tests showed that both
matrices can immobilize Mn and Ni in dosages of added heavy metal 0. 1 – 2, 5%. Higher
dosages caused deterioration of the matrices and increasing of leachability of fly ash
matrices. After alkali activation both heavy metals were transformed into the form of
insoluble salts.
Keywords
fly ash, blast furnace slag, alkaline activation, leachability
Acknowledgements This work was financially supported by the project ʺMaterials Research Centre at FCH BUTʺ
– Sustainability and Development, REG LO1211, with financial support from National
Programme for Sustainability I (Ministry of Education, Youth and Sports).
126
******
Effect of Phosphates on the Hydration Process of Alkali Activated Materials
Kalina, L., Bílek, V., Komosná, K., Novotný, R., Tkacz, J.
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 118,
CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
The study deals with the one of the important feature of alkali activated blast furnace slag
which is very rapid initial setting. Therefore, the influence of the retarding agents such as
phosphates was tested. It is shown that phosphates decreases the hydration heat evolution
and retards the hydration reaction of alkali activated slag effectively. The mechanism of
retardation is studied through the microcalorimeter and electron microscopy equipped with
energy dispersive analyzer (SEM EDS). The optimal dosage of retarding admixture in the
means of mechanical properties has been determined.
Keywords alkali activation, blast furnace slag, phosphates
Acknowledgements
This work was financially supported by the project: Materials Research Centre at FCH BUT‐
Sustainability and Development, REG LO1211, with financial support from National
Programme for Sustainability I (Ministry of Education, Youth and Sports.
******
Mechanisms of Macro‐Pores Origin in The MDF Composites Fabrication
Masilko, J., Soukal, F., Zurova, M., Havlica, J.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Paper deals with the description of the MDF composite microstructure and the possible
emergence of macro‐pores. MDF composites show enhanced mechanical properties,
especially flexural strength. Where, the flexural strength can be associated with the
elimination of critical cracks in the material. One of the steps of production of MDF
composites is high‐shear mixing, that just helps to achieve defect‐free structure. The primary
aim of this work is to specifically describe the origin of the macro‐pores in the structure of
MDF composites. The secondary one is to find appropriate setup for high‐shear mixing
equipment in order to eliminate main macro‐pores (shear speed, distance between the rollers
etc.).
Keywords
macro‐defect‐free, composite, macro‐pore, high‐shear mixing
127
Acknowledgements
The work has been supported by grant project no. GA13‐41018S financed by Czech Science
Foundation and by project Materials Research Centre at FCH BUT ‐ Sustainability and
Development, REG LO1211, with financial support from National Programme for
Sustainability I (Ministry of Education, Youth and Sports of Czech Republic).
References
[1] BIRCHALL J. D., HOWARD A. J., and KENDALL K., Flexural strength and poros¬ity of
cement. Nature (1981) 289, (29) : p. 388 – 390
[2] ODLER I., Special inorganic cement. 1st ed. London: E & F. N. Spon (2000) p. 226 247,
ISBN: 0‐419‐22790‐3
[3] POPOOLA O. O., KRIVEN W. M., YOUNG J. F., Microstructural and microchemical
characterisation of a calcium aluminate–polymer composite (MDF cement). Journal of
the American Ceramic Society (1991) 74, (8) : p. 1928 – 33
******
The Role of Temperature on Binary System of Metakaolin/Portland Cement
Martin Boháč, Radoslav Novotný, Miroslava Hajdúchová, Jakub Tkacz, František Šoukal,
Tomáš Opravil, Martin Palou
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
The role of temperature of metakaolin/Portland cement binary system was studied by
isothermal calorimetry. Samples with 10, 20, 30, 40 and 50 % of metakaolin replacement were
monitored at 30 °C, 40 °C 50 °C and 60 °C and compared to pure Portland cement. Structural
and chemical characterization of hardened pastes was obtained by scanning electron and
Raman microscopy. Paper deals with kinetics of main exothermal reactions during early
hydration of the system. Activation energies were calculated for each heat flow exothermic
peak. The role of composition on activation energies of separate peaks is discussed. The
nature of hydration products at different temperatures was revealed by microstructural
studies.
Keywords
Portland cement, metakaolin, role of temperature, hydration, activation energy,
microstructure
128
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The Influence of Barium Compounds on the Formation of Portland Cement
Clinker
Zezulova, A.1, Stanek, T.1, Opravil, O.2
1Research Institute for Building Materials, Hněvkovského 65, CZ‐617 00 Brno, CZECH REPUBLIC 2Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Portland clinker is thanks to its large‐scale production a continuously studied topic. Clinker,
or Portland cement, is used for construction purposes or for insulation and special
applications. One of these special applications could be shielding of different types of
radiation by making use of the content of barium ions. The present article examines the
influence of barium oxide on the formation and properties of Portland clinker, which could
be, by incorporation of barium ions into the system, used as a binder for buildings resistant
to various types of radiation.
Barium sulphate and barium carbonate were added to the raw meal in order to prepare
clinkers with different content of barium oxide. The effect of barium on the formation of
clinker phases was studied (by XRD – Rietveld analysis and by the microscopic point
counting method), as well as the rate of alite formation under isothermal conditions.
Furthermore, the ability of barium to become a part of clinker minerals was studied by SEM
with EDS.
Keywords
Portland clinker, alite, belite, barium oxide, barium content determination, Portland cement,
raw meal, barium carbonate, barium sulfate.
Acknowledgements
This paper was elaborated with the institutional support for long‐term development of
research organizations by the Ministry of Industry and Trade of the Czech Republic.
References
[1] N. K. KATYAL, S. C. AHLUWALIA, R. PARKASH, Effect of barium on the formation of
tricalcium silicate, Cement and Concrete Research. 1999, vol. 23, 1857‐1862.
[2] I. JUEL, E. JONS, The influence of earth alkalis on the mineralogy in a mineralized
Portland cement clinker, Cement and Concrete Research. 2001, vol. 31, 893‐897.
[3] L. CHEN, X. SHEN, S. MA, Y. HUANG, B. ZHONG, Effect of barium oxide on the
formation and coexistence of tricalcium silicate and calcium sulphoaluminate, Journal of
Wuhan University of Technology‐Mater. 2009, vol. 24, issue 3, 457‐461.
[4] W. KURDOWSKI, R. WOLLAST, Solid solution of BaO in tricalcium silicate, Silicate
Industriels. 1970, vol. 35, 153‐159.
[5] P. APPENDINO, M. MONTORSI, The influence of Sr, Ba, and Mg on the polymorphous
transformations of tricalcium silicate, II, Cemento. 1971, vol. 68, 89‐98.
129
[6] M. R. REZAIE, H. R. REZAIE, R. NAGHIZADEH, The effect of SiO2 additions on
barium aluminate cement formation and properties, Ceramics International. 2009, vol.
35, issue 6, 2235‐2240.
[7] T. STANĚK, Vliv SO3 a MgO na tvorbu portlandského slínku, Sborník Cement 93, Stará
Lesná 1993, 203 – 208.
[8] S. HORKOSS, R. LTEIF, T. RIZK, Influence of the clinker SO3 on the cement
characteristics, Cement and Concrete Research. 2011, vol. 41, issue 8, 913‐919.
******
Possibilities of Using Energy by‐Products as Raw Materials for
Hydrothermal Reaction
Galvánková, L., Opravil, T.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
The aim of this contribution is study of possibilities of processing energy by‐products,
especially coal fly ash, by hydrothermal treatment. Thanks to hydrothermal conditions and
proper alkali activation of fly ashes we can obtain new materials, mainly zeolites. The results
of hydrothermal synthesis are influenced by many factors, while temperature of reaction,
solution/fly ash ratio and different concentration of alkali activator (NaOH) were examined.
Phase composition of prepared samples was characterized by X‐ray diffraction (XRD) and
scanning electron microscopy (SEM). Also the ability of exchanging Mg2+ cations of
prepared samples was determined.
Keywords
Fly ash, hydrothermal reaction, zeolites, alkali activator, cation exchange capacity.
Acknowledgements
This study was supported by project of Materials Research Centre on Faculty of Chemistry,
Brno University of Technology ‐ sustainability and development r. c. LO1211 with financial
support of National program of sustainability I (The Ministry of Education, Youth and
Sports).
References
[1] M. AHMARUZZAMAN, A review on the utilization of fly ash, Prog. Energy Combust.
Sci. 36, (2010) 327‐363.
[2] A. MOLINA, C. POOL, A comparative study using two methods to produce zeolites
from fly ash, Miner. Eng. 17, (2014) 167‐173.
[3] X. QUEROL, N. MORENO, J. C. UMAÑA, A. ALASTUEY, E. HERNÁNDEZ, A. LÓPEZ‐
SOLER, F. Plana. Synthesis of zeolites from coal fly ash: an overview, Int. J. Coal Geol.
50, 1‐4, (2002) 413‐423.
[4] M. MIYAKE, Ch. TAMURA, M. MATSUDA, Resource recovery of waste incineration fly
ash: synthesis of zeolites A and P, J. Am. Ceram. Soc. 85, (2002) 1873‐75.
130
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Synthetic Preparation of Thaumasite
Masarova, A.
Masarova, A. : Research Institute for Building Materials, Hněvkovského 65, CZ‐617 00 Brno,
CZECH REPUBLIC
Abstract
AFt phases – mainly ettringite and thaumasite, as products of sulfate attack in concrete, can
cause serious damage to cement binder. The second mentioned, thaumasite
CaSiO3·CaCO3·CaSO4·15H2O, is connected to lower temperatures. It is less common and less
known. For further research of this mineral, it is fundamental to prepare thaumasite in clear
form in laboratory conditions. The aim of this work was to try several possibilities of
thaumasite preparation ‐ firstly by burning of mixes consisting of stoichiometric proportions
of particular components in thaumasite and secondly by method in sugar solution and in
MgSO4 solution.
Keywords
sulfate attack, AFt phases, ternesite, thaumasite, cement, X‐ray powder diffraction
Acknowledgements This paper was elaborated with the institutional support for long‐term development of
research organizations by the Ministry of Industry and Trade of the Czech Republic.
******
The Basics of Low Volume Weight Aerated Autoclaved Concrete
Preparation
Koutný, O., Opravil, T.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
This work deals with the basics and possibilities of preparation non‐bearing, heat‐insulating
material based on autoclaved aerated concrete. The ultra‐low volume weight (under 200
kg/m3) and sufficient compressive strength is achieved using standard industrial technology.
The low volume weight and therefore low heat conductivity can be reached due to highly
porous structure. Such a material can be prepared by foaming very fine material powder like
silica fume and very finely ground sand. Unfortunately, foams consisting of fine inorganic
hydrophilic particles are highly unstable. Therefore it is necessary to use an effective
stabilization mechanism. In this work the stabilization mechanism is based on addition of
small amount of water‐soluble organic admixtures.
Keywords autoclaved aerated concrete, inorganic foam stabilization, heat‐insulanting material, volume
weight
131
Acknowledgements
This work was financially supported by Materials Research Centre at FCH BUT –
Sustainability and Development, REG LO1211, with financial support from National
Programme for Sustainability I (Ministry of Education, Youth and Sports)
References
[1] KOUTNÝ, O. OPRAVIL, T. POŘÍZKA, J. Application of Metakaoline in Autoclaved
Aerated Concrete Technology. Advanced Materials Research, 2014, vol. 1000, pp. 174‐
177. ISSN: 1022‐ 6680.
[2] BROTHÁNKOVÁ, A. Technologie pórobetonu. Brno: Brno University of Technology,
Faculty of Chemistry, 2012. pp 41. Supervisor Ing. Tomáš Opravil, Ph. D..
[3] VIVALDINI, D. O., A. P. LUZ, V. R. SALVINI a V. C. PANDOLFELLI. Why foams
containing colloidal hydrophilic particles are unstable?. Ceramics International. 2013,
vol. 39, pp. 6005 – 6008.
[4] KRUGLYAKOV, Pyotr M., Svetlana I. ELANEVA a Natalya G. VILKOVA. About
mechanism of foam stabilization by solid particles. Advances in Colloid and Interface
Science. 2011, vol. 165, pp. 108 ‐ 116
******
Application of Sol‐Gel Method to Investigate the Influence of P2o5 on the
Course of Reactions in CaO‐SiO2 system
Baraček, J., Palou, M., Másilko, J., Wasserbauer, J., Šoukal, F., Boháč, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Slovak Academy of Sciences, Institute of Construction and Architecture, Dúbravská cesta 9, 845 03
Bratislava 45, SLOVAK REPUBLIC
Abstract
The influence of P2O5 or calcium phosphate upon the reactivity and burnability of cement
raw meal has been intensively investigated during the last decade [1‐4]. The main motivation
to undertake this research program was the potentiality of meat and bone meal (MBM) to be
used as secondarzy energy source for the production of Portland clinker, since the organic
part serves as energy source while the inorganic part may serve as raw materials for the
formation of clinker minerals reducing thus the part of natural raw materials [1, 2]. The ashes
of bone meal (rich in Ca3P2O8, referred to as Ca3 (PO4) 2 or C3P) are the origin of phosphorus
incorporation into the phases of clinker. The main obstacle facing the massive use of MBM is
the relatively high content of P2O5 found as Ca3 (PO4) 2 or hydroxyapatite compound[4‐6] in
bone ashes. Thenceforth CaO from apatite in bone meal has been accounted in material
balance as potential reactant susceptible to produce clinker phases. Our recent works [3, 4]
undertaken to elucidate the preferential distribution of P2O5 inside the clinker minerals has
established the formulas of C2S and C3S solid solutions. Also, a high level of phosphorus
oxide inhibits the C3S (3CaO. SiO2 or Ca3SiO5) formation. Stanek et al. [2] has proved that
with increasing content of P2O5 in raw meal up to 3 %, the formation of C3S is fully hindered.
The progress in the knowledge upon the kinetics and mechanism of clinker formation,
132
namely the formation of C3S, has revealed that higher amounts of P2O5 lead to preferential
formation of phosphatic dicalcium silicate solid solutions with the stabilization of high
temperature polymorphs ’ and ? of C2S (2CaO. SiO2 or Ca2SiO4) [6‐8]. Diouri et al. [5]
showed that the substitution of SiO44‐ by PO43 ‐ ions stabilizes the high temperature forms of
C2S. It is proposed that P5+ substitutes for Si4+ in the C2S lattice with the average chemical
composition set primarily by the mechanisms available for charge compensation[6]:Ca2+ +
2Si4+ = V0 + 2P5+ (1a) 2SiO44‐ = 2PO43‐ + ?Ca, where ?Ca is a Ca2+ vacancy. (1b) During the P5+
ion substitution for Si4+ ion the vacancies are built up as a result of need to maintain
electroneutrality [7]. General formula of dicalcium silicates solid solutions with stabilized
P2O5 is following: (Ca2‐x/2?Ca x/2) (Si1‐xPx) O4, where 0, 02
Keywords
Sol‐gel method, reactivity, mechanism of reaction, microstructure, phase diagram, element
distribution
Acknowledgements
The authors are grateful to the VEGA Grant No. 2/0082/14 and also to project „Excellent
young researchers at Brno University of Technology“, CZ. 1. 07/2. 3. 00/30. 0039.
References
[1] S. PUNTKE, Auswirkungen des Phosphateintrages in Drehofenanlagen der
Zementindustrie auf Klinkermineralogie und Zementeigenschaften, Dissertation, TU
Clausthal, 2004.
[2] T. STANĚK, P. SULOVSKÝ, The influence of phosphorous pentoxide on the phase
composition and formation of Portland clinker, Mater. Charact. 60 (2009) 749‐755.
[3] T. IFKA, M. T. PALOU, Z. BAZELOVÁ, The influence of CaO and P2O5 of bone ash
upon the reactivity and the burnability of cement raw mixtures, Ceram. Silik. 56 (1)
(2012) 76–84.
[4] T. IFKA, M. PALOU, J. BARAČEK, F. ŠOUKAL, M. BOHÁČ, Evaluation of P2O5
distribution inside the main clinker minerals by the application of EPMA method, Cem.
Concr. Res. 59 (2014) 147‐154.
[5] A. DIOURI, A. BOUKHARI, J. ARIDE, F. PUERTAS, T. VAZQUEZ, Elaboration of ?‐C2S
form of belite in phosphatic clinker. Study of hydraulic activity, Mater. Constr. 48 (249)
(1998) 23– 32.
[6] B. MATKOVICH, J. F. YOUNG, Dicalcium silicates doped with phosphates, in: Finep
(Ed.), 2, 8th ICCC, Rio de Janeiro, Brazil, 1986, pp. 276– 281.
[7] W. GUTT, High temperature phase equilibria in thesystem 2CaO. SiO2–3CaO. P2O5–
CaO, Nature 197 (1963) 142 – 149. 8. R. W. Nurse, J. W. Welch, W. Gutt, High
temperature phase equilibria in the system dicalcium silicate – tricalcium phosphate, J.
Chem. Soc. (1959) 1077–1083.
133
Organic Electronics
Simple Method for Determination of Type Charge Carriers in
Semiconductors
Florian, P., Pospisil, J., Zmeskal, O.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
It is important to know type of charge carriers for right function of electronic and
optoelectronic applications structures (e.g. organics photovoltaic devices) in the thin layers of
electronic components. Three basic methods of determination type charge carriers’ are
known. First is based on the principle Hall effect, i. e. on the measurement of Hall voltage
generated by electrical current in external magnetic field, the second is based on the
measurement voltage induced by diffusion of thermally generated charge carriers during
local heating, the third method is based on the measurement dependence capacitance of
sandwich structure on voltage at gap structure at adequately high frequencies of alternating
current.
This work is focused on next very simple method of determination type charge carriers by
measurement of current‐voltage characteristics of gap structure (between two equal
interdigital electrodes) for constant positive and negative voltages at upper sandwich (gate)
electrode. Magnitude of electric current between gap electrodes depends on polarity of
voltage on sandwich structure. This polarity determines type of charge carriers. When the
current‐voltage characteristic is more linear than in the case of opposite voltage on gate
electrode, the current is going dominantly through the underside of semiconducting layer,
where charge carriers are here concentrated. If voltage on gate electrode is positive for this
case, the material is of p‐type, if voltage on gate electrode is negative, the material is of n‐
type.
Keywords
Hall effect measurement, Hot point probe, MOS analysis, Determination of type charge
carriers
Acknowledgements Authors thank to Ministry of Education, Youth and Sports of Czech Republic for support by
national project COST LD14131 and for support by project Sustainability and Development
REG LO1211 addressed to Materials Research Centre at FCH VUT.
References
[1] VAN ZEGBROECK, Barth. Principles of Semiconductor Devices: The ʺhot‐probeʺ
experiment (2011) on http://ecee. colorado. edu/~bart/book/book/chapter2/ch2_11.
htm#2_11_9
[2] VAN ZEGBROECK, Barth. Principles of Semiconductor Devices: The Hall Effect (2011)
on http://ecee. colorado. edu/~bart/book/book/chapter2/pdf/ch2_7_5. pdf
134
[3] VAN ZEGBROECK, Barth. Principles of Semiconductor Devices: MOS Capacitors (2011)
on http://ecee. colorado. edu/~bart/book/book/chapter6/ch6_3. htm
[4] ZMEŠKAL, O. DZIK, P. POSPÍŠIL, J. ŠEDINA, M. AC and DC Characterization of Gap
and Sandwich Structures Based on ZnPc/PCBM Composite. International Conference on
Recent Trends in Advanced Materials ICRAM‐2012. Vellore, India: VIT University, 2012.
pp. 227‐227.
[5] ZMEŠKAL, O. NEŠPŮREK, S. WEITER, M. Charge carrier transport in semiconductors:
a fractal approach. International Conference on Recend Trends in Advanced Materials
ICRAM‐2012. Vellore, India: VIT University, 2012. pp. 16‐16.
[6] ZMEŠKAL, O. POSPÍŠIL, J. ALTŠMÍD, J. NEŠPŮREK, S. Barrier Properties of Printed
Composite Zinc Phthalocyanine/ Fullerene Sandwiched between Indium Tin Oxide and
Alluminium Electrodes. International Journal of Information and Electronics
Engineering, 377 (2013) 156‐160. ISSN: 2010‐ 3719.
******
Optical Characterization of Graphene Oxide Films by Spectroscopic
Ellipsometry
Schmiedova V.1, Pospisil J.1, Zmeskal O.1, Vretenar V.2
1Brno University of Technology, Faculty of Chemistry, Purkynova 118, CZ‐612 00 Brno, CZECH
REPUBLIC 2Danubia NanoTech, s. r. o, Ilkovicova 3, SK‐841 04 Bratislava, SLOVAK REPUBLIC
Abstract Optical properties of graphene oxide films attract considerable attention due to their
potential application in many technological fields such as nanoelectronics, nanocomposites
and sensors. Graphene oxide (GO) could be used as a transparent and flexible electronic
materials. It can be used as interlayer of photovoltaic cells for hole carriers transport. The
paper deals with the study of optical properties of inject‐printed GO. Defined structure of
GO can be obtained by reducing of prepared layers either by heating or by UV radiation
(rGO). The dispersion function for refractive index and extinction coefficient of GO and both
rGO thin films were measured by spectroscopic ellipsometry in the wavelength range of 200
– 850 nm. Spectroscopic ellipsometry (SE) was used characterize the optical response of layer
UV reduced GO and thermal reduction GO in visible range. The Tauc Lorentz model was
used for this matter. Thickness of the layers were measured by mechanical profilometer and
used as an input parameter for optical modeling. Based on the developed model, the
ellipsometric data were analyzed with respect to the molecular structure of studied GO and
morphology of thin film layers. Thus, the detailed analysis of the ellipsometric data provides
a unique tool for qualitative and also quantitative description of the optical properties of
graphene oxide thin films for electronic applications. The results will be used for
optimization of the layer properties in terms of thickness and absorption properties
Keywords
Graphene Oxide Spectroscopic Ellipsometry Optical properties
135
Acknowledgements
Authors thanks to Ministry of Education, Youth and Sports of Czech Republic for support by
national project COST LD14131 and for support by project Sustainability and Development
REG LO1211 addressed to Materials Research Centre at FCH BUT.
References
[1] YANG, J. et al. Applied Surface Science, 258 (2012) 5056‐5060
[2] JUNG, I. et al. J. Phys. Chem. C, 112 (2008) 8499‐8506
[3] SHEN, Y. et al. Appl. Phys. Lett. 99, 141911 (2011)
******
Diketopyrrolopyrrole Based Donors for Bulk Heterojunction Organic Solar
Cells
Honova, J., Kovalenko, A., Vala, M., Weiter, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Nowadays, strong effort has been put on searching for the new materials to use in low cost
organic electronics. Compared to frequently used polymers, small molecules show many
advantages, as higher possibility of supramolecular organization, higher purity and easier
production. In this study we focused on diketopyrrolopyrrole based small molecules, which
are high performance materials, originally used in dye industry, recently successfully used in
organic electronics and photovoltaics as well. Up to now, our group has synthesised various
diketopyrrolopyrrole derivatives and studied them with respect to their structure‐property
relationship. As a result of previous study and theoretical calculations, we have introduced
groups of novel diketopyrrolopyrrole derivatives and characterised their properties with
various optical and electrical methods. Hole transporting properties were described, using
those materials as a semiconductors for organic field effect transistors. Solar cell prototypes
were prepared, using mentioned materials as a donor. Basic optimization of photovoltaic
properties was performed for each material in following parameters: Choice of solvent,
donor:acceptor ratio, different acceptor material, thermal annealing, solvent annealing and
spin‐coating optimization. Results of performed study will be discussed within the
contribution. Studied materials showed to be well working donor materials for organic
photovoltaics.
Keywords
Diketopyrrolopyrrole, organic solar cells
Acknowledgements
This work was supported by Czech Science Foundation via project No. 15‐05095S, research
infrastructures was supported by project MSMT No. LO1211.
136
******
New Ionic Liquid Based Electrolytes for Application in Electrochemical
Sensors
Altsmid, J.1, 2, Kubersky, P.2, Navratil, J.2, Nespurek, S.1, 2, Hamacek, A.2, Zmeskal, O.1
1Brno University of Technology, Faculty of Chemistry, Purkynova 464/118, 612 00 Brno, CZECH
REPUBLIC 2University of West Bohemia, Faculty of Electrical Engineering/RICE, Univerzitni 8, 306 14 Plzen,
CZECH REPUBLIC
Abstract
Amperometric NO2 sensor with a new type of printed solid polymer electrolyte has been
developed. The sensor, prepared in planar three electrode configuration, consisted of two
platinum electrodes (counter and pseudoreference), polymer electrolyte containing ionic
liquid and a working top electrode prepared from carbon nanotubes (CNT) by aerosol jet
printing (AJP). The thickness of the fully functional electrode was in order of tenths of
nanometers. Thus, the AJP technique enabled us to significantly save electrode material,
especially in comparison with previously used drop casting technique [1]. The solid polymer
electrolyte, consisting of ionic liquid, poly (vinylidene fluoride) (PVDF), and 1‐methyl‐2‐
pyrrolidone (1:1:3 weight), was prepared according to procedure described in Ref. [1]. Before
the AJP deposition of carbon nanotubes the sample was heated at 120 oC for about 3 min.
The analyte, gaseous nitrogen dioxide, was detected by reduction at ‐500 mV vs. platinum
pseudoreference electrode. The measurement of electrochemical response during NO2
exposure was performed under laboratory conditions by KEITHLEY 2636. Required
concetrations of the analyte were obtained by the mixing of the nitrogen dioxide (mixture
with synthetic air, concentration 100 ppm) with pure synthetic air. The analyte flow rate was
500 ml/min.
Five ionic liquids were used in this study:
1‐ethyl‐3‐methylimidazolium bis (trifluoromethylsulfonyl) imide [EMIM][N (Tf) 2], No. 1
(lab. mark)
1‐butyl‐3‐methylimidazolium trifluoromethanesulfonate [BMIM][CF3SO3], No. 4
1‐butyl‐1‐methylpyrrolidinium bis (trifluoromethylsulfonyl) imide [BMPYR][N (Tf) 2],
No. 5
1‐ethyl‐3‐methylimidazolium tetrafluoroborate [EMIM][BF4], No. 9 and
1‐hexyl‐3‐methylimidazolium tris (pentafluoroethyl) trifluorophosphate [HMIM][FAP],
No. 26.
First let us discuss first the properties of the sensor with ionic liquid [EMIM][N (Tf) 2] and
carbon printed electrode. The sensor showed a linear behavior in the whole tested range, i. e.,
0 ‐ 5 ppm. Its sensitivity was 185 nA per 1 ppm. The rise/recovery (t90/t10 – time when
response magnitude reaches 90%/10% of it’s maximal/minimal value after start/end of NO2
exposition) times were in order of tens of seconds. The use of carbon nanotubes for the
preparation of working electrode resulted in the increase of the sensor sensitivity to 327
nA/ppm. Thus, we demonstrated an improvement of sensitivity while the order of
rise/recovery times (1 min for both) remained the same. This fact induced a decision to test
also other ionic liquids (see above). However, no important improvement of the parameters
137
was observed. The parameters were the following (sensitivity ‐ rise/recovery time in
minutes) :
[BMIM][CF3SO3] carbon nanotubes: 142nA/ppm – 1. 33/1. 06
[BMPYR][N (Tf) 2] carbon nanotubes: 177nA/ppm – 1/0. 73
[EMIM][BF4] carbon nanotubes: 163nA/ppm – 1/1. 56
[HMIM][FAP] carbon nanotubes: 168nA/ppm – 1. 03/0. 6
Keywords NO2 sensor, ionic liquid, electrochemistry, aerosol jet printing, carbon nanotubes.
Acknowledgements
This research was supported by the European Regional Development Fund by the Ministry
of Education, Youth and Sports of the Czech Republic under the Regional Innovation Centre
for Electrical Engineering (RICE), project No. CZ. 1. 05/2. 1. 00/03. 0094
Authors also thanks to Ministry of Education, Youth and Sports of Czech Republic for
support by project Sustainability and Development REG LO1211 addressed to Materials
Research Centre at FCH BUT.
References [1] P. KUBERSKY, A. HAMACEK, S. NESPUREK, R. SOUKUP, R. VIK, Effect of the
geometry of a working electrode on the behavior of a planar amperometric NO2 sensor
based on solid polymer electrolyte Sensors and Actuators B 187 (2013) 546– 552.
******
Materials with High Fluorescence in Solid State: The Influence of Chemical
Structure on Optical Properties
Jan Koutný1, Martin Vala1, Stanislav Luňák1, Karel Pauk2, Zdeněk Eliáš2, Aleš
Imramovský2, Martin Weiter1
1Brno University of Technology, Faculty of Chemistry, Materials Research CenterPurkyňova 464/118,
Brno, CZ‐61200, CZECH REPUBLIC 2Faculty of Chemical Technology, University of Pardubice, Studentská 573, CZ‐532010 Pardubice,
CZECH REPUBLIC
Abstract Study of a relationship between fluorescence emission in a solid state and chemical structure
has received considerable attention in the recent years. Acquisition of new material with high
emission in the solid state is important, particularly because of their multiple potential
applications such as organic light‐emitting diodes, organic light emitting thin‐film transistors
and organic solid state lasers. The performance of conjugated molecules in solution and in
solid state is very different due to molecular aggregation. This difference is caused by
intermolecular interaction of the excited molecules with the adjacent molecules. This
interaction may be caused by transfer of energy and electrons, formation of excimers etc.
This interaction leads to new quenching channels that reduce fluorescence emission. Most of
these interactions depend on the distance between the molecules and their mutual position.
Relatively small variation of the chemical structure brings significantly different molecules
138
geometry in solid‐state and thus diverse optical properties. Dependence on distance between
‐conjugated planes were studied using diketopyrrolopyrrole sulfonic anionts with varying
size of the counter cations. The influence of chemical structure modification was investigated
with the help of various donor‐?‐conjugated bridge‐acceptor molecules where the bridge
represents framework with bulky substituents oriented perpendicular to conjugated plane. Optical properties such as absorption, fluorescence, fluorescence quantum yield (PLQY) and
lifetime in the solid state were studied and discussed.
Keywords
solid state fluorescence, fluorescence quantum yields, fluorescence lifetime,
diketopyrrolopyrrole
Acknowledgements
This work was supported by Czech Science Foundation via project No. 15‐05095S, research
infrastructures were supported by projects MŠMT No. LO1211.
******
Optimization of Screen Printing Process for Printed Electronic Devices
Hrabal, M., Omasta, L., Vala, M., Weiter, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Semiconducting properties of inorganic materials have been known for more than a century
but in the last four decades new organic materials have been recorded to have similar
properties. Among such materials are PEDOT (poly (3, 4‐ethylenedioxythiophene), DPPs
(diketopyrrolopyrroles), derivatives of phthalocyanines and many others. The great potential
of semiconducting devices based on organic materials lies in the cost and time consumption
of their preparation. Organic semiconducting materials can be used in many different fields
as solar cells, thin‐film transistors (TFTs), light‐emitting diodes to name just few. The aim of
this work is mainly focused on organic electrochemical transistors (OECTs) that could find
application as detectors and biosensors in various biological systems. Gas sensors, pH
sensors or sensors for detecting cell growth are just few examples. Such devices usually
consists of source (S) and drain (D) electrodes that form a transistor channel and a gate
electrode (G) which function is to modify the drain current by application of an external gate
voltage. Electrolyte works in this type of devices both as a connecting bridge between the
S/D and G and as a supplier of ions. PEDOT doped with PSS poly (styrene sulfonic acid) is
reduced by an applied voltage. Conductivity of a reduced form of PEDOT:PSS is very low
compared to the oxidized form. Our OECTs consist of conductive silver busbars, polymer
electrodes (source, drain and gate) from PEDOT:PSS and the electrolyte phosphate buffered
saline (PBS). In the last thirty years a novel approach to manufacture such devices, have been
developed in contrast to the traditional lithography. Deposition from a solution (specifically
various printing methods) is much more cost and time convenient compared to the
traditional method. Both the system of electrodes and conductive busbars have been printed
by a screen printing. Silver paste CB 115 Ag Conductor from Dupont has been used for
printing of conductors and PEDOT:PSS from Heraeus – Clevios for the electrodes. Device IV
139
characteristics and morphology of prepared layers are key factors for evaluation whether the
optimal print parameters have been achieved or not.
Keywords
Screen printing, organic electrochemical transistors, printed electronics, organic
semiconductor, biosensors
Acknowledgements
This work was supported by Czech Science Foundation via project No. 13‐29358S, research
infrastructures were supported by projects MŠMT No. LO1211.
******
New Diketopyrrolopyrrole Derivatives in OFET Transistors
Stanislav Stritesky1, Martin Weiter1, Martin Vala1, Petra Horáková2, Lenka Dokládalová2,
Luboš Kubáč2
1Brno University of Technology, Faculty of Chemistry, Material Research CentrePurkynova 464/118,
612 00 Brno, CZECH REPUBLIC 2Centre for Organic Chemistry Ltd., Rybitví 296, CZ‐533 54 Rybitví, CZECH REPUBLIC
Abstract
Nowadays, there are several organic semiconductors with relatively high charge carrier
mobilities which are used for the construction of organic field‐effect transistors (OFETs). In
particular, small molecules such as derivatives of pentacenes, rubrenes and perylenes, and
polymers such as P3HT and PCDTBT have been widely studied so far. At the present time,
known dyes and pigments are modified for use in organic electronics. To this group of
organic semiconducting materials also include diketopyrrolopyrroles (DPP) that represent
the family of originally high performance pigments with high thermal and light stability and
weather fastness. The aim of this study is to elucidate the influence of diketopyrrolopyrroles
derivatives chemical structure modifications on the performance of organic field effect
transistors (OFETs). Performance of OFETs is strongly dependent on the charge carrier
injection from contact and their transport within the first organic semiconductor (OSC)
monolayers at the interface with the gate dielectric. Therefore, in this contribution we
focused on modification of self‐assembled monolayers (SAMs) on OFETs prototypes
prepared on silicon substrates (Fraunhofer IPMS). Other optimization of OFETs was
performed in following parameters: choice of solvent, spin‐coating and thermal annealing
optimization. Results of this study charge carrier mobility, contact resistance, on/off ratio will
be discussed within this contribution. The studied materials showed to be promising for
organic electronics applications based on the obtained results.
Keywords
Organic transistor, diketopyrrolopyrrole, charge carrier mobility, contact resistance
Acknowledgements This work was supported by Czech Science Foundation via project No. 13‐29358S, research
infrastructures were supported by project MŠMT No. LO1211.
140
******
Preparation and optimization of printed layers for biosensing
Omasta, L., Salyk, O., Hrabal, M., Weiter, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Organic electrochemical transistors (OECTs) have achieved recognition as useful devices for
a variety of applications, particularly in the area of sensing and biosensing. OECTs exploit
the ability of organic semiconductors to conduct ions in addition to electronic charge and
provide unique opportunities when integrated into biomedical systems as transducers.
Devices can be easily patterned by printing, individually functionalized, and directly
interfaced with biomolecules and living cells. OECTs offer a unique set of advantages in the
development of biomedical tools due to simple and low voltage operation regime and
flexibility. Moreover electrochemical transistors are of high interest for biosensing
applications, as they are able to operate in liquid environment. In our research we focused on
preparation and characterization of screen and inkjet printed OECTs based on conductive
polymer (PEDOT:PSS) (poly (3, 4 ethylenedioxythiophene) doped with poly (styrene sulfonic
acid) as the active transistor channel material. The silver circuit matrix together with
PEDOT:PSS active layer formed electrochemical transistors with lateral architecture. All
layers were printed on flexible substrates polyethylene naphthalate (PEN) and polyethylene
terephthalate (PET). Printing processes were done using screen printer RokuPrint SD 05 and
inkjet Fujifilm Dimatix Material Printer. Structure and morphology of prepared layers were
evaluated via mechanical profilometer. Adhesivity and mechanical properties of printed
structures in various aqueous solutions were tested. Electrical properties of screen printed
electrochemical transistors were investigated by testing output and transfer characteristics in
phosphate buffered saline. The influence of thickness of active layer, different pattern
designs and geometry on OECTs behaviour were evaluated.
Keywords
organic electronics, PEDOT:PSS, biosensor, printed electronics, screen printing, inkjet
printing, organic electrochemical transistor
Acknowledgements This work was supported by Czech Science Foundation via project No. 13‐29358S, research
infrastructures was supported by projects MŠMT No. LO1211.
141
******
Characterization of Novel Small Molecules for Organic Electronics and
Photonics
Sionová, M., Vala, M., Černý, J., Kubáč, L., Krajčovič, J., Weiter, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Organic molecules are potential materials for cheap organic electronics and photonics. Small
molecules have some main benefits when compared to polymeric materials (a perfectly
defined chemical structure, purification of a single molecule is easier, the analysis of the
relationship between structure and properties is more straightforward, etc.) which lead to
greater interest in these materials. The aims of this study were to synthetize and characterize
novel small molecule materials (based on phthalocyanines or diketopyrrolopyrroles) for use
in organic electronics and photonics. The easy solubility some of the prepared materials
facilitate the preparation of thin film structures, eg. by printing technology which is
appropriate for possible their future commercial production. The materials were
characterized with respect to their molecular structure. Optical and electrical properties of
the devices were investigated. These small molecules thin films were prepared by spin‐
coating and vacuum evaporation. Their optical properties was studied by absorption and
fluorescence spectroscopy, the electrical conductivity were studied by steady state current‐
voltage characterization. Subsequently, the different structures of organic solar cells were
prepared. Their optoelectronic and electrical properties such as spectrally resolved
photoconductivity, charge carrier photogeneration and photovoltaic conversion efficiency
was studied.
Keywords
small molecule, organic solar cell, diketopyrrolopyrrole, phthalocyanine
Acknowledgements
This work was supported by Czech Science Foundation via project No. 15‐05095S, research
infrastructures were supported by projects MŠMT No. LO1211.
******
Functionalization of Textile Materials by Conductive Polymers for Smart
Textile Applications
Kubáč, L., Akrman, J., Josefík, F., Dvorský, D., Martinková, L., Marek, J.
Centre for Organic Chemistry Ltd., Rybitví 296, 533 54, CZECH REPUBLIC
Inotex Ltd., Štefánikova 1208, 544 01, Dvůr Králové n. L., CZECH REPUBLIC
Abstract Smart textile applications is based on the connection of sensory elements with the evaluation
and communication systems. This connection must be done by stable conductive prints or by
142
stable conductive fibres. The most critical part of stability is the process of textile washing.
The most common way of the connection is the metal based fibres, which are knitted into
fabrics structure [1‐5]. Second possibility based on the similar solution is the knitting of
carbon wire into fabric structure [6‐8] and last one possibility is the printing of metal inks
onto fabric structure connected with encapsulation [9‐11]. The conductive polymers, mainly
complex poly‐3, 4‐ethylenedioxythiophene‐polystyren sulfonate (PEDOT/PSS) are widely
used in the organic electronic systems [12‐14]. Dispersion PEDOT/PSS creates highly stable
conductive layers and it is one of the most useful parts of the printed organic electronic
systems. Application of this dispersion in the field of smart textile is not effective. The layer
is not stable after washing and its ability of the charge transfer is low. Alternative way is in
situ polymerisation of PEDOT directly on chosen textile material surface. The common way
consists from in combination of starting EDOT and iron (III) toluensulfonate is insufficient
too, because the layer is not homogenous on the structured textile surface and it is washed
out too. Highly efficient is in situ polymerisation if the textile materials are modified by
materials containing two functional groups, one for permanent fixation in the textile
structure on the second create by sulfo or carboxy group, which serve as dopant during
polymerisation of EDOT. Such PEDOT modified textile fabrics or fibres have sheet resistance
less than 102 Ohm.
Keywords conductive polymers, PEDOT, textile fabric, fibre
Acknowledgements
This work was supported by TA CR, project TE01020022, Flexprint
References
[1] ZHOU, T. ZHANG, C. H., CHANG B. FAN, F. R. TANG, W. WaNg, Z. L. : Woven
Structured Triboelectric Nanogenerator for Wearable Devices, ACS Applied Materials &
Interfaces (2014), 6 (16), 14695‐147012)
[2] PAN, S. YANG, Z. CHEN, P. DENG, J. Li, H. PENG, H. : Wearable Solar Cells by
Stacking Textile Electrodes, Angewandte Chemie, International Edition (2014), 53 (24),
6110‐61143)
[3] LOU, C. W. LIN, C. ‐M. HSING, W. ‐H. CHEN, A. ‐P. LIN, J. ‐H. : Manufacturing
techniques and electrical properties of conductive fabrics with recycled polypropylene
nonwoven selvage, Textile Research Journal (2011), 81 (13), 1331‐13434)
[4] KYLBERG, W. de CASTRO, F. A. CHABRECEK, P. SONDEREGGER, U. CHU, B.
NUEESCH, F. HANY, R. : Woven electrodes for flexible organic photovoltaic cells,
Advanced Materials (2011), 23 (8), 1015‐10195)
[5] PERUMALRAJ, R. DASARADHAN, B. S. NALANKILLI, G. : Copper, stainless steel,
glass core yarn, and ply yarn woven fabric composite materials properties, Journal of
Reinforced Plastics and Composites (2010), 29 (20), 3074‐30826)
[6] WANG, Lu; FENG, Xiao; REN, Lantian; PIAO, Qiuhan; ZHONG, Jieqiang; WANG,
Yuanbo; LI, Haiwei; CHEN, Yifa; WANG, Bo: Flexible Solid‐State Supercapacitor Based
on a Metal‐Organic Framework Interwoven by Electrochemically‐Deposited PANI, J.
Am. Chem. Soc. (2015), 137 (15), 4920‐49237)
[7] ZHANG, D., MIAO, M., NIU, H., WEI, Z.: Core‐Spun Carbon Nanotube Yarn
Supercapacitors for Wearable Electronic Textiles, ACS Nano (2014), 8 (5), 4571‐4579.
143
[8] WU, M. ‐S. GUO, Z. ‐S. JOW, J. ‐J. : Highly Regulated Electrodeposition of Needle‐Like
Manganese Oxide Nanofibers on Carbon Fiber Fabric for Electrochemical Capacitors,
Journal of Physical Chemistry C (2010), 114 (49), 21861‐218679)
[9] MAHLTIG, B. NATARAJAN, H. S. El BRINI, O. WISSLING, P. HAASE, H. : Metal‐
containing coatings on textiles: concepts and properties, Textilplus (2013), (1/2), 30‐3310)
[10] GAIKWAD, A. M. ZAMARAYEVA, A. M. ROUSSEAU, J. CHU, H. DERIN, I.
STEINGART, D. A. : Highly Stretchable Alkaline Batteries Based on an Embedded
Conductive Fabric, Advanced Materials (2012), 24 (37), 5071‐507611)
[11] KAZANI, I. HERTLEER, C. de MEY, G. SCHWARZ, A. GUXHO, G. van
LANGENHOVE, L. : Electrical conductive textiles obtained by screen printing, Fibres &
Textiles in Eastern Europe (2012), 20 (1), 57‐6312)
[12] KIM W. KIM N. KIM J. K. PARK I. CHOI Y. S. WANG D. H. CHAE H. PARK J. H. :
Polymer bulk heterojunction solar cells with PEDOT:PSS bilayer structure as hole
extraction layer, ChemSusChem (2013), 6 (6), 1070‐513)
[13] JEONG J. NAM S. KIM J. WOO S. KIM H. KIM Y. : Effect of inorganic nanoparticle
addition to the hole‐collecting buffer layers in polymer solar cells, Journal of nanoscience
and nanotechnology (2012), 12 (7), 5696‐914)
[14] KIM J. ‐R. JUNG J. H. SHIN W. S. SO W. ‐W. MOON S. ‐J. : Efficient TCO‐free organic
solar cells with modified poly (3, 4‐ethylenedioxythiophene) : poly (styrenesulfonate)
anodes, Journal of nanoscience and nanotechnology (2011), 11 (1), 326‐30
******
Molecular Tuning Powerful Tool at Synthesis of Smart Molecules for
Organic Electronics
Krajčovič, J.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Understanding and prediction of the consequences following the structural modification of
the molecules and polymers plays significant role in the organic chemistry synthesis.
During the last twenty years, the organic chemists have developed tremendous amounts of
molecular building blocks which have been employed to design various oligomers, polymers
or supramolecular systems according to individual demands for specific applications. The
synthesis of well‐defined intermediates based on monomers and oligomers with a target
range of properties is approach which can be considered as a major challenge for the
construction advanced “smart” molecules applicable in organic electronics.
One particular synthetic approach is to achieve the alternating donor (D) and acceptor (A)
units to steer the molecular orbital energy gaps, as well as the band gap of the resulting
copolymers (so‐called D–A oligo‐/polymers). This strategy is suitable for tailoring the
properties of conjugated molecules for different applications like OFETs and PSCs [1].
144
Specifically, the systematic synthetic modification of the bandgap a series of
diketopyrrolopyrroles (DPP) [2] and atom substitutions in the key positions bis (2‐thienyl)
phenylene units [3] will be illustrated.
Keywords molecular tuning, diketopyrrolopyrroles (DPPs), bis (2‐thienyl) phenylenes, energy gaps
Acknowledgements
This work was supported by Czech Science Foundation via project No. 15‐05095S, research
infrastructures were supported by project MŠMT No. LO1211.
References [1] G. XIN, M. BAUMGARTEN, K. MÜLLEN, Progress of Polymer Science, 38 (2013) 1832‐
1908.
[2] M. VALA, J. KRAJČOVIČ, S. LUŇÁK Jr., I. OUZZANE, J‐P. Bouillon, M. Weiter, Dyes
and Pigments 106 (2014) 136‐142
[3] J. KRAJČOVIČ, A. KOVALENKO, P. HEINRICHOVÁ, M. VALA, M. WEITER, Journal
of Luminiscence, (in press, DOI: 10. 1016/j. jlumin. 2015. 06. 043)
******
Hybrid Organic‐Inorganic Perovskite Solar Cells with Printed Photo‐Anode
Michal Hatala, Pavol Gemeiner, Milan Mikula
Slovak University of Technology in Bratislava, Faculty of Chemical and Food Technology,
Department of Printing Arts Technology and Photochemistry, Radlinského 9, 821 37, Bratislava,
SLOVAK REPUBLIC
Abstract Perovskite solar cells can be classified as one of the most promising photovoltaic
technologies of the 3rd generation of photovoltaic systems. Primary structure is based on
solid state Dye Sensitized Solar Cells (ssDSSC), with the exception that these systems employ
hybrid organometallic perovskites (CH3NH3MX3 M=Sn, Pb X=F, Cl, Br) in the role of light
harvester. High absorption in the full range of visible light spectrum and high mobilities and
diffuse lengths of free charge carriers formed in perovskites allow to achieve high
photovoltaic performance. Moreover, thanks to their ambipolar character, perovskites can act
as p‐ or n‐ type semi‐conductors. Depending on the structure of the solar cell, perovskites
can serve not only as a sensitizer, but they can partially fulfill also the function of hole ‐
transporting material (HTM). This characteristic allows to modify the basic structure,
especially in terms of the necessity of mesoporous conductive oxide layer. In this paper we
focused on the preparation of the monolithic perovskite solar cells on the rigid glass
substrates. The mesoporous titanium dioxide (TiO2) photoanode was prepared using a
screen printing technique. One‐step and two‐step method were used for the deposition of
perovskite layer at ambient conditions. Spin coated precursors contained two elementary
components Lead iodide (PbI2) and Methylammonium iodide (CH3NH3PbI3). Metal back
contacts were sputtered directly onto perovskite layer or onto subsequently spin‐coated
HTM layer.
145
Keywords
perovskite, solar cells, TiO2 mesoporous photo‐anode, printed electronics
******
Fully Conjugated Alcohol ‐ and Water Soluble Metallo‐Supramolecular
Polymers
Bondarev, D.1 Gladyš, S.2 Polášková, M.1 Huťťa M.1
1Tomas Bata University in Zlin, Faculty of Technology, Vavrečkova 275, CZ‐762 72, Zlín, CZECH
REPUBLIC 2Charles University in Prague, Faculty of Science, Hlavova 2030, CZ‐128‐43, Prague, CZECH
REPUBLIC
Abstract Metallo‐supramolecular polymers represent special class of polymer materials (1). Typical
metallo‐supramolecular (MSM) polymer consists of the organic unit end‐capped with two
ligands which are capable of chelating selected metal ions. Linear MSM polymer is formed if
two ligands are chelating one metal ion. Special type of MSM polymers is the one with
conjugated organic block as a ligand‐bearing unit (2). In such case we can achieve fully
conjugated architecture which offers the (prospective) properties emerging from the
conjugated units (absorption‐emission characteristic, electron conductivity, non‐linear
optical responses, charge generation) with constitutional dynamics as the coordination bonds
are much more suitable for rearrangements than the covalent ones and simultaneously the
coordination bonds are significantly more stable than hydrogen bonds which are also being
utilized in dynamers ‐ constitutionally dynamic polymer (3) of another classes. Main
advantages of constitutional dynamics are in the tuning of the composition of MSM polymer
by simple combination of building blocks or tuning its molecular weight characteristics by
selection of organics to metal ion ratios. It is also possible to combine both above mentioned
approaches in combination with other materials like common conjugated polymers or
inorganic counterparts to achieve supramolecular assembling of such composites. It was
shown in numerous examples (4) that architecture of functional devices, e. g. in
optoelectronics, strongly influences the performance of the device. Therefore, there is
necessary to interest ourselves not only in the properties of conjugated polymers/materials
but also in its assembly in thin layers or in other functional arrangements. One of the
approaches in supramolecular assembling is the utilization of polymers (or other conjugated
compounds) with different polarity. As example, layer‐by‐layer assembly in thin layer might
be achieved by coating the surface alternately by hydrophobic and hydrophilic polymers.
Second example is the utilization of block or gradient polymers combining units or side
groups with different polarity or affinity to the selected surface. In our contribution we focus
on alcohol‐ and water‐soluble fully conjugated metallo‐supramolecular polymers as (i) it
represents almost unstudied systems with only rare references (5) offers a (ii) possibility of
utilization as sensor systems for biomolecules and biomacromolecules (soluble only in water
and polar solvents) (iii) polar groups can take part in the tuning of the final assembly and
finally, (iv) present polar groups might contribute to overall conductivity by its ionic
conductivity and/or can exhibit self doping (6) and thus improve charge transport and
generation properties.
146
Keywords
Metallo‐supramolecular polymer, organic electronics, polythiophene, self‐assembly,
conjugated polymer, organometalics
References
[1] J. B. BECK, S. J. ROwan J. Am. Chem. Soc., 2003, 125 (46), 13922
[2] A. WINTER, et al. Macromol. Rapid Commun. 2008, 29, 1679
[3] J. LEHN, Prog. Polym. Sci., 2005, 30, 814
[4] H. SIRRINHAUS Nature, 1999, 401, 865
[5] P. ŠTENCLOVÁ‐BLÁHOVÁ et al. DOI: 10. 1039/c5cp01000d
[6] A. VIINIKANOJA et al. Langmuir 2003, 19, 2768
******
SEC‐DAD – Application of the Method for the Characterization of ‐conjugated polymers
Trhlíková, O.1, Gladyš, S.2 Sedláček, J.2 Bondarev, D.3
1Institute of Macromolecular Chemistry, Academy of Sciences of Czech Republic, Heyrovského nám.
2, CZ‐162 06, CZECH REPUBLIC 2Charles University In Prague, Faculty of Science, Hlavova 2030, CZ‐143 28, Prague, CZECH
REPUBLIC 3Tomas Bata University in Zlin, Faculty of Technology, Vavrečkova 275, CZ‐762 72, Zlín, CZECH
REPUBLIC
Abstract
Conjugated polymers represent important class of advanced macromolecular materials.
Extraordinary development in the area of conjugated polymers is stimulated not only by the
scientist´s personal incentives to the research but also by the large scope of already utilized
or near‐future applications such as polymer light emitting diodes, organic photovoltaics,
organic transistors, various sensors or non‐linear optics. The unique properties of conjugated
polymers originate from its covalent structure. The main‐chain double or triple bonds
alternate and therefore the ‐electrons are more or less delocalized. Generally, the
conjugation i. e. delocalization of ‐electrons in the polymer is most visibly manifested in the
absorption characteristics. The band gap decreases with increasing delocalization of ‐electrons (extent of conjugation) and simultaneously occurs the red shift in the absorption
spectrum. Therefore, the absorption characteristics are in principle the first and easily
accessible measure/parameter of the conjugation in the polymer backbone. Molecular weight
(MW) characterization is important in all areas of polymer research. Chromatographic
techniques belong to the most relevant methods of investigation of MW characteristics. Size
exclusion chromatography (SEC) is well established and expanded method although it has
some limitations and disadvantages. Main advantage of the SEC is that it provides the MW
distribution whereas other methods like viscometry, osmometry, and light scattering
techniques provide averaged molecular weights. Investigation of absorption characteristics
of the conjugated polymers is important as the absorption of conjugated macromolecules or
polymer segments is the macroscopic representation of the conjugation degree. It is obvious
that the extent of conjugation is crucial parameter especially in the case of polymers
147
utilizable in the optoelectronic applications. Secondly, the absorption characteristics are
given primarily by the covalent structure. Therefore, changes in the absorption
characteristics can reflect some changes in the covalent structure. SEC‐DAD (in the literature
called also SEC‐PDA (PDA stand for photodiode array detector) is a technique which
combines chromatography and spectrophotometry but the reports on this method are still
rare. In our contribution we show several examples of utilization of SEC‐DAD in study of (i)
alternating copolymers of various compositions, the effect of molecular weight
characteristics on the optical properties (ii) linear polythiophenes in which the optical
properties depend not only on the molecular weight but also on the orientation isomerism of
the polymer backbone (iii) investigation of solution and solid state degradation of MEH‐PPV
which is one of most important conjugated polymers utilized nowadays and its comparison
with degradation of linear high‐cis polyacetylene. We show that SEC‐DAD allows obtaining
the results un‐accessible by simple chromatography or absorption spectroscopy, especially
pointing out the importance of the data in the field of conjugated polymers.
Keywords
Size exclusion chromatography, conjugated polymers, polymer characterization
******
Printed Organic Sensor for Cardiomyocytes Research
Salyk, O., Omasta, L., Vala, M. and Weiter, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Organic electronics devices occurred as a proper solution for bioelectronics sensor
development due to obvious biocompatibility of organic semiconductors. So called
biosensors can convert electrochemical processes in touch with cell membranes convert into
electronic signal. A matrix of such biosensors can simultaneously scan a number of biological
samples as well as a tissue in living body. The core of the device is a transistor, nowadays
mostly OECT (Organic Electro Chemical Transistor) fabricated by thin film technique from
semiconducting biocompatible polymer PEDOT:PSS (poly (3, 4‐ethylenedioxythiophene)
polystyrene sulfonate) Such transistors were printed both by Ink‐Jet [1] and by screen
printing [2] technique and their main characteristics are presented.
Keywords Bioelectronics, organic electrochemical transistor, cardiomyocyte
References
[1] OMASTA, L. et al. Preparation and optimization of printed layers for biosensing,
Chemistry and Life 2015, Brno[2] HRABAL, M. et al. Optimization of screen printing
process for printed electronic devices, Chemistry and Life 2015, Brno
148
******
Sensors Fabrication Using Screen Printing Technique
T. Syrový1, P. Kuberský2, J. Řeboun2, L. Syrová1, A. Hamáček2, J. Stejskal3, S. Nešpůrek2
1Department of Graphic Arts and Photophysics, University of Pardubice, Pardubice, CZECH
REPUBLIC 2Department of Technologies and Measurement, University of West Bohemia, Faculty of Electrical
Engineering/RICE, Plzeň, CZECH REPUBLIC 3Institute of Macromolecular Chemistry, Academy of Sciences of the Czech Republic, Heyrovsky Sq. 2,
162 06 Prague 6, CZECH REPUBLIC
Abstract
During last years was performed research in fabrication of several types of sensing elements,
which were in many cases printed by using screen printing technique. This technique has
several years strong position in area of printed electronics by its process simplicity and
unique advantage ‐ possibility to print large variety of thickness of layers in dependence to
printing condition and printing setup. Driven by needs of specific sensor element layers
were prepared different layers with thickness from tens nanometres to hundreds of
micrometres by using tens of different ink formulations under optimized specific printing
conditions for given applications. In many cases the ink formulation was developed.
By using screen printing technique were prepared different types of humidity sensors, where
for many of them was sensing response given by dependence of resistivity of sensing layers
on relative humidity. During development of printing process and ink formulation for
preparation of humidity sensor elements were optimized used printing inks for printing ID
structures and sensing layers, their layer thicknesses, GAP/Finger geometry, etc. In studied
humidity sensors elements were used various types of sensing layers consisting of small
molecules like phtalocyanines, diketopyrrolopyrroles or selected polymeric layers. For some
optimized configurations were printed stable sensors with high quality response within the
range of 20‐95 % of relative humidity and temperature range from 20 to 50 °C.
Lots of majority of process parameters influenced the fabrication and sensing response of
nitrogen oxide sensor, where its sensing properties are evaluated by amperometric
(electrochemical) detection. During the fabrication process the lots of problems come from
side of proper drying condition of electrolyte layers, printing of working electrode over
hundreds micrometer high electrolyte edge and some other process conditions had to be
optimized. Using optimized printing condition parameters and ink formulation
compositions were printed nitrogen oxide sensor elements with sensing range within 0‐20
ppm NO2.
The chemoresistive ammonia sensing elements were printed from various polyaniline
dispersions, where response of each type was evaluated in test chamber. For these type of
sensor elements were tested influence of different geometry of interdigital electrode,
GAP/finger dimension and ordering of selected layers of sensor element to sensing
properties. By using optimal structure was fabricated sensor element with sensing range 0‐
100 ppm.
149
In presentation will be discussed some other fabrication process problems, pitfalls,
experiences and will be included some other types of sensors which were printed by using
screen printing technique.
Keywords Sensors, relative humidity sensor, NO2 sensor, amonia sensor, printed electronic, screen
printing
Acknowledgements
This research was supported by the project European Regional Development Fund, by the
Ministry of Education, Youth and Sports of the Czech Republic under the Regional
Innovation Centre for Electrical Engineering (RICE, ED2. 2. 00/03. 0094c) and by Technology
Agency of the Czech Republic (TE01020022).
References [1] KUBERSKÝ, P., SYROVÝ, T., HAMÁČEK, A., NEŠPŮREK, S., SYROVÁ, L. Towards a
fully printed electrochemical NO2 sensor on a flexible substrate using ionic liquid based
polymer electrolyte (2015) Sensors and Actuators, B: Chemical,. Article in Press.
[2] KUBERSKÝ, P., SYROVÝ, T., HAMÁČEK, A., NESPŮREK, S., SYROVÁ, L. Fully printed
electrochemical NO2 sensor (2014) Procedia Engineering, 87, pp. 1043‐1046.
[3] SYROVÝ T., SYROVÁ L., KAPLANOVÁ. M., ČERNÝ J., KUBÁČ l., ŘEBOUN J.,
HAMÁČEK A., Printed humidity sensor for measuring in wide range of temperatures
and relative humidities, Utility model PUV 2013‐27805, 2013.
******
Diketo‐Pyrrolo‐Pyrrole: A Versatile Chromophore for Organic Electronics
and Photonics
Vala Martin1, Weiter Martin1, Krajčovič Jozef1, Stanislav Luňák1, Jan Vyňuchal2, Luboš
Kubáč3
1Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova
464/118, CZ‐612 00 Brno, CZECH REPUBLIC 2Synthesia, a. s., Semtín 103, CZ‐530 02 Pardubice, CZECH REPUBLIC
3Centre for Organic Chemistry Ltd., Rybitví 296, CZ‐533 54 Rybitví, CZECH REPUBLIC
Abstract
The rapidly progressing fields of organic photonics research has led to a renaissance in the
chemistry of dye molecules, compelling scientists to revitalize old pigments, transform them
into soluble dyes and apply them in the construction of new and complex semiconducting
materials. Among other materials (e. g. (iso) indigo, benzodipyrrolidone, benzodifurannone,
and others), the dyes based on diketo‐pyrrolo‐pyrrole (DPP) unit becomes to be highly
studied nowadays. Derivatives of 3, 6‐diphenyl‐2, 5‐dihydro‐pyrrolo[3, 4‐c]pyrrole‐1, 4‐
dione, commonly referred to as DPPs, constitute recent industrially important class of high‐
performance pigments. They are endowed with brilliant shades and exhibit exceptional
chemical, heat, light, and weather fastness. If we add to this a large conjugated system, the
materials represent an attractive basic core for organic photonics. It has been proved that the
150
DPPs can serve as an efficient structure for organic solar cells materials, can exhibit high p‐
and n‐type mobility and allow for construction of electroluminescent devices.
In this contribution we present the study of the effect of DPP chemical structure on the
electrical, optical and optoelectronic properties for photonic applications. We discuss the
influence of various substitutions (polar groups, solubilizing groups). These modifications
allow fine‐tuning of the frontier molecular orbitals, molecular geometries and the resulting
optical and electrical properties. We show that these dyes can offer efficient base for optical
applications (solid state lasers, two‐photon absorption) and optoelectrical applications such
as photovoltaics. Model devices were prepared and characterized and the experimental
outcomes compared with theoretical results obtained with the help of quantum chemical
calculations.
Keywords
Organic semidonductors, oerganic electronics, organic photonics, diketopyrrolopyrrole
Acknowledgements
This work was supported by the Ministry of education youth and sport of the Czech
Republic, project No. LO1211 and by Czech Science Foundation via project No. 15‐05095S.
151
Photochemistry and Photocatalysis
Aqueous Photochemistry of Bisphenols: Mechanistic Aspects
Salomatova, V.1, Pozdnyakov, I.1, 2, Sherin, P. 3, Grivin, V.1, Bazhin, N.1, Plyusnin, V.1, 2
1V. V. Voevodsky Institute of Chemical Kinetics and Combustion, 3 Institutskaya str., 630090
Novosibirsk, RUSSIAN FEDERATION 2Novosibirsk State University, 2 Pirogova St., 630090 Novosibirsk, RUSSIAN FEDERATION
3International Tomography Center, 3a Institutskaya str., 630090 Novosibirsk, RUSSIAN
FEDERATION
Abstract
Bisphenols (BPs) are widely used in production of polycarbonate plastics, epoxy resins,
adhesives, coatings for drink packages and food cans. As a consequence BPs have been
widely detected in the environment and food products [1]. However, many (e. g. well‐known
bisphenol A) of them refer to endocrine‐disrupting chemicals (EDCs) and were reported to
possess acute toxicity and estrogenic activity [2]. Conventional treatment techniques are not
effective enough for the removal of majority of EDCs, while photochemical and
photocatalytic processes have proved themselves as perspective methods for water
purification and disinfection from these compounds. Besides the broad number of
investigations devoted to decomposition of BPs using photochemical approaches, there is
almost no information about mechanistic aspects regarding the photochemistry of BPs. Using
combination of pulsed photochemical techniques with stationary methods is comparable
rarely used but very informative approach for construction full and reliable model of
photodegradation of organic pollutants. In this work aqueous photochemistry of three
bisphenols (4, 4’‐hydroxyphenylmethane (BPF), 4, 4’‐hydroxyphenylethane (BPE) and 4, 4‐
Bis (4‐hydroxyphenyl) valeric acid (DPA)) was studied by means of stationary (XeBr excimer
lamp, 282 nm) and laser flash photolysis (6 ns, Nd:YAG laser, 266 nm). Main attention was
paid to determination of primary photochemical processes, nature, spectral and kinetic
properties of excited states and primary intermediates and their further transformation
products. For all studied BPs the main primary photochemical process was observed to be
photoinization with formation phenoxyl radical – hydrated electron pair. It was found that
phenoxyl radical decays in recombination and reaction with superoxide anion radical
formed during scavenging of hydrated electron by dissolved oxygen with formation of one
main product which was determined by LC‐MS method as product of BP hydroxylation. In
present work quantum yields of primary intermediates formation and BPs
photodegradation, rate constants of intermediates disappearance and their spectral
properties were determined. Also, on the basis of all obtained data, scheme of BP
transformation in aqueous solutions was proposed. UV‐method was found to be sufficiently
effective way for BPs removal from water, but obviously this method is needed in further
improvements and modifications to reach endurable results. Cyclodextrin complexation has
recently emerged as a new catalytic technology complement to the photochemical treatment
approaches. It was found for all studied compounds that inclusion of BPs in cyclodextrin
cavity leads to great increase of photoionization and fluorescence quantum yields as well as
152
fluorescence lifetime due to decreasing of solvent quenching of the singlet excited state of
BPs.
Keywords
Bisphenols, endocrine disruptors, flash photolysis, photodegradation, phenoxyl radical
Acknowledgements
The work was financially supported by the Russian Foundation for Basic Research (No. 14‐
03‐00692_a)
References
[1] T. SUZUKI, Y. NAKAGAWA, I. TAKANO, K. YAGUCHI, Y. KAZUO, Environ. Sci.
Technol., 38, 2004, pp. 2389–2396[2] M. ‐Y. Chen, M. Ike, M. Fujita, Environ. Toxicol., 17,
2002, pp. 80‐86
******
Preparation of Covalently Bonded Polyacrylic Layers onto the
Polypropylene Surface
Pospíšek, M., Kučera, F.
B rno University of Technology, Faculty of Chemistry, Purkyňova 464/118612 00 Brno, CZECH
REPUBLIC
Abstract
Radical graft polymerization onto the polypropylene surface was observed in solution of
various acrylic monomers (acrylic acid, sodium ionomer of acrylic acid and acryl amide) in
proper solvent (water‐acetone mixture). The process was initiated by photoinitiator
(benzophenone and acetophenone) and ultraviolet light source (medium pressure mercury
lamp). Polypropylene used to modification was commercial extrusion type with basic
stabilization. Modified surfaces were characterized by infrared spectroscopy with ATR
technique. The comparative parameter was carbonyl index determined from absorption
peaks of functional methyl groups (2950 cm‐1) and functional carbonyl groups (1700 ‐
1750cm‐1) of FTIR‐ATR spectra. There was determined effect of modification solution
thickness on the modification process. Maximum of modification intensity was reached in
thickness of modification solution 100 μm. Influence of initiator concentration on the
modification process was tested for both acetophenone and benzophenone. Intensity of
modification process increased with initiator concentration for both initiators and
modification intensity increased clearly more in case of benzophenone. Time dependence of
grafting yield of acrylic monomers expressed as carbonyl index was determined for
modification time from 30 to 600 s. The highest modification intensity was reached with
modification of acrylamide. Test specimens designed for preparation of adhesive joints were
modified in time from 30 to 600s. Joints were bonded by cyanoacrylate adhesive that
provided reaction with surface of polyacrylic acid. There were founded conditions of
modification that provided strength of adhesive joints higher than strength of
polypropylene. Confocal microscopy was used to observe changes of surface morphology,
where surface roughness and thickness of grafted surfaces that reached up to 4 μm was
determined. Modification of polypropylene surfaces by acrylic monomers seems to be
153
promising for various industrial applications such as thin layer printing, dying, coating,
improving adhesion in polymer blends, composites and polar adhesives.
Keywords
Polypropylene, modification, surface, photo‐grafting, adhesion, FTIR‐ATR, acrylic acid, acryl
amide.
******
Principal Component Analysis of NIR Spectral Data used as Forensic
Method for Inkjet Printed Document
Oravec, M., Gál, L., Čeppan, M.,
Slovak University of Technology in Bratislava, Faculty of Chemical and Food Technology,
Radlinského 9, 812 37 Bratislava, SLOVAKIA
Abstract The basic procedure of analysing properties of the graphic documents includes their material
analysis. Currently used analytical techniques as TLC, HPTLC, GC‐MS, and HPLC [1‐3]
require suetable pre‐treatment of a sample before analysis. This approach brings several
drawbacks, which finally leads to the serious destruction of analysed evidence. This paper is
focused on the combination of fibre optic reflection spectroscopy in the NIR spectral region
and multivariate statistical method – Principal component analysis (PCA). The approach of
the method can be used to verify the authenticity of analyzed documents or identification of
inks from documents for forensic and technical analysis. The spectral data of new samples
were added to the inkjet prints database in order to improve results of PCA. The most
important part of this work was to design an appropriate procedure of pre‐processing
methods to prepare optimal spectral data for PCA. PCA models of various categories
depending on the measurement conditions and data processing were created. The
combinations of transformation methods were selected with regard to result in PCA model.
The main goal was to describe maximum variance by the first two principal component. We
chose transformation methods for example detrending, baseline correction, standard normal
variate, and we applied them to all spectra. One of the most important outputs of PCA is a
scatter plot of the component scores. Groups of points localized in this plot represented
samples with analogous spectral properties. The next step of the experiment was
confrontation of the created groups with the information which we have about devices such
as device manufacturer, type of printer or originality of used ink of printing documents. The
last step of experiment was test of one treated NIR spectrum label as “unknown” with the
rest of the dataset. The “unknown” sample was projected as point, in the scatter plot of the
component score near the sample which represented document, printed by the same,
compatible type of ink. In this way we demonstrated the potential of comparability of the
samples in the method. In most cases the analyzed samples of the same category (the same
type of paper, measuring conditions and data processing), it is possible to use the differences
and relations between the spectral properties of different samples for successful
identification of ink in documents by multivariate statistical analysis. The results suggest,
that the combination of non‐destructive fibre optic reflection spectroscopy in the NIR
spectral region and chemometric method PCA can be a useful tool for investigating of
154
questioned documents. The measured set of the data collected in this study has established a
database of the samples printed by inkjet devices. This database will be extended in the near
future.
Keywords PCA analysis, NIR spectroscopy, chemometric method
Acknowledgements
This work was supported by the Slovak Research and Development Agency under the
contract no. APVV‐0324‐10. This publication is the result of the project implementation:
Centrum excelentnosti bezpečnostného výskumu (Center of Excellence for Security
Research) ITMS code: 26240120034 supported by the Research & Development Operational
Program funded by the ERDF. Michal Oravec was also supported by an internal STU grant.
References [1] WILSON, J. D. et al: Differentiation Of Black Gel Inks Using Optical And Chemical
Techniques, Journalof Forensic Science, Vol. (2004) 49., pp. 364‐370
[2] WEYERMANN, C. et al: Differentiation of Blue Ballpoint Pen Inks by Laser Desorption
Ionization MassSpectrometry and High–performance Thin–layer Chromatography, In
Journal of Forensic Science., Vol. (2007) 52., pp. 216‐220
[3] HOFER, R.: Dating of Ballpoint Pen Ink, Journal of Forensic Science, Vol. (2004) 49., pp.
1353‐1357
******
Direct And Fulvic Acid Assisted Photolysis Of Drug Propranolol In
Aqueous Solution: the nanosecond laser flash photolysis study
Makunina, M., Pozdnyakov, I., Grivin, V., Plyusnin, V.
Voevodsky Institute of Chemical Kinetics and Combustion SB RAS, Laboratory of Photochemistry,
Institutskaya str. 3, 630090, Novosibirsk, RUSSIAN FEDERATION
Abstract Propranolol (PR) is a sympatholytic non‐selective ?‐blocker which is used to treat
hypertension, anxiety and panic. ?‐blockers are in use for a long time in Europe and North
America [1]. In natural waters they were generally detected in the ng‐μg/L range, but the
continual infusion into the aquatic environment leads to the chronic exposure of water biota
with largely unknown consequences [2]. Humic substances (HS) were found to sensitize the
degradation of many organic pollutants under the sunlight. Application of these compounds
as photocatalysts or photosensitizers is promising for the water purification photoprocesses
[3]. This study is devoted to the photochemistry of fulvic acid (FA) (Henan ChangSneng
Corporation) and the effect of FA on photodegradation of propranolol (hydrochloride salt)
(99%, Acros) in aqueous solution by laser flash and steady state photolysis methods. Flash
excitation (355 nm) of FA solutions leads to instant appearance of wide absorption band with
maximum at 620 nm. In oxygen‐saturated solution we observed dramatic reduction of the
intermediate lifetime, which allows us to suggest FA triplet state (3FA) formation. Rate
constant of triplet state quenching by oxygen is equal to 7?108 ?‐1s‐1. Kinetic curves of 3FA
decay in deoxygenated solution could be well fitted by the third‐order kinetic law. 3FA
155
decay kinetics depends weakly on pH (2‐10), but the amplitude of the transient absorption
signal reaches the maximum value in the neutral (6‐7) media and falls in alkaline and acidic
solutions. This fact is most likely explained by the presence of acid‐base equilibriums for the
chromophores of FA, as well as by the quenching of excited singlet chromophore states with
protons of medium, which affects the efficiency of intersystem crossing. Global processing of
a set of kinetic curves in the range of 50‐800 s allowed us to determine the characteristic
times of the FA triplet state decay: t1 = 4. 3 ± 2. 2 s, t2 = 54 ± 28 s, t3 = 830 ± 240 s [4]. A mechanistic study of PR photodegradation in the presence of fulvic acid in aqueous solution
using flash (355 nm) and steady‐state photolysis (365 nm) techniques was performed. Pure
PR was found to be stable under irradiation with UV‐A but stationary photolysis (365 nm) of
oxygenated FA and PR mixture led to photodegradation of amine drug. Flash excitation led
to reduction of 3FA yield, thus indicating of complexation of FA with PR and static
quenching of 3FA by PR via an electron transfer mechanism. Less than 1% of the total 3FA
participated in PR degradation, and the quantum yield of this process was 3. 5?105. The
triplet state yield (?T ? 0. 6%) and the T–T absorption coefficient (?T620 nm = 5?104 M‐1?cm‐
1) were estimated for the first time by modeling the yields of the FA triplet state in the
presence of PR [5]. Thus, fulvic acid was shown to be a promising agent for propranolol
photodegradation catalysis in aqueous solutions under UV‐A light irradiation. This process
is mediated with FA triplet states.
Keywords
Propranolol, fulvic acid, aqueous solution, laser flash photolysis, triplet state,
photodegradation.
Acknowledgements
This work was supported by the Russian Foundation for Basic Research (projects 11‐03‐
00268, 12‐03‐00482, 14‐03‐31003_mol_a).
References
[1] IMS 2005. IMS Health, MIDAS 21/03/2005.
[2] Y. CHEN, C. HU, X. HU, J. QU. Environ. Sci. Technol., 2009, vol. 43, P. 2760–2765.
[3] G. STOCHEL, M. BRINDELL, W. MACYK, Z. STASICKA and K. SZACILOWSKI.
Bioinorganic Photochemistry, Wiley, 2009, p. 377.
[4] M. P. MAKUNINA, I. P. POZDNYAKOV, V. P. GRININ, V. F. PLYUSNIN. High Energy
Chem., 2014. vol. 48, P. 197–201.
[5] M. P. MAKUNINA, I. P. POZDNYAKOV, V. P. GRININ, V. F. PLYUSNIN. Chemospere,
2015. vol. 119, P. 1406‐1410.
156
******
Boron‐Doped Polycrystalline Diamond layers For Organic Photovoltaic
Devices
Alexander Kovalenko, Petr Ashcheulov, Patricie Heinrichová, Ladislav Fekete, Martin
Vala, Martin Weiter, Germà Garcia Belmonte and Irena Kratochvílová
1Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 118,
612 00 Brno, CZECH REPUBLIC 2Photovoltaic and Optoelectronic Devices Group, Departament de Física, UniversitatJaume I, ES‐
12071 Castelló, SPAIN 3Institute of Physics, Academy of Sciences Czech Republic v. v. i, Na Slovance 2, CZ‐182 21,
Prague 8, CZECH REPUBLIC 4Faculty of Nuclear Physics and Physical Engineering, Czech Technical University in Prague, Zikova
1, 160 00 Prague 6, CZECH REPUBLIC
Abstract Considering organic solar cells, which seem to have particular potential, one of the limiting
factors is the development of transparent electrodes. At first glance, the widely‐used
compound indium tin oxide (ITO) seems to be the perfect candidate as a material for
transparent electrode, as it exhibits superior transparency and a sheet resistance of below 100
?/sq. However, the declining availability of indium compels us to look for an alternative
solution. One possibility is to substitute ITO with carbon‐based electrodes such as heavily
boron‐doped conductive diamond polycrystalline films [1‐3]. Polycrystalline diamond films
can be produced by a large variety of chemical deposition techniques, such as hot filament
deposition, bias enhanced deposition, and Plasma‐Enhanced Chemical Vapor Deposition
(PECVD) with linear antenna delivery, where precursor gases are ionized to enhance their
chemical reaction rates [1, 2]. One of the advantages of the PECVD technique is the
possibility to operate on a large variety of substrates at low deposition temperatures, which
can be a crucial condition in the manufacture of semiconductors. With respect to
photovoltaic devices, light‐harvesting materials can be directly manufactured by the PECVD
process. Diamond is recognized to be a remarkable material due to its particularly attractive
properties combining chemical resistance, optical transparency, thermal conductivity, and
electrochemical properties. Once successfully doped, diamond, which is generally
recognized as an insulating material, becomes a wide‐band gap semiconductor material with
excellent potential due to the unique combination of its physical and electronic properties.
The dependence of the above‐mentioned parameters on the optical and electrical properties
of each BDD was studied in order to achieve optimal conditions for the effective application
of diamond electrodes in organic electronics as a replacement for ITO. Bulk‐heterojunction
polymer‐fullerene organic solar cells were fabricated to test the potency of BDD application
in photovoltaic devices. The obtained results demonstrated the possibility of the described
application [3].
Keywords
boron doped polycrystalline diamond layer, Plasma‐Enhanced Chemical Vapor Deposition,
organic solar cells,
157
Acknowledgements
Special thanks to Patrik Foral from Westinghouse Electric Czech Republic s. r. o. for
cooperation. The authors acknowledge financial support from European R&D projects,
TACR grants TA01011165, TA04020156, MEYSCR grants LM2011026 and RVO14000 and
grants of the Czech Science Foundation 13‐31783S and 14‐10279S.
References
[1] P. ASHCHEULOV, J. ŠEBERA, A. KOVALENKO, V. PETRÁK, F. FENDRYCH, M.
NESLÁDEK, A. TAYLOR, Z. VLCKOVÁ ŽIVCOVÁ, O. FRANK, L. KAVAN, M.
DRACÍNSKÝ, P. HUBÍK, J. VACÍK, I. KRAUS, and I. KRATOCHVÍLOVÁ, Eur. Phys. J.
B 86 (2013) 443.
[2] Frantisek FENDRYCH, Andrew TAYLOR, Ladislav PEKSA, Irena KRATOCHVILOVA,
Jan VLCEK, Vladimira REZACOVA, Vaclav PETRAK, Zdenek KLUIBER, Ladislav
FEKETE, Michael LIEHR and Milos NESLADEK: J. Phys. D: Appl. Phys. (2010) 43,
374018
[3] Alexander KOVALENKO, Petr ASHCHEULOV, Antonio GUERRERO, Patricie
HEINRICHOVÁ, Ladislav FEKETE, Martin VALA, Martin WEITER, Irena
KRATOCHVÍLOVÁ, and Germà GARCIA‐BELMONTE Solar Energy Materials and
Solar Cells, 143 (2015) 73‐79,
******
Spectral Analysis of Laser Prints for Forensic Investigation
Belovičová, M., Čeppan, M., Baráthová, A.
Slovak University of Technology in Bratislava, Faculty of Chemical and Food Technology,
Department of Graphic Arts Technology and Applied Photochemistry, Radlinského 9, 812 37,
Bratislava, SLOVAK REPUBLIC
Abstract An important part of forensic analysis is identification or document authentication which
carries some information. This investigation regards many types of documents can give rise
to many different problems. One of them is characterizing the toners and inks used to print
the document. The aim of this study is linking the two approaches: chemometry and spectral
analysis of laser prints of toners from different manufacturers. Methods of molecular
spectroscopy in IR, Vis and NIR area were used. Forty‐eight samples of prints from different
types of cartridges produced by 9 manufacturers were studied using ATR‐Fourier transform
infrared spectrometry (ATR‐FTIR) and fiber optic reflection spectroscopy in the Vis‐NIR
region. The sets of spectra were processed by chemometric method ‐ Principal Component
Analysis (PCA). This combination appears to be a suitable tool for the study of properties
and identification of toners in questioned documents. Selected samples were subjected to
accelerated light and thermal aging and spectral properties of prints during ageing were
studied. The obtained results allow creating database of spectral properties of laser prints,
which could be useful in forensic investigations of questioned documents.
Keywords
Toner, ATR‐FTIR, Principal Component Analysis, Forensic
158
******
Printed UV Dosimeter
Michal Veselý, Petr Dzik, Mária Veselá, Ivana Uhrová, Oldřich Zmeškal
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Sun bathing is very important for maintenance of health but the excessive exposure to sun
light during leisure or working time can cause deleterious effects such as skin burns,
immunosuppression, and skin cancer. For this reason, sun protection products for topical
application are strongly recommended to minimize those effects. For safe sun bathing people
need a simple indicator of UV exposure dose – a simple UV dosimeter which would warn
people against excessive exposure to UV light. This warning can be realised through
coloured strip which would change its colour after reaching the maximal UV dose still safe
for people sun bathing. UV dosimeter based on nanocrystaline titanium dioxide was
prepared and studied. This dosimeter utilises photocatalytical degradation of suitable
azodye controlled by additives to achieve required sensitivity. Colour change after required
UV dose can be further tuned by means of auxiliary dye. A successful preparation of such
dosimeter on a substrate suitable for dosimeter application strongly depends of carefully
tuning of surface tension of titanium dioxide suspension with polymeric binder and
additives. Initially, coating of such composition on plastic foil was realized by a doctor blade
film applicator, later by printing. The printing process with slot‐die technique was realized in
roll‐to‐roll material printer. The optical density, layer thickness UV light sensitivity and
deviation from Bunsen‐Roscoe reciprocity law of the printed dosimeters were evaluated.
Keywords
UV dosimeter, titanium dioxide, material printing, slot‐die
Acknowledgements
Authors thank to Technology Agency of the Czech Republic for support by project
TA03010548.
******
Automated Monitoring of Self‐Cleaning Glass Photocatalytic Activity
Dzik, P., Veselý, M., Bednárková, J., Uhrová I.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Self‐cleaning surfaces account for a rather successful example of commercial application of
photocatalytic processes. They are almost exclusively composed of thin transparent titania
coating of various origin, sometimes accompanied by auxiliary layers improving adhesion,
durability and activity. The principle of their action is based on the combined effect of
photoinduced superhydrophilicity and oxidizing activity of photogenerated holes it the
159
semiconducting titania valence band. Once these materials entered the markets, the need for
standard quality evaluation tools became urgent. Many methods have been proposed and
some eventually were articulated in the form of ISO standards. However, the issue has not
been settled completely in a satisfactory way yet and several new ISO standards are under
consideration at the moment. Dye bleaching is a very popular approach to photocatalytic
activity testing. The methylene blue test has been generally recognized and transformed into
an ISO standard. Another proposal utilizing this process is under consideration at the
moment. It is based on the bleaching of a thin semi‐dry colored layer of indicator ink. The
color change is supposed to be monitored by means of cheap digital imaging devices such as
flatbed scanner or digital camera. We investigated this approach in more details and would
like to report on our findings. We constructed a compact dedicated reactor featuring UV‐
LED actinic radiation source for photocatalyst excitation and a visible wavelength LED for
the indicator color change observing. The indicator ink bleaching can be conveniently
monitored by a compact USB spectrometer equipped with fiber optics. This approach
enables an automated continuous recording of the sample transmittance/reflectance changes
and a quick analysis of the recorded kinetic profiles. Moreover, the accuracy and
repeatability of the method can be further improved when a better defined method is used
for the indicator ink deposition. While the present proposal suggests the use of a spiral bar,
we employed material printing (inkjet preferably) for the indicator ink deposition. The inkjet
printing provided us a complete control over the deposition process parameters and gave us
the possibility to easily fabricate patterns of arbitrary shape and thickness. The additive
nature of the process together with the excellent efficiency of material consumption makes
this approach very economic and environment friendly. Moreover, our tests have clearly
shown that also a digital multimeter with an optical sensor can provide relevant
transmittance data. This further minimizes the equipment investment without compromising
the method robustness.
Keywords
photocatalysis, self‐cleaning surface, indicator ink, activity testing, material printing
Acknowledgements
Authors thank to Technology Agency of the Czech Republic for support by project
TA03010548.
******
CO2 Photocatalytic Reduction in Gas Phase over Photocatalyst Based on the
TiO2
Huo, P., Matějová, L., Šihor, M., Reli, M., Obalová, L., Kočí, K.
Institute of Environmental Technology, Energy Units for Utilization of non Traditional Energy
Sources, Faculty of Metallurgy and Materials Engineering, VŠB‐Technical University of Ostrava, 17.
listopadu 15/2172, 708 33 Ostrava, CZECH REPUBLIC
Abstract
Over the past years, a serious contemplation has revealed the need to resolve two major
complications: global warming due to rising levels of atmospheric carbon dioxide (CO2) and
160
the alarming consumption of energy resources. CO2 is the main contributor to the
greenhouse effect. The global concentration of CO2 in the atmosphere is increasing mainly
due to the emissions from fossil fuel combustion. The reduction of CO2 by photocatalysis is
one of the most promising methods since CO2 can be reduced to useful compounds by
irradiating it with UV light at room temperature and ambient pressure.
TiO2 supported on spheres was prepared by the sol‐gel process controlled within reverse
micelles and impregnation under vacuum. Textural, structural, optical and electronic
properties of photocatalysts were characterized in detail by using nitrogen physisorption,
powder X‐ray diffraction and diffuse reflectance UV‐Vis spectroscopy and their performance
was explored in the CO2 photocatalytic reduction by water vapor. The reaction was carried
out in homemade photoreactor. Methane and hydrogen were observed as the main products.
The ratio of CO2/water vapor played the key role in the CO2 photocatalytic reduction.
Keywords
CO2 reduction, Photocatalysis, TiO2
Acknowledgements
The financial support of the Grant Agency of the Czech Republic ( (projects No. 14‐23274S
and 14‐35327J), “National Feasibility Program I”, project LO1208 “TEWEP” from Ministry of
Education, Youth and Sports of the Czech Republic and SP2015/125 are acknowledged.
******
Determination of Photocatalytic Activity of Self‐Cleaning Paints Using
Smart Inks
Baudys, M., Krýsa, J.
Department of Inorganic Technology University of Chemistry and Technology Prague, Technická 5
166 28 Praha 6, CZECH REPUBLIC
Abstract
Self‐cleaning paints contain besides usual pigments and fillers also particle of photocatalytic
material mostly TiO2 of anatase modification. The current commercial application of
photocatalytic paints is mainly with regard to exterior facade paint which, via the
photocatalytic processes are not susceptible to soiling and so help to keep the exterior of
building clean.
This work is a continuation of a previous report [1] from this group which focused on the
effect of weathering of acrylic photocatalytic paints containing TiO2 and ZnO, on their
photocatalytic activities as assessed using a test based on the bleaching of Acid Orange 7
(AO7) in aquesous solution. The objective of this work is an application of a new method of
photocatalytic activity assessment based on smart inks. This method recently published in
papers [2. 3] is based on irreversible colour change of dye in ink on photocatalytic surface.
Excited positive holes are trapped by sacrificial electron donor mostly glycerol which is than
oxidized to glyceric acid and excited electrons reduce dye in ink which is than connected
with colour change. Compared to oxidative bleaching of dyes this process is due to good
charge separation very quick and the color change take few seconds. The results of this test is
161
calculation of time in which 90% of overall color change occurs (Ttb90). The aim of this work
is the determination of photocatalytic activity of various paints using Resazurin (Rz) and
Acid Violet 7 (AV7) ink. Results of photocatalytic activity of two commercial paints – exterior
and interior is compared with laboratory acrylic formulation containing 8% of TiO2 P25.
Exterior paint shows the lowest photocatalytic activity. The Ttb90 for Rz ink was about 4000
s, and for AV7 no measurable photocatalytic activity (no color change) was observed even
after 70 minutes of UV irradiation. Contrary in case of exterior paint the situation is opposite.
This paint exhibits very high activity. This can be due to the higher amount of the
photocatalyst. The reduction of Resazurin to Resorufin is very quick and Resorufin is than
reduced to another form which is colourless. For determination of photocatalytic activity we
had to use AV7 ink and the Ttb90 was about 360 s. In the case of laboratory acrylic paint
various Ttb90 values for each ink was observed. For Rz the Ttb90 was about 80 s on the other
hand for Acid Violet 7 Ttb90 was about 2770 s.
Keywords photocatalytic paints, smart inks, Resazurin, Acid Violet 7
Acknowledgements
Financial support of INTEC project (FP7‐NMP‐2012‐CSA‐6, GA No. 319210)
References
[1] M. BAUDYS, J. KRÝSA, M. ZLÁMAL, A. MILLS, Chemical Engineering Journal 261
(2015) 83‐87.
[2] A. MILLS et all, J. Photochem and Photobiol A: Chemistry 272 (2013) 18‐20.
[3] A. MILLS et all, J. Photochem and Photobiol A: Chemistry 290 (2014) 63‐71
******
TiO2 Nanostructures for Electrochemical Water Splitting
Paušová Š., Kment Š., Krýsa J.
1Department of Inorganic Technology, UCT Prague, Technická 5, Prague 6, 166 28, CZECH
REPUBLIC 2Institute of Physics of the Czech Academy of Sciences, Na Slovance 1999/2, Praha 8, 182 21 CZECH
REPUBLIC
Abstract
With increasing demands on energy supply, necessity of usage of an efficient renewable
source of energy is growing. One of the possibilities is conversion of solar light to electricity
or fuel. Since the photocatalytic water splitting on TiO2 was discovered by Fujishima and
Honda [1], the great effort has been devoted to application of TiO2 in energy conversion.
Although TiO2 is a suitable candidate for water splitting, some main drawbacks have to be
overcome, such as high electron‐hole recombination or short excited state life time. Using 1‐
D nanostructures (nanotubes, nanorods, nanowires or nanofibers) seems to be one of the
possible ways how to increase the TiO2 effectivity. However, even usage of TiO2
nanostructures is limited by usage of UV light irradiation, so the modification of the TiO2
162
with metal and/or non‐metal ion doping to narrow the bandgap or sensitization by quantum
dots or plasmon enhancement is necessary.
1‐D nanostructures can be prepared by many different methods. Nanotubes are commonly
prepared by anodization of Ti substrates or Ti thin layers, by template synthesis or
hydrothermal synthesis nanorods by hydrothermal synthesis, oblique‐angle deposition or
metal‐organic chemical vapour deposition and nanowires or nanofibers by template
synthesis, electrospinning synthesis, hydrothermal synthesis or hydrothermal corrosion of Ti
metal substrate.
So far for pristine TiO2, nanorods seems to be the nanostructure exhibiting the highest
usability for water splitting showing photocurrent density of 1. 01 mA/cm2 at 0. 62 V vs RHE
[2]. Among the modified structures, CdTe quantum dots modified TiO2 nanotubes exhibit
photocurrent density six times higher than pristine TiO2 ‐ 6 mA/cm2 at 0. 6 V vs RHE [3].
Keywords
TiO2 nanostructures, water splitting, photocurrent
Acknowledgements
Authors acknowledge the financial support from Grant Agency of the Czech Republic
(project number 15‐19705S).
References
[1] A. FUJISHIMA and K. HONDA, Nature, 238 (1972) 37.
[2] B. SUN, T. SHI, Z. PEng, W. SHENG, T. Jiang and G. LIAO, Nanoscale Res Lett, 8
(2013) 1.
[3] X. ‐F. GAO, H. ‐B. LI, W. ‐T. SUN, Q. CHEN, F. ‐Q. TANG and L. ‐M. PENG, The Journal
of Physical Chemistry C, 113 (2009) 7531.
163
Physical Chemistry & Life
“Vinum Regnum – Rex Vinorum”. 1H NMR Spectroscopy Study of the
Slovak Tokaj Wines
Milan Mazur, Lucia Husáriková, Michal Kaliňák, Marián Valko
Faculty of Chemical and Food Technology, Slovak University of Technology in Bratislava,
Radlinského 9, SK ‐ 812 37 Bratislava, SLOVAK REPUBLIC milan. mazur@stuba. sk
Abstract The present contribution analyses the characteristic properties of the Slovak Tokaj wines by
high resolution 1H NMR spectroscopy. The following original wines of various vintages
were selected for NMR experiment: Tokaj Furmint, Tokaj Lipovina, Tokaj Yellow Muscat,
Tokaj “samorodne” dry and sweet wine, Tokaj 2‐, 3‐, 4‐, 5‐ and 6‐ puttony select wines, and
Tokaj essence. All Tokaj wines were produced by classic Tokaj „oxidative” processing
technology. Additionally, the Tokaj select wines and Tokaj essence were prepared using
„cibebs“ ‐ grape raisins affected by noble rot Botrytis cinerea and were stored in Tokaj tuff
cellars for 3‐6 years of aging in oak wood barrels. In summary, the NMR spectroscopy can be
used for the detection of organic and amino acids present in the Tokaj wines. The 1H NMR
spectra can be utilized as the unique “fingerprints” of the original Slovak Tokaj wines.
Keywords
NMR spectroscopy, Tokaj wines, minor compounds
Acknowledgements
This work was supported by the Scientific Grant Agency of the Slovak Republic (Projects
VEGA 1/0765/14 and VEGA 1/0041/15)
******
Binding of Surfactant to Polyelectrolyte in Non‐Standard Conditions ‐
Fluorescence Study
Mondek, J., Mravec, P., Pekař, M.
Brno University of Technology, Materials Research Centre, Faculty of Chemistry, Purkyňova 118,
CZ‐612 00 Brno, CZECH REPUBLIC
Abstract Steady‐state and time‐resolved fluorescence and UV‐vis techniques were used to study the
formation and dissociation of dodecylacridine orange in order to investigate hyaluronan‐
dodecylacridine orange, hyaluronan‐CTAB (cetyltrimethylammonium bromide),
polystyrenesulfonate‐acridine orange, and polystyrenesulfonate‐CTAB interactions in
aqueous solution. Steady‐state and time‐resolved fluorescence and the dimer:monomer
absorbance ratio of dodecylacridine orange (DAO) were used to determine dimer formation
on polymer chains of polyelectrolytes. After the addition of surfactant, we observed an
enhancement of fluorescence intensity, indicating the dissociation of DAO dimers into
164
monomers and the replacement of dodecylacridine orange on polymer chains by surfactant
molecules. Importantly, we show that surfactant molecules bind to polymer chains before
the critical micelle concentration is reached and form the so‐called “bottle‐brush” structure.
Keywords Hyaluronan, Surfactant, acridine orange dimer, dodecylacridine orange
Acknowledgements
This work was supported by the Materials Research Centre at FCH BUT‐ Sustainability and
Development, REG LO1211, with financial support from the National Programme for
Sustainability I (Ministry of Education, Youth and Sports).
References
[1] COSTANTINO, L. GUARINO, G. ORTONA, O. VITAGLIANO, V., Journal of Chemical
& Engineering Data 29, 1 (1984).
[2] PEYRATOUT, C. DONATH, E. DAEHNE, L., Journal of Photochemistry and
Photobiology A: Chemistry 2001, 142, 1 (2001)
[3] LAMM, M. E. NEVILLE, D. M., The Journal of Physical Chemistry 69, 11 (1965).
[4] ANTONOV, L. GERGOV, G. PETROV, V. KUBISTA, M. NYGREN, J., TALANTA 49, 1
(1999).
[5] LAURETTI, F., Lucas de MELO, F., BENATI, F. CIO, J. de MELLO Volotão, E. SANTOS,
N. LINHARES, R. E. C. NOZAWA, C., Journal of Virological Methods 114, 1 (2003).
[6] ITO, F. KAKIUCHI, T. Nagamura, T., The Journal of Physical Chemistry C 111, 19 (2007).
[7] SARKAR, D. MISRA, T. N., Biomaterials 10, 3 (1989).
[8] SMAL, J. KATHURIA, S. De MEYTS, P., FEBS Letters 1989, 244, 2 (1989).
[9] WANG, F. YANG, J. WU, X. WANG, X. FENG, L. JIA, Z. GUO, C., Journal of Colloid
and Interface Science 2006, 298, 2 (2006).
[10] MONDEK, J., MRAVEC, F., HALASOVÁ, T., HNYLUCHOVÁ, Z., PEKAŘ, M.,
Langmuir, 30, 29 (2014).
[11] MATTEINI, P. DEI, L. CARRETTI, E. VOLPI, N. GOTI, A. PINI, R., Biomacromolecules,
10, 6 (2009).
[12] BAIN, C. D. CLAESSON, P. M. LANGEVIN, D. MESZAROS, R. NYLANDER, T.
STUBENRAUCH, C. TITMUSS, S. von KLITZING, R., Advances in Colloid and Interface
Science, 155, 1‐2 (2010).
[13] GODDARD, E. D., Journal of Colloid and Interface Science, 256, 1 (2002).
165
******
Study of Agarose Gelation Process by Unconventional Dynamic Light
Scattering Method
Michal Kalina, Jiří Smilek, Romana Kratochvílová, Šárka Krňávková, Marcela
Laštůvková, Martina Klučáková
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Hydrogels represent nowadays material with broad application in different areas (medicine,
agriculture, food…). One of the important parameters of these systems is their temperature
of gelation. The main purpose of this contribution was the utilization of dynamic light
scattering technique as new tool for the study of gelation process. As an example of
thermoreversible hydrogel, agarose was selected. The gelation process of this linear
polysaccharide is well‐known and discussed in literature. Results obtained from dynamic
light scattering measurement were in good agreement with classical macrorheology
(oscillation test and temperature ramp). The temperature of gelation of 1 wt. % agarose
hydrogel determined by macrorheology tests was 45. 2 °C, 40. 2 °C in case of dynamic light
scattering method. These results are indicating that the method of determination of gelation
point based on dynamic light scattering seems to be very useful tool in investigation of sol‐
gel processes of different substances especially biopolymers and biocolloids and can be
comparable with different conventional techniques.
Keywords
agarose, dynamic light scattering, gelation, rheology
Acknowledgements
This work has been supported by Materials Research Centre at FCH BUT‐ Sustainability and
Development, REG LO1211, with financial support from National Program for Sustainability
I (Ministry of Education, Youth and Sports).
******
Characterization of Nanoporous Membranes with Controlled Permeability
Smilek, J., Kynclová, H., Sedláček, P., Prášek, J., Klučáková, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 464/118, CZ‐61200 Brno, CZECH
REPUBLIC
Abstract Thin two‐dimensional nanostructured films are abundantly used for the development of the
whole range of sensors especially biosensors. Growing interest about usage of nanoporous
materials in sensory analysis is given mainly by their specific permeability, which is primary
driven by pore size and shape. These important parameters can be influenced by the
modification of preparation process. Necessary assumption for practical utilization of these
nanoporous membranes is their characterization especially with regard to their transport
166
properties – determination the critical size of particle, which are penetrated through
membrane undisturbed. Promising methodology for the study on penetration of chosen
diffusion probe through nanoporous membranes seems to be diffusion cell technique.
Diffusion of suitable probes (organic dyes) will be realized through prepared nanoporous
membranes and fundamental transport parameters, such as effective diffusion coefficient,
will be calculated from the concentration change of chosen diffusion probe in acceptor part
of diffusion cell. The change of concentration will be determined by UV‐VIS spectroscopy.
Results obtained from these experiments will contribute to the draft of electrochemical
microsensor for detection of various substances in solutions and pores as well.
Keywords nanoporous membrane diffusion conductivity permeability
Acknowledgements
This work has been supported by the project FCH/FEKT‐J‐15‐2663 IGA Development of
sensors based on nanoporous membranes with controlled ion permeability, by project FEKT‐
S‐14‐2300 A new types of electronic circuits and sensors for specific applications and by
project ʺMaterials Research Centre at FCH BUT ‐ Suistainability and Developmentʺ No.
LO1211 of Ministry of Education, Youth and Sports of the Czech Republic.
******
Preparation and Utilization of Alumina Oxide Membranes for Sensor
Devices
Kynclová, H., Smilek, J., Prášek, J., Sedláček, P., Klučáková, M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 464/118, CZ‐61200 Brno, CZECH
REPUBLIC
Abstract
Anodic alumina oxide is promising material for application into sensor devices based on
sorting of substances, filtration and purification. Alumina membranes are fabricated by two
step anodic oxidation of high purity aluminium foil in acidic solutions under the constant
voltage. Obtained membranes contain hexagonally arranged nanopores which are uniform,
straight and perpendicular to the surface. The nanopores have diameter in range from 4 nm
to 250 nm and thick from 1 μm to tens of micrometers. Morphological parameters are
controllable by changing of experimental condition such as anodization voltage, current
density, type of acidic electrolyte (oxalic acid, sulphuric acid, phosphoric acid), temperature
and time of anodization. Anodic oxidation of aluminium sheet is relatively low cost method
with good reproducibility which provides nanoporous membranes with unique properties
like chemical stability, hydrophility, hardness, inertness and biocompatibility.
Keywords
nanoporous membrane anodic alumina alumina oxide anodization sensor
Acknowledgements
This work has been supported by the project FCH/FEKT‐J‐15‐2663 IGA Development of
sensors based on nanoporous membranes with controlled ion permeability, by project FEKT‐
167
S‐14‐2300 A new types of electronic circuits and sensors for specific applications and by
project ʺMaterials Research Centre at FCH BUT ‐ Suistainability and Developmentʺ No.
LO1211 of Ministry of Education, Youth and Sports of the Czech Republic.
******
Overview of the Polysaccharide‐Protein Complexes
Martin Chytil, Pavla Hájovská, Vasile Simulescu, and Alena Sereda
1Brno University of Technology, Faculty of Chemistry, Institute of Physical and Applied Chemistry,
Purkyňova 118, Brno, CZ‐612 00, CZECH REPUBLIC
Abstract Albumin with its incredible binding to various kinds of organic molecules, metabolites,
drugs, etc., and hyaluronan, which has been utilized in medicine, pharmacy and cosmetics
for several years due to its unique properties can provide an intriguing combination of their
properties. The mutual interactions between these two polymers were investigated using
rheology, interfacial rheology, turbidity measurements, dye‐solubilization method,
tensiometry, and SEC‐MALLS (Size Exclusion Chromatography‐Multi‐Angle Laser Light
Scattering) in order to elucidate the formation of the hyaluronan‐albumin complexes,
stoichiometry of the interactions, solubilization ability of the complexes and their gelation
behavior. The mentioned methods approved a formation of complexes and aggregates by e.
g. relative decrease in viscosity, increase in turbidity or capability of the dye probe
solubilization by the complexes. The complex gels formation occurred at temperatures nearly
9 °C lower than for the protein sample of the same polymer concentration and exhibited
values of the storage modulus higher nearly by one order in the magnitude.
Keywords
hyaluronan, bovine serum albumin, mutual interactions, complexes, gelation, rheology,
interfacial rheology
References [1] K. THALBERG, B. LINDMAN. Interaction between hyaluronan and cationic surfactants.
J. Phys. Chem. 93 (1989) 1478–1483.
[2] K. HOLMBERG, B. JÖNSSON, B. KROBERG, B. LINDMAN, Surfactants and polymers
in aqueous solution, John Wiley ? Sons Ltd, 2002.
[3] M. PISÁRČIK, M. SOLDÁN, D. BAKOŠ, F. DEVÍNSKY, I. LACKO, Viscometric study of
the sodium hyaluronate‐sodium chloride‐alkyl‐ (n) ‐ammonium surfactant system,
Colloid. Surface. A 150 (1999) 207–216.
[4] ?. HERSLÖF, L. O. SUNDELÖF, K. EDSMAN, Interaction between polyelectrolyte and
surfactant of opposite charge. Hydrodynamic effects in the sodium
hyaluronate/tetradecyltrimethylammonium bromide/sodium chloride/water system, J.
Phys. Chem. 96 (1992) 2345–2348.
[5] K. FUKADA, E. SUZUKI, T. SEIMIYA, Rheological properties in
decyltrimethylammonium bromide aqueous solutions, Langmuir 15 (1999) 4217–4221.
[6] M. CHYTIL, S. STRAND, B. E. CHRISTENSEN, M. PEKAŘ, Calorimetric and light
scattering study of interactions and macromolecular properties of native and
hydrophobically modified hyaluronan. Carbohyd. Polym. 81 (2010) 855–863.
168
[7] T. HALASOVÁ, J. KROUSKÁ, F. MRAVEC, M. PekAř, Hyaluronan‐surfactant
interactions in physiological solution studied by tensiometry and fluorescence probe
technique, Colloid Surf. A‐Physicochem. Eng. Asp. 391 (2011) 25–31.
[8] L. LAPČÍK, L. LAPČÍK jr, S. De SMEDT, J. DEMEESTER, P. CHRABREČEK,
Hyaluronan: Preparation, structure, properties, applications. Chemical Reviews 98
(1998) 2663–2684.
[9] M. K. COWMAN, S. MATSUOKA, Experimental approaches to hyaluronan structure.
Carbohyd. Res. 340 (2005) 791–809.
[10] K. P. VERCRUYSSE, G. D. Prestwich, Hyaluronate derivatives in drug delivery. Critical
Reviews in Therapeutic Drug Carrier Systems 15 (1998) 513–555.
[11] A. PRŮŠOVÁ, D. ŠMEJKALOVÁ M. CHYTIL, V. VELEBNÝ, J. KUČERÍK, An
alternative DSC approach to study hydration of hyaluronan. Carbohyd. Polym. 82 (2010)
498–503.
[12] W. E. KRAUSE, E. G. BELLOMO, R. H. COLBY, Rheology of sodium hyaluronate under
physiological conditions. Biomacromolecules 2 (2001) 65–69.
[13] I. GATEJ M. POPA, M. RINAUDO, Role of the pH on hyaluronan behavior in aqueous
solution. Biomacromolecules 6 (2005) 61–67.
[14] P. MLČOCHOVÁ, S. BYSTRICKÝ, B. STEINER, E. MACHOVÁ, M. KOOS, V.
VELEBNÝ, Synthesis and characterization of new Biodegradable hyaluronan alkyl
derivatives. Biopolymers 82 (2006) 74–79.
[15] S. NAVEENRAJ, S. ANANDAN, Binding of serum albumins with bioactive substances –
Nanoparticles to drugs. J. Photoch. and Photobio. C 14 (2013) 53–71.
[16] H. LENORMAND, F. TRANCHEPAIN, B. DESCHREVEL, J. C. VINCENT, The
hyluronan–protein complexes at low ionic strength: How the hyaluronidase activity is
controlled by the bovine serum albumin. Matrix Biology 28 (2009) 365–372.
[17] H. LENORMAND, B. DESCHREVEL, J. C. VINCENT, Chain length effects on
electrostatic interactions between hyaluronan fragments and albumin. Carbohyd. Polym.
82 (2010) 887–894.
******
Protein‐Polysaccharide Gels
Hájovská, P., Chytil M.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
Albumin and hyaluronic acid are biodegradable, endogenous substances with potential use
as drug carriers. These properties combined with the physical structure of the gel can lead to
the formation of biologically active materials with application in medicine. The aim of this
study is to examine the gelation process of albumin solutions and mixed solutions of
albumin and the high molecular weight hyaluronic acid due to heating. Study was carried
out by measuring rheological properties of the solutions, formed gels and gelation process.
With increasing concentration of the polymeric component, the gel point is shifted towards
lower temperature values. The resulting gels exhibit higher values of loss and storage
moduli. Similar behavior was observed also in the samples influenced by the ionic strength
169
as a result of alternation of the electrostatic interactions between the charged groups of the
polymer chains and as a result of change of this charge due to the pH reduced below the pI
value of the protein. For the mixed solutions of protein and polysaccharide the effect of the
polysaccharide concentration was observed. Based on the measurements, it can be assumed
that the dependence of the complex modulus on the polysaccharide concentration will reach
a peak at the certain concentration and after exceeding this limit concentration, the values of
complex modulus will decrease.
Keywords
albumin, hyaluronic acid, protein‐polysaccharide interactions, gels, rheology
******
From Atom of Hydrogen to Molecule of Water
Pavel Osmera, Pavel Werner, Pavel Osmera junior
1Brno University of Technology, Department of Automation and Computer Science, Technicka 2, 2Brno, Czech RepublicDepartment of Imaging Methods, Faculty of Medicine of Masaryk University
Brno, CZECH REPUBLIC
Abstract
Properties of atoms are largely determined by the structure of their electron shells. However,
the standard model does not allow this structure determine exactly. Fractal descriptions of
Nature are very promising [1‐3]. New VFRT (vortex‐fractal‐ring‐theory) can solve this lack
[3]. VFRT works with fractal annular structure of the electron, proton and neutron, and can
describe the inner structure of atomic nuclei. This theory assumes that the arrangement of
electron shells arises from the structure of the atomic nucleus. Electrons are not in orbit
around the atomic nucleus, but each electron levitates with the corresponding proton of the
nucleus. The levitation bond is formed by an electromagnetic vortex structure. The atomic
nucleus can be built from the ring protons and neutrons using the following rules:1. The
proton cannot be directly connected with the proton, except for two parallel protons with the
same axis that are connected together by nuclear forces. 2. Next proton with a different axis
can be connected via the coupling neutron to another proton. 3. On one axis can be
maximally two protons and two neutrons and two electrons with opposite spins. 4. Next one
or two neutrons can be inserted between two parallel protons to form isotopes. It seems that
the combination of these four basic rules can create any real structure of atoms. Nucleons in
the nucleus are not arranged in the shells as in case of electrons, but forms spherical
substructures with a maximum of 10 nucleons. Nuclear forces can bind only a small number
of neighbouring nucleons. Spherical substructures of the nucleus (GS globe sub‐structures)
are sequentially occupied by pairs of proton‐neutron in the number 3, 4, and 5 pairs. These
GSs are connected via two parallel protons into more complex units. GS with a maximum
occupation of nucleons is an extremely stable part of the nucleus analogously to atom with a
completely filled electron levels. The hydrogen and the helium have an atypical structure of
the nucleus and the electron shells. At the hydrogen, the electron ring levitates in the plane
to the ring proton, i. e. with zero distance of their centres of gravity. At isotopes of individual
elements, the number of neutrons in the nucleus increases and these neutrons are typically
located between two parallel protons. The covalent bond is formed by two bound electrons
170
with opposite outer spins. These two electrons may have the same quantum number, then
have the same radius or have different quantum numbers, and then have different radii.
Different radii of electrons have for example polar covalent bonds between the hydrogen and
the oxygen. The electron of the hydrogen has quantum number n = 1 and the electron of the
oxygen has quantum number n = 2. Two counter‐rotating electron rings can create a pair that
behaves like a classical point electron. VFRT (vortex‐ring‐fractal theory) is a new and original
view of elementary particles and the structure of atomic nuclei, atoms and molecules. Its
basics are simple for understanding through comprehensive topological structure that does
not need to describe their complicated mathematical apparatus. This theory, based on the use
of the vortex, fractal and ring structures, interconnects all the current knowledge, based on
quantum theory and quantum fractal theory. VFRT is trying to achieve some progress in
understanding the phenomena related to the physics of elementary particles and atomic
structures that we have not been able to clarify within existing theories. It allows us to
understand the fundamental physical and chemical reasons for the stability and reactivity of
atoms and molecules. VFRT gives us a tool that helps us explain phenomena so far
unexplained and meet new laws, phenomena and processes that we are not able in detail to
know. We believe that this theory will allow us expand our horizons of knowledge and push
the frontiers of knowledge.
Keywords vortex‐fractal‐ring‐structures, covalent bond, models of atoms and molecules, atom of
hydrogen, molecule of water
References
[1] L. PAULING. : General Chemistry, Dover publication, Inc, New York, 1988
[2] O. ZMESKAL, M. NEZADAL, M. BUCHNICK: Fractal‐Cantorial geometry, Hausdorf
dimension and fundamental laws of physics, Chaos, Solitons and Fractals 17, 2003, 113‐
119
[3] P. OSMERA: The Vortex‐ring‐fractal Structure of Hydrogen Atom, Proceeding of
WCECS 2009, 2009, San Francisco, USA, 89‐94More about VFRT on http://www.
pavelosmera. cz/public/public. html
******
Thermal and Chemical Stability of Metal‐Humic Complexes
Klucakova M.
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 118,
CZ‐612 00 Brno, CZECH REPUBLIC
Abstract The aim of this work was the study of relation between chemical and thermal stability of
complexes of humic acids with heavy metals (nickel, cobalt and copper). Complexes were
prepared with metal solutions of three different initial concentrations. Chemical stability was
determined as an amount of releasedmetal ions, two of extraction agents were used (solution
of MgCl2 and HCl), total boundedamount was distribute into three different fractions
residual fraction, strongly bound fractionand mobile and ion‐exchangeable fraction. Changes
that occured in the structure of humic acidsafter complexation and extraction were
171
investigated by FT‐IR spectrometry. Thermo‐oxidative stability was tested by means of
thermal analysis.
Keywords
humic acid, metal, stability
Acknowledgements
This work was supported by Ministry of Education, Youth and Sports, Project LO1211.
******
Conformational Arrangement of Humic Particles in Aqueous Solutions
Klucakova M., Veznikova K., Kalina M., Chytilova A.
Brno University of Technology, Faculty of Chemistry, Materials Research Centre, Purkyňova 118,
CZ‐612 00 Brno, CZECH REPUBLIC
Abstract
Conformational changes of humic acids in different aqueous solutions are studied by means
of several methods. The method of ultrasound spectrometryis based on the measurement of
parameters of ultrasonic waves propagating throughthe sample. The attenuation describes
the decay of the amplitude of the ultrasonic wave with distance traveled. The velocity is the
speed of this wave and is related to the wavelength and the frequency of oscillation of the
deformation. It is determined by the density and elasticity of the sample, which is strongly
influenced by the molecular arrangement. Mathod of dynamic light scattering provided data
characterizing particle sizes and polydisperzity. Their combination with charge and
rheological characteristics can give a complex description of conformational arrangement of
humic particles in solutions.
Keywords humic acids, conformational arrangement, particle size and charge
Acknowledgements
This work was supported by Ministry of Education, Youth and Sports, Project LO1211
******
Decomposition of Selected Alkaloids by Diaphragm Discharge
Klimova, E. J., Jonisova, L., Krcma, F.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Plasma discharges in contact with or directly inside liquids represent a rapidly growing field.
Their possible applications cover broad range from material science (functionalization,
surface modification) to biomedicine (sterilization, wound healing). A lot of the interest goes
into environmental applications. In this work, two representatives of alkaloids have been
subjected to a diaphragm discharge to evaluate the possibility of their degradation. Caffeine
172
is considered to be an indicator of human pollution in environment. Quinine is known for its
use as an antimalaric drug, and also serves as an additive in drinks and cosmetics. Batch
diaphragm reactor was used with 1 hour experimental time. Discharge efficiency was
quantified by hydrogen peroxide production its concentration was compared for reference
solutions (NaCl in purified water) and solutions containing the alkaloid. For detection of
caffeine decomposition, UV‐VIS spectrometry was utilized. Concentration of quinine was
studied by fluorescence spectrometry. Final solution after the treatment was subjected to
HPLC‐MS analysis. Up to 92 % of degradation was reached for caffeine and 98 % for quinine
in anode part. Detected hydrogen peroxide dropped by half in alkaloid solutions, as a part of
it goes into the degradation process.
Keywords
plasma, diaphragm, underwater discharge, hydrogen peroxide, alkaloid, caffeine, quinine
Acknowledgements
This work has been supported by COST TD1208 Action – Electrical discharges with liquids
for future applications and by Czech Ministry of Education, Youth and Sports, project No.
LD14014.
******
Radical Reactions of Secondary Amines in the Presence of Some H‐
Abstracting Agents
Omelka L., Šafaříková L.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐61200 Brno, CZECH
REPUBLIC
Abstract Typical H‐abstracting agents, RO2? radicals and PbIV+ compounds (PbO2, Pb (OAc) 4) were
applied by the reaction with different types of secondary amnines R1–NH–R2.
Consecutively, the radical products of the reaction were identified using EPR spectroscopy1,
2. By the action of catalytically generated RO2? radicals prepared using the system tBuOOH‐
Co (acac) 2 the generation of aminoxyl radicals R1–NO?–R2 proceeds in the first step.
However, RO2? radicals can enter the reactions with primary aminoxyl radicals in the case
when mentioned radicals contain –CH2– groups in the vicinity of –NO?– function in
alkylaryl‐ and dialkylamines. Here, the attack of peroxyradicals on this group under
intermediate formation of nitrones is observed. The nitrone formed react in later steps of the
reaction as spin traps and, as a result of this series of consecutive reactions, the formation of
secondary aminoxyl radicals X–CH (OOtBu) –NO?–Y was proved. By the action of PbIV+
agents (PbO2, Pb (OAc) 4) on secondary amines R1–NH–R2 their hydrogen‐abstracting effect
was evidenced not only in relation to –NH– group (formation of aminyl radicals R1–N?–R2)
but to C–H bonds in substituent R1 and R2 as well. In both cases, it was possible to identify
N– and C–radicals using spin‐trapping method. The application of first or second model
depends on the structure of secondary amine or PbIV+ agent used. For example, clear
tendency to the abstraction of hydrogen atom –NH– group was observed by the series of
alkylarylamines (N‐alkylanilines). Active site for the formation of C–radicals is ?‐position in
173
substituents R1 and R2, in numerous cases the abstraction of hydrogen from terminal CH3–
group was proved. Simultaneously, it has to be emphasized that EPR spectra of above
mentioned radical products were in many cases combined with EPR spektra of some radical
additives formed by the reaction of PbIV+ agents with spin trap (nitrosobenzene) which
results in the formation either of diphenylaminoxyl radical Ph–NO?–Ph or phenylaminoxyl
radical Ph–NO?–H.
Keywords EPR spectroscopy, secondary amines, spin trapping
References
[1] ŠAFAŘÍKOVÁ L., OMELKA L., MAJZLÍK P., SVĚTLÍK J. : Monatsh. Chem. 144, 163
(2013)
[2] ŠAFAŘÍKOVÁ L., OMELKA L. : Monatsh. Chem. 146, 79 (2015)
******
Plasma Chemical Reduction of Model Corrosion Brass Layer Prepared in
Soil
Radkova, L., Fojtikova, P., Prikryl, R., Krcma, F.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
This paper discusses the removal of corrosion layers form archaeological artifacts. The low
pressure plasma reduction was used for this purpose. Plasma chemical reduction of
corrosion layers was developed by Stanislav Veprek et. al. at the end of the 20th century at
Institute of Inorganic Chemistry, University of Zürich. This method was applied mainly for
the treatment of iron artifacts [1]. Before Veprek, Daniels used similar method for plasma
reduction of silver tarnish on Daguerreotypes [2]. Under the presented study, the brass
plates were prepared with model corrosion layer because the real archaeological artifacts
could be damaged during the method optimization and they have too different corrosion
history. Samples corroded naturally more than two years in the soil in the vertical and
horizontal positions, so the corrosion layers were the most similar to the corrosion layer of
original archaeological artifacts. The samples were treated in the low pressure (150 Pa)
quartz glass plasma reactor (90 cm long and 9. 5 cm in diameter). The reactor was
surrounded by two external copper electrodes supplied by radio‐frequency generator (13. 56
MHz). The experiments were carried out in a hydrogen‐argon gas mixture at mass flows of
30 sccm for hydrogen and 20 sccm for argon for 90 minutes. 13 samples were treated. The
plasma power was 100, 200, 300, and 400 W in continuous and pulsed mode. Maximum
sample temperature was set at 120 °C. To avoid exceeding this temperature, power control or
the duty cycle in pulse mode were automatically controlled. The whole process was
monitored by optical emission spectroscopy and the obtained data were used to calculate the
relative intensity of OH radicals and rotational temperature. The relative intensity of OH
radicals is associated with the degradation of the corrosion layer. The main reactions during
reduction were the reaction between oxygen and chloride contained in the corrosion layer
174
and the hydrogen ions and neutral atoms generated in the plasma. The results showed that
the higher power had the greater maximum intensity of the OH radicals and rapidly
degraded the corrosion layer. Corrosion layer was not completely removed during the
reduction, but due to the reactions which occur in the plasma corrosion layer became brittle
and after plasma chemical treatment can be removed easily.
Keywords
Brass, plasma chemical treatment, relative intensity of OH radicals
Acknowledgements
This work was supported by the Ministry of Culture of the Czech Republic, project No.
DF11P01OVV004.
References
[1] S. VEPŘEK, J. PATSCHEIDER, J. ELMER, Recent progress in the restoration of
archeological metallic artifacts by means of low‐pressure plasma treatment, Plasma
Chemistry and Plasma Processing. 8 (1988) 445‐466
[2] V. DANIELS, Plasma reduction of silver tarnish on Daguerreotypes, Studies in
Conservation. 26 (1981) 45‐49
******
Density Functional Theory Study of the Anticorrosive Properties of Two
Quinoline Chalcones
Gece, G.
Bursa Technical University, Faculty of Natural Sciences, Architecture and Engineering, Osmangazi,
16190 Bursa, TURKEY
Abstract The use of inhibitors is the most appropriate way to isolate the metal from corrosive agents
and thus to reduce corrosion reactions. Most of the well‐known acid corrosion inhibitors are
organic compounds containing heteroatoms (nitrogen, sulfur, and oxygen atoms) and
aromatic rings [1, 2]. There has been a considerable surge of experimental inquiry in recent
years into understanding the factors responsible for the corrosion inhibition efficiency of
chalcones, however, the question of what actually determines the efficiency still remains a
topic of debate. In the recent years, quantum chemical calculations have been proven to be an
important tool for investigation of the structure and inhibition properties of corrosion
inhibitors and for the interpretation of experimental data arising from industrial interest and
applications [3]. The geometry of the inhibitors in their ground states, as well as the nature of
their molecular orbitals, HOMO (highest occupied molecular orbital) and LUMO (lowest
unoccupied molecular orbital) are involved in the properties of inhibitors’ activity. Thus,
insights obtained from computational methods are extremely valuable. In this study, the
dependence of the inhibition effect of such two compounds, namely, 3‐ (3‐oxo‐3‐phenyl‐
propenyl) ‐1H‐quinolin‐2‐one and 3‐ (3‐oxo‐3‐phenyl‐propenyl) ‐1H‐benzoquinolin‐2‐one on
their molecular and electronic structure is analyzed using density functional theory
calculations. Quantum chemical parameters such as highest occupied molecular orbital
energy (EHOMO), lowest unoccupied molecular orbital energy (ELUMO), and energy gap
175
(?E) have been calculated at the B3LYP/6‐311++G (d, p) basis set. In agreement with
experiments, this study found strong evidence to link corrosion inhibition property of the
compounds to their actual molecular structures in acidic media.
Keywords corrosion inhibitors chalcones DFT carbon steel
References
[1] G. GECE, Drugs: A review of promising novel corrosion inhibitors, Corros. Sci., 53, 2011,
pp. 3873‐3898.
[2] G. GECE, Theoretical evaluation of the inhibition properties of two thiophene
derivatives on corrosion of carbon steel in acidic media, Mater. Corros., 64, 2013, pp. 940‐
944.
[3] G. GECE, The use of quantum chemical methods in corrosion inhibitor studies, Corros.
Sci., 50, 2008, pp. 2981‐2992.
******
The Aggregation Properties of Triton X‐100 and Rhamnolipid Mixtures
Mańko, D., Zdziennicka, A., Jańczuk, B.
Maria Curie‐Skłodowska University, Faculty of Chemistry, pl. Marii Curie‐Skłodowskiej 3, 20‐031
Lublin, POLAND
Abstract
Biosurfactants are natural surface active agents synthesized by different types of
microorganisms. These compounds are an ecological alternative for classical surfactants
produced by chemical synthesis. Biosurfactants have very interesting properties such as:
good biodegradability, low toxicity or effectiveness at extreme temperature, pH and salinity
and they are biocompatible with human skin and mucous membranes. Among natural
surfactants rhamnolipids are of a special interest. They are produced by Pseudomonas
aeruginosa and they are a mixture of different homologous. Rhamnolipids can be treated as
potential substitutes of chemical compounds because of their valuable properties (e. g. : high
surface activity, low value of critical micelle concentration and very high biodegradability).
They have various applications such as pharmaceuticals, cosmetics products, food items,
detergents and bioremediation enhancers. On the other hand, the high cost of their
production limits their wide practical application. But they can be used as additive for
classical surfactants. Among of synthetic surfactants the most important are nonionic
polyoxyethylene ones. However, in the literature the practical applications of such kind of
mixtures are not exactly explained by physicochemical properties. For this reason the
aggregation properties of the rhamnolipid and Triton X‐100 mixtures were studied by the
surface tension, density and viscosity measurements. From the obtained results the critical
micelle concentration (CMC) was determined and the thermodynamic considerations
dealing with the mutual influence of the rhamnolipid and Triton X‐100 on their micellization
process were carried out. The tendency of rhamnolipid and Triton X‐100 mixtures to
micellization was compared to their adsorption efficiency. The obtained results suggest e. g.
that CMC should be treated rather as a range of concentration at which aggregates can be
formed but not as one pinpoint or that each method of CMC determination is sensitive to
176
different sizes of aggregates. Moreover, it is interesting that the presence of rhamnolipid,
even at its very low concentration, considerably decreases the critical micelle concentration
of Triton X‐100.
Keywords biosurfactant, rhamnolipid, Triton X‐100, micellization
******
Using of Argon‐Hydrogen Plasma as a Tool for Removing of Corrosion
Layers from Bronze Samples
Fojtikova, P.1, Radkova, L.1, Janova, D.2, Krcma, F.1,
1Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC 2Brno University of Technology, Faculty of Mechanical Engineering, Technická 2896/2, CZ‐612 00
Brno, CZECH REPUBLIC
Abstract Our research is focused on application of low‐pressure low‐temperature plasma on corroded
samples. In presented case, the bronze plates with dimension of 20 × 50 mm, were used as a
samples. The process of corrosion layers creation taken place in the soil for 2 years at the
ambient conditions and thus simulated natural process. The samples with corrosion layers
were treated in the plasma chemical apparatus. The argon‐hydrogen mixture was chosen as
a working gas. The power was supplied to the system from the rf generator by two copper
electrodes places outside of the reactor. The reactor was evacuated by the rotary oil pump.
The plasma chemical apparatus was controlled by the specially designed software. After the
sample temperature approached to 120 °C, the delivered power was reduced. The sample
temperature exceeding this limit is dangerous for bronze because tin can be sputtered due to
overheating at atomic scale. The emission spectra were scanned every minute during the
plasma treatment by the optical emission spectrometer. For the process monitoring, the
spectrum between 307 and 310 nm is significant because it corresponds to OH radicals,
which are produced by the reaction of hydrogen atoms from plasma with oxygen bounded
in the corrosion layers. The relative integral intensity of OH radicals was calculated from
obtained data and reflects the removal process. The samples were analysed by a scanning
electron microscope (SEM) in order to obtain high resolution surface morphology and
chemical composition by energy dispersive X‐ray analysis (EDX).
Keywords
argon‐hydrogen plasma, bronze, optical emission spectroscopy, scanning electron
microscopy
Acknowledgements
This research has been conducted within the project DF11P01OVV004 „Plasma chemical
processes and technologies for conservation of archaeological metallic objects“ founded by
the Ministry of Culture of the Czech Republic.
177
******
Artefact Conservation Using Thin Films Based on Parylene C and Silicone‐
Acrylate Resin
Prochazka, M.1, Blahova, L.1, Horak, J.1, Pekarek, J.2, Prikryl, R.1, Krcma, F.1
1Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC 2Brno University of Technology, Faculty of Electrical Engineering and Communication, Technicka
3058/10, CZ‐616 00 Brno, CZECH REPUBLIC
Abstract
Archaeological depositories are being filled by newly discovered artefacts. These items wait
there until they are cleaned and conserved. Cleaning and conservation are demanding
processes, regarding both time and human resources. New approaches are required to
reduce costs and time needed for their treatment. Deposition of thin films might bring
interesting results to the field of artefact conservation. Protective thin films have already
been used successfully in many industrial applications, e. g. automotive, electrotechnics,
microelectronics and medicine. Their use in archaeology can profit from previous success in
those branches. This study focusses on conservation of metallic archaeological items. Using
thin film deposition methods, new protection layers for artefacts are suggested: Parylene C
(or chlorinated poly‐p‐xylylene) and Laksil (silicon‐acrylate resin). Both of them show good
protection properties against gases, water and corrosion in their respective fields of use.
Parylene C and Laksil were compared to standard protection layers – microcrystalline wax
and acrylic resin (Paraloid B72). Several types of samples were coated by these films.
Corrosion resistance was tested as well as oxygen transmission rate and colour difference.
Parylene C provides excellent protection against corrosion in comparison with standard
protection layers. Parylene films are compact, pin‐hole free layers, protecting the artefact
even on edges. Laksil barrier properties are nearly as good as those of standard layers.
However, the best protection was achieved by combination of Laksil and Parylene C.
Furthermore, Laksil can be removed easily from the substrate which enables to inspect the
artefact surface after many years. Both Parylene C and Laksil form transparent films, making
almost no change to the appearance of the artefact. They succeeded in all tests (compared to
standard microcrystalline wax and acrylic resin) and are suitable for application in
archaeological artefacts conservation.
Keywords
archaeological artefacts, metals, conservation, corrosion protection, parylene C
Acknowledgements
This work has been supported by the Ministry of Culture of the Czech Republic, project No.
DF11P01OVV004.
178
******
The Fourth Phase of Water: Beyond Solid, Liquid, and Vapor
Gerald H. Pollack
University of Washington, Seattle, USA, ghp@u. washington. edu
Abstract School children learn that water has three phases: solid, liquid and vapor. But we have
recently uncovered a fourth phase. This phase occurs next to water‐loving (hydrophilic)
surfaces. It is surprisingly extensive, projecting out from the surface by up to millions of
molecular layers. And, its properties differ substantially from those of bulk water.
Of particular significance is the observation that this fourth phase is charged and, the water
just beyond is oppositely charged, creating a battery that can produce current. We found that
light charges this battery. Thus, water can receive and process electromagnetic energy drawn
from the environment in much the same way as plants. Absorbed electromagnetic (light)
energy can then be exploited for performing work, including electrical and mechanical work.
Recent experiments confirm the reality of such energy conversion.
The energy‐conversion framework implied above seems rich with implication. Not only does
it provide an understanding of how water processes solar and other energies, but also it may
provide a foundation for simpler understanding natural phenomena ranging from weather
and green energy all the way to biological issues such as the origin of life, transport, and
osmosis.
The presentations will cover the evidence for this surprisingly extensive phase of water, and
will consider its potentially broad implications for physics, chemistry, biology, and
technology, and particularly for health.
The recent book dealing with this subject is now available.
Keywords
Phase of Water
179
Polymer Composites and Nanocomposites
******
Morphogenesis of Photo‐Polymerized Dimethacrylate Networks, Network
Formation Kinetics and Viscoelastic Parameters
Bystricky, Z., Jancar, J.
1Brno University of Technology, Faculty of Chemistry, Institute of Materials Chemistry, Purkyňova
484/118, CZ‐612 00 Brno, CZECH REPUBLIC
2CEITEC – Central European Institute of Technology, Brno University of Technology, Technická
3058/10, CZ‐616 00 Brno, CZECH REPUBLIC
Abstract This contribution refers to the process of morphogenesis of dimethacrylate networks used,
inter alia, in the field of restorative dentistry. In the study, the most commonly employed
monomers considering nowadays dental practice were used. This includes rigid aromatic
monomers, bisphenol A glycerolate dimethacrylate (Bis‐GMA), ethoxylated Bis‐GMA
(EPBDMA), as examples of bulky and viscous base monomers, and triethylene glycol
dimethacrylate (TEGDMA) as an example of viscosity reducer.
Kinetics of polymerization was studied regarding the structural differences and varying
molar ratio of the co‐monomers employed. Data provided the base for understanding the
supra‐molecular structure evolution. Consequently, an attempt to quantify the relationship
between the network morphology and complex viscoelastic moduli was made. Curing
kinetics was studied using differential photo‐calorimetry (DPC). Complex modulus was
measured using dynamic‐mechanical analysis (DMA). Thermal degradation kinetics data
(TGA) were used in order to confirm the estimated morphology of cured networks.
Monomer reactivity is derived from its molecular structure. The potential for non‐covalent
physical interactions along with monomer backbone rigidity significantly decrease
polymerization rate, double bond conversion, and hasten the diffusion‐controlled kinetics of
fundamental reaction steps. Dilution by the flexible monomer backbones leads to the
synergistic shift of the diffusion controlled kinetics to higher conversion and overall increase
of the reaction rate. However, the flexibility of the monomer backbone promotes the
origination of structural heterogeneities characterized by micro‐gel domains formation
associated particularly with the primary cyclization reactions and ineffective cross‐linking.
Keywords
Dimethacrylate monomers polymer network curing kinetics photo‐polymerization
viscoelastic parameters
Acknowledgements
This work was supported by the project ʺCEITEC ‐ Central European Institute of
Technologyʺ (CZ. 1. 05/1. 1. 00/02. 0068) from European Regional Development Fund.
180
******
Mechanical Response of Plasma Interlayers in Polymer composites
Knob, A., Babik, A., Cech, V., Drzal, L. T.
Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract
The study is aimed at preparation of glass fiber reinforced polymer composites with
controlled interphase formed by plasma‐polymerized tetravinylsilane and
tetravinylsilane/oxygen thin film. The polymer films of specific physicochemical properties
and thickness were deposited to improve interfacial adhesion of GF/polyester composites.
The fiber surface was modified by using plasma enhanced chemical vapor deposition
(PECVD) in low‐temperature pulsed RF plasma operating in an effective power range of 0. 1
– 10 W and different treatment time. The process of plasma‐polymerization was preceded by
pretreatment, improving the film adhesion using oxygen and argon gasses or their mixtures.
Pretreated surface of glass fibers was modified by single and double layer of plasma‐
polymerized thin film. Mechanical response of plasma interlayers was evaluated by direct
method of testing the interfacial shear strength using unique ITS (Interfacial Testing System)
apparatus developed by Dow Chemical Company (USA). The interfacial adhesion of
unsized, industrially sized, and plasma coated fibers was compared. The interfacial shear
strength of optimized pretreatment and plasma coating shows an increase of 36% compared
to the industrial sizing. Test results were examined in relation to the interlayer thickness and
interlayer modulus.
Keywords Adhesion, interphase, tetravinylsilane, microindentation, PECVD
******
Role of Water in Electrically Charged Hydrogels During Deformation
Molecular Dynamics Study
Kulovaná, E., Žídek, J., Jančář, J.
1Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC 2Central European Institute of Technology Brno University of Technology, Technická 10, 616 00
Brno, Czech Republic
Abstract Hydrogels are three‐dimensional networks consisting of chemically and/or physically‐
crosslinked hydrophilic polymers that absorb large amounts of water. It is supposed that the
water plays an active role during deformation of the gels. Most of recent model approaches
are focused to behavior of organic and macromolecular components. The role of water is in
its persistence in the vicinity of macromolecular network. The structure of hydrogel model
was formed by the core of micelle from physically interacting acrylic acid (AA) groups, and
181
the shell was formed by hydrophilic PEG chains. The simulation box was solvated by 2447
molecules of water. The forward‐reverse shear deformations were applied to the model
network. The model enables us to set different charges on the flexible chains from 0. 0 to ‐1. 0
e (electron charge). The charge distribution on the molecule of water was constant and
characteristic for the standard models of water. We found, that the distribution of water and
the deformation response depend on the charge applied on the network. Structure of water
was analysed by radial distribution functions, by analysis of hydrogen bonds distribution
and by correlation functions. The model data enable us to test our hypothesis about the
active participation of water on the deformation response of hydrogel. The knowledge can be
applied to the tuning of hydrogel properties by setting a charge in the network.
Keywords
hydrogel, molecular dynamics study, forward‐reverse shear deformation
Acknowledgements
This work was supported by the project CEITEC ‐ Central European Institute of Technology,
(CZ. 1. 05/1. 1. 00/02. 0068) from European Regional Development Fund.
******
Natural Polysaccharide Gum Karaya as Novel Biomaterial for Medical
Applications
Postulkova, H., Vojtova, L., Jancar, J.
Brno University of Technology, Central European Institute of Technology, Technická 3058/10, CZ‐
616 00 Brno, CZECH REPUBLIC
Abstract
Natural polysaccharides are biodegradable, freely available, relatively cheap and nontoxic
materials with great potential in medical applications. The polysaccharide hydrogels
supports wound healing by providing moist environment and can be utilized as wound
dressing for soft tissue regeneration (e. g. skin burns or ulcers). Suitable candidate is Gum
Karaya (GK), anionic polysaccharide containing D‐galactose, L‐rhamnose, D‐glucuronic acid
and D‐galacturonic acid. Natural GK is partially acetylated high molecular weight polymer
(Mw ? 9 mil Da), water insoluble, having high swelling and retention capacity, high viscosity
and inherent antimicrobial activity. [1, 2, 3] The objective of this study is to prepare a soluble
sample of GK by alkali treatment followed by designing new procedure for GK hydrogel
preparation meeting properties of wound healing coverings. Prepared samples were
characterized by SEM, FTIR, NMR, TGA, DSC and rheological evaluated.
Keywords
natural gum, polysaccharide, gum karaya, modification, characterization, water solubility,
deacetylation
Acknowledgements This work was supported by the project CEITEC (CZ. 1. 05/1. 1. 00/02. 0068) from the
European regional development fund.
182
References
[1] B. SINGH, N. SHARMA: Development of novel hydrogels by functionalization
of sterculia gum for use in antiulcer drug delivery. Carbohydrate Polymers. 2008, 74, p.
489‐497.
[2] B. SINGH, L. Pal: Development of sterculia gum based wound dressings for use in drug
delivery. European Polymer Journal. 2008, 44, p. 3222‐3230.
[3] D. VERBEKEN, S. DIERCKX, K. DEWETTINCK: Exudate gums: occurrence, production,
and applications. Applied Microbiology and Biotechnology. 2003, 63, p. 10‐21.
******
Preparation of Poly (Lactic Acid) Grafted with Itaconic Anhydride via
Radical Grafting in Melt
Petrus, J., Kucera, F., Petruj, J.
Brno University of Technology, Faculty of Chemistry, Purkyňova 464/118, 612 00 Brno, Czech
RepublicCentral European Institute of Technology, Technická 3058/10, 616 00 Brno, Czech Republic
Abstract
Proposed study deals with functionalization of poly (lactic acid) (PLA) with itaconic
anhydride (IAH) via radical grafting in melt. Reaction was initiated by 2, 5‐dimethyl‐2, 5‐bis
(tert‐butylperoxy) hexane (L101). Residence time was 6 min and the reaction temperature of
187. 4 °C was calculated according to Arrhenius equation. At these reaction conditions L101
is completely decomposed and degradation of PLA is limited. Structure of thus prepared
PLA‐g‐IAH and grafting yield depend on several key parameters such as temperature,
IAH/L101 ratio and reaction time. IAH was covalently bonded onto PLA backbone which
was proved by Fourier transform infrared spectroscopy (FTIR). Isomerization of IAH to
citraconic anhydride (CAH) was studied by FTIR where new functional groups were
observed depending on the reaction temperature. According to results of structure analysis
the effect of reaction conditions upon grafting reaction on reaction mechanism was
predicted. Influence of reaction parameters on grafting yield, reaction kinetics and extent of
side reactions was evaluated. Grafting yield depends on IAH/L101 ratio which was proved
by acid‐base titration. It was concluded that extent of side reaction depends on IAH/L101
ratio. Kinetics of grafting reaction was determined as a function of reaction temperature,
reaction time and L101 concentration. Kinetic data proved strong influence of both reaction
temperature and concentration of L101 on the reaction rate. Proposed methodology of PLA
modification can be used for preparation of polymeric materials with specific properties. It is
expected that PLA modified with IAH exhibits reactivity towards synthetic polymers
(polyamides), natural polymers (proteins) or filler with variable functional properties.
Keywords
poly (lactic acid), itaconic anhydride, radical grafting
Acknowledgements
This work was supported by the project “CEITEC ‐ Central European Institute of
Technology” (CZ. 1. 05/1. 1. 00/02. 0068) from European Regional Development Fund. ʺ
183
******
Stable Gelatin Nanofibers Modified with Oxidized Cellulose for Soft
Tissue Engineering
Švachová Veronika1, 2, Vojtová Lucy2, Jurtíková Veronika3, 4, Hampl Aleš3, Pavliňák David5
1Vysoké učení technické v Brně, Chemická fakulta Purkyňova 464/118, 612 00 Brno 2CEITEC – Central European Institute of Technology, Vysoké učení technické, Technická 3058/10,
616 00 Brno 3 Masarykova univerzita, Lékařská fakulta, Ústav histologie a embryologie, Kamenice 3, 625 00 Brno 4Mezinárodní centrum klinického výzkumu ‐ Centrum biomolekulárního a buněčného inženýrství,
Fakultní nemocnice u sv. Anny v Brně, Brno, Česká republika 5Ústav fyzikální elektroniky, Masarykova universita, Kotlářská 2, 602 00, Brno
Abstract
The present work deals with the preparation of (bio) polymer nanofibers by Nanospider
technology. The obtained nanofibers are biocompatible, bioadhesive, porous and mimic the
structure of the extracellular matrix forming the structure of tissues. Gelatin nanofibers
modified by addition of sodium or calcium salt of oxidized cellulose were successfully
prepared. Gelatin is a biocompatible and biodegradable polymer. Oxidized cellulose and its
salts are biocompatible, biodegradable and they also exhibit hemostatic and bactericidal
efficiency. Crosslinking process was an another important step to improve hydrolytic
stability and mechanical properties of nanofibers. H441 cell lines (human papillary
adenocarcinoma cells) were seeded on prepared electrospun nanofibers. The viability of
H441 cell lines on nanofibers was evaluated. Newly prepared material may have a potential
application in surgery and regenerative medicine of soft tissues (e. g. decubitus and burns).
Keywords
Electrospinning, gelatin, oxidized cellulose, inhibitory effect, nanofibers, tissue engineering
Acknowledgements
This research has been supported by the project CZ. 1. 05/2. 1. 00/03. 0086 funded by
European Regional Development Fund and project LO1411 (NPU I) funded by Ministry of
Education Youth and Sports of Czech Republic and by the project “CEITEC – Central
European Institute of Technology” (CZ. 1. 05/1. 1. 00/02. 0068) from European Regional
Development Fund.
184
******
Radical Grafting of Maleic Anhydride onto Polypropylene via Reactive
Extrusion
Matláková, J., Kučera, F., Jančář, J.
Department of Materials Chemistry, Faculty of Chemistry, Brno University of Technology Purkyňova
464/118, 612 00 BrnoCentral European Institute of Technology, Technická 3058/10, 616 00 Brno
Abstract
This work contributes to extension of the knowledge in the field of chemical modification of
polypropylene carried out using reactive extrusion. The grafting reaction is affected by many
parameters, such as concentration of initiators, monomers or stabilizers. The first part is
focused on stabilizers function during grafting reaction. Considerable decrease in grafting
yield of maleic anhydride (MAH) was observed at concentration of primary stabilizers
higher than its induction period. Two radical initiators containing the different amount of
peroxide groups (the commonly used Luperox 101 and the new Trigonox 301) were
employed and compared. The yield of the PP‐g‐MAH was determined by means acid‐base
titration and FT‐IR spectroscopy. The grafting reactions are accompanied by ?‐scission of
backbone irrespective of the nature and concentration of peroxide and monomers. The
degree of degradation was measured by melt‐flow rate (MFR). The slight changes in melting
temperature and crystallinity were caused by degradation using differential scanning
calorimetry (DSC).
Keywords
reactive extrusion, polypropylene, grafting
******
Polyurethane‐Polyhydroxybutyrate Composites: Synthesis, Biodegradation
and Morphological Evaluation
Vojtech Kupka1, 2, Pavla Benesova3, Stanislav Obruca3, Jana Brtnikova2, Lucy Vojtova2,
Ivana Marova3, Josef Jancar1, 2
1Institute of Materials Chemistry, Faculty of Chemistry, Brno University of Technology, Purkyňova
118, 612 00 Brno, Czech Republic 2CEITEC ‐ Central European Institute of Technology, Brno University of Technology, Technická
3058/10, 616 00 Brno, Czech Republic 3Materials Research Centre, Faculty of Chemistry, Brno University of Technology, Purkyňova 118,
612 00 Brno, Czech Republic
Abstract
Polyurethane‐polyhydroxybutyrate (PU‐PHB) composites were synthesized by solvent free
method and degradation ability of prepared materials was tested in standard compost
media. Changes in the material during the degradation were investigated from structural
and morphological point of view. Commercial PHB from Sigma‐Aldrich and PHB prepared
at Faculty of Chemistry BUT were both used in the amount of 1, 5 and 10 filler weight
185
content in composites. Scanning electron microscopy revealed better dispersion of
commercial PHB particles in the material which affected its slower rate of degradation. The
rate of the degradation for both PHB fillers was quite low signing that the material is stable
when exposed to the degradation media. Structural changes of the PU‐PHB composites
during degradation were studied by differential scanning calorimetry (DSC) and wide‐angle
X‐ray scattering (WAXS). Both DSC and WAXS confirmed less ordered crystalline phase in
PHB particles after the degradation test. Mechanical properties testing showed that materials
were less stiff, however the elongation at break increased. Thus, less ordered structure of
PHB crystalline phase decreased stiffness of the material, but increased the number of tie
molecules which resulted in higher elongation at break. Renewable PHB microfiller
improved mechanical properties when added to the PU matrix and did not initiate any
unfavorable process (e. g. cracking) when exposed to the degradation media.
Keywords Polyurethane, polyhydroxybutyrate, composite, renewable, morphology, degradation
Acknowledgements
This work was supported by the project “CEITEC ‐ Central European Institute of
Technology” (CZ. 1. 05/1. 1. 00/02. 0068) from European Regional Development Fund.
******
Rheological Study of Core‐shell Particles in Thermosensitive Copolymer
Matrix for Bone Regeneration Utilization
Ivana Chamradová1, 2, Lucy Vojtová2, Josef Jančář1, 2
1Brno University of Technology, Faculty of Chemistry, Institute of Materials Science, Purkyňova
464/118, 612 00 Brno, Czech Republic, xcchamradova@fch. vutbr. cz 2CEITEC ‐ Central European Institute of Technology, Brno University of Technology, Technická
3058/10, 616 00 Brno, Czech Republic
Abstract The goal of this work was preparation and rheological study of thermosensitive polymer
composite paste as a potential resorbable injectable material for bone regeneration. Newly
prepared thermosensitive composite paste was consisted of aqueous solution of polymer
matrix based on the hydrophilic poly (ethylene glycol) (PEG) and hydrophobic poly
(lactide—co—glycolide) (PLA/PGA) copolymer (PLGA—PEG—PLGA) thermogelling at
body temperature with homogeneously distributed hydroxyapatite‐polymer core‐shell (CS)
particles1. The core in CS was composed from inorganic bioactive nano‐sized hydroxyapatite
(n‐HAp), whereas the shell was based on the same PLGA—PEG—PLGA copolymer as the
matrix only different in end‐functionalization with itaconyl groups. The polymer shell was
additionaly end‐crosslinked by carbodiimide coupling (zero crosslinks) and stabilized by
poly (vinyl alcohol). The original PLGA—PEG—PLGA copolymer matrix exhibited in
aqueous solution two phase sol‐gel and gel‐suspension transitions. However, addition of 20
wt. % of CS particles in copolymer solution exhibited stable gel state without the sol‐gel
transition. On the other hand, incorporation up to 10 wt. % of CS particles increased the
stiffness of the original hydrogel matrix almost 4 times (from 40 kPa up to 150 kPa) while
186
maintaining two‐phase sol‐gel transitions. Therefore, this material is suitable as drug
delivery carriers.
Keywords
rheology, core‐shell particles, thermosensitive copolymer
Acknowledgements
This work was supported by the project “CEITEC” (CZ. 1. 05/1. 1. 00/02. 0068) from
European Regional Development Fund.
References
VOJTOVÁ L., CHAMRADOVÁ I., MICHLOVSKÁ L., JANČÁŘ J. : Czech Intelectual
Property, Prague, PUV 2014‐09‐11, registered.
******
Force‐Assembled Fe3O4 Particle Chains in Polyurethane Matrix
Zboncak, M., Ondreas, F., Jancar, J.
1Brno University of Technology, CEITEC, Technická 10, CZ‐616 00 Brno, CZECH REPUBLIC 2Brno University of Technology, Faculty of Chemistry, Purkyňova 118, CZ‐612 00 Brno, CZECH
REPUBLIC
Abstract Despite substantial research efforts, the potential of polymer nanocomposites has still not
been fully revealed, mainly due to poor control over the dispersion and alignment of
nanoparticles (NPs). Since nanocomposite properties are controlled by the structural
variables, it is crucial to achieve control over the NP assembly process.
Self‐assembly of NPs offers limited control over the NP spatial arrangement. This process
results in a poorly controlled variation of simple structures such as agglomerates, clusters
and dispersed NPs with the resulting structure strongly dependent a on wide range of
thermodynamic parameters.
On the other hand, force‐assembly exploits interactions between particles induced by
external force fields overcoming the thermodynamic ones. Stimulus of external electric,
magnetic or electro‐magnetic field is applied as the main force controlling the assembly of
NPs. Understanding this process gives us the opportunity to create prescribed NP structures
with controlled shape, size, and anisotropy by simple change of the force field. Precise
control of structure formation on different length scales (from nano to macro) gives us the
opportunity to imitate hierarchical biological structures possessing unique balance of
stiffness and toughness.
Here, we report on magnetic field force assembly of Fe3O4 nanoparticles in the polyurethane
matrix. Resulting NP chain structures were several NP wide and tens of micrometers long
aligned along the magnetic force lines. Without the magnetic field, NP agglomerates of
random size and shape were formed due to their self‐assembly.
187
Keywords
Polymer nanocomposites, Force‐assembly, Biomimetics
Acknowledgements Authors would like to gratefully thank for magnetic field intensity measurement to Zdenek
Roubal from FEEC, Brno University of Technology. Funding under the Project 205/15/18495S
from the Czech Grant Agency is greatly appreciated.
References
[1] J. JANCAR, J. F. DOUGLAS F. W. STARR, S. K. KUMAR, P. CASSAGNAU, A. J.
LESSER, S. S. STERNSTEIN a M. J. BUEHLER. Current issues in research on structure–
property relationships in polymer nanocomposites, Polymer. 51 (2010) 3321‐3343.
[2] P. J. KROMMENHOEK, J. B. TRACY, Magnetic Field‐Directed Self‐Assembly of
Magnetic Nanoparticle Chains in Bulk Polymers, Particle. 30 (2013) 759‐763.
[3] U. G. K. WEGST, H. BAI, E. SAIZ, A. P. TOMSIA, R. O. RITCHIE, Bioinspired structural
materials, Nature Materials. 14 (2014) 23‐36.
[4] M. A. MEYERS, P. Y. CHEN, M. I. LOPEZ, Y. SEKI, A. Y. M. LIN. Biological materials: A
materials science approach, Journal of the Mechanical Behavior of Biomedical Materials.
4 (2011) 626‐657.
[5] J. AIZENBERG, J. C. WEAVER, M. S. THANAWALA, V. C. SUNDAR, D. E. MORSE, P.
Fratzl, Skeleton of Euplectella sp: Structural Hierarchy from the Nanoscale to the
Macroscale, Science. 309 (2005) 275‐278.
[6] J. B. TRACY, T. M. CRAWFORD, Magnetic field‐directed self‐assembly of magnetic
nanoparticles. MRS Bulletin. 38 (2013) 915‐920.
[7] D. FRAGOULI, R. BUONSANTI, G. BERTONI, C. SANGREGORIO, C. INNOCENTI, A.
FALQUI, D. GATTESCHI, P. D. COZZOLI, A. ATHANASSIOU, R. CINGOLANI,
Dynamical Formation of Spatially Localized Arrays of Aligned Nanowires in Plastic
Films with Magnetic Anisotropy. ACS Nano. 4 (2010) 1873‐1878.
******
Rheological Behavior of Polymer Nanocomposite Suspensions
Lepcio, P., Jancar, J.
Brno University of Technology, Central European Institute of Technology, Technicka 3058/10, CZ‐
616 00, Brno, CZECH REPUBLIC
Abstract
Nanoparticles (NPs) cause nontrivial changes in mechanic response of polymers with a
potential for properties enhancement at substantially lower loadings than conventional
fillers. A threshold length scale is supposed to exist at approximately 50 nm. [1] Above this
limit, conventional fillers were found to reinforce polymer matrices regardless their chemical
nature whereas smaller particles can act either as a reinforcement or as a plasticizer [2]
because highly attractive nanoparticles slow down chain dynamics and highly repulsive
particles accelerate it. [1] NPs significantly influence the reptation dynamics region present at
low frequencies, whereas the influence on the Rouse dynamic region at high frequencies is
quite low. [3] According to the computer simulations, there are four basic spatial
organization states of nanoparticles in polymer matrix with regard to interfacial polymer‐
188
particle strength at contact and spatial range of particles attraction. [4] As the polymer‐
particle interaction strength increases, the potential of mean force (PMF) exhibits higher
oscillation tendency with more energy wells separated by energy barriers, thus leading to an
assumption that formation of kinetic structures dominates the behavior of such systems.
Since nanoparticles are often dispersed in matrix in thermodynamically non‐equilibrium
state, a kinetic insight on aggregation phenomena would be more relevant to practical
applications however, only little is known about this field. This work is an initial stage of a
study which aim is to link macroscale mechanical properties with nanoscale structures found
in polymer nanocomposites. To do so, a suitable experimental protocol for preparing
differently organized NPs in polymer matrix has to be find first in which both kinetic and
thermodynamical parameters should be taken into account, i. e. solution casting has being
investigated. The results presented here found differences between nanoparticle induced
changes on rheological behavior of polymer solution under large amplitude oscillation shear
(LAOS).
Keywords
Polymer nanocomposite, nanoparticle, rheology, LAOS
Acknowledgements
Funding of this work under the Project 205/15/18495S from the Czech Grant Agency is
greatly appreciated.
References
[1] JANCAR, J. DOUGLAS, J. F. STARR, F. W. KUMAR, S. K. CASSAGNAU, P. LESSER, A.
J. STERNSTEIN, S. S. BUEHLER, M. J. Current issues in research on structure–property
relationships in polymer nanocomposites. Polymer 2010, 51, 3321–3343.
[2] KOPESKY, E. T. HADDAD, T. S. McKINLEY, G. H. COHEN, R. E. Miscibility and
viscoelastic properties of acrylic polyhedral oligomeric silsesquioxane–poly (methyl
methacrylate) blends. Polymer 2005, 46, 4743–4752.
[3] HASSABANDI, H. J WILHELM, M. A rheological criterion to determine the percolation
threshold in polymer nano‐composites, Rheological Acta 2014, 53, 869–882.
[4] HOOPER, J. B. SCHWEIZER K. S. Theory of Phase Separation in Polymer
Nanocomposites, Macromolecules 2006, 39, 5133–5142.
******
Thermo‐Mechanical Behavior of Polymer Glasses Probed by Nano‐Particles
Ondreas, F., Lepcio, P., Zbončák M., Jancar, J.
Brno University of Technology, Central European Institute of Technology, Technická 3058/10, CZ‐
616 00 Brno, CZECH REPUBLIC
Abstract
Discovering the relationship between nano‐scale segmental dynamics and macro‐scale
mechanical properties of polymer glasses is challenging scientific problem with extreme
technological importance. Interest in the basic study of nanostructured polymer materials
arose out of recognition that as discrete volumes within the constituent phases approach
molecular dimensions, the morphology of the constituent phases and the intrinsic properties
189
of the structural material become dependent upon constituent size, shape and local and
global spatial packing. The understanding of the origin of the observed large changes of
properties and functions remains in its infancy, partly due to the non‐existence of generally
accepted molecular models of glassy polymers and their nano‐composites and partly by the
lack of reliable experimental data. In addition to detailed knowledge of the molecular
structure of the polymer matrix, the development of a suitable theory also requires a
sufficient description of particle dispersion, particle‐chain interactions and effects related to
the kinetics of nano‐composite preparation processes [1‐3]. We utilized rigid inorganic
nanoparticles in the polymer matrix as “probes” that affect segmental ordering and
relaxation dynamic heterogeneity in amorphous polymers during the preparation and
vitrification. We investigated preparation‐structure‐property relationship of polymer
nanocomposites constituted by polymethylmethacrylate (PMMA) as polymer matrix and
commercial colloidal nano‐silica as nano‐filler. We found significant variation of viscoelastic
properties of prepared nano‐composites connected to changes of their structure caused by
different preparation protocols.
Keywords polymer nanocomposite, viscoelastic properties, PMMA, nano‐silica
Acknowledgements
Funding of this work under the Project 205/15/18495S from the Czech Grant Agency is
greatly appreciated.
References [1] JANCAR, J., J. F. DOUGLAS, F. W. STARR, S. K. KUMAR, P. CASSAGNAU, A. J.
LESSER, S. S. STERNSTEIN a M. J. BUEHLER. Current issues in research on structure–
property relationships in polymer nanocomposites. Polymer. 2010, vol. 51, issue 15, s.
3321‐3343.
[2] HOOPER, J. B. a K. S. SCHWEIZER. Theory of Phase Separation in Polymer
Nanocomposites. Macromolecules. 2006, vol. 39, issue 15, s. 5133‐5142.
[3] LIU, J., Y. GAO, D. CAO, L. ZHANG a Z. GUO. Nanoparticle Dispersion and
Aggregation in Polymer Nanocomposites: Insights from Molecular Dynamics
Simulation. Langmuir. 2011, vol. 27, issue 12, s. 7926‐7933.
******
Bi‐Functional Silver Nanoparticle Design and Characterization for Bone
Regeneration Applications
Matea T. C., Mocan T., Iancu C., Mocan L.
3rd Surgery Clinic, Department of Nanomedicine, “Iuliu Hatieganu” University of Medicine and
Pharmacy, Cluj‐Napoca, ROMANIA
Abstract Silver nanoparticles have attracted the attention of the scientific community due to their ease
of synthesis, biocompatibility and antibacterial effect. Their unique properties make them
ideal candidates for applications in the field of biology and medicine. We have proposed a
novel bio‐nanostructure based on a silver nanoparticle core functionalized with a
190
osteogenetic peptide for applications in bone infections treatment and bone regeneration. In
order to obtain aqueous stable and monodisperse silver nanoparticles they were synthetized
by reducing Ag+ ions to Ag0 with the aid of citrate ions. For promoting an osteogenetic effect
in osteoblasts, we have chosen the JAG‐1 peptide, which mimics the function of full‐length
Jagged‐1 protein activating the Notch pathway. This pathway is a complex network that
orchestrates cell fate decisions in organisms ranging from insects to humans. The
functionalization of AgNPs with the JAG‐1 peptide was achieved via direct thiol‐Ag
interaction. The obtained bio‐nanocomposite AgNP‐JAG‐1 was assessed by means of UV‐Vis
spectroscopy for stability assays, dynamic light scattering for nanoparticle size
determination, ATR‐FT‐IR spectroscopy for the confirmation of the functionalization step
and atomic force microscopy for nanoparticle size and shape measurements. Also
evaluations regarding the AgNP‐JAG‐1 stability in biological media was addressed by
subjecting the bio‐nanocomposite to different concentrations of NaCl and also culture media.
Keywords
silver nanoparticles, peptide delivery, AgNP functionalization, JAG‐1 peptide
Acknowledgements
This work was suported under the frame of European Social Found, Human Resources
Development Operational Programme, Human Resources Development Operational
Programme 2007‐2013, project no. POSDRU/159/ 1. 5/S/138776.
******
Mucin‐1 Functionalized Gold Nanoparticles for Immunological
Applications
Mocan T., Matea T. C., Orasan R., Mocan L.
3rd Surgery Clinic, Department of Nanomedicine, “Iuliu Hatieganu” University of Medicine and
Pharmacy, Cluj‐Napoca, ROMANIA
Abstract Due to their low toxicity and ease of synthesis, gold nanoparticles have drawn much interest
from the scientific community. Their applications range from electronics, sensors, probes to
diagnostics, photodynamic therapy and drug delivery. The Mucin‐1 glycoprotein is
overexpressed and aberrantly glycosylated in >70% of human colon cancer, making it a
possible target for anticancer immunotherapy. We have designed a gold nanoparticle based
bio‐nanocomposite for targeted delivery of Mucin‐1. Citrate capped gold nanoparticles
(GNPs) were synthetized by employing a modified Turkevich method were afterwards
functionalized with mucin‐1 (MUC‐1) protein. The obtained GNP‐MUC‐1 bio‐nanostructure
was characterized by means of UV‐Vis spectroscopy for aqueous stability assays, dynamic
light scattering for nanoparticle size determination, ATR‐FT‐IR for the detection of MUC‐1
presence on the GNP surface after functionalization and atomic force microscopy for size
and shape the obtained bio‐nanocomposite. Because GNPs tend to aggregate in biological
media, we have subjected the GNP‐MUC‐1 to stability evaluations in cell culture media.
Keywords
gold nanoparticles, mucin‐1 peptide, GNP functionalization
191
Acknowledgements
This work was suported under the frame of European Social Found, Human Resources
Development Operational Programme, Human Resources Development Operational
Programme 2007‐2013, project no. POSDRU/159/ 1. 5/S/138776. Also, we wish to
acknowledge grant numbers PN II‐ID‐PCE‐2012‐4‐0243 and PN‐II‐PT‐PCCA‐2011‐3. 1‐1586.
192
List of registered participants
1. Jakub Altsmid, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
2. Monika Bartošková, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
3. Jan Bednárek, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
4. Haider Behbehani, Kuwait University, Kuwait, [email protected]
5. Michaela Belovičová, Slovak University of Technology in Bratislava, Faculty of
Chemical and Food Technology, Bratislava, Slovakia, [email protected]
6. Pavla Benešová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
7. Nataliya Bevz, National University of Pharmacy, Kharkiv, Ukraine,
8. Vlastimil Bílek, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
9. Lucie Blahová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
10. Martin Boháč, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
11. Jitka Bokrová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
12. Dmitrij Bondarev, Tomas Bata University in Zlin, Faculty of Technology, Zlín, Czech
Republic, [email protected]
13. Emília Breierová, SAS, Institute of Chemistry, Bratislava, Slovakia,
14. Monika Bukačkova, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
15. František Buňka, Tomas Bata University in Zlin, Faculty of Technology, Zlín, Czech
Republic, [email protected]
16. Lenka Butorová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
17. Zdeněk Bystřický, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
18. Alfred Crosby, University of Massachusetts, Amherst, United States,
19. Josef Čáslavský, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
20. Michal Čeppan, Slovak University of Technology, Faculty of Chemical and Food
Technology, Bratislava, Slovakia, [email protected]
21. Milan Čertík, Slovak University of Technology Bratislava, Faculty of Chemical and
Food Technology, Bratislava, Slovakia, [email protected]
22. Lucie Drábová, University of Chemistry and Technology Prague, Faculty of Food and
Biochemical Technology, Prague, Czech Republic, [email protected]
193
23. Petr Dzik, Brno University of Technology, Faculty of Chemistr, Brno, Czech Republic,
24. Pavel Florián, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
25. Pavel Fojt, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
26. Petra Fojtíková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
27. Františka Frajkorová, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
28. Michaela Fričová, Faculty of chemistry Brno University of technology, Brno, Czech
Republic, [email protected]
29. Lucie Galvánková, Brno University of Technology, Faculty of chemistry, Brno, Czech
Republic, [email protected]
30. Gökhan Gece, Bursa Technical University, Faculty of Natural Sciences,Architecture
and Engineering, Bursa, Turkey, [email protected]
31. Magdalena Hábová, Mendelova univerzita v Brně, Fakulta Agronomická, Brno, Czech
Republic, [email protected]
32. Radek Hájek, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
33. Pavla Hájovská, Brno University of Technology, Faculty of chemistry, Brno, Czech
Republic, [email protected]
34. Jana Hajšlova, University of Chemistry and Technology, Prague, Czech Republic,
35. Michal Hatala, Slovak University of Technology in Bratislava, Bratislava, Slovakia,
36. Jaromír Havlica, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
37. Patricie Heinrichova, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
38. Viliam Hlaváček, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
39. Jakub Hofman, Masaryk University, Faculty of Science, Brno, Czech Republic,
40. Jana Honová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
41. Jakub Horák, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
42. Michal Hrabal, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
43. Jaromir Hradecký, University of Chemistry and Technology, Prague, Department of
Food Analysis and Nutrition, Prague, Czech Republic, [email protected]
44. Helena Hudečková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
45. Pengwei Huo, VŠB‐Technical University of Ostrava, Ostrava ‐ Poruba, Czech Republic,
194
46. Kamila Hůrková, University of Chemistry and Technology Prague, Faculty of Food
and Biochemical Technology, Prague, Czech Republic, [email protected]
47. Ivana Chamradová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
48. Silvia Christovova, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
49. Jaromíra Chýlková, University of Pardubice, Faculty Chemical Technology, Pardubice,
Czech Republic, [email protected]
50. Vaclav Chytil, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
51. Martin Chytil, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
52. Petra Innemanová, Charles University in Prague, Faculty of Science, Prague, Czech
Republic, [email protected]
53. A.M. Iordache, INC‐DTCI ICSI Rm. Valcea, National Institute R&D of Cryogenics and
Isotopic Technologies, Ramnicu Vlalcea, Romania, [email protected]
54. Josef Jančář, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
55. Lenka Janíková, University of Pardubice, Institute of environmental and chemical
engineering, Pardubice, Czech Republic, [email protected]
56. Lukáš Kalina, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
57. Radek Kavřík, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
58. Tatiana Klempová, Slovak University of Technology, Faculty of Chemical and Food
Technology, Bratislava, Slovakia, [email protected]
59. Edita Klímová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
60. Martina Klučáková, Brno university of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
61. Antonín Knob, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
62. Renata Komendová, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
63. Jana Konečná, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
64. Jan Koplík, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
65. Mária Kopuncová, National Agricultural and Food Centre, Food Research Institute,
Bratislava, Slovakia, [email protected]
66. Hedvika Kosárová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
67. Josef Kotlík, VUT v Brně, Fakulta chemická, Brno, Czech Republic, [email protected]
68. Silvie Kotlíková, VUT v Brně, Fakulta chemická, Brno, Czech Republic,
69. Jan Koutný, Brno University of Technology, Faculty fo Chemistry, Brno, Czech
Republic, [email protected]
195
70. Ondřej Koutný, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
71. Karin Kovar, Zurich University of Applied Sciences ZHAW, School of Life Sciences
and FAcility Management, Institute of Biotechnology, Wädenswil, Switzerland,
72. Jozef Krajčovič, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
73. Jiří Kratochvíl, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
74. Irena Kratochvílová, Institute of Physics AS CR,, Prague 8, Czech Republic,
75. Romana Kratochvílová, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
76. Aleš Krmela, University of chemistry and technology, Prague, Department of Food
Analysis and Nutrition, Prague, Czech Republic, [email protected]
77. Jitka Krouská, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
78. Lubomír Kubáč, Centre for Organic Chemistry Ltd., Rybitví, Czech Republic,
79. Eva Kulovaná, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
80. Vojtěch Kupka, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
81. Darina Lanková, UCT Prague, Prague, Czech Republic, [email protected]
82. Marcela Laštůvková, Materials Research Centre, Brno University of Technology,, Brno,
Czech Republic, [email protected]
83. Petr Lepcio, Brno University of Technology, Central European Institute of Technology,
Brno, Czech Republic, [email protected]
84. Martina Mahdalová, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
85. Ivana Márová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
86. Martin Palou, CMV‐CMR, Faculty of Chemistry, Brno University of Technology, Brno,
Czech Republic, [email protected]
87. Alexandra Masárová, Research Institute of Building Materials, JSC,, Brno, Czech
Republic, [email protected]
88. Jiří Másilko, Brno University of Technology, CMV ‐ Faculty of Chemistry, Brno, Czech
Republic, [email protected]
89. Josef Mašek, Veterinary Research Institute, Brno, Czech Republic,
90. Cristian T. Matea, “Iuliu Hatieganu” University of Medicine and Pharmacy Cluj‐
Napoca, Department of Nanomedicine, Cluj‐napoca, Romania,
91. Jana Matláková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
92. Petra Matoušková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
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93. Milan Mazur, Slovak University of Technology in Bratislava, Faculty of Chemical and
Food Technology, Bratislava, Slovakia, [email protected]
94. Lisa Melymuk, Masaryk University, RECETOX, Brno, Czech Republic,
95. Přemysl Menčík, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
96. Ewa Miękoś, University of Lodz, Faculty of Chemistry, Lodz, Poland, [email protected]
97. Vladu Mihaela, Institute for Cryogenic and Isotopic Technologies,, Ramnicu valcea,
Romania, [email protected]
98. Milan Mikula, Slovak University of Technology, Faculty of Chemical and Food
Technology, Bratislava, Slovakia, [email protected]
99. Premysl Mikula, Masaryk University, RECETOX ‐ Research Centre for Toxic
Compounds in the Environment, Brno, Czech Republic, [email protected]
100. Renata Mikulíková, Research Institute of Brewing and Malting,, Praha, Czech
Republic, [email protected]
101. Jakub Mondek, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
102. Iman Nazari, University of Tabriz, Chemical engineering, Tehran, Iran,
103. Stanislav Nespurek, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
104. Suvar Niculina‐Sonia, ʺBabe‐Bolyaiʺ University, Faculty of Physics, Cluj‐Napoca,
Romania, [email protected]
105. Stanislav Obruča, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
106. Zuzana Olejníčková, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
107. Zuzana Olšovcová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
108. Lukáš Omasta, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
109. Ladislav Omelka, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
110. František Ondreáš, Brno University of Technology, Central European Institute of Technology, Brno, Czech Republic, [email protected]
111. Michal Oravec, Slovak University of Technology in Bratislava, Faculty of Chemical
and Food Technology, Bratislava, Slovakia, [email protected]
112. Pavel Ošmera, Brno University of Technology, Mechanical Engineering, Automation
and Computer Science, Brno, Czech Republic, [email protected]
113. Ladislav Pařízek, Brno university of technology, Faculty of Chemistry / Materials
research center, Brno, Czech Republic, [email protected]
114. Šárka Paušová, University of Chemistry and Technology Prague, Faculty of Chemical
Technology, Praha 6 ‐ Dejvice, Czech Republic, [email protected]
115. Miloslav Pekař, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
116. Kateřina Perútková, Photon Systems Instruments,, Drásov, Czech Republic,
197
117. Josef Petruš, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
118. Tereza Pilgrová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
119. Gerald H. Pollack, University of Washington,, Seattle, United States,
120. Martin Polovka, Agricultural and Food Centre, VUP Food Research Institute, National, Bratislava, Slovakia, [email protected]
121. Ladislav Pooláček, BABAB,, Brno, Czech Republic, [email protected]
122. Jaromír Pořízka, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
123. Lubica Pospisilova, Mendel university in Brno, Faculty of Agronomy, Brno, Czech
Republic, [email protected]
124. Marek Pospíšek, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
125. Hana Postulkova, Brno University of Technology, CEITEC, Brno, Czech Republic, [email protected]
126. Radek Prikryl, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
127. Michal Procházka, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
128. Adrian Pryszcz, VŠB ‐ TU Ostrava, Institute of Environmental Technologies, Ostrava,
Czech Republic, [email protected]
129. Helena Půčková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
130. Jana Pulkrabová, University of Chemistry and Technology, Prague, Faculty of Food
Biochemistry and Technology, Prague, Czech Republic, [email protected]
131. Johanna Rajasärkkä, Masaryk University, RECETOX (Research Centre for Toxic
Compounds in the Environment), Faculty of Science, Brno, Czech Republic,
132. Martina Repková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
133. Lucie Řádková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
134. Veronika Řezáčová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
135. Jiří Sadílek, POLYMER INSTITUTE BRNO, spol. s r.o.,, Brno, Czech Republic,
136. Vika Salomatova, Voevodsky Institute of Chemical Kinetics and Combustion,
Novosibirsk, Russian Federation, [email protected]
137. Ota Salyk, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
138. Ota Samek, Ústav přístrojové techniky AV ČR, v. v. i.,, Brno, Czech Republic, [email protected]
139. Veronika Schmiedová, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
198
140. Marcela Sionová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
141. Jiří Smilek, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
142. Michaela Smutná, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
143. Tomas Solny, Brno University of Technology, Materials Research Centre, Faculty of
Chemistry, Brno, Czech Republic, [email protected]
144. Theodor Staněk, Výzkumný ústav stavebních hmot,a.s.,, Brno, Czech Republic,
145. Radovan Stanovič, Nitra Slovak University of Agriculture, Department of Chemistry,
Faculty of Biotechnology and Food Sciences, Nitra, Slovakia,
146. Stanislav Stříteský, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
147. Michal Stupák, University of Chemimstry and Technology,, Praha 6, Cyprus,
148. Kateřina Sůkalová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
149. Pavel Šiler, Brno University of Technology, Centre for Material Research, Faculty of
Chemistry, Brno, Czech Republic, [email protected]
150. František Šoukal, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
151. Veronika Švachová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
152. Jiří Švec, Brno University of Technology, Faculty of Chemistry, Brno, Czech Republic,
153. Tereza Švestková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
154. Lenka Tobková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
155. Markéta Tomášková, University of Pardubice, Faculty Chemical Technology,
Pardubice, Czech Republic, [email protected]
156. Valerii Tonkopii, Institute of Limnology Rus.Acad.Sci., Ecotoxicology,Pharmacology,
St. Petersburg, Russian Federation, [email protected]
157. Tomáš Tóth, Slovak University of Agriculture in Nitra, Faculty of Biotechnology and
Food Sciences, Nitra, Slovakia, [email protected]
158. Irena Turkeova, Materials Research Centre, Brno University of Technology, Faculty of
Chemistry, Brno, Czech Republic, [email protected]
159. Martin Vala, Brno Universtiy of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
160. Markéta Valicová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
161. Milada Vávrová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
162. Michal Veselý, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, vesely‐[email protected]
199
163. Milena Vespalcova, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
164. Libuše Vítková, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
165. Eva Vítová, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
166. Raghvendra Singh Yadav, Brno University of Technology, Faculty of Chemistry, Brno,
Czech Republic, [email protected]
167. Florentina Diana Yudin, Babes Bolyai University, Faculty of Physics, Cluj‐Napoca,
Romania, [email protected]
168. Jaroslav Záhora, Mendelu Brno, Agronomy, Brno, Czech Republic,
169. Marek Zbončák, Brno University of Technology, Central European Institute of Technology, Brno, Czech Republic, [email protected]
170. Anežka Zezulová, Research Institute for Building Materials, JSC,, Brno, Czech
Republic, [email protected]
171. Ying Zhao, East China University of Science and Technology, ShangHai, China,
172. Marek Zieliński, University of Lodz, Faculty of Chemistry, Lodz, Poland,
173. Helena Zlámalová Gargošová, Brno University of Technology, Faculty of Chemistry,
Brno, Czech Republic, [email protected]
174. Oldrich Zmeskal, Brno University of Technology, Faculty of Chemistry, Brno, Czech
Republic, [email protected]
200
Title Chemistry & Life 2015 – Book of Abstracts
Editor Oldrich Zmeskal
Publisher Brno University of Technology, Faculty of Chemistry
Purkynova 464/118, CZ‐612 00 Brno
Print Brno University of Technology, Faculty of Chemistry
Purkynova 464/118, CZ‐612 00 Brno
Edition first
Year of first edition 2015
Number of pages 200
Number of copies 250
ISBN: 978‐80‐214‐5228‐2
201
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