PG EMRpgemr.org/sites/default/files/Book of abstracts IV Forum...3 Scientific Committee Julia Jezierska – University of Wroclaw, Wrocław Kazimierz Dziliński – University of Technology,

Honorary patronage:

Dean of the Faculty of Physics, Adam Mickiewicz University

Professor dr hab. Antoni Wójcik

Director of the Institute of Molecular Physics Polish Academy of Sciences

Professor dr hab. Bogdan Idzikowski

Organizers:

Sponsors:

Streszczenia przyjęto do druku bez poprawek merytorycznych

i na odpowiedzialność autorów

Zdjęcie na okładce: Ratusz w Poznaniu, Poznań 2016

Autor zdjęcia: Karol Tuśnio

3

Scientific Committee

Julia Jezierska – University of Wroclaw, Wrocław

Kazimierz Dziliński – University of Technology, Częstochowa

Nikos Guskos – West Pomeranian University of Technology, Szczecin

Stanisław Hoffmann – Institute of Molecular Physics PAS, Poznań

Wojciech Kempiński – Institute of Molecular Physics PAS, Poznań

Małgorzata Komorowska – University of Technology, Wrocław

Ryszard Krzyminiewski – Adam Mickiewicz University, Poznań

Jerzy Krzystek – Florida State University, Tallahassee

Marian Kuźma – University of Rzeszów, Rzeszów

Jacek Michalik – Institute of Nuclear Chemistry and Technology, Warszawa

Andrzej Ożarowski – Florida State University, Tallahassee

Bohdan Padlyak – University of Zielona Góra, Zielona Góra

Lidia Piekara-Sady – Institute of Molecular Physics PAS, Poznań

Barbara Pilawa – Medical University of Silesia, Katowice

Czesław Rudowicz – West Pomeranian University of Technology, Szczecin & Adam

Mickiewicz University, Poznań

Zbigniew Sojka – Jagiellonian University, Kraków

Ewa Szajdzińska-Piętek – University of Technology, Łódź

Zbigniew Trybuła – Institute of Molecular Physics PAS, Poznań

Stefan Waplak – Institute of Molecular Physics PAS, Poznań

Organizing Committee

Wojciech Kempiński – Chairman IMP PAS

Ryszard Krzyminiewski – Chairman AMU

Czesław Rudowicz – Chairman of the PG EMR

Magdalena Wencka – Secretary

Waldemar Bednarski

Adam Ostrowski

Szymon Łoś

Maria Augustyniak-Jabłokow

Aldona Krupska

Bernadeta Dobosz

Agnieszka Boś-Liedke

Tomasz Kubiak

Krzysztof Tadyszak

Piotr Decyk

Alina Zalewska

4

Welcome Address

Honoured Guests, Ladies and Gentlemen:

On behalf of the Council of the Polish EMR Group and the Local Organising Committee,

co-chaired by Prof. Wojciech Kempiński (Institute of Molecular Physics, Polish Academy of

Sciences [PAS]) and Prof. Ryszard Krzyminiewski (Faculty of Physics, Adam Mickiewicz

University [AMU]), I welcome you to the IV Forum EMR-PL organized under the auspices of

the Polish EMR Group. We all appreciate very much the hard work and organisational efforts of

our colleagues in Poznań, which have brought this Forum to fruition. On personal side, I am

pleased that this Forum is held at the Adam Mickiewicz University, since this is my Alma Mater.

Returning to AMU in 2015, after over 27 years living abroad and 10 years in Szczecin, I can

appreciate the tremendous developments, exemplified, e.g. by the Morasko campus. I believe

that this Forum may play an important role in enhancing the strength of the EMR research groups

in Poznań, which were, to a great extent, created due to the pioneering efforts led by the late Prof.

Jan Stankowski.

Continuing with the spirit of the 1st Forum in Rzeszów, 2

nd in Huciska, and 3

rd in

Kraków, this Forum is open to all participants involved in EMR basic research and applications.

The main aims are to bring together EMR (EPR/ESR & FMR/AFMR) spectroscopists working

in Poland as well as to promote and facilitate collaboration among the Polish EMR community. I

am confident that the scientific program of the IV Forum EMR-PL will satisfy most participants

and provide ample opportunities to meet fellow researchers and to discuss various topics of

interest.

For the first time we have invited as plenary speakers two eminent EMR researchers from

abroad: Prof. Hitoshi Ohta, President of the International EPR/ESR Society and Head of the

Molecular Photoscience Research Center at Kobe University, Japan and Prof. K. Lips, Vice-

President of the European Society for Quantum Solar Energy Conversion and Head of the

Energy Materials In-situ Laboratory Berlin, Germany. We are grateful for accepting our

invitation and hope that their participation will be beneficial to all colleagues.

I would also like to invite all participants, irrespective of their present status of

membership in the Polish EMR Group, to join us at the General Meeting (GM) of the Society, to

be held during the Forum. A whole range of topics of interest to the whole EMR community will

be discussed. Hence, your votes and opinions are of great importance as they may shape the

future course of events.

My sincere thanks go to all members of the Local Organising Committee, especially

Profs. Kempiński and Krzyminiewski, for their dedicated work to make the IV Forum EMR-PL a

successful meeting. Support from the Scientific Committee in nominating the invited speakers

and maintaining the high standard of this Forum is also much appreciated. I wish to express our

gratitude to all sponsors for their financial support: Institute of Molecular Physics, PAS; Faculty

of Physics, AMU; Committee of Physics of PAS; APVACUUM; Bruker Polska; Euro-Hel;

noviLET; Krio-Serwis; Cavipan. Thanks are due to all speakers and participants, who by their

attendance will help to make this Forum a great success.

I wish you all an enjoyable and stimulating experience at the Forum and in Poznań.

Thank you.

Czesław Rudowicz

Chairman, Polish EMR Group [established in Rzeszów, 2010]

Founder President, Asia-Pacific EPR/ESR Society [established in Hong Kong, 1997]

5

Program IV FORUM EMR-PL

Monday, 27 June

8:00 - 9:30 Registration

9:30 - 9:50 Opening ceremony

9:50 Modern EMR techniques: new solutions, measurement techniques,

systems and equipment

Chairman: C. Rudowicz

9:50 - 10:35 Plenary lecture:

H. Ohta: Exotic Quantum Spin Systems Studied by Multi-Extreme THz EMR

10:35 - 11:05 Invited speaker:

T. Czechowski: New Methods in Electron Paramagnetic Resonance Imaging

Field

11:05 - 11:25 Oral presentation:

K. Tadyszak: Adaptive Modulation Amplitude Method in 2D Spectral-Spatial

EPR Imaging

11:25 - 11:40 Coffee Break

11:40 EMR in physics, chemistry and material research

Chairmen: H. Ohta, R. Fedaruk


N. Guskos: Magnetic Resonance and DC Magnetization Study of Phases in

FeVO4–Co3V2O8 System


V. D. Popowych: Ferromagnetic Resonance in CdTe:Cr Single Crystals

Containing Dopant-Related Macrodefects


T. Bodziony: Magnetic Study of Nanocrystalline TiB2,TiC, B4C Powders

Doped to AISI 316L Austentic Steel


R. Strzelczyk: FMR/EPR Study of Ferromagnetic Properties of Pristine and

Modified Graphene

13:10 - 14:30 Lunch

14:30 Quantum-chemical modeling in EMR spectroscopy and spectra

simulation

Chairman: J. Jezierska, S. Łoś


Z. Sojka: Molecular Interpretation of EPR Parameters – Computational

Spectroscopy Approaches


C. Rudowicz: Comparative Analysis of the Experimental and Theoretical

Zero Field Splitting and Zeeman Electronic Parameters for Fe2+

Ions in

FeX2∙4H2O (X = F, Cl, Br, I) and [Fe(H2O)6](NH4)2(SO4)2


M. Kozanecki: Effective Spin S~

= 2 Versus Fictitious S' = 1 Approach -

Conversions of the 2nd

-Rank Zero Field Splitting Parameters Measured by

High-Frequency EMR for Fe2+

Ions in Forsterite

6

Tuesday, 28 June


Chairmen: M. Komorowska, W. Kempiński


K. Lips: Ultra-Sensitive in-Operando Detection and Imaging of

Paramagnetic Defects in Silicon Solar Cells


J. Jezierska: Isotropic And Anisotropic Spin-Spin Interactions In

Metallacycles With Single M-X-M Bridges


M. Witwicki: EPR and DFT Insight into Interaction between O-Semiquinone

Radicals and Metal Ions


K. Sobańska: Formation of Reactive Oxygen Species on the Amorphous

Nonredox Materials During Reaction With H2O2

11:40 - 12:00

Oral presentation:

B. V. Padlyak: Radiation-Induced Paramagnetic Centers in some Borate

Glasses


12:20 EMR in biology and medicine

Chairman: K. Lips, Z. Sojka


M. Komorowska: Fatty Acids Binding Sites and Conformational Changes by

the Binding of them on Bovine Serum Albumin


R. Krzyminiewski: ESR investigation of functionalized magnetite

nanoparticles


M. Kurdziel: Application of Qualitative Standards to Interpretation of EPR

Spectra of Plant Material


Z. Matuszak: Electron Donor-Acceptor Properties of Melanin Studied by

EPR And Redox Potentiometry

14:00 - 15:30 Lunch


Chairman: M. Augustyniak-Jabłokow, R. Krzyminiewski


S. Łoś: Graphene Oxide – EPR And Impedance New Interpretation


Z. Trybuła: Dielectric and EPR Studies on Fullerenes: C60 and C70


P. Pietrzyk: Insight into Electronic and Magnetic Structure Of Ni(II)-NO

Adduct inside the Channels of ZSM-5 Zeolite from Molecular Modeling, EPR

And HYSCORE Measurements

16:00 - 17:00 General Meeting of the Polish EMR Group

17:00 - 19:00 Poster session/ Get together party

7

Wednesday, 29 June

9:45 Physical fundamentals and novel topics in EMR

Chairman: N. Guskos


C. Rudowicz: Magnetic Transition-Metal and Rare-Earth Adatoms on

Surfaces – EMR Perspective


R. Fedaruk: The EPR Spectra of Bulk Anthracite under Strong Coupling of a

Spin Ensamble to Resonator


M. A. Augustyniak-Jabłokow: Interpretation of “Anomalous” Temperature

Dependencies of EPR Signal Intensity in Various Systems


11:40 - 11:50 Poster Awards

11:50 - 13:10 Micro Orals

13:10 - 13:25 Closing ceremony

13:30 - 15:00 Lunch


M. Kuźma: Structural and Magnetic Order and Disorder in Metamagnetic

Shape Memory Alloys Ni2Mn1+xIn1-x


I. Stefaniuk: Electron Paramagnetic Resonance and Optical Study of

Ca4GdO(BO3)3 Single Crystals after Irradiation by Bismuth Ions

19:00 Conference Dinner – Działyński Palace

8

Table of Contents

ORAL CONTRIBUTIONS 13

Plenary lecture

EXOTIC QUANTUM SPIN SYSTEMS STUDIED BY MULTI-EXTREME THZ EMR

H. Ohta 14

Invaited speaker

NEW METHODS IN ELECTRON PARAMAGNETIC RESONANCE IMAGING FIELD

T. Czechowski 15

Oral presentation

ADAPTIVE MODULATION AMPLITUDE METHOD IN 2D SPECTRAL-SPATIAL EPR IMAGING

K. Tadyszak 16

Invaited speaker

MAGNETIC RESONANCE AND DC MAGNETIZATION STUDY OF PHASES IN FeVO4–Co3V2O8

SYSTEM

N. Guskos 17

Oral presentation

FERROMAGNETIC RESONANCE IN CdTe:Cr SINGLE CRYSTALS CONTAINING DOPANT-RELATED

MACRODEFECTS

V.D. Popovych 18

Oral presentation

MAGNETIC STUDY OF NANOCRYSTALLINE TiB2,TiC, B4C POWDERS DOPED TO AISI 316L

AUSTENTIC STEEL

T. Bodziony 19

Oral presentation

FMR/EPR STUDY OF FERROMAGNETIC PROPERTIES OF PRISTINE AND MODIFIED GRAPHENE

R. Strzelczyk 20

Invaited speaker

MOLECULAR INTERPRETATION OF EPR PARAMETERS – COMPUTATIONAL SPECTROSCOPY

APPROACHES

Z. Sojka 21

Oral presentation

COMPARATIVE ANALYSIS OF THE EXPERIMENTAL AND THEORETICAL ZERO FIELD SPLITTING

AND ZEEMAN ELECTRONIC PARAMETERS FOR Fe2+

IONS IN FeX2∙4H2O (X = F, Cl, Br, I) AND

[Fe(H2O)6](NH4)2(SO4)2

C. Rudowicz 22

Oral presentation

EFFECTIVE SPIN �̃� = 2 VERSUS FICTITIOUS S' = 1 APPROACH - CONVERSIONS OF THE 2ND

-RANK

ZERO FIELD SPLITTING PARAMETERS MEASURED BY HIGH-FREQUENCY EMR FOR Fe2+

IONS IN

FORSTERITE

M. Kozanecki 23

Oral presentation

INSIGHT INTO ELECTRONIC AND MAGNETIC STRUCTURE OF NI(II)-NO ADDUCT INSIDE THE

CHANNELS OF ZSM-5 ZEOLITE FROM MOLECULAR MODELING, EPR AND HYSCORE

MEASUREMENTS

P. Pietrzyk 24

9

Plenary lecture

ULTRA-SENSITIVE IN-OPERANDO DETECTION AND IMAGING OF PARAMAGNETIC DEFECTS IN

SILICON SOLAR CELLS

K. Lips 25

Invaited speaker

ISOTROPIC AND ANISOTROPIC SPIN-SPIN INTERACTIONS IN METALLACYCLES WITH SINGLE M-

X-M BRIDGES

J. Jezierska 26

Oral presentation

EPR AND DFT INSIGHT INTO INTERACTION BETWEEN O-SEMIQUINONE RADICALS AND METAL

IONS

M. Witwicki 27

Oral presentation

FORMATION OF REACTIVE OXYGEN SPECIES ON THE AMORPHOUS NONREDOX MATERIALS

DURING REACTION WITH H2O2

K. Sobańska 28

Oral presentation

RADIATION-INDUCED PARAMAGNETIC CENTERS IN SOME BORATE GLASSES

B. V. Padlyak 29

Oral presentation

FATTY ACIDS BINDING SITES AND CONFORMATIONAL CHANGES BY THE BINDING OF THEM ON

BOVINE SERUM ALBUMIN

M. Komorowska 30

Invaited speaker

ESR INVESTIGATION OF FUNCTIONALIZED MAGNETITE NANOPARTICLES

R. Krzyminiewski 31

Oral presentation

APPLICATION OF QUALITATIVE STANDARDS TO INTERPRETATION OF EPR SPECTRA OF PLANT

MATERIAL

M. Kurdziel 32

Oral presentation

ELECTRON DONOR-ACCEPTOR PROPERTIES OF MELANIN STUDIED BY EPR AND REDOX

POTENTIOMETRY

Z. Matuszak 33

Invaited speaker

GRAPHENE OXIDE – EPR AND IMPEDANCE NEW INTERPRETATION

S. Łoś 34

Oral presentation

DIELECTRIC AND EPR STUDIES ON FULLERENES: C60 AND C70

Z. Trybuła 35

Oral presentation

STRUCTURAL AND MAGNETIC ORDER AND DISORDER IN METAMAGNETIC SHAPE MEMORY

ALLOYS Ni2Mn1+xIn1-x

M. Kuźma 36

Oral presentation

ELECTRON PARAMAGNETIC RESONANCE AND OPTICAL STUDY OF Ca4GdO(BO3)3 SINGLE

CRYSTALS AFTER IRRADIATION BY BISMUTH IONS

I. Stefaniuk 37

10

Plenary speaker

MAGNETIC TRANSITION-METAL AND RARE-EARTH ADATOMS ON SURFACES – EMR

PERSPECTIVE

C. Rudowicz 38

Invaited speaker

THE EPR SPECTRA OF BULK ANTHRACITE UNDER STRONG COUPLING OF A SPIN ENSEMBLE TO

RESONATOR

R. Fedaruk 39

Oral presentation

INTERPRETATION OF “ANOMALOUS” TEMPERATURE DEPENDENCIES OF EPR SIGNAL INTENSITY

IN VARIOUS SYSTEMS

M. A. Augustyniak-Jabłokow 40

POSTER CONTRIBUTIONS 41

Poster I

EUPHORBIA TURKESTANICA TANNINS – ANTIRADICAL ACTIVITY, INTERACTION WITH ALPHA-

HEMOLYSIN AND ERYTHROCYTES LIPIDS

M. Bitiucki 42

Poster II

MAGNETIC INVESTIGATIONS OF Nb6Sb3VO25

M. Bobrowska 43

Poster III

SPATIAL- AND SPECTRAL-SPATIAL IMAGING - AN APPLICATION TO EPRI OXIMETRY

A. Boś-Liedke 44

Poster IV

EMR SPECTRA OF ZNO THIN FILMS DOPED WITH HIGH CONCENTRACTION OF CO AND CR ON

QUARTZ AND SAPPHIRE SUBSTRATES

B. Cieniek 45

Poster V

EPR STUDY OF Cu-Mn-Zn SPINELS SUPPORTED ON DEALUMINATED HY(–Al) ZEOLITE

P. Decyk 46

Poster VI

FERROMAGNETIC RESONANCE IN NiCoMnIn LAYERS OBTAINED BY PULSED LASER DEPOSITION

Ł. Dubiel 47

Poster VII

WIDE TEMPERATURE RANGE SYSTEM FOR EPR MEASUREMENTS UP TO 1300 K

Z. J. Frączek 48

Poster VIII

MAGNETIC PROPERTIES OF STEEL BALLS INVESTIGATED BEFORE AND AFTER NITRIDING

PROCESS

H. Fuks 49

Poster IX

MONITORING OF PLATELET MEMBRANE FLUIDITY DURING DIALYSIS OF SHEEP

K. Gałecka 50

Poster X

SPIN LABELING STUDIES OF ERYTHROCYTES PROPERTIES IN VARICOSE VEINS PATIENTS

K. Gwoździński 51

11

Poster XI

RADIATION DEFECTS IN CALCITE AND THEIR INFLUENCE ON MECHANICAL PROPERTIES

Z. Kabacińska 52

Poster XII

EPR INVESTIGATIONS INTO FORMATION OF NITROSYL COMPLEXES OF PALLADIUM CATIONS IN

ZEOLITES Y AND ZSM-5

A. Krasowska 53

Poster XIII

EPR STUDY OF PARAMAGNETIC CENTERS ON A SURFACE OF MODIFIED NANODIAMONDS

A. Krupska 54

Poster XIV

EPR STUDY OF THE MAGNETIC PROPERTIES OF IRON OXIDE NANOPARTICLES IN HUMAN BLOOD

AND SERUM

T. Kubiak 55

Poster XV

OPTIMIZATION OF ANTIOXIDANT PROPERTIES OF WATER-IN-OIL AND OIL-IN-WATER CREAMS

WITH BILBERRY, CHOKEBERRY AND ELDERBERRY EXTRACTS BY ARTIFICIAL NEURAL

NETWORKS

K. Makarova 56

Poster XVI

HYPERFINE STRUCTURE OF VANADIUM IONS IN LIQUIDS AND SOLIDS

I. Mrówka 57

Poster XVII

SPECIFICITY OF FREE RADICAL-SCAVENGING PROPERTIES OF SUMAC TANNINS IN PROTECTION

OF ERYTHROCYTES AGAINST OXIDATIVE STRESS

E. Olchowik-Grabarek 58

Poster XVIII

MICROWAVE X-BAND RESONANCES IN DOPED Cd2Nb2O7 MONOCRYSTALS

A. Ostrowski 59

Poster XIX

POTENTIAL ROLE OF SUPEROXIDE ANION IN HOMOCYSTEINE-INDUCED FLUIDIZATION OF

PLATELET MEMBRANES – EVIDENCE FROM PRELIMINARY EPR MEASUREMENTS

A. Pieniążek 60

Poster XX

THEORETICAL INVESTIGATIONS OF THE SPIN HAMILTONIAN PARAMETERS AND THE LOCAL

STRUCTURE OF Co2+

IONS IN PbMoO4 CRYSTAL

D. Piwowarska 61

Poster XXI

THE STUDY OF FREE RADICALS IN THE ENRICHED PEAT OF SPENT OIL – EPR TECHNIQUE

B. Pytel 62

Poster XXII

FERROMAGNETIC RESONANCE STUDY OF HIGHLY CHROMIUM DOPED CdTe ALLOY

I. Rogalska 63

Poster XXIII

RELATION OF TOTAL POLYPHENOL AND FLAVONOID CONTENTS TO ANTI-RADICAL

PROPERTIES AND STABILITY OF TINCTURES OF GEISSOSPERMUM RETICULATUM:

CHEMOMETRIC ANALYSIS AND LAG PHASE EPR

J. J. Sajkowska-Kozielewicz 64

12

Poster XXIV

EMR DATA ON HIGH-SPIN Mn3+

(S = 2) IONS IN MnTPPCl COMPLEX MODELLED BY MICROSCOPIC

SPIN HAMILTONIAN APPROACH

K. Tadyszak 65

Poster XXV

MAGNETIC DEFECTS IN Nb2SbVO10

J. Typek 66

Poster XXVI

INTERACTION BETWEEN SPIN – LABELED Fe3O4 NANOPARTICLES AND HUMAN BLOOD STUDIED

BY EPR METHOD

K. Urbaniak 67

Poster XXVII

UV-INDUCED RADICALS IN STATINES – LIPID-LOWERING MEDICATIONS

M. Wencka 68

Poster XXVIII

Cu2+

DOPED MOLECULAR SIEVES FOR MONITORING STRUCTURAL CHANGES AND GUEST-HOST

INTERACTIONS

A. Zalewska 69

Poster XXIX

SPIN TRAP AND SPIN PROBE ESR FOR THE OPTIMIZATION OF ANTIOXIDANT PROPERTIES OF

HERBAL BATHING SALTS

K. Zawada 70

Poster XXX

EPR STUDIES OF THE FREE RADICAL SCAVENGING ACTIVITY OF SIMVASTATIN

M. Zdybel 71

PosterXXXI

THE INFLUENCE OF SIMVASTATIN ON FREE RADICALS IN HUMAN MELANOMA MALIGNUM

CELLS – EPR EXAMINATION

M. Zdybel 72

Poster XXXII

EPR/FMR STUDY OF nCoO/(1-n)ZnO (n=0.4, 0.5, 0.6 AND 0.7) NANOCOMPOSITES

G. Zolnierkiewicz 73

13

Oral contributions

14

IV FORUM EMR-PL 27-29.VI. 2016

Plenary lecture

EXOTIC QUANTUM SPIN SYSTEMS STUDIED BY MULTI-EXTREME THZ EMR

H. Ohta1,2

, S. Okubo1,2

, E. Ohmichi2, T. Sakurai

3, S. Hara

3, H. Takahashi

4

1 Molecular Photoscience Research Center, Kobe University, Kobe, 657-8501 Japan

2 Graduate School of Science, Kobe University, Kobe, 657-8501, Japan

3 Center for Support to Research and Education Activities, Kobe University, Kobe, 657-8501, Japan

4 Organization of Advanced Science and Technology, Kobe University, Kobe, 657-8501, Japan

[email protected]

Development of multi-extreme THz EMR is one of our main activities in Kobe. It

covers the frequency region between 0.03 and 7 THz using Gunn Oscillators, multipliers,

backward wave oscillators (BWO) and the optically pumped far-infrared (FIR) laser [1], the

temperature region between 1.8 and 300 K [1], the magnetic field region up to 55 T using the

pulsed magnetic field [1], and the pressure region up to 1.5 GPa using the transmission type

piston cylinder pressure cell made by NiCrAl alloy and ceramic piston parts [2]. Recently we

have extended the pressure region up to 2.7 GPa using the hybrid-type pressure cell [3]. The

hybrid-type pressure cell is the double layered cell which consists of NiCrAl alloy inner cell

and Cu-Be alloy outer cell. Moreover, we have also developed the highly sensitive

mechanically detected micro-cantilever ESR, which enables the measurements of micrometer

size sample [4] Very recently the micro-cantilever ESR measurements has been extended up to

1.1 THz, which is the world record for such mechanical detection of EMR.[5] As for the

longitudinal EMR measurement, we have also succeeded in the magnetization detected EMR

using SQUID (Superconducting Quantum Interference Device) magnetometer (SQUID EMR)

[6]. As applications of such multi-extreme EMR, we would like to refer to two topics. First is

the high field EMR study of the multiferroic substance YCrO3, which shows a ferroelectric

transition below TC = 470 K and an antiferromagnetic transition with a weak ferromagnetism

due to Dzyaloshinskii–Moriya (DM) interaction below TN = 140 K [7]. As we have extended

the AFMR measurement up to 35 T in the high field region and 0.722 THz at 1.9 K compared

to the previous one [8], we have found a new AFMR mode and unconventional behaviors.

Secondary the high pressure THz EMR results of Shastry-Sutherland model substance

SrCu2(BO3)2 single crystal up to 2 GPa at 2 K will be presented. Possible pressure induced

phase transition predicted by the theory [9] will be discussed.

References [1] H. Ohta et al., J. Low Temp. Phys. 2013, 170, 511.

[2] T. Sakurai et al., Rev. Sci. Inst. 2007, 78, 065107; T. Sakurai, J. Phys.: Conf. Series, 2010,

215, 012184.

[3] K. Fujimoto et al., Appl. Mag. Res. 2013, 44, 893; H. Ohta et al., J. Phys. Chem. B 2015,

119, 13755; T. Sakurai et al., J. Mag. Res., 2015, 259,108.

[4] H. Ohta et al., AIP Conf. Proceedings 2006, 850, 1643; E. Ohmichi et al., Rev. Sci.

Instrum. 2008, 79, 103903; E. Ohmichi et al., Rev. Sci. Instrum. 2009, 80, 013904; H. Ohta

and E. Ohmichi, Appl. Mag. Res. 2010, 37, 881; E. Ohmichi et al., J. Low Temp. Phys.

2010, 159, 276; Y. Tokuda et al., J. Phys.: Conf. Series 2012, 400, 032103; E. Ohmichi et

al., J. Mag. Res. 2013, 227, 9.

[5] H. Takahashi, E. Ohmichi, H. Ohta, Appl. Phys. Lett. 2015, 107, 182405.

[6] T. Sakurai et al., J. Phys.: Conf. Series 2011, 334, 012058; T. Sakurai et al., J. Mag. Res.

2012, 223, 41; T. Sakurai et al., J. Magnetics 2013, 18, 168.

[7] C. R. Serrao et al., Phys. Rev. B 2005, 72, 220101(R)/4.

[8] V.A. Sanina et al., Phys. Lett. 1970, 33A, 291.

[9] A. Koga and N. Kawakami, Phys. Rev. Lett. 2000, 84, 4461.

15


Invaited speaker

NEW METHODS IN ELECTRON PARAMAGNETIC RESONANCE IMAGING

FIELD

T. Czechowski1, M. Baranowski

2, W. Chlewicki

3, K. Jurga

2, P. Szczepanik

4, P. Szulc

4, K.

Tadyszak5, P. Kedzia

4, P. Malinowski

6, J. Jurga

4

1noviLET, Poznan, Poland.

2Adam Mickiewicz University, Department of Physics, Poznan, Poland.

3West Pomeranian University of Technology, Faculty of Electrical Engineering, Szczecin, Poland.

4Poznan University of Technology, Laboratory of EPR Tomography, Poznan, Poland.

5Adam Mickiewicz University, NanoBioMedical Centre, Poznan, Poland.

[email protected]

This presentation outlines a concept for fast spectral and spectral-spatial electron

paramagnetic resonance imaging (EPRI). We report on progress in shortening acquisition time,

increasing signal to noise ratio and image resolution towards the implementation novel

detection and signal analysis methods. We demonstrate that application of modern CW and

rapid scan EPR methods can provide unique insight into the EPRI field. The presented results

are based on experiments using rotated magnetic field gradient, adaptive method of choosing

modulation amplitude for each projection, multiharmonics analysis, high resolution

deconvolution and sinogram fitting procedures.

One of the method to reduce measurement time is combining rapid scan of Zeeman

magnetic field using high frequency sinusoidal modulation with simultaneously applied

magnetic field gradient, which orientation or amplitude are changed at low frequency. The

presented method allows to reduce the image acquisition time up to 10 ms for 2D spatial [1],

and 200ms for 2D spectral-spatial EPRI [2]. To improve the signal to noise ratio (SNR) of the

projections in CW EPR technique a more consciously selected modulation amplitude

parameter could be applying. In the case of the projections obtained by this adaptive

modulation method, the SNR was more constant (in all projections) than for the fixed

modulation amplitudes values.

References [1] T. Czechowski, W. Chlewicki, M. Baranowski, K. Jurga, P. Szczepanik, P. Szulc, K. Tadyszak, P. Kedzia, M.

Szostak, P. Malinowski, S. Wosinski, W. Prukala, J. Jurga, J. Magn. Res. 248 126 – 130, (2014).

[2] T. Czechowski, W. Chlewicki, M. Baranowski, K. Jurga, P. Szczepanik, P. Szulc, P. Kedzia, M. Szostak, P.

Malinowski, S. Wosinski, W. Prukala, J. Jurga, J. Magn. Res.243, 1 – 7, (2014).

16


Oral presentation

ADAPTIVE MODULATION AMPLITUDE METHOD IN 2D SPECTRAL-SPATIAL

EPR IMAGING

T. Czechowski*1,5

, Z. Kabacińska1,6

, A. Samolej4, M. Baranowski

3,5, A. Boś-Liedke

6, W.

Chlewicki2,5

, M. Jancelewicz1, J. Jurga

4,5, K. Tadyszak

1**

1 NanoBioMedical Centre, Adam Mickiewicz University, ul. Umultowska 85, PL 61614 Poznań, Poland

2 Faculty of Electrical Engineering, West Pomeranian University of Technology, al. Piastów 17, 70-310 Szczecin,

Poland 3 Physics Department, Faculty of Physics, Adam Mickiewicz University, ul. Umultowska 85, PL 61614 Poznań,

Poland 4 Laboratory of EPR Tomography, Poznan University of Technology, ul. Piotrowo 3, PL 60965 Poznań, Poland

5 noviLET, ul. Romana Maya 1, PL 61371 Poznań, Poland

6 Medical Physics Department, Faculty of Physics, Adam Mickiewicz University, ul. Umultowska 14, PL 61614

Poznań, Poland

[email protected]

A study concerning the image quality in Electron Paramagnetic Resonance Imaging

(EPRI) in 2D spectral-spatial (2D SSI) experiments is presented. The aim of the measurements

was to improve the signal to noise ratio (SNR) of the projections by applying a more

consciously selected modulation amplitude parameter. Data was gathered by applying three

constant and one adaptive modulation amplitude. Three modulation amplitude values were

used in this experiment, leading to undermodulated, partially overmodulated and fully

overmodulated projections. The advantages of the adaptive method of choosing modulation

amplitude for each projection were demonstrated in the study performed on a phantom

containing four tubes of LiPc and TCNQ, characterized by a different peak to peak linewidth

and spin concentration. In the case of the projections obtained by the adaptive modulation

method, the SNR was more constant (in all projections) than for the fixed modulation

amplitudes values. The linewidths obtained from 2D SSI were in the best agreement with the

values expected for the phantom used for the adaptive modulation amplitude method.

mailto:[email protected]

17


Invaited speaker

MAGNETIC RESONANCE AND DC MAGNETIZATION STUDY OF PHASES IN

FeVO4–Co3V2O8 SYSTEM

N. Guskos1, G. Zolnierkiewicz

1, M. Pilarska

1, J. Typek

1, A. Blonska-Tabero

2

1Department of Physics, West Pomeranian University of Technology, Al. Piastow 48, 70-311 Szczecin, Poland

2Department of Inorganic and Analytical Chemistry, West Pomeranian University of Technology, Al. Piastow 42,

70-065 Szczecin, Poland

Magnetic properties of four samples obtained from reactions between FeVO4 and

Co3V2O8 have been investigated byusing magnetic resonance spectroscopy and dc

magnetization (in ZF and ZFC modