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XI Copernican International Young Scientists Conference organized by

Faculty of Chemistry, Nicolaus Copernicus University in Toruń, Poland

Toruń 2017

The study includes: Abstracts of materials presented in the form of oral presentations and posters during the XI Copernican International Young Scientists Conference. Publication is based on the abstracts provided by the authors. Authors of individual abstracts are responsible for the content and substantive value.

Typesetting and proofreading:

PhD A. Filipiak‐Szok MSc J. Gromowska MSc M. Kołodziej MSc S. Kowalska MSc M. Plaskacz‐Dziuba

Graphic design of the cover: Msc M. Ćwiklińska

Publication of the conference materials is funded by the President of the City of Toruń.

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Conference organizer: Faculty of Chemistry NCU in Toruń, Poland

Local Organizing Committee: Prof. DSc E. Szłyk – Dean of the Faculty of Chemistry Prof. DSc H. Kaczmarek, DSc I. Łakomska, prof. NCU, DSc J. Ścianowski, prof. NCU DSc U. Kiełkowska PhD A. Filipiak‐Szok MSc J. Gromowska MSc M. Kołodziej MSc S. Kowalska MSc M. Plaskacz‐Dziuba

Scientific Committee: Prof. DSc E. Szłyk – Dean, Faculty of Chemistry NCU Prof. DSc H. Kaczmarek Prof. DSc S. Koter DSc P. Gauden, prof. NCU DSc I. Łakomska, prof. NCU DSc J. Ścianowski, prof. NCU DSc A. Katafias DSc U. Kiełkowska DSc M. Krzemiński DSc A. Nowaczyk DSc J. Nowaczyk DSc K. Roszek DSc I. Szymańska PhD A. Bajek PhD M. Cichosz PhD J. Czarnecka PhD O. Impert PhD A. Jastrzębska PhD J. Kozłowska PhD M. Kurzawa PhD P. Płóciennik PhD. A. Zawadzka PhD J. Skopińska‐Wiśniewska PhD A.Wolan PhD M. Ziegler‐Borowska

Special Guest: DSc Marcin Kwit, prof. Adam Mickiewicz University in Poznań

Honorary Patronage:

Marshal of the Kuyavian‐Pomeranian Voivodeship

Piotr Całbecki

President of the City of Toruń

Michał Zaleski

Rector Magnificus NCU in Toruń

Prof. DSc Andrzej Tretyn

Dean of Faculty of Chemistry

Prof. DSc Edward Szłyk

Polish Chemical Society

Association of Engineers and Technicians

of Chemical Industry

Polish Physical Society

Polish Pharmaceutical Society

Scientific publishing,Nicolaus Copernicus University

Physical Society

Polish Pharmaceutical Society

Scientific publishing, Nicolaus Copernicus University

Media patronage

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General Sponsor

Sponsors

General Sponsor

Sponsors

SCHEDULE

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WEDNESDAY 28.06.2017

9.00 – 10.30 Conference Registration

10.30 – 10.40 Opening Ceremony - E. Szłyk - Dean, Faculty of Chemistry, NCU (Auditorium I)

10.40 – 11.25 Keynote Lecture – Marcin Kwit, Adam Mickiewicz University in Poznań

"Artificial molecular switches, motors, propellers and bevel gears - guiding principles and stereochemical relevance"

11.25 – 11.35 Grzegorz Trykowski, Faculty of Chemistry NCU, Central Laboratory (Instrumental Analysis Laboratory)

11.35 – 13.00 Lunch break*

Chemical Panel Biological and Medical Panel Physical and Technical Panel

Oral presentations (Auditorium I) 13.00 – 15.00 Chairmen: Prof. DSc H. Kaczmarek PhD M. Krzemiński PhD M. Kurzawa 1. Karina Kocot 2. Maja Zakrzyk 3. Agnieszka Tąta 4. Piotr Kamedulski 5. Dawid Grabarek 6. Jan Lorkowski 7. Sylwia Matysiak 8. Magdalena Grzelak

Oral presentations (Auditorium II) 13.00 – 14.30 Chairmen: DSc K. Roszek PhD A. Bajek PhD J. Czarnecka

1. Katarzyna Matuszczak 2. Paweł Staszek 3. Maja Czerwińska PL 4. Katarzyna Barchiewicz 5. Kamila Karpicka-Ignatowska 6. Anna Maria Dobosiewicz PL

Oral presentations ( Lecture room 61) 13.00 – 14.00 Chairmen: Prof. DSc S. Koter PhD P. Płóciennik PhD A. Zawadzka 1. Agnieszka Bracławska 2. Sabina Lachowicz 3. Jagoda Ryba 4. Katarzyna Siudzińska

15:00 – 15.15 Coffee break

SCHEDULE

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Oral presentations (Auditorium I) 15.15– 17.15 Chairmen: Prof. DSc E. Szłyk PhD M. Kurzawa PhD A.Wolan 1. Justyna Dąbrowska PL 2. Sylwia Grabska PL 3. Bartosz Orwat PL 4. Anna Kmieciak 5. Marcin Czapla 6. Kamil Wójcik 7. Kamila Pruszkowska 8. Grzegorz Wilkowski

Oral presentations (Auditorium II) 15.15 – 16.45 Chairmen: DSc I. Łakomska, prof. NCU DSc K. Roszek PhD M. Ziegler-Borowska 1. Łukasz Fijałkowski 2. Aleksandra Wasiluk 3. Igor Staszewski 4. Gracjan Różański 5. Zofia Korbut 6. Aleksandra Góralczyk

Oral presentations ( Lecture room 61) 15.15 – 16:30 Chairmen: Prof. DSc S. Koter PhD P. Płóciennik PhD A. Zawadzka 1. Beata Zjawin 2. Ewelina Janicka 3. Hubert Jóźwiak 4. Anna Adamska 5. Łukasz Niewiara

Poster session 17.15 – 18.15 Chairmen: PhD A. Jastrzębska DSc M. Krzemiński 1. Anna Kazimierczyk 2. Izabela Jęśkowiak 3. Izabela Jęśkowiak 4. Karina Kocot 5. Maja Zakrzyk 6. Agnieszka Richert 7. Agnieszka Richert 8. Ewelina Krzyszkowska 9. Agnieszka Tąta 10. Piotr Kamedulski 11. Jan Lorkowski 12. Sylwia Grabska 13. Sylwia Matysiak 14. Justyna Dąbrowska 15. Magdalena Grzelak 16. Bartosz Orwat 17. Magdalena Jakubczyk 18. Magdalena Jakubczyk 19. Angelika Kamizela 20. Angelika Kamizela 21. Katarzyna Pauter 22. Anna Kmieciak 23. Marcin Czapla 24. Kamil Wójcik 25. Artur Jabłoński 26. Artur Jabłoński 27. Justyna Jonik 28. Justyna Jonik

Poster session 17.00 – 18.00 Chairmen: DSc K. Roszek PhD J. Czarnecka

1. Katarzyna Matuszczak 2. Joanna Rychtyk 3. Małgorzata Konopka 4. Anna Lichota 5. Anna Lichota 6. Agnieszka Knioła 7. Agnieszka Knioła 8. Paweł Staszek 9. Maja Czerwińska 10. Katarzyna Barchiewicz 11. Anna Maria Dobosiewicz 12. Łukasz Fijałkowski 13. Marta Cyman 14. Agata Olejniczak 15. Igor Staszewski 16. Gabriela Gajek 17. Gabriela Gajek 18. Gracjan Różański 19. Beata Marciniak 20. Aleksandra Góralczyk 21. Małgorzata Girek 22. Małgorzata Girek 23. Karol Kłosiński 24. Karol Kłosiński 25. Katarzyna Rodzik 26. Katarzyna Rodzik 27. Katarzyna Szot 28. Katarzyna Szot

Poster session 16.30 – 17.00 Chairmen: PhD P. Płóciennik PhD A. Zawadzka 1. Katarzyna Gaładyk 2. Agnieszka Bracławska 3. Sabina Lachowicz 4. Daria Larowska 5. Daria Larowska 6. Jagoda Ryba 7. Katarzyna Siudzińska 8. Paweł Lesiak 9. Beata Zjawin 10. Ewelina Janicka 11. Hubert Jóźwiak 12. Anna Adamska 13. Łukasz Niewiara 14. Rokas Vilniškis1

SCHEDULE

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29. Grzegorz Wilkowski

29. Agnieszka Malinowska-Gniewosz 30. Agnieszka Malinowska-Gniewosz 31. Justyna Błażejak

20:00-24:00 Gala Dinner,

Sala Mieszczańska Gołębiewscy

ul. Międzymurze 7, Old Town, Toruń

THURSDAY 29.06.2017

Chemical Panel Biological and Medical Panel Physical and Technical Panel

Oral presentations (Auditorium I) 8.00 – 10.00 Chairmen: Prof. DSc H. Kaczmarek DSc M. Krzemiński DSc J. Nowaczyk 1. Marta Plaskacz-Dziuba 2. Agata Mrowiec 3. Joanna Kaźmierczak 4. Wojciech Kaspera 5. Justyna Gromowska 6. Zuzanna Wujkowska 7. Beata Kaczmarek 8. Marta Chrzanowska

Oral presentations (Auditorium II) 8.30 – 9.30 Chairmen: DSc A. Nowaczyk PhD J. Czarnecka PhD J. Skopińska-Wiśniewska 1. Przemysław Trzepiński 2. Adriana Schumacher 3. Patryk Nowicki 4. Bartosz Jania

10.00 – 10.15 Coffee break

Oral presentations (Auditorium I) 10.15 – 12.00 Chairmen: PhD J. Kozłowska PhD M.Kurzawa PhD A.Wolan 1. Monika Skibińska 2. Natalia Tereba 3. Patrycja Mrowiec 4. Agata Komorowska 5. Robert Dec PL 6. Sylwia Berbeć PL 7. Adrianna Kamińska PL

Oral presentations (Auditorium I) 10.15 – 11.30 Chairmen: PhD J. Czarnecka PhD J. Skopińska-Wiśniewska PhD M. Ziegler-Borowska 1. Anastazja Krzyżanowska PL 2. Edyta Grzyb 3. Anna Pasternak-Winiarska 4. Katarzyna Głombik PL 5. Przemysław Piotr Tomczyk PL

12.00 – 13.30 Lunch break*

SCHEDULE

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Oral presentations (Auditorium I) 13.30 – 15.15 Chairmen: DSc P. Gauden, prof. NCU DSc I. Szymańska DSc J. Nowaczyk 1. Monika Kołodziej 2. Anna Zep 3. Justyna Grzybek 4. Dawid Zych 5. Joanna Ginter 6. Kaja Spilarewicz-Stanek 7. Aneta Kurpanik

Poster session

15.15 – 16.15

Chairmen:

PhD A. Jastrzębska

PhD M. Kurzawa

1. Monika Skibińska 2. Agata Mrowiec 3. Aleksandra Korzeniowska 4. Aleksandra Korzeniowska 5. Kinga Gołąbek 6. Kinga Gołąbek 7. Justyna Grzybek 8. Maciej Strzempek 9. Maciej Strzempek 10. Wojciech Kaspera 11. Tomasz Jakubek 12. Tomasz Jakubek 13. Klaudia Ciura 14. Klaudia Ciura 15. Zuzanna Wujkowska 16. Beata Kaczmarek 17. Natalia Tereba 18. Katarzyna Węgrzynowska-Drzymalska 19. Katarzyna Węgrzynowska-Drzymalska 20. Agata Komorowska 21. Robert Dec 22. Sylwia Berbeć 23. Małgorzata Skibińska 24. Małgorzata Skibińska 25. Mateusz Kondratowicz 26. Justyna Gromowska 27. Kamil Kupietz 28. Joanna Kaźmierczak

Poster session 13.30 –14:30 Chairmen: DSc A. Nowaczyk PhD J. Czarnecka 1. Weronika Strzempek 2. Weronika Strzempek 3. Przemysław Trzepiński 4. Adriana Schumacher 5. Patryk Nowicki 6. Bartosz Jania 7. Marta Lemieszewska 8. Ewa Trojan 9. Katarzyna Chamera 10. Joanna Ślusarczyk 11. Katarzyna Ciaćma 12. Marcin Listowski 13. Patrycja Rachubik 14. Maria Szrejder 15. Renata Wolińska 16. Renata Wolińska 17. Karolina Pawlik 18. Karolina Pawlik 19. Przemysław Piotr Tomczyk

SCHEDULE

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19.00 – 19.45 Astronomical show in Planetarium in Toruń**

15.00(PL), 17.00(ENG), 20.00(PL) - Guide tours in the Old Town of Toruń***

Dinner in MANEKIN Restaurant (vouchers)****

FRIDAY 30.06.2017

Chemical Panel Biological and Medical Panel Physical and Technical Panel

Oral presentations (Auditorium I) 8.00 – 9.30 Chairmen: DSc M. Krzemiński PhD M. Kurzawa PhD O. Impert 1. Patryk Rzepiński 2. Aleksandra Wojciechowska 3. Sylwia Kutyła 4. Natalia Stachowiak PL 5. Anna Kaczmarkiewicz PL 6. Sylwia Kowalska PL

Poster session 9.30 – 10.00 Chairmen:

PhD A. Jastrzębska

PhD M. Kurzawa

1. Kornelia Kadac 2. Marta Plaskacz-Dziuba 3. Krzysztof Hus 4. Krzysztof Hus 5. Maciej Kisiel 6. Maciej Kisiel 7. Dawid Zych 8. Joanna Ginter 9. Marta Chylińska 10. Marta Chylińska 11. Jan Albert Zienkiewicz 12. Kaja Spilarewicz-Stanek 13. Sylwia Kowalska 14. Anna Filipiak-Szok 15. Anna Filipiak-Szok 16. Karolina Kowalska1 17. Eyad M. Hamad1 18. Samer Al-Gharabli1

10.00 – 11.00 Coffee break

SCHEDULE

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The numbers next to the names correspond to the order of speeches or number of poster boards. PL near the name means presentation in polish. *Bar Wydziału Prawa i Administracji UMK,ul. Władysława Bojarskiego 3 ** Planetarium, ul. Franciszkańska 15-21, Old Town Toruń *** ENG - guide in english, PL - guide in polish ****Three locations in Toruń: ♦ul. Rynek Staromiejski 16,♦ ul. Wysoka 5, ♦ ul. Gagarina 152; The possibility to use vouchers between 16-22 1 "in absentia" Participant

11.00 – 11.30 Closing Ceremony of the Conference along with prize giving (Auditorium I)

11.30 – 13.00 Lunch break*

XI COPERNICAN INTERNATIONAL YOUNG SCIENTISTS CONFERENCE - INAUGURAL LECTURE

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ARTIFICIAL MOLECULAR SWITCHES, MOTORS, PROPELLERS AND BEVEL GEARS - GUIDING PRINCIPLES AND STEREOCHEMICAL RELEVANCE

Marcin Kwit

Department of Chemistry, A. Mickiewicz University Umultowska 89B, 61 614 Poznan

Wielkopolska Center for Advanced Technologies (WCAT) Umultowska 89C, 61 614 Poznan

e-mail: marcin.kwit@amu.edu.pl

Organization of (bio)organic molecules into more complex systems, molecular recognition, induction and transfer of chirality are one of the most important phenomena taking place in living organisms. In the living organisms, biomolecules organized in the complex systems can perform specific functions that are necessary to sustain existence. Understanding the mechanism of action and the relationship between the components of such supramolecular systems remains a very demanding task that requires analysis of each element independently.

In general, the molecules or supermolecules, those resemble shape and/or the mechanism of action of the macroscopic objects bearing the name of molecular machines. Such molecular devices are able to perform mechanical work or collect or process information at the single molecule level. Depending on the role these molecules can be further divided to molecular motors (capable of performing one-way motion under the influence of an external stimulus), switches (able to switch from one stationary state to another under the influence of external stimuli), sensors, receptors or reporters (specifically responding to stimuli), gears (where there is a correlated motion between parts of the molecule), propellers (representing one-way synchronized movement). The same molecule (or molecular fragment) may be classified to different sub-classes depend on the function playing in a given system.

For instance – the shape and structural dynamic of the trityl group can be described as propeller or three-leaved clover. On the other hand, lowering the propeller molecular symmetry together with suitable substitution pattern at the sp3 carbon atom of Tr group, converts the propeller into a bevel gear.

This talk will focus mainly on the usability and versatility of trityl (and in general – triarylmethyl) derivatives as stereochemical probes, molecular receptors and inclusion-forming compounds. The mechanism of action of these compounds based on some fundamental processes, namely chirality induction, molecular recognition, aggregation and assembly. Trityl chromophore is sensitive to very small changes in the size of substituents (eg methyl and ethyl) of the stereogenic center.

Bibliography [1] R. Ballardini, V. Balzani, A. Credi, M. T. Gandolfi, M. Venturi, Acc. Chem. Res., 2001, 34, 445. [2] K. E. Drexler, Nanotechnology: Molecular Machinery, Manufacturing and Computation, Wiley, New York, 1992. [3] J. M. Berg, J. L. Tymoczko, L. Stryer, Biochemistry, W. H. Freeman & Co, 2010. [4] J. W. Steed, J. L. Atwood, Supramolecular Chemistry, Wiley-VCH, 2009. [5] N. Prusinowska, W. Bendzińska-Berus, M. Jelecki, U. Rychlewska, M. Kwit, Eur. J. Org. Chem. 2015, 738.

MARCIN KWIT

PRESENT POSITION Assistant Professor and Head of Laboratory of Organic Stereochemistry

INSTITUTION A. Mickiewicz University, Department of Chemistry

EDUCATION M. Sc., A. Mickiewicz University, 1998

Ph. D., A. Mickiewicz University, 2003

D. Sc., A. Mickiewicz University, 2012

OTHER POSITIONS HELD

University of Groningen, Prof. Ben L. Feringa Group (2003-2004)

Institute of Organic Chemistry PAS (2013-2015)

RESEARCH INTERESTS Stereoselective organic synthesis, structural chemistry and stereochemistry, chiroptical spectroscopy and its application to stereochemical studies, computational methods, macrocyclic and macrocage chemistry, material science, reaction mechanisms, chirality transfer, molecular devices and machines.

AWARDS 1997-1998 Scholarship of the Minister of Education of Poland

2004-2005 Scholarship of the Foundation for Polish Science

2004 The Prime Minister's Award for the Ph.D. dissertation

2005-2006 Scholarship of the Foundation for Polish Science

2010 Honorable Mention of the Kemula Prize of Polish Chemical Society

XI COPERNICAN INTERNATIONAL YOUNG SCIENTISTS CONFERENCE

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CHeMICAL seCtIoN orAL preseNtAtIoNs

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

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HIGLY SENSITIVE SERS PLATFORMS BASED ON SILVER NANOPARTICLES (AGNPS) AND GRAPHENE OXIDE (GO)

Sylwia Berbeć, Barbara Pałys

Department of Chemistry, Biological and Chemical Research Centre, University of Warsaw

Keywords: silver nanoparticles, graphene oxide, rhodamine 6G

Graphene oxide is a material that is widely used as platform for immobilizing molecules. The

hydrophilic character of the surface is due to the presence of oxygen containinggroups(eg. ethers, carboxyl, hydroxyl). The presence of carbon rings gives the surface a hydrophobic character. That makes a graphene oxide an ideal material for immobilizing both the organic and inorganic molecules. Interesingly, the nature of graphene’s surface can be modified for example by changing the composition of functional groups. Electrochemical reduction of graphene oxide allows the removal of oxygen containing groups thus the hydrophobic contribution of the whole surface increase. The composition of the functional groups is closely related to the orientation of the adsorbed particle. Analyzing the intensity of the bands that appear in the SERS spectrum of immobilized moleclethe orientation of the specific groups relative to the surface can be determined.

Here we demonstrated a facile method for the synthesis of hybrid platform ofsilver nanoparticles and graphene oxide (GO) or partly reduced graphene oxide (rGO).

AgNPS were obtained electrochemically by reducing silver nitrate (AgNO3) on the surface of graphene oxide or by etching of the silver electrode. Rhodamine 6G (R6G) was used as a SERS probe. It turns that the highly electronegative oxygen species, which can introduce a strong local electric field on the adsorbed molecules are responsible for the large enhancement.

Furthermore, the orientation of the R6G and the intensity of its spectrum enhancement depends on the thickness of the GO/rGO layer, the number of reduction cycles and the order of AgNPs and GO/rGOlaout on the surface. The best enhancement of the R6G spectrum was achieved after one reduction cycle of GO. This may be due to the fact that along with the loss of oxygen function, the hydrophobic nature of the surface increases and the R6G is immobilized on the layer in a different way eg. crucial role play the aromatic rings interactions.. Bibliography: [6] SoumenDutta et al., ACS APPLIED MATERIALS&INTERFACES, 2013, 5, 8724-8732. [7] Jun Yan et al., ACS APPLIED MATERIALS&INTERFACES, 2012, 5, 2752-2756.

STRUCTURE AND REACTIVITY OF [RUII(TERPY)(N^N)CL]CL COMPLEXES. CONSEQUENCES FOR BIOLOGICAL APPLICATIONS

Marta Chrzanowska1, Anna Katafias1, Rudi van Eldik2

1Faculty of Chemistry, N. Copernicus University, Gagarina 7, 87-100 Toruń, Poland

2Department of Chemistry and Pharmacy, University of Erlangen-Nuremberg, Egerlandstr. 1, 91058 Erlangen, Germany

Keywords: Kinetics, ruthenium complexes, substitution

The crystal structures of [RuII(terpy)(bipy)Cl]Cl·2H2O and [RuII(terpy)(en)Cl]Cl·3H2O, where

terpy = 2,2':6,2''-terpyridine, bipy = 2,2'-bipyridine and en = ethylenediamine, were determined and compared to the structure of the complexes in solution obtained by multi-nuclear NMR spectroscopy in DMSOd-6 as solvent. In aqueous solution, both chlorido complexes aquate fully to the corresponding aqua complexes, viz. [RuII(terpy)(bipy)(H2O)]

2+ and [RuII(terpy)(en)(H2O)]2+, within

2 h and 3 min at 37 °C, respectively. The spontaneous aquation reactions can only be suppressed by chloride concentrations as high as 2-4 M, i.e. concentrations much higher than that found in human blood. The corresponding aqua complexes are characterized by pKa values of ca. 10 and 11, respectively. Substitution reactions of the aqua complexes with chloride, cyanide and thiourea show that the [RuII(terpy)(en)(H2O)]

2+ complex is between 30 and 64 times more labile than the [RuII(terpy)(bipy)(H2O)]

2+ complex at 25 °C. Thermal and pressure activation parameters for the mentioned water exchange and ligand substitution reactions support the operation of an associative interchange (Ia) process. The difference in reactivity between these complexes can be accounted for in terms of π-back bonding effects of the terpy and bipy ligands, and steric hindrance on the bipy complex. Consequences of these findings for eventual biological applications of the chlorido complexes are discussed [1]. Bibliography: [1] M.Chrzanowska, A.Katafias, O. Impert, A. Kozakiewicz, A. Surdykowski, P. Brzozowska, A. Franke, A. Zahl, R.

Puchta, R. van Eldik, submitted to Inorganic Chemistry.

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

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SUPERHALOGENS AS STRONG OXIDIZING AGENTS

Marcin Czapla

Faculty of Chemistry, Laboratory of Quantum Chemistry,University of Gdańsk, Poland Keywords: superhalogens,calculations, ionization

One of the important properties of neutralsuperhalogen systems is their ability to oxidize molecules or atoms characterized by the large ionization potentials (IP), for example water, benzene, carbon dioxide [1-3]. These investigations concerning the efficiency of oxidizing molecules characterized by the large ionization potential with the use of superhalogens revealed that the proper balance between the molecule’s IP and the superhalogen’s excess electron binding energy (manifested by the VDE of its corresponding anion) must be assured.

It is notable that the binding energy between the reactants seems one of the most important criterion that allows to quantitatively judge whether the nature of the interaction between the fragments may be considered as ionic.

On the basis of our quantum chemistry calculations performed at the QCISD/6-311+G(d)/LANL2DZ//B3LYP/6-311+G(d)/LANL2DZ level for the series of SbnF5n+1(n = 1–3) neutral superhalogensinteracting with CO2, we demonstrated that the Sb3F16superhalogenis capable of efficiently oxidizing the carbon dioxide molecule.

Therefore, the AlF4and MgF3systems, due to their large tendency tobind an extra electron (manifested by the large electron stabilities of their daughter anions, spanning the 8.79–9.79 eVrange), are capable of ionizing benzene molecule and formingstrongly bound products of ionic nature, whereas the BF4 and AlF4superhalogenmolecules are capable of ionizing single H2O molecule and small water clusters (up to the tetramer). The ability of ionizing (H2O)n (n = 1–4) systems by these superhalogens is also related to very large electron affinities characterizing BF4 and AlF4molecules and to the significant vertical electron binding energies of their anionic daughters. Bibliography: [1] M. Czapla, P. Skurski,Phys. Chem. Chem. Phys., 2017, 19, 5435. [2] M. Czapla, S. Freza, P. Skurski, Chem. Phys. Lett., 2015, 619, 32. [3] M. Marchaj, S. Freza, O. Rybacka, P. Skurski, Chem. Phys. Lett., 2013, 574, 13.

THE EFFECT OF OZONATION ON THE BIOACTIVITY, CHEMICAL COMPOSITION AND YIELD

OF ESSENTIAL OIL FROM CELERY SEEDS (APIUM GRAVEOLENS L.)

Justyna A. Dąbrowska1, Krzysztof B. Śmigielski1, Alina Kunicka-Styczyńska2

1Faculty of Biotechnology and Food Sciences, Institute of General Food Chemistry,Lodz University of Technology

2Faculty of Biotechnology and Food Sciences, Institute of Fermentation Technology and Microbiology, Lodz University of Technology

Keywords: ozonation, DPPH, bioactivity,essential oil, Apiumgraveolens

Essential oils are mixtures of volatile organic and aliphatic compounds obtained by steam distillation or hydrodistillation. They are characterized by biological activity because of possessing antibacterial, antiviral, antifungal, insecticidal, antiparasitic, and antioxidant properties [1]. These bioactivities and intensive aroma have an impact on their common application in cosmetics, food, and pharmaceutical industry.Due to such a keen interest in essential oils, new technologies are sought to improve their extraction, facilitate exploitation of the potential of plants and achieve more effective migration of the extractant (water), thus enhancing the recovery of intracellular metabolites.

This study presents a method of ozonation pretreatment of plant material prior to hydrodistillation. Ozone is one of the most powerful oxidants. Ozonation is a type of advanced oxidation process, involving the production of very reactive oxygen species able to attack organic compounds which build plant tissues. This process may help to increase the porosity of the plant material, leading to better circulation of the solvent, and increase the extraction efficiency.

The experiment involved thepretreatment of celery seeds (Apiumgraveolens L.) without any commercial value with ozone.Ozone disintegrate in water into OH-radicals, which have a high oxidation potential. Because of this fact, the ozonation process was carried out in the water environment in different pH conditions: non-modifying, acidic, alkaline, and in alkaline buffer solution.

The effects of ozonation on the antimicrobial and antioxidantbioactivities, chemical composition, chemical properties, sensory properties, and yield of the essential oil were investigated.Also, obtained oils were compared with the use of near-infrared spectroscopy (NIRS).

This research not only creates a new strategy for extraction of essential oils but also a new way of using the bioactive potential of plant material to the fullest. The use of ozone increases the efficiency of the essential oils extraction process, changesthe qualitative and quantitative composition and has an impact on the bioactivity of the obtained products.

This work was supported by the Polish Ministry of Science and Higher Education (Grant Number: DS 530-8375-D499-16). The calculations have been carried out using resources provided by Wroclaw Centre for Networking and Supercomputing (http://wcss.pl) Grant No. 350.

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

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EXTRAORDINARILY DOCKING INTERACTIONS IN CROSS-SEEDING OF BOVINE INSULIN

Robert Dec1, Weronika Surmacz-Chewdoruk1,2, Wojciech Dzwolak1,3

1Department of Chemistry, Biological and Chemical Research Centre, University of Warsaw

2Institute of Biotechnology and Antibiotics, Staroscinska 5, Warsaw 3Institute of High Pressure Physics, Polish Academy of Sciences, Sokolowska 29/37, Warsaw

Keywords: insulin, human insulin analog, amyloid fibrils, cross-seeding

The coupling of phase- and conformational transitions taking place upon amyloidogenesis results in a dynamic complexity that is inaccessible to high resolution biophysical tools. Moreover, secondary nucleation events, fragmentation, and branching often accompany elongation of filaments which strongly complicates computational models of amyloid growth [1]. As a consequence, the molecular-scale events accompanying integration of monomers with amyloid tips remain poorly understood. In one of models of amyloidogenesis, it has been proposed that amyloid elongation encompasses two distinct phases: docking followed by locking [2] and this claim has been supported by in silico studies [3]. Of these two, the locking phase is envisioned as markedly less reversible. On the other hand, reversible binding of monomers to amyloid tips has been observed for several proteins [4].

Cross-seeding of fibrils of bovine insulin (BI) and LysB31-ArgB32 humaninsulin analog (KR) induces self-propagating amyloid variants with infrared features inherited from mother seeds.We noticed that when native insulin (BI or KR) is simultaneously seeded with mixture of equal amounts of both templates (i.e., of separately grown fibrils of BI and KR), the phenotype of resulting daughter fibrils is as in the case of the purely homologous seeding: heterologous cotemplates accelerate the fibrillation but do not determine infrared traits of the daughter amyloid. This implies that fibrillation-promoting and structure-imprinting properties of heterologous seeds become uncoupled in the presence of homologous seeds. We argue that explanation of such behavior requires that insulin molecules partly transformed through interactions with heterologous fibrils are subsequently recruited by homologous seeds. The selection bias toward homologous daughter amyloid is exceptional: more than 200-fold excess of heterologous seed is required to imprint its structural phenotype upon mixed seeding. Our study captures a snapshot of elusive docking interactions in statunascendi of elongation of amyloid fibril and suggests that different types of seeds may collaborate in sequential processing of soluble protein into fibrils.

Bibliography: [1] Gillam J. E., MacPhee C. E., J. Phys.: Condens. Mater., 2013, 25, 373101. [2] EslerW. P., Stimson E. R., Jennings J. M., Vinters H. V., Ghilardi J. R., Lee J. P., Mantyh P. W., Maggio J. E.,

Biochemistry, 2000, 39, 6288−6295. [3] Straub J. E., Thirumalai D., Annu. Rev. Phys. Chem., 2011, 62, 437−463. [4] Carulla N., Caddy G. L., Hall D. R., Zurdo J., Gairí M., Feliz M., Giralt E., Robinson C. V., Dobson C. M., Nature,

2005, 436, 554−558.

COMPARISON OF PHOTOCATALYTIC PROPERTIES OF TITANIUM DIOXIDE PHOTONIC CRYSTALS MODIFIED WITH SILVER AND PLATINUM NANOPARTICLES

Joanna Ginter, Kaja Spilarewicz-Stanek, Aneta Kisielewska, Ireneusz Piwoński

Faculty of Chemistry, Department of Materials Technology and Chemistry, University of Lodz Keywords: photonic crystals, titanium dioxide, silver nanoparticles, platinum nanoparticles, photocatalytic activity

In recent years a large number of investigations have been reported on better utilization of light in the electron-hole separation improving the photocatalytic properties of titanium dioxide (TiO2). A promising way to improve the light absorption properties is an increase of the length path of light in the material. It was shown in several studies that the structure of hierarchically, porous TiO2 exhibit an important light harvesting effect allowing the light waves to penetrate deeper inside the whole volume of the photocatalyst. This kind of material called also photonic crystal (PC) structure is characterized by an open, interconnected macroporous ordered structure and nanosized wall components. Additionally, these structures, having a periodic dielectric contrast, allow the modulation of light propagation in the TiO2 PC volume. Another characteristic feature of PC is the occurrence of the photonic band gap (PBG). Upon irradiation, photons near PBG edges propagate with strongly reduced group velocity leading to the occurrence of slow photons. If this phenomenon of slow photons overlaps the edge of semiconductor absorption band, the photocatalytic properties of TiO2 PC can be improved. The second way to enhance the photocatalytic properties is surface modification of TiO2 PC by metallic nanoparticles. In the presence of silver or platinum nanoparticles decomposition reactions of organic compounds run faster due to the longer life-time of the electron-hole pair. The phenomenon responsible for this change is transfer of electron via semiconductor-metal interphase (Schottky barrier) and trapping the electron in metals [1-3].

In this study the TiO2 PCs modified with silver and platinum nanoparticles were obtained with the use of polystyrene template and sol-gel method. In the first step the polymer templates were immersed into the sol of TiO2 and after the calcination the inorganic TiO2 skeletons were obtained. The next step included the photoreduction of metallic ions on the TiO2 PC resulting in an appearance of silver nanoparticles (AgNPs) and platinum nanoparticles (PtNPs). Afterwards the obtained structures doped with AgNPs and PtNPs were used to explore the photocatalytic activity by monitoring the rhodamine B photodegradation. This study shows the synergistic effect between photonic crystal structure and metallic nanoparticles causing of enhancement the photocatalytic properties of TiO2.

Bibliography: [1] J. Ginter, A. Kisielewska, K. Spilarewicz-Stanek, M. Cichomski, D. Batory, I. Piwoński, Micropor. Mesopor. Mat.

2016, 225, 580-589 [2] M. Wu, J. Liu, J. Jin, C. Wang, S. Huang, Z. Deng, Y. Li, B.-L. Su, Appl. Catal. B-Environ.2014, 150-151, 411-420 [3] A. Zielińska-Jurek, A. Zalewska, Catal. Today 2014, 230, 204-111

This work was supported by National Science Centre of Poland under research Grant no 2016/21/N/ST8/01144.

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

16

INITIAL EXCITED-STATE RELAXATION OF RING-LOCKED RETINAL CHROMOPHORE MODEL. INSIGHT FROM XMC-QDPT2 AND CC2 CALCULATIONS

Dawid Grabarek, Tadeusz Andruniów

Advanced Materials Modelling and Engineering Group, Faculty of Chemistry,

Wroclaw University of Science and Technology Keywords: retinal model, excited-state relaxation, electron correlation

Retinal is a chromophore of various photoactive proteins responsible for e.g. vision at higher

organisms and active transport of ions in bacteria [1]. The chromophore is covalently bound to the protein through protonated iminium moiety (RPSB) [Fig. 1] and its light-induced photoisomerization is the first step that triggers biochemical cascades leading to various activities of retinylidene proteins.

Due to remarkable rate of the photoisomerization (the first intermediate is formed in merely 200-250 fs) [2], the theoretical chemistry methods played an invaluable role in revealing the most probable mechanism of the photoprocess. Nevertheless, the experimental studies of rhodopsin pigment comprising the artificial RPSB with the photoreactive bond incorporated into eight-membered ring have shown that discussed photoreaction can be accelerated as concluded from the excited-state lifetime of the artificial pigment being 90 fs shorter than of the native rhodopsin without loss of its remarkably high quantum yield [3].

The present contribution is an assessment of complete active space self-consistent field (CASSCF) and approximated second-order coupled cluster (CC2) quantum chemistry methods in reference to extented multiconfiguration quasidegenerate second-order perturbation theory

XMC-QDPT2 approach for description of initial geometrical excited-state (the S1 state) relaxation of locked-11.8 retinal model [Fig. 1]. The relaxation in terms of energy difference between the Franck-Condon and the excited-state equilibrium structures as well as emission energies from the latter were calculated with complete active space second-order perturbation theory (CASPT2) approach. As the eight-membered ring is flexible, three conformers, found by De Vico et al. [4], were investigated.

Our analysis clearly shows that the S1 state minimum energy structures are in a very good agreement in terms of bond lengths and dihedral angles along the system of conjugated double bonds according to all investigated methods. Nevertheless, the energetic relaxation is ca. 0.20 eV greater for CASSCF-optimized structures due to known drawbacks of the CASSCF method in representing bond lengths of the ground-state geometries. What is more, the emission energies are ca. 0.15-0.25 eV greater for CASSCF- and CC2-optimized geometries compared to reference ones. These data suggest that geometrical details of the S1 state XMC-QDPT2 structures have considerable impact on the energetic properties of investigated conformers. In effect, even though CASSCF and CC2 methods seem to provide reliable excited-state geometries at least in the initial phase of locked-11.8 retinal model photoisomerization, the results obtained with them should be taken with caution.

Bibliography: [1] Ernst O. P., Lodowski D. T., Elstner M., Hegemann P., Brown L. S., Kandori H., Chem. Rev., 2013, 114, 126-163 [2] Haran G., Morlino E. A., Matthes J., Callender R. H., Hochstrasser R. M., J. Phys. Chem. A, 1999, 103, 2202-2207 [3] Kandori H., Sasabe H., Nakanishi K., Yoshizawa T., Mizukami T., Shichida Y., J. Am. Chem. Soc., 1996, 118,

1002-1005 [4] [De Vico L., Garavelli M., Bernardi F., Olivucci M., J. Am. Chem. Soc., 2005, 127, 2433-2442 This work was financed by Wroclaw Research Centre EIT+ under the project BIOMED ``Biotechnologies and advanced medical technologies'' (POIG 01.01.02-02-003/08)

INFLUENCE OF MAGNETIC PARTICLES ON PHYSICO-CHEMICAL PROPERTIES OF 3D COLLAGEN MATRICES

Sylwia Grabska, Alina Sionkowska

Faculty of Chemistry, Department of Chemistry of Biomaterials and Cosmetics, Nicolaus Copernicus

University in Toruń, Gagarin 7, 87-100 Toruń Keywords: biopolymers, collagen, chitosan, magnetic particles

Biopolymers are widely used for preparation of 3D materials for biomedical applications. In this work we use collagen from young rat tail tendons and chitosan. Collagen was prepared in our laboratory. Two or even more biopolymers (e.g.: collagen, chitosan) can be mixed together and such the blends can lead to new materials. Biopolymer blends are widely used in biomedical industry because they are fiber-forming and film-forming. Materials from natural polymers for biomedical and cosmetic applications should be non-toxic, because these materials are brought into contact with the skin or body [1]. The blends of natural polymers can be also used as matrices for incorporation of several inorganic particles, such as metals and ceramics.

Materials containing metals are widely used in biomedical applications, such as: tissue repair, drug delivery, magnetic resonance imaging (MRI), hyperthermia, magnetofection and cellular therapy. They are non-toxic, biodegradable and biocompatible. Magnetic particles are extremely reactive toward oxidizing agents and in the presence of water or humid air. Therefore, the protection of magnetic particles is of prime importance for obtaining physical and chemical stability. Such protection can be achieved through surface coating using appropriate polymeric stabilizers/surfactants. Polymeric coating materials can be classified into two categories, synthetic (PVP, PEG, PVA) and natural (gelatin, dextran, chitosan) [2,3].

In this work, we are studying influence of magnetic nanoparticles on physico-chemical properties of 3D biopolymeric matrices. Magnetic particles were synthesized by precipitation of iron (II) sulfate heptahydrate and iron (III) chloride hexahydrateand then added to a biopolymeric mixture solution. Next, materials were prepared by lyophilization technique. Starch dialdehyde (DAS) was used as a cross-linking agent for the materials. The properties of the obtained materials were studied using scanning electron microscopy. Additionally, porosity, density, and moisture content were measured.

Bibliography: [1] A. Sionkowska, Prog. Polym. Sci., 2011, 36, 1254–1276. [2] A.K. Gupta, M. Gupta, Biomaterials, 2005, 26, 3995-4021. [3] L.H. Reddy, J.L. Arias, J. Nicolas, P. Couvreur, Chem. Rev.,2012, 112, 5818−5878[27].

Financial support from the National Science Centre (NCN, Poland) Grant No UMO 2013/11/B/ST8/04444 is gratefully acknowledged.

Fig. 1. Comparison of full and investigated retinal models

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

17

THE MECHANISM OF CARBON/POLYMER NANOCOMPOSITE FORMATION - COMPUTER SIMULATIONS AND EXPERIMENTS

Justyna Gromowska1, Piotr A. Gauden1, Sylwester Furmaniak1, Piotr Kowalczyk2

1 Faculty of Chemistry, Physicochemistry of Carbon Materials Research Group, Nicolaus Copernicus

University in Toruń, Gagarin St. 7, 87-100 Toruń, Poland 2 School of Engineering and Information Technology, MurdochUniversity, Murdoch, Western

Australia 6150, Australia Keywords: carbon black, polymer binder, nanocomposites, adsorption, computer simulation

Poly(vinylidene fluoride), PVDF, is a highly non-reactive thermoplastic fluoropolymer produced by the polymerization of vinylidened fluoride. It has attracted the attention of researchers for many years and a large number of experimental and theoretical studies have appeared. PVDFis the standard binder material used in the production of composite electrodes, for example lithium-ion batteries and supercapacitors.Molecular dynamics simulations have been widely used to investigate the separation behaviour at various interfaces such as carbon nanotube/polymer [1,2] and graphene/polymer [3,4]. What is more, atomic simulations can be useful to estimate the porosity, heterogeneity and adsorption properties of such systems.

The main attention of the study is paid to the separation behavior at the interface of the binder and the carbon black. Polyvinylidene fluoride PVDF and the ideal graphite (the basal plane of graphite) are selected for the binder and carbon black, respectively, which are commonly used in current commercial batteries and theoretical considerations [5,6]. The PVDF/binder interface is modeled at the atomic level, where the PVDF is attached to the basal plane of graphite. The simulation package GROMACS [7]is used for the MD studies presented here. These simulations are used to study the melting of these systems. The results indicate that the adhesion strength of the PVDF on the graphite basal plane is weak and an interparticle fracture therefore potentially initiates from the PVDF/graphite interface. Additionally, taking into account the obtained nanocomposites the low-temperature nitrogen adsorption isotherms are simulated. Finally, theoretical results are compared with experimental observations for the following nanoncomposites (commercial PUREBLACK® carbon black (Superior Graphite Co.)/PVDF), i.e. the analysis of change in the adsorption properties and texture of the series of carbon black/PVDF nanocomposites (low temperature nitrogen adsorption and thermogravimetry measurements). Bibliography: [1] Y. Zhang, X. Zhuang, J. Muthu, T. Mabrouni, M. Fontaine, Y. Gong, T. Robczuk, Compos. Part B: Eng.63 (2014) 27. [2] F. Liu, N. Hu, H. Ning, S. Atobe, Ch. Yan, Y. Liu, Carbon 115 (2017) 694. [3] A.P. Awasthi, D.C. Lagoudas, D.C. Hammerand, Modelling Simul. Mater. Sci. Eng. 17 (2009) 015002. [4] S. Lee, J. Nanomaterials 28 (2016) 1. [5] S. Lee, J. Park, J. Yang, and W. Lu, “Molecular dynamics simulations of the traction-separation response at the

interface between PVDF binder and graphite in the electrode of Li-Ion batteries,” Journal of the Electrochemical Society, vol. 161, no. 9, pp. A1218–A1223, 2014.

[6] Kenji Takahashi, Kenneth Higa, Sunil Mair, MahatiChintapalli, NitashBalsara, Venkat Srinivasan, Journal of The Electrochemical Society, 163 (3) A385-A395 (2016)

[7] Hess B, Kutzner C, van der Spoel D, Lindahl EJ. ChemTheorComput 2008;4(3): 435-47.

INCOMPLETELY CONDENSED SILSESQUIOXANES

Magdalena Grzelak1, Dawid Frąckowiak2, Bogdan Marciniec2

1Adam Mickiewicz University in Poznań, Faculty of Chemistry,

Umultowska 89b, 61-614 Poznań, Poland 2Adam Mickiewicz University in Poznań, Centre for Advanced Technologies,

Umultowska 89c, 61-614 Poznań, Poland Keywords: POSS, silsesquioxanes, germasilsesquioxanes, incompletely condensed POSS

Silsesquioxanes is the general name for organosiloxide species with (RSiO3/2)n formula. For these

compounds irregular, ladder, and cage structures are known, of which the latter are the most familiar. These cage structures can be regarded as small three-dimensional pieces of silica as their oligomerization is sufficient to result in rigid structures. The additional asset of silsesquioxanes is vast range of their derivatives with different functional groups and substituents which can be easily modified, depending on the required parameters. There is a considerable number of reactions allowing for the straightforward functionalization of POSS with well-defined physical, chemical and biological properties [1].

The number of reports regarding incompletely condensed silsesquioxanes is limited. However, these compounds may exhibit distinct physicochemical properties and different reactivity [2]. Only a few examples are reported in literature about the modification of POSS silanols in reactions with chlorosilanes that lead to the formation of incompletely condensed silsesquioxane derivatives. Lorenz et al. provided only one example of complete substitution of the trisilanolcyclohexyl POSS -OH groups with chlorodimethylvinylsilane [3]. Other examples are based on the substitution of one group in trisilanol POSS , and then the formation of the complexes, e.g. with tetrahedrally coordinated tin atom. Additionally, there are also reports on trimethylsilyl(TMS)-capped compounds [4].

Much attention in the POSS field has been also focused on heterosilsesquioxanes, i.e. germasilsesquioxanes in which one or more silicon atoms are replaced by germanium atom. Compounds containing Ge-O-Si moiety in their structure combine the features of the known properties of silsesquioxanes and compounds comprising of Ge-O-Si, along with improved parameters, e.g. higher refractive index [5],so they are believed to find many applications. So far, there has been no reports on the synthesis of incompletely condensed POSS with germanium atoms.

This research was carried out in order to design incompletely condensed vinylsubstituted silsesquioxane and germasilsesquioxane derivatives and to provide efficient procedure for their synthesis. Additionally, reactivity of these new class of compounds will be discussed.

Bibliography: [1] C. Hartmann-Thompson, Applications of Polyhedral Oligomeric Silsesquioxanes, Springer, 2011 [2] E. A. Quadrelli, J. M.Basset, Coordination Chemistry Reviews,2010, 254, 707 [3] V. Lorenz, M. Spoida, A.Fischer, F. T. Edelmann, Journal of Organometallic Chemistry, 2001, 625, 1-6 [4] R. Duchateau, Chemical Reviews, 2002, 102, 10, 3525 [5] W. M. Risen, Jr., Y. Z. Wang, A. Honore, US Patent: 6248852, 2001

Authors thank for financial support from the National Science Centre (Poland) - Project ‘Maestro’ No. UMO-2011/02/A/ST5/00472

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

18

MONO- AND MULTI-LAYER MWW ZEOLITES SYNTHESIZED BY DESIGN WITH THE USE OF BIFUNCTIONAL LONG-CHAIN SDA

Justyna Grzybek, Aleksandra Korzeniowska, Barbara Gil, Wiesław J. Roth, Monika Skoczek,

Lucjan Chmielarz

Faculty of Chemistry, Jagiellonian University in Kraków, Poland Keywords: layered zeolites, MWW, structure directing agent

One of the main pillars of the petrochemical industry and heterogeneous catalysis [1] are framework structures named zeolites. The basis for the applicability of zeolites as catalysts are their microporous structures and strong acid centers, located in the channels available through windows with diameters not exceeding 1 nm. This constrain appears to limit accessibility of catalytic sites and does not allow complete utilization of the potential of these materials. This leads to an increased interest in the synthesis of new zeolites with unique structures that are capable for catalyze reaction with bulky molecules. One of the surprising breakthroughs with great promise for catalysis was the recent recognition that zeolites can produce ultrathin sheets in various arrangements, referred to as layered or 2-dimensional forms [2] MFI zeolite was produced by design in two layered forms: single- and multi-layered, using bifunctional long-chain structure-directing agents (SDA)[3]. By similar strategy the SDA designated Ada-4-16 (C10H15-N

+(CH3)2-C4H8-N+(CH3)2-C16H33) was

used to prepare single-layer zeolite with MWW topology named MIT-1 [4]. Using the same SDA we obtained the multi-layered analogue with equally spaced layers but

misaligned in the 3rd dimension, producing X-ray diffraction pattern resembling the known EMM-10 material. This is unexpected outcome because the SDA contains large moieties that are supposed to keep the layers separated. This work concerns synthesis of both new materials and characterization by various physical methods, acidity determination and catalytic testing.

Both obtained materials, the mono-layered MIT-1 and multi-layered EMM-10 analogue showed high crystallinity and specific areas of 500 cm2/g, and 572 cm2/g, respectively, with about half of it being the external surface area. The EMM-10 analogue showed higher concentration of Brønsted acid sites (899 μmol/g) in comparison to MIT-1 (307 μmol/g). The multi-layered material was swollen to produce the pillared MCM-36-like product with increased surface area (1063 cm2/g). Catalytic testing of the EMM-10-like product included alcohol conversion and comparison to MCM-56. The latter was more active towards methanol but with ethanol the order switched.

Bibliography: [1] Davis, M. E. Nature, 2002, 417, 813-821. [2] Roth, W. J.; Nachtigall, P.; Morris, R. E.; Čejka, J. Chem. Rev., 2014, 114, 4807-4837. [3] Choi, M.; Kim, N. A.; Sakamoto, Y.; Ryoo, R. Nature, 2009, 461, 246-250. [4] Luo, H. Y.; Michaelis, V. K.; Hodges, S.; Griffin, R. G.; Roman-Leshkov, Y. Chem. Sci., 2015, 6, 6320-6324.

Financial support by National Science Centre in Poland, grant no. 2016/21/B/ST5/00858.

THE MANAGEMENT OF FOOD INDUSTRY WASTES TO OBTAIN GLYCOSAMINOGLYCANS FOR TISSUE ENGINEERING

Beata Kaczmarek, Alina Sionkowska, Ewelina Markiewicz

Faculty of Chemistry, Department of Chemistry of Biomaterials and Cosmetics, Nicolaus Copernicus

University in Toruń Keywords: natural polymers, glycosaminoglycans, food industry wastes, tissue engineering

The management of food industry wastes is extremely important. The need of biodegradable wastes processing routes is related with their high biological activity which is risky for the human life directly and indirectly. It has been reported that the fish skin can be a natural source of collagen [1,2] as well as the glycosaminoglycans [3].

Glycosaminoglycans (GAGs) are the group of polysaccharides. The main compounds from the GAGs group are hyaluronic acid, chondroitin sulfate, heparin and keratin sulfate [4]. GAGs can be isolated from fish skin what have been already reported [5]. However, the application of isolated glycosaminoglycans is the novel aspect in tissue engineering science.

Fish skin from the Koral s. c. company (Tychy, Poland) were used as the source of glycosaminoglycans. GAGs were isolated following the procedure published elsewhere [5]. The isolated mixture was analyzed by spectrophotometric method with the use of DMB dye [6]. Moreover, the cytotoxicity of GAGs mixture was carried out in the collagen matrixes by the MTS assay for the human cells line SaOS.

The results showed that in the isolated glycosaminoglycans mixture both, hyaluronic acid and chondroitin sulfate were detected. Moreover, obtained mixture after addition to the collagen scaffold did not cause any toxicity of material. Based on the obtained results the conclusions can be made that the food industry wastes could be the promising source of compounds for tissue engineering science.

Bibliography: [1] A. Sionkowska, B. Kaczmarek, K. Lewandowska, J. Mol. Liq., 2014, 199, 318-323 [2] A. Sionkowska, J. Kozlowska, M. Skorupska, M. Michalska, Int. J. Biol. Macromol., 2015, 80, 605-609 [3] L. Bower, J. Braven, G. Manley, J. Pharm. Biomed. Anal., 1988, 6, 67-74 [4] J. K. F. Su, H. W. T. Matthew, Biomaterials, 2000, 21, 2589-2598 [5] G. Sadhasivam, A. Muthuvel, A. Pachaiyappan, B. Thangavel, Int. J. Biol. Macromol. 2013, 54, 84-89 [6] R.W. Farndale, C.A. Sayers, A.J. Barrett, Connect Tissue Res. 1982, 9, 247-248

Financial support from the National Science Centre (NCN, Poland) Grant No UMO-2015/19/N/ST8/02176 is gratefully acknowledged. Authors would like also to thank the Koral s. c. company (Tychy, Poland) for the fish skin.

ORAL PRESENTATION

MODIFICATION OF COL

Faculty of Chemistry, Department of Chemistry of Biomaterials and Cosmetic

Keywords: microcapsules, collagen, retinyl palmitate, matrix, encapsulation

Microcapsules are round forms of size from 5 to 1000 are about 100-500 μm. They consist of a coresubstance, but the core may be different substances such as: crystalline, adsorbent molecules, emulsions or smaller microcapsules. Active compounds or drugs often react easily with other substances and they may be sensitive to external factors. Closing them into a microcapsule protects them from pH, ultraviolet radiation, heat or oxidation. At the same time it improves the stability of compounds by preventing them of degradation reactions. Microencapsulodor, which is very important for some medicines. Controlled release of substances closed in microcapsule after reaching right temperature and pH is also an important aspect. The most popular methods of microencapsulation are coacemethod. The coacervation method is based on the separation of phases in a solution of colloids or polymers which results with the formation of a minimum two liquid phases. In the coacervation process core must be compatible with the encapsulating polymer and also insoluble in the coacervation environment.The aim of this study was to obtain and investigate a new materials for cosmetic applications.

Microcapsules were obtained by coacervation method. Twas coated by poly(vinylalcohol). In the next step the microcapsules were incorporated into polymer matrices prepared from collagen which was isolated from fish scales (Polymer matrices were crosslinked with EDC / NHS mixture. The structure and topography of microcapsules and matrices were observed by Scanning Electron Microscopy, using a camera and optical microscope. The mechanical properties of polymer matrices were tested, ATR spmade, swelling properties and degradation resistance were examined.

Bibliography: [1] J. Kozlowska, A. Sionkowska, J. Skopinska

BiologicalMacromolecules, [2] S. Jyothi, A.Seethade

Sciences,2012, 3, 509[3] I. M. Martins, M. F. Barreiro, M. Coelho, A. E. Rodrigues, [4] A. Gonçalves, B. N. Estevinho, F Final support from National Science Centre (NCN, Poland) Grant no. UMOacknowledged.

PRESENTATION

MODIFICATION OF COLLAGEN MATRIX WITH ADDITION OF MICROCAPSU

Anna Kaczmarkiewicz, Justyna Kozlowska

Faculty of Chemistry, Department of Chemistry of Biomaterials and CosmeticNicolaus Copernicus University in Toruń

: microcapsules, collagen, retinyl palmitate, matrix, encapsulation

Microcapsules are round forms of size from 5 to 1000 μm, but the most common microcapsules m. They consist of a core which is surrounded by shell.Shell is made from solid

substance, but the core may be different substances such as: crystalline, adsorbent molecules, emulsions or smaller microcapsules. Active compounds or drugs often react easily with other

they may be sensitive to external factors. Closing them into a microcapsule protects them from pH, ultraviolet radiation, heat or oxidation. At the same time it improves the stability of compounds by preventing them of degradation reactions. Microencapsulodor, which is very important for some medicines. Controlled release of substances closed in microcapsule after reaching right temperature and pH is also an important aspect. The most popular methods of microencapsulation are coacervation, polymer-polymer incompatibility and spray drying method. The coacervation method is based on the separation of phases in a solution of colloids or polymers which results with the formation of a minimum two liquid phases. In the coacervation

s core must be compatible with the encapsulating polymer and also insoluble in the coacervation environment.The aim of this study was to obtain and investigate a new materials for cosmetic applications.

Microcapsules were obtained by coacervation method. The core was made of retinyl palmitate and was coated by poly(vinylalcohol). In the next step the microcapsules were incorporated into polymer matrices prepared from collagen which was isolated from fish scales (

ices were crosslinked with EDC / NHS mixture. The structure and topography of microcapsules and matrices were observed by Scanning Electron Microscopy, using a camera and optical microscope. The mechanical properties of polymer matrices were tested, ATR spmade, swelling properties and degradation resistance were examined.

J. Kozlowska, A. Sionkowska, J. Skopinska - Wisniewska, K. Piechowicz, BiologicalMacromolecules, 2015, 81, 220-227. S. Jyothi, A.Seethadevi, K.SuriaPrabha, P.Muthuprasanna ,P.Pavitra,, International Journal of Pharma and Bio

2012, 3, 509-531. I. M. Martins, M. F. Barreiro, M. Coelho, A. E. Rodrigues, Chemical Engineering JournalA. Gonçalves, B. N. Estevinho, F. Rocha,Trends in Food Science & Technology

Final support from National Science Centre (NCN, Poland) Grant no. UMO

CHEMICAL

19

DITION OF MICROCAPSULES

, Justyna Kozlowska

Faculty of Chemistry, Department of Chemistry of Biomaterials and Cosmetics, University in Toruń

: microcapsules, collagen, retinyl palmitate, matrix, encapsulation

m, but the most common microcapsules which is surrounded by shell.Shell is made from solid

substance, but the core may be different substances such as: crystalline, adsorbent molecules, emulsions or smaller microcapsules. Active compounds or drugs often react easily with other

they may be sensitive to external factors. Closing them into a microcapsule protects them from pH, ultraviolet radiation, heat or oxidation. At the same time it improves the stability of compounds by preventing them of degradation reactions. Microencapsulation allows to mask the odor, which is very important for some medicines. Controlled release of substances closed in microcapsule after reaching right temperature and pH is also an important aspect. The most popular

polymer incompatibility and spray drying method. The coacervation method is based on the separation of phases in a solution of colloids or polymers which results with the formation of a minimum two liquid phases. In the coacervation

s core must be compatible with the encapsulating polymer and also insoluble in the coacervation environment.The aim of this study was to obtain and investigate a new materials for

he core was made of retinyl palmitate and was coated by poly(vinylalcohol). In the next step the microcapsules were incorporated into polymer matrices prepared from collagen which was isolated from fish scales (Esoxlucius) in our laboratory.

ices were crosslinked with EDC / NHS mixture. The structure and topography of microcapsules and matrices were observed by Scanning Electron Microscopy, using a camera and optical microscope. The mechanical properties of polymer matrices were tested, ATR spectra were made, swelling properties and degradation resistance were examined.

Wisniewska, K. Piechowicz, International Journal of

,, International Journal of Pharma and Bio

Chemical Engineering Journal, 2014, 245, 191–200. ,Trends in Food Science & Technology, 2016, 51, 76-87.

Final support from National Science Centre (NCN, Poland) Grant no. UMO-2016/21/D/ST8/01705 is gratefully

Keywords

carbonization of a grapheneprecursors were carbonized in the range of 600hard template, a binder and the temperature of carbonization significantly influenced on the surface area and the pore structure of the obtained graphenemethod let to obtaiof this study, we demonstrated that the obtained graphenethe adsorption of selected oligothiophenes: 2,2':5',2”2':5',2''chemical and physical properties of graphene and oligothiophene dyes in the form of hybrid system. Such a hybrid may offer a series of fascinating spectral properties of high application potent

oligothiophenes containing from one up to six heterocyclic units. The oligomers interacting with graphene layers were analyzed within the DFT formalism with inclFor the characterization of the obtained and lowflexible, lightweight, highhave potential applications in future opto

Bibliography: [1]

[2]

[3]

CHEMICAL SECTION

MODIFICATIONS OF THE GRAPHENE LAYERS WITHMOL

Piotr Kamedulski

Faculty of Chemistry, Department of Materials Chemistry, Adsorption and Catalysis, Nicolaus Copernicus University

Keywords: graphene, chemical activator, carbonization, adsorption, semiconducting oligom

In the first step of this paper we present results on the 3D functionalization of the graphene by carbonization of a graphene-based precursor in the presence of a hard templated (Naprecursors were carbonized in the range of 600hard template, a binder and the temperature of carbonization significantly influenced on the surface area and the pore structure of the obtained graphenemethod let to obtain mesoporous structures of increased surface area up to 269 mof this study, we demonstrated that the obtained graphenethe adsorption of selected oligothiophenes: 2,2':5',2”2':5',2'':5'',2'''-quaterthiophene and α-sexithiophene. In this we were intend to combine exceptional chemical and physical properties of graphene and oligothiophene dyes in the form of hybrid system. Such a hybrid may offer a series of fascinating spectral properties of high application potent

In the present study an introductory computational investigation was performed for small oligothiophenes containing from one up to six heterocyclic units. The oligomers interacting with graphene layers were analyzed within the DFT formalism with inclFor the characterization of the obtained materials were applied: elemental analysis, SEM, HRand low-temperature adsorption of nitrogen. flexible, lightweight, high-performance, and environmentally friendly materials. These materials can have potential applications in future opto-electronic devices [1

Bibliography: [1] M. Melucci, M. Durso, M. Zambianchi, E. Treossi, Z.

F. De Angelis, V. Palermo, J. Mater. Chem., 2012, 22, 18237[2] M.A. Loi, J. Gao, F. Cordella, P. Blondeau, E. Menna, B. Bartova, C. Hebert, S. L

C. Ambrosch-Draxl, Adv. Mater., 2010, 22, 1635-[3] T. Leydecker, D.T. Duong, A. Salleo, E. Orgiu, P. Samori, ACS Appl. Mater. Interfaces 2014, 6, 21248

ORAL PRESENTATION

GRAPHENE LAYERS WITH SMALL ORGANIC MOLECULES

Piotr Kamedulski, Jerzy Paweł Łukaszewicz

Faculty of Chemistry, Department of Materials Chemistry, Adsorption and Catalysis, Nicolaus Copernicus University

: graphene, chemical activator, carbonization, adsorption, semiconducting oligom

In the first step of this paper we present results on the 3D functionalization of the graphene by based precursor in the presence of a hard templated (Na

precursors were carbonized in the range of 600-800°C under the flow of nitrogen. The addition of the hard template, a binder and the temperature of carbonization significantly influenced on the surface area and the pore structure of the obtained graphene-based materials. The discovered synthesis

n mesoporous structures of increased surface area up to 269 m2/g. In the next step of this study, we demonstrated that the obtained graphene-based materials were very efficient towards the adsorption of selected oligothiophenes: 2,2':5',2”-terthiophene, 3,3'''

sexithiophene. In this we were intend to combine exceptional chemical and physical properties of graphene and oligothiophene dyes in the form of hybrid system. Such a hybrid may offer a series of fascinating spectral properties of high application potent

In the present study an introductory computational investigation was performed for small oligothiophenes containing from one up to six heterocyclic units. The oligomers interacting with graphene layers were analyzed within the DFT formalism with inclusion of dispersion corrections.

materials were applied: elemental analysis, SEM, HRtemperature adsorption of nitrogen. The proposed method for obtained materials leads to

rformance, and environmentally friendly materials. These materials can electronic devices [1-3].

M. Melucci, M. Durso, M. Zambianchi, E. Treossi, Z.-Y. Xia, I. Manet, G. Giambastiani, L. Ortolani, V. Morandi, De Angelis, V. Palermo, J. Mater. Chem., 2012, 22, 18237-18243.

M.A. Loi, J. Gao, F. Cordella, P. Blondeau, E. Menna, B. Bartova, C. Hebert, S. Lazar, G.A. Botton, M. Milko, -1639.

ker, D.T. Duong, A. Salleo, E. Orgiu, P. Samori, ACS Appl. Mater. Interfaces 2014, 6, 21248-

PRESENTATION

SMALL ORGANIC

Faculty of Chemistry, Department of Materials Chemistry, Adsorption and Catalysis,

: graphene, chemical activator, carbonization, adsorption, semiconducting oligomer

In the first step of this paper we present results on the 3D functionalization of the graphene by based precursor in the presence of a hard templated (Na2CO3). The

addition of the hard template, a binder and the temperature of carbonization significantly influenced on the surface

The discovered synthesis /g. In the next step

based materials were very efficient towards 3'''-dihexyl-2,

sexithiophene. In this we were intend to combine exceptional chemical and physical properties of graphene and oligothiophene dyes in the form of hybrid system. Such a hybrid may offer a series of fascinating spectral properties of high application potential.

In the present study an introductory computational investigation was performed for small oligothiophenes containing from one up to six heterocyclic units. The oligomers interacting with

usion of dispersion corrections. materials were applied: elemental analysis, SEM, HR-TEM

The proposed method for obtained materials leads to rformance, and environmentally friendly materials. These materials can

ni, V. Morandi,

azar, G.A. Botton, M. Milko,

-21255.

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

20

THE CHEMICAL DERIVATIZATION IN HIGH PERFORMANCE LIQUID CHROMATOGRAPHY

Adrianna Kamińska, Patrycja Olejarz, Kamila Borowczyk, Grażyna Chwatko

Faculty of Chemistry, Department of Environmental Chemistry, University of Łódź

Keywords: chromophoric group, derivatization, derivatization reagent, fluophoric group, high performance liquid chromatography

Many of biologically active compounds do not possess in their structure a moiety compatible with an adequate detector. Derivatization in most cases can solve the problem. The chemical modification of analyte with the adequate derivatization reagent allows to increase sample volatility, to improve selectivity, to increase stability and detectability. Depending on analytical method, derivatization reaction can be carried out in pre-, post- and on-column mode. In the pre-column derivatization, the reaction is generally performed manually in vials before HPLC injection or in some cases automatically, and then the reaction products are separated and detected. In the post-column derivatization, the reaction is performed automatically by adding the derivatization reagent after separation but before detection. The third mode is based on reaction, which simultaneously proceeds with column separation [1, 2].

There are several methods for derivatization of analytes. Derivatization reagent can react with various functional groups occurring in the examined molecules such as amino, sulfhydryl, hydroxyl and carboxyl groups. This chemical modification transforms the compounds into derivatives, which obtain necessary properties required for chromatographic separation and accurate analysis [3].

The derivatization methods combined with HPLC are a powerful tool in the modern analytical laboratories. Chemical derivatization of the analyte operating with commonly available derivatization reagents can be easily automated to eliminate the errors and to lead to increase in the reproducibility of results. Numerous advantages and a wide range of derivatization reagents guarantee the continuous development of derivatization techniques as well as give a chance to implement new and improved procedures for determining various analytes. Bibliography: [1] J. Kalembkiewicz, T. Ruman, Wiad. Chem., 2004, 58, 263-276. [2] J. Namieśnik, W. Chrzanowski, P. Szpinek, Nowe horyzonty i wyzwania w analityce i monitoringu środowiskowym,

CEEAM, Gdańsk 2003, 493-525. [3] A. Kamińska, M. J. Krawczyk, G. Chwatko, Wiad. Chem., 2016, 70, 787-817.

ENHANCING THE EFFICIENCY OF TRANSITION METAL OXIDES IN SOOT COMBUSTION BY MOBILE ACTIVITY PROMOTORS

W. Kaspera, T. Jakubek, P. Legutko, A. Kotarba

Faculty of Chemistry, Jagiellonian University in Cracow

Keywords: soot combustion, heterogeneous catalysis

Particulate matter (PM) emission is one of the most current problemsof urban areas. It consists mostly of soot, which is considered very harmful for human health and the environment. Among many soot sources, diesel engines are the most significant. The most efficient solution for soot emission from diesel engines reduction are diesel particulate filters (DPF) [1]. In such filters, the fumes are forced to pass through the walls of the ceramic support resulting in soot accumulation. Then the accumulated soot can be combusted as a result of the temporary increase of the temperature, or the filter can be continuously regenerated in the standard engine working conditions by application of the oxidizing catalyst deposited on the walls of the filter.

Active phases in catalytic diesel particulate filters (cDPF) used commercially are based on noble metals like platinum or palladium. As a result of the high cost of such materials, there is an intensive pursuit for a substitute, that would follow the so called “3E rule”, according to which the catalyst should be Effective, Economic, and Environmentally friendly. Transition metal oxides (like spinels, perovskites, hydrotalcites) are one of the classes of the materials that fulfill these criteria therefore they are being intensively investigated in the field of soot combustion catalysis.

The high activity of transition metal oxides is usually connected with very mobile lattice oxygen (when oxidation proceeds through Mars van Krevelen mechanism) or active oxygen surface species formed as a result of molecular O2 chemisorption on the catalyst surface. Although such materials may be very efficient in oxidation of soot being in close, so called tight contact, the majority of them do not preserve their activity in the real conditions, where the number of soot-catalyst contact points is much lower. One of the proposed solutions for this phenomenon is to use mobile activity promoters, which would work without direct soot-catalyst contact:

It has been shown, that soot reacts with NO2 in much lower temperatures than with molecular O2. Since nitrogen(II) oxide is present in diesel exhaust gases, nitrogen(IV) oxide which may be formed in diesel operating condition in the presence of proper oxidizing catalysts may be used as an active oxygen carrier. Preliminary results show, that some of the transition metal oxides (mainly those based on manganese) exhibit high efficiency in NO oxidation reaction.

Alkali doping is a very common way of enhancing the catalytic activity in soot oxidation [2]. One of the proposed explanations of the phenomena is based on the very high mobility of alkali species (atoms, cations, Rydberg clusters). According to this hypothesis, the alkali species desorb from the catalyst surface and interact with soot particles increasing their susceptibility for oxidation with molecular O2.

Since the two mentioned mobile activity promoters operates through different mechanism, there is a possibility for designing the composite catalyst in a way resulting in the synergic effect leading to the very high activity in soot oxidation. Bibliography: [1] Fino D., Bensaid S., Piumetti M., Russo N., Applied Catalysis A: General, 2016, volume 509, pages 75-96. [2] H. An, C. Kilroy, P.J. McGinn,Catalysis Today, 2004, volume 98, pages 423-429

ORAL PRESENTATION CHEMICAL SECTION ORAL PRESENTATION

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SYNTHESIS OF FUNCTIONALIZED DISILAZANES

Joanna Kaźmierczak, Krzysztof Kuciński, Grzegorz Hreczycho

Faculty of Chemistry, Department of Technology and Synthesis of Inorganic Polymers, Adam Mickiewicz University in Poznań

Keywords: disilazanes, hydrosilylation, platinum, Karstedt

The presentation focuses on the convenient catalytic approach to the synthesis of novel symmetrical and unsymmetrical functionalized disilazanes with substituents of varying nature as well as the potential application of new disilazane derivatives.

Disilazanes are a class of organosilicon compounds containing Si-N-Si bond and have received considerable attention due to their application as silylating agents. They are used in the silylation of alcohols, polyols, phenols, silanols and hydroxyl groups on the surface of various organic and inorganic materials. In particular, the modification of silica using disilazanes is widely applicable because this method allows to introduce various functional groups on the surface of silica under mild conditions.

The aim of the presentation is to demonstrate the highly effective and selective method for the synthesis of functionalized disilazanes through the Pt-catalyzed hydrosilylation reaction of easily accessible 1,1,3,3-tetramethyldisilazane with a variety of unsaturated substrates in the presence of Karstedt catalyst.[1] The use of Karstedt catalyst in the synthesis of mono-substituted as well as bi-functionalized disilazanes turns out to be a very successful synthetic pathway. The advantages include mild reaction conditions, relatively short time of reactions, small amount of the catalyst, good yields of isolated products, as well as high selectivity and efficiency. This methodology tolerates all manner of functional groups (e.g., esters, ethers, halogens, amines, etc.) and can be applied to a wide range of unsaturated compounds, e.g. various boron- and germanium-containing olefins. This is a favourable synthetic route for the synthesis of boron- and germanium-functionalized disilazanes.[2] Such multi-element compounds are very beneficial and useful in material chemistry and can be used as silylating agents to introduce functional groups (e.g., substituents containing boron and/or germanium atoms) e.g. on the surface of silica. They seem to be particularly attractive in modification and functionalization of different organic and inorganic materials and can be further applied in many fields of material chemistry.

Bibliography: [1] K. Kuciński, J. Szudkowska-Frątczak, G. Hreczycho, Chem. Eur. J., 2016, 22, 13046 – 13049. [2] J.Kaźmierczak, K. Kuciński, J. Szudkowska-Frątczak, G. Hreczycho, Eur. J. Inorg. Chem. 2017, 2017, 1888–1891.

SYNTHESIS OF THE NEW CHIRAL DIPHOSPHINE LIGANDS FROM α-PINENE

Anna Kmieciak, Marek Krzemiński

Nicolaus Copernicus University, Faculty of Chemistry, Gagarina St. 7, 87-100 Toruń, Poland

Keywords: phosphine, chiral ligand, pinene

One of the main aims of modern organic synthesis is the preparation of the compounds in optically pure form. In stereocontrolled synthesis, the most widely used reactions are these catalyzed by transition metals with chiral ligands. Chiral diphosphine ligands are the most important class of ligands for the transition metal catalysis. Preparation of the chiral diphosphine ligands, which have many chiral centers is often expensive and time consuming. Therefore, it is important to search for the new structures of this class, as well as the new methods for their synthesis.

Diphosphine ligands with a rigid cyclic structure are an important class of currently used chiral phosphine ligands. In our research, we synthesized the new chiral 1,3-diphosphines derived from verbanone and α-pinene through exo-epoxides. Diphosphines were prepared in optically pure form and they were applied as ligands in transition metal catalyzed asymmetric syntheses.

Bibliography: [1] W. S. Knowles, Acc. Chem. Res. 1983, 16, 106; [2] H. Brunner, W. Pieronczyk, Angew. Chem. Int. Ed. 1979, 18, 620; [3] M. Lauer, O. Samuel, H. B. Kagan, J. Organometall. Chem. 1979, 177, 309; [4] S. Demay, F. Volant, P. Knochel, Angew. Chem. Int. Ed., 2001, 40, 1235; [5] A. Gavryushin, K. Polborn, P. Knochel,

Tetrahedron: Asymmetry, 2004, 15, 2279.

Acknowledgments This work was financially supported by the NCN Program 2012/07/N/ST5/02194

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PHTHALOCYANINE IN HYBRID PHOTOCATALYST MPC-TIO2 FOR DEGRADATION 4-NITROPHENOL IN WATER

Karina Kocot, Gabriela Dyrda

Faculty of Chemistry, Department of General Chemistry, University of Opole Keywords: phthalocyanine, 4-nitrophenol, titanium dioxide, photocatalysis

At present, environmental pollution is a serious problem, particularly pollution of ground- and surface water. Phenols are the most important contributors to this situation, especially 4-nitrophenol (4-NP). Phenols are aromatic compounds that exhibit toxicity, mutagenicity and carcinogenicity towards living organisms, even in small quantities.

There are methods causing degradation of organic compounds into water and carbon dioxide. One of them is heterogeneous photocatalysis, in particular photocatalytic oxidation using semiconductor as catalysts, e.g. titanium dioxide (TiO2).

Among its polymorphic variants, particularly noteworthy is anatase which, depending on the size of the seeds, is known in two forms: microanatase and nanoanatase. It is commonly believed that the more active form is the nano form. It has been found that the effectiveness of titanium dioxide can be improved if a light-absorbing dye is introduced into the system. A hybrid system is created, in which TiO2 is covered with a dye layer.

Suitable dyes are phthalocyanines, i.e. synthetic derivatives of porphyrins. These are macrocyclic compounds composed of four interconnected benzopyrrole rings, forming numerous complexes, mainly with metals. Depending on the type and number of substituents, they can form more or less complex molecular systems. These compounds exist in a form of monophthalocyanines, containing in their structure one ring of phthalocyanine and a metal atom, but there are also known as diphthalocyanines composed of two macrorings, coordinated by one metal atom, called sandwich complexes. A classic example of such phthalocyanines is the lanthanide ion complexes. Anatase impregnated with lanthanide sandwich complexes is a very good photocatalyst that can be used for photodegradation of phenols.

The photodegradation of 4-nitrophenol in aqueous solution was investigated in the presence of photocatalysts: TiO2, TiO2-ZcPc, TiO2-GdPc2, TiO2-YbPc2. Within the presence of catalyst, 4-NP does not degrade. The use of pure TiO2 accelerated the process, while the decomposition of 4-NP was the fastest in the presence of TiO2-LnPc2 hybrid photocatalysts. It was found, that the monophthalocyanine catalyst TiO2-ZnPc did not increase the photooxidation rate compared to pure TiO2. Bibliography: [1] Słota R., Dyrda G., Szczegot K., Mele G., Pio I., Photochemical&PhotobiologicalSciences, 2011, 10, 361-366. [2] Słota R., Dyrda G., Galbas M., Mele G., Chemik, 2014, 68, 388-390.

ASYMMETRIC DIETHYLZINC ADDITIONS TO ALDEHYDES CATALYZED BY TERPENIC AMINO ALCOHOLS

Monika Kołodziej, Marek Krzemiński

Department of Organic Chemistry, Faculty of Chemistry, Nicolaus Copernicus University,

7 Gagarina Street, 87-100 Torun, Poland Keywords: asymmetric additions, organozinc compounds, amino alcohols

Modern organic synthesis focuses on development of catalytic, asymmetric reactions, which lead to compounds of high enantiomeric purity.[1]One of those reactions is enantioselective organometallic compound addition to aldehydes. It leads to optically active secondary alcohols. Chiral, secondary alcohols are components of many natural products, biologically active and intermediate for syntheses of many functional groups. Among organometallicreagents, organozinc additions, especially diethylzinc, are included to the most effective method of synthesis of secondary alcohols.[2]Since Oguni and Omi`s report on diethylzinc addition to benzaldehyde in the presence of (S)–leucinol an interest of this reaction has grown dramatically. Nowadays there is synthesized a number of optically active, structurally diversified amino alcohols, which are successfully utilized in diethylzinc additions. Among established chiral ligands monoterpenes derivatives are significant, from 3-exo-dimethyloaminoisoborneoldeveloped byNoyori[3], by apopinane derivatives[4], to aziridyne derivatives of alcohols received from limonene oxide.[5]

In presenting studies amino alcohols received from 3– karene and α–pinene with tertiary amine group were synthesized. These compounds were utilized in diethylzinc additions to aromatic aldehydes, cinnamon aldehyde and alkyl aldehydes as catalysts. To define enantiomeric excess of received alcohols, racemic, model samples of 1–substitute–1–propanoles were prepared in ethylmagnesium bromide additions to aldehydes. Enantiomers of those racemates were separated on chiral columns GC and HPLC. It was tested if a structure of amino alcohols and substituents of aldehydes has influence on enantioselectivity of additions.

Bibliography: [1] Catalytic Asymmetric Synthesis, 2nd Edition, I. Ojima Ed., J. Wiley, New York 2000; [2] L. Pu, H.-B. Yu, Chem. Rev.2001, 101, 757-824; [3] M. Kitamura, S. Suga, K.Kawai, R.Noyori, J. Am. Chem. Soc.1986, 108, 6071-6072; [4] C. M. Binder, A. Bautista, M. Zaidlewicz, M. P. Krzemiński, A. Oliver, B. Singaram, J. Org. Chem.2009, 74, 2337-

2343; [5] M. Rachwalski, Tetrahedron: Asymmetry2014, 25, 219–223.

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THE NANOCRYSTALLINE IRON NITRIDING – NUMERICAL MODELLING OF GAS SOLID REACTION

Agata Komorowska, Paweł Adamski, Marlena Nadziejko, Adam Sarnecki

Faculty of Chemical Technology and Engineering, WestPomeranian University of Technology,

Szczecin Keywords: nanocrystalline iron, nitriding, grain size, numerical simulations, gas-solid reaction

The gas-solid reaction is usually a complex process, consisted of different stages: external mass

transfer, pore diffusion, adsorption, chemical reaction, desorption of products, product pore diffusion and external mass transfer. There are a lot models of gas–solid reactions described in literature. Many of them are applied to analyse behaviour of coarse-grained materials. The nanocrystalline substances behave differently and applicability of a given model must be always proven.The presentation considers the nitriding of nanocrystalline iron under ammonia-hydrogen atmospheres as a gas-solid reaction. An evolution of nanoparticles during nitriding process was analysed in light of three models: 1.The Shrinking Core Model – SCM [1], The Crackling Core Model – CCM [2], The Adsorption Range Model – ARM [3].

A test sample was generated numerically and the simulations of nanomaterials transformations were performed.The virtual sets of nanocrystalline particles was characterized by a log-normally distributed grain size with different mean value of particle size andits standard deviation. The variation of the mean size of crystallites was tested as a function of conversion during the nitriding of nanocrystalline iron. The results were compared to the data given in literature [4].

The accurate empirical determination of the mean size of iron nanocrystallites for several conversion degrees gives the possibility to indicate a feasibility of the considered models. The differences between the sizes calculated for the shrinking core and cracking core models are relatively small. However, the results based on Adsorption Range Model are distinctly different from the other two functions. The comparison of empirical data [4] with calculations led us to the conclusion that the adsorption range model was the most suitable one to describe the considered system. Moreover the analysis indicated that with the increasing nitriding potential in the reaction space the iron nanocrystallites reacted in a sequence according to their size. Transformation started with the biggest particles and the smallest particles required the highest nitriding potential.

Bibliography: [1] S. Yagi i D. Kunii, Fifth Symposium (International) on Combustion, Reinhold, New York1955, 231. [2] J. Y. Park i O. Levenspiel, Chemical Engineering Science, 1975, 30, 1207-1214 [3] W. Arabczyk i R. Wróbel, Solid State Phenomena 2003,94, 185-188 [4] D. Moszyński, I. Moszyńska i W. Arabczyk, Applied Physics Letters 2013, 103, 253108

ANALYSIS OF TYROSINE AND TRYPTOPHAN IN FOOD SAMPLES BY CAPILLARY ISOTACHOPHORESIS

Sylwia Kowalska, Aneta Jastrzębska, Kamila Stasiewicz, Edward Szłyk

Faculty of Chemistry, Chair of Analytical Chemistry and Applied Spectroscopy,

Nicolaus Copernicus University in Toruń Keywords: tyrosine, tryptophan, capillary isotachophoresis, food product analysis

Amino acids, i.e. tyrosine (Tyr) and tryptophan (Trp) are necessary for the proper functioning of the nervous system. Their metabolic transformations are carried out in the central nervous system, resulting in formation of serotonin, dopamine and noradrenaline [1].

A disordered proportion of the discussed ingredients in the daily diet, in particular their deficiencies may affect producing a sufficient amount of the neurotransmitters followed by emotional problems, psychical disorders, a lack of memory and concentration and depression [2]. Due to the impact of tyrosine and tryptophan on our organism it is necessary to control their concentration in the different groups of the food.

High-performance liquid chromatography (HPLC) is most used for determination the discussed food compounds. High-performance liquid chromatography (HPLC) is most used for determination the discussed food compounds.

However, in order to improve selectivity and sensitivity of the determinations, complicated derivatization stage is necessary and most of applied reagents are harmful to the environment and humans. Therefore, there is stil