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XIIIth International Conferenceon
Molecular Spectroscopy
Under the auspices of
and
The European Academy of Sciences, Arts and Humanities
FROM MOLECULES
TO MOLECULAR MATERIALS,
BIOLOGICAL MOLECULAR SYSTEMS AND
NANOSTRUCTURES
Organized by
for Biotechnology: Leading National Research Center (KNOW)
Wroclaw Branch of the Polish Academy of Sciences
Institute of Low Temperature and Structure Research of the Polish Academy of Sciences
International Advisory Committee
J.-M. Lehn (Strasbourg) - Honorary President
The 1987 Nobel Prize Winner in Chemistry
CNR. Rao (Bangalore) - President
J-P. Connerade (London)- Vice President
J. Lipkowski (Warsaw) - Vice President
D. Xue (Changchun) - Vice President
A. J. Barnes (Salford), B. Galabov (Sofia), R. Fausto (Coimbra), T. A. Ford (Durban),
M. Handke (Cracow),
I. Ledoux-
. G. Tokhadze (St. Petersburg),
Scientific Committee
- Chairman
M. Handke (Cracow) - Vice Chairman
- Vice Chairman
- Secretary
J. Baran (Wroc
Local Organizing Committee
A. Mickiewicz - Chairperson
M. Drozd - Co-Chairperson
J. Baran, D. Hreniak, M. M. Ilczyszyn, M. K. Marchewka, S. Tomczak, M. Wierzejewska
Sponsored by
Polish Academy of Sciences
The Polish Copper Fundation-KGHM
for Biotechnology: The Leading National Research Center (KNOW)
SHIM-POL A.M. BORZYMOWSKI E. Borzymowska-Reszka, A. Reszka SP.J.
Ranishaw Sp. z o. o.
PROGRAMME
9th September (Wednesday)
1830 - Get-Together Party
10th September (Thursday)
9 00 - 9 20Opening ceremony: H. Ratajczak
Chairperson: J. Lipkowski
9 20 - 10 05
L1J.- M. Lehn
Perspectives in Chemistry: From Supramolecular
Chemistry Towards Adaptive Chemistry.
10 10 - 10 55
L2B. Silvi
Celebration the 99th Anniversary of Lewis's Theory.
1100 1120 Coffee break
UNESCO YEAR - 2015 of LIGHT
Chairperson: C.N.R. Rao
11 25 - 12 00
L3J.- P. Connerade
Light in the Service of Mankind.
12 05 - 12 30
L4A. Glibota
Light Between Arts and Sciences.
12 35 - 13 00
L5W.
Laser Induced White Emission from Graphene Ceramics.
1305 1430 Lunch
5
Chairperson: M. Handke
14 30 - 15 15
L6C.N.R. Rao
Generation of Hydrogen by Photochemical and
Thermochemical Splitting of Water.
15 20 - 15 55
L7G. Zerbi
The Puzzling Chemistry of Carbonaceous Particles: the
Contribution by Molecular Dynamics and Spectroscopy.
16 00 - 16 35
L8I. Ledoux-Rak
Multiscale Molecular Engineering for Nonlinear
Molecular Photonics.
1640 1710 Coffee break
Chairperson: R. Fausto
17 15 - 17 50
L9A. Barnes
Matrix Effects on Hydrogen-Bonded Complexes Trapped in
Low-Temperature Matrices.
17 55 - 18 30
L10T. Ford
Homo- and Hetero-Dimers of the Methyl Halides. Singly-,
Doubly- or Non-Hydrogen-Bonded?
18 35 - 19 10
L11B. Galabov
Application of Spectroscopic and Theoretical Methods in
Elucidating Reaction Mechanisms.
6
11th September (Friday)
Chairperson: A. J. Barnes
9 00 - 9 35
L12M. Handke
Vibrational Spectra of Si-O Bond in Silicates and Siloxanes.
9 40 - 10 15
L13D. Xue
In Situ IR Spectroscopy of Crystallization: Mesoscale
Identification of Symmetry Variations From Molecules to
Molecular Materials.
10 20 - 10 55
L14R. Fausto
Hunting Elusive Molecular Species: an Overland Journey to
the Highlands.
1100 1115 Coffee break
Chairperson: B. Silvi
11 15 - 11 50
L15A. Sobolewski
Photovoltaics Without p-n Junction: Computational Study of
Ferroelectric Organic Systems.
11 55 - 12 30
L16 Four Decades Later Has C60 Met its Noble Expectations?
12 35 - 13 10
L17H. Burrows
Theoretical and Experimental Studies of Excited and
Charged States of Fluorene Based Conjugated
Polymers and Copolymers.
1315 - 1430 Lunch
7
Chairperson: G. Zerbi
14 30 - 15 00
L18J. Durig
Recent Advances in Microwave, Raman and Terahertz
spectroscopy.15 05 - 15 35
L19M. Czarnecki
Near-Infrared Spectroscopy as a Tool for Molecular
Structure and Interaction Studies.
15 40 - 16 10
L20I. Matulkova
Study of Phase Transformation by Vibrational Spectroscopy
and X-ray Diffraction in Crystals for NLO Applications.
16 15 - 16 40
L21A.M. Yaremko
Investigation of Phonon Spectra of Thin Nanosized MoS2
Layer Crystals: Theory and Experiment.
1650 1705 Coffee break
Chairperson:
17 05 - 17 25
L22A. Nowicka
Characterization of Acrylate/ Carbon
Nanotubes Composites.
17 30 - 17 50
L23L. Kurpaska
In-Situ Phase and Stress Analysis of High Temperature
Zirconia Scale Developed on Pure Zirconium and Zr-Nb1%
Alloy as Studied by Raman Spectroscopy.
17 55 - 18 15
L24K. Brylewska
Quantitative Aspects of the Identification of Fe(II) Moieties
in Zeolites ZSM-5 with Various Pore Hierarchy.
18 20 - 18 40
L25A. Atac
The Quantum Chemical Calculations by Combined Most
Common Spectroscopic Techniques for Pentafluoropehol.
EVENING WALK with GUIDE
8
12th September (Saturday)
Chairperson: J.-M. Lehn
09 00 - 9 40
L26J. Lipkowski
Hydrogen Bonds in Hydrophobic Hydration.
9 45 - 10 20
L27A. Sokalski
Particular Role of Electrostatic Interactions in Modeling
Molecular Materials.
10 25 - 11 00
L28S. Jurga
Structure and Dynamics of Diblock Copolymers in the Bulk
and Thin Films.
1105 1120 Coffee break
Chairperson: H. M. Heise
11 20 - 11 55
L29 How to Recognize Endothelium from Other Isolated Liver
Cells by Means of Confocal Raman Spectroscopy?
12 00 - 12 30
L30 Corroles as Potential Agents for Optoelectronics and
Photodynamic Therapy.
12 35 - 13 00
L31M. Wierzejewska
Photochemistry of the Interstellar Molecule HNCS.
1305 1430 Lunch
9
Chairperson: T. Ford
14 30 - 14 50
L32A.
Raman Imaging Techniques Open New Horizons.
14 55 - 15 15
L33T. Karthick
Studies on Structural Insights of Anti-Cancer Drug
15 20 - 15 40
L34M.A. Cipiloglu
Effect of Halogenation on the Bioactivity and Spectroscopic
Features in Transition Metal Complexes of Pharmaceutical
Ligands: The Case of Co2(INO)3X4 Complexes.
15 45 - 16 05
L35M. Karabacak
Spectral and Electronic Features of 2-Bromoethylbenzene.
1610 1630 Coffee break
Chairperson: H. Burrows
16 30 - 17 00
L36J. Legendziewicz
Photophysical and Theoretical Studies of Structure and
Spectroscopic Behaviour of Axially Substituted Yb(III)
Mono-Phthalocyanines in Different Media.
17 05 - 17 35
L37Cz. Paluszkiewicz
Investigation of Cataractous Lenses by Vibrational
Microspetroscopy.
17 40 - 18 15
L38H.M. Heise
Blood Glucose Monitoring Based on Micro-Dialysis and
Infrared Spectrometry as Reliable Diabetes Technology: Can
External-Cavity Quantum Cascade Lasers Replace FTIR-
Spectrometers?
1820- 1830 Closing Ceremony: H. Ratajczak
2000 Conference Dinner
10
LECTURES
L1 Perspectives in Chemistry: From Supramolecular Chemistry Towards
Adaptive Chemistry.
Jean-Marie Lehn
L2 Celebration the 99th Anniversary of Lewis's Theory.
Bernard Silvi
L3 Light in the Service of Mankind.
J.-P. Connerade
L4 Light Between Arts and Sciences.
Ante Glibota
L5 Laser Induced White Emission from Graphene Ceramics.
, , , , ,
Dariusz Hreniak
L6 Generation of Hydrogen by Photochemical and Thermochemical Splitting of Water.
CNR. Rao
L7 The Puzzling Chemistry of Carbonaceous Particles: the Contribution by Molecular
Dynamics and Spectroscopy.
Giuseppe Zerbi
L8 Multiscale Molecular Engineering for Nonlinear Molecular Photonics.
Isabelle Ledoux-Rak, Joseph Zyss
L9 Matrix Effects on Hydrogen-Bonded Complexes Trapped in Low-Temperature Matrices.
Austin Barnes, Zofia Mielke
L10 Homo- and Hetero-Dimers of the Methyl Halides. Singly-, Doubly- or Non-Hydrogen-
Bonded?
Ponnadurai Ramasami, Thomas Ford
L11 Application of Spectroscopic and Theoretical Methods in Elucidating
Reaction Mechanisms.
B. Galabov
L12 Vibrational Spectra of Si-O Bond in Silicates and Siloxanes.
L13 In Situ IR Spectroscopy of Crystallization: Mesoscale Identification of Symmetry
Variations From Molecules to Molecular Materials.
Dongfeng Xue, Congting Sun, Henryk Ratajczak
L14 Hunting Elusive Molecular Species: an Overland Journey to the Highlands.
Rui Fausto
13
L15 Photovoltaics Without p-n Junction: Computational Study of Ferroelectric Organic
Systems.
Andrzej Sobolewski
L16 Four Decades Later Has C60 Met its Noble Expectations?
Jerzy Leszczynski
L17 Theoretical and Experimental Studies of Excited and Charged States of Fluorene Based
Conjugated Polymers and Copolymers.
Hugh D. Burrows
L18 Recent Advances in Microwave, Raman and Terahertz spectroscopy.
James Durig, Bhushan Deodhar
L19 Near-Infrared Spectroscopy as a Tool for Molecular Structure and Interaction Studies.
L20 Study of Phase Transformation by Vibrational Spectroscopy and X-ray Diffraction in
Crystals for NLO Applications.
, , ,
L21 Investigation of Phonon Spectra of Thin Nanosized MoS2 Layer Crystals: Theory and
Experiment.
Anatoliy Yaremko, Volodymyr Yukhymchuk, Yuriy Romanjuk, Jan Baran, Henryk Ratajczak
L22 Characterization of Acrylate/ Carbon Nanotubes Composites.
Ariadna Nowicka, , Marek Weiss, ,
L23 In-Situ Phase and Stress Analysis of High Temperature Zirconia Scale Developed on
Pure Zirconium and Zr-Nb1% Alloy as Studied by Raman Spectroscopy.
, , Renata Jadach, Marta Gapinska, Maciej Sitarz,
Jean-Luc Grosseau-Poussard
L24 Quantitative Aspects of the Identification of Fe(II) Moieties in Zeolites ZSM-5 with
Various Pore Hierarchy.
Kamila Brylewska, -Marek, Karolina Tarach
L25 The Quantum Chemical Calculations by Combined Most Common Spectroscopic
Techniques for Pentafluoropehol.
Ahmet Atac, Etem Kose, Mehmet Karabacak
L26 Hydrogen Bonds in Hydrophobic Hydration.
Janusz Lipkowski
L27 Particular Role of Electrostatic Interactions in Modeling Molecular Materials.
W. Andrzej Sokalski
L28 Structure and Dynamics of Diblock Copolymers in the Bulk and Thin Films.
Stefan Jurga
14
L29 How to Recognize Endothelium from Other Isolated Liver Cells by Means of Confocal
Raman Spectroscopy?
Kamila Kochan, , ,
L30 Corroles as Potential Agents for Optoelectronics and Photodynamic Therapy.
, Bartosz Bursa, ,
L31 Photochemistry of the Interstellar Molecule HNCS.
Maria Wierzejewska, Justyna Krupa, Iwona Kosendiak
L32 Raman Imaging Techniques Open New Horizons.
L33 Studies on Structural Insights of Anti-
Karthick Thangavel, Poonam Tandon, Parag Agarwal
L34 Effect of Halogenation on the Bioactivity and Spectroscopic Features in Transition Metal
Complexes of Pharmaceutical Ligands: The Case of Co2(INO)3X4 Complexes.
Mustafa Ali Cipiloglu, Fehmi Bardak, Ahmet Atac, Mehmet Karabacak
L35 Spectral and Electronic Features of 2-Bromoethylbenzene.
Mehmet Karabacak, Sibel Bilgili, Ahmet Atac
L36 Photophysical and Theoretical Studies of Structure and Spectroscopic Behaviour of
Axially Substituted Yb(III) Mono-Phthalocyanines in Different Media.
Yu. Gerasymchuk, L. Tomachynski, M. Guzik, A. Koll, , Y. Guyot, ,
G. Boulon, Janina Legendziewicz
L37 Investigation of Cataractous Lenses by Vibrational Microspetroscopy.
, P. Chaniecki, W.M. Kwiatek, , J. Adamczyk, M. Gajda,
-
L38 Blood Glucose Monitoring Based on Micro-Dialysis and Infrared Spectrometry as
Reliable Diabetes Technology: Can External-Cavity Quantum Cascade Lasers Replace
FTIR-Spectrometers?
H. Michael Heise, Thorsten Vahlsing, Sven Delbeck, Janpeter Budde, Dieter Ihrig,
Markus Grafen, Konstantinos Nalpantidis, Andreas Ostendorf
15
L1
Perspectives in Chemistry: From Supramolecular Chemistry Towards
Adaptive Chemistry
Jean-Marie Lehn
Supramolecular chemistry is actively exploring systems undergoing self-
organization, i.e. systems capable of spontaneously generating well-defined functional
supramolecular architectures by self-assembly from their components, on the basis of
the molecular information stored in the covalent framework of the components and read
out at the supramolecular level through specific non-covalent interactional algorithms,
thus behaving as programmed chemical systems.
Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability
of the interactions connecting the molecular components of a supramolecular entity and
the resulting ability of supramolecular species to exchange their components. The same
holds for molecular chemistry when the molecular entity contains covalent bonds that
may form and break reversibility, so as to allow a continuous change in constitution by
reorganization and exchange of building blocks. These features define a Constitutional
Dynamic Chemistry (CDC) covering both the molecular and supramolecular levels.
CDC introduces a paradigm shift with respect to constitutionally static chemistry. It
takes advantage of dynamic diversity to allow variation and selection and operates on
dynamic constitutional diversity in response to either internal or external factors to
achieve adaptation.
CDC generates networks of dynamically interconverting constituents, constitutional
dynamic networks, presenting agonistic and antagonistic relationships between their
constituents, that may respond to perturbations by physical stimuli or to chemical
effectors.
The implementation of these concepts points to the emergence of adaptive and
evolutive chemistry, towards systems of increasing complexity.
References
[1] Lehn, J.-M., Supramolecular Chemistry: Concepts and Perspectives, VCH Weinheim, 1995.
[2] Lehn, J.-M., Dynamic combinatorial chemistry and virtual combinatorial libraries, Chem. Eur. J.,
1999, 5, 2455.
[3] Lehn, J.-M., Programmed chemical systems : Multiple subprograms and multiple
processing/expression of molecular information, Chem. Eur. J., 2000, 6, 2097.
[4] Lehn, J.-M., Toward complex matter: Supramolecular chemistry and self-organization, Proc. Natl.
Acad. Sci. USA, 2002, 99, 4763.
[5] Lehn, J.-M., From supramolecular chemistry towards constitutional dynamic chemistry and adaptive chemistry, Chem. Soc. Rev., 2007, 36, 151.
[6] Lehn, J.-M., Chapter 1, in Constitutional Dynamic Chemistry, ed. M. Barboiu, Topics Curr. Chem,
2012, 322, 1-32.
[7] Lehn, J.-M., Perspectives in Chemistry Steps towards Complex Matter, Angew. Chem. Int. Ed.,
2013, 52, 2836-2850.
[8] Lehn, J.-M., Perspectives in Chemistry Aspects of Adaptive Chemistry and Materials, Angew.
Chem. Int. Ed., 2015, 54, 3276-3289.
17
L2
Celebrating the 99th anniversary of Lewis's Theory
Bernard Silvi
Sorbonne Universites, UPMC, Univ Paris 06, UMR 7616, Laboratoire de Chimie
Theorique, case courrier 137, 4 place Jussieu, F-75005 Paris, France,
e-mail: [email protected]
Lewis's valence theory has been published 99 years ago. It aims to explain the
structure of molecule and solids, it has been complemented by the mesomery concept of
Ingold a the VSEPR model enabling the interpretation of molecular geometries. The
Lewis's approach relies on the hypothesis that the electrons of a molecule are
distributed in different stable groups, the group of two playing an essential role. This
model which is remarkably simple and efficient is one of the basements of chemical
education. The electron localization function (ELF) approach to chemical bonding is
revisited as a tool to check the falsifiability of the Lewis's hypotheses. It is shown that the
boundaries of the ELF basins correspond to zero-flux surfaces of the local integrated
same spin pair probability enabling the determination of regions of the molecular space
which maximizes the opposite spin pair density and therefore groups of electrons. The
ELF yields a partition into core and valence basins which matches the Lewis's model.
The ELF population analysis provides a picture of the charge distribution which takes
into account the mesomery and therefore which describes the electron delocalization. The
organization of the basins around the atomic cores often complies with the VSEPR rules.
The behaviour of the ELF basins upon deformation of the nuclear frame sheds light onto
the reactivity and reaction mechanisms whereas the basin compressibilities provide
chemical explanations of pressure induced phase transitions.
18
L3
Light in the Service of Mankind
J.-P. Connerade
Faculty of Physical Sciences
Department of Physics
Imperial Collage London
London, Great Britain
Email: [email protected]
19
L4
Light Between Arts and Sciences
Ante Glibota
Historian of Art and Architecture, Vice-President of the European Academy of Sciences,
Arts and Humanities, 76 Bis Rue de Rennes, 75006 Paris France, mobil tel. + 33(0)
611 08 55 40; Email: [email protected]
Light, from the spiritual and symbolic systems, from that made by God on the
first day of Creation to its newest and highest technological and scientific expressions,
has a wide range of facets; its interactive and structural vocabulary paves the way for
the advent of a holistic learning process that shapes the creative psyche of multi linear
artists to help produce one resonant signification of scientific confines.
Light, as an electronic and kinetic perception, is also the quintessence of science,
as new insights can be gained from works of art, in the Hegelian sense of plastic arts,
of the four elements and light is its direct expression; indeed, light is veiled in the
mysterious visual ramifications of destruction and deconstruction and has become one
of the most powerful universal symbols.
The authors who made the most concrete contributions to our understanding of
light remind us that the puzzle of light is a triptych of spiritual, artistic and scientific
involvement; this theme has sparked the interest of men throughout the centuries and
civilizations, giving this passion for light its ultimate sense and fundamental poetic
meaning.
20
L5
Laser Induced White Emission from Graphene Ceramics
W. Strek, B. Cichy, L. Radominski+, P. Gluchowski, L. Marciniak, D. Hreniak
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
Wroclaw, Poland+Technical University of Wroclaw, Poland
The laser induced white emission (LIWE) from graphene ceramics was investigated.
The intense white broadband emission centred at 650 nm was measured. The LIW
emission was observed for a number of different excitation wavelengths from visible
(VIS) up to near infra-red (NIR) range. It was found that LIWL emission from graphene
ceramics was the threshold process that decreased with of incident photon energy of
laser beam.
exc = 975 nm. (b) The power
dependence of LIW emission under different excitation wavelengths.
It was found that LIW emission intensity increased nonlinearly with incident laser
power above the power threshold scaled with the power law PN. The order of the
process N decreased with the frequency of incident laser light. Temperature of the
sample was measured using nano- thermometers incrusted at the graphene ceramic
surface. The
975 nm, temperature of the sample was lower than 900 K and for excitation powers
lower than 1 W, the temperature was lower than 700 K. No temperature dependence of
LIWE intensity was found and LIW emission was also observed in the cryogenic
temperatures as low as 10 K. This result provides an unquestionable point that even the
sample is hot its temperature is still far too low to explain the emission according to the
black body theorem.. An origin of the multiphoton induced white emission in graphene
ceramic was discussed within the concept of multiphoton ionization leading to the
transient domain-like phase sp2 sp3 transition.
21
L6
Generation of Hydrogen by Photochemical and Thermochemical
Splitting of Water
C.N.R. Rao
J.Nehru Center for Advanced Research
Bangalore, India
22
L7
The Puzzling Chemistry of Carbonaceous Particles: the Contribution
by Molecular Dynamics and Spectroscopy
G.Zerbi
Politecnico di Milano; Dipartimento Chimica, Materiali e Ingegneria Chimica
In the past few years it has been demonstrated that inhalation of diesel exhaust particles
(DEP) or of carbonaceous particles in general (PM) represents a dangerous threat to
human health and to cultural heritage, when deposited on the surface of any work of art.
On the other hand nature offers a variety of carbonaceous materials which are
commonly used by industry (tires, filters, absorbers, pharmaceutical). The toxicity of
DEPM and PM has been ascribed to the fact that the combustion processes produce
carbonaceous/graphitic particles mixed with organic molecules most of which belong to
the class of polyaromatic molecules (PAH) some of which contain quinonic structures.
These molecules are able to catalyze the generation of oxygen superoxide radicals (O2
which produce reactive oxygen species (ROS), thus inducing an oxidative stress in
biological systems.
The request by basic and applied science is that to be able to carry out qualitative and
quantitative experiments in order to understand the relationship between chemical
composition, size of PM and DEPM particles and their capability of producing ROS.
Thanks to the collaboration with Prof. Muellen (Mainz) we had the opportunity to
develop an earlier basic study of the vibrational spectra and molecular dynamics of
several very large synthetic molecules as models of structurally clean and defect free
polyaromatics (PAH). The role in the RRS by the edges of the carbonaceous particles
was previously detected by us and by others. More recently with the collaboration of
Prof. Camatini (Milano Bicocca) we have moved into the study of the interactions of
PM with living cells. The analysis of the spectra is not straightforward . Since
Cytochome C (Cyt C) is a very suitable biosensor for the detection of oxygen
superoxide (based on the conversion of Fe+++ to Fe++ ) and its Raman spectrum is well
understood (Spiro) we have developed a Raman spectroscopic method to monitor the
reduction process of Cyt C in samples even at very small concentrations. The reactions
are generally activated by a suitable catalyst.
Our studies were concerned with multi-wavelength RR spectra of PM (dressed with
PAH) and of chemically pure graphite (HOPG), HOPG ball milled for 10 or 20hrs and
of nanocarbon. The kinetic constants of the reactions
turn out to be related to the average size of the Carbon particles even in pure
carbonaceous samples. The details of the results and the implications will be presented
and critically discussed.
23
L8
Multiscale Molecular Engineering for Nonlinear Molecular Photonics
Isabelle Ledoux-Rak and Joseph Zyss
Cachan, France
The emergence of Molecular Photonics at the cross-road of physics, chemistry and
device engineering has been triggered by an increasing demand in various fields such as
high bit rate telecommunications, sensors, bio-
structures and the exploitation of their functional and structural flexibility open-up
thoroughly renewed horizons in this domain.
Designing highly efficient molecules with optimised photonic properties remains a
major challenge after 50 years of continuous development, based on fruitful and
interdisciplinary cooperation between chemists and physicists. Such a molecular
engineering strategy for nonlinear optics (NLO) is related to a wide range of
applications such as frequency conversion of laser sources, high bandwidth electro-optic
devices, integrated optoelectronic components, sensors and nanosciences.
In the first part of this talk, the basic principles of Molecular Engineering for quadratic
nonlinear optics will be developed, with a special emphasis on metal complexes and
lanthanide derivatives, on nonlinear optical characterization methods and on the role of
molecular symmetry in the optimization of microscopic and macroscopic molecular
NLO responses. A few examples will illustrate the relevance of these molecular
structures.
In the second part, special attention will be paid at the new directions opened-up by
Nanophotonics, where nano-objects may display huge NLO responses with various
origins. Examples of self-organized dendrimers and nanocrystals will be presented, as
lecular species with highly promising
perspectives. Other highly nonlinear nano-objects are based on metallic nanoparticles,
to be discussed in relation with the growing interest to plasmonics.
Finally, we are going to provide a few perspectives of molecular photonics towards
device
given device is strongly conditioned by a large number of criteria among which the
magnitude of the optical response is not the unique one. Conversely, materials designed
to optimise several performance criteria simultaneously may trigger the development of
new device architectures adapted to these unique material properties. This continuous
feed-back between material and device optimization is one of the crucial aspects
favouring the emergence of innovative components and related systems.
24
L9
Matrix Effects on Hydrogen-Bonded Complexes Trapped in Low-
Temperature Matrices
Austin J. Barnes1*, Zofia Mielke2
1Materials & Physics Research Centre, University of Salford, Salford M5 4WT,
Great Britain2 0-
We have used the matrix isolation technique to study a wide variety of hydrogen-bonded
complexes over a period of more than 40 years. In comparison with gas phase studies,
the technique has obvious attractions in providing relatively narrow infrared absorption
bands with no rotational structure. Furthermore matrix spectra can be obtained for
complexes ranging from the very weak, where the concentration in the gas phase may be
too low to observe, to the very strong, where the components may react together in the
gas phase (e.g. ammonia hydrogen chloride). It has always been an assumption of
matrix isolation spectroscopy that the infrared spectra of molecules trapped in inert
matrices are to a good approximation the same as those in the gas phase. The same
assumption has generally been considered to be applicable to the spectra of hydrogen-
bonded complexes. However our studies of the strongly hydrogen-bonded amine-
hydrogen halide complexes demonstrated that for these systems the spectra were
extremely sensitive to the matrix environment.
There are several different possible matrix effects on hydrogen-bonded complexes
trapped in low-temperature matrices: hydrogen-bonded complexes may be stabilised
(compared with the gas phase) as a result of being trapped in a low-temperature matrix;
metastable hydrogen-bonded complexes may be trapped in matrices; the matrix may
influence the extent of proton transfer in a hydrogen-bonded complex; the matrix may
influence the structure of a hydrogen-bonded complex. Each of these possible effects
will be examined in turn using selected examples from the literature as well as our own
work.
25
L10
Homo- and Hetero-Dimers of the Methyl Halides. Singly- Doubly- or
non-Hydrogen-Bonded?
Ponnadurai Ramasami1 and Thomas A. Ford2
1Computational Chemistry Group, Department of Chemistry, University of
2School of Chemistry and Physics, University of KwaZulu-Natal, Westville Campus,
Private Bag X54001, Durban 4000, South Africa
Four homodimers and six heterodimers of the methyl halides, CH3X (X = F, Cl, Br, I),
have been examined by means of ab initio calculations at the second order level of
-Plesset perturbation theory and with an augmented correlation-consistent
polarized valence triple-zeta basis set. Three families of dimers have been found. All
four homodimers optimize as both cyclic doubly-hydrogen-bonded CH...X species and
as non-hydrogen-bonded van der Waals C...X aggregates. All six heterodimers also
belong to the cyclic doubly-bonded group; in addition, three of them are non-hydrogen-
bonded with C...X linkages, and the three containing CH3I are singly-bonded, with a
CH...I interaction. The properties normally regarded as distinguishing features
separating red-shifted from blue-shifted hydrogen bond interactions (CH bond length
changes, shifts of the CH stretching wavenumbers and the CH stretching band intensity
ratios) have been determined, and their variations with respect to the structures of the
adducts have been rationalized.
26
L11
Application of Spectroscopic and Theoretical Methods in Elucidating
Reaction Mechanisms
Boris Galabov
Department of Chemistry and Pharmacy, University of Sofia,
Sofia 1164, Bulgaria
Application of theoretical quantum chemistry methods have become an
invaluable approach in evaluating fine details of chemical reaction pathways.
Nevertheless, the outcomes of computational modeling may depend on the level of
theory applied, how the reaction medium is simulated, and other factors. Additionally,
multiple pathways are possible for many processes and theory cannot always resolve
satisfactorily which mechanism dominates. On the experimental side, spectroscopy
has proved the method of choice in kinetic studies. In favorable cases, spectroscopic
methods may also provide information on key reaction intermediates. In this talk, the
combined application of quantum chemical modeling and spectroscopic (IR, UV,
NMR) methods in evaluating the mechanisms and quantifying reactivity for several
organic reactions will be discussed. The following organic reactions are considered:
aminolysis of esters, aminolysis of carbamates, alkaline hydrolysis of amides, SN2
reactions, and electrophilic aromatic substitution (halogenation, nitration).
References
1. S. Ilieva, D. Nalbantova, B. Hadjieva, B. Galabov, J. Org. Chem. 78 (2013) 6440.
2. B. Galabov, G. Koleva, S. Simova, B. Hadjieva, H. F. Schaefer, P. v. R. Schleyer, Proc. Natl. Acad. Sci. USA 111 (2014) 10067.
3. B. Galabov, G. Koleva, J. Kong, H. F. Schaefer, P. v. R. Schleyer, Eur. J. Org. Chem. 31 (2014)
6918.
4. J. Kong, B. Galabov, G. Koleva, J. J. Zou, H. F. Schaefer, P. v. R. Schleyer, Angew. Chem. Int.
Ed., 50 (2011) 6809.
5. B. Galabov, V. Nikolova, J. J. Wilke, H. F. Schaefer III, W. D. Allen, J. Am. Chem. Soc. 130
(2008) 9887.
27
L12
Vibrational Spectra of Si-O Bond in Silicates and Siloxanes
AGH University of Science and Technology; Faculty of Materials Science and
Ceramics; Al. Mickiewicza 30, 30-
The Si-O bond is the most abundant chemical bond in inorganic nature, it dominates
In the
crystalline or amorphous silicates structure, the SiO bond occurs in the form of SiO4
tetrahedra and can form complex anions or networks of connected tetrahedra e.g. in
various structures of SiO2. The second large group of chemical compounds based on Si-
O bond are siloxanes that do not occur in nature at all.
Both groups of compounds, i.e. silicates and siloxanes, are based on the same silicon-
oxygen chemical bond even though they are chemically very different. Silicates are ion-
covalent crystals but siloxanes are molecular ones. The aim of this study was to find a
direct relationship between the position of Si-O stretching vibrations bands and
properties of the silicon oxygen bond in different silicate and siloxane structures.
The Si-O bond is very strong (536 kJ / mol) and has a different nature in silicates as
well as siloxanes. In both so different groups of compounds silicon-oxygen bonds form
bridged systems ... O-Si-O-Si-O ... or terminal: Si-O- in silicates or Si-OR group in
siloxanes. Silicon-oxygen bond length and angle between bonds in Si-O-Si-O linkage
vary considerably depending on the type of silicates, however in in siloxanes they are
similar.
In this study for silicon-oxygen bond characterization, reviewing author's works on
silicates and siloxanes, the characteristic bands due to Si-O modes in IR and Raman
spectra were used. Bands due to Si-O asymmetric stretching vibration in IR spectra and
symmetric stretching vibration in Raman spectra were chosen. Bands due to stretching
vibration of Si-O bond in the IR and Raman spectra at about 1200 - 800 cm-1 are
relatively intensive and easy to assign.
The spectra of silicate structures with different complex silicate anion containing
various numbers of SiO4 tetrahedra, from monosilicate to tectosilicate with Si : O ratio
from 4 to 2, respectively were studied. In the case of terminal oxygen in SiO4
tetrahedron, the type of cations in the silicate structure was taken into account.
For IR and Raman spectroscopic analysis, the spectra of siloxanes and silsesquioxanes
with different degrees of polycondensation were selected. For comparison, the spectra
of monomeric siloxane molecules: M - (C2H5O)Si(CH3)3, D - (C2H5O)2Si(CH3)2, T -
(C2H5O)3Si(CH3) and Q - (C2H5O)4Si were taken. These molecules represent structural
units in siloxanes and silsequioxanes.
In conclusion of this study it has been found that when Si-O stretching vibration
bands are correctly assigned, their positions can be directly related to Si-O bond
characteristics and thus to the properties of the compounds.
Keywords: silicon-oxygen bond, silicates and siloxanes vibrational spectra
* Corresponding author: Tel: +48 12 617 25 30 FAX: +48 12 633 71 61 mailto:[email protected]
E-mail: [email protected]
28
L13
In Situ IR Spectroscopy of Crystallization: Mesoscale Identification of
Symmetry Variations from Molecules to Molecular Materials
Dongfeng Xue1, Congting Sun1, Henryk Ratajczak2
1State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of
Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China,
[email protected] of Chemistry, University of Wroclaw, Poland, [email protected]
The crystallization is still a mystery to many researchers, its whole process includes two
steps, i.e., both initial nucleation and following crystal growth. It has been confirmed
that crystallization is dramatically important to various performances of functional
materials [1-3]. Crystallization study thus becomes attractive in the community. Our
previous work shows that in situ ATR-IR spectroscopy can be used to identify the
mesoscale process [4,5], such as structural symmetry of molecules, aggregations, and
crystalline solid in this solution system.
Fig. 1 Schematic drawing of in situ IR observation of mesoscale process of molecular materials in
aqueous solution.
Acknowledgment
Financial support from the National Natural Science Foundation of China (grant nos. 51125009,
91434118, and 21401185), National Natural Science Foundation for Creative Research Group (grant nos.
20921002 and 21221061) and the Hundred Talents Program of the Chinese Academy of Sciences is
acknowledged.
References
[1] K. Chen, S. Song, D. Xue, CrystEngComm, 2015, 17, 2110-2117.
[2] K. Chen, C. Sun, D. Xue, Phys. Chem. Chem. Phys., 2015, 17, 732-750.
[3] K. Chen, S. Song, D. Xue, J. Mater. Chem. A, 2015, 3, 2441-2453.
[4] C. Sun, D. Xue, CrystEngComm, 2015, 17, DOI: 10.1039/C5CE00196J.
[5] C. Sun, D. Xue, J. Phys. Chem. C, 2014, 118, 16043-16050.
29
L14
Hunting Elusive Molecular Species: an Overland Journey to the
Highlands
Rui Fausto
Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal
The recent development of experimental techniques based on the combination of
matrix isolation with in situ narrow band irradiation either in infrared or UV/visible
ranges has opened the gate to the investigation of high-energy molecules. Selective
vibrational excitation (mostly using near-infrared light) of the low-energy conformers
may lead to production of higher-energy rare
conformers, while UV-laser induced
chemical processes may allow production
and characterization of high-energy species
that have been escaping to experimental
investigation for long.
These overland expeditions on the
terra incognita
potential energy surfaces have allowed
observation of a plethora of novel molecular
structures, some of them exhibiting rather
unusual properties and being pivotal
intermediates in the thermally- or/and
photochemically-induced reactivity of
important chemical systems.
In this talk, the attendees will be
invited to make an excursion on molecular
landscapes, learn how the expedition can be
prepared, enjoy the contact
molecular systems will be addressed, ranging from simple molecules exhibiting only two
conformers to complex multi-dimensional systems that embrace not only different
conformers but also other types of isomers.
Acknowledgements: Present and past members of the Laboratory for Molecular Cryospectroscopy and
Biospectroscopy, Coimbra, Portugal, who have contributed to the studies addressed in this talk, are
acknowledged. I thank also the Portuguese Science Foundation (FCT) for financial support.
30
L15
Photovoltaics Without p-n Junction: Computational Study of
Ferroelectric Organic Systems
Andrzej L. Sobolewski
Institute of Physics, Polish Academy of Sciences, PL-02668 Warsaw, Poland
E-mail: [email protected]
In the field of photovoltaics, in which manufacturing cost is essential, organics that
can be solution-processed at low temperatures offer great advantages as compared to
their inorganic counterparts [1]. On the other hand, organic photovoltaic (OPV) devices
still suffer from several drawbacks, such as; (i) low exciton diffusion lengths, (ii)
non-radiative recombination of charges, and (iii) low carrier mobilities [2]. The latter
drawback can be overcome in a promising class of organic materials disquotic liquid
crystals (DLC). The main feature of DLC is that they form columnar phases, where the
molecules stack on top of each other and the columns are packed in a parallel fashion on
a two-dimensional regular lattice. The -orbital overlap between adjacent aromatic
molecular cores favors a one-dimensional charge transport along the columns. A charge
carrier mobility as high as 1 cm2V-1s-1 was observed in the DLC phase of derivatives of
hexabenzocoronene [3] and triindole [4].
In this contribution results of ab initio theoretical explorations of photophysical
properties of ferroelectric molecular stacks will be presented. It will be show that in
such systems the photogenerated, due to absorbed light, electrons and holes are driven
by the polarization-induced internal electric field in opposite directions; toward the
cathode and anode, respectively, and thus directly contribute to the photovoltaic output
without a need for construction of the p-n junction [5].
References
[1] W. Cao and J. Xue, Energy Environ. Sci., 2014, 7, 2123.
[2] J. Xue, Polym. Rev., 2010, 50, 411.
[3]
Mater. 1999, 11, 1469.
[4] - -
-Lor, Chem. Mater. 2013, 25, 117.
[5] A. L. Sobolewski, Phys. Chem. Chem. Phys., submitted, arXiv:1505.00592
31
L16
Four Decades Later Has C60 Met Its Noble Expectations?
Jerzy Leszczynski
Department of Chemistry and Biochemistry Jackson State University,
Jackson, MS, USA
There are not too many cases when a discovery of a single compound had been
recognized by the Nobel Committee. Fullerene represents such an outstanding example. The
original paper describing this unique compound was published in 1985 and the Nobel Prize
follows in 1996. Such noble recognition had raised many expectations associated with a new
carbon form. They were not limited just to its basic chemistry but also include possible
applications of C60. Sorry to say but such expectations have not entirely materialized and two
other members of the carbon family carbon nanotubes and graphene have been significantly
more utilized.
By now one recognizes that pristine (i.e. non-functionalized) C60 fullerene has
functional groups are promising candidates for medicinal applications since properly
designed functional groups facilitate solubility in water and assure interactions with
only targeted protein. In addition, the way such a group is constructed allows
maximizing desired interactions. Recently, the progress with a functionalizing of C60
provides a pool of fullerene derivatives that due to a new set of characteristics could
find a potential application in medicine.
As always, a prediction of possible effects of newly studied species on
biological targets should precede their commercial applications. The talk summarizes
the results of recently performed comprehensive computational study of interactions
between a large set of fullerene nanoparticle derivatives (169 functionalized, C60, C70
and C80 compounds) with the group of almost 1200 proteins that are responsible for
various diseases. The study has been carried out using innovative approach that
combines various complementary computational techniques such as a high-throughput
virtual screening (virtual HTS) supported by comprehensive protein-ligand docking
studies and cheminformatics techniques to assure reliability of obtained data. Several
significant relationships between structural characteristics and biological activities are
noticed that could be revealed only by investigating a sizable set of fullerenes together
with a large set of proteins. Importantly, we determined a set of fullerene derivatives
which are most likely to be very potent against some target proteins. This conclusion is
augmented by a list of fullerene derivatives that could be potentially toxic because of
low selectivity and high binding activity for a number of target proteins.
32
L17
Theoretical and Experimental Studies of Excited and Charged States of
Fluorene Based Conjugated Polymers and Copolymers
Hugh D. Burrows
Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal.
Conjugated polymers are now a commercially important group of materials, with
applications including light emitting devices (PLEDs), photovoltaic cells, field-effect
transistors (FETs), sensing and imaging [1]. Their electronic properties can easily be tuned by
appropriate chemical substitution, and they can be readily processed from solution to produce
cheap, large area devices. However, optimization of their properties requires a detailed
understanding of the electronic spectral properties of both excited states and charged species.
Fluorene based conjugated polymers and copolymers are particularly important, and
widely used, for these applications, since they have good fluorescence quantum yields, and
normally emit in the blue, which favours electronic energy transfer. In addition, they show
good chemical stability. Experimental data will be presented on the absorption spectra of
their excited singlet and triplet states under conditions of isolated conjugated polymer chains,
and the results compared with DFT and TD-DFT calculations [2]. Steady-state and time
resolved fluorescence spectra will be given, and the importance of backbone conformational
relaxation on spectral shapes discussed [3,4]. Concentrated solutions and thin films of the
conjugated polymers generally show broadening of absorption bands, accompanied by red
shifts and decreases in intensity in fluorescence spectra. However, with poly(9,9-
dialkylfluorene)s, an intense, highly structured emission may be observed due to chain
planarization, and formation of the so-called -phase. The importance of interchain
interactions in this [5] will be discussed.
The one-electron oxidized and reduced species of conjugated polymers, termed
radical ions .by chemists and polarons by semiconductor physicists, are important for many
optoelectronc applications. UV/vis/NIR absorption spectra of charged states of fluorene
polymers and copolymers will be discussed, based on results of DFT calculations [6].
Acknowledgements: I am indebted in these studies to the work of many students, colleagues and collaborators.
Thier names are included in the references. Funding the FCT
(UID/QUI/00313/2013) and COMPETE is gratefully acknowledged.
References
[1] J.-L. Bredas, S. R. Marder, E. Reichmanis, (Eds.) Chem. Mater. 23 (2011), 309-922.
[2] L. L. G. Justino, M. L. Ramos, P. E. Abreu, A. Charas, J. Morgado, U. Scherf, B. F. Minaev, , H.
D. Burrows, J. Phys. Chem. C, 117 (2013) 17969-17982.
[3] F. B. Dias, A. D. Burrows, A. P. Monkman,
J.Chem.Phys. 118 ( 2003) 7119-7126.
[4] T. Costa, R. E. Di Paolo, L. E. Garner, A. W. Thomas, J. A. S. Almeida, L. L.G. Justino, , G.
C. Bazan, H. D. Burrows, J. Phys. Chem. C 117 (2013) 18353-18366.
[5] L.L.J. Justino, M.L. Ramos, M. Knaapila, A.T.; Marques, C. Kudla, U. Scherf, L.Almasy, R. Schweinz,
H. D. Burrows, A. P. Monkman, Macromolecules, 2011, 44, 334-343
[6] S. Fratilou, S.M. Fonseca, F.C. Grozema, H.D. Burrows, M.L. Costa, A. Charas, J. Morgado, L.D. A.
Siebbeles, J. Phys .Chem.C 2007, 111, 5812-5820.
.
33
L18
Recent Advances in Microwave, Raman and Terahertz Spectroscopy
James R. Durig and Bhushan S. Deodhar
University of Missouri-Kansas City United States of America
By the use of some new technology it has become possible to determine the structural
has become developed which has made it possible to obtain infrared spectra in the far
infrared region, where in this region it was initially difficult to obtain spectral data. This
is a very interesting technique which is used for materials which are in the gas, liquid
and solid state. Spectroscopy is extensively used throughout and consequently is
important that the information is obtained relatively quickly and is very clear.
Additionally the use of Microwave spectroscopy which can now provide the spectral
data now obtained from the new technique of pulse chirped in a relatively short time.
This technique makes it possible to obtain several thousand vibrational wavenumbers.
From this large amount of data it is possible to obtain the spectral parameters of isotope
of the compounds with those that have only one percent in natural abundance. Therefore
these significant techniques can make it possible to obtain new important knowledge.
For example some important materials may have several confirmations and it can be
important to determine the relative stability or the number of the confirmations of the
material from this study.
The use of the Raman data do not have problems of overtones and combination bands
so the normal vibrational data is usually more easily assigned to the fundamental
modes. The Raman spectral information can be used to reduce significantly the spectral
information so that the scientific data can be used readily. Some spectral data of both
types will be utilized and spectral data of materials that have significant number of
conformers and how they can be identified in terms of their amounts and the enthalpy
difference will be presented. Therefore the information provided should be very useful
for a large number of different scientific problems and the differences of materials.
34
L19
Near-Infrared Spectroscopy as a Tool for Molecular Structure
and Interaction Studies
M. A. Czarnecki
Faculty of Chemistry University of Wroclaw, F. Joliot-Curie 14, 50-
Poland, [email protected]
During the last two decades near-infrared (NIR) spectroscopy has made
significant progress due to improvement in instrumentation and spectral analysis.
Development of FT-NIR instruments, combined with chemometrics, generalized two-
dimensional correlation analysis (2DCOS), and quantum chemical calculations have all
stimulated numerous studies on molecular structure and interactions. All these works
clearly demonstrate that the NIR region is not a simple extension of the MIR region, but
it provides specific information on molecular structure and hydrogen bonding not
available from any other spectral range.
The basic molecules and their mixtures with water are commonly used as
models of more complex systems Hence, the systematic studies of these systems
provides reliable basis for interpretation of NIR spectra of composite materials like
polymers, lipids, proteins and aqueous solutions of biologically important molecules.
Here are shown exemplary studies on molecular structure and hydrogen bonding by
using NIR spectroscopy, chemometrics, 2DCOS and theoretical calculations.
The first part of this presentation provides a short introduction to NIR
spectroscopy and methods of data analysis. Next, an application of NIR spectroscopy to
studies of the molecular structure and hydrogen bonding in basic molecules like
aliphatic alcohols, diols, diamines, amides, aminoalcohols and carboxylic acids in the
pure liquid phase and in solutions is presented. Finally, the studies on binary mixtures
of basic molecules with water are discussed. A special attention is paid for examination
of the heterogeneity at a molecular level (microheterogeneity) in the binary mixtures.
Acknowledgment
This work was supported by Grant NCN 2013/11/B/ST4/00501.
References
[1] M. A. Czarnecki, Y. Morisawa, Y. Futami, Y. Ozaki, Chem. Revs. (in press).
[2] M. A. Czarnecki, Appl. Spectrosc. Rev. 46 (2011) 67-103.
[3] P. Tomza, M. A. Czarnecki, J. Mol. Liq. 209 (2015) 115 120.
35
L20
Study of Phase Transformation by Vibrational Spectroscopy and
X-Ray Diffraction in Crystals for NLO Applications
1 1 2 1
1Faculty of Science, Charles University in Prague, Hlavova 2030/8, 128 43 Prague 2,
Czech Republic, [email protected] of Physics, Academy of Sciences of the Czech Republic, v.v.i., Na Slovance
1999/2, 182 21 Prague 8, Czech Republic
The recent research is focused on the preparation of the materials with non-
linear optical properties. The used materials are mainly based on the organic molecules
carrying the non-linear optical properties and its salts with inorganic oxyacids or
organic acids. Mostly, the anions formed the network, which is filled by the organic
cations. The hydrogen bonds play the key role during the crystal structure arrangement
can protect the formation of centrosymmetric pair of organic molecules with high
dipole moment. The hydrogen interactions, which are investigated by X-ray diffraction
and vibrational spectroscopy, play important role in design of above mentioned
materials.
The thermal stability of the prepared materials is very important for their
potential optical applications. The temperature dependent crystal structure analysis and
vibrational spectroscopy are fundamental methods for monitoring of thermal behaviour.
The temperature-dependent infrared spectroscopy is very powerful for the determination
of the weak thermal changes connected with hydrogen bonds rearrangement (slight
change in donor-acceptor distances). The detailed X-ray study can exhibit significant
discontinuity in thermal changes of cell parameters or in the geometry of organic bases.
Additionally, the theoretical studies of vibrational manifestation and non-linear
optical properties of organic bases were performed for the detailed assignment of
observed spectra and also for the prediction and selection of useful candidates for the
material preparation. The detailed interpretation of vibrational spectra leads to the
deeper understanding of the thermal effects observed for prepared compounds based on
the triazoles, aminothiadiazoles and biguanides.
Acknowledgment
This work was supported by the Czech Science Foundation (grant no. 14-05506S).
36
L21
Investigation of Phonon Spectra of Thin Nanosized MoS2 Layer
Crystals: Theory and Experiment
A.M. Yaremko1, V.O. Yukhymchuk1, Yu.A. Romanjuk1, J. Baran2, H. Ratajczak3
1V. Lashkarov Institute of Semiconductor Physics of the National Academy of Sciences
of Ukraine,45 Prospect Nauki, Kiev 03028, Ukrain;, E-mail: [email protected] of Low Temperature and Structure Research of the PAS, 50-
PO Box 937, Poland3 F. Joliot-Curie 14,
50-
The spectroscopic study of layer type crystals was fulfilled during long time of
both the electron and the vibration properties of many layer crystals: GaSe, GaS, MoS2,
As2S3, MoSe2, MoW2 etc. The new period in the study of such crystals begins with using
method of Novoselov et al. [1] for graphen that allows preparation of a very thin crystal
structure that has 1-10 atomic layers. Layer type crystals MoS2 and MoSe2 are
especially perspective in this field, while they show interesting spectroscopic features if
crystal structure consists of only several n=1-6 atomic layers [2]. Recently, a detailed
study of the vibration spectra of MoS2 layer crystals consisting of several layers, n=1-6
was made in [2, 3]. Strong signals of the in-plane (1
2gE ) and out-of-plane ( gA1 ) of
Raman modes of all 1-6 layers were observed. Both modes showed well-defined
thickness dependence. The most striking feature is that the low frequency 1
2gE vibration
softens (red shift), while the high frequency gA1 vibration stiffens (blue shift) with the
increasing thickness of the sample. For the films of four or more layers, the frequencies
of both modes converge to values of the bulk crystals. Within a classical model for
coupled harmonic oscillators, 1
2gE , and gA1 modes are expected to stiffen as additional
layers are added.
In the present work it was shown that even a weak interlayer interaction in
crystals can affect intralayer bonding and lattice dynamics. This is similar to Fermi-
states is admitted new states, f , and g
in the crystal due to the weak interlayer interaction and exchange excitations between
these states: diagonal, ffff MD , ,
gggg MD , and non-diagonal gfgf MD , . The last ones
give rise to repulsion between the new crystal states therefore high- and low-frequency
components of doublet should be shifted in different sides. Similar fact was observed in
[2, 3]
References
[1] Novoselov K.S., Jang D., Schedin F., Booth T.J., Khotkevich V.V., Morozov S.V., Geim A.K,
Proc. Nat. Acad. Sci. USA, 2005, 102, 10451-10453.
[2] Lee C., Yan H., Brus L.E., Heinz T.F., Hone J., Ryu S., ACS NANO, 2010, 4 (N5), 2695-2700.
[3] M. Placidi et al., 2D Materials 2015 (to be published)
37
L22
Characterization of Acrylate/ Carbon Nanotubes Composites
A. Nowicka , M. Weiss, M. Szybowicz, M.Drozdowski
Poznan University of Technology, Faculty of Technical Physics, Poznan
[email protected], [email protected],
[email protected], [email protected],
Polymer nanocomposites are a new class of composite materials, which recently
are receiving significant attention. They contain nanofillers, which have only a few
nanometers in dimension and offer ultra-large interfacial area per volume between the
nano-element and polymer matrix. They also possess both, greater thermal and
oxidative stability, and better barrier and mechanical properties [1, 2]. In comparison
with different range of nanofillers, carbon nanotubes (CNTs) are promising as
nanofillers for polymer composites, due to their remarkable mechanical and electrical
properties [3, 4].
In this work we present the study of both, monomer/ multiwall carbon
nanotubes (MWCNTs) compositions and their polymer composites. The composites
being under study were based on difunctional monomer poly(ethylene glycol) diacrylate
(PEGDA) The composites were prepared by the UV-induced polymerization of
mixtures containing MWCNTs. In order to enhance the solubility and chemical activity
nanotube functionalization was performed. MWCNTs functionalized by oxygen groups
has been used.
To characterize the MWCNTs, the monomer/MWCNTs mixture and its polymer
composites we used different experimental methods: Raman spectroscopy, atomic force
microscopy (AFM) and laser scanned confocal microscopy (LSCM).
Results obtained using Raman spectroscopy allowed us to obtain information
concerning the nature of the band dispersion of the carbon nanotubes both, before and
after functionalization and their interaction with polymer matrix.
The atomic force microscopy and laser scanned confocal microscopy methods
allowed us to characterize the morphology of the obtained polymer composites and
dispersion of MWCNTs in polymer matrix.
Acknowledgement
This work was supported by the Research Project of Poznan University of Technology
06/64/DSMK/0415.
References
[1] F. Hussain, M. Hojjati, M. Okamoto, RE. Gorga, Journal of Composite Materials, 40 (2006) 1511.
[2] ET. Thostenson, C. Li, TW. Chou, Composites Science and Technology, 65 (2005) 491.
[3] H. Dai, Accounts of Chemical Research, 35 (2002) 1035.
[4] Z. Spitalsky, D. Tasis, K.Papagelis, C. Galiotis, Progress in Polymer Science 35 (2010) 357.
38
L23
In-situ Phase and Stress Analysis of High Temperature Zirconia Scale
Developed on Pure zirconium and Zr-Nb1% alloy as Studied by
Raman Spectroscopy
L. Kurpaska1), R. Jadach2), M. Sitarz2), J.J. Jasinski3), M. Gapinska4),
J-L. Grosseau-Poussard5)
1)National Centre for Nuclear Research, st. A. Soltana 7/23, Otwock-Swierk, Poland
[email protected])Faculty of Materials Science and Ceramics, AGH University of Science and
Technology, av. Mickiewicza 30, 30-059 Krakow, Poland, [email protected],
[email protected])Institute of Materials Science, Czestochowa university of Science and Technology, av.
Armii Krajowej 19, 42-200, Czestochowa, Poland, [email protected])University of Warsaw, College of Inter-Faculty Individual Studies in Mathematics and
Natural Sciences, st. Zwirki i Wigury 93, 02-089 Warsaw, Poland
[email protected])LaSIE UMR-
Raman spectroscopy is a powerful tool to study structural changes developed in the
material during high temperature treatment [1]. Recent advances in this technique, allow one to
collect information recorded during oxidation process, i.e. in in-situ conditions [2]. This option
is particularly interesting for nuclear engineers where very often there is no possibility to cut or
damage studied sample. Record of the signal in in-situ conditions opens new possibilities for
researchers interested in corrosion, and environmental impacts on mechanical and structural
properties of nuclear materials. In addition, recent publications suggested possibility of
calculating stress state of the material based on the Raman peak shift [3-4]. Due to the very
small number of valuable, non-destructive and fast measurement techniques, Raman
spectroscopy is becoming more and more interesting tool, to fill the created gap of lack of high
temperature structural and mechanical data.
In this study we present effect of high temeprature on location of seleted Raman bands. The
structural and mechanical properties of pre-
alloy (Zr-Nb1%) have been studied in the range of temperatures 25-
selscted monoclinic Raman bands allowed us to calculate the stress state developed in the oxide
during high temperature treatment in both materials. Continuous, individual for each sample
Raman band displacements have been registered. Presented results showed a good correlation
between two studied materials.
References
[1] L. Kurpaska, J. Favergeon, L. Lahoche, M. El-Marssi, G. Moulin, J-M. Roelandt, Journal of Nuclear Materials
(2015)
[2]
PhD Thesis Institute National Politechnique de Grenoble 2000
[3] L. Kurpaska, M. Kozanecki, J.J. Jasinski, M. Sitarz, Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy 131 (2014) 691 - 695
[4] B. Panicaud, J-L. Grosseau-Poussard, D. Retraint, M. Guerain, L. Li, Corrosion Science 68 (2013) 263 274
39
L24
Quantitative Aspects of the Identification of Fe(II) Moieties in Zeolites
ZSM-5 with Various Pore Hierarchy
K. Brylewska1,2 -Marek1, K.A. Tarach1
1
30-2Faculty of Materials Science and Ceramics, AGH University of Science and
-
Corresponding author: Kamila Brylewska, e-mail: [email protected]
Iron sites which are dispersed in aluminium poor pentasil zeolites deserve
particular attention due to their high catalytic activity and selectivity in many catalytic
reactions, e.g. in oxidation of benzene to phenol with N2O [1,2], N2O decomposition,
and stable activity in SCR-NOx with alkanes in the presence of water vapour [3,4].
Particularly, in the case of zeolite modified with iron ions, a broad spectrum of possible
iron forms can be achieved: Fe(II) present as isolated iron cations in exchangeable
positions, Fe(II)/Fe(III) sites in oxide forms of more or less defined steichiometry and
many others. The main problem in the elucidation of catalytic path is detailed
identification of the nature of active iron species. Such variety of possible formed active
species requires detailed speciation analysis to identify the Fe-sites active in particular
catalytic process.
The aim of this work was to determine the properties of iron sites in zeolites and
to examine their interaction with adsorbed probe molecules (CO and NO), followed by
IR spectroscopy. The main emphasis was placed on speciation analysis of iron sites in
ZSM-5 zeolites of different micro- and mesopore topology, both in qualitative and
quantitative aspect.
As reference material a parent ZSM-5 (Si/Al=32) was used. Zeolite D-ZSM-5
was obtained by alkaline leaching in the 0.2 M NaOH solution at 338 K for 0.5 h.
Zeolites M1-ZSM-5 and M2-ZSM-5 of tunable mesoporosity were obtained via a direct
synthesis route using the amphiphilic organosilanes as a mesopore-directing agent. All
zeolites were subjected to two-fold ion-exchange procedure with 0.5 M Fe(NO3)3 that
was performed at 873 K for 1 h. In some experiments iron form in Fe-zeolites ZSM-5
undergone the reduction in H2 atmosphere (60 Torr in gas phase) at 873 K for 1 h.
Otherwise, the iron forms were reoxidised using O2 (60 Torr in gas phase) at 873 K for
1 h.
The status and the concentration Fe2+ ions were investigated in quantitative IR
studies with CO and NO as probe molecules. The elaborated IR procedure guaranteed
assignation the concentration of Fe2+ sites in studied materials. The sorption of small
amounts of NO on zeolites exchanged with iron at 170 K performed fulfilled
requirement for the selective reaction of NO with Fe2+ cations. In the IR spectra there
were Fe2+(NO) recorded at 1890-1880 cm-1 for all materials of various pore hierarchy.
Spectroscopic quantitative measurement allowed to obtain the value of the absorption
coefficients of the respective mononitrosyl Fe2+(NO) IR bands ( mol).
Furthermore calculated concentrations of Fe2+ were correlated with the Fe sites amount
derived from chemical analysis (the Si/Al and Fe/Al ratios).
40
L24
Determination of the concentration of Fe(II) species in studied materials
required the saturation of all Fe2+ species with Fe2+(NO). Therefore, the sorbed NO
doses until the maximum intensities of the Fe2+(NO) bands were achieved in all samples
(non-treated zeolites and previously H2-reduced and reoxidised). The concentrations of
Fe2+ sites were calculated from the maximum intensities and their absorption
coefficients.
Fig. 1 The value of the absorption coefficients of the mononitrosyl fe2+(NO) IR band for ZSM-5
Similar quantitative methodology has been developed for CO sorption and obtained
results were correlated with those derived from quantitative studies of NO sorption.
Developed methods seems to be unique and powerful tool for the quantification
of Fe2+ in zeolites.
Acknowledgment
This work was financed by Grant No. 2013/09/B/ST5/00066 from the National Science Centre, Poland.
References
[1] I. Panov, V.I. Sobolev, K.A. Dubkov and A.S. Kharitinov, Stud. Surf. Sci. Catal., 1996, 101, 496.
[2] K. Uriarte, M.A. Rodkin, M.J. Gross, A.S. Kharitonov and G.I. Panov, Proc. 3rd Int. Congress
Oxidation Catal., Elsevier, Amsterdam, 1997, 857.
[3] Y. Chen, T. Voskoboinikov and W.M.H. Sachtler, J. Catal., 1998, 180, 171.
[4] Y. Chen and W.M.H. Sachtler, Catal. Lett., 1998, 50, 125.
41
L25
The Quantum Chemical Calculations by Combined Cost Common
Spectroscopic Techniques for Pentafluoropehol
A. Atac1, E. Kose1, M. Karabacak2
1Department of Physics, Celal Bayar University, Manisa, Turkey,
[email protected], [email protected] of Mechatronics Engineering, H.F.T. Technology Faculty, Celal Bayar
University, Turgutlu, Manisa, Turkey, [email protected]
In this paper include quantum chemical calculations by combined most common
spectroscopic techniques (FT-IR, FT-Raman, 1H, 13C and 19F NMR spectra) for
pentafluoropehol (PFP). FT-IR and FT-Raman spectra of the PFP molecule were
recorded in the region 4000 400 cm 1 and 3500 10 cm 1, respectively. The chemical
shifts of nuclear magnetic resonance (1H, 13C and 19F NMR) are obtained in DMSO
solution. The following theoretical calculations are prepared by combined experimental
results; Firstly, geometry of title molecule are optimized and point group are provided
by DFT (B3LYP)/6-311++G(d,p) basis set calculations. The vibrational (FT-IR and
FT-Raman) spectra are investigated same method after optimization of the title
molecule and fundamental vibrational modes are assigned based on potential energy
distributions by VEDA program. The nuclear magnetic resonance (1H, 13C and 19F
NMR) properties are achieved by using the gauge-invariant atomic orbital (GIAO)
method and same basis set.
LUMO energies, density of state (DOS) diagrams and molecular electro-static potential
surface (MEPs) are also presented. Nonlinear optical properties (NLO) are given
theoretically. An excellent correlation is seen between theoretical and experimental
results. These results are provides a detailed description of the structural and a deep
understanding of the characteristics physicochemical properties of the molecule.
Fig. 1 Structure of investigated molecule
Acknowledgment
The Authors thank to Celal Bayar University Research fund for supporting our title study.
42
L26
Hydrogen Bonds in Hydrophobic Hydration
Janusz Lipkowski
Cardinal Stefan Wyszynski University, Faculty of Mathematics and Natural Sciences -
School of Sciences, Wojcickiego 1/3, 01-938 Warszawa, Poland
Hydrophobic hydration is the hydration of hydrophobic molecules and surfaces.
Hydrophobic hydration (for reviews see [1]) produces a reduction in density and an
increase in the heat capacity [2]. The expanded network causes the density decrease
whereas the ordered bonds must be bent on increasing the temperature, so affecting the
heat capacity. Hydrophobic hydration is accompanied by a negative enthalpy change,
due in part to the multiple van der Waals interactions between water and the
hydrophobic material, a negative entropy change due to the increased order in the
surrounding water and positive heat capacity change (CP) due to the negative enthalpy
change (i.e. the stronger hydrogen bonds at the surface). For example, adding CH2
groups to aliphatic alcohols increases the heat produced on solution ( H/CH2 = -5.4 kJ
mol-1) but causes a greater decrease in the entropy (-T S/CH2 = +7.1 kJ mol-1) [this
introductory text was taken form the ref. 3].
In its pure form the structure of hydrophobic hydration is observed in clathrate hydrates.
In numerous examples a combination of hydrophobic and hydrophilic hydration has
been found.
In the present paper a series of x-ray structures will be used to demostrate the
characteristic of hydrophobic bonding of organic and metallorganic species. These
include macrocyclic crown polyethers and diaza-crowns, cyclodextrins, cucurbiturils
and selected metal complexes of the compounds listed above. The hydrophilic
counterpart will be illustrated using x-ray structures of selected strongly ionic
compounds.
A variety of interesting topologies were found and hydrogen bonding geometries
characterized using statistics of bond lengths and angles.
Some dynamic aspects of selected structures will be illustrated with the use of
temperature dependence of lattice parameters of highly hydrated structures (CD
complexes). Open, zeolite-like structures, demonstrate fast solvent exchange in the
systems, what can be observed microscopically as cracking of crystalline samples. This
phenomenon will be displayed with the use of short microscope movies.
References
[1] (a) V. V. Yaminsky and E. A. Vogler, Hydrophobic hydration, Curr. Opin. Colloid Interface Sci. 6
(2001) 342-349; (b) B. Widom, P. Bhimalapuram and K. Koga, The hydrophobic effect, Phys. Chem.
Chem. Phys. 5 (2003) 3085-3093 (G. Graziano, Comment on "The hydrophobic effect" by B.Widom,
P. Bhimalapuram and K. Koga, Phys. Chem. Chem. Phys., 2003, 5, 3085, Phys. Chem. Chem. Phys.
6 (2004) 4527-4528.) (c) D. Chandler, Interfaces and the driving force of hydrophobic assembly,
Nature 437 (2005) 640-647.
[2] V. Gutmann, Fundamental considerations about liquid water, Pure Appl. Chem. 63 (1991) 1715-1724
[3] www.lsbu.ac.uk/water).
43
L27
Particular Role of Electrostatic Interactions in Modeling Molecular
Materials
W. Andrzej Sokalski
Wroclaw University of Technology, Department of Chemistry, K1/W3
- -mail:[email protected])
Intermolecular interactions determine numerous properties of matter including
structure, cohesion energy, activity of drugs and biocatalysts, etc. Due to the large size
of systems involved the theoretical modeling has been mostly limited to approximate
methods not capable to represent all intermolecular interaction terms correctly. Using
hybrid variation-perturbation theory (HVPT) [1] and differential transition state stabili-
zation approach (DTSS) [2] several enzyme systems have been analyzed indicating
mostly dominant role electrostatic effects in catalytic [1,3] or inhibitory [4] activity. In
such case one may employ catalytic field technique [1] which yields in one computa-
tional step charge distribution of optimal catalytic environment aiding rational catalyst
design. Results obtained within DTSS approach in conjunction with cumulative atomic
multipole moment expansion [5] will be presented to resolve unexplained activity [6] of
several mutants of two different mutated theozymes [7-8]. This indicates existing room
for improvements of conventional catalyst design methodology, where mostly transition
state stabilization is considered only. The role of electrostatic term will be also dis-
cussed in relation to drug design and scoring [9-10].
Acknowledgements: This work was supported
-02-003/08) financed from
European Regional Development fund Operational Programme Innovative Economy 1.1.2.
Bibliography
[1] B. Szefczyk, A. Mulholland, K. Ragunathan, W.A. Sokalski, J.Am.Chem.Soc., 126, 16148-16159
(2004)
[2] W.A. Sokalski, J.Mol.Catal., 30, 395-410 (1985)
[3] P. Szarek, E. Dyguda-Kazimierowicz, A. Tachibana, W. A. Sokalski, J.Phys.Chem., B 112, 11819-
11826 (2008)
[4] E. Dyguda-Kazimierowicz, J. Grembecka, W. A. Sokalski, J. Leszczynski, J. Am. Chem. Soc. 127,
1658-1659 (2005)
[5] W.A. Sokalski, R.A. Poirier, Chem Phys Lett 98:86 92 (1983)
[6] G. Ghirlanda, Nature, 453, 164-166 (2008)
[7] J.L. Gallaher, E.
A. Althoff, A. Zanghellini, O. Dym, S. Albeck, K. N. Houk, D. S. Tawfik, D. Baker; Nature, 453,
190-195 (2008)
[8] S.D. Khare, Y. Kipnis, P. Jr Greisen, R. Takeuchi, Y. Ashani, M. Goldsmith, Y. Song, J. L Gallaher, I.
Silman, H. Leader, J. L Sussman, B. L Stoddard, D. S Tawfik , D. Baker; Nature Chem. Biol., 8, 294
(2012)
[9] K.M. Langner, W. Beker, W.A. Sokalski, J.Phys.Chem.Lett., 3,2785-2789 (2012)
[10] W. -Piasecka, E. Dyguda-Kazimierowicz, W. Beker, M. Mor, A. Lodola, W.A. Sokalski,
J.Phys.Chem.B, 118, 14727-14736(2014)
44
L28
Structure and Dynamics of Diblock Copolymers in the Bulk and
Thin Films
S. Jurga
NanoBioMedical Centre, Adam Mickiewicz University, 61-
Email: [email protected]
Block copolymers (BCPs) have received considerable attention due to their self-
assembling nature into periodic nanostructures and potential applications in
nanotechnology and nanobiomedicine. Linear AB-type diblock copolymers have been
most widely studied due to their simple structures that can self-assemble into well-
ordered nanodomain morphologies ranging from ordered bulk phases including body-
centered-cubic arrays of spheres, hexagonally packed cylinders, lamellae and
bicontinuous gyroid structures. Thin films, being of special interest, are obtained by
spatial confinement of the bulk. In a spatially confined environment due to various wall
interactions of nanodomains and confinement-induced entropy loss one can get different
from bulk novel structures, characterized, e.g. by long-range order, single crystalline
and dendritic forms, specific crystalline growth dynamics.
In this talk mentioned above aspects will be discussed using such techniques as:
GISAXS, Atomic Force Microscopy, optical microscopy, Nanoindentation, NMR and
Dielectric Spectroscopy. Detailed discussion will be focused on PS-b-PEO diblock
copolymer in the bulk and thin films, obtained via spin-coating technique on
reconstructed sapphire substrate, as visualized in Fig.1
Fig. 1 Schematically shown the cylindrical domain morphology of a polymer film deposited on a) flat
substrate and b) reconstructed sapphire substrate. AFM micrographs (800 nm X 800 nm) of PS-PEO
copolymer film deposited onto c) flat substrate and d) reconstructed substrate.
Acknowledgement: This work was supported by the National Science Centre under research Grant no
2013/11/B/ST3/04190 (Contract no. DEC-2013/11/B/ST3/04190) and the National Centre for Research
and Development, contract number PBS1/A9/13/2012.
45
L29
How to Recognize Endothelium from Other Isolated Liver Cells
by Means of Confocal Raman Spectroscopy?
K.Kochan1,2, E.Maslak2, S. Chlopicki2,3 and M.Baranska1,2
1Faculty of Chemistry, Jagiellonian University, Krakow, Poland2Jagiellonian Centre for Experimental Therapeutics, Jagiellonian University, Krakow,
Poland3Department of Experimental Pharmacology, Jagiellonian University, Krakow, Poland
The advantages as well as limitations of Raman spectroscopy in biomedical samples analysis
are presented. In particular, an identification of individual cells and their composition is
discussed.
Liver is the largest internal organ in human body with a great variety of functions of crucial
importance. It consists of highly specialized cells, i.a. hepatocytes, and hepatic stellate cells
(HSC), Kupffer cells and endothelial cells1. Hepatocytes are parenchymal cells that account for
approximately 80 % of all liver mass. Hepatic stellate cells on the other hand are an example of
non-parenchymal cells that play an important role in storage of vitamin A. Liver sinusoidal cells
(LSEC) along with Kupffer cells line liver sinusoids and play an important role i.a. in
phagocytosis.
Confocal Raman spectroscopy (RS) is a powerful tool for the study of biological materials,
including single cells2-3. It allows for investigation of the biochemical composition (and its
changes) to obtain information about processes going on at the subcellular level. RS applied for
cells isolated from the liver tissue enables their specific characterization. In addition, this
methodology will support other approaches for tracking changes at the cellular level due to
pathology development.
Here, an application of RS confocal mapping for studies of cells isolated from healthy mice
liver is shown. Hepatocytes, HSC, Kupffer and endothelial cells were identified and subjected
for RS studies. With the use of chemometric tools we present a complex spectral characteristic
of each investigated cell.
Fig. 1. Raman maps showing of distribution: (A) vitamin A in HSC, and (B) lipid droplets in hepatocyte.
Acknowledgment
This work was supported by the European Union under the European Regional Development Fund (grant
coordinated by JCET-UJ, POIG.01.01.02-00-069/09) and by National Science Center (grant DEC-
2013/09/N/NZ7/00626 and DEC-2013/08/A/ST4/00308).
References
[1] Z. Kmiec, Adv Anat Embryol Cell Biol., 2001;161:III XIII, 1 151.
[2] C. Methods in Cell
Biology, 2008, 89, 275 308.
[3] B. R. Wood, D. McNaughton, J. Raman. Spectrosc., 2002, 33,517 523.
46
L30
Corroles as Potential Agents for Optoelectronics and Photodynamic
Therapy
1, B. Bursa1, M. Kotkowiak1, B. Barszcz1,2
1Faculty of Technical Physics, Institute of Physics, Poznan University of Technology,
60-965 Poznan, Poland, email: [email protected],
[email protected], [email protected] of Molecular Physics, Polish Academy of Sciences, 60-179 Poznan, Poland,
email: [email protected]
Corroles are synthetic aromatic porphyrin-analogue dyes, in which one meso
carbon bridge is absent [1,2]. Thus, the different redistribution of electron density in
corroles versus that in porphyrins can result in changes of spectroscopic properties and
can implicate them promising candidates as photoactive agents. Large del -
electron conjugation and reasonable stability make them new excellent organic
materials for light energy capture and its conversion.
This contribution deals with new free-base corroles substituted with different
peripheral groups. The basic spectroscopic studies of the corroles in organic solvents of
low and high polarity are presented with the use of UV-Vis-IR absorption, fluorescence
and light-induced optoacoustic methods. The presence of monomeric dye structures are
concentration independent and it was confirmed by the absorption and fluorescence
experiments. The multi-structural character of the bands in the Soret (410 430 nm)
and in the Q-band regions (500 650 nm) indicates the presence of more then one
electronic transitions assigned to the tautomers T1 and T2. The origin of the absorption
both porphyrins and corroles [3]. Absorption band shapes and fluorescence life-time
values confirm the monomeric structure of the corroles. The spectra were confronted
with the time-dependent density functional theory (TD-DFT) results for the
HOMO/LUMO states [4]. In some of the corroles used in the experiments the HOMO
and the LUMO are shown as localized on the corrole ring and not on substituents [4].
The activation and deactivation of the triplet state of selected corroles was discussed on
the basis of the light-induced optoacoustic spectroscopy and population and singlet
oxygen generation parameters were estimated.
Acknowledgement
The paper was supported by Poznan University of Technology, the grant DS 06/62/DSPB/0215. The
authors are much grateful to Prof. D.T. Gryko (Institute of Organic Chemistry, Polish Academy of
Sciences, Warsaw, Poland) for the gift of the corrole samples.
References
[1] D.T. Gryko, J.P. Fox, D.P. Goldberg, J. Porphyrins Phthalocyanines 2004, 8, 1091-1105.
[2] A. Graja, Liq. Cryst. Mol. Cryst.,554, 31 (2012).
[3] M. Gouterman , G. Wegnierie, L.R. Snyder, J. Mol. Struct. 1963, 11, 108-127
[4] B. Bursa, B. Barszcz, W. Bednarski, J.P. Lewtak, D. Koszalewski, O. Vakuliuk, D. T. Gryko, Phys. Chem. Chem. Phys, 2015, 17, 7411-7423
47
L31
Photochemistry of the Interstellar Molecule HNCS
M. Wierzejewska, Justyna Krupa, Iwona Kosendiak
Faculty of Chemistry University of Wroclaw, Poland,
The isothiocyanic acid HNCS is well known as an interstellar molecule and was
detected 35 years ago in the rich molecular cloud Sagittarius B2. Photo-transformations
of HNCS induced by tunable UV laser were studied using low-temperature matrix
isolation coupled with FTIR spectroscopy. Two isomers of the precursor molecule are
formed during UV irradiation of HNCS/Ar and HNCS/N2 matrices: thiocyanic acid
HSCN and isothiofulminic acid HSNC. In addition, a complex between hydrogen
cyanide and a ground state (3P) sulfur atom appears at irradiation with wavelength <
290 nm. The vibrational bands of the S...HCN complex are observed at 3217.0 and
746.5 cm-1 in Ar and 3223.5 and 764.5/752.0 cm-1 in N2. The main source that gives rise
to formation of the S...HCN species is thiocyanic acid HSCN but a small impact of
HSNC into the process is also evident. In solid nitrogen, HCN monomers are observed
besides S...HCN indicating efficient escape of atomic sulfur out of the matrix sites.
Differences in the extent of the observed processes are discussed in relation to sulfur
atoms mobility and the type of matrices. Results of the computational studies performed
on the S...HCN geometry and infrared spectra are presented and compared with the
experimental data.
Acknowledgment
The research was supported by the National Science Centre Project No. 2013/11/B/ST4/00500. A grant of
acknowledged.
48
L32
Raman Imaging Techniques Open New Horizons
-823 Warsaw, Poland
In the past decade we observed the increased use of Raman imaging techniques
in a wide range of applications especially in nano-materials and biological materials like
cells and tissues. Raman imaging has been used for providing crucial detailed
information on the chemistry and distribution of inherent constituents, as well as
exogenous molecules. Recent innovations in Raman microscopy provide new modern
tools for studding complex systems and open new frontiers in material and life science
research.
Renishaw innovations like ultra-fast Raman imaging techniques combined with
rapid mathematical and statistical evaluation algorithms allows for large surface
characterization. The unparalleled ability to manage very large data files, containing up
to 50 million spectra per data set, enables the collection of 3D chemical images over
large volumes with sub-micrometer resolution and high definition confocal Raman
images provides 3D spatial information adding heterogeneity, both spatial and
chemical, to the morphological information.
Furthermore, the access to low frequency vibrations as low as 9 cm-1 to be
detected, enables identification of many inorganic and crystalline materials that is
difficult to characterize using other technologies. The rich information in fingerprint and
high frequency regions allow distinguishing even very similar materials.
The sub-micron order measurement volume ensures the localization of chemical
characterization for small or agglomerated particles.
Transmission Raman Spectroscopy (TRS) is a new tool in investigation of large
volumes, bulk material, tens of centimeters cubed, of powder blends. This novel
technique enables content uniformity to be statistically analyzed using multivariate
techniques. TRS presents significant benefits over the more conventional backscattering
Raman Spectroscopy by providing an average through the entire sample, offering fast
and effective analysis of content uniformity
State of the art innovations in Raman Spectroscopy technique will be illustrated
in this presentation.
49
L33
Studies on Structural Insights of Anti- l
T. Karthick, Poonam Tandon, Parag Agarwal
Department of Physics, University of Lucknow, Lucknow, Uttar Pradesh, 226007, India,
Email: [email protected]
The investigation of conformational analysis, spectroscopic characterization, the
interactions of anti-cancer drug with various proteins, enzymes which involved in cancerous
activity is essential in order to find the similar kind of drugs without any side effects.
In the present study, the multiple coordinates scan has been performed to find the
stable conformer of busulfan. The FT-IR and FT-Raman spectra of busulfan have been
recorded. Vibrational assignments of entire vibrational modes have been reported based on
Gar2ped results. The presence of inter- and intramolecular hydrogen bonding interactions
have been predicted using NBO and AIM analysis. To enumerate the activity of busulfan
against various proteins and enzymes, molecular docking studies have been performed by
SwissDock web server. Docking results revealed that busulfan is active with protein targets
such as; 2V7A, 3AYU, 12CA, 1Z93, 3D2N which responsible for cancerous growths.
Fig. 1. Optimized Electronic strucutre of Busulfan
Table 1. Docking Results of Busulfan against various targets
Targets Chain FF Score (kcal/mol) Binding Affinity (kcal/mol)Hydrogen Bond
Activity
2V7AA 1825.4354 6.7307 2.5489 Active
B 1846.2772 6.7309 Inactive
3AYU A 930.6630 7.05712.2536 Active
2.4877 Active
12CA 1482.5260 6.7906 1.9955 Active
1Z93 1463.1700 6.5895 2.0808 Active
3D2N 675.7211 6.80072.0054 Active
3.5305 Moderate
50
L34
Effect of Halogenation on The Bioactivity and Spectroscopic Features
in Transition Metal Complexes of Pharmaceutical Ligands: The Case
of Co2(INO)3X4 Complexes
M.A. Cipiloglu1, F. Bardak1, A. Atac1, M. Karabacak2
1Department of Physics, Celal Bayar University, Manisa, Turkey, [email protected],
[email protected], [email protected] of Mechatronics Engineering, H.F.T. Technology Faculty, Celal Bayar
University, Turgutlu, Manisa, Turkey, [email protected]
The structure and spectroscopic features of three Co2(INO)3X4 [Co:
Cobalt, INO: Isonicotinic acid N-oxide, and X: Cl, Br, I] complexes were investigated
experimentally by using C, H, N elemental analysis, FT-IR and UV-Vis spectroscopies,
and theoretically via density functional theory, DFT, calculations at LSDA/SDD level
of theory. Weak interactions and dimerization situations were analyzed through reduced
density gradient analysis and all type of interactions were visualized. The existence and
strength of different type of interactions were interpreted depending on the
characteristics of the halogens in the structures. Electronic structure and molecular
orbital properties obtained from time dependent DFT calculations were used to
enlighten the observed UV-Vis spectra. The possibility of red/blue shifts due to d-
splitting and halogenation was explored. Using a full population analysis, total, partial,
and overlap population density of states were determined to explore the possible ligand-
ligand, metal-ligand, metal-halide, and ligand-halide interactions in the structures.
Bioactivities of isolated ligand and the complexes were tested through the comparison
of their molecular docking properties. Docking examination shows that the transition
metals always increase the bioactivity of pharmaceutically active ligands.
51
L35
Spectral and Electronic Features of 2-Bromoethylbenzene
M. Karabacak1, S. Bilgili2, A. Atac2
1Department of Mechatronics Engineering, H.F.T. Technology Faculty, Celal Bayar
University, Turgutlu, Manisa, Turkey, [email protected] of Physics, Celal Bayar University, Manisa, Turkey,
[email protected], [email protected]
In this study, the molecular structure and vibration analysis of 2-bromoethyl
benzene were presented using experimental techniques as FT-IR, FT-Raman, UV and
quantum chemical calculations. FT-IR and FT-Raman spectra of 2-bromoethyl benzene
(2-BrEB) in the liquid phase were recorded in the region 3500-400 cm-1 and 3500-50
cm-1, respectively. The geometrical parameters and energies were obtained from density
functional theory (DFT) with B3LYP/6-311G(d,p) basis set. The complete assignments
were performed on the basis of the potential energy distribution (PED) of the vibrational
modes calculated with scaled quantum mechanics (SQM) method. The UV absorption
spectrum of the studied compound was recorded in the range of 190 400 nm by
dissolved in ethanol and water. The optimized geometric parameters were compared
with experimental data via the X-ray results of different derivatives of ethyl benzene.
Total and partial density of state (TDOS, PDOS) of the 2-BrEB and molecular
electrostatic potential (MEP) were calculated and analyzed. The electric dipole moment,
polarizability and the first static hyper-polarizability values for 2-BrEB were calculated
at the DFT/ B3LYP with 6-311G(d,p) basis set.
Fig. 1 Structure of the investigated molecule
Acknowledgment
The Authors thank to Celal Bayar University Research fund for supporting our title study.
52
L36
Photophysical and Theoretical Studies of Structure and Spectroscopic
Behaviour of Axially Substituted Yb(III) Mono-Phthalocyanines in
Different Media
Yu. Gerasymchuk1, L. Tomachynski2, M. Guzik3, A. Koll3 3, Y. Guyot4,1, G. Boulon4, J. Legendziewicz3
1 -422
2V.I. Vernadskii Institute of General and Inorganic Chemistry, 32/34 Palladin Ave.,
Kiev, Ukraine3 liot-Curie 14 str., 50-
Poland4Institute Light Matter, UMR5306 CNRS-University of Lyon 1, University of Lyon,
Bat. Kastler, 69622 Villeurbanne, France
Lanthanide complexes with phthalocyanines (Pc) and porphyrins belong to the group of
most investigated compounds because of their unique luminescence properties and
variety of applications. The special interest is directed to medical applications, mainly in
photodynamic therapy. This paper is devoted to photophysical studies of acetato- and
chloro-ytterbium monophthalocyanine complexes in the solid state, solutions, silica
matrices and PMMA polymer which can design their applicability. The structures, IR,
and Raman spectra were calculated applying Hartree Fock and density functional
theory methods and further correlated with experimental findings. The theory
reproduces reasonably spectroscopic frequencies of YbPcOAc2DMSO chelate. Two
molecules of DMSO with somewhat different spectroscopic behaviour were found to
exist in this complex.
The mechanism of the effect of conformation changes, steric obstacles, extra-
coordination of solvent molecules and molecule immobilization in polymer and
inorganic matrices on lanthanide and phthalocyanine emission spectra was discussed.
Attention was paid to the radiative and non-radiative processes, intramolecular energy
transfer and the role of charge-transfer state in this process, electron phonon coupling,
multiion cooperative interactions, non-linear proceses and dynamics in excited states.
The role of solvent molecule exchange dynamic in possible interaction of Yb(III)
complexes with biological systems was also analysed.
53
L37
Investigation of Cataractous Lenses by Vibrational
Microspectroscopy
C. Paluszkiewicz1, P.Chaniecki2, W. M. Kwiatek1, M. 3, J. Adamczyk1,
M. Gajda4, A. - 5
1Institute of Nuclear Physics, Polish Academy of Sciences, Radzikowskiego 152,
31-25th Wroclawska 1-3, 30-
Poland, [email protected]
04-141 Warszawa, Poland,[email protected] Medicum, Jagiellonian University, Kopernika 7, 31-
Poland,
[email protected] of Chemistry, Jagiellonian University, Ingardena 3, 30-
Poland, [email protected]
Cataract is mostly associated with the age of patient and decreasing the transparency
of lenses caused by the change of its chemical structure and phase composition. In order to
solve the problem the surgical operation is required to remove the cloudy lens and
replaced it by the eye lens polymer.
This study was performed on human lenses. The samples were partially cryosectioned
r FTIR and
Raman study. The adjacent sections were placed on microscopic glass for histopathology
-Raman spectrometer equipped
with 1064 nm laser. An example of 2D map of Lipids distribution overlaid on histological
image is shown in Figure 1.
Fig. 1 An example of 2D map of Lipids distribution overlaid on histological image of cataractous lens.
The results obtained by both FTIR and Raman microspectroscopy indicate
degradation of analyzed cataractous lenses.
Acknowledgements
The project has been supported by National Science Centre Poland under decision no. DEC
2012/05/B/ST4/ 01150.
54
L38
Blood Glucose Monitoring Based on Micro-Dialysis and Infrared
Spectrometry as Reliable Diabetes Technology: can External-Cavity
Quantum Cascade Lasers Replace FTIR-Spectrometers?
H.M. Heise1, T. Vahlsing1, S. Delbeck1, J. Budde1, D. Ihrig1, M. Grafen2,
K. Nalpantidis2 and A. Ostendorf2
1Interdisciplinary Center for Life Sciences, South-Westphalia University of Applied
Sciences, Frauenstuhlweg 31, D-58644 Iserlohn, Germany, [email protected] of Applied Laser Technologies, Ruhr-University Bochum, U
D-44801 Bochum, Germany
Nowadays, point-of-care diagnostics is demanding for continuous sensing systems,
especially for blood glucose monitoring, although intermittent testing is still practiced
even for critically ill patients.1 In this context, micro-dialysis has often been used in the
clinical environment for continuously harvesting body fluids in a minimal invasive
manner, but a drawback of this process are variable recovery rates. By using
multivariate infrared spectroscopy and its inherent multi-analyte capability for whole
blood, interstitial fluid or dialysate measurements, the application of a marker substance
containing perfusates has been investigated. The use of an internal standard for reliable
recovery assessment allows also a safe extension of micro-dialysis catheter lifetimes [1].
Recently, FTIR-mini-spectrometers have been successfully employed for the
development of bed-side monitoring systems. In-vivo applications for intensive care
patients can be envisaged, especially as further analytes and parameters are accessible,
which are of interest for intensive medicine such as lactate, urea, pCO2 and pH [2].
However, for implementation in further miniaturized portable systems, quantum
cascade lasers (QCL) appear to be most suitable. External cavity (EC) - QCLs promise
gapless spectral recording and broad tuning ranges, especially if the infrared fingerprint
region has to be covered for quantitative multi-parameter analysis [3,4]. We present
measurements taken with an ultra-broadly tunable EC-QCL system covering a spectral
range from 1920 to 780 cm-1 and discuss its performance also with regard to trans-
mission measurements of aqueous biofluids. A comparison and discussion of weak-
nesses and advantages versus the performance of FTIR-spectrometers will be presented.
Acknowledgments
VIP-
03V0433 and VIP-03V0434). Financial support from the European Commission under the CLINICIP
project (contract no. 506965 within the 6th Framework program) is also gratefully acknowledged.
References
[1] T. Vahlsing, S. Delbeck, J. Budde, L. Cocchieri, D. Ihrig, S. Leonhardt, and H.M. Heise, Proc. of
SPIE 2015, 9332, 933209
[2] H.M. Heise, V.R. Kondepati, U. Damm, M. Licht, F. Feichtner, J.K. Mader and M. Ellmerer, Proc.
of SPIE, 2008, 6863, 686308.
[3] H.M. Heise and T. Vahlsing, Proc. SPIE, 2014, 8951, 895108.
[4] T. Vahlsing, H. Moser, M. Grafen, K. Nalpantidis, M. Brandstetter, H.M. Heise, B. Lendl,
S. Leonhardt, D. Ihrig and A. Ostendorf, Proc. of SPIE-OSA, 2015, 9537, 953713
55
POSTERS
P1 Synthesis of Rhodium Nanoparticles Using Water as Reducing Agent.
Waleed Al-Salahi, Anna Trzeciak
P2 Polarised IR and FIR Spectra of -Glycine Single Crystal Measured by Specular
Reflection Method.
Jan Baran, Marek Drozd, Henryk Ratajczak
P3 Supported with Microwaves Synthesis and the Spectroscopic Analysis of
Bis(etoxycarbonylpyridinium) Salts.
Adam Zarecki, , Anna Komasa,
P4 Structural and Spectroscopic Studies of 1,3-bis[3-(1-
carboxypropyl)benzimidazolium]propane Dibromide Dihydrate.
, Anna Komasa, -Sitarz, Andrzej Katrusiak,
P5 NMR Investigations of Azuliporphyrins' Complexes.
, -
P6 The OH Initiated Oxidation of CS2 in the Presence of NO. FTIR Matrix Isolation and
Theoretical Study.
Andrzej Bil, Katarzyna Grzechnik, Zofia Mielke
P7 8 MR Zeolites with Hierarchical Structure The Case of Ferrierite.
Kamila Brylewska, -Marek, Karolina Tarach, erz Mozgawa
P8 Experimental and Theoretical Investigation of 4-[(2-hydroxy-3-
Methylbenzylidene)Amino]Benzenesulfonamide.
, Mustafa Durgun, , , Ahmet Kilic,
P9 Crystal Structure, Spectroscopic Investigations and Quantum Chemical Computational
Studies of 2-[(3-Nitrophenylimino)Methyl)]-5-Diethylaminophenol.
, , ,
P10 Thiol-Thione Tautomeric Analysis, Spectroscopic (FT-IR, Laser-Raman, NMR and UV-
vis.) Properties and DFT Computations of 5-(3-Pyridyl)-4H-1,2,4-Triazole-3-Thiol
Molecule.
, , , ,
P11 The Effect of Derivative of Promazine on the Hydrophobic Region of DPPC and SM
Lipid Membranes.
-Boczula
P12 Effect of Temperature on the Low-frequency Raman Spectra of Two Polymorphs of
4-Bromobenzophenone.
Nadia Davydova, Jan Baran, Marek Drozd, Oleg Pyshkin
59
P13 The Infrared Spectra of C60(OH)24 Fullerenol Conformers in Water Reaction Field DFT
Study.
Aleksander Dawid, Zygmunt Gburski
P14 The Interaction Induced Spectra of Two-Dimensional Krypton Layer Confined Between
Graphite Slabs MD Simulation.
Aleksander Dawid, Zygmunt Gburski
P15 The Infrared and Raman Spectra of interacting Acetaminophen with Cholesterol:
DFT Study.
Aleksander Dawid, Zygmunt Gburski
P16 Spectroscopic and Theoretical Studies of 4-Cyano-4-(Phenylcarbonothioylthio)Pentanoic
Acid.
Serkan Demirci, Hasan Tanak
P17 A Joint Photoelectron Spectroscopy and Theoretical Study on Anion NiAu9 Clusters.
, , , L. S. Wang
P18 Crystal Structures and Vibrational Spectra of Molecular-Ionic Complexes of Guanidine
with Terephthalic Acids.
, , Mariusz Marchewka,
P19 Molecular Structure and Vibrational Spectra of 3-Chlorocoumarin.
Dereli, , ,
P20 A DFT Study on Possible Radicals of 4-Piperidinecarboxylic Acid Molecule.
, Ahmet Bak, ,
P21 Spectroscopic Studies of Thermal Conversion of Electrospun Membrane from
Polyacrylonitrile (PAN) Precursor to Carbon Nanofibers.
, Piotr Szatkowski, Ewa Stodolak-Zych,
P22 FTIR/ATR Study of Hybrid Ceramic Coatings Modified by CNT and Silica
Nanoparticles.
Ewa Stodolak-Zych, - , , Wiktor Niemiec,
P23 Nitric Oxide Interactions with Red Blood Cells Studied by Resonance Raman
Spectroscopy, EPR and UV-VIS.
Jakub Dybas, Katarzyna Marzec, Bartosz Proniewski, Piotr Berkowicz, ,
P24 Vibrational Spectroscopy and DFT Calculations as a Diagnostic Tool of
the Cytosine Methylation.
, Jadwiga Lorenc, Urszula Korzun, Jan Szopa, Jerzy Hanuza
60
P25 The Thermal Behaviour of Li/Na/KY(WO4)2 Nanocrystalline Powders Co-doped with
Er3+ and Tm3+ Ions.
-Robak, Lucyna Macalik, , ,
Jadwiga Lorenc, Jerzy Hanuza
P26 Insight Into the Mechanism of Antibacterial Activity of Tetra-p-
Quanidinoethylcalix[4]Arene. An Experimental and Molecular Dynamics Study.
Marcelina Gorczyca, Beata Korchowiec, Jacek Korchowiec, Jean-Bernard Regnouf De Vains,
Ewa Rogalska
P27 Structural and Thermal Studies of Modified Silica-strontium-barium Glass from CRT.
Iwona Grelowska, Magda Kosmal, Manuela Reben, , Maciej Sitarz,
Zbigniew Olejniczak
P28 Structural and Optical Study of Tellurite-Barium Glasses.
Iwona Grelowska, Manuela Reben, , , Jan Cisowski, Yousef El
Sayed, , Maciej Sitarz
P29 Substituent Influence on the Spectra of Some Benzo-f-Quinoline Derivatives.
Gabriel Oanca, Antonina Gritco Todirascu, Dorina Creanga, Dana Dorohoi
P30 Methyl Group Effect on to the IR Spectral Properties of the Hydrogen Bond in Two
Thioamides: N-Benzylthioacetamide and N-Benzylthioformamide.
, Edyta Turek, -Lindert, Piotr Lodowski
P31 Near-Infrared Laser-Induced Generation of Three Rare Conformers of Glycolic Acid.
, , Igor Reva, Hanna Rostkowska, Rui Fausto, Maciej J. Nowak
P32 On Optimization of Absorption-Dispersion Spectra.
Jerzy P. Hawranek, Justyna Grabska,
P33 Vibrational Spectra, NBO Analysis and Antitumor Properties of the Novel, cis-
Diammine(5-Fluoroorotato)Platinum(II) Complex.
Katarzyna Helios, , Magdalena Malik, Joanna Wietrzyk, Danuta Michalska
P34 Khibina and Lovoziero Syenites Microanalysis Using ICP and 34S Stable Isotope
Analyses.
, , Lesia Lata
P35 A New Possibility of Flints Identification Using Spectrometric Methods.
, , , Jerzy Libera, Marcin Szeliga, Janusz
Budziszewski
P36 Study of Sulphides from Piechenga Rocks Using Geochemical and Stable Isotope
Analyses.
, , Lesia Lata, Yuri Nieradovski, Artem Mokrushin
61
P37 Pollution Destruction Processes in Architecture Detail of Old Lublin.
, Lesia Lata
P38 Raman Scissor Mode and 13C Chemical Shift of Betaine Carboxylate Group in Structural
Analysis of Betaine Acid Crystals.
Marek Ilczyszyn, Maria Ilczyszyn
P39 What is a Crystal Structure of Pyridinium Methanesulfonate? Vibrational and
XRD Studies.
Maria Ilczyszyn, Dominik Jesariew
P40 Spectroscopic Studies of Free carbon in SiOxCy Glasses.
, , Maciej Sitarz
P41 Theoretical Analysis of Vibrational Spectra of Sodalite Structure.
, ,
P42 Comprehensive Analysis of Vibrational Spectra of Selected Smectite Type Minerals.
,
P43 Theoretical and Experimental IR, Raman, UV, and NMR Spectra of
1,4-Di(3-Hydroxymethylpyridinium)Butane Dibromide.
Anna Komasa
P44 Spectroscopic, X-ray and Theoretical Analysis of
1, -Di(3-Hydroxymethylpyridinium)Pentane and Hexane Dibromides.
Anna Komasa, , -Sitarz, Andrzej Katrusiak, Zofia Dega-
Szafran,
P45 FT-IR Spectroscopic Studies of Cd2+ Adsorption onto Zeolite Synthesized from
Perlite Waste.
, Edyta Matras, ,
P46 Raman Spectroscopy Study of Lightweight Concrete Structure.
, ,
P47 IR Spectroscopy Studies of Zeolites in Geopolymeric Materials Derived from Kaolinite.
, Justyna Minkiewicz
P48 UV-Tunable Laser Induced Phototransformations of Matrix Isolated Anethole.
Justyna Krupa, Maria Wierzejewska, , Rui Fausto
P49 UV-Tunable Laser Induced Photolysis of Matrix Isolated Anisole.
Justyna Krupa, Maria Wierzejewska
P50 Studies of Substituent and Solvent Effect on Spectroscopic Properties of 6-OH-4-CH3, 7-
OH-4-CH3 and 7-OH-4-CF3 Coumarin.
Sanjay Kumar
62
P51 Influence of Ar-Irradiation on Structural and Nanomechanical Properties of Zirconium.
, Marta Gapinska, , Maciej Sitarz, Krzysztof Wozniak,
Jacek Jagielski
P52 Effect of ZnO on the Microstructure of the Glazes from SiO2-Al2O3-CaO-MgO-Na2O-
K2O System.
, Janusz Partyka
P53 Structural Study of Aluminosilicate Raw Glass-Ceramic Glazes by IR and Raman
Spectroscopies.
, Maciej Sitarz
P54 New Picoplatin - Orotate Complexes Revealing Anticancer Activity: Vibrational Spectra,
Conformations and DFT Calculations.
Magdalena Malik, Katarzyna Helios, Joanna Wietrzyk, Danuta Michalska
P55 Infrared Spectra of SO42- -type
Chains Na2M(SeO4)2 2O (M = Co, Ni, Zn, Cd) and
K2M(CrO4)2 2O (M = Mg, Co, Ni, Zn, Cd).
Delyana Marinova Manasieva, Manfred Wildner, Christian Lengauer, Mitko Georgiev, Donka
Stoilova, Veronika Karadjova
P56 Double Matrix Infrared Spectroscopy as a Tool to Monitor the Cation Distribution in
MgxZn1-x(HCOO)2 2O and MgxMn1-x(HCOO)2 2O Mixed Crystals.
Delyana Marinova Manasieva, Veronika Karadjova, Donka Stoilova
P57 Broad Band Anti-Stokes White Emission from LiYbF4 Nanocrystals.
, Robert Tomala, , Dariusz Hreniak,
P58 Light Wavelength Influence on Surface Plasmon Resonance in
Citrate-Gold Nanosystems.
Maria Andries, Daniela Pricop, Raul Lupusoru, Emil Puscasu, Felicia Iacomi,
Dorina Creanga
P59 Fat Quantification in Potato Chips by Vibrational Spectroscopy.
Sylwester Mazurek, Roman Szostak, Agnieszka Kita
P60 Quantitative Analysis of Topical Gels and Ointments by FT-Raman Spectroscopy.
Sylwester Mazurek, Roman Szostak
P61 Photocatalytic Partial Water Splitting with Visible Light.
Olaf Morawski, Elena Karpiuk, Andrzej Sobolewski
P62 Terahertz Dynamics of Polymorphic Pharmaceutical Indomethacin.
Tatsuya Mori, Tomohiko Shibata, Kei Iwamoto, Hiroshi Matsui, Seiji Kojima
P63 Terahertz Time-Domain and Low-Frequency Raman Scattering Spectroscopic Study on
Polypropylene Glycol.
Shota Koda, Tatsuya Mori, Mikitoshi Kabeya, Seiji Kojima
63
P64 7-Azaindole Complexes with Pd(II): Vibrational Spectra, Crystal Structure and DFT
Calculations.
Barbara Morzyk-Ociepa, Karolina Dysz, Ilona Turowska-Tyrk, Danuta Michalska
P65 Solvatochromic Study on Chlortetracycline in Binary and Ternary Solutions.
Gabriel Oanca, Claudia Nadejde, Adrian Fifere, Antonina Gritco Todirascu, Dorina Creanga,
Dana Dorohoi
P66 Spectroscopic Thermal Analysis of Sterols: Cholesterol and Lithocholic Acid.
Magdalena Ordon, - , Dorota Chudoba
P67 UV Laser Induced Phototransformations of 1,2,4-Triazole Derivatives.
Magdalena Pagacz-Kostrzewa, , Maria Wierzejewska, Dmytro Khomenko
P68 Optical Properties of Eu3+/Gd3+ Ions in Silica Xerogels and Powders Obtained by
Sol-gel Method.
Natalia Pawlik, Barbara Szpikowska-Sroka, Wojciech Pisarski
P69N-acetylglycinate Dehydrate.
Katarzyna Pawlus, Hasan Tanak, Jan Janczak, Mariusz Marchewka
P70 Polarized Vibrational Spectra and DFT Studies of Bis(2-Aminopyridinium) Fumarate
Fumaric Acid (1:1).
Katarzyna Pawlus, Mariusz Marchewka
P71 Spectral Investigation and Phase Transition in Pyridazine Perchlorate - the Crystal with
Hydrogen Bonds.
, , Zbigniew Czapla
P72 Relationship Between Morphology and Spectral Characteristics of Ag and Au
Nanoparticles/terpyridyl-based Oligomers Interfacial Films.
Marketa Pruskova, Ivana Sloufova, Blanka Vlckova, Jiri Vohlidal, Miroslav Slouf
P73 Experimental Study on the Core-Shell Interactions in the Case of Magnetic Grains
Coated with Organic Molecules.
Emil Puscasu, Maria Andries, Mihaela Racuciu, Felicia Iacomi, Dorina Creanga
P74 Light Wavelength Influence on Surface Plasmon Resonance in
Citrate-Gold Nanosystems.
Maria Andries, Daniela Pricop, Raul Lupusoru, Emil Puscasu, Felicia Iacomi,
Dorina Creanga
P75 Electric-Field Induced Molecular Switching Based on Double Proton Transfer:
Dynamical Simulations.
, Joanna Jankowska, Andrzej Sobolewski
64
P76 Mononuclear Arene Ruthenium Complex Containing 2- -Pyridyl)Benzimidazole as
Chelating Ligand. Synthesis, Crystal Structure and Spectral Properties.
Patrycja Rogala, Barbara Barszcz, -Wawrzycka, Grzegorz Czerwonka,
Katarzyna Kazimierczuk
P77 Ruthenium(III) Complex Containing Organic Ligand Transformed in Situ. Synthesis,
Structural and Spectral Characterization.
-Wawrzycka, Patrycja Rogala, Grzegorz Czerwonka, Maciej Hodorowicz,
Barbara Barszcz
P78 Proton Donor and Acceptor Properties of N-Hydroxyurea.
P79 Formaldoxime Hydrogen Bonded Complexes with Ammonia and Hydrogen Chloride.
, Barbara Golec, Austin J. Barnes, Zofia Mielke
P80 Conformation of the -Dimethyl- -Tetranitro-2,2-
Hydrazobipyridine: Structure, Vibrational Studies and DFT Calculations.
Edyta Kucharska, Iwona Bryndal, , Jadwiga Lorenc, Jerzy Hanuza
P81 Molecular Structures, Vibrational Studies and Quantum Chemical Calculations for 3(or
4)-Methyl-2-(Methylsulfanyl)-3-(or 5)-Nitropyridine.
, Jadwiga Lorenc, Jerzy Hanuza, Irena Maliszewska
P82 UV-VIS Study of 1-(2-Pyridylazo)-2-Naphthol (PAN) and its Metal Complexes with
Al(III), Mn(II), Fe(III), Cu(II) and Pb(II).
Botond Lorand Simon, Laszlo Szabo, Vasile Chis
P83 Influence of GeO2 Content on Structural and Luminescent Properties of Antimony Glass
Doped with Sm3+ Ions.
, Marcin Kochanowicz, Piotr Miluski, Maciej Sitarz, Wojciech Pisarski,
Joanna Pisarska, Dominik Dorosz
P84 Oxygen Transport in Hybrid Titanium Oxidation Processes.
, , , Maciej Sitarz,
P85 Size Dependence of Optical Properties of Eu3+:Sr2CeO4 Nanocrystals.
, , Dariusz Hreniak,
P86 SERS Spectra of Glass-Deposited Single Layer Graphene/Ag NP Aggregates Hybrid
System Measured in the Inverted Sample Geometry at Various Excitation Wavelengths.
Veronika Sutrova, Ivana Sloufova, Blanka Vlckova, Martin Kalbac
P87 Influence of Gd3+ Concentration on Luminescence Properties of Eu3+ Ions in Silica
Sol-Gel Materials.
Barbara Szpikowska-Sroka, Natalia Pawlik, Wojciech A. Pisarski
P88 A Phase Transition Investigation in NLO Compound: Guanidinium 4 Nitrobenzoate.
, Marek Drozd
65
P89 Raman and IR Studies of Non-Centrosymmetric BaHf(BO3)2 and La2CaB10O19 crystals.
Katarzyna Szymborska- , , Andrzej Majchrowski, Maciej Ptak,
P90 Spectroscopic Investigations and DFT Modeling Studies of
2-{[(5-Nitrothiophen-2-yl)Methylidene]amino}Phenol.
Hasan Tanak, Figen Koak, ,
P91 Experimental (XRD, FT-IR and NMR) and Theoretical Investigations on 1-(2-
Nitrobenzoyl)3,5-Bis(4-Methoxyphenyl) 4,5-Dihydro-1H-Pyrazole.
Meryem Evecen, Hasan Tanak, Necmi Dege, , Feyza Tinmaz
P92 Hierarchical L Zeolite Synthesized by Sequential Acid-Base Treatment.
Justyna Tekla, -Marek, Karolina Anna Tarach
P93 Infrared Laser Induced White Emission of Yb2Si2O7 Nanocrystals.
Robert Tomala, , Dariusz Hreniak,
P94 Synthesis, Optical Properties and White Lighting of ZnSe:Yb.
Robert Tomala, , Janina Legendziewicz, Yuri Gerasymchuk,
P95 Structure and Microstructure of the Glasses from NaMgPO4-SiO2 System.
Aleksandra Wajda, , Maciej Sitarz
P96 Aluminium Influence on the Microstructure and Structure of Glasses from NaMgPO4-
SiO2 System.
Aleksandra Wajda, , Maciej Sitarz
P97 Structural and Microstructural Studies of Copper Doped Glasses from
NaCaPO4-SiO2 System.
Aleksandra Wajda, Maciej Sitarz
P98 Dehydration Process in DL- -Phenylglycinium Trifluoromethanesulfonate Monohydrate
Crystal.
, Maria Ilczyszyn, Vasyl Kinzhybalo
P99 Resonance Raman Optical Activity of Astaxanthin Supramolecular Aggregates.
, Agnieszka Kaczor, Ana Pallares Zazo, ,
P100 Crystal Structures and Spectroscopic Properties of Mn(II) and Cu(II) Complexes
Containing N,O-Donor Ligands.
-Machnik, Joanna Masternak, Barbara Barszcz,
Katarzyna Kazimierczuk, Maciej Hodorowicz, Julia Jezierska
P101 Application of Infrared Spectroscopy and Pyrolysis Gas Chromatography for
Characterization of Adhesive Tapes.
-Palus, ,
66
P102 A Novel Highly Sensitive and Selective Chemosensors Based on Bidentate Hydrazone
Ligands of 2-Hydroxy Acetophenone Doped in Sol-Gel Matrix for Detection of Zinc in
Human Hair.
Badr Elsayed, Mohamed Abo-Aly, Sally Gamal
P103 Conformation of the Azo Bond and its Influence on the Molecular and Crystal Structure,
IR and Raman Spectra and Electron Properties of 6-Methyl-3,5-Dinitro-2-[(E)-
Phenyldiazenyl]Pyridine Quantum Chemical DFT Calculations.
J. Michalski, Iwona Bryndal, J. Lorenc, Jan Janczak, Jerzy Hanuza
P104 Light-Soaking Effect under Various Spectral Ranges in Inverted Organic Solar Cells.
, , Filip Granek
P105 In Situ and Operando Spectroscopic Studies of Sonically Aided Catalysts for Biogas
Exhaust Abatement.
, , Damian Chlebda, Ewelina Piwowarczyk, Magdalena
Chrzan, , Maciej Sitarz, Marzena Iwaniszyn, ,
P106 Amyloidogenic Proprties of the Fragment 52-65 of the Human Cystatin C.
, Martyna Maszota, ,
P107 Nuclear Magnetic Resonance Studies of the Wild-Type Human Cystatin C and V57G
Mutant.
Martyna Maszota, Daria Bortkiewicz, , , Piotr Skowron,
, Sylwia Rodziewicz-
P108 Methodology of Experimental and Theoretical Approach to the Study of the HF
Konstantin Tokhadze, Valentin Bulychev, Elena Gromova
P109 Infrared Spectroscopic and DSC Studies of Hydrogen-Bonded Liquid Crystals in
Confined Volume: 4-Hexylbenzoic and 4-Butylcyclohexane Carboxylic Acids in AlMCM-
41 Mesoporous Molecular Sieves.
I. Gnatyuk, T. Gavrilko, O. Yaroshchuk, N. Holovina, N. Lysenko, J. Baran, M. Drozd
67
P1
Synthesis of Rhodium Nanoparticles Using Water as Reducing Agent
Waleed Al-salahi, Anna Trzeciak
-Curie, 50-
Poland
Transition metal colloids have been synthesized, according to the literature, in
five general synthetic methods: (1) chemical reduction of transition metal salts, (2)
ligand reduction and displacement from organometallics, (3) thermal, photochemical, or
sonochemical decomposition, (4) electrochemical reduction, and (5) metal vapor
synthesis. The most widely used method of nanoparticles preparation is reduction of
transition metal salts in the presence of stabilizing agents, such as polymers or
surfactants. A wide range of reducing agents have been used in nanoparticles synthesis:
gas, such as hydrogen or carbon monoxide, hydrides or salts such as sodium
borohydride or sodium citrate, or even oxidable solvents such as alcohols. [1-3]
We discovered novel green methodology for the synthesis rhodium
nanoparticles from Rh(acac)(CO)2, Rh2(OAc)4 and RhCl3.3H2O as precursors, using
water as reducing agent at 25 - 80 oC. Rhodium nanoparticles were obtained in the
absence and in the presence of polymers, such as polyvinylpyrrolidone (PVP) and
polyvinyl alcohol (PVOH) as the stabilizing agents. Rh(0) nanoparticles have been
characterized by means of transmission electron microscopy (TEM), X-ray
photoelectron spectroscopy (XPS) and Infrared spectroscopy (IR), Catalytic activity of
the synthesized Rh/PVP was successfully tested in the hydrogenation of benzene and
the hydroformylation of 1-hexene in a water medium. In both cases excellent results
were obtained.
Rh(acac)(CO) 2
OH2Rh NPs (2 nm)
800C
Rh(acac)(CO) 2PVP, H2O
800C
Rh NPs (2 nm)
Acknowledgment
-2018, is
gratefully acknowledged.
Literature
[1] A. Roucoux, J. Schulz, and H. Patin., Reduced Transition Metal Colloids: A Novel Family of
Reusable Catalysts?. Chem. Rev. 2002, 102, 3757-3778.
[2] A. Gniewek and A. M. Trzeciak., Rh(0) Nanoparticles: Synthesis, Structure and Catalytic
Application in Suzuki Miyaura Reaction and Hydrogenation of Benzene., Top Catal., 2013,
56,1239 1245
[3] D. Nowicki, F. Hapiot, A. Roucoux, E. Monflier, and K.
Philippot., About the Use of Rhodium Nanoparticles in Hydrogenation and Hydroformylation
Reactions., Current Organic Chemistry, 2013, 17, 364-399.
[4] J. D. Aiken, R. G. Finke, A review of modern transition-metal nanoclusters: their synthesis,
characterization, and applications in catalysis., J. Mol. Catal. A: Chemical 1999, 145, 1 44
69
P2
Polarised IR and FIR Spectra of -Glycine Single Crystal Measured
by Specular Reflection Method
J. Baran, M. Drozd and H. Ratajczak
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
- , Poland
Glycine, the simplest amino acid, appears in three crystals modifications: , and
[1-3]. The vibrational properties of the glycine have been subjects of many papers [at
least of 32].These papers are devoted both to the experimental and theoretical
investigations of glycine molecule being in various forms and appearing in various
surroundings. One hopes that the polarised properties of the vibrational bands may be
used as an additional criterion which will allow to decide which proposed assignments
(supported by modern quantum chemical calculations of the force constants) is correct.
According to our knowledge, the full set of the polarised IR and FIR spectra (4000 60
cm-1) for -glycine crystal have not been published yet. This is a subject of the present
paper. Thus, the polarised IR and FIR spectra, for the (001) and (010) samples were
measured by the specular reflection method. Applying the Kramers-Kronig
transformation procedure, the spectra of the imaginary part of the refractive indices
were calculated
Unfortunately, the data published so far, do not allow to predict precisely an
orientation of the transition dipole moments for the internal vibrations, especially for
those with many PED contributions [6]. Therefore, we decided to perform a calculation
of normal coordinate analysis exactly for the basic molecular geometry determined by
neutron diffraction for an individual molecule/zwitterion in the -glycine crystal [4, 5]
and to calculate, not only the wavenumbers (and PED) of the normal modes, but also an
orientation of their transition dipole moments. The normal coordinate analysis has been
carried out for the molecule according to the procedure described and recommended by
Fogarasi and Pulay [7]. For all normal vibrations, the eigenvectors of molecular
displacements were isolated from of the Games output file. According to the
eigenvectors corresponding to each normal vibrations, the values of the new atomic
positions in the molecule were calculated. In a such way 24 new structural data (called
as mode structures) were obtained. For initial (crystallographic) structure and these new
24 structures the values of the dipole moments vectors were calculated. The vectors
differences were calculated between the dipole moment vectors calculated for each
mode structures and the dipole moment vector calculated for the initial (crystal)
structure, respectively. We assumed that these vectors differences determine the
orientations of the transition dipole moments of the internal normal modes of the
glycine zwitterions.
References[1] G. Albrecht, R.B. Corey, J. Am. Chem. Soc. 61(1939) 1087.
[2] Y. Iitaka, Acta Crystallogr. 13 (1960) 35
[3] Y. Iitaka, Acta Crystallogr., 14(1961) 1
[4] P.G. Jonsson, A. Kvick, Acta Cryst. 28B (1972) 1827.
[5] L.F. Power, K.E.Turner and F.M. Moore, Acta Cryst. B32 (1976) 11.
[6] D. Chakraborty, S. Manogaran, Chem. Phys. Lett, 294 (1998) 56-64.
[7] G. Fogarasi and P. Pulay; in Vibrational Spectra and Structure , ed. J.R. Durig ; Elsevier, N.Y. 1985, Vol.13
70
P3
Supported with Microwaves Synthesis and the Spectroscopic Analysis
of Bis(Ethoxycarbonylpyridinium) Salts
A.
Faculty of Chemistry, Adam Mickiewicz University,
Umultowska 89b, 61- .edu.pl
Bis-pyridinium diquaternary salts have recently gained the special significance
on account of applying them in many fields of chemistry and biology [1-3].
Obtaining salts containing in their structure dications of ethyl nicotinate or
isonicotinate and oxaalkyl and arylalkyl links and examining their spectroscopic
properties and the biological activity was a purpose of this work.
The synthesis of these salts supported by microwaves was led without the participation
of solvent, in environmentally friendly conditions, what is becoming part of so-called
green chemistry. Easily separated solid products were received with very good yields. In
two cases, apart from the dimer a monomer is also formed as by-products (Fig. 1).
Fig.1. The synthesis and the structures of investigated compounds.
Structures of obtained compounds were confirmed by elementary analysis and by
spectroscopic methods (FT-IR, Raman, 1H and 13C NMR). In the infrared spectra in the
region of stretching vibrations of C=O and C-O bonds the characteristic absorptions for
ester groups are observed. Assigning signals in NMR spectra to appropriate protons or
carbon atoms were made by 2-D NMR experiments. Additionally all compounds were
testing for their fungicidal and antibacterial activities.
Acknowledgment
The study was supported by Polish Norwegian Research Program No. Pol-Nor/203119/32: Superior bio-
friendly systems for enhanced wood durability.
References
[1] M. Komloova, K. Musilek, A. Horova, O. Holas, V. Dohnal, F. Gunn-Moore, K. Kuca, Bioog. Med.
Chem. Lett. 2011, 21, 2505-2509.
[2] K. Musilek, M. Komloova, O. Holas, A. Horova, M. Pohanka, F. Gunn-Moore, V. Dohnal, M.
Dolezal, K. Kuca, Bioorg. Med. Chem. 2011, 19, 754-762
[3] B. Furdui, O. Constantin, A. Tabacuru, R.M. Dinica, Rev. Chim. (Bucharest) 2012, 63, 667-671.
N
COOC2H5
+ L(X)2
N
COOC2H5
N
COOC2H5
L
COOC2H5 COOC2H5
OL =
+ +
or or
COOC2H5 COOC2H5
+ + + +
COOC2H5 COOC2H5
+ +N
O
N
3-COOC2H5 or 4-COOC2H5
2Br- 2Br- 2Br-
X = Br
2X-
N
COOC2H5
+
L-X
+ X-
NNNN
MW
71
P4
Structural and Spectroscopic Studies of 1,3-Bis[3-(1-Carboxypropyl)
Benzimidazolium]Propane Dibromide Dihydrate
-Sitarz, A. Katrusiak,
Faculty of Chemistry, Adam Mickiewicz University,
Umultowska 89b, 61-
Ionic compounds formed with organic cations often show much lower melting
point than inorganic analogous and are usually defined as ionic liquids (ILs). The
physical and chemical properties of ILs can be readily manipulated by controlling the
nature and functionality of the cations and anions to allow a myriad of applications [1].
Due to the structure difference, the dicationic ILs are expected to exhibit different
physical properties (such as thermal stability, solubility, and magnetic susceptibility)
from their corresponding monocationic ILs [2].
We synthesized a new type of geminal dicationic salt containing two
benzimidazolium rings which are linked by trimethylene chain. The synthesis procedure
and the structure of the examined compound (determined by X-ray single-crystal
diffraction) are shown in Fig 1.
Fig.1. Synthesis procedure and structure of investigated molecule in crystal
Additionally the molecular structure of 1,3-bis[3-(1-carboxypropyl)
benzimidazolium]propane dibromide has been characterized by FTIR, Raman and
NMR spectra. The FTIR spectrum is consistent with the X-ray results. The continuous
absorption in the 3000-1800 cm-1 region is attributed to the O-H Ow vibration, while
the broad band assigned to the Ow- -1.
Acknowledgment
The study was supported by Polish Norwegian Research Program No. Pol-Nor/203119/32: Superior bio-
friendly systems for enhanced wood durability.
References
[1] M. Freemantle, An Introduction to Ionic Liquids, Royal Society of Chemistry, 2010.
[2] J.-C. Chang, W.-Y. Ho, I-W. Sun, Y.-K. Chou, H.-H. Hsieh, T.-Y. Wu, Polyhedron 2011, 30, 497-
507.
72
P5
NMR Investigations of Azuliporphyrins' Complexes
, L. Latos-
Faculty of Chemistry, University of Wroclaw, Poland, [email protected]
Carbaporphyrins, including azuliporphyrins, are a family of modified porphyrins that
possess at least one carbon atom in a coordination cavity. This enables specific carbon-
metal interactions and their stabilization due to the presence of a macrocyclic frame.
Stabilized organometallic complexes provide insights into the nature of analogues
catalytic systems.
NMR spectroscopy provides information on atoms connectivity, molecules
conformation, dynamic processes, also connected with the coordination center, observed
in solution or spin density distribution when paramagnetic complexes are considered.
Presented studies show coordination reactivity of azuliporphyrin against
ruthenium and cobalt. Reaction of the azuliporphyrin complexes with direct M-C bonds
with oxygen leads to oxygenated complexes [1]. Bridging oxygen atom may coordinate
to the second molecule giving dimer. Solution saturated with auxiliary ligand contains
only monomeric species. This dynamic behavior is easily observed with NMR. In the
case of paramagnetic Co(II) complexes additional information on spin density
distribution may be acquired, which correlates well with DFT calculations. Postulated
conformational flexibility of 23-thiaazuliporphyrin ruthenium complex has also been
"caught" via variable temperature 1H NMR spectroscopy.
-coordination of a Ru cluster to the azulene moiety [2] induced
exceptional changes imprinted in the spectrum and connected with alteration of an
electronic structure and conformation of the molecule.
Scheme 1 Outline of reactivity and dynamics of azuliporphyrin complexes
Acknowledgment
Participation in the conference was financed from the 2014-2018 KNOW project for
Center for Biotechnology.
References
[1] - -6194; in preparation
[2] - -9272
73
P6
The OH Initiated Oxidation of CS2 in the Presence of NO.
FTIR Matrix Isolation and Theoretical Study
A. Bil, K. Grzechnik, Z. Mielke
Faculty of Chemistry University of Wroclaw, Poland,
[email protected], [email protected],
Carbon disulfide, CS2, is released by plants and by biomass burning and is
disulfide produces an estimated 30% of the atmospheric OCS. Understanding the
mechanism for transforming sulfur compounds into OCS is important because OCS is
the most abundant sulfur compound in the atmosphere. Early experimental studies of
the reaction CS2+OH indicated that the reaction (1) is too slow to be of relevance to
atmospheric CS2 degradation. However, it was shown later, that the reaction is
significantly faster in the presence of molecular oxygen (2) [1].
CS2+OH CS2OH OCS + SH (1)
CS2OH + O2 products (2)
The experimental and theoretical studies demonstrated that reaction (2) is
extremely complex with over 25 exothermic product channels [2].
Here we present the FTIR matrix isolation and theoretical study on the
mechanism of the OH initiated oxidation of CS2 in the presence of NO, an important
molecule of atmospheric relevance:
CS2OH + NO products (3)
The source of the OH and NO radicals in the matrix was HONO
photodissociation. The products of the CS2OH+NO reaction were identified by using
2H, 13C, 15N isotopic substitution. Four reaction channels were analysed by optimizing
minima and transition states with DFT/B3LYP/aug-cc-pVTZ method. Both the
SC(OH)S adduct with OH group attached to the carbon atom and the SCSOH one with
the OH group attached to the sulfur atom were considered as the reaction substrates.
Experimental and theoretical data show that the major reaction channel leads to
formation of OCS and HONS from SC(OH)S radical. The NO molecule has a major
impact on yield of OCS lowering considerably the energy barrier for its formation and
making it more favorable in terms of kinetics. The SCSOH radical as substrate was
found to produce SO2 and HSCN. The identification of these products in the matrix
constitutes an indirect evidence that both SC(OH)S and SCSOH radicals are formed in
the CS2+OH reaction.
Acknowledgment
Andrzej Bil is thankful for financial support (the conference expenses) within the framework of KNOW
action.
References
[1] B.M.R. Jones, R.A. Cox, S.A. Penkett, J. Atmos. Chem., 1983, 1, 65-86.
[2] M.L. McKee, P.H. Wine, J. Am. Chem. Soc., 2001, 123, 2344-2353
74
P7
8 MR Zeolites with Hierarchical Structure the Case of Ferrierite
K. Brylewska1,2 -Marek1, K.A. Tarach1, W. Mozgawa2
1
30-2 Faculty of Materials Science and Ceramics, AGH University of Science and
-
Corresponding author: Kamila Brylewska, e-mail: [email protected]
It is known that good diffusion of reagents in materials is very important in
many catalytic processes. From the point of catalytic activity it is important to obtain
materials that combine the presence of strongly acidic centres with mesopore system
ensuring overcoming the diffusional limitations. Secondary mesopore system can be
generated in many manners. "Top down" methods cover post-synthesis treatments
including demetalation, eg. dealumination [1] in the presence of acid solution and
desilication [2] in alkaline media. Good results gives the combination of these two
methods [3].
This work was focused on adaptation and development of the methods of the
generation of an additional mesopore system within the zeolite grains in zeolite
structures. It was realized by demetalation procedure (desilication and dealumination)
which in the presence of PDA (pore directing agent). The main emphasis of this work
was placed on
Lewis acid sites in hierarchical and conventional 8 MR zeolite FER. Additionally, the
textural and structural properties were characterized.
The parent zeolites FER with Si/Al = 9 and 23 were modified by desilication and
dealumination using alkali solutions (LiOH and TBAOH - tetrabutylammonium
hydroxide) and acid solutions (HNO3), respectively. The textural parameters, such as
surface area SBET, micropore volume and surface, respectively Vmicro and Smicro were
examined with low temperature N2 sorption studies. Additionally, the solid-state MAS
NMR spectra, XRD measurements, and chemical composition (ICP method) were
performed. For acidity description the IR spectroscopy was adapted with sorption of
pyridine as probe molecule.
All of the hierarchical samples preserved fully crystalline character after
sequential treatment with acid and base solutions. After desilication, the Si/Al ratio
decreased, and an expected result after dealumination was an increase of this parameter.
Such observation was confirmed by 29Si MAS NMR and 27Al MAS NMR spectra. The
structural and textural studies showed that desilication enhanced the mesopore surface,
maintaining the microporous character of modified materials (Fig. 1). Only acid
treatment resulted in a decrease in the micropore volume, which can be explained by
formation of significant amount of extraframework material plaguing the micropores.
Lewis acid sites and this effect is independent of the Si/Al ratio.
75
P7
Fig. 1 Porosity studies for FER (Si/Al = 23)
Acknowledgment
This work was financed by Grant No. 2013/09/B/ST5/00066 from the National Science Centre, Poland.
References
[1] T. Sano, Y. Uno, Z.B. Wang, C.H. Ahnand K. Soga, Micropor. Mesop. Mater., 1999, 31, 89-95.
[2] , Catal. Today, 2010, 152, 24-32.
[3]
Finiels, V. Hulea and F. Fajula, Angew. Chem. Int. Ed., 2010, 49, 10074-10078.
76
P8
Experimental and Theoretical Investigation of 4-[(2-Hydroxy-3-
Methylbenzylidene)Amino]Benzenesulfonamide
a, Mustafa Durgunb, c, d, Ahmet b e
aDepartment of Medical Services and Techniques, Vocational High School of Health
Services, Giresun University, 28100Giresun, TURKEY, [email protected] of Chemistry, Faculty of Arts and Sciences, Harran University, 63190
Y, [email protected] , [email protected] of Medical Pharmacology, Faculty of Medicine, Harran University, 63190
Sanliurfa, TURKEY, [email protected] Laboratory, Osmanbey Campus, Harran University, 63190
TURKEY, [email protected]
55139 Samsun, TURKEY, [email protected]
The sulfonamide compound, 4-[(2-hydroxy-3-methylbenzylidene)amino]benzenesulfo-
namide was synthesized and grown as a high quality single crystal by the slow
evaporation solution growth technique. The structure of the compound was
characterized by FT-IR, 1H and 13C-NMR, UV-Vis and X-Ray single crystal techniques.
Z = 4 in the unit cell.
Density functional theory (DFT) calculations were carried out for the title compound by
utilizing DFT level of theory using B3LYP/6-311++G(d,p) as basis set. In addition,
DFT calculations of the title compound, Molecular Electrostatic Potential (MEP),
Natural Bond Orbital (NBO), Frontier Molecular Orbital (FMO) analysis,
thermodynamic properties, dipole moments, and HOMO-LUMO energy were also
computed [1].
Figure The molecular structure of the title compound.
Acknowledgment
This study supported by Harran University Scientific Research Project Coordinator (HUBAK) Project
nos. 1136, 12040 and 12167.
References
[1]
2015.06.036.
77
P9
Crystal Structure, Spectroscopic Investigations and Quantum
Chemical Computational Studies of 2-[(3-Nitrophenylimino)Methyl)]-
5-Diethylaminophenol
a, b c c
a
[email protected] of Medical Services and Techniques, Vocational School of Health Services,
Giresun University, 28200, Giresun, Turkey, [email protected]
55139,Samsun, Turkey, [email protected] ; [email protected]
intermediates important for a production of chemical specialties, e.g. pharmaceuticals,
or additives to rubber. A basic reaction synthesis involves an aromatic amine and
aldehyde[1 3]. The Schiff base compound, 2-[(3-nitrophenylimino)methyl)]-5-
diethylaminophenol, C17H19O3N3, was synthesized and characterized by IR, UV-Vis
and X-ray diffraction technique. The title compound prefers enol tautomeric form in
solid state as to X-ray, IR and UV-Vis spectra results. Also, using the TD-DFT method,
the electronic absorption spectra of the title compound computed in both the gas phase
and ethanol solvent. According to calculated results support that the enol form is more
stable than keto form. The molecular geometry was also calculated using the Gaussian
03 software and structure was optimized using the HF and DFT/B3LYP methods with
the 6-311++G(d,p) basis set in ground state. The harmonic vibrational frequencies of
the title compound were calculated using the same methods with the 6-311G++(d,p)
basis set. The calculated results were compared the experimental determination results
of the compound. Besides, the molecular electrostatic potantial map (MEP), frontier
molecular orbitals (FMO) analysis and thermodynamic properties for the title
compound were obtained with the same levels of theory. To investigate second order
nonlinear optical properties of the title compound,
- HF
and DFT/B3LYP methods with the 6-311++G(d,p) basis set.
Keywords: Schiff Base, X-ray Diffraction (XRD), Hartree Fock (HF), Density Functional Theory
(DFT).
References
[1] H. Schiff, Justus Liebigs Ann. Chem. 140 (1867) 93; H. Schiff, Justus Liebigs Ann. Chem. 148
(1868) 330; H. Schiff, Justus Liebigs Ann. Chem. 201 (1880) 355; H. Schiff, Justus Liebigs Ann.
Chem. 210 (1881) 119.
[2] E.H. Cordes, W.P. Jenks, J. Am. Chem. Soc. 84 (1962) 832.
[3] J. March, Advanced Organic Chemistry, Reactions, Mechanism and Structure, fourth ed., Wiley,
New York, 1992, p. 986.
78
P10
Thiol-Thione Tautomeric Analysis, Spectroscopic (FT-IR, Laser-
Raman, NMR and UV-vis). Properties and DFT Computations of 5-(3-
Pyridyl)-4H-1,2,4-Triazole-3-Thiol Molecule
1 1 2 3,1
1Giresun University, Vocational High School of Health Services, 28100, Giresun,
Turkey, [email protected]; [email protected];
[email protected] Vocational High School, Giresun University, 28950, Giresun, Turkey,
[email protected] of Biophysics, Faculty of Medicine, Giresun University, 28100,
Giresun,Turkey, [email protected]
In this study, the 5-(3-pyridyl)-4H-1,2,4-triazole-3-thiol molecule (C7H6N4S) molecule
has been characterized by using FT-IR, Laser-Raman, NMR and UV-Vis.
spectroscopies. Quantum chemical calculations have been performed to investigate the
molecular structure (thione-thiol tautomerism), vibrational wavenumbers, electronic
transition absorption wavelengths in DMSO and vacuum, proton and carbon-13 NMR
chemical shifts and HOMOs-LUMOs energies at DFT/B3LYP/6-311++G(d,p) level for
all five tautomers of the title molecule. The obtained results show that the calculated
vibrational wavenumbers, NMR chemical shifts and UV-vis. wavelengths are in a good
agreement with experimental data [1,2].
Figure.The molecular structure of the title compound.
References
[1] K.T. Potts, Chem. Rev. 61 (1961) 87-127.
[2] M.D. Davari, H. Bahrami, Z.Z. Haghighi, M. Zahedi, J. Mol. Model. 16 (2010) 841-855.
79
P11
The Effect of Derivative of Promazine on the Hydrophobic Region of
DPPC and SM Lipid Membranes
-Boczula
Faculty of Chemistry University of Wroclaw, Poland,
Promazine molecules belong to the phenothiazine group of antipsychotic drugs
[1]. Additionally, they can serve as a very effective anti-multidrug resistance (MDR)
agents [1]. It is postulated that phenothiazine-related compounds decrease the activity of
outward transport of anticancer drugs of membrane glicoprotein P (Pgp) in tumor cells
by increasing the fluidity and the permeability of the lipid membrane environment. The
membrane perturbing potency of propionyl derivative of promazine (PP) (see Figure
below) has been studied using attenuated total reflectance Fourier-transfer infrared
spectroscopy (FTIR-ATR). The temperature- and PP-dose-dependent evolutions of the
infrared spectra of PP/sphingomyelin (SM) or dipalmitoilophosphatidylcholine (DPPC)
mixtures were analyzed using principal component analysis (PCA).
The spectral parameters of as,sCH2 and CH2 lipid bands were changed
according to variations in the trans to gauche conformer ratio of the CH2 groups in the
hydrocarbon lipid chains and to alterations in lateral lipid chain packing, respectively
[2-5]. A reduction in the temperature of the chain-melting phase transition was observed
in both PP-mixed SM and DPPC membranes. The phase transition cooperativity and
lateral lipid chain packing were estimated for liposomes mixed with different
concentration of PP.
N
S
N
O
Fig. 1 Structure of propionyl derivative of promazine (PP)
Acknowledgment
This work was supported by the consortium KNOW (Faculty of Chemistry, University of Wroclaw) and
the grant no. DEC-2012/05/B/ST4/02029 (OPUS) from the National Science Centre. We thank the
Foundation for Polish Science the programme POMOST, co-financed by the European Union within
additional financial support.
References
[1] G. Sudeshna and K. Parimal, Eur. J. Pharmacol. 648, 2010, 6-14.
I.M. Asher, I.W. Levin, Biochim. Biophys. Acta 468, 1977, 63.
[2] H.H. Mantsch and R.N. McElhaney, Chem. Phys. Lipids 57, 1991, 213-226.
[3] -Boczula and A. Koll, Biophys. Chem. 140, 2009, 51-56.
[4] -Boczula, B. Czarnik-Matusewicz, M.G. Perevozkina, A. Filarowski, N.
Boens, W.M. De Borggraeve and A. Koll, J. Mol. Struct. 878, 2008, 162-168.
[5] -Boczula, J. Maniewska, G. Grynkiewicz, W. Szeja, A. Koll and A.B.
Hendrich, Vib. Spectrosc. 62, 2012, 64-69.
80
P12
Effect of Temperature on the Low-Frequency Raman Spectra of Two
Polymorphs of 4-Bromobenzophenone
J. Baran1, N. A. Davydova2, M. Drozd1, O.S. Pyshkin3
1Institute of Low temperature and Structure Research, PAS, Okolna 2, 50-950,
Wroclaw, Poland, [email protected],wroc.pl, [email protected] of Physics, NAS of Ukraine, Prosp. Nauky 46, Kyiv-28, 03680, Ukraine,
[email protected] Institute for Low Temperature Physics and Engineering, NAS of Ukraine, 47
Lenin Ave., Kharkiv 61103, Ukraine
Motivation for the present study was the recent discovery of polymorphism in 4-
bromobenzophenone (4BrBP) [1] which enables investigation of different polymorph in
terms of structure-property relationship.
We carry out a study on the influence of the temperature on the low-frequency
Raman spectra of triclinic (t-form) and monoclinic (m-form) polymorphs of 4BrBP
in the temperature range 60-295 K.
The unit cell of the t-form is approximately half that of the m-form and it contains
two molecules as opposed to the four molecules in the m-form. Space group of the m-
form is P21/c, and of the t-
two polymorphs determines a pronounced difference in the temperature behavior of the
low-frequency Raman spectra of both polymorphs in the temperature range 60-295 K.
The point to which we address attention anomalous temperature dependence of
the intensity of the band at ~ 155 cm-1 and at ~ 30 cm-1 in the t-form as compared with
its behavior in the m-form. In the t-form with a decrease in temperature the band at
~155 cm-1 narrows sharply, its intensity increases exponentially, and its position shifts
to the high-frequency side from 144 cm-1 at 295 K to 155.6 cm-1 at 60 K. The
temperature behavior of the band at ~ 30 cm -1 is opposite: its intensity decreases
sharply with decreasing temperature. The bands in the m-form in the same temperature
range vary insignificantly. Anomalous growth of the intensity of the bands in the t-form
at their simultaneous narrowing with decreasing temperature usually associated with the
presence of the anharmonicity [2].
Additionally, the thermal properties of both polymorphs have been investigated by
means of differential scanning calorimetry (Perkin-Elmer DSC7) method. We have
found the melting temperature of the m-form, Tm =356.4 K (Tonset = 354.4 K) and of the
t-form, Tm=358.0 K (Tonset = 355.4 K). We want to draw attention that these values
strongly differ from that in Ref. [1] where melting temperature of the m-form was found
to be 355.2 K, and of the t-form 354.0 K.
References
[1] M.A. Strzemechny, V.N. Baumer, F.F. Avdeenko, O.S. Pyshkin, R.V. Romashkin, L.M. Buravtseva,
Acta Crystallogr. B 63, 2007, 296-302.
[2] H. Ratajczak, A.M. Yaremko, J. Baran, J. Mol. Str. 275, 1992, 235.
81
P13
The Infrared Ipectra of C60(OH)24 Fullerenol Conformers in Water
Reaction field DFT Study
A. Dawid, Z. Gburski
Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007, Katowice, Poland,
The fullerenes functionalized by OH groups are considered to be a potential
antioxidative agents and free radical scavengers in biological system. The experimental
study carried out by Mirkov et al. shows that the C60(OH)24 fullerenol is able to reduce
nitric oxide in mammals body [1]. In other side the classical molecular dynamics
simulations study shows slight NO scavenging by fullerenol in water solution [2]. The
scavenging observed in MD simulations was smaller than in experimental report. The
key role in scavenging of free radicals would be the distribution of OH groups over
fullerene sphere. The quantum mechanical calculations of infrared and Raman spectra
show that distribution of hydroxyl groups is responsible for hydrogen bond formation
between various OH sites [3]. In this study the influence of aqueous solution on
different fullerenol C60(OH)24 conformers is investigated using the first principle
density functional theory (DFT) calculations at the B3LYP/6-31G(d,p) level of theory
with polarizable continuum model of the solvent reaction field. The conformers were
modeled using Avogadro software and optimized by the DFT calculations. Three
different conformers were investigated with uniform, polar and equatorial distribution
of OH groups (Fig. 1). The infrared spectra were calculated, analyzed and compared
with the appropriate spectra of isolated conformers. All DFT calculations were
performed using Gaussian09 package.
Fig. 1 Structure of investigated C60(OH)24 conformers.
References
[1] S.M. Mirkov, A.N. Djordjevic, N.L. Andric et al., Nitric Oxide., 2004, 11, 201 207.
[2] 380.
[3] -Molecular And Biomolecular
Spectroscopy, 2015, 136,
82
P14
The Interaction Induced Spectra of Two-Dimensional Krypton Layer
Confined Between Graphite Slabs MD Simulation
A. Dawid, Z. Gburski
Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007, Katowice, Poland,
The dynamics of fluids in a confined space has been increasingly studied in the
recent years due to its potential applications in nanoelectronic devices, nanoscale
molecule sensors [1] and gas storage devices. The interacting pair of rare gas atoms
induce a short-lived dipole moment, which can be measured in the interaction induced
light scattering (depolarized Rayleigh) experiment [2]. Depolarized Rayleigh light
scattering spectrum is related to the polarizability anisotropy of colliding pairs of atoms.
The polarizability anisotropy can be described by the dipole-induced-dipole mechanism
(DID). The DID interactions comes from the fact that the incident light beam induces an
oscillating dipole on the ith partic
the jth particle. In order to take a closer look at the light scattering phenomenon, the
molecular dynamics simulations are helpful. The simulated spectra for Ar13 cluster
proved their sensitivity on the phase transition in the small aggregates of atoms or
molecules [3]. The properties of argon and xenon change in porous, confined space [4,
5]. In this work we have calculated the interaction-induced light scattering many-body
correlation function and its spectrum in thin krypton layer located between two parallel
graphite walls, using the classical molecular dynamics (MD) simulations. Our
calculations show substantial dependence of the interaction-induced light scattering
correlation functions of krypton atoms on the number of krypton layers between
graphite slabs (Fig. 1). To compare our research to well-known experimental data, we
have calculated the interaction-induced light scattering many-body correlation function
for the bulk krypton.
Fig. 1 The investigated krypton layer, a) projection XY, b) projection XZ
References
[1] B. Huang, Z. Li, Z. Liu, G. Zhou, S. Hao, J. Wu, et al., J. Phys. Chem. C 2008, 112, 13442.
[2] F. Barocchi, M. Zoppi, M. H. Proffitt, and L. Frommhold, Can. Journal of Physics, 1981, 59, 1418.
[3] A. Dawid and Z. Gburski, Phys. Rev. A 1997, 56, 3294.
[4] -1650.
83
P14
[5] -Molecular
And Biomolecular Spectroscopy, 2014, 129, 594-600.
84
P15
The Infrared and Raman Spectra of interacting Acetaminophen with
Cholesterol: DFT Study
A. Dawid, Z. Gburski
Institute of Physics, University of Silesia, Uniwersytecka 4, 40-007, Katowice, Poland,
It is known, that oxidative modification of the low-density lipoprotein (LDL),
which is the major carrier of cholesterol in blood stream, contributes to the development
of atherosclerosis [1]. Therefore, the properly chosen antioxidants may protect LDL
against oxidative modification. Acetaminophen, also known as paracetamol, is used as
an analgesic and antipyretic in small doses, it has also significant antioxidant properties
[2]. In this work, the infrared and Raman spectra of the system composed of
acetaminophen and cholesterol molecules were calculated using the density functional
theory (DFT). The calculations were performed at the B3LYP/6-31G(d,p) level of DFT
theory. The molecules were modeled using Avogadro software. A few different
configurations of cholesterol against acetaminophen were optimized by classical
dynamics methods and then used as starting configurations for further DFT
optimization. The binding energy, hydrogen bond formation and shapes of HOMO and
LUMO molecular orbitals are presented. All calculations were carried out with the use
of Gaussian09 package.
a) b)
Fig. 1 Chemical formula of acetaminophen (a) and cholesterol (b)
References
[1] C. Weber, H. Noels, Nature Medicine, 2011, 17, 1410-1422.
[2] J. Clin. Biochem. Nutr. 2007, 41, 27 31.
85
P16
Spectroscopic and Theoretical Studies of 4-Cyano-4-
(Phenylcarbonothioylthio)Pentanoic Acid
S. Demirci1, H. Tanak2
1 Department of Chemistry, Amasya University, 05100 Amasya, Turkey,
[email protected], [email protected] Department of Physics, Amasya University, 05100 Amasya, Turkey,
Reversible addition-fragmentation chain transfer (RAFT) polymerization, a
reversible deactivation radical polymerization, is one of the most effective and versatile
methods for providing living characteristics to radical polymerization [1]. In RAFT
polymerization, the RAFT agent, that is, sulfur-contained chain transfer agent (CTA), is
the key factor, as it plays a crucial role on the polymerization profiles, including kinetics
and control over molecular weights [2,3]. The ultimate goal of computation studies of
RAFT polymerization is to design new and improved RAFT agent to tackle any specific
control problem.
In this study, the synthesis of RAFT agent, 4-cyano-4-(phenylcarbonothioylthio)
pentanoic acid, was carried out according to the methods in the literature [4]. The
synthesized RAFT aget was characterized using FTIR, FT-Raman, 1H NMR and 13C-
NMR techniques. The structural and spectroscopic analysis of the RAFT agent was
carried out using Density Functional Theory (DFT) employing the standard 6-31G(d)
basis set, and the optimized geometries and calculated vibrational frequencies were
evaluated via comparison with experimental values.
Fig. 1 Structure of 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid
References
[1] G. Moad, E. Rizzardo and S. H. Thang, Polymer 49, 2008, 1079-1131.
[2] S. Demirci, S. Kinali- -5350.
[3] C. Barner-Kowollik, Handbook of RAFT Polymerization, Wiley-VCH: Weinheim, Germany, 2008.
[4] R. T. A. Mayadunne, E. Rizzardo, J. Chiefari, Y. K. Chong, G. Moad and S. H. Thang,
Macromolecules, 32, 1999, 6977-6980.
86
P17
A Joint Photoelectron Spectroscopy and Theoretical Study on Anion
NiAu9 Clusters
1*, O.Dereli2 1 and L. S.Wang3
1Department of Physics, University of Ahi Evran, 40100, Kirsehir, TURKEY2A. Education Faculty, Department of Physics, Necmettin Erbakan
University, Meram 42090, Konya, Turkey3Department of Chemistry, University of Brown, 02912, Providence, Rhode Island, USA
Introduction
Doped gold clusters provide opportunities to tune the properties as a function of composition
and may lead to the design of novel materials. Hence, they have attracted increasing attention in
recent years. Photoelectron spectroscopy (PES) has been combined with theoretical calculations
as an effective approach to study the electronic and structural properties of bimetallic gold-
containing clusters [1].
Transition-metal (TM) doped noble metal alloy clusters constitute an active field of research
because of their potential applications in nanoalloy catalysts and nanoelectronic devices. There
have also been numerous studies of doped gold clusters with main group elements [2].
However, to the best of our knowledge, there have been no experimental studies on Ni doped
gold clusters. In the current work, we report a combined PES and density functional theory
(DFT) study of the anionic Nickel doped gold clusters. Our goal is to elucidate their structures
and the nature of the chemical bond between Ni and Au.
Theoretical Method
The DFT structural searches for the anionic clusters were performed using the Coalescence
Kick (CK) global minimum search program [3] at the B3LYP/LANL2DZ level of theory [4].
The low-lying candidate structures were then re-optimized at the PBEPBE /Stuttgart ECP
(SDD) [5] levels. Frequency calculations were done to confirm that the reported structures are
true minima. These calculations were done using GAUSSIAN 09 [6].
Photoelectron spectroscopy
The experiment was carried out using a magnetic-bottle PES apparatus equipped with a laser
vaporization cluster source, details of which were published elsewhere [7]. Briefly, the NiAu9
cluster was produced by laser vaporization of a composite disk target made of Au and Ni.
Clusters formed in the source were entrained by a He carrier gas and underwent a supersonic
expansion to from a collimated cluster beam. The He carrier gas was seeded with 5% Ar to
achieve better supersonic cooling [8]. The cluster anions were extracted from the cluster beam
and analyzed using a time-of-flight mass spectrometer. The NiAu9 -selected
and decelerated before being photodetached.
References[1] G. V. Lopez, J. Czekner, T. Jian, W. L. Li, Z. Yang, and L. S. Wang, The J. Chem. Phys. 141, 224309 (2014)
[2] -611 (2014) 23-28
[3] A. P. Sergeeva, B. B. Averkiev, H. J. Zhai, A. I. Boldyrev, L. S. Wang, J. Chem. Phys. 134 (2011) 224304.
[4] P. J. Hay, W. R. Wadt, J. Chem. Phys. 82 (1985) 299.
[5] J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77 (1996) 3865.
[6] M. J. Frisch, et al., GAUSSIAN 09, revision A.2, Gaussian, Inc., Wallingford, CT, 2009.
[7] L. S. Wang, H. S. Cheng, J. Fan, J. Chem. Phys. 102 (1995) 9480.
[8] W. Huang, L. S. Wang, Phys. Rev. Lett. 102 (2009) 153401
87
P18
Crystal Structures and Vibrational Spectra of Molecular-Ionic
Complexes of Guanidine with Terephthalic Acids
1*, O.Dereli2, M. Marchewka3 1
1Department of Physics, University of Ahi Evran, 40100, Kirsehir, Turkey2 lu Education Faculty, Department of Physics, Necmettin Erbakan
University, Meram 42090, Konya, Turkey3Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
Okolna 2, 50-422 Wroclaw, Poland
Literature reveals that to the best of our knowledge DFT calculations and experimental
studies on infrared spectra of Guanidine with terephtalic acids have not been reported so far.
Therefore, we have carried out detailed theoretical and experimental investigation on the
vibrational spectra of this compound completely.
The starting compounds, guanidyne (Aldrich, 99%) and terephthalic acid (Aldrich, 94%)
was used as supplied and prepared in the ratio of 1:3. The dissolved acid was addedb to the
hot solution of melamine (2g) with the help of dropper. After the solution was cooled to
room temperature, it remained clear, without any precipitants. Then, the solution was
purified with the aid of active charcoal. Infrared spectra were taken with a Bruker IFS-88
spectrometer in the region 4000-80 cm-1 while powder Fourier Transform Raman (FT-
Raman) spectra were taken with an FRA-106 attachment to the Bruker IFS-88 spectrometer
equipped with Ge detector cooled to liquid nitrogen temperature.
Fig. Atomic numbering and molecular structure
The calculations were performed at DFT levels by using Gaussian 09 [1-2] program
package, invoking gradient geometry optimization [3-4]. The optimized structural
parameters were used in the vibrational frequency calculations at the DFT level to
characterize all stationary points as minima. Then, vibrationally averaged nuclear positions
of title compund were used for harmonic vibrational frequency calculations resulting in IR
and Raman frequencies. In the present work, the DFT method B3LYP with 6-311++G(d,p),
cc-pVDZ and cc-pVTZ basis sets were used for the computation of molecular structure,
vibrational frequencies and energies of optimized structures. The vibrational modes were
assigned on the basis of TED analysis for 6-311++G(d,p) basis set, using SQM program [5].
References
[1] M. J. Frisch, et all., Gaussian 03, Revision C.02, Gaussian, Inc., Wallingford, CT, 2004.
[2] H.B. Schlegel, J. Comput. Chem. 3 (1982) 214-218
[3] I. Kostova, N. Trendafilova, I. Georgieva, Spectrosc. Lett. 2007, 40, 65.
[4] T. Mihaylov, N. Trendafilova, I. Kostova, I. Georgieva, G. Bauer,Chem.Phys. 2006, 327, 209.
[5] G. Rauhut, P. Pulay, J. Phys. Chem. 99 (1995) 3093
88
P19
Molecular Structure and Vibrational Spectra of 3-Chlorocoumarin
1 1 1 2
1
Department, Konya, Turkey, [email protected]
Turkey, [email protected]
Coumarins are important molecules found in green plants and display numerous
biological properties [1-4]. They are commonly used for photo chemotherapy, anti-
tumor therapy, and anti-HIV therapy[5]. 3-Cholorocoumarin is one of important
no structural study
of this molecule.
To obtain molecular structure, conformational analysis of 3-Chlorocoumarin was
performed and only one conformer was determided. Vibrational frequences of this
conformer were calculated by B3LYP/6-311++G(d,p) level of Density Functional
Theory. The FT-IR and Raman spectra of 3-Chlorocoumarin were recorded and
compared with the calculated values for vibrational assignments.
The calculated molecular geometry parameters, molecular electrostatic
potentials (MEPs), HOMO-LUMO energies, were also given for further researchers.
Fig. 1 Structure of investigated molecule
Acknowledgment
The Authors thank to BAP (Scientific Research Projects Coordinator) office of Konya Necmettin
Erbakan University. This work was financially supported by the BAP office, Konya Necmettin Erbakan
University
References
[1] Borges, F.; Roleira, F.; Milhazes, N.; Santana, L.; Uriarte, E. Curr. Med. Chem.2005, 12, 887 916;
[2] Emmanuel-Giota, A. A.; Fylaktakidou, K. C.; Hadjipavlou-Litina, D. J.; Litinas, K. E.; Nicolaides,
D. N. J. Heterocycl. Chem. 2001, 38, 717 722;
[3] Neyts, J.; Clercq, E. D.; Singha, R.; Chang, Y. H.; Das, A. R.; Chakraborty, S. K.; Hong, S. C.; Tsay,
S. C.; Hsu, M. H.; Hwu, J. R. J. Med. Chem. 2009, 52, 1486 1490;
[4] Soine, T. O. J. Pharm. Sci. 2006, 53, 231 264.
[5] Kostova, I.; Raleva, S. Bioinorg. Chem. Appl. 2006, 1 9.
89
P20
A DFT Study on Possible Radicals of 4-Piperidinecarboxylic Acid
Molecule
1, A.Bak1 1 2
1
Department, Konya, Turkey, [email protected]
Turkey, [email protected]
Possible radicals which can be obtained from gamma-irradiated single crystal of
4-Piperidinecarboxylic acid were modelled in this study. Including recommended
radical in experimental study, total 11 radicals were modeled. Electron Spin Resonance
parameters of these model radicals were calculated and then they were compared with
the experimental ones. Geometry optimizations of the molecule and model radicals were
performed by B3LYP functionals of Density Functional Theoryand 6-311++G(d,p)
basis sets. Electron Spin Resonance parameters were calculated by the same functional
and TZVP basis sets.
Fig. 1 Structure of investigated molecule and radical
Acknowledgment
The Authors thank to BAP (Scientific Research Projects Coordinator) office of Konya Necmettin Erbakan
University. This work was financially supported by the BAP office, Konya Necmettin Erbakan University
90
P21
Spectroscopic Studies of Thermal Conversion of Electrospun
Membrane from Polyacrylonitrile (PAN) Precursor to Carbon
Nanofibers
E. Stodolak-Zych1, P. Szatkowski1, 2 1
1Department of Biomaterials, Faculty of Materials Science and Ceramics, AGH-Univ.
of Science and Technology, A. Mickiewicz 30 Ave. 30-059 Cracow, Poland,
[email protected], [email protected], [email protected] of Silicate Chemistry and Macromolecular Compounds, Faculty of
Materials Science and Ceramics, AGH-Univ. of Science and Technology, A. Mickiewicz
30 Ave. 30-059 Cracow, Poland, [email protected]
Nanoparticles are materials that have a high potential for the use in medical
applications. They can help to treat a disease by delivering drugs reducing side effects, in
diagnose diseases and by enhancing detection methods (MRI). The nanoparticles can be
used in diagnosis as well as in medical therapy. Nanoparticles thanks to their unique
properties, can be used to functionalize and the production of materials for regenerative
medicine. The focus of medicine are nanoparticles including metallic, polymeric and carbon
nanoforms. CNTs as an example of carbon nanoforms, display diverse physical, chemical
and mechanical properties suitable for a variety medical applications such as drug delivery,
support of diagnostic methods or materials to manufacturing scaffolds for regenerative
medicine [1].
Carbon nanofibers are a new biomaterial that can be used especially in the field of
regenerative medicine. The nanofibers may constitute a unique scaffolds for the
regeneration of nervous system as well as for the treatment of tissue defects in the skeletal
system. The biocompatibility of the carbon materials depend on their structure and chemical
state of the surface [2]. Controlling these parameters during manufacturing process allows
to obtain materials with desirable properties for medical use.
The aim of our work was spectroscopic analysis of thermal conversion of PAN- based
fibers manufactured by electrospinning method from the polymer solution (PAN/DMF) into
carbon nanofibers. Spectroscopic study (FTIR transmission mode and FTIR-ATR
technique) showed that during oxidation process (280-300oC) intensity of the band
attributed to nitrile CN groups in the PAN polymer decreases. This effect was accompanied
by mass loss (TG/DSC) and macroscopic shrinking of the fibers diameter (SEM). In the
next step of heat treatment, called carbonization, up to 1000oC in argon atmosphere, the
relation between intensities of C-N and C-C bands changed. Further mass losses (TG/DSC)
and macroscopic shrinkage of the fibers diameter (SEM) were observed, and those effects
were much lower than in case of typical micrometric carbon fibers.
Acknowledgments
This work has been supported by the National Science Center, Poland, under grant no. UMO-
2014/13/B/ST8/01195
References
[1] Sagadevan S., Savitha S., Preethi R., Beneficial Applications of Nanoparticles in Medical Field A
Review International Journal of PharmTech Research.2014,6(5),pp 1711-1717
[2] Blazewicz, M., Carbon materials in the treatment of soft and hard tissue injuries. Eur Cell Mater,
2001. 2: p. 21-9
91
P22
FTIR/ATR Study of Hybrid Ceramic Coatings Modified by CNT and
Silica Nanoparticles
E. Stodolak-Zych1, A. Weselucha- 3, 2, W. Niemiec2,1
1Department of Biomaterials Science, Faculty of Materials Science and Ceramics,
AGH-Univ. of Science and Technology, A. Mickiewicz 30 Ave. 30-059 Cracow, Poland,
[email protected], [email protected] Silicate Chemistry, Faculty of Materials Science and Ceramics, AGH-
Univ. of Science and Technology, A. Mickiewicz 30 Ave. 30-059 Cracow, Poland,
[email protected] of Chemical Physics, Faculty of Chemistry, Jagiellonian University,
Ingarden 3 St., 30-060, Cracow, Poland, [email protected]
The sol-gel process is a very flexible route for the fabrication materials in various
configurations such as monoliths, coatings, fibres and films. This method is prospective for
modifying the surface of metal by ceramic materials. However, such materials can not
provide an adequate protection against corrosion due to their high potential to cracks
formation in the ceramic layer obtained on the metal surface. Therefore, the preparation of
such layers is modified with organic compounds which are introduced into to sol-gel
system. Another route leading to the manufacture of functional ceramic coatings on metal is
the introduction of inorganic nanoparticles to the sol gel system [1]. This procedure not
only enhances protection against corrosion but it offers to manufacture the layers displaying
new attractive features in the range of applications in environmental protection and
medicine. This is a method allowing for the preparation of high strength layers which may
display several new features such as, e.g. self-cleaning, self-repairing, antimicrobial,
bioactive properties and others.
The aim of our work is spectroscopic study of nanocomposite layers produced using the
two-step method that combines the sol-gel and the electrophoretic deposition. In this way,
we obtained several types of hybrid silica coating which are modified by the use of carbon
(CNT) or silica nanoparticles. In our method the first step was electrophoretic deposition of
nanoparticles on the metal surface followed by covering the nanoparticles layer with silica
deposited by sol-gel method. We have developed a two-phase method that allows to obtain
a surface with a controlled structure and topography.The characteristics of the layers were
studied using FT-IR with the ATR technique, SEM, AFM and wettability contact angle
measurements. IR spectra of the samples show that the nanoparticles strongly modify the
structural parameters of the coatings. An analysis of these spectra indicates that the
structure of the hybrid layer depends not only on the type of nanoparticles, but also on the
number of OH groups on its surface. FT-IR ATR spectroscopy has also proved to be an
important and useful tool to indentify the evolution of the material following the presence
of carbon and ceramic nanoparticles.Acknowledgements This work has been supported by the National Science Center, Poland, the grant no.
UMO-2014/13/B/ST8/01195
References
[1] D.P. Pham, K.K. Huynh, C.V. Tran, V. Quang Vu, T.T. Van Tran, Preparation and structural
characterization of sol-gel-derived silver silica nanocomposite powders, International Journal of
Materials Science and Applications, 2014; 3: 147-151
92
P23
Nitric Oxide Interactions with Red Blood Cells Studied by Resonance
Raman Spectroscopy, EPR and UV-vis
J. Dybas1,2, K. M. Marzec2, B. Proniewski2, P. Berkowicz2, M. Baranska1,2,
S. Chlopicki2,3,*
1Faculty of Chemistry, Jagiellonian University, Ingardena 3, Krakow, Poland.2Jagiellonian Centre for Experimental Therapeutics (JCET), Jagiellonian University,
Bobrzynskiego 14, Krakow, Poland.3Department of Experimental Pharmacology, Jagiellonian University Medical
College, Grzegorzecka 16, Krakow, Poland.
Corresponding author: [email protected]
Despite many studies on biological role of nitric oxide (NO) in interaction with
hemoglobin (Hb) there are still some ambiguity. It has been shown, that NO molecule,
responsible for vasodilation and inhibition of platelet aggregation, can react with the
iron ion in hemoglobin on both II and III oxidation state. Whereas nitrosylHb (HbIINO)
is well known and regarded rather as an inactive source of NO, the function of
nitrosylmetHb (HbIIINO) is unclear. Nevertheless, it has been proposed, that due to the
higher diffusion rate of HbIIINO in comparison to HbIINO, this adduct can serve as NO
transporter. To test this hypothesis and formation of both derivatives in various
physiological/pathophysiological conditions, an interaction of NO with isolated human
erythrocytes was studied including low, moderate and high oxyhemoglobin (oxyHb)
content of RBC.
For analysis of Hb-NO adducts four complementary techniques were used: Resonance
Raman Spectroscopy (RRS), Electron Paramagnetic Spectroscopy (EPR), UV-Vis
Absorption Spectroscopy as well as Blood Gas Analysis (BGA). Nitric oxide was
released from NO-donor (PAPA-NO), which releases NO in half time of 15 min.
Reaction of NO with RBC was carried out in low ( <5%), moderate ( 5-35%) and high
(>90%) oxyHb content, hereby called low-, mid- and high oxyHb. To obtain such
amounts of oxyHb, the experiments were carried out in the hypoxic chamber.
Beside HbIINO and HbIIINO also the formation of methemoglobin (metHb) was
considered. In low oxyHb, an addition of PAPA-
increase but only in HbIINO formation. In mid oxyHb, mostly the level of metHb was
elevated, whereas in high oxyHb some amount of HbIIINO was identified by using RRS.
Obtained results clearly indicate, that the content of oxyHb in blood determines the way
of Hb-NO reaction and the physiological significance of HbIIINO has to be further
investigated by a multi-complementary approach.
Acknowledgement
This work was supported by the European Union from the resources of the European Regional
Development Fund under the Innovative Economy Programme (grant coordinated by JCET-UJ, No
POIG.01.01.02-00-069/09). PB is a recipient of the stipend from JMRC Foundation
93
P24
Vibrational Spectroscopy and DFT Calculations as a Diagnostic Tool of
the Cytosine Methylation
1, J. Lorenc1, U. Korzun2, J. Szopa2 J. Hanuza3
1 Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology,
2
3 Department of Solid State Spectroscopy, Institute of Low Temperature and Structure
Methylation status plays an important role in the regulation of gene expression and
influences the dynamics, bending and flexibility of DNA. It was recognized that DNA
methylation patterns differ between healthy and diseased (cancerous) tissues and therefore,
DNA methylation can be used as a biomarker for disease states [1,2].
Fourier Transform IR and Raman spectroscopies are excellent tools for
characterization of the DNA methylation status. The intensity of respective bands related to
the methyl group vibrations are particularly useful in the quantitative estimation of the
methylation degree of cytosine containing nucleic basis. The integrated intensities of these
bands can be used to evaluate the relative concentration of the methyl group formed in the
process of cytosine methyl group metabolism. In these calculations DFT quantum chemical
calculations have been used to characterize and compare the structural and vibrational
properties of N-heterocyclic molecules such as cytosine and 5-methylcytosine.
In the geometry optimization the Gaussian 03 programme package has been used
with the 6-311G(2d,2p) basis set and B3LYP functional. The PED data have been applied
to compare the methylation status of normal and methylated cytosine.
4000 3500 3000 2500 2000 1500 1000 500
N
NNH2
H
H
CH3
O
N
NNH2
H
H
H
O
5-methylcytosine
Ab
so
rba
nce
Wavenumber / cm-1
cytosine
Conclusion: Vibrational spectroscopy is an effective diagnostic tool for quantitative
estimation of methylation degree of cytosine nucleotide.
References
[1] Z. Taleat, K. Mathwig, E.J.R. Sudholter, L. Rassaei, Detection strategies for methylated and
hypermethylated DNA, Trends in Analytical Chemistry 66 (2015) 80-89
[2] Kai Wu, Xing Su, Mineo Yamakawa, Detection of DNA methylation using Raman spectroscopy, US
20080241828 A1
94
P25
The Thermal Behaviour of Li/Na/KY(WO4)2 Nanocrystalline Powders
co-Doped with Er3+ and Tm3+ Ions
-Robak1, L. Macalik2, P.E. Tomaszewski2, 1,
J. Lorenc1, J. Hanuza2
1 Institute of Chemistry and Food Technology, Faculty of Engineering and Economics,
-2 Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
-
MY(WO4)2 (M = Li, Na, K) nanopowders doped with Er3+ and Tm3+ ions have been
synthesized by Pechini method. The samples were calcined in the temperature range from
grain size. Structural properties are characterised by X-ray diffraction (XRD), Raman and
IR spectroscopy.
NaY(WO4)2 crystalizes in the I41/a tetragonal structure. The respective values of the
lattice parameters is observed, the lowering of lattice parameter values is characteristic for
nanocrystalline matter. The samples calcined in the temperature range 550 -
same diffraction pattern with different broadening of Bragg lines indicating nanocrystalline
character of the samples.
The X-ray powder diffraction of potassium yttrium double tungstates shows that the
samples are biphasic for low-temperature calcination and monophasic for calcination at the
-temperature phase corresponding to greater
crystallites, is monoclinic, and the same as the room-temperature phase of bulk crystal. The
However, in the case of LiY(WO4)2 two types of structures were found: there is a
transition from monoclinic to tetragonal phase at calcination temperature higher than
parameters 1/a tetragonal
phase of LiY(WO4)2 has the unit cell parameters as follows: a
Although the lattice parameters of both phases are quite similar and do not change with
calcination temperature (Fig. 1.), the
crystal motives are significantly different.
The monoclinic phase is built of zig-zag
chains of WO6 octahedra connected by
common edge and going along c-direction
contains separated tetrahedra WO4. Thus,
the molecular mechanism of the structural
phase transition is not clear.
Figure 1.
Lattice parameters versus calcination
temperature.
95
P26
Insight into the Mechanism of Antibacterial activity of
Tetra-p-Quanidinoethylcalix[4]Arene.
An Experimental and Molecular Dynamics Study
M. Gorczyca1*, B. Korchowiec1, J. Korchowiec1, J. -B. Regnouf de Vains2,
E. Rogalska2
1Faculty of Chemistry, Jagiellonian University, R. Ingardena 3, 30-060 Krakow,
Poland, * [email protected]
euvre- -Nancy cedex, France
Calixarenes, a class of macrocyclic oligomers, have shown antibacterial activity.
In this regard, we demonstrated recently that different calixarene derivatives modify the
properties of model membranes [1-2]. In the present work the behavior of tetra-p-
guanidinoethylcalix[4]arene (CX) and its monomer p-guanidinoethylphenol (mCX) in
a membrane environment was studied. CX was synthesized as an antibacterial agent.
Indeed, this derivative is active against different Gram-positive and Gram-negative
bacteria and does not show cell toxicity [3]. Interestingly, the antibacterial activity of
mCX is much weaker compared to CX. Here, all atom molecular dynamics simulations
(MD) and surface pressure measurments were employed to better understand the
mechanism of the the interaction of CX and mCX with lipid membranes. A zwitterionic
1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and a negatively charged 1,2-
dimyristoyl-sn-glycero-3-phospho-L-serine (DMPS) were used as models of eukaryotic
and bacterial cell membranes, respectively. All MD simulations were performed using
NAMD2 package and CHARMM27 force field. The simulations were carried out under
a constant number of particles (N), constant temperature (T), constant normal pressure
(pN) and constant surface tension ( ): NpN T ensemble. The results obtained show that
the two guanidinoethyl derivatives have different impact on model lipid membranes. It
was demonstrated that CX and mCX concentrate near the anionic DMPS monolayer.
Moreover, in contrast to the p-guanidinoethylphenol, calixarene penetrates the
hydrophobic part of the phospholipid film. In the case of the zwitterionic DMPC, no
significant effect of CX and mCX on the properties of phospholipd film was observed.
The overall results indicate that charge-charge and apolar interactions between CX and
lipids are responsible for the reorganization of model membranes.
Acknowledgements: This work was supported by the Polish National Science Centre, project No.
2012/07/B/ST5/00890. M. G. acknowledges the financial support from the project Interdisciplinary PhD
-financed by the European Social Fund within the Human
Capital Operational Programme).
Literature
[1] Korchowiec B., Gorczyca M., Ben Salem A., Regnouf de Vains J.-B., Rogalska E., Colloids Surf. B
2013, 103, 217-222.
[2] Korchowiec B., Korchowiec J., Gorczyca M., Regnouf de Vains J.-B., Rogalska E.,
J. Phys. Chem. B 2015, 119(7), 2990-3000.
[3] Mourer M., Duval R. E., Finance C., Regnouf de Vains J.-B., Bioorg. Med. Chem. Lett. 2006, 16,
2960-2963.
96
P27
Structural and Thermal Studies of Modified Silica-Strontium-Barium
Glass from CRT
I. Grelowska1*, M. Kosmal2, M. Reben1, P. Pichniarczyk2, M. Sitarz1,
Z. Olejniczak3
1AGH University of Science and Technology,Faculty of Materials Science and
Ceramics,Mickiewicza 30, 30-059 Cracow, Poland2Institute of Ceramics and Building Materials, Division of Glass in Cracow,
Lipowa 3, 30-702 Cracow, Poland3Institute of Nuclear Physics PAN, Department of Magnetic Resonance Spectroscopy,
Radzikowskiego 152, 31-342 Cracow, Poland, * [email protected]
Glasses were prepared by conventional melting method from 100 g batches.
The influence of alumina and calcium oxide onto crystallization process of silica-
strontium-barium glass from Cathode Ray Tube (CRT) were studied by means of 27Al MAS NMR and FTIR spectroscopy. This made possible to determine the influence
of additives e.g. blast furnace slag and cement dust on the structural changes of glasses
(changes in the spectra shapes). The introduction of waste modifiers to the glass
structure leads to leads to breaking of Al O Si and Si O Si bonds what causes the
depolymerization of the glass network. From the FTIR spectra the narrowing of bands
at 1022 and 1027 cm-1 was observed, which may indicate the ordering of glass network.
Appearance of alumina in coordination 4 was confirmed by NMR investigations.
The effects of compositional variation, thermal treatment on the nature, type and
stability field of crystallizing phases and microstructure formed in CaO and/or Al2O3
silica-strontium-barium glasses were described using DTA/DSC method. Thermal
characteristics of glasses like the transition temperature Tg, the temperature for the
crystallization Tc, thermal stability parameter were determined. The crystalline phase
was determined by the X-ray diffractometry. The micro-structure of the samples was
studied by SEM technique. Analysis of the local atomic interactions in the structure
of glasses has been used to explain the course of the crystallization.
97
P28
Structural and Optical Study of Tellurite-Barium Glasses
Grelowska1*, M. Reben1, B. Burtan2, 2, J. Cisowski2,
El Sayed Yousef3 1, M. Sitarz1
1AGH University of Science and Technology,Faculty of Materials Science and
Ceramics, Mickiewicza 30, 30-059 Cracow, Poland2
30-084 Cracow, Poland3King Khalid University, Department of Physics, Faculty of Sciences,
P. O. Box 9004, Abha, Saudi Arabia* [email protected]
The goal of this work was to determine the effect of barium oxide on the
structural, thermal and optical properties of the TeO2-BaO-Na2O (TBN) and
TeO2-BaO-WO3 (TBW) glass systems. FT-IR and Raman spectra allow to relate the
glass structure and vibration properties (i.e. vibrational frequencies and Raman
intensities) with the glass composition. FT-IR and Raman spectra show the presence of
TeO4 and TeO3+1/TeO3 units that conform with the glass matrix. Differential thermal
analysis DTA, XRD measurements have been considered in term of BaO addition. The
spectral dependence of ellipsometric angles of the tellurite-barium glass has been
studied. The optical measurements were conducted on Woollam M2000 spectroscopic
ellipsometer in spectral range of 190 1700 nm. The reflectance and transmittance
measurements have been done on spectrophotometer Perkin Elmer, Lambda 900 in the
range of 200 2500 nm (UV-VIS-NIR). From the transmittance spectrum, the energy
gap was determined.
98
P29
Substituent Influence on the Spectra of Some Benzo-f-Quinoline
Derivatives
G. Oanca, A. Gritco Todirascu, D. Creanga, D. Dorohoi
The study was focused on organic compounds derived from benzo-f-quinoline,
following the addition cycle formation to the nitrogen atom (named BQCD) aiming to
compare electronic absorption spectra as well as electro-optical parameters like dipole
moment and polarizability. The structural and energetic properties of the radical
substituent to the addition cycle were estimated by quantum chemical modeling. The
optimized molecular structures (or geometries) were calculated using Gaussian 09, DFT
with B3LYP/6-31G(d,p) basis set. The VMD (Molecular Visual Dinamics) was used
only to represent the geometry based on the Gaussian output data. From this calculation
were also extracted the dipole moment and polarizability, energetic parameters etc. The
same mathematical approach was applied to the corresponding derivatives of benzo-f-
quinoline (named BQCD1-3, Fig. 1, with possible applications as staining agents in
textile industry).
Fig. 1. Structures of studied compounds and linear dependence between polarizability values
Linear correlations was emphasized between substituent and BQCD dipole
moments (with correlation coefficient of 0.96); still higher linear correlation coefficient
(0.99) was obtained for the polarizability dependence.
Discussion was developed based on the electronic mobility along the benzo-f-
quinoline structure and the influence of substituent (close to nitrogen atom) on that one.
Comparison between theoretical simulated spectra in the U-Vis range and those
recorded in experimental conditions was also discussed.
Acknowledgement
This study was sustained by POSDRU/187/1.5/S/155397 program of European Social Fund in
Romania under the responsibility of the Managing Authority for the Sectored Operational Program for
Human Resources Development 2007- ite
99
P30
Methyl Group Effect on to the IR Spectral Properties of the Hydrogen
Bond in Two Thioamides: N-Benzylthioacetamide and N-
Benzylthioformamide
E. Turek1, 1 -Lindert2, P. Lodowski1
1Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland,
[email protected], [email protected], [email protected] of Mechanized Construction and Rock Mining, Al. W. Korfantego 193A,
Katowice, Poland, [email protected]
Polarized IR spectroscopy constitutes a very sensitive tool for characterizing hydrogen bonds in
terms of their diversity as well as of the strength of the vibrational exciton coupling acting in
multiple hydrogen bond systems [1]. Amides are widely exploited in crystal engineering
because they generate reliable catemer supramolecular synthons via hydrogen bonding [2].
The fine structure patterns of the N-H and N-D bands of N-benzylthioacetamide (NBTA)
and N-benzylthioformamide (NBTF) and their spectral effects are significantly different as for
very similar molecular systems. Exciton interaction between hydrogen bonds in infinitely long
chains in the lattice of NBTA prefer side-to-side type coupling in comparison with NBTF where
tail-to-head type coupling is more privileged. The source of these differences has its base in
electronic structure both molecular systems, especially in their electronic charge density.
Functional group linking to the carbon atoms in the thioamide fragments strong affects the
electronic properties of the associating molecules. In turn, these molecular electronic properties
are responsible for the generation mechanisms of the IR spectra of the hydrogen bond.
In this work we will try to confirm these relations by carrying out quantum-chemical
calculations of the electronic density distribution in thioamide groups of NBTA and NBTF.
Fig. 1. Influence of electronic density distribution in the thioamide fragments of NBTA and NBTF on
generation of the IR spectra of the hydrogen bond
References
[1] 338.
[2] V. Suryanti, M. Bhadbhade, R. Bishop, D. StC Black and N. Kumar, CrystEngComm, 2012, 14,
7345 7354.
100
P31
Near-Infrared Laser-Induced Generation of Three Rare Conformers
of Glycolic Acid
Anna Halasa , Leszek Lapinski , Igor Reva , Hanna Rostkowska , Rui Fausto ,
and Maciej J. Nowak
Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, 02-668 Warsaw, Poland.
CQC, Department of Chemistry, University of Coimbra, 3004-535 Coimbra, Portugal. [email protected]
Conformational changes of glycolic acid isolated in cryogenic matrices were induced by
excitation of the OH stretching overtones with monochromatic near-IR light, generated
by a tunable diode laser [1].
In Ar matrices, molecules of glycolic acid were trapped in their most stable SSC
conformational structure. Upon narrowband near-IR excitation of SSC, two higher-
energy conformers (GAC and AAT) were generated. More detailed investigation
revealed a stepwise SSC GAC AAT scheme of this phototransformation.
Furthermore, GAC and AAT conformers were shown to transform into each other, in a
photoreversible way, upon selective near-IR excitations.
A dramatically different transformation was observed for the compound isolated in N2
matrices, where the most stable SSC form converted, upon near-IR excitation, solely
into a new conformer (SST). This process was demonstrated to be photoreversible.
Moreover, when the N2 matrix was kept at cryogenic temperature and in the dark, the
photoproduced SST conformer converted spontaneously, by proton tunneling, to the
most stable SSC form.
Reference
[1] A. Halasa, L. Lapinski, I. Reva, H. Rostkowska, R. Fausto, M. J. Nowak, J. Phys. Chem. A, 118
(2014) 5626-5635.
101
P32
On Optimization of Absorption Dispersion Spectra
J. P. Hawranek,
F. Joliot-Curie 14, 50-
Poland.
A novel procedure for analysing spectra of the complex electric permittivity:
)()()( i
of liquids in the Infrared region is presented. These spectra are derived from
experimental spectra of the complex refractive index determined by various methods
[1,2]. Subsequently, they are used to determine important quantities, e.g. spectra of
complex molecular polarizabilities and an integral property the molar vibrational
polarization. The accuracy of these quantities depends essentially on the accuracy of
both components of the complex electric permittivity spectrum.
In the proposed procedure, the spectra of the complex electric permittivity are
approximated using the Classical Damped Harmonic Oscillator model for the
description of individual bandshapes. The final band parameters are obtained by
simultaneous optimization of both the real and imaginary parts of the spectrum, with an
expected gain in accuracy. Hitherto, to our best knowledge, only the imaginary ( i.e.
absorptive ) part was optimized in existing software.
Due to the complexity of the problem, we restricted the choice only to non-
gradient methods of optimization. The performance of several gradientless methods was
tested. Among the numerous procedures the Powell General Least Squares Method
Without Derivatives [3], available in MATLAB, was found to be the most efficient. The
reliability of the obtained results of the band separation process was tested on several
simulated spectra of increasing complexity.
An important advantage of the procedure is the possibility to determine the
molar vibrational polarization separately for each mode, what is particularly useful in
studies of hydrogen-bonded systems. Examples of application of the method to analysis
of experimental spectra are presented.
References
[1] J.E Bertie, in Handbook of Vibrational Spectroscopy, J.M. Chalmers and P.R. Griffiths, Eds., John
Wiley and Sons Ltd, Chichester 2002, vol.1, p.88.
[2] J.P.Hawranek, A.M. Muszy Chem., 22(1998)95.
[3] MJ.D.Powell, Comp.J., 7(1964)155.
102
P33
Vibrational Spectra, NBO analysis and Antitumor Properties of
the Novel, cis-Diammine(5-fluoroorotato)platinum(II) Complex
K. Helios1 1, M. Malik1, J. Wietrzyk2, D. Michalska1
1 chowskiego 23,
50- [email protected] ,[email protected],
[email protected], [email protected] of Immunology and Experimental Therapy of the Polish Academy of Sciences,
Weigla 12, 53- [email protected]
The discovery of the antitumor activity of cisplatin, cis-[PtCl2(NH3)2], has
initiated an intense search for new platinum-based chemotherapeutic agents with
reduced toxicity and a broader spectrum of activity.
In this work we synthesized the novel platinum(II) complex with 5-fluoro
derivative of orotic acid, cis-[Pt(5-FOro)(NH3)2], Fig. 1.
Fig. 1. The molecular structure of cis-[Pt(5-FOro)(NH3)2].
The FT-Raman and FT-IR spectra of the complex have been measured.
Comprehensive theoretical studies have been performed by using density functional
B3LYP and PBE0 methods with the LanL2TZ(f) ECP/basis set for Pt and D95V(d,p)
basis set for the remaining atoms. The theoretically predicted IR and Raman spectra
show very good agreement with experiment. The clear-cut assignment of the
experimental vibrational spectra has been made on the basis of the calculated potential
energy distribution (PED). The Natural Bond Orbital (NBO) analysis has provided the
detailed insight into the type of hybridization and the nature of platinum-ligand bonding
in the title compound. Both the theoretical results and the experimental vibrational
spectra reveal the presence of strong intramolecular hydrogen bonding between the
carbonyl oxygen atom of the orotate ligand and the NH3 group coordinated to Pt i, Fig. 1), which stabilizes the structure of the title complex.
The anticancer activities and toxicity of the title complex have been studied and
the results are very promising. Cis-[Pt(5-FOro)(NH3)2] shows very strong activity
against human prostate adenocarcinoma (LNCaP) and it is much less toxic to normal
healthy cells than cisplatin.
103
P34
34S
Stable Isotope Analyses
M. Huber1 2, L. Lata1
1Earth Science and Spatial Management Faculty, Maria Curie
Lublin, Poland, [email protected] Institute, Maria Curie
The Khibina and Lovoziero Massifs are intrusions of alkaline rocks, built in concentric
circles of rocks. In Khibina inner part of the intrusion is fojaites, the outer is a massive syenite
called khhibinites and between them is ore zone (apatite-nephelines) and numerous veins mainly
filling rifts and fault zones. Rocks veins is primarily various kinds of microsyenits, tinguaites
and melteigites. The Lovoziero Massif is composed of a portion where the inner luyavrites and
outer constructed with syenites, porphirites. Present there are also numerous and pegmatite ore
body.
In all these rocks encountered mineralization containing inclusions or their own phase in
which the REE are present (Arzamastsev et al., 2008, Boruckiy 1989 Kramm et al. 1993,
Kukharenko et al 1965). As a result of microprobe analysis determined that these are often
minerals such as ilmenite, sphene, rutile, apatite and sulphides. Quite often these minerals
encountered numerous additions of Sr, Nb, Ce, Th, U (fig 1). In addition, these rocks are also
numerous rare earth minerals such as loparite, murmanite, epistolite like.
Stable 34S isotope also examined from sulphides determined multi-stage mineralization
of these rocks. It is present a pyrite, chalcopyrite, and galena, sphalerite, cubanite.
Fig. 1 Examples spectrum of cerium group elements in the analyzed rocks
References[1] A.A. Arzamastsev, Unique Paleozoic Intrusions of the Kola Peninsula. Apatity: Kola Scientific Centre: 1994,
79.
[2] B.E. Boruckiy, Rock-forming minerals of the high-alkaline complexes. Nauka, 1989, 214.
[3] M. Huber, Preliminary characterization of the mineral veins occurring in the Malaya Belaya Valley in the
Khibiny. J. Biol. Earth Sci. 3 (1) 2013, E1-E11.
[4] M. Huber, Microanalysis of alcaline rocks from the Khibina Massif using SEM-EDS and mathematical
methods. Journal of Biology and Earth Sciences 5(1), 2015 82-99.
[5] M. Huber, First discovery of melteigite rocks with perovskite from the Khibina Massif. Journal of Biology and
Earth Sciences 5(1), 2015, 74-81.
[6] A.F. Mitrofanov, Geological characteristics of Kola peninsula. Russian Academy of Science, Apatity, 2000,
166.
[7]
104
P35
A New Possibility of Flints Identification Using Spectrometric Methods
Huber M.1, Gruszecki W.2 , .2, Libera L.3,
Szeliga M.3, Budziszewski J.4
1Earth Science and Spatial Management Faculty, Maria Curie
Lublin, Poland,[email protected] of Phisic, Maria Curie
3Institute Archeology, Humanistic Faculty, Maria Curie
Poland, e-mail: [email protected] 4Archeology Institute UKSW Warsaw, Poland
Specialists in the identification of the origin of chocolate flint (founded in the
secondary anthropogenic accumulations) for many years trying to find a way to classify
this material to repeatedly and unequivocally can determine its origin. For this purpose
were conducted by numerous researchers study different but to date have failed to
clearly define the typical characteristics of flint allowing for unambiguous distinguish
them from each other. Some light on the present state of research casts the possibility of
using spectroscopic methods and fluorescent in visible light to identify color
components of flint and attempts at cataloging. For this purpose is used
Spectrofluorometer FS-5 (Edinburgh Instruments, UK) which was performed
fluorescence spectra and then a division of the components. In calculating the surface
area of these components they compared them with each other to determine the
coefficient of saturation. This factor was determined at wavelengths 460nm and 555nm
(Figure 1). In carrying out the comparison for several groups of flint (Oronsko,
Rejowiec, striped) yielded results that might shed new light on their classification.
Fig. 1 Structure of flint fluorescence spectrum
References
[1] M. J. Black, R. B. Brandt, Spectrofluorometric analysis of hydrogen peroxide Analytical
Biochemistry Volume 58, Issue 1, March 1974, Pages 246 254
[2] K. Osseo-Asare, F.J. Arriagada, Preparation of SiO2 nanoparticles in a non-ionic reverse micellar
system Colloids and Surfaces Volume 50, 1990, Pages 321 339
105
P36
Study of Sulphides from Piechenga Rocks Using Geochemical and
Stable Isotope Analyses
M. Huber1 2, L. Lata1, Yu. N. Neradovski 3, A. Mokrushin3
1Earth Science and Spatial Management Faculty, Maria Curie
Lublin, Poland, [email protected] Institute, Maria Curie
[email protected] Science Center, Apatity, Russia, [email protected]
Piechenga is a multi-stage Archean (2,9-2,5Ga) age intrusion, composed mostly
of ultrabasic rock [1,2]. They are accompanied by lot of secoundary type rocks (younger
granitoide intrusions) and hydrothermal veins. There are rocks such as dunites,
pyroxenites and gabbronorites. In these rocks are identified sulfides such as pyrite,
chalcopyrite, pentlandite. Microanalysis of these rocks are analyzed shows a multistage
association with polimetallic mineralization of these rocks. Stable isotope 34S analyzes 14 18O in carbonates associated in some veins.
Carbonates isotopic values refer to the fluids from the deep structure of Earth. The
sulfur analysis indicate polysynthetic mineralization present in these rocks has been
investigated in detail.
References
[1] A.F. Mitrofanov, Geological characteristics of Kola peninsula. Russian Academy of Science,
Apatity, 2000, pp. 166.
[2] , Apatity ,
2002, pp.360
106
P37
Pollution Destruction Processes in Architecture Detail of old Lublin
M. Huber, L. Lata
Earth Science and Spatial Management Faculty, Maria Curie
Lublin, Poland, [email protected]
rodzaju wapienie i piaskowce
o wykwity siarczanowe oraz domieszki metali kolorowych (fig 1).
Fig 1 Addition of metals in wall samples from center of Lublin
Literatura
[1] -
450.
[2] Gawarecki H O dawnym Lublinie. Szkice z przesz miasta. Wyd. Lubelskie, 1974 Lublin.
[3] Gawarecki H , Gawdzik C , Lublin krajobraz i architektura. Arkady, 1964 Warszawa.
[4] Menclt T . Dzieje Lubelszczyzny. 1 9 7 4 PWN, Warszawa.
[5] A, Lubelskie staromiejskie w procesie formowania redniowiecznego miasta. Wyd. 1997
UMCS, Lublin .
[6] A, R, Stasiak M, Lublin wczesno redniowieczny: studium rozwoju przestrzennego.
Fundacja na Rzecz Nauki Polskiej. 2006 Wyd. Trio, Warszawa.
107
P38
Raman Scissor Mode and 13C Chemical Shift of Betaine Carboxylate
Group in Structural Analysis of Betaine Acid Crystals
M.Ilczyszyn, M.M. Ilczyszyn
Faculty of Chemistry University of Wroclaw, Poland,
[email protected], [email protected]
Hydrogen bonds in series of crystals formed by betaine with different acids water,
boric acid, selenic acid, othoarsenic acid, orthophosphoric acid are characterized by
f the H-bonds,
scissoring mode of the carboxylate group, 13C chemical shift of the carboxylate group,
Raman and NMR tensors based on the corresponding parameters.
The main motifs in these crystals are the betaine acid structural units, treated by
us as com -3]. These complexes are formed by the
strongest (shortest) H-bonds in the crystal, (O1 H-O)com or (O1-H O)com, between the
acidic O-H and betaine CO1O2 groups. The complexes are linked by additional and
weaker H-bonds, (O2 H-O)net and/or (O1 H-O)net, thus forming the H-bonding
network.
More acidic acids form stronger complexes accompanied by stronger network
H-bonds and this tendency is very regular. The R(O1 com distances also correlate
with the 13C isotropic chemical shift of the betaine CO1O2 group and wavenumber of
its scissoring band. Some principal components of the corresponding tensors (the
Raman and 13C NMR ones) are much more sensitive on considered H-bonding.
References
[1] M. Ilczyszyn, D. Godzisz, M. M. Ilczyszyn, K. Mierzwicki. Chem. Phys., 2006, 323, 231 242.
[2] M. Ilczyszyn, D. Chwaleba, Z. Ciunik, M.M. Ilczyszyn, Chem. Phys., 2008, 352, 57 64.
[3] M. Ilczyszyn, D. Chwaleba, K. Mierzwicki, M.M. Ilczyszyn, Chem. Phys., 2008, 351, 99 105.
108
P39
What is a Crystal Structure of Pyridinium Methanesulfonate?
Vibrational and XRD Studies
M.M. Ilczyszyn1, D. Jesariew2
1
[email protected] 2 Poland
A stoichiometric pyridine-methanesulfonic acid complex (pyridinium
methanesulfonate; PyHMS) was found as a suitable model to study proton transfer and
hydrogen bonding phenomena [1]. On the other hand, due to the proton transfer from
the acid (methanesulfonic acid) to the base (pyridine) the studied complex appears as a
promising non-aqueous, solid electrolyte (protonic conductor) [2].
To consider the proton transfer, hydrogen bonding and the proton conductivity
in PyHMS the precise crystal structure of this compound is needed. Two contributions
on the crystal structure of PyHMS are available in the scientific literature [1,3].
Unfortunately the both reported structures are different. According to the data in Ref.
[1] PyHMS crystallizes in the centrosymmetric Pbca space group. In turn, according to
the data reported in Ref. [3] PyHMS crystallizes in the non-centrosymmetric Pna21
space group. It is worth to note, that in both cases, Ref. [1] and Ref. [3], the XRD data
were collected at the same temperature.
To explain difference of the reported crystal structure of PyHMS we have
examined its properties by: (1) DSC studies; (2) single crystal XRD at various
temperature and (3) vibrational spectroscopy in the wide temperature range (298
11K).
The most interesting and important results obtained in this contribution are as follows:
1. The PyHMS crystal exhibits two polymorphic forms in the 100 453 K
temperature range and phase transition at Tonset=255.8 K.
2. PyHMS crystallizes in the non-centrosymmetric Pna21 group (in the high
temperature phase I) and in the centrosymmetric Pbca group (in the low
temperature phase II).
3. The structural properties of the PyHMS crystal strongly dependent on the way of
cooling of the sample. This finding may explain the differences in the crystal
structure reported in Ref. [1] and Ref. [3].
4. Collected experimental results show that the PyHMS crystal undergoes a fully
reversible displacive structural phase transition.
References
[1] O. Lehtonen, J. Hartikainen, K. Rissanen, O. Ikkala, L.-
[2] D. De Sousa meneses, P. Simon, Y. Luspin, Phys. Rev. B, 2000, 61, 14382.
[3] M. Bolte, Ch. Griesinger, P. Sakhaii, Acta Crystallogr., 2001, E57, o458.
109
P40
Spectroscopic Studies of Free carbon in SiOxCy Glasses
AGH University of Science and Technology, Faculty of Materials Science and Ceramics
Al. Mickiewicza 30-
Glasses from SiOxCy system are materials where two O2- ions are substituted by
one C4- ion. The amount of carbon that can be introduced to the glass matrix is limited.
Too high concentration of carbon leads to creation of carbon inclusions, thus changing
the key properties of the material (i.e. electrical, chemical, mechanical, etc.).
SiOxCy glasses (bulk and layers on steel substrate) were prepared from ladder
like silsesquioxanes of defined T/D units ratio using a sol-gel method. This parameter
allows controlling the amount of C atoms introduced into the glass structure. Samples
were fired in tube furnace in flowing argon atmosphere at temperatures ranging from
500 to 800oC.
XRD measurements confirmed that obtained samples are fully amorphous. SEM
with EDX studies of both bulk and layers material reveled presence of carbon inclusions
in SiOC matrix. Further Raman and XPS investigations allowed determining the nature
of free carbon phase.
Acknowledgements
-like
110
P41
Theoretical Analysis of Vibrational Spectra of Sodalite Structure
1 1 1
1 Faculty of Materials Science and Ceramics, AGH University of Science and
Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland,
A series of ab initio calculations (geometry optimization and vibrational spectra
calculations) for periodic model of sodalite framework with Si/Al ratio equal to 1 and
various alkaline and alkali-earth metal cations (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+,
and Ba2+) by means of Crystal14 program within HF formalism has been carried out.
The analysis of obtained results allowed (based on visualizations of calculated normal
modes of vibrations) the assignment of respective bands to particular vibrations and
thus detailed spectra characterization.
Calculated spectra agree well with experimental ones and it follows from the
results that the changes in IR spectra envelope are strictly related to relative locations of
non-tetrahedral cations as well as to coordination and the nature of interaction between
these cations and aluminosilicate framework. Since main building block of sodalite
( -cage) is a very common unit present in many zeolite frameworks (e.g. LTN, FAU,
LTA, MAR or TSC), presented approach can be also successfully applied to theoretical
analysis of experimental spectra measured for other more complex structures based on
sodalite cage.
Acknowledgment
This research was supported in part by PL-Grid Infrastructure and in part the calculations have been
carried out using resources provided by Wroclaw Centre for Networking and Supercomputing
(http://wcss.pl), grant No. 297.
111
P42
Comprehensive Analysis of Vibrational Spectra of Selected Smectite
Type Minerals
1 1
1 Faculty of Materials Science and Ceramics,
AGH University of Science and Technology,
30 Mickiewicza Av., 30-059 Krakow, Poland, [email protected]
Smectites are a group of 2:1 type fylloaluminosilicate, which lattice consists of
two-dimensional layers (every such layer is built out of two tetrahedral silicate
sublayers separated by octahedral sheet of alumina). Isomorphic substitution in such
packet (either within tetrahedral or octahedral or both sublayer type) generates negative
charge, compensated by easily replaceable, the so-called exchangeable, alkali or
alkaline earth cations between the packets.
Numerous studies available in literature focus on the use of vibrational spectra in
determination of the structure of clay minerals or analysis of various processes with
their use. On the other hand, despite well known fact that theoretical analysis of
vibrational spectra can provide important data allowing better understanding and
characterization of respective experimental ones, there are only few studies devoted to
such analysis available for clay minerals, which is due to a significant computational
difficulties resulting from low symmetry of unit cell, big number of symmetrically
nonequivalent atoms and partial occupation of some of atomic positions within a cell. In
presented work, selected minerals belonging to smectite group were characterized by
FT-IR and Raman spectroscopy. The ab initio calculations of IR and Raman spectra
were carried out for corresponding model crystal structures by means of Crystal14
program and the obtained theoretical spectra were used in detailed analysis of
experimental ones.
Acknowledgment
This research was supported in part by PL-Grid Infrastructure
112
P43
Theoretical and Experimental IR, Raman, UV, and NMR Spectra of
1,4-Di(3-Hydroxymethylpyridinium)Butane Dibromide
A. Komasa
Faculty of Chemistry, Adam Mickiewicz University,
Umultowska 89b, 61-
3-Hydroxymethylpyridine (3HMP) is a very interesting pyridine derivative as it is a
nicotinic acid analogue known for its anti-lipolytic and anti-inflammatory properties.
3HMP has the ability to reduce blood fats and is an ingredient of drugs dilating blood
vessels [1,2]. Moreover, 3-hydroxymethylpyridine acts as a ligand which binds to
different metal atoms forming coordination complexes [3].
In this communication a new compound built of two 3HMP units connected by
butane linker: 1,4-di(3-hydroxymethylpyridinium)butane dibromide is reported. It was
synthetized in reaction of 3-hydroxymethylpyridine with 1,4-dibromobutane in
acetonitrile.
Fig. 1 The optimized structure of 1,4-di(3-hydroxymethylpyridinium)butane dibromide.
This compound was characterized by IR, Raman, UV-Vis, 1H and 13C NMR spectro-
scopies. Quantum-chemical calculations were performed at B3LYP/6-311++G(d,p)
level of theory to support interpretation of the spectra. In the IR and Raman spectra the
most intensive bands were assigned to theoretically predicted vibrational frequencies.
The assignment was made with the help of the potential energy distribution (PED)
analysis. Quantum chemical simulation of UV-absorption was performed using time-
dependent DFT approach and the effect of a solvent on the predictions of the spectra
was considered. The 1H and 13C magnetic isotropic calc) were
pred calc has been obtained
exp) data.
Acknowledgment
The study was supported by Polish Norwegian Research Program No. Pol-Nor/203119/32: Superior bio-
friendly systems for enhanced wood durability.
part by PL-Grid Infrastructure.
References
[1] M. Cohen, Life Sciences, 37, 1985, 1949-1961.
[2] S.C. Mojumdar, M. Melnik, E. Jona, J. Thermal. Anal. Cal. 61, 2000, 915-922.
[3] M. Koman, G. Onrejovic, Advanced Science, Engineering and Medicine 5, 2013, 598-602.
113
P44
Spectroscopic, X-RAY and Theoretical Analysis of
-Di(3-Hydroxymethylpyridinium)Pentane and Hexane Dibromides
A. Komasa -Sitarz, A. Katrusiak,
Z. Dega-Szafran, M. Szafran
Faculty of Chemistry, Adam Mickiewicz University,
Umultowska 89b, 61-
Pyridinium and bis-pyridinium quaternary salts are classes of compounds having a
wide range of interesting properties useful for biological and industrial applications and
continuing to receive an increasing attention. Some of them are used as biocides, drugs, and
herbicides [1] and in the treatment of diseases such as Alzheimer's, glaucoma and
myasthenia gravis because they are acetylcholinesterase inhibitors [2].
In the present study we report on the crystal and molecular structure of 1,5-di(3-
hydroxymethylpyridinium)pentane dibromide [3HMP(5)Br2] and 1,6-di(3-hydroxy-
methylpyridinium)hexane dibromide [3HMP(6)Br2] resolved on the basis of X-ray
diffraction and DFT calculations as well as by FTIR, Raman and NMR spectroscopy.
The X-ray analysis revealed significant differences between the structures of these
two salts. The molecule of 3HMP(5)Br2 is asymmetric with two different hydrogen bonds
O-H Br while compound 3HMP(6)Br2 occurs in two symmetric non-equivalent crystal
structures, which differ in all geometric parameters (Fig. 1). The geometry differences of
hydrogen bonds are reflected in the IR spectrum.
-di(3-hydroxymethylpyridinium)pentane (a) and hexane (b)
dibromides.
Quantum-chemical calculations were performed at B3LYP/6-311++G(d,p) level of
theory. After geometry optimization theoretical NMR and IR spectra were computed. The 1H and 13
calc) were obtained by GIAO approach.
calc were obtained.
In the FTIR spectrum the most intensive bands were assigned to theoretically predicted
vibrational frequencies and modes on the basis of Potential Energy Distribution (PED)
analysis.
Acknowledgment
The study was supported by Polish Norwegian Research Program No. Pol-Nor/203119/32: Superior bio-
friendly systems for enhanced wood durability.
computing and Networking Centre and supported in
part by PL-Grid Infrastructure.
References
[1] B. Furdui, O. Constantin, A. Tabacaru, R. M. Dinica, Rev. Chim. 2012, 63, 667.
[2] K. Musilek, M. Komloova, O. Holas, A. Horova, M. Pohanka, F. Gunn-Moore, V. Dohnal, M.
Dolezal, K. Kuca, Bioorg. Med. Chem. 2011, 19, 754.
(a) (b)
114
P45
FT-IR Spectroscopic Studies of Cd2+ Adsorption
onto Zeolite Synthesized from Perlite Waste
1, E. Matras1 1, W. Mozgawa1
1 Faculty of Materials Science and Ceramics,
AGH University of Science and Technology,
30 Mickiewicza Av., 30-059 Krakow, Poland, [email protected]
In this work, the results of FT-IR spectroscopic studies of synthetic zeolite X
(obtained from expanded perlite waste) after Cd2+ cations immobilization are presented.
Spatial framework of its structure is formed by [SiO4] tetrahedra, which linked to so-
called secondary building units (SBU) double six-rings (D6R) in this case. Based on
the results of ab initio studies using Gaussian09 program (DFT formalism and
LanL2DZ basis sets), normal vibrations of the D6R unit combined with different cations
have been visualized. The results of calculations have been applied to interpret
experimental spectra of synthetic zeolite X before and after ion-exchange process. It
was proven that Cd+ -IR spectra of the
zeolites. The most significant changes have been determined for the band in the range
610 550 cm 1.
One of the aims of this study was to obtain suitable absorbent material for
environmental applications using difficult to storage fine-grained by-product. The
specific aims were to analyze the resulting zeolite material in terms of structure and
cation exchange capacity (CEC). The results of the synthesis of zeolites from expanded
perlite using hydrothermal method are presented. By-product obtained during the
production of expanded perlite was used as the starting material. Resulting products
were analyzed regarding phase composition. In particular, the structures of materials
were examined using FT-IR spectroscopy both in the mid and far infrared range. The
results were compared by those obtained by XRD measurements as well as SEM
observations. It was found that material with excellent sorption capacity can be
Theoretical and practical aspects of Cd2+ ions sorption process onto material
synthesized in selected conditions will be presented. The atomic absorption
spectroscopy (AAS) has been used as method, from which the proportion of ion
exchange to chemisorption in the process and the effective cation exchange capacity
(CEC) have been determined. Structural analysis of the sample before and after sorption
process has been also carried out by the measurement of spectra in the middle infrared.
Pseudolattice range of the spectra (800 400 cm 1) was detailed analyzed in which
changes caused by ion exchange of non-tetrahedral ions have been observed.
Acknowledgment
Financial support this work was provided by The National Centre for Research and Development under
grant no. PBS1 177 206.
115
P46
Raman Spectroscopy Study of Lightweight Concrete Structure
1 1, W. Mozgawa1
1 Faculty of Materials Science and Ceramics,
AGH University of Science and Technology,
30 Mickiewicza Av., 30-059 Krakow, Poland, [email protected]
Lightweight concrete structure was studied by Raman spectroscopy, to establish
a nondestructive method to analyze the distribution of phases on the interface concrete-
aggregate. The results of spectroscopic investigations were compared to the XRD and
SEM observations.
The composition of ordinary Portland cement, lightweight aggregate and
aggregate were first analyzed by Raman spectroscopy to determine a spectrum database
of the specific phases located in the concrete. Then spectroscopic method was used to
analyze, directly, the fractures surface of hardened concrete after compressive strength
tests. Many cementitious, or hydrated phases such as: alite, belite, tricalcium aluminate,
ferrite or portlandite could be clearly identified using Raman spectroscopy. Due to its
own specificities, Raman spectroscopy is also useful to describe the amorphous phases.
This technique can be used to describe the structure of individual phases present both in
aggregate and in the binder (cement paste). It was concluded that the results indicate
possibilities of Raman spectroscopy applying for the qualitative determination of
mineral matter in concrete and suggesting the potential of the method for routine
laboratory testing.
Acknowledgment
Financial support this work was provided by The National Centre for Research and Development under
grant no. PBS1/A2/7/2012.
116
P47
IR Spectroscopy Studies of Zeolites in Geopolymeric Materials
Derived from Kaolinite
, J. Minkiewicz
Faculty of Materials Science and Ceramics,
AGH University of Science and Technology,
30 Mickiewicza Av., 30-059 Krakow, Poland, [email protected]
This study investigated the influence of alkali activation process conditions on
the amount and types of zeolites in the resultant geopolymers. Kaolinite was used as
into the amorphous aluminosilicate phases (metakaolinite) and then activated with
sodium silicate (as water glass) and sodium hydroxide. The effects of reaction systems
composition (expressed as SiO2/Al2O3 and Al2O3/Na2O molar ratios) as well as
synthesis temperature and time on the phase composition of obtained products have
been determined. In particular, the structures of materials were examined using FT-IR
spectroscopy in the middle infrared range. The results were compared to the XRD
measurements, as well as SEM observations.
Alkali-activation treatment of the metakaolin yielded bulk materials with
different amounts and types of zeolite and different compressive strength. With proper
selection of the initial conditions (temperature, time, composition), it is possible to
obtain a solid material containing zeolite phase such as zeolite X, zeolite A or sodalite.
The presence of zeolite phase was confirmed by the measurement of spectra in the
middle infrared. In particular in pseudolattice range of the spectra, i.e. 800 400 cm 1,
there are bands associated with the ring vibrations, which are characteristic for
secondary building units (SBU) occurred in zeolite structure. IR spectroscopy is also
useful in the studies of resulting amorphous phase structure.
117
P48
UV-Tunable Laser Induced Phototransformations of Matrix Isolated
Anethole
J. Krupa1, M. Wierzejewska2, C. M. Nunes3 and R. Fausto4
1Faculty of Chemistry University of Wroclaw, Joliot-Curie 14, 50-
[email protected] of Chemistry University of Wroclaw, Joliot-Curie 14, 50-
Poland, [email protected] of Chemistry University of Coimbra, 3004-535Coimbra, Portugal,
[email protected] 4Department of Chemistry University of Coimbra, 3004-535Coimbra, Portugal,
Anethole (1-methoxy-4-(1-propenyl)benzene) occurs naturally as a major
component of the essential oil of star anise. This compound exists in two isomeric
forms, differing in the relative position of the substituents about the propenylic C=C
bond: the E and Z isomers, the E form being the most abundant isomer. A matrix
isolation study of the infrared spectra and structure of anethole has been carried out,
showing the presence of two E conformers of the molecule in freshly deposited
matrices.
Phototransformations of the monomeric anethole isolated in low temperature
argon matrices were induced by narrow-band UV radiation from the OPO laser system.
The UV radiation in the 308-301 nm range induced conformationally selective
transformations of E forms into less stable Z conformers and the back reactions.
Photolysis of the studied compound was also observed, with initial methoxyl
O-C bond cleavage and formation of methyl and p-propenylphenoxy radicals, followed
by radical recombination to form 2-methyl-4-propenyl-2,4-cyclohexadienone. The latter
molecule subsequently transforms by ring opening into the long-chain ketenes.
Interpretation of the experimental observations was supported by DFT (B3LYP and
B2PLYD) calculations.
Acknowledgment
Tecnologia (FCT, Project PTDC/QUI/111879/2009) and Bilateral Poland/Portugal Exchange Agreement
Programme 2013-2014.C.M.N. acknowledges FCT by the post-doctoral grant ref. SRH/BPD/86021/2012.
J.K. also acknowledges EU for the scholarship within the European Social Funds and The Human Capital
Operational Programme (Project No. POKL.04.01.01-00-054/10-00 - V edition 2013).
118
P49
UV-tunable Laser Induced Photolysis of Matrix Isolated Anisole
J. Krupa1, M. Wierzejewska2
1 Faculty of Chemistry University of Wroclaw, Joliot-Curie 14, 50-
Poland, [email protected] of Chemistry University of Wroclaw, Joliot-Curie 14, 50-
Poland, [email protected]
Anisole (methoxybenzene) is an interesting molecule mainly because of the fact
that most of the aromatic rings present in plant material contain methoxy groups.
Therefore anisole serves as an important model compound in studies of the pyrolysis
mechanisms of such materials.
Although the thermal decomposition of anisole was extensively studied there is
much less data on the UV photolysis of this compound. Here we report the UV-tunable
laser induced decomposition reactions of the anisole isolated in a low-temperature argon
matrix. The progress of photochemical transformations was followed by FTIR
spectroscopy that allowed for identification of several photoproducts. They were
distinguished according to their different patterns of bands and their intensity changes
during UV photolysis. Among these products the phenoxy and methyl radicals were
observed that recombined to form two isomers of methylcycloheksadienone. One of
them readily decomposed producing different isomers of long-chain ketenes and
bicyclohexenone molecules. Decarbonylation reaction was also detected in the studied
systems.
Interpretation of the experimental observations was supported by DFT
calculations at the B3LYP/6-311++G(2d,2p) level.
Acknowledgment
acknowledged.
119
P50
Studies of Substituent and Solvent Effect on Spectroscopic Properties
of 6-OH-4-CH3, 7-OH-4-CH3 and 7-OH-4-CF3 Coumarin
Dr. Sanjay Kumar
Department of Physics, Rajdhani College, Delhi University, Raja Garden, New Delhi
110015, India., E-mail: [email protected]
This paper reports the solvent effects on the electronic absorption and fluorescence
emission spectra of 6-OH-4-CH3, 7-OH-4-CH3 and 7-OH-4-CF3 coumarin derivatives
having -OH, -CH3 and -CF3 substituent at different positions in various solvents ( Polar
and Non-Polar). The first excited singlet state dipole moment and ground state dipole
moment were calculated using Bakhshiev, Kawski-Chamma-Viallet and Reichardt-
Dimroth equations and were compared for all the coumarin studied. In all cases the
dipole moments were found to be higher in the excited singlet state than in the ground
-electron density in the excited state.
The angle between the excited singlet state and ground state dipole moment is also
calculated. The red shift of the absorption and fluorescence emission bands, observed
for all the coumarin studied upon increasing the solvent polarity indicating that the * nature.
Keywords : Coumarin, Solvent effects, Absorption spectra, Emission spectra, Excited singlet state dipole
moment, Ground state dipole moment, Solvatochromism.
6-OH-4-CH3 Coumarin
7-OH-4-CH3 Coumarin
7-OH-4-CF3 Coumarin
Fig. : Structure of Coumarins Studied
120
P51
Influence of Ar-Irradiation on Structural and Nanomechanical
Properties of Zirconium
L. Kurpaska1), M. Gapinsk2), J. Jasinski3),M. Sitarz4), K. Wozniak5), J. Jagielski1)
1)National Centre for Nuclear Research, st. A. Soltana 7/23, Otwock-Swierk, Poland,
[email protected], [email protected])University of Warsaw, College of Inter-Faculty Individual Studies in Mathematics and
Natural Sciences, st. Zwirki i Wigury 93, 02-089 Warsaw, Poland,
[email protected])Institute of Materials Science, Czestochowa university of Science and Technology, av.
Armii Krajowej 19, 42-200, Czestochowa, Poland, [email protected])Faculty of Materials Science and Ceramics, AGH University of Science and
Technology, av. Mickiewicza 30, 30-059 Krakow, Poland, [email protected])Warsaw University, Chemistry Department, Crystallochemistry Laboratory, st.
Pasteura 1, 02-093 Warsaw, Poland, [email protected]
Due to its high corrosion resistance, good mechanical properties and low neutron
absorption rate, zirconium based alloys are of special interest for engineering use in
nuclear reactors [1]. For example, Zr-based alloys can serve as a future fuel claddings,
spreaders for fuel elements and for core structural materials. One may note, that in
reactor these elements are irradiated by neutrons, especially fast neutrons, which results
in radiation damage. Ion implantation is not only an excellent tool for modifying surface
of materials but also for simulating radiation damage. Despite of abundant amount of
research, corrosion behaviour, structural and mechanical properties of zirconium and its
alloys, subjected to the influence of neutrons or effect of ion implantation demage are
still under consideration [2-5].
In this study, effect of Ar irradiation on structural and nanomechanical properties of
pure zirconium at room temperature were investigated. In order to simulate the
irradiation damage, the argon ions were implanted in the pure zirconium with fluences
ranging from 1 x 1015 to 1 x 1017 ions / cm2. Surface of zirconium samples were
chemically polished in a solution of HF/HNO3/H2O. Than, structural properties of
implanted layer were studied using XRD technique. The nanomechanical response of
the material was measured using a nanoindentation technique. The results revealed
correlation between effect of Ar-implantation dose, hardness and Young modulus and
displacement of recorded peak.
References
[1] Zinkle S.J, Was G.S, Acta Materialia 2013, 61: 735
[2] Cox B, Journal of Nuclear Materials 2005, 336: 331
[3] Peng D.Q, Bai X.D, Pan F, Sun H, Chen B.S, Applied Surface Science 2006, 252: 2196
[4] Peng D.Q, Bai X.D, Pan F, Physica B 2007, 391: 72
[5] Jagielski J, Aubert P, Maciejak O, Piatkowska A, Labdi S, Jozwik-Biala I, Jozwik P, Wajler A,
Nuclear Instruments and Methods in Physics Research B 2012, B 286:196
121
P52
Effect of ZnO on the Microstructure of the Glazes from
SiO2-Al2O3-CaO-MgO-Na2O-K2O System
, J. Partyka
AGH University of Science and Technology, Faculty of Materials Science and
Ceramics, Al. Mickiewicza 30, 30- h.edu.pl
The results of the synthesis of glass-ceramic glazes from the SiO2-Al2O3-CaO-
MgO-K2O-Na2O system with ZnO additions (2.5, 5, 10, 15, 15, 20 and 25 wt%) were
presented. The compositions were designed based on constant molar ratio of
SiO2/Al2O3. In the resulting glazes diopside (CaMg[Si2O6]), willemite (Zn2SiO4) and
vitreous phase were identified by X-ray diffraction. Morphological and structural date
of these glazes were supplementary determined by EPMA, MIR and Raman
Spectroscopy.
Fig. 1 MIR spectra of the tested glazes
In the glazes with a high content of ZnO dominating bands are associated with
bonds characteristic of silicon-oxygen tetrahedral and crystallization of willemite.
In turn, at lower content of zinc oxide, decrease of intensity of the band associated with
the vibrations of Si-O-Si with the simultaneous increase of intensity of the band
associated with the vibrations of Si-O-Al is due to crystallization diopside. The results
of the XRD and SEM-EDS studies confirm the conclusions regarding the FTIR
analysis.
Acknowledgment
This research work has been carried out thanks to financing in the framework of NCBiR (Polish National
Research and Development Committee) program PBS1/B5/17/2012 and N N508 477734.
122
P53
Structural Study of Aluminosilicate Raw Glass-Ceramic Glazes
by IR and Raman Spectroscopies
, M. Sitarz
AGH University of Science and Technology, Faculty of Materials Science
and Ceramics, Department of Silicate Chemistry and Macromolecular Compounds
Al. Mickiewicza 30, 30- [email protected]
This paper is focused on the effect of the molar ratio of SiO2/Al2O3 on the
microstructure and structure of the internal aluminium-silicon-oxide lattice of the glass-
ceramic glazes from the SiO2-Al2O3-Na2O-K2O-CaO system.
In order to examine the real composition of the obtained glazes research on
Wavelength Dispersive X-Ray Fluorescence Spectrometer (WDXRF) were done. These
studies have shown that glazes of assumed compositions were obtained. In order to
determine the state of the surface (microstructure) research on the scanning electron
microscope (SEM) with EDS were done. For structural studies X-ray diffraction (XRD),
Raman spectroscopy and MIR and FIR spectroscopic studies were performed.
Changing SiO2/Al2O3 ratio in the SiO2-Al2O3-K2O-Na2O-CaO system has
a decisive influence on the type and amount of the crystalline phase in the glass-ceramic
glazes. At the highest SiO2/Al2O3 ratios, the tested materials are typical glass-crystalline
materials, in which calcium silicate - pseudowollastonite occurs, apart from the vitreous
phase. By lowering the SiO2/Al2O3 ratio gradually to 4.77, the quantity of the crystalline
phase is decreased, and with SiO2/Al2O3 equal to 3.88, the material is completely
amorphous (SEM, XRD). With the SiO2/Al2O3 ratio equal to 3.23, the vitreous phase
and calcium aluminium silicate anorthite occurs in the glaze.
The results of spectroscopic research show that the change in the SiO2/Al2O3
ratio only slightly influences the chemical composition (the type of structure modifiers)
and the internal structure of the vitreous phase-bonding crystallites to form a uniform
material. This influence is exposed by the degree of polymerisation (the number
of broken silico-oxygen bridges).
In the tested glazes, independently of the SiO2/Al2O3 ratio, aluminium ions occur
only in tetrahedral coordination, i.e. they form the amorphous phase structure.
Acknowledgment
This research work has been carried out thanks to financing in the framework of NCBiR (Polish National
Research and Development Committee) program PBS1/B5/17/2012 and N N508 477734.
123
P54
New Picoplatin - Orotate Complexes Revealing Anticancer Activity:
Vibrational Spectra, Conformations and DFT Calculations
M. Malik1, K. Helios1, J. Wietrzyk2, D. Michalska1
1
50-
[email protected] of Immunology and Experimental Therapy of the Polish Academy of Sciences,
Weigla 12, 53- [email protected]
Picoplatin, cis-[PtCl2(NH3)(2-picoline)] is a new generation platinum anticancer
agent which shows remarkable activity against a wide range of cisplatin-resistant
tumors. To increase the selectivity of its action, we have replaced the chloride ions of
picoplatin by the orotate ion and its fluoro- and nitro-derivatives (orotic acid is involved
in biosynthesis of the pyrimidine nucleotides in living organisms). Thus, three new
complexes have been synthesized: Pt(Oro)(NH3)(2-pic), Pt(5-NO2Oro)(NH3)(2-pic) and
Pt(5-FOro)(NH3)(2-pic), Fig. 1.
Fig. 1. Molecular structure of Pt(5-ROro)(NH3)(2-pic), R=H, NO2, F.
The molecular structures of these complexes have been determined by the
spectroscopic methods (IR, Raman, NMR, ESI-MS), elemental analyses and density
functional theory (DFT) calculations. Recently [1,2], we have shown that the use of the
LanL2TZ(f) ECP/basis set for Pt, in conjunction with the DFT methods, improves the
calculated geometry of the complex and predicts very well the frequencies of the Pt-
ligand vibrations. The theoretical vibrational spectra of these complexes computed by
the PBE0 and B3LYP methods are in good agreement with experiment. The detailed
assignment has been made on the basis of the calculated PED. The spectroscopic results
confirm the postulated structure, as shown in Fig.1.
The in vitro biological studies have demonstrated that the 5-fluoroorotate
derivative of picoplatin reveals a higher anti-proliferative activity against human
colorectal adenocarcinoma (LoVo) and human pharyngeal squamous carcinoma (FaDu)
than picoplatin. Moreover, this complex is remarkably less toxic to normal cells, in
comparison to picoplatin and cisplatin.
References
[1] M. Malik and D. Michalska, Spectrochim. Acta 125A, 2014, 431-439.
[2] Chem 118A, 2014,
6922-6934.
124
P55
Infrared Spectra of SO42- Guest Ions Included in Compounds with
-Type Chains Na2M(SeO4)2 2O (M = Co, Ni, Zn, Cd) and
K2M(CrO4)2 2O (M = Mg, Co, Ni, Zn, Cd)
D. Marinova1, M. Wildner2, Chr. Lengauer2, V. Karadjova3, M Georgiev3,
D. Stoilova1
1Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences,
1113 Sofia, Bulgaria, [email protected]
A-1090 Wien, Austria3Department of Inorganic Chemistry, University of Chemical Technology and
Metallurgy, 8 Kliment Ohridski, 1756 Sofia, Bulgaria
Matrix infrared spectroscopy provides important information about the type of the
admixtures included in minerals, either as isomorphous (isodimorphous) substitutions or as
distinct phase inclusions. The vibrational spectra of distinct phase inclusions are similar to
those of the respective neat compounds. However, the vibrational spectra of isomorphously
included guest ions are essentially determined by both the site-symmetry, which is assumed
to be the same as that of the respective host ions (substitutional type of mixed crystals), and
the potential at the lattice sites where the guest ions are located, as shown by the extend of
energetic distortion of the matrix-isolated ions.
In the present study, several phases belonging to the large number of natural and
-type chains have been synthesized as model phases.
The crystal structures of Na2M(SeO4)2 2O (M = Co, Ni, Zn, Cd) and K2M(CrO4)2 2O
(M = Zn, Cd) were determined from X-ray single-crystal diffraction data and those of
K2M(CrO4)2 2O (M = Co, Ni) by X-ray powder diffraction. The structures as build up
from MO4(H2O)2 octahedra and XO4 ite-type octahedral-
tetrahedral chains, which are linked by alkali cations to layers and further to a three-
dimensional framework via hydrogen bonds. The sodium cobalt, nickel and zinc
compounds as well as the potassium cobalt, nickel and cadmium compounds crystallize in
the triclinic space group P1 (type A), the sodium cadmium selenate in the monoclinic space
group P21/c (type D), and the potassium zinc chromate in the monoclinic space group C2/c,
thus representing a new structural type (type H).
The vibrational behavior of SO42- guest ions included in these chromate and selenate
matrices has been studied by infrared spectroscopy. It has been established that the extent of
energetic distortion of the SO42- guest ions as deduced from the values of as and max
depends on both the electronic configurations of the M2+ ions and the degree of covalency
of the respective M2+ O bonds. The matrix-isolated SO42- guest ions are stronger distorted
in the selenates than in the chromates due to the smaller unit-cell volumes of the selenate
host compounds as compared to those of the chromate ones and the different ionic radius of
the K+ and Na+ ions. The smaller Na+ ions cause a stronger electrostatic field (shorter Na O
bonds), thus leading to remarkably larger values of as and max of the guest ions in the
sodium compounds.
125
P56
Double Matrix Infrared Spectroscopy as a Tool to Monitor the Cation
Distribution in MgxZn1-x(HCOO)2 2O and MgxMn1-x(HCOO)2 2O
Mixed Crystals
D. Marinova1, V. Karadjova2, D. Stoilova1
1Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, 1113
Sofia, Bulgaria, [email protected] of Inorganic Chemistry, University of Chemical Technology and
Metallurgy, 8 Kliment Ohridski, 1756 Sofia, Bulgaria
The different coordination environment of the metal ions (M(1) and M(2)) in the
structures of isomorphic series M(HCOO)2 2O (SG P21/c) (M = Mg, Mn, Fe, Co, Ni,
Cu, Zn, Cd), suggest the possibility that when mixed crystals are formed among the
above formates, cations depending on their nature might occupy preferentially one of
the two available positions. The method of double matrix infrared spectroscopy (matrix-
isolated HDO molecules and metal ions in the structures of mixed formates) was used to
analyze the cation distribution over the two metal positions in the title mixed crystals. A
hypothesis is made that Mg2+ ions will occupy preferentially the M(2) sites due to their
strong affinity to water molecules.
Our previous investigations show that the spectral regions 2300 2500 cm-1 ( OD
of matrix-isolated HDO molecules; hydrogen bonding systems) and 1300 1400 cm-1
(symmetric COO stretching modes 2 and bending CH modes 5 of the formate ions)
are mostly sensitive to the metal ion environment.
The inclusion of Mg2+ and Zn2+ in the structures of Zn(HCOO)2 2O and
Mg(HCOO)2 2O, respectively, leads to an appearance of new infrared bands
corresponding to OD of HDO molecules bonded to the incorporated ions. The
respective new bands are observed at small concentrations of included Mg2+ ions
(x = 0.05) and at considerably higher concentrations of included Zn2+ ions (x = 0.7). In
the case of MgxMn1-x(HCOO)2 2O mixed crystals the new bands corresponding to
OD appear at x = 0.13 and x = 0.92 (Mg2+ in Mn(HCOO)2 2O and Mn2+ in
Mg(HCOO)2 2O, respectively). The new hydrogen bonds of the type
Zn OH2 Mg and Mn OH2 Mg are stronger than those in the neat
magnesium formate due to the stronger synergetic effect of these ions (strong Zn OH2
and Mn OH2 bond interactions owing to the covalent character of these bonds). Both
the positions and the intensity of the new bands corresponding to the 2 and 5 modes
arising from formate ions coordinated to the included metal are also analyzed.
Thus, the analysis of the infrared spectra (positions and intensities of the infrared
bands) show that the Mg2+ ions are mostly localized at M(2) sites in the case of
MgxZn1-x(HCOO)2 2O mixed crystals, while in the case of MgxMn1-x(HCOO)2 2O
mixed crystals both cations are distributed almost over the two positions with a slight
preference of Mg2+ ions to M(2) sites. Single crystal X-ray measurements confirm the
results obtained from the infrared spectroscopic experiments.
126
P57
Broad Band Anti-Stokes White Emission from LiYbF4 Nanocrystals
L. Marciniak, R. Tomala, M. Stefanski, D. Hreniak, W. Strek
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
Spectroscopic properties of hexagonal LiYbF4 nanocrystals under high dense
NIR excitation under vacuum condition were investigated. White, broad emission band
covering whole visible part of the spectrum from LiYbF4 nanocrystals was observed
(Fig. 1). Its intensity strongly depends on the excitation power and ambient pressure.
Temperature of the nanocrystals under 975 nm excitation was determined as a function
of excitation power. Strong photo-induced current was observed from LiYbF4 pallet.
The kinetic of the emission was analyzed. The mechanism of the anti-Stokes white
emission was discussed in terms of laser-induced charge transfer emission from Yb2+
states.
400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600
norm
aliz
ed
inte
nsity
wavelength (nm)
LD
exc
2F
5/2
2F
7/2(Yb
3+)
Fig. 1 Emission spectra of LiYbF4 nanocrystals in vacuum under 975 nm excitation
Acknowledgment
Authors would like to acknowledge NCS project for financial support grant No NCN-
2012/06/A/ST5/00212.
127
P58
Light Wavelength Influence on Surface Plasmon Resonance in Citrate-
Gold Nanosystems
D. Pricop, M. Andries, R. Lupusoru*, E. Puscasu, F. Iacomi, D. Creanga
Medicine and Pharmacy, Iasi, Romania
Gold nanoparticles (AuNPs) are used in biomedicine for photothermal and
photodynamic therapies, targeted delivery of drugs, DNA and antigens, optical
bioimaging of issues and cells and others. We studied the spectral proprieties of AuNPs
yielded through single phase water based reduction of a gold, in different synthesis
media. Equal volumes of gold colloidal suspension were exposed to visible light with
different wavelengths for 90 min at room temperature. UV-Vis and FTIR spectroscopy
were used to investigate the response of AuNPs to visible light influence.
Fig. 1. UV-Vis and IR absorption spectra of colloidal gold nanoparticles exposed to white light (W), blue
light (B), green light (G) and yellow light (Y)
The UV-Vis spectra showed that all colloidal suspensions exposed to visible light
exhibited the intensity increasing in the band characteristic to AuNPs which was put in
relationship with the light influence on the surface plasmon resonance (SPR) related to
interband transition of the electrons in surface layer of metallic gold. Light irradiation
and possibly SPR changes influenced the vibrations of stabilizing ion species bond to
gold surface; the green light excitation photon had stronger influence on 1546 nm
vibration (FTIR data).
Acknowledgement
This study was sustained by POSDRU/187/1.5/S/155397 program of European Social Fund in Romania
under the responsibility of the Managing Authority for the Sectored Operational Program for Human
Resources Development 2007-
128
P59
Fat Quantification in Potato Chips by Vibrational Spectroscopy
Sylwester Mazurek,1 Roman Szostak1 and Agnieszka Kita2
1 -Curie
50-2Department of Food Storage, Faculty of Food Science, Agricultural University of
-
Potato chips are important products in the snack industry. The most significant
parameter which is monitored in their quality control process is fat content. Commonly
applied for this purpose Soxhlet extraction method is time consuming and expensive.
We demonstrate that both infrared and Raman spectroscopy can effectively replace the
extraction method.
Laboratory prepared chips were obtained from potatoes cut into slices and then
fried in oil, varying temperature and time of frying. Mid-infrared (MIR) and near-
infrared (NIR) spectra of the homogenized samples were recorded 5-6 times for each
sample using diffuse reflection (DRIFT) and specular reflection (SR) accessories, while
Raman spectra were collected once with a rotating sample holder.
On the basis of obtained spectra, partial least squares (PLS) calibration models
were constructed. They were characterized by the values of relative standard errors of
prediction (RSEP) in the 1-2% range for both calibration and validation data sets.
Using the developed models, seven commercial products were successfully quantified
with recovery in the 98-102% range against the AOAC extraction method. The quality
of spectra and homogeneity of measured samples can substantially influence
quantification errors. The proposed method for fat quantification in potato chips based
on Raman spectroscopy can be easily adopted for on-line product analysis.
129
P60
Quantitative Analysis of Topical Gels and Ointments by FT-Raman
Spectroscopy
Sylwester Mazurek and Roman Szostak
-Curie,
50-
A method for quantitative determination of ibuprofen (IBU), naproxen (NAP),
methyl salicylate (MES) and menthol (MEN) in commercial topical gels and ointments
using partial least squares (PLS) models based on FT-Raman spectra is described. The
calculated relative standard errors of prediction (RSEP) were found to be in the range of
2.1-3.2 % for the calibration and validation data sets. Two commercial topical gels
containing 5.0 % of IBU and 10 % of NAP (w/w), as well as one ointment containing
15 % of MES and 10 % of MEN (w/w) as active pharmaceutical ingredients (APIs)
were successfully quantified using the developed models with recoveries in the 99.2 -
101.5 % range. The proposed procedure can be used as a fast, reliable and economic
method for the APIs quantification in topical gels and ointments.
130
P61
Photocatalytic Partial Water Splitting with Visible Light
Olaf Morawski, Elena Karpiuk, Andrzej L. Sobolewski
Institute of Physics, Polish Academy of Sciences, [email protected]
Two strategies are used for water splitting with solar light. In the photoelectrochemical
approach, a semiconductor photoanode is used to generate holes which are able to
oxidize water molecules [1]. Alternatively, a supramolecular structure consisting of
electron donor, acceptor, and chromophore absorbs photons and triggers charge
separation. The separated charges may neutralize hydroxide anions and protons [2,3].
chromophore, has been proposed [4]. In that computational study the excited state of
water oxotitanium porphyrin hydrogen bonded complex decays into TiPOH -
In this work we study the photopysical and photochemical properties of Oxo Titanium
TetraphenylPhorphirin (TiOTPP), Oxo Titanium Phthalocyanine (TiOPc) and
Methylene Blue (MB) in water to check if the mechanism proposed in [4] occurs. The
compounds have been selected as they have strong absorption bands in the VIS range of
solar spectrum while possessing same potential to form hydrogen bonded complexes
with water as the theoretically studied TiOP molecule.
The photocatalytic partial water splitting occurs with all molecules. Reaction yields of
hydroxyl radicals generation are determined what gives insight into the mechanism of
partial water splitting. For TiOTPP and TiOPc small photocurrents have been detected
proving the existence of ionic channel of water splitting, although of very low
efficiency.
TiOTPP TiOPc MB
Figure 1. Structures of molecules
Literature
[1] A.Fujishima , K.Honda, Nature, 238, (1972), 37
[2] M. R. Wasielewski, Chem. Rev., 92, (1992), 435.
[3] D. Gust, T. A. Moore and A. L. Moore, Acc. Chem. Res., 34, (2001), 40.
[4] A.L.Sobolewski, W.Domcke, PhysChemChemPhys., 14 (2012) 12807
131
P62
Terahertz Dynamics of Polymorphic Pharmaceutical Indometacin
Tatsuya Mori1, Tomohiko Shibata1, Kei Iwamoto2, Hiroshi Matsui2,
and Seiji Kojima1
1Division of Materials Science, University of Tsukuba, Tsukuba, Ibaraki 305-8573,
Japan, [email protected] of Physics, Graduate School of Science, Tohoku University, Sendai 980-
8578, Japan
Indometacin (C19H16ClNO4, IMC) is a pharmaceutical that is classified as non-steroidal
anti-inflammatory drugs, and it has a complicated molecular structure (Fig. 1) and
shows a polymorphism in a crystalline state. For higher glass transition temperature,
IMC can exhibit a glassy state at room temperature and is a model substance for
studying the amorphous drugs [1].
Terahertz time-domain spectroscopy (THz-TDS) is useful as a vibrational
spectroscopy to elucidate not only intra-molecular vibration but also inter-molecular
vibration of organic materials. In addition, combination with terahertz (low-frequency)
Raman scattering measurement is a more powerful tool, because the selection rules are
different between THz-TDS and Raman scattering, and considered as complementary
for centrosymmetric materials [1]. In this study, we performed temperature dependent
THz-TDS and low-frequency Raman scattering measurements for pharmaceutical IMC
of and forms, and a glassy state.
Fig. 1 Structure of indometacin molecule.
Acknowledgment
This study was partially supported by a Grant-in-Aid for Young Scientists (B) (24740194) from JSPS, the
Sasakawa Scientific Research Grant from The Japan Science Society.
References
[1] Shibata, T. Mori, and S. Kojima, Spectrochim. Acta A: Mol. Biomol. Spectrosc., in press.
132
P63
Terahertz Time-Domain and Low-Frequency Raman Scattering
Spectroscopic Study on Polypropylene Glycol
Shota Koda, Tatsuya Mori, Mikitoshi Kabeya, and Seiji Kojima
Division of Materials Science, University of Tsukuba, Tsukuba, Ibaraki 305-8573,
Japan, [email protected]
Glass-forming liquids show several excitations such as fast relaxation and vibrational
density of states (VDOS) peak in the terahertz region. To detect those excitations, we
performed terahertz time-domain spectroscopy (THz-TDS) and low-frequency Raman
scattering spectroscopy on polypropylene glycols (PPG).
Figure 1 shows the complex dielectric constants of several PPG with different
molecular weights obtained by broadband THz-TDS [1]. The observed dielectric spectra
consist of two relaxation processes. The lower relaxation mode below about 1 THz will
be attributed to the fast relaxation, and other broad peak at around 2 THz is VDOS peak.
The observed frequency of VDOS peak decreases as molecular weight of PPG increases.
1 2 3 4 5
0.5
'' (
)
Frequency (THz)
0.1
2
2.5
PG
PPG725
PPG2000
' (
)
Fig. 1 Complex dielectric constant of three samples, PG (closed circles), PPG725 (open circles), and
PPG2000 (open squares) obtained from THz-TDS.
Acknowledgment
This study was partially supported by a Grant-in-Aid for Young Scientists (B) (24740194) from JSPS, the
Sasakawa Scientific Research Grant from The Japan Science Society.
References
[1] Mori, H. Igawa, D. Okada, Y. Yamamoto, K. Iwamoto, N. Toyota, and S. Kojima, J. Mol. Struct.
1090, 93 (2015).
133
P64
7-Azaindole Complexes with Pd(II): Vibrational Spectra,
Crystal Structure and DFT Calculations
B. Morzyk-Ociepa1, K. Dysz1, I. Turowska-Tyrk2, D. Michalska2
1 -200
[email protected], [email protected] -
[email protected], [email protected]
In the last decade, the 7-azaindole based compounds have attracted growing
attention in medicine as a new class of promising anticancer agents. Recently, it has
been reported that the trans-palladium complexes containing relatively large
monodentate ligands (e.g. pyridine derivatives) show a better antitumor activity than the
cis-platinum isomers.
Therefore, in this work we synthesized a new Pd(II) complexes with 7-azaindole
(7AI), trans-[PdCl2(7AI)2] (1) and 1 DMF. The FT-IR and FT-Raman spectra were
measured. The structures of these complexes were determined by a single crystal X-ray
diffraction and vibrational spectroscopy. The results have shown that the palladium
cation is bound to two pyridine nitrogen atoms of the 7AI ligands and to two chloride
ions, in a square-planar trans arrangement (Fig. 1). Comprehensive theoretical studies
on 1 have been performed by the B3LYP and PBE0 density functional methods using
the 6-311G++(d,p)/LanL2DZ basis set. As follows from the comparison of the
experimental and theoretical results, the PBE0 functional shows slightly better
performance than B3LYP in the calculations of the molecular parameters and
vibrational frequencies of 1. The unequivocal assignment of the vibrational spectra has
been made. The obtained results can be used in the further studies of new biologically
active Pd(II) complexes with pyridine-based ligands, by using vibrational spectroscopy.
Fig. 1. Molecular structure of trans-[PdCl2(7-azaindole)2].
134
P65
Sosvatochromic Study on Chlortetracycline in Binary and Ternary
Solutions
G. Oanca, C. Nadejde, A. Gritco Todirascu, A. Fifere*, D. Creanga, D. Dorohoi
ar Chemistry, Iasi, Romania
Chlortetracycline was chosen for the study due to its therapeutic properties
most recent one in cancer therapy. Experimental investigations were carried out using
electronic absorption spectra as well as fluorescence ones (Fig. 1). Spectral shift to the
solvent polarity changing was measured in various solvents (binary solutions) and
graphical correlations were evidenced between the electronic band wavenumbers and
some theoretical functions on solvent electro-optical macroscopic parameters (refractive
index and dielectric constant); interpretation was done based on the solvatochromic
theories from literature. Fluorescence spectra were also studied in various solvents and
mixture of solvents (ternary solutions) the experimental data being processing based on
the dependence of spectral shift on the properties of the binary solvent.
Fig. 1. Absorption and emission spectra of chlortetracycline
Molecular modeling was applied based on DFT approach implemented in Gaussian
software. The differences between simulated electronic spectra and those recorded
experimentally were analyzed considering also the energetic parameters (total energy,
binding energy, heat of formation, EHOMO of highest occupied molecular orbital and
ELUMO of lowest unoccupied molecular orbital) resulted from mathematical
simulation.
135
P66
Spectroscopic and Thermal Analysis of Steroids: Cholesterol and
Lithocholic acid
M. Ordon 1,2, M.D. Ossowska 2, D. Chudoba 1,3
1 Joint Institute for Nuclear Research, Frank Laboratory of Neutron Physics,
Dubna, Russian Federation2 Siedlce University of Natural Sciences and Humanities, Institute of Chemistry,
Siedlce, Poland, [email protected]
The properties of two derivatives from series of sterols: cholesterol and lithocholic
acid (LCA) are reported [1]. These are natural alcohols characterized by the presence of
the saturated cyclopenthanoperhydrophenantrene ring constituting the rigid part of the
molecule.
Phase situation and enthalpies of phase transitions were characterized using
differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and
transmitted light intensity (TLI). Derivatography method was used to determine the
thermal stability of both sterols (Fig.1.) [2].
100 200 300 400 500 600
22
24
26
28
30
32
34
36
38
40
2.5%
508
381348260199.53: 15%
2: 78%
Q [a
.u.]
Temperatura [oC]
1: 7%
0
10
20
30
40
50
60
DTA
TG
mg
DTG
100 200 300 400 500 600
-2.0
-1.5
-1.0
-0.5
0.0
Fig.1. TG, DTG and DTA curves for lithocholic acid [2].
Neutron characteristic of stability of crystal and glass phases and dynamics of
selected functional groups for both steroid was obtained by incoherent inelastic neutron
scattering (IINS) and neutron powder diffraction (ND), by using NERA spectrometer,
working at IBR-2 pulsed reactor at Joint Institute for Nuclear Research [3].
undergoes cooling down to the metastable glass state of very long relaxation time
more than a year. Infrared spectroscopy studies revealed the differences between the
stable (crystal) phase and the glass state.
136
P66
Acknowledgment
The Authors thanks to Frank Laboratory of Neutron Physic JINR in Dubna and Institute of
Nuclear Physic in Cracow for ability to use NERA and Excalibur spectrometers.
References
[1] 3154441,
Elsev., 2012.
[2] A. Rudzki, M.D. Ossowska-
J Therm Anal Calorim, DOI 10.1007/s10973-015-4656-3, 2015.
[3] - eutron
Journal of
Molecular Structure 693, 2004, pp. 49 71.
137
P67
UV Laser Induced Phototransformations of 1,2,4-Triazole Derivatives
M. Pagacz-Kostrzewa1 1, M. Wierzejewska1, D. Khomenko2
1Faculty of Chemistry University of Wroclaw, Poland, magdalena.pagacz-
[email protected], [email protected], maria.
[email protected] Taras Shevchenko University, Department of Chemistry,
Volodymyrska Street 64, 01033 Kyiv, Ukraine, [email protected]
Substances containing the tetrazole and triazole rings represent one of the most
biologically active classes of compounds and receive many applications in the synthesis
of compounds with diverse pharmacological activities. In order to understand the
biological activity of these species the knowledge of their conformational preferences
becomes really important. In turn, the obtained information on conformational
equilibria and tautomerization processes of selected azoles can be used to explain the
conformation/tautomerism effect on photochemical preferences in these species.[1-3]
Azole derivatives possessing a free pyrrole (N-H) group exhibit annular
tautomerism resulting from the hydrogen migration between different nitrogen atoms
within the ring. The studied compounds (AT and TF) exist in two tautomeric forms: 1H-
and 2H-tautomers. According to the theoretical prediction, the predominating form in
the gas phase is the 1H-tautomer. The infrared spectra of the AT and TF isolated in low-
temperature matrices show that both tautomers are present. According to the B3LYP/6-
311++G(2d,2p) calculations, the population at the deposition temperature of the 1-AT
and 2-AT forms equals 79 and 21 % whereas the population of the 1-TF and 2-TF
equals 90 and 10 %, respectively.
Irradiation of the studied species isolated in argon and nitrogen matrices with the
tunable UV laser source induces two different photochemical processes occurring at
different rates: the reaction of intramolecular proton transfer between two nitrogen
atoms of the triazole ring and triazole ring cleavage.
Acknowledgment
The research was supported by the National Science Centre Project No. 2014/13/D/ST4/01741. A grant
of computer time from the Wro
acknowledged.
References
[1] M. Pagacz-Kostrzewa, M. Mucha, M. Weselski, M. Wierzejewska, J. Photochem. Photobiol. A:
Chem., 2013, 251, 118-127.
[2] M. Pagacz-Kostrzewa, J. Krupa, M. Wierzejewska, J. Photochem. Photobiol. A: Chem., 2014, 277,
37-44.
[3] M. Pagacz-Kostrzewa, J. Krupa, M. Wierzejewska, J. Phys. Chem. A, 2014, 118, 2072-2082.
138
P68
Optical Properties of Eu3+/Gd3+ Ions in Silica Xerogels and Powders
Obtained by Sol-Gel Method
N. Pawlik, B. Szpikowska-Sroka, W. Pisarski
University of Silesia, Institute of Chemistry, 9 Szkolna Street, 40-007 Katowice, Poland,
Over last few years, much attention has been paid to the development of
efficient red emitting sources. The most commonly used phosphors are basing on red
luminescence originated from Eu3+ ions [1]. In order to enhance the characteristic
luminescence of Eu3+-doped materials some sensitizers such as Gd3+ ions are used. The
presence of Gd3+ ions significantly improves the luminescence properties of rare earths,
since the 6PJ8S7/2 emission of Gd3+ overlaps with their 4f-4f absorption bands [2,3].
The sol-gel materials with different quantitative composition have been studied
for down-conversion luminescence, based on excitation and emission measurements
and luminescence decay analysis. Emission spectra of Eu3+ ions were registered upon
two different excitation wavelengths related to direct excitation ( exc = 393 nm) and
Gd3+ 3+exc = 273 nm). Upon direct
excitation of Eu3+ (7F05L6 transition) it was observed a significantly increase the
intensity of characteristic emission bands assigned to the 5D07F1,2 electronic
transitions and prolongation of powders luminescence lifetime in comparison to
xerogels. Also, it was found that the enhanced luminescence of Eu3+ is a result of
change the excitation parameter via energy transfer phenomenon (8S7/2 6IJ transition
of Gd3+) and occurred in both xerogel and powder samples. In this way, a UV photon
absorbed by Gd3+ is down-converted into one visible photon emitted by Eu3+. Moreover,
the red photoluminescence from Gd3+ ions due to the 6GJ6PJ transitions was
registered. The excited state absorption (ESA) mechanism of visible emission originated
from Gd3+ ions was discussed. Obtained results clearly indicated that high concentration
of Gd3+ in powders led to particularly strong enhance the emission in red spectral range
and allowed for more than 12-fold prolongation of luminescence time for the 5D0
excited state of Eu3+ compared to silica xerogel samples.
References
[1] W.A. Pisarski, Phys. Stat. Sol. 242, 2005, 14, 2910-2918.
[2] Y.-C. Li, Y.-S. Chang, Y.-C. Lai, Y.-J. Lin, C.-H. Laing, Y.-H. Chang, Mater. Sci. Eng B 146, 2008,
225-230.
[3] Y. Sheng, L. Zhang, H. Li, J. Xue, K. Zheng, N. Guo, Q. Huo, H. Zou, Thin Solid Films 519, 2011,
7966-7970.
139
P69
and DFT Modeling Studies of
Melaminium n-Acetylglycinate Dihydrate
Hasan Tanak1, Jan Janczak2, Mariusz K. Marchewka2, Katarzyna Pawlus2
1Department of Physics, Faculty of Arts and Sciences, Amasya University,05100,
Amasya, Turkey2Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
-
The new crystal was obtained in reaction of melamine and N-acetylglycine in
the water solution. Melaminium N-acetylglycinate dihydrate crystallizes in triclinic
system, in P-1 space group. The lattice constants at room temperature are: a=5.642(1),
The asymmetric unit comprises one monoprotonated melaminium cation, one N-
acetylglycinate anion and two water molecules.
Fig. 1 Structure of investigated molecule
The NBO analysis has revealed tha -H1) interaction gives the
strongest stabilization to the system. In the crystal structure of studied compound, chain
patterns of hydrogen bond occur in ab plane. Two chains propagate along main
crystallographic directions a,b. They are created without the melaminium cations. The
cations form chain patterns exclusively along [110] direction.
The IR and Raman spectra were obtained for the protonated and deuterated
crystals. The vibrational spectra were interpreted by using PEDs (Potential Energy
Distributions). The theoretical and observed frequencies have been compared and
several stretching and deformation modes confirm the presence of intermolecular
hydrogen bonding in the title crystal.
The frontier molecular orbitals show that the stability of the title compound
increases in going from the gas phase to the solution phase.
References
[1] M.H. Jamroz, Vibrational Energy Distribution Analysis VEDA 4, Warsaw, 2004-2010
140
P70
Polarized Vibrational Spectra and DFT Studies of bis(2-
Aminopyridinium) Fumarate Fumaric Acid (1:1)
K. Pawlus, M. K. Marchewka
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
- int.pan.wroc.pl
The polarized Raman and reflective infrared spectra of bis(2-aminopyridinium)
fumarate fumaric acid (1:1) monocrystal were measured. The spectra are discussed in
the basis of earlier crystallographic studies (especially the network of hydrogen bonds)
[1].
The theoretical calculations in oriented gas model approximation were
performed. Additionally the theoretical DFT calculations of vibrational and chemical
properties were made. Based on PEDs [2] calculations, bands were finally assigned. The
optimized geometry, energies and shape of HOMO and LUMO molecular orbitals,
NBO analysis are presented, as well.
Fig. 1 Structure of investigated molecule
References
[1] A. Ballabh, D. R. Trivedi, P. Dastidar, E. Suresh, Cryst. Eng. Comm. (2002), 4(24), 135
[2] M. H. Jamroz, Vibrational Energy Distribution Analysis VEDA 4, Warsaw, 2004-2010
141
P71
Spectral Investigation and Phase Transition in Pyridazine Perchlorate
the Crystal with Hydrogen Bonds
1 2 and Z.Czapla3
1Institute of Experimental Physics, Wroclaw University, 9 M.Born Sqr., 50-204, Wroclaw,
Poland, [email protected], [email protected] -Curie 14, 50-
Poland, [email protected] of Physics, Opole University of Technology, Ozimska 75, 45-271 Opole,
Poland, [email protected]
Pyridazine perchlorate [(C4H4N2)HClO4] crystal, abbreviated as PClO, consists
of pyridazinium cations and ClO4 anions. It belongs to organic inorganic compounds.
Pyridazine, a component of the studied crystal, is a heterocyclic aromatic compound
with the molecular formula C4H4N2. It contains a six-membered ring with two adjacent
nitrogen atoms. The results of the X-ray diffraction method [1,2] indicate that the
crystal is monoclinic at room temperature, with the space group P21/n and Z = 4. The
hydrogen bonds of the C H O, N H O and N H N types [1], which link the ClO4
groups and the pyridazine rings stabilize the crystal structure. Dielectric and optical
studies [1] have revealed the first order structural phase transition (PT) at 343 K with
thermal hysteresis of about 3K. The room temperature phase (II) is the ordered one
while above the PT temperature the phase I is disordered. At 350 K, at phase I the
crystal is hexagonal, with the space group R 3 m and Z = 3. The molecules in the crystal
are disordered in this phase, the hydrogen bonds are broken [1]. So, the pyridazinium
cations and ClO4 anions reveal orientational disorder above the phase transition and
held rigidly the crystal lattice at room temperature.
The vibrational infrared spectra of powdered pyridazine perchlorate crystal in
Nujol and Perfluorolube mulls are studied in the wide temperature range, from room
temperature to 380 K. For more detailed band assignment spectrum at KBr pellet and
Raman spectrum at room temperature, at ferroelectric phase have been carried out.
The special attention is put on the temperatures near the phase transition
temperature at 340 K (the phase transition temperature from DSC measurements). The
temperature changes of wavenumbers, centre of gravity and intensity of the bands are
analyzed to clarify the molecular mechanism of the phase transitions. Information about
hydrogen bonds are obtained.
Spectroscopic methods are expected to provide a detailed knowledge of any
molecular framework. As a means of learning more about the nature of the chemical
bonds involved, the intermolecular forces and the behavior of normal modes and their
connections with the structural phase transition a brief study was made on the IR
spectrum of pyridazine perchlorate crystal.
References
[1] J. Phys. Condens. Matter 19 (2007) 086219
[2] 63 (2007) o1199
142
P72
Relationship Between Morphology and Spectral Characteristics of Ag
and Au Nanoparticles/Terpyridyl-Based Oligomers Interfacial Films
1 1 1, Ji 1,2
1Charles University in Prague, Faculty of Science, Department of Physical and
Macromolecular Chemistry, Hlavova 8, Prague 2, 128 40, Czech Republic
mailto:[email protected] of Macromolecular Chemistry AS CR, Heyrovskeho nam. 2, Prague 6, 162 06,
Czech Republic
-terpyridine (tpy) complexes and tpy-based oligomers [1] are currently
the subject of interest due to their applications as building blocks of light-emitting devices
and dye-sensitized solar cells as well as the building blocks of metallosupramolecular polymers
[2] and dynamers [3]. Assembling of plasmonic (predominantly Ag and Au) nanoparticles
(NPs) through selected molecules into 2D and 3D systems allows the observation of adsorbed
molecules by surface-enhanced Raman scattering (SERS) spectroscopy [4].
In this contribution, we have focused on the preparation, morphological
and spectroscopical characterization of 2D assemblies of Ag and Au NPs derivatized
by the adsorbates based on molecules with terpyridyl end groups (interfacial Ag and/or Au NPs/
adsorbate films [5]). Interparticle distances, determined from transmission electron micrographs
(TEM, Fig. 1), were correlated with the surface plasmon adsorption spectra (SPA) as a function
of the variable length of tpy-based adsorbates. The coordination of the adsorbates to Ag and Au
NPs was investigated by SERS spectroscopy (Fig. 2). SERS spectra revealed different means of
adsorption of studied molecules to Ag and/or Au NP surfaces.
Figure 1 TEM of Au -
bis(tpy)terthiophene film
Figure 2 SERS spectra of interfacial Ag NPs/adsorbate
films
Acknowledgment Financial support: Grant Agency of Charles University (project 363515) and Czech
Science Foundation (P108/12/1143) grant.
References
[1] Soft Materials, 2014, 12, 214-229;
J. Tetrahedron, 2011, 67, 75-79.
[2] A. Harriman, R. Ziessel, Chem. Commun. 1996, 1707-1716.
[3] J. M. Lehn, Prog. Polym. Sci. 2005, 30, 814-831.
[4] R. Aroca, Surface-Enhanced Vibrational Spectroscopy, John Wiley and Sons, Ltd., Chichester, UK,
2006.
[5] Langmuir 1993,9, 3234-3238.
143
P73
Expermimental Study on the Core-Shell Interactions in the Case of
Magnetic Grains Coated with Organic Molecules
E.Puscasu1, M. Andries1, M.Racuciu2, F.Iacomi1, D. Creanga1
1
2
Magnetic nanoparticles prepared by co-precipitation adapted method were
stabilized in suspension form by surface modification with organic compounds like
tetramethylammonium hydroxide (TMA-OH), citric acid, tartaric acid, perchloric acid.
The interaction between magnetic grains and the coating molecules ensured suspension
stability over time. Transmission electron microscopy (TEM), X-ray diffraction (XRD),
FTIR spectra and UV-Vis ones were applied to evidence the properties of the colloidal
suspension. FTIR was found to be able to provide deepest insight on the studied
phenomena of organic compounds adsorption on the surface of the metallic particles
Fig.1.
Fig. 1. FTIR recording for magnetite/ TMA-OH nanoparticles
In the case of each colloidal nanoparticles type the identification of vibration
modes of ferrophase and organic phase was accomplished based on literature and
experimental data. TEM and XRD offered only complementary information on the
study interaction phenomena resulted in either electrostatic or steric repulsion of
colloidal nanoparticles in suspension.
Acknowledgement
This study was sustained by POSDRU/187/1.5/S/155397 program of European Social Fund in
Romania under the responsibility of the Managing Authority for the Sectored Operational Program for
Human Resources Development 2007-
144
P74
Light Wavelength Influence on Surface Plasmon Resonance in Citrate-
Gold Nanosystems
D. Pricop, M. Andries, R. Lupusoru*, E. Puscasu, F. Iacomi, D. Creanga
Medicine and Pharmacy, Iasi, Romania
Gold nanoparticles (AuNPs) are used in biomedicine for photothermal and
photodynamic therapies, targeted delivery of drugs, DNA and antigens, optical
bioimaging of issues and cells and others. We studied the spectral proprieties of AuNPs
yielded through single phase water based reduction of a gold, in different synthesis
media. Equal volumes of gold colloidal suspension were exposed to visible light with
different wavelengths for 90 min at room temperature. UV-Vis and FTIR spectroscopy
were used to investigate the response of AuNPs to visible light influence.
Fig. 1. UV-Vis and IR absorption spectra of colloidal gold nanoparticles exposed to white light (W), blue
light (B), green light (G) and yellow light (Y)
The UV-Vis spectra showed that all colloidal suspensions exposed to visible light
exhibited the intensity increasing in the band characteristic to AuNPs which was put in
relationship with the light influence on the surface plasmon resonance (SPR) related to
interband transition of the electrons in surface layer of metallic gold. Light irradiation
and possibly SPR changes influenced the vibrations of stabilizing ion species bond to
gold surface; the green light excitation photon had stronger influence on 1546 nm
vibration (FTIR data).
Acknowledgement
This study was sustained by POSDRU/187/1.5/S/155397 program of European Social Fund in
Romania under the responsibility of the Managing Authority for the Sectored Operational Program for
Human Resources Development 2007-
145
P75
Electric-Field Induced Molecular Switching Based on Double Proton
Transfer: Dynamical Simulations
M.F. Rode,1) J. Jankowska,2) and A.L. Sobolewski 1)
1) Institute of Physics, Polish Academy of Sciences, Warsaw, Poland,
[email protected], 2)College of Inter-Faculty Individual Studies in Mathematics and
Natural Sciences, University of Warsaw, Poland, [email protected]
In this communication we report ab initio and on-the-fly dynamics predictions of the
variation of the electric-field induced double proton transfer (DPT) reaction mechanism
in the model Schiff base molecule: (2Z)-1-(6-((Z)-2-hydroxy-2-phenylvinyl)pyridin-3-
yl)-2-(pyridin-2(1H)-ylidene)ethanone (DSA)[1,2].
In the ground electronic state, the DSA molecule possesses four enantiomeric forms
(see Fig. 1), which are interconnected by the transfer of two protons engaged in two
hydrogen bonds. Both these protons may undergo barrierless transfer from the ee form
toward kk upon exposure to the electric field applied to the system along the main
molecular axes.[3] The reversible reaction, from kk toward ee, is also possible if the
field is applied in opposite direction so the model molecule may function as a molecular
switch.
Fig. 1 Tautomeric forms of the DSA molecule
Both ab initio and dynamical
studies show that, in the lack of
the external stimuli, the DPT
reaction between the ee and kk
forms is a two-step-wise reaction,
while a synchronous concerted
DPT process is blocked by an
energy barrier.[4] The situation
changes when an external electric
field is applied to the molecule.
The dynamics results indicate that
if the electric field is of sufficient
magnitude, the synchronous
downhill
DPT process becomes dominating. The conclusion emerging from the obtained results
indicates that the applied electric field may induce the double proton transfer process in
a reversible fashion by modulation of the shape of the potential energy surface.
Dynamical calculations performed for the DSA molecule placed in an external electric
field give insight into the mechanism of the double proton transfer in the system. The
results indicate the mechanism of the DPT reaction is sensitive to the magnitude of
electric field applied.
References
[1] A. Accardi, I. Barth, O. Kuhn, J. Manz, J. Phys. Chem. A, 114 (2010) 11252
[2] A. A. Arabi, C. F. Matta, Phys. Chem. Chem. Phys. 13 (2011) 13738
[3] J. Jankowska, J. Sadlej, and A. L. Sobolewski, Phys. Chem. Chem. Phys. 17 (2015) 14484
[4] M. F. Rode, A. L. Sobolewski, Chem. Phys. 409 (2012) 41.
N
N
O
O
H
H
N
N
O
O H
H
N
N
O
O H
H
N
N
O
O
H
H
PT
PT
PTPT
ee ke
ek kk
146
P76
Mononuclear Arene Ruthenium Complex Containing
2- -Pyridyl)Benzimidazole as Chelating Ligand. Synthesis,
Crystal Structure and Spectral Properties
P. Rogala1*, B. Barszcz1 Wawrzycka1, G. Czerwonka2,
K. Kazimierczuk3
1Institute of Che -406
Kielce, Poland, *e-mail: [email protected] of Microbiology, Institute of Biology, Jan Kochanowski University, 15G
okrzyska Str., 25-406 Kielce, Poland,3Department of Inorganic Chemistry,
Technology, 11/12 G. Narutowicza Str., 80-
6-arene ruthenium compounds, piano-stool
complexes are definitely the most studied ones. The applications of half-sandwich 6-arene ruthenium complexes are wide, particularly in synthetic organic chemistry as
homogeneous catalysts [1]. They have also used as anticancer drugs, and have shown
antiviral, antibacterial, antimalarial activity [2].6-p-cymene)RuII -
PyBIm)]PF6 has been synthesized from bidentate N,N-donor ligand, viz.
2,- - -PyBIm) and the corresponding chloro complex 6-p- -Cl)Cl]2. The isolated complex was characterized by X-ray
crystallography, IR and UV-Vis spectroscopies. The ionic nature of the compound is
identified by a strong band at around 830 cm 1 due to the (P F) stretching mode of the
PF6 counter ion. The electronic spectrum of monomeric complex display high intensity
bands in the ultraviolet region at ~215-
The X-ray crystal structure analysis of complex reveals a typical piano-stool
geometry around the metal centre. The cation exhibits a pseudo-octahedral three-legged
piano- 6-p-
cymene ligand. -stool structure are formed by one chloride ion
and two nitrogen donor atoms of the chelating ligand -PyBIm. Moreover, biological
properties of ruthenium complex were analyzed. The tests with pUC18 (2686 bp) 6-p-
cymene)RuII -PyBIm)]PF6. The interaction of ruthenium complex with DNA was
studied by agarose gel electrophoresis in water environment.
References
[1] P. Kumar, R. K. Gupta and D. S.Pandey, Chem. Soc. Rev., 43, 2014, 707-733.
[2] A. K. Singha, D. S. Pandeyb, Q. Xua and P. Braunsteinc, Coord. Chem. Rev., 270 271, 2014, 31-56.
147
P77
Ruthenium(III) Complex Containing Organic Ligand Transformed in
situ. Synthesis, Structural and Spectral Characterization
Wawrzycka1*, P. Rogala1, G. Czerwonka2, H. Hodorowicz3,
B. Barszcz1
1Institute of Chemistry, Jan Kochanowski Univers -406
Kielce, Poland, *e-mail: [email protected] of Microbiology, Institute of Biology, Jan Kochanowski University, 15G
rzyska Str., 25-406 Kielce, Poland,3Faculty of Chemistry, Jagiellonian University, 3 Ingardena Str., 30-
Poland
Ruthenium-based molecules have been studied as promising compounds from
both chemical and biological views. Further, an oxidation state of ruthenium is often
essential for applicability of these complexes. Thus, Ru(II) and Ru(III) compounds with
diazoles can be used as alternatives to platinum complexes because they are predicted to
show antitumor activity and clinical toxicity [1-4]. Ruthenium complexes possess
different geometry in comparison to platinum compounds and different oxidation states.
They can bind to DNA or biological target other than DNA [5].
Our studies aim to present the synthesis and characterisation of ruthenium(III)
complex in which new ligand in situ was formed. The complex was formed by reacting
mother solution of ruthenium(III) chloride with 3-hydroxy-2-quinoxalinecarboxylic acid
as ligand in experimental conditions. The presence of air atmosphere, HCl and ethanol
solvent contribute to redox process and then the formation of the 2,3-dioksoqunexaline
-
of complex anion and it does not participate in forming of coordination bonds.
Ruthenium(III) complex crystallizes in the monoclinic space group C 2/c. Trivalent
ruthenium is surrounded by two molecules of acetonitrile and four coplanar chloride
anions to give RuN2Cl4 chromophore. Coordination sphere is distorted octahedral. The
anionic complexes are held together by H-bonds of N-H Cl, C-H O and C-H Cl
type. They form zig-zag chain along [1 0 0] direction. Additionally, there are also some
contacts which complete the supramolecular architecture. The UV-Vis spectrum
recorded in water is characterized by relatively intense bands at ~400 nm, and by a
t2gRu
LMCT (Ru-Cl) transitions involving the four coplanar chlorides. The new Ru(III)
complex were also screened for respective biological activity.
References
[1] M. J. Clarke, Coord Chem Rev., 236, 2003, 209-233.
[2] E. S. Antonarakis and A. Emadi, Cancer Chemother Pharmacol., 66, 2010, 1-9.
[3] D. Griffith, S. Cecco, E. Zangrando, A. Bergamo, G. Sava and C. J. Marmion, J. Bil. Inorg. Chem.,
13, 2008, 511-520.
[4] V. Brabec and O. Novakova, Drug Resistance Updates, 9, 2006, 111-122.
[5] C. S. Allardyce and P. J. Dyson, Platinum Metals Rev., 45 (2), 2001, 62-69.
148
P78
Proton Donor and Acceptor Properties of N-Hydroxyurea
N-hydroxyurea (HU) is a representative of hydroxamic acids with the
N(OH)CONH2 grouping occurring in numerous biologically active compounds. It
demonstrates a complex pharmacological profile and is used as a human
chemotherapeutic agent. I have recently studied the isomerical and structural properties
of N-hydroxyurea and showed that HU trapped from the gas phase into solid argon
exists in the matrix preferentially in the 1E keto form.[1] Hydroxamic acids are N-
hydroxy substituted derivatives of amides and involve the fragment of the simplest
protein structure HNC=O. In addition to the two basic centres characteristic for the
HNC=O group, hydroxamic acids have the third basic centre which is the oxygen atom
of the hydroxyl group. In order to evaluate proton donor and acceptor abilities of the
acidic and basic centres of the N-hydroxyurea molecule the infrared matrix isolation and
theoretical studies of the self-association of N-hydroxyurea and complexes with strong
proton donors: HCl and HF were performed.
The 1:1 HU HX complexes, identified for both hydrogen halide molecules,
have the cyclic structures stabilized by the X-H O and N-H X bonds; for the HU HF
system another isomeric 1:1 complex is also observed in which the F-H O and (H)N-
H F bonds are present. Two 1:2 complexes were identified for the N-hydroxyurea
hydrogen chloride system characterised by the Cl-H O and N-H Cl bonds. In the first
complex HU interacts with the HCl dimer, one HCl molecule acts as a proton donor
toward the oxygen atom of the carbonyl group, whereas the second HCl molecule acts
as a proton acceptor for the NH2 group of HU. In the second complex the carbonyl
group of HU acts as a double proton acceptor toward two HCl molecules.[2]
The obtained results evidence that in the matrix are formed two (HU)2 dimers
stabilized by a strong OH O hydrogen bond. There is an additional weak interaction
between the oxygen atom of the OH group of the proton donor molecule and the NH or
NH2 group of the proton acceptor in both dimers, respectively. The presence of the
structures not characterised by the lowest values of the binding energy in the studied
matrices indicates that the formation of N-hydroxyurea dimers is kinetically and not
thermodynamically controlled.[3]
Acknowledgements
percomputer Centre (WCSS) for providing computer time and
facilities.
References
[1] Chem. Chem. Phys., 2010, 12, 15111-15118.
[2] Phys., 2014, 444, 15-22.
[3]
149
P79
Formaldoxime Hydrogen Bonded Complexes with Ammonia and
Hydrogen Chloride
1, B. Golec2, A. J. Barnes3, Z. Mielke1
1
[email protected],[email protected] of Physical Chemistry, Polish Academy of Sciences, [email protected]
3Materials and Physics Research Centre, University of Salford, United Kingdom,
Oximes are important biological and chemical systems. The >C=NOH group
involves the OH hydrogen bond donor and two hydrogen bond acceptor sites, namely
the C=N nitrogen and the O-H oxygen, so, oximes may form a variety of hydrogen
bonds. The intermolecular hydrogen bond motifs involving oximes play an important
role in molecular design. Oximes exhibit significant molecular association even in the
dilute gas phase which is relatively rare phenomenon. The ability of oximes to form
hetero-aggregates with various proton donors and acceptors was much less studied than
oximes homo-aggregation. Formaldoxime complexes with nitrogen [1], nitrous acid [2]
and water [3] were recently studied by help of matrix isolation technique and quantum
chemistry methods. Ammonia and hydrogen chloride serve as archetypal strong proton
acceptor and strong proton donor, respectively, in the studies of hydrogen bonding. The
study of the formaldoxime complexes with these two molecules shall provide
information on the proton acceptor and proton donor abilities of the >C=NOH group.
An infrared spectroscopic and MP2/6-311++G(2d,2p) study of the complexes of
formaldoxime with NH3 and HCl trapped in solid argon matrices is presented [4]. Both
1:1 and 1:2 complexes have been identified in the CH2NOH/NH3/Ar, CH2NOH/HCl/Ar
matrices, respectively, their structures were determined by comparison of the spectra
with the results of calculations. In the 1:1 complexes present in the argon matrices the
OH group of CH2NOH acts as a proton donor for NH3 and a nitrogen atom acts as a
proton acceptor for HCl. In the 1:2 complexes ammonia or hydrogen chloride dimers
interact both with an OH group and a nitrogen atom of CH2NOH to form seven
membered cyclic structures stabilized by three hydrogen bonds. The theoretical spectra
generally agree well with the experimental ones, but they seriously underestimate the
shift of the OH stretch for the 1:1 CH2NOH NH3 complex.
Acknowledgements
viding computer time and
facilities.
References
[1] B. Golec, J. Grzegorzek, Z. Mielke, Chem. Phys. 2008, 353, 13-18.
[2] B. Golec, A. Bil, Z. Mielke, J. Phys.Chem. A, 2009, 113, 9434-9441.
[3] B. Golec, M. Mucha, Z. Mielke, Spectrochim. Acta. Part A, 2012, 86, 461-466.
[4]
68-75.
150
P80
Conformation of the Hedrazo Bond in -Dimethyl- -
Tetranitro-2,2-Hydrazobipyridine: Structure, Vibrational Studies and
DFT Calculations
E. Kucharskaa, I. Bryndala, a, J. Lorenca and J. Hanuzab
aDepartment of Bioorganic Chemistry, Institute of Chemistry and Food Technology,
University of Economics, 118/120 Komandorska, 53 -bInstitute of Low Temperature and Structure Research, Polish Academy of Sciences,
-
Hydrazo compounds attract considerable attention because of their unique physicochemical
properties, tautomerism and potential applications (in chemical synthesis, e.g. azo compounds,
amino derivatives, polymers) [1].
-dimethyl- -tetranitro-2,2-hydrazobipyridine (4MNHP) has
been described. The crystal and molecular (Fig. 1) structures of this compound have been
determined by X-ray diffraction and quantum chemical DFT analysis. 4MNHP crystallizes in
the monoclinic C2/c space group with one-half of the molecule in the asymmetric unit.
Similarly to the earlier described 2-amino-3-nitropyridine derivatives [5], the intramolecular N-
adjacent molecules are linked by weak C-
chain with a ladder motif.
IR and Raman spectra have been measured and compared to the calculated wavenumbers
and to those of similar compounds previously reported by us [2-4]. The 6-311G(2d,2p) basis set
with the B3LYP functional has been used to discuss the optimized structure and vibrational
dynamics of the studied compound. The vibrations of hydrazo bond are characterized by (NH),
(C N), (HNNH), (CNH), (N-N) and torsional vibrations (C-NN) (HNNH), (CNH) and
(CNNC). These vibrational characteristics have been reported with their relation to the
conformation of the molecule. Normal modes of hydrazo bond, nitro and methyl groups and
pyridine rings have been identified together with the PED values. It was found that the
characteristic vibrational bands observed in the range 3400-3000 cm-1 originate from the
intramolecular N- between the NH and NO2 groups.
Fig. 1. The molecular structure of 4MNHP
References [1] R.A. Cox and E. Buncel. Rearrangements of hydrazo, azoxy and azo compounds. In "The Chemistry of the
Hydrazo, Azo and Azoxy groups", edited by S. Patai, Wiley-Intersicence, New York, Chapter 18, pp. 775-859
(1975).
[2] -14.
[3] -
325.
[4] E. Kucharska, I. Bryndal, J. Hanuza, T. Lis, Spectrochim. Acta A. 127 (2014) 303-309.
[5] I. Bryndal, E. Kucharska, W. Sasiadek, M. Wandas, T. Lis, J. Lorenc, J. Hanuza, Spectrochimica Acta Part A,
96 (2012) 952-962.
151
P81
Molecular Structures, Vibrational Studies and Quantum Chemical
Calculations for 3(or 4)-Methyl-2-(Methylsulfanyl)-3-(or 5)-
Nitropyridine
1, J. Lorenc1, J. Hanuza2, I. Maliszewska3
1 Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology,
Faculty of
Poland2 Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
-3 Division of Medicinal Chemist
University of -
Sulfur derivatives of pyridine constitute an interesting family of compounds with
bioactive properties. They are used as an agrochemicals and pharmaceuticals.
The methylsulfanyl derivatives of the pyridine show, among other, fungicidal
an anxiolytic properties.1,2
The studied here three structural isomers of 2-methylsulfanylpyridine
were synthesized according to the procedure developed by Talik.3 These compounds
contain three substituents: methylsulfanyl, methyl and nitro groups, which are situated
in different places of pyridine ring.
I 4-methyl-2-(methyl-
sulfanyl)-5-nitropyridine
II 4-methyl-2-(methyl-
sulfanyl)-3-nitropyridine
III 3-methyl-2-(methyl-
sulfanyl)-5-nitropyridine
The molecular structures of the studied compounds have been optimized using
quantum chemical calculations. Their vibrationals levels have been obtained from
the optimized geometry for all the molecules. The experimental IR and Raman
wavenumbers have been compared to those obtained from DFT quantum chemical
calculations performed with the use of B3LYP/6-311G(2df,2dp) approximation.
In the discussion the literature data have been taken into account.
Special attention has been paid to steric effects and coplanarity of the nitro group
in the compounds under study. The most twisted nitro group, relatively to the pyridine
plane, is observed in II at II
isomer shows antimicrobial activity against various bacterial and fungal strains.
References
[1] J. F. Cryan, P. H. Kelly, F. Chaperon, et al., JPET, 2004 vol. 310 no. 3, 952,
[2] J. Vicente, M.-T. Chicote, C. Rubio, Chem. Ber., 1996 (129) 327,
152
P81
[3] T. Talik, Z. Talik, Pol. J. Chem., 1978 (52) 163.
153
P82
UV-Vis Study of 1-(2-Pyridylazo)-2-Naphthol (PAN) and its Metal
Complexes with Al(III), Mn(II), Fe(III), Cu(II) and Pb(II)
Botond L. Simon*
- -Napoca,
Romania, *e-mail: [email protected]
PAN is a non-selective azo dye, widely used as colorimetric reagent for metal ions
spectrophotometric determination. It forms very stable, methanol-soluble and highly
colored complexes with the vast majority of transition metals [1 2]. PAN has also been
used as a chelating agent for the separation and
preconcentration of heavy metal traces from
various media, including natural waters [3].
This study reports, a Uv/Vis study on PAN
(Fig.1) and its metal complexes with Al(III),
Mn(II), Fe(III), Cu(II), and Pb(II).
Experimental electronic absorption spectra
where acquired at different pH values, within
the 2-13 range.
Quantum chemical calculations based on time
dependent density functional theory (TD-
DFT) were performed in explain the experimental findings, with particular emphasis on
vertical absorption and emission energies, geometries of the emitting structures,
adiabatic and 0-0 transition energies [4-6]. For this purposes, extensive TD-DFT
calculations have been carried out using the hybrid exchange-correlation functionals
B3LYP and PBE0, as well as the long-range corrected CAM-B3LYP functional,
coupled to the 6-31+G(2d,2p) and 6-311G(d,p) basis sets. To account for solvent effects
we used the implicit PCM continuum model.
Calculated data are compared to reference experimental results where available or to
previously reported computational data. Even though the ES are environmentally
sensitive using appropriate models and computational methods we were able to
reproduce the existing experimental data within the experimental errors.
Acknowledgment
This work was supported by CNCSIS-UEFISCSU, project number PN-II-RU-TE-2012-3-0227/2013.
References
[1] P. Sett, N. Paul, S.K. Brahma, S. Chattopadhyay, J. Raman Spectrosc. 30 (1999) 611.
[2] L. Szabo , K. Hermana , N. E. Mircescu , A. Falamas, L. F. Leopold , N. Leopold, C. Buzumurg, V.
273
[3] M. Soylak, Y.E. Unsal, N. Kizil, A. Aydin, Food Chem. Toxicol. 48 (2010) 517.
[4] D. Jacquemin, A. Planchat, C. Adamo, B. Mennucci, J. Chem. Theory Comput., 8 (2012)
2359 2372.
[5] N. De Mitri, S. Monti, G. Prampolini, V. Barone, J. Chem. Theory Comput., 9 (2013) 4507 4516.
[6] M. Oltean, A. Calborean, G. Mile, M. Vidrighin, M. Iosin, L. Leopold, D. Maniu, N. Leopold, V.
-710.
Fig. 1 Optimized molecular structure of PAN
154
P83
Influence of GeO2 Content on Structural and Luminescent Properties
of Antimony Glass Doped with Sm3+ Ions
J. Zmojda1, M. Kochanowicz1, P. Miluski1, M. Sitarz2, W. Pisarski3, J. Pisarska3
and D. Dorosz1
1Department of Power Engineering, Photonics and Lighting Technology, Bialystok
University of Technology, Wiejska Street 45D, 15-351 Bialystok, Poland2Faculty of Materials Science and Ceramics, AGH University of Science and
Technology, 30 Mickiewicza Av., 30-059 Krakow, Poland3Institute of Chemistry, University of Silesia, Szkolna 9, 40-007 Katowice, Poland
In this work glasses from the system Sb2O3 GeO2 SiO2 have been prepared by
conventional melt-quenching technique. Structural and luminescent properties of fabricated
glasses doped with samarium ions were studied. The structure of fabricated glasses has been
studied by infrared and Raman spectroscopy. The effect of GeO2 concentration on the
structural properties of antimony glasses was determined. In earlier work we confirmed that
antimony is the ion co-forming the network of antimony-silicate (SiO2-Sb2O3) glasses [1].
In this study we focus on another low-phonon oxide glass forming element germanium
and his influence on structural and spectroscopic properties of antimony glasses (Fig.1.).
Fig. 1. MIR spectra of antimony-
germanate glasses as a function of GeO2
content.
Fig. 2. Luminescence spectra of antimony-germanate glasses doped with
Sm3+ ions as a function of GeO2 content. (inset) Lifetime of 6H7/2 excited
level.
Additionally, the influence of GeO2 concentration on the luminescent properties was
determined (Fig. 2). In results of optical excitation at 405 nm multi-wavelength
luminescence with characteristic pink colour at 603 nm corresponding to transitions 4G5/26H7/2 were measured. In the case of luminescence decay the increase of GeO2 content
slightly increasing lifetime of 6H7/2 energy level.
The project was funded by the National Science Centre (Poland) granted on the basis of the decision No.
DEC-2012/07/B/ST8/04019
Reference
[1] Dorosz, J. Zmojda, M. Kochanowicz, P. Miluski, P. Jelen, M. Sitarz Spectrochim. Acta Part A 134
(2015) 608-613.
155
P84
Oxygen Transport in Hybrid Titanium Oxidation Processes
1 2 3,
Maciej Sitarz4 1
1Czestochowa University of Technology, Faculty of Management2National Center for Nuclear Research, Material Research Laboratory
3Czestochowa University of Technology, Materials Science Institute4AGH University of Science and Technology, Faculty of Materials
Science and Ceramics
The paper presents the study of hybrid Ti Grade 2 oxidation (FADT - Fluidized
bed atmospheric diffusive treatment + PVD - magnetron sputtering). It also presents the
influence of the oxidation method on the change in the mechanism of oxygen transport
to the substrate, in order to improve bioactivity. The method used consists in forming
the titanium surface layer saturated with oxygen by means of diffusion and depositing
a tight homogeneous oxide coating on the Ti surface. The processes influenced
a decrease in the surface roughness parameter and an increase in its bio-compatibility,
which resulted in easier hydroxyapatite cluster deposition. The diffusion process was
realized in Al2O3 fluidized bed in air, at 913K for 8 h, while the deposition of the oxide
coatings was carried out with magnetron sputtering at a pressure of 3 x 10-2 mbars and
power of 350W. To investigate the effects of hybrid oxidation and to determine the
mechanism of oxygen transport, the following research methods were applied:
spectroscopy (SIMS, RS), microscopic methods (SEM-EDS, SEM-EBSD,
TEM-EFTEM), X-ray tests -XRD, GID). The results obtained were used to identify
the type of oxide coatings, to assess the thickness of the layers, the influence of
crystallographic orientation on oxygen transport and concentration in the surface layer
and in the oxide coating. It has been found that the formation of oxide coatings with the
use of a hybrid method (FADT+PVD), as opposed to conventional methods, leads to
a change in oxygen concentration in the substrate, due to its defects. In contrast,
forming a tight homogeneous oxide coating on Ti surface improves the
biocompatibility, which is particularly important in the context of biomedical
applications.
Keywords: Titanium Grade2, hybrid oxidation, bioactivity, oxide coating, hydroxyapatite
156
P85
Size Dependence of Opical Properties of Eu3+:Sr2CeO4 Nanocrystals
M. Stefanski*, L. Marciniak, D. Hreniak, W. Strek
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
-* corresponding author: [email protected]
Phosphors based on oxides were widely applied in many kinds of optoelectronic
and display devices because of their good chemical stability, high luminescent
efficiency and unique optical properties.
We present synthesis method and spectroscopic characterization of the
Eu3+:Sr2CeO4 nanocrystals in terms of size effect. The fine powders were prepared
using modified sol-gel method and annealed in temperature range of 750-1050 oC.
X-ray diffraction patterns confirmed phase purity of the samples calcined above 800 oC.
The average grain sizes were determined by Rietveld refinement to be in range of 57-
207 nm. The impact of size effect on luminescent properties was investigated. The
absorption, excitation and emission spectra as well the emission kinetics of the
Eu3+:Sr2CeO4 nanocrystals were studied.
Acknowledgment
The authors acknowledge the support from NCN grant no. 2012/06/A/ST5/00212
References
[1] Danielson, M. Devenney, D.M. Giaquinta, J.H. Golden, R.C. Haushalter, E.W. McFarland, D.M.
Poojary, C.M. Reaves, W.H. Weinberg and X.D. Wu, Science 1998, 279, 837.
[2] Stefanski, L. Marciniak, D. Hreniak, W. Strek, J. Chem. Phys. 2015, 142, 184701.
157
P86
SERS Spectra of Glass-Deposited Single Layer Graphene/Ag NP
Aggregates Hybrid System Measured in the Inverted Sample
Geometry at Various Excitation Wavelengths
V. Sutrova1, I. Sloufova1, B. Vlckova1, M. Kalbac2
1Department of Physical and Macromolecular Chemistry, Charles University, Hlavova
2030, 128 40, Prague, Czech Republic, [email protected] 2J. Heyrovsky Institute of Physical Chemistry of the ASCR, v.v.i, Dolejskova 3, 182 21
Prague 8, Czech Republic
Graphene/plasmonic metal hybrid systems are currently explored as promising composite
materials for nanoelectronics. SERS spectroscopy of such hybrid systems has recently emerged
as an appropriate tool for investigation of the effect of the hybrid system formation on the
structure, electronic structure and optical responses of its components [1,2].
In this contribution, we report SERS spectra of single layer graphene (SLG) deposited on a
glass slide [2] overdeposited by chloride-modified, fused aggregates of Ag nanoparticles (NPs)
[3] measured at 780, 633, 532 and 445 nm excitation wavelengths from several specific
locations within the optical image of the inverted, i.e. Ag NP aggregates/SLG/glass sample.
Using of the inverted sample geometry allows for obtaining SERS signal of SLG located on the
top of Ag NP aggregates without the actual neccessity to deposit SLG onto the rough aggregate
surface.
SERS spectra at the same selected locations (Fig.1A) were measured at all four excitation
wavelengths. For each of these wavelengths, SERS spectra of SLG obtained from different
locations on the Ag aggregate/SLG sample showed a faily good match, as demonstrated for the
spectra obtained at 780 nm excitation in Fig. 1B. Furthermore, the average SLG signal intensity
expressed in terms of 2D mode enhancement was found to increase with the increasing
excitation wavelength, and, simultaneously, the increase of the D/2D mode intensity ratio was
observed. All these results will be compared with those of SERS spectral studies of samples
with different hybrid system geometries, and thoroughly discussed.
Fig. 1 A: Locations of SERS signal acquisition at the optical image of SLG/Ag agregate hybrid
system, B: SERS spectra of SLG obtained from these locations
Acknowledgment Financial support: Czech Science Foundation 15-01953S grant, GAUK 363515 grant
References
[1] Schedin F., Lidorikis E., Lombardo, A., Kravets V.G., Geim, A.K. Grigorenko, A.N., Novoselov,
K.S., Ferrari A.C. (2010) ACS Nano 4 (10), 5617-5626.
[2] Kalbac M., Vales V., Vejpravova J. (2014) RCS Advances 4 (105), 60929-60935.
[3] Sloufova I., Prochazka M., Vlckova B. (2015) J. Raman. Spectr. 46 (1), 39-46.
158
P87
Influence of Gd3+ Concentration on Luminescence Properties of Eu3+
Ions in Silica Sol-Gel Materials
B. Szpikowska-Sroka, N. Pawlik, W.A. Pisarski
University of Silesia, Institute of Chemistry, 9 Szkolna Street, 40-007 Katowice, Poland,
In the field of luminescence materials, phosphors based on europium and
gadolinium compounds are commonly used as emitters in visible spectral scope [1, 2].
The trivalent Gd3+ ions are well known as sensitizers to enhance the 5D07F1,2
emissions of Eu3+ through an efficient energy transfer [3]. The red-emitting materials
are important for optoelectronic applications.
The aim of conducted studies was to investigate the spectroscopic properties of
silica sol-gel powders doubly-doped with Gd3+/Eu3+ with different concentration of
Gd3+ ions. The spectroscopic characterization of prepared samples were conducted
based on excitation and emission spectra as well as luminescence decay analysis. Upon
direct excitation of Eu3+ active ions, the characteristic emission bands 5D07F1
(orange) and 5D07F2 (red) were observed. The energy transfer from Gd3+ to Eu3+ ions
exc exc = 545 nm excitation.
An efficient down-conversion of ultraviolet radiation into visible luminescence
was successfully observed. Furthermore, the visible emission corresponding to the 6GJ
6PJ transition of Gd3+ ions was registered. The excited state absorption (ESA)
mechanism of visible emission originated from Gd3+ ions was presented and discussed.
The energy transfer process ( exc = 273 nm) from Gd3+ to Eu3+ led to longer
luminescence decay from the 5D0 state in comparison to that one obtained under direct
excitation of Eu3+ ions exc = 393 nm). Obtained results clearly indicated the beneficial
influence of increasing concentration of Gd3+ ions on luminescence properties of Eu3+ in
studied silica sol-gel phosphors.
References
[1] B. Szpikowska-
J. Sol-Gel Sci. Techn. 68, 2013, 278-283.
[2] U. Rambabu, N.R. Munirathnam, D.P. Amalnerkar, T. L. Prakash, B. Sudhakar Reddy, S. Chatterjee,
Mater. Chem. Phys. 142, 2013, 459-468.
[3] J. Li, J.G. Li, Y. Sakka, Int. J. Mater. Sci. Eng. 1, 2013, 1, 15-19.
159
P88
A Phase Transition Investigation in NLO Compound: Guanidinium
4 nitrobenzoate
1, M. Drozd2
1
2Institute of Low Temperature and Structure Research Polish Academy of Sciences,
The crystallographic structures of guanidinium 4-nitrobenzoate salt is known in
literature. According to x-ray crystallographic study performed by Adams and co. [1]
4-nitrobenzoate guanidinium crystal belongs to monoclinic system with space group:
P21 or P21/m. The additional research [2] shown that this crystal is cetrosymmetric and
belongs to P21/m space group. Extended investigations made by Arumanayagam and
Murugakoothan [3] indicate that this crystal is noncetrosymmetric (P21) and has NLO
properties.
Our detailed DSC studies shown that in this crystal a low temperature phase
transition was found. On the basis of calorimetric study the phase transition is noticed at
ca. 180 K in both cooling and heating cycles. The phase transition has continuous
character with change of entropy equal to ca. 0.03 J/g*K.
To explain in detail the discovered phase transition phenomenon the temperature
dependent infrared powder spectra were recorded. The temperature dependencies of
bands position and intensities for titled crystal in the range 11 300 K are analyzed. On
the basis of obtained results the phase transition mechanism will be discussed.
References
[1] J. M. Adams and R. G. Pritchard, J. Appl. Cryst. (1975), 8, p.392.
[2] D. CHr. Kleb, M. Schurmann, H. Preut and P. Bleckmann, Z. Kristallogr. 213 (1998), p. 581.
[3] T. Arumanayagam, P. Murugakoothan, J. of Cryst. Growth 362 (2013), p. 304.
160
P89
Raman and IR Studies of non-Nentrosymmetric BaHf(BO3)2 and
La2CaB10O19 Crystals
K. Szymborska- 1 1, A. Majchrowski2, M. Ptak1,
P. E. Tomaszewski1
1 Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
50- k.malek @int.pan.wroc.pl2 Institute of Applied Physics, Military University of Technology, Kaliskiego 2, 00-908
Warsaw, Poland
Borate crystals are extensively studied materials, because of their promising
applications in photonic and optoelectronic technologies such as lasers, nonlinear
optics, optical data storage systems, optical communication, and several others [1-2].
These materials have high nonlinear coefficients, high laser damage threshold, high
optical quality, wide transparency range far into ultraviolet, good chemical, thermal and
mechanical stability [3].
In this contribution, we present and discuss the results of IR and Raman studies
performed for two crystals, BaHf(BO3)2 and La2CaB10O19.
BaHf(BO3)2 crystallizes in polar and achiral space group R3c and its structure is
built up of alternating HfO6 and BaO6 layers connected through borate groups. The
results of X-ray diffraction and IR spectroscopic studies showed small deviations of the
structure from centrosymmetry. This conclusion was supported by observation of
negligible LO TO splitting. Furthermore, high-pressure Raman scattering studies
showed that BaHf(BO3)2 undergoes two pressure-induced phase transitions. The first
phase transition is a first-order and reversible, and occurs in the 3.9 4.4 GPa pressure
range. Second structural change was observed at 9.2 GPa. These studies revealed that
BaHf(BO3)2 is more compressible than calcite-type orthoborates and calcite, aragonite
or dolomite carbonates
Another investigated crystal, La2CaB10O19 (LCBO), is biaxial and it crystallizes
in the monoclinic system with space group C2. It has layered structure and each layer is
built up from B5O12 double-ring pentaborate groups, which are linked together forming
an infinite two-dimensional double layer. The layers are almost perpendicular to the c
axis [4]. There are no reports in literature on vibrational study on LCBO crystal. Herein,
we report for the first time polarized IR reflectance and polarized Raman spectra of
LCBO single crystal. The results of IR and Raman studies clearly show the presence of
large LO TO splitting, making it an attractive candidate for nonlinear optical material.
References
[1] D.A. Keszler, Curr. Opin. Solid State Mater. Sci., 1, 1996, 204-211.
[2] G.V. Karas (editor), New Developments in Crystal Growth Research, Nova Publishers, 2005.
[3] K.S. Bartwal, R. Bhatt, S. Kar, V.K. Wadhawan, Mater. Sci. Eng. B, 85, 2001, 76-79.
[4] Y. Wu, J. Liu, P. Fu, J. Wang, H. Zhou, G. Wang, C. Chen, Chem. Mater. 13, 2001, 753-755.
161
P90
Spectroscopic Investigations and DFT Modeling Studies
of 2-{[(5-Nitrothiophen-2-yl)Methylidene]Amino}Phenol
Hasan Tanak1 1 2, Onur Erman Do an2
1Department of Physics, Faculty of Arts and Sciences, Amasya University, 05100,
Amasya, Turkey, [email protected], [email protected] of Chemistry, Faculty of Arts and Sciences,
55139, Kurupelit, Samsun, Turkey, [email protected]
Schiff-bases (known as azomethine), having imine groups (CH=N) and phenyl rings in
-conjugated, exhibit interest as materials for wide
spectrum applications, particularly as corrosion inhibitors, a metal ion complexing
agents, in biological systems and thermo-stable materials [1]. The Schiff bases have
been also under investigation during last years because of their potential applicability in
optical communications and many of them have NLO behavior.
The experimental and theoretical vibrational spectra of the title compound were
studied. The FT-IR spectra were recorded in the solid phase. The molecular geometry
and vibrational frequencies of the title compound in the ground state have been
calculated using the density functional method (B3LYP) with 6-311++G(d,p) basis set.
The results of the optimized molecular structure are presented and compared with the
experimental X-ray diffraction. By using the TD-DFT method, electronic absorption
spectra of the title compound have been predicted and a good agreement with the TD-
DFT method and the experimental one is determined.
The non-linear optical properties are also addressed theoretically. The hydrogen
bonding interactions of the title compound have been investigated using natural bonding
orbital analysis. It reveals that the O- and O-
influence crystal packing of this molecule. Additionally, DFT calculations of the title
compound, molecular electrostatic potential and fronier orbitals were also performed at
6-311++G(d,p) level of theory.
Fig. 1 Hydrogen bonding motif of the title compound.
Acknowledgment
This study was supported financially by the Research Centre of Amasya University (Project No:
FMB
References
[1] H. Tanak, J. Mol. Struct.: THEOCHEM, 2010, 950, 5-12.
162
P91
Experimental (XRD, FT-IR and NMR) and Theoretical Investigations
on 1-(2-Nitrobenzoyl)3,5-bis(4-Methoxyphenyl) 4,5-Dihydro-1H-
Pyrazole
Meryem Evecen1, Hasan Tanak1, Necmi Dege2, 3, Feyza Tinmaz3
1Department of Physics, Faculty of Arts
Amasya, Turkey, [email protected], [email protected] of Physics, Faculty of Arts and Sciences
55139 Kurupelit, Samsun, Turkey, [email protected] of Chemistry, Faculty of Sciences, Erciyes University, 38039 Kayseri,
Turkey, [email protected]
The pyrazole compound 1-(2-nitrobenzoyl)3,5-bis(4-methoxyphenyl)-4,5-dihydro-1H-
pyrazole has been synthesized and characterized by IR, NMR and X-ray diffraction
methods.
The compound crystallizes in the monoclinic space group C2/c with a= 36.126(5)
vibrational frequencies and gauge including atomic orbital (GIAO) 1H and 13C NMR
chemical shift values of 1-(2-nitrobenzoyl)3,5-bis(4-methoxyphenyl)-4,5-dihydro-1H-
pyrazole in the ground state have been calculated using the density functional method
(B3LYP) with 6 311++G(d,p) basis set. The calculated results show that the optimized
geometry can well reproduce the crystal structure, and the theoretical vibrational
frequencies and chemical shift values show good agreement with experimental values.
In addition, molecular electrostatic potential, frontier molecular orbitals and NBO
analysis of the title compound were investigated by theoretical calculations.
Keywords: Vibrational spectra; NLO; TD-DFT; MEP; NBO
Acknowledgment
This study was supported financially by the Research Centre of Amasya University (Project No: FMB-
BAP 15-091, FMB-BAP 15-092).
163
P92
Hierarchical L Zeolite Synthesized by Sequential Acid-Base Treatment
J. Tekla -Marek, K.A. Tarach
30-
Zeolites are defined as crystalline aluminosilicates with structure based on a three
dimensional network of [AlO4]- and [SiO4] tetrahedra. Application of those materials as
catalysts and supports in heterogeneous catalysis, originates from their considerably high
specific surface area, which is implied by the presence of this well-defined system of
micropores. Microporous character, in spite of its indisputable advantages, is a serious
limitation for the applicability of zeolites in catalytic reactions involving large molecules.
Due the fact that acidic active centres involved in catalytic reactions are located mostly
within the microporous channels they are not accessible for reagents with large kinetic
diameter. Consequently the reactions undergo only on the outer surface of the catalyst grain,
while the inner sphere of crystal remains unperturbed. The diffusional limitations influence
the activity, selectivity and lifetime of catalyst and they still remain open problem. Many
studies have been devoted to obtain structures that combine features of the strongly acidic
centres and the system of mesopores ensuring overcoming the diffusional limitations. This
requirement seems to be fulfilled by the concept of hierarchical zeolites materials
combining pore systems at different levels. For zeolites with a low silicon content (Si/Al <
25) it has been found that the effective way of hierarchization is the sequential
dealumination/desilication process.
The main goal of this work was focused on elaboration of the hierarchization
methods of zeolite L. Due to a high content of aluminium atoms in structure of these zeolite
(Si/Al = 3) and its low stability upon ion-exchange procedure, this attempt appears to be
challenging. The Al atoms located in terahedral positions impose the negative charge and
repeal OH- ions. As a consequence, the Si-O-Al bond is only slightly subjected to the
hydrolysis process and the extraction of Si atoms is significantly inhibited.
The sequential acid-base treatment performed with use of HNO3 and NaOH in
properly elaborated conditions (long time of treatment and low concentration of base and
acid) ensured the generation of mesopore surface area as high as
134 m2/g. In line with that the Si/Al ratio increased to value of 8 upon removal of silicon
atoms in majority. The main part of studies was focused on identifying of properties of
protonic and aprotonic centers in hierarchical zeolites L and their conventional analogue.
The leading research technique used in this work was FT-IR spectroscopy. Analysis of
spectra recorded with the FT-IR method enabled to obtain information on the nature and
properties of active centers. One of the most significant stages of the studies was the
quantitative investigation of concentration of acid centers, carried out with using
conventional probe molecules such as pyridine and CO. Analysis of FT-IR spectra of
adsorbed reactant can be straightforwardly used to predict the catalytic behaviour.
Acknowledgment This work was financed by Grant No. 2013/09/B/ST5/00066 from the National
Science Centre, Poland
164
P93
400 500 600 700 800 900 1E-4 1E-3 0.01 0.1 1
Inte
nsity (
a.u
.)
wavelength (nm)
Inte
nsity (
arb
. u.)
pressure (mbar)
Yb2Si
2O
7 exc = 975 nm
Infrared Laser Induced white Emission of Yb2Si2O7 Nanocrystals
R. Tomala, L. Marciniak, D. Hreniak, W. Strek
Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
The infrared induced broadband white emission of Yb2Si2O7 nanocrystals in
vacuum was investigated. The intensity of white emission has significantly decreased
with increasing pressure. The white emission of Yb2Si2O7 exhibits the long rise time
dependent on excitation power. The influence of power excitation on emission intensity
under 975 nm laser diode excitation was investigated. The emission peak shifts in blue
with excitation power.
Fig. 1 Influence of surrounding pressure on emission Fig. 2 Image of Yb2Si2O7 emission
intensity of Yb2Si2O7
Acknowledgment
The Authors would like to acknowledge NCN Maestro NCN-2012/06/A/ST5/00212 project for financial
support.
165
P94
Synthesis, Optical Properties and White Lighting of ZnSe:Yb
R. Tomala1, W. Strek1, J. Legendziewicz2, Y. Gerasymchuk 1, M. Guzik1
1Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
- [email protected] -Curie 14, 50-
Zinc selenide doped ytterbium was synthesized by solid-state reaction at 1000oC and 8
GPa. ZnSe:Yb exhibits the broadband emission centered at 515 nm (Fig. 1). The band
can be attributed to the emission from the Yb2+ centers due to spin and parity allowed
4f13 14 interconfigurational transitions and the emission in exciton region and
emission caused by recombination of carriers bound to donor-acceptor pairs [1] .
The laser induced anti-stokes white emission under 975 nm excitation was also
observed (Fig. 1). The emission band was centered at 630 nm. The intensity of emission
was dependent on pressure. The intensity of white emission was characterized by
threshold dependence and increased nonlinearly with the power of incident laser light
accarding to the multiphoton absorption I oc PNexc = 975 nm.
400 500 600 700 800 900
0.0
0.2
0.4
0.6
0.8
1.0
exc = 975 nm
exc
= 266 nm
norm
aliz
ed
inte
nsity (
arb
. u.)
wavelength (nm)
ZnSe:Yb
x200
Fig. 1. The emission spectra of ZnSe:Yb under 266 nm and 975 nm excitation
References
[1] I. Radevici, K. Sushkevich, V. Sirkeli, H. Huhtinen, D. Nedeoglo, P. Paturi, J. Lumin., 143 (2013)
275-279
166
P95
Structure and Microstructure of the Glasses from NaMgPO4-SiO2
System
A. Wajda1 1,2, M. Sitarz1
1AGH University of Science and Technology, Faculty of Materials Science and
Ceramics, 30-059 Krakow, Al. Mickiewicza 30, Poland2Jagiellonian University, Faculty of Chemistry, 30-060 Krakow, Ingardena 3, Poland
e-mail: [email protected]
Structure and microstructure of silico-phosphate glasses belonging to NaXPO4-
SiO2 (where X = Ca or/and Mg) systems were examined. Glasses from this system are
bioactive materials, with an ability to form direct bonds with living tissue. Application
of glasses as biomaterials is limited mainly due to their very low strength and chemical
stability. One of the best way to improve the mechanical properties of the glasses is to
carry out their partial devitrification to obtain glass-crystalline materials. In order to
fully control the direct crystallization process properly, it is necessary to know the
structure and microstructure of the glassy precursor.
Scanning electron microscopic studies combined with EDX made it possible to
show the appearance of a glass phase separation in the obtained materials. Structural
investigations of the obtained glasses as well as of the corresponding crystalline
materials showed that the studied glasses exhibit domain composition. Structure of the
domains is close to that of the corresponding crystalline phases. MIR spectra analysis
allowed to determine that the complete substitution of calcium ions by magnesium ions
causes homogenization of these glasses structure.
To obtain glass-crystalline materials, besides the understanding of the
microstructure and glass structure, it is necessary to know its thermal parameters,
especially temperature of devitrification (TD). For this purpose, DSC studies of selected
glasses were carried out.
167
P96
Aluminium Influence on the Microstructure and Structure of Glasses
from NaMgPO4-SiO2 System
A. Wajda1 1,2, M. Sitarz1
1AGH University of Science and Technology, Faculty of Materials Science and
Ceramics, 30-059 Krakow, Al. Mickiewicza 30, Poland2Jagiellonian University, Faculty of Chemistry, 30-060 Krakow, Ingardena 3, Poland
e-mail: [email protected]
The aluminium effect on the structure and microstructure of silico-phosphate
glasses belonging to NaXPO4-SiO2 (where X = Ca or/and Mg) systems were
investigated. Glasses from this system show good compatibility and good bioactivity.
The use of bioactive glasses in implants production is limited because of their low
mechanical strength, fragility and chemical instability. One of the best ways to improve
the mechanical properties of the glasses is to change their chemical composition (for
example, the introduction of Al3+ or B3+ ions) or to carry out their partial devitrification
that allows to obtain glass-crystalline materials. In order to have full control over the
direct crystallization process, it is necessary to know the structure, microstructure and
thermal properties of the glassy precursor.
It was found that even small amount of aluminium ions (5 mol. % of AlPO4) in
the glass has a homogenising effect on the microstructure (microscopic and EDX
studies) and its structure (spectroscopic studies). Addition of aluminium ions causes the
chemical compositions inversion of the matrix and the inclusions. Spectroscopic
investigations involving spectra decomposition into component bands were made it
possible to establish the homogenising effect of aluminium on the structure of silicate-
phosphate glasses. Presence of alumina leads to elimination of P=O bonds as well as
replacement of Si-O-P by the Al-O-P ones.
To obtain glass-crystalline materials, thermal analysis (DSC) of selected glasses
were carried out. It indicated that crystallization of all studied glasses is multistage -
the matrix and inclusions crystallize separately. Considering the chemical composition
inversion of inclusions and matrix in the glasses containing aluminum ions, the studied
glass are very promising precursors to a variety of glass-crystalline material.
168
P97
Structural and Microstructural Studies of Copper Doped Glasses from
NaCaPO4-SiO2 System
A. Wajda1, M. Sitarz1
1AGH University of Science and Technology, Faculty of Materials Science and
Ceramics, 30-059 Krakow, Al. Mickiewicza 30, Poland
e-mail: [email protected]
The aim of this study was to obtain silicate-phosphate glasses and glass-ceramics
materials from NaCaPO4-SiO2 system containing copper ions. Glasses from this system
are well-known bioactive materials with an ability to form a layer of hydroxycarbonate
apatite (similar to biological apatite) on their surface when the materials are implanted
or in contact with biological fluids. A serious complication during implantation is a risk
of adherence and colonization of bacteria on the surface of the implants. That is why, it
is very important to develop multifunctional bioactive materials, which combine
osteostimulation and antibacterial properties for bone regeneration. They can reduce
microbial numbers on implants surface and kill bacteria or inhibit their growth.
Several compositions of bioactive glass containing copper ions were
synthesized by sol-gel method and then melted at 1700oC. X-ray, IR and Raman
spectroscopy measurements were done to characterize amorphous state and the structure
of the samples. The morphology and chemical composition of the glasses were defined
by scanning electron microscopy equipped with energy dispersive spectroscopy (EDS).
Microscopic investigation showed that liquation takes place in all the studied glasses.
The influence of copper doping on the microstructure and structure of the glasses from
NaCaPO4-SiO2 system was researched. Moreover thermal analysis (DSC) was carried
out to check if the direct crystallization of the glass is possible. DSC measurements
indicated that crystallization of all studied glasses is multistage.
169
P98
Dehydration Process in DL- -Phenylglycinium
Trifluoromethanesulfonate Monohydrate Crystal
1, M. M. Ilczyszyn2, V. Kinzhybalo3
1 Faculty of Chemistry University of Wroclaw, Poland,
[email protected] Faculty of Chemistry University of Wroclaw, Poland,
Phenylglycine, non-protic amino acid, attracts attention because of its medical
application, i.e. as a starting material in semisynthetic penicillins and cephalosporins
production [1]. Some of trifluoromethanesulfonic acid salts prove to be the plastic
crystals [2], showing high thermal stability and high temperature phase transitions.
Many crystalline salts containing trifluoromethanesulfonic anion, because of its motion
in the crystalline net, demonstrate large ionic conductivity (solid electrolytes ) [3].
In this work, single crystal X-ray diffraction, vibrational and calorimetric data
for DL- -phenylglycinium trifluoromethanesulfonate monohydrate crystal (PGTFH) are
presented and discussed. Additionally, powder X-ray diffraction at various temperatures
and infrared spectra above room temperature were measured in order to explain
mechanism of a dehydration process in the studied crystal. Our preliminary results show
that dehydration process is accompanied by significant changes in the PGTFH structure.
The selected results obtained by us are as follows:
1. PGTFH crystallizes in the monoclinic system, C2/c. The asymmetric unit
consists of a protonated form of phenylglycine, a trifluoromethanesulfonic anion
and a water molecule. Three types of hydrogen bonds were found in PGTFH:
O-H O (with O O distances of 2.6- -H O (with N O distances of
2.8- -H O (with C O distance of ca.
2.
transformation of the monocrystalline sample during dehydration into multi-
crystal. The model of a structure of a dehydrated phase (PGTF) was determined
from multiple twin. Powder X-ray diffraction experiment was carried out on
PGTF sample to confirm the model obtained from the single crystal XRD study.
3. DSC and TG experiments confirmed the dehydration process of the PGTFH
crysta
XRD experiment.
4. Structural changes arise from dehydration in PGTFH are clearly visible on the
temperature dependent infrared spectra. The changes are detected mainly in the
region of stretching vibrations of hydrogen bonds (3500-2000 cm-1) and the
C=O bond (1800-1700 cm-1).
References
[1] A. Satyam, M. D. Hocker, K. A. Kanemaguire, A. S. Morgan, H. O. Villar, M. H. Lyttle, J. Med.
Chem., 1996, 39, 1736-1747.
[2] J. M. Pringle, P. C. Howlett, D. R. MacFarlane, M. Forsyth, J. Mater. Chem., 2010, 20, 2056-2062.
[3] Solid State Ionics, 2005, 176, 1449-1456.
170
P99
Resonance Raman Optical Activity of Astaxanthin Supramolecular
Aggregates
Grzegorz Zajac1,2, Agnieszka Kaczor1,2, Ana Pallares Zazo1,2, Jacek Mlynarski1
1,2,*
1 Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland2 Jagiellonian Centre for Experimental Therapeutics (JCET), Bobrzynskiego 14,
30-348 Krakow, Poland
E-mail: [email protected]
Astaxanthin (3,3'-dihydroxy- -carotene-4,4'-dione), a strong antioxidant, is a red
xanthophyll pigment used in diet of salmonids and crustaceans. It prevents cardiovascular,
immune, inflammatory, and neurodegenerative diseases.1 Racemic mixture of synthetic
astaxanthin consists of 3S S, meso and 3R R isomers in the 1:2:1 ratio.2
Raman optical activity (ROA) spectroscopy is based on observation of small
difference between intensity of Raman scattering from chiral molecules in right- and left-
circularly polarized incident light. ROA provides information about absolute configuration
and conformational equilibrium of chiral compounds (spectra of two enantiomers are mirror
images of each other). ROA can be also used to study secondary and tertiary structure of
biomolecules. As ROA effect is extremely weak, it requires usually a long accumulation
and high concentrated samples. The theory of resonance Raman optical activity (RROA) in
single electronic state (SES) limit predicts that each band in RROA spectrum exhibit the
same sign. Furthermore, the sign of bands should be opposite to the related electronic
circular dichroism (ECD) band.3
Previously, we have discussed ROA spectra calculated for a set of conformers of
astaxanthin.4 In this work we report for the first time experimental observation of resonance
ROA (RROA) effect from chiral, supramolecular carotenoid assemblies of both astaxanthin
enantiomers, obtained from various acetone-water solutions. Carotenoids dissolved in
organic-water media can form H (card-packed) and J (head-to-tail) aggregates, that exhibit
hypsochromic and batochromic shift of chromophore absorption, respectively.5 ROA
spectra obtained from both aggregates of astaxanthin are monosigned (in agreement with
the SES theory of the Resonance) and they are mirror images of each other. Overtones and
the phenomena called transfer of chirality are also observed and discussed. RROA spectra
were measured using the ChiralRAMAN-2X spectrometer (BioTools Inc.) with 532 nm
excitation.
Acknowledgment
This work was financially supported by National Centre of Science (DEC-2012/07/B/ST5/00889).
References
[1] Hussein, G.; Sankawa, U.; Goto, H.; Matsumoto, K.; Watanabe, H. J. Nat. Prod., 2006, 69, 443.
[2] Muller, R.K.; Bernhard, K.; Mayer, H.; Ruttimann, A.; Vecchi, M. Helv. Chim. Acta, 1980,
63,1654..
[3] Nafie, L. A. Chemical Physics 1996, 205, 309-322.
[4] Zajac, G.; Kaczor, A.; Chruszcz-Lipska, K.; Dobrowolski, J.Cz.; Baranska, M. J Raman Spectr,
2014, 45, 859.
[5] Simonyi, M.; Bikadi, Z.; Zsila, F.; Deli, J. Chirality 2003, 15, 680.
171
P100
Crystal Structures and Spectroscopic Properties of Mn(II) and Cu(II)
Complexes Containing N,O-Donor Ligands
M. Zienkiewicz-Machnik1, J. Masternak1, B. Barszcz1, K. Kazimierczuk2,
M. Hodorowicz3, J. Jezierska4
1Institute of Chemistry, Jan Kochanowski University in Kielce, 25-406 Kielce, Poland,
e-mail: [email protected]
2Faculty of Chemistry, -3Faculty of Chemistry, Jagiellonian University, 30-4 -
Manganese and copper complexes are an important class of synthetic
antioxidants [1] inspired by natural enzymatic systems that contain these metal ions,
which are able to neutralize reactive oxygen (ROS) and nitrogen (RNS) species. Hence,
our work is focused on the synthesis and physicochemical characterisation of Mn(II)
and Cu(II) containing complexes with biologically relevant N,O-donor ligands:
2-hydroxymethylpyridine (2-CH2OHpy) and 2-hydroxyethylpyridine (2-(CH2)2OHpy).
Here we report the structural, spectroscopic characterisation (X-ray, FTIR, Raman,
EPR) and magnetic properties of Mn(II) and Cu(II) complexes:
[Mn(2-(CH2)2OHpy)2(H2O)2](NO3)2 (1), [Cu2(2-CH2OHpy)5(2-CH2Opy)](ClO4)3 (2).
Moreover, the antioxidant study of the complexes was evaluated by using
1,1-diphenyl-2-picrylhydrazyl (DPPH) and (3-ethylbenzthiazoline-6-sulfonic acid)
(ABTS) free-radical assays.
a) b)
Fig. 1 Molecular structure of [Mn(2-(CH2)2OHpy)2(H2O)2](NO3)2 (1) (a) and absorption spectrum of
ABTS in the presence of 1 (b). The arrow shows the intensity changes on increasing the compound 1-5 -5 M).
References
[1]
University Press, 2001.
172
P101
Application of Infrared Spectroscopy and Pyrolysis Gas
Chromatography for Characterisation of Adhesive Tapes
-Palusa b, Rafal Kowalskia
a Institute of Forensic Research, Westerplatte 9, 31-033, Krakow, Polandb Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland
Adhesive tapes are often subject of forensic examination as they are used by
offenders to bind a victim as well as to prepare explosive charges or to seal threatening
letters. Examination of adhesive tapes is performed in order to identify the kind of the tape
and to define their probable producer. It includes application of optical methods which
enable one to observe its structure, colour, thickness, width, birefringence or fluorescence
as well as chemical analysis - of both glue (adhesive) and backing of the tape - providing
mainly information of their polymer components. Infrared spectroscopy (IR) could be used
for these purposes [1]. An attempt was made to evaluate the usefulness of the IR method in
differentiation of adhesive tapes for forensic purposes and in classification of the samples.
About 50 adhesive tapes of different types (packing, office and electrical tapes) and
makes were examined. All tapes were purchased from supermarkets and stores. The
infrared spectra of backings and glues of tapes were recorded on Digilab FTS 40Pro
spectrometer combined with UMA 500 microscope in transmission mode. For the Py-
GC/MS analysis, a TurboMass Gold System (Perkin Elmer Instruments) was applied. A
small amount of glue as well as a small piece of clean backing of each tape were analysed.
Samples were pyrolysed with the use of a CDS 2000 pyrolyser (Analytix, USA). The GC
maintained for 2
-35MS
m) was used. The stationary phase consisted of
35% diphenyl-polysiloxane and 65% dimethyl-polysiloxane. The scan range was 35 500
On the basis of the obtained IR spectra it was possible to identify the main
polymers and fillers and to classify tapes into particular groups. On the base of chemical
contents of backings the tapes were classified into one of 4 groups and on the base of the
type of glue also into 4 groups. Within each group small differences were observed, which
were originated from the presence of minor components of the sample, making possible to
create subgroups. The majority of tapes contained polyethylene or polypropylene backing
and styrene butadiene rubber glue. It was possible to differentiate 27 tapes from the whole
set of the examined samples. The application of Py-GC/MS enabled discrimination of
samples with similar infrared spectra.
It was found that IR spectroscopy providing crucial information about polymer
content is useful for identification of adhesive tapes found at the crime scene and enables
one to classify samples into several chemical classes. IR method, together with a more
sensitive method, e.g. pyrolysis gas chromatography (Py-GC/MS) analyzing the thermal
destruction products, provide a better discriminations of the studied tapes.
Keywords: adhesive tapes; infrared spectroscopy; classification; pyrolysis gas chromatography
Reference
[1] J. -Palus, A. Augustynek, Problems of Forensic Sciences 86 (2011) 103-113
173
P102
A Novel Highly Sensitive and Selective Chemosensor Based on
Bidentate Hydrazone Ligand of 2-Hydroxy Acetophenone
Doped in Sol Gel Matrix for Detection of Zinc in Human Hair
Badr A. Elsayed1, M. M. Abo Aly2 and Sally M. Gamal2
1Chemistry Department, Faculty of Science, Alazhar University, Cairo, Egypt.2Chemistry Department, Faculty of Science, Ain Shams University, Cairo, Egypt.
The Chemosensor ligand 2-hydroxy acetophenone hydrazone was synthesized via
condensation of 2-OH acetophenone and hydrazine monohydrate. Photoluminescence
characteristics of the ligand were investigated in different solvents including acetonitrile
(AC), ethanol (ETOH), dimethyl formamide (DMF) and dimethyl sulphoxide (DMSO).
The ligand was found to have higher emission intensity in DMSO solution. The
Chemosensor was synthesized for detecting Zinc in human hair for males and females
with age range (15y 31y). The assessment of zinc was sensing from the remarkable
enhancement of the luminescence intensity at 425 nm of the ligand sensor doped in sol-
gel matrix by various concentrations of the zinc. The calibration plot was achieved over
the concentration range 1.0 x 10-8 2.0 x10-4 mol L 1 of zinc with a correlation 9 mol L 1. The sensor shows
excellent selectivity toward Zn2+ with respect to common coexisting cations. The
proposed fluorescence sensor was successfully applied to detect Zn2+ in human hair for
both females and males.
Keywords : Fluorescent enhancement, Chemosensor, 2-OH-Acetophenone Hydrazone,
Zinc.
174
P103
Conformation of the Azo Bond and its Influence on the Molecular and
Crystal Structure, IR and Raman Spectra and Electron Properties of
6-Methyl-3,5-Dinitro-2-[(E)-Phenyldiazenyl]Pyridine
Quantum Chemical DFT Calculations
J. Michalski1, I. Bryndal1, J. Lorenc1, J. Janczak2, J. Hanuza2
1Department of Bioorganic Chemistry, Institute of Chemistry and Food Technology,
Komandorska 118/120, 53-2Institute of Low Temperature and Structure Research, Polish Academy of Sciences,
-
Azo compounds belong to the group of the most versatile pigments and therefore are
called FD&C dyes due to their use in food, drug and cosmetics.1 Their biological activity was
reported due to their inflammatory, anticancer properties. The main factor that decides on such
broad applications of the azo compounds is their cis-trans isomerization and protonation and
deprotonation processes leading to the color changes.2
The present paper is a continuation of our previous work on azo and hydrazo derivatives
of pyridine.3 The crystal and molecular structures of 6-methyl-3,5-dinitro-2-[(E)-
phenyldiazenyl]pyridine have been determined by X-ray diffraction (Fig. 1) and quantum
chemical DFT calculations. The crystal is monoclinic, space group Cc (No. 9) with Z = 4 with
the unit cell parameters: a = 12.1497(13), b = 13.027(11), c = 8.2495(8) = 95.191(9) .
The azo-bridge appears in the trans conformation in which C2-N2- -
a value -
rings is 3.5(2) . The molecular structure and simulated vibrational spectra of the studied
compound have been determined using B3LYP/6-311G(2d,2p) approach. Because the molecule
is built of three coupled -electron systems, the electron absorption and emission spectra have
been measured and analyzed in terms of Mulliken population parameters, non-bonding orbital
approach and HOMO-LUMO transition calculations.
References
[1] H. Zollinger, Color Chemistry, Syntheses, Properties and Applications of Organic Dyes and
Pigments, 3rd ed. Wiley-VCH, Weinheim, Germany, 2003.
[2] Y. Dong, J. Chen, C. Li, H. Xzhu, Dyes and Pigments 73 (2007) 261.
[3] Acta A, 107
(2013) 317, and references therein.
Fig. 1. Molecular conformation of the
studied compound, showing the atom
numbering scheme. Displacements
ellipsoids are drawn at the 50%
probability level and H atoms are
shown as small spheres of arbitrary
radii.
175
P104
Light-Soaking Effect Under Various Spectral Ranges in Inverted
Organic Solar Cells
Michal Dusza1,2,*, Wieslaw Strek2, Filip Granek1
1Wroclaw Research Centre EIT+, Stablowicka 147, 54-066 Wroclaw, Poland,
*e-mail: [email protected] of Low Temperature and Structure Research, Polish Academy of Science,
Okolna 2, 50-422 Wroclaw, Poland
Technology of organic solar cells have gained serious attention in the past few years and
have a great potential to reduce the energy consumption of manufacturing processes. Short
exposure to light of organic solar cells improves their properties for a long period of time (few
hours). This effect, so-called light-soaking, is related to the excitation of metal oxide buffer
layers and filling the trap states [1][2]. Zinc oxide or titanium oxide are commonly used as a
electron transport layer. Well-defined light-soaking effect is crucial for reliable measurements
of efficiency and analysis of degradation dynamics of organic solar cells. In this work spectrum
influence on the light-soaking effect in inverted organic solar cells with zinc oxide layer was
investigated. Solar cell devices were fabricated in structure
glass/ITO/ZnO/P3HT:PCBM/MoO3/Ag. Zinc oxide layers were deposited using the
nanoparticle dispersion in ethanol. Using the sun simulator and optical filters various spectra
were used for light-soaking illumination (full spectrum, only UV, spectrum without UV, only
IR and spectrum without IR). Measurements of solar cell before and after 10 min of light-
soaking were performed. Relative efficiency improvements over than 70% due to light-soaking
effect were observed for all spactra with UV component. For VIS spectrum and even for only
IR spectrum improvement in range 20-30% were observed. I-V curves of sample before and
after light-soaking were shown in the figure 1a. Short-circuit currents were monitored during
the illumination (figure 1b). Spectral dependency of light-soaking is related to the amount and
the depth of trap states in ZnO layer and understanding this phenomenon is crucial for reliable
measurements.a) b)
Figure 1. I-V curves for sample before and after light-soaking (a), short-circuit current as a function of
time during the light-soaking illumination
Acknowledgment
The work was supported by the National Centre for Research and Development (NCBR) within the
project POSCiS (Grant agreement no. LIDER/09/129/L-3/11/NCBR/2012).
References
[1] Journal of Applied Physics 111, 114511, 2012
[2] Solar Energy Materials & Solar Cells 98, 491 493, 2012
176
P105
In Situ and Operando Spectroscopic Studies of Sonically Aided
Catalysts for Biogas Exhaust Abatement
1 1, D. Chlebda2, E. Piwowarczyk3, M. Chrzan3, R. 4, M. Sitarz5, M. Iwaniszyn6 6,7 2
1Faculty of Chemical Engineering and Technology, Cracow University of Technology,
Warszawska 24, 31-2Jagiellonian University, Faculty of Chemistry, Ingardena 3, 30-
3Faculty of Process and Environmental Engineering, Technical University of Lodz,
-4Malopolska Centre of Biotechnology, Jagiellonian University, Gronostajowa 7A,
30-387 Krakow5Faculty of Materials Science and Ceramics, AGH University of Science and
Technology, al. Mickiewicza 30, 30- d6
44-100 Gliwice, Poland7Faculty of Civil Engineering, Opole University of Technology, Katowicka 48,
45-061 Opole, Poland
Nanomaterials have revolutionized many areas of science and technology. The
reactivity of nanomaterials differs from macro and micro structured materials. This
difference is due not only to smaller particles but also their specific confirmation and
surface properties. Shape-selective synthesis of nanoparticles is the next step in the catalysts
preparation. A review of the literature studies indicate sonochemistry as having great
potential for shape-selective synthesis of nanomaterials for catalytic purposes [1][2]. The
currently used preparation techniques, based mainly on impregnation and sol-gel methods
do not allow for the free design of catalyst nanoparticles shape. The optimized
sonochemical aided methods allow to obtain the wide range of nanoparticles shapes from
nanobelts, through nanowires to nanoflakes. Such an approach, correlated with the design of
the active sites at the catalyst surface and catalytic activity allow for the design of a highly
efficient catalytic structures for the gas exhaust abatement purposes.
In this study we focus on in situ and operando spectroscopic and microscopic
characterization of the catalysts prepared using sonochemically aided methods for catalytic
removal of biogas exhaust from. The obtained catalytic combustion results have revealed
the great activity of prepared catalysts, which can be used as an alternative for noble metals.
Acknowledgments
The Project was financed by the National Science Center Poland based on the decision No.
2013/09/B/ST8/00171 and partly within C-2/318/2015/DS-M.
References
[1] J. Zhang, J. Du, B. Han, Z. Liu, T. Jiang, Z. Zhang, Sonochemical formation of single-crystalline
gold nanobelts., Angew. Chem. Int. Ed. Engl. 45 (2006) 1116 9.
[2] P. Estifaee, M. Haghighi, N. Mohammadi, F. Rahmani, CO oxidation over sonochemically
synthesized Pd-Cu/Al2O3 nanocatalyst used in hydrogen purification: effect of Pd loading and
ultrasound irradiation time., Ultrason. Sonochem. 21 (2014) 1155 65.
177
P106
Amyloidogenic Properties of the Fragment 52-65 of the Human
Cystatin C
1 2 1
1
2Center for Biocrystallographic Research, Institute of Bioorganic Chemistry,
e-mail: [email protected]
Steric zipper is a structural motif formed by characteristic sequence tracts of
amyloidogenic proteins. based on the assumption, that in the protein sequence there are
short fragments with very high propensity for formation of the -stand conformation
and subsequent strong self-association [1, 2]. Recent results suggest that it may operate
independently, or in combination with 3D domain swapping as a mechanism of amyloid
fiber formation. The propensity of a given sequence to fulfill the requirements for
effective steric zipper can be calculated theoretically using 3D profile method
elaborated by Eisenberg and coworkers [1, 3]. Cystatin C is one of many proteins that
have not been studied in this respect. Amyloid of human cystatin C (hCC) is the cause
of cerebral angiopathy and death in patients with "Icelandic" mutation in hCC sequence
[4]. We have shown before that HCC oligomerizes via a mechanism that involves 3D
domain swapping. The 3D profile method and calculated Rosetta algorithm values for
hCC show that in this protein there are two fragments, for which high fibrillization
propensity can be expected: fragment of loop L1 (Ala52-Asp65) and C-terminal part of
the molecule between Arg93 and Cys117 [5]. In the present project we search for steric
zipper forming peptides in the HCC sequence that is connected with a conformational
transition on domain swapping (fragment Ala52 Asp65).
Acknowledgements
Work supported by grants: DS/8440-4-0172-15 and NCN 2011/03/N/ST4/01293.
References
[1] Goldschmidt L. et al., Proc Natl Acad USA, 2010, 107, 3487-92
[2] Sawaya M.R. et al., Nature, 2007, 447, 453-7
[3] Nelson R. et al.,Nature, 2005, 435, 773-8
[4] Grubb A., Adv. Clin. Chem., (2000), 35, 63-69
[5] http://services.mbi.ucla.edu/zipperdb
178
P107
Nuclear Magnetic Resonance Studies of the Wild-Type Human
Cystatin C and V57G Mutant
Martyna Maszota-Zieleniak-
Faculty of Chemistry, [email protected]
Human cystatin C (hCC), member of the superfamily of papain-like cysteine protease inhibitors, is the most widespread cystatin in mammalian body fluids. It is small, 13 kDa and 120 amino acid residues protein, involved in various diseases, including cerebral amyloid angiopathy, cerebral hemorrhage, stroke, and dementia [1]. In pathological conditions human cystatin C participates in the formation of amyloid deposits together with
Under physiological conditions hCC is a monomer but attempts to crystallize allowed receiving only the dimeric form [3], formed as a result of the three-dimensional exchange domains (3D domain swapping) [4]. While the experimental structure of wild-type hCC occurs as a dimer, the monomeric crystal structure is known for two hCC variants: V57N hCC and stab1 hCC. The first hCC mutant is stable in monomeric form and crystallizes as a monomer [5]. In our group we have designed and performed biophysical investigations for two groups of hCC mutants: one located in loop L1 [5,6] (residues 56-57) and second introduced to the hydrophobic core of the molecule (residue 68) [7]. In this project we selected V57G mutant to our NMR investigations as the most promising to give a monomeric form of hCC in solution.
Ekiel et al. [8] were very close to finding of the NMR structure of the human cystatin C. Unfortunately, many sequential NOE signals were missing and they could not find the proper structure of the hCC. Compared with 1997, when Ekiel et al. performed those studies, NMR techniques have now increased resolution, and there are new opportunities for protein structure determination. We plan to obtain a triple labeled form of the wild-type hCC and V57G mutant in solution and record sets of 2D and 3D NMR spectra using 700 Mhz spectrometer which should provide complete information about the structure and dynamic properties of the proteins.
AcknowledgmentThis work is financially supported by the grant from National Science Centre Poland UMO/2011/03/N/ST4/01293.
References[1] , Grubb A (2006) Brain Pathol. 16(1): 60-70[2] Olafsson I, Grubb A (2000) Amyloid 7: 70-79[3] Proteins 61(3): 570-578[4] Liu Y, Eisenberg D (2002) Protein Sci. 11(6): 1285-1299[5] Orlikows J Struct Biol.
173(2): 406-413[6] Rodziewicz-
Stachowiak K, Liwo A (2009) Biopolymers 91(5): 373-383[7] Or Acta
Crystallogr. Sect. F Struct. Biol. Cryst. Commun. 67: 1608-1611[8] Ekiel I, Abrahamson M, Fulton DB, Lindahl P, Storer AC, Levadoux W, Lafrance M, Labelle S,
Pomerleau Y, Groleau D, LeSauteur L, Gehring K (1997) J Mol Biol. 271(2): 266-77
179
P108
Methodology of Experimental and Theoretical Approach to the Study
Absorption Band of C
V. P. Bulychev, E. I. Gromova and K.G. Tokhadze
Physical Faculty, St. Petersburg State University, Peterhof, St. Petersburg, 198504,
Russia, [email protected]
The investigation of anharmonic interactions between the high-frequency and low-frequency
vibrational degrees of freedom of H-bonded complexes is among the topical problems of
modern spectroscopy. The absorption bands of H-bonded complexes can differ in the
overall shape, integral intensity, width, intensity distribution within the band, the
presence or absence of a pronounced structure. These spectral characteristics are
governed by the dependence of the potential energy of a molecular complex on its
vibrational degrees of freedom, the dependence of wave functions of the vibrational
states on masses of nuclei, and the overlap of the dipole moment function with the
wave functions of states involved in spectral transitions. The optimum approach to the
determination of mechanisms of the formation of complicated absorption bands of H-
bonded complexes consists in conducting concerted experiments and theoretical
calculations [1,2].
The 1(HF) abso 3
in the region 4000-3200 cm-1 at a resolution from 0.1- 0.005 cm-1 with a Bruker IFS-120 HR
vacuum Fourier spectrometer in a cell 10 cm in length. It is shown that the fine structure of
the 1(HF) absorption bands is formed primarily due to hot transitions from excited states of
the low- 7 librational vibration. These fine structure bands have a profile
characteristic of rovibrational bands, the distance between the maxima of rovibrational bands
of first transitions equals 17 = 4.18 cm 1 for and 17 = 2.48 cm-1 for
3 complexes. The observed bands were reconstructed using the nonempirical
high-precision electronic structure calculation of these complexes and variational solutions of
equations in one four dimensions. The theoretical data
allowed us to reveal the reason for the low intensity of sum and difference transitions
involving the intermolecular vibrations in the complexes of HF with HCN and CH3CN. In the
case of , the theoretical 1(HF) band reconstructed on
the basis of the 4D anharmonic calculation, including the H-F and H-bond stretches and
rotation of monomers in the same plane, is in excellent agreement 17(calc) = 4.22 cm-1 with
the experimental value. In contrast, for the symmetric top complex CH3
necessary to solve a 5D vibrational problem, although the fundamental frequencies of the H-
F and H-bond stretches and the CH3CN bending vibration is well reproduced in 3D
calculations.
Acknowledgment
This study was supported by the Russian Foundation for Basic Research, grant. 15-03-04605. The
References
[1] V.P. Bulychev, E.A. Svishcheva, K.G. Tokhadze, Spectrochimica Acta, Part A, 2014, 117, 679-685.
[2] V.P. Bulychev, K.G. Tokhadze, Vibrational Spectroscopy 2014, 73, 1-9.
180
P109
Infrared Spectroscopic and DSC Studies of Hydrogen-Bonded
Liquid Crystals in Confined Volume: 4-Hexylbenzoic and 4-
Butylcyclohexane Carboxylic Acids in AlMCM-41 Mesoporous
Molecular Sieves
I. Gnatyuk1, T. Gavrilko*1, O. Yaroshchuk1, N. Holovina2, N. Lysenko3, J. Baran4,
M. Drozd4
1 Institute of Physics, NAS of Ukraine, 46 Nauki Prosp., 03068 Kyiv, Ukraine,2 Les a Ukrainka Volyn National University, Physical Department, 13 Prospect Voli,
43025 Lutsk, Ukraine3Institute of Physical Chemistry NAS of Ukraine, 31 Nauki Prosp., 03028 Kyiv, Ukraine4 Institute of Low Temperatures and Structure Research, PAN, 2 Okolna Str., Wroclaw,
Poland
During the last two decades, the problem of condensed matter behaviour under
confinement to nanoscale spaces has received considerable attention both from
theoretical and experimental points of view since the physical properties of confined
materials are very different from those in their bulk state. Among the brightest
representatives of such systems studied up to date are liquid crystals (LC) confined to
inorganic porous matrices. The aim of the present research was to study the new class of
LC, hydrogen-bonded liquid crystals (HBLC), under their confinement to nanoporous
AlMCM-41 molecular sieves. Specifically, the effect of bonding strength between the
organic and inorganic components on thermotropic properties and molecular dynamics
of the confined HBLC was investigated for the first time with the help of FTIR
spectroscopy and differential scanning calorimetry.
Two model typical HBLC compounds, 4-hexylbenzoic C6H13-C6H4-COOH (4-
HBA) and 4-butylcyclohexanecarboxylic C4H9-C6H10-COOH (4-BCA) acids confined
to AlMCM-41 molecular sieves were studied. With FTIR spectroscopy, it is found that
some part of incorporated acid molecules located in the inner space of the AlMCM-41
pores are in undissociated form of open dimers or chain associates and show
spectroscopic features characteristic to a bulk-like species. The other FTIR spectra
components indicate strong interaction of the incorporated monomeric molecules with
the pore surface. Two specific mechanisms are shown to be involved in molecular
interactions at the interface: deprotonation of monomeric acid molecules on the
AlMCM-41 surface with formation of COO- carboxylate ion, and subsequent bonding
of this carboxylate ion to the pore surface by a coordinated bond R-COO--Al+ with
Lewis acid sites. It is shown that thermotropic behavior of confined 4-HBA and 4-BCA
significantly differs from that observed in a bulk materials, the divergence being related
to both surface interactions and geometrical constraints.
Acknowledgment
VC-157).
181
LIST OF AUTHORS
Abo-Aly Mohamed P102
Adamczyk J. L37
P9, P90
Agarwal Parag L33
P10
Al-Salahi Waleed P1
Andries Maria P73, P74
Atac Ahmet L25, L34, L35
Bak Ahmet P20
Baran Jan L21, P2, P12,P109
L29, P23, P99
P3, P4, P44
Bardak Fehmi L34
Barnes Austin L9, P79
Barszcz Barbara P76, P77, P100
L30
P32
Berkowicz Piotr P23
P5
Bil Andrzej P6
Bilgili Sibel L35
P10
P21, P22
Bortkiewicz Daria P107
Boulon G. L36
Brylewska Kamila L24, P7
Bryndal Iwona P80, P103
Budde Janpeter L38
Budziszewski Janusz P35
P95, P96
Bulychev Valentin P108
Burrows Hugh D. L17
Bursa Bartosz L30
P28
P8, P9, P10
Chaniecki P. L37
Chis Vasile P82
Chlebda Damian P105
L29, P23
Chrzan Magdalena P105
Chudoba Dorota P66
L5
-Boczula Katarzyna P11
Cipiloglu Mustafa Ali L34
Cisowski Jan P28
Connerade J.-P. L3
Creanga Dorina P29, P65, P73, P74
185
L20
Czapla Zbigniew P71
L19
P4
Czerwonka Grzegorz P76, P77
P71
Davydova Nadia P12
Dawid Aleksander P13, P14, P15
Dega-Szafran Zofia P44
Dege Necmi P91
Delbeck Sven L38
Demirci Serkan P16
Deodhar Bhushan L18
P17, P18, P19, P20
P21, P22, P40
P90
Dorina Creanga P58
Dorohoi Dana P29, P65
Dorosz Dominik P83
Drozd Marek P2, P12, P88, P109
L22
Durgun Mustafa P8
Durig James L18
P104
Dybas Jakub P23
P24, P25
Dysz Karolina P64
El Sayed Yousef P28
Elsayed Badr P102
P17, P18, P19, P20
Evecen Meryem P91
Fausto Rui L14, P31, P48
Fifere Adrian P65
Ford Thomas L10
P46
Gajda M. L37
Galabov B. L11
Gamal Sally P102
Gapinska Marta L23, P51
Gavrilko T. P109
Gburski Zygmunt P13, P14, P15
Georgiev Mitko P55
Gerasymchuk Yuri L36, P94
Glibota Ante L4
L5
Gnatyuk I. P109
P10
Golec Barbara P79
186
-Marek Kinga L24, P7, P92
Gorczyca Marcelina P26
Grabska Justyna P32
Grafen Markus L38
Granek Filip P104
Grelowska Iwona P27, P28
Gritco Todirascu Antonina P29, P65
Gromova Elena P108
Grosseau-Poussard Jean-Luc L23
P35
P35
Grzechnik Katarzyna P6
P17, P18
P9
Guyot Y. L36
Guzik M. L36
P94
P30
P34, P36
P31
L12
Hanuza Jerzy P24, P25, P80, P81, P103
Hawranek Jerzy P. P32
Heise H. Michael L38
Helios Katarzyna P33, P54
Hodorowicz Maciej P77, P100
Holovina N. P109
Hreniak Dariusz L5, P57, P85, P93
P34, P35, P36, P37
Iacomi Felicia P58
Iacomi Felicia P73, P74
Ihrig Dieter L38
Ilczyszyn Marek P38
Ilczyszyn Maria P38, P39, P98
P91
P106, P107
Iwamoto Kei P62
Iwaniszyn Marzena P105
-Wawrzycka Agnieszka P76, P77
Jadach Renata L23
Jagielski Jacek P51
Janczak Jan P69, P103
Jankowska Joanna P75
L36
P28
Jasi L23, P51, P84
P84
P106
187
P105
P28, P40
Jesariew Dominik P39
Jezierska Julia P100
P105
P107
Jurga Stefan L28
Kabeya Mikitoshi P63
Kaczor Agnieszka P99
Kalbac Martin P86
Karabacak Mehmet L25, L34, L35
Karadjova Veronika P55, P56
Karpiuk Elena P61
Katrusiak Andrzej P4, P44
Kazimierczuk Katarzyna P76, P100
L22
Khomenko Dmytro P67
Kilic Ahmet P8
Kinzhybalo Vasyl P98
Kita Agnieszka P59
Koak Figen P90
Kochan Kamila L29
Kochanowicz Marcin P83
Koda Shota P63
Kojima Seiji P62, P63
P41, P42
Koll A. L36
P105
Komasa Anna P3, P4, P43, P44
Korchowiec Beata P26
Korchowiec Jacek P26
Korzun Urszula P24
Kose Etem L25
Kosendiak Iwona L31
Kosmal Magda P27
L30
P101
P41, P42, P45, P46, P47
Krupa Justyna L31, P48, P49
Kucharska Edyta P80
Kumar Sanjay P50
L23, P51, P84
Kwiatek W.M. L37
P31
Lata Lesia P34, P36, P37
Latos- P5
Ledoux-Rak Isabelle L8
Legendziewicz Janina L36, P94
188
Lehn Jean-Marie L1
Lengauer Christian P55
P52, P53
Leszczynski Jerzy L16
Libera Jerzy P35
Lipkowski Janusz L26
Lodowski Piotr P30
P105
Lorenc Jadwiga P24, P25, P80, P81, P103
P84
Lupusoru Raul P74
Lupusoru Raul P58
Lysenko N. P109
Macalik Lucyna P25
P89
Majchrowski Andrzej P89
Malik Magdalena P33, P54
Maliszewska Irena P81
Manasieva Delyana Marinova P55, P56
Marchewka Mariusz P18, P69, P70
L5, P57, P85, P93
Maria Andries P58
Marzec Katarzyna P23
L29
Masternak Joanna P100
Maszota Martyna P106, P107
Matras Edyta P45
Matsui Hiroshi P62
L20
Mazurek Sylwester P59, P60
Michalska Danuta P33, P54, P64
Michalski J. P103
Mielke Zofia L9, P6, P79
drzej P41, P45
Miluski Piotr P83
Minkiewicz Justyna P47
P99
Mokrushin Artem P36
Morawski Olaf P61
Mori Tatsuya P62, P63
Morzyk-Ociepa Barbara P64
P7, P45, P46
Nadejde Claudia P65
Nalpantidis Konstantinos L38
L20
Niemiec Wiktor P22
Nieradovski Yuri P36
P101
189
P3
Nowak Maciej J. P31
Nowicka Ariadna L22
P48
Oanca Gabriel P29, P65
Olejniczak Zbigniew P27
Ordon Magdalena P66
Ossowska- P66
Ostendorf Andreas L38
P8
P9
P10
Pagacz-Kostrzewa Magdalena P67
Pallares Zazo Ana P99
L37
Partyka Janusz P52
Pawlik Natalia P68, P87
Pawlus Katarzyna P69, P70
P27
P8
Pisarska Joanna P83
Pisarski Wojciech P68, P83, P87
Piwowarczyk Ewelina P105
P71
Pricop Daniela P58
Pricop Daniela P74
Proniewski Bartosz P23
Pruskova Marketa P72
Ptak Maciej P89
Puscasu Emil P58
Puscasu Emil P73, P74
Pyshkin Oleg P12
Racuciu Mihaela P73
L5
Ramasami Ponnadurai L10
Rao C.N.R. L6
Ratajczak Henryk L13, L21, P2
Ratajczak- P4, P44
Reben Manuela P27, P28
Regnouf De Vains Jean-Bernard P26
L37
Reva Igor P31
P75
Rodziewicz- P107
Rogala Patrycja P76, P77
Rogalska Ewa P26
Romanjuk Yuriy L21
-Robak Paulina P25
190
Shibata Tomohiko P62
Silvi Bernard L2
Simon Botond Lorand P82
Sitarz Maciej L23, P27, P28, P40, P51, P53, P83, P84, P95,
P96, P97, P105
Skowron Piotr P107
Slouf Miroslav P72
Sloufova Ivana P72, P86
-Lindert Wioleta P30
Sobolewski Andrzej L15, P61, P75
Sokalski W. Andrzej L27
L32
P57, P85
Stodolak-Zych Ewa P21, P22
Stoilova Donka P55, P56
L5, L36, P57, P85, P93, P94, P104
Sun Congting L13
Sutrova Veronika P86
Szabo Laszlo P82
P44
Szatkowski Piotr P21
Szeliga Marcin P35
Szopa Jan P24
Szostak Roman P59, P60
Szpikowska-Sroka Barbara P68, P87
L22
P88
P106, P107
Szymborska- P89
P105
Tanak Hasan P16, P69, P90, P91
Tandon Poonam L33
Tarach Karolina L24, P7
Tarach Karolina Anna P92
Tekla Justyna P92
Thangavel Karthick L33
Tinmaz Feyza P91
Tokhadze Konstantin P108
Tomachynski L. L36
Tomala Robert P57, P93, P94
P25, P89
Trzeciak Anna P1
Turek Edyta P30
P8
Turowska-Tyrk Ilona P64
P19
Vahlsing Thorsten L38
L20
191
Vlckova Blanka P72, P86
Vohlidal Jiri P72
Wajda Aleksandra P95, P96, P97
Wang L. S. P17
Weiss Marek L22
- L37, P22
Wierzejewska Maria L31, P48, P49, P67
Wietrzyk Joanna P33, P54
Wildner Manfred P55
P98
Wozniak Krzysztof P51
L30
P33
Xue Dongfeng L13
Yaremko Anatoliy L21
Yukhymchuk Volodymyr L21
P99
Zarecki Adam P3
Zerbi Giuseppe L7
Zi -Palus Janina P101
Zienkiewicz- P100
Zyss Joseph L8
P83
192
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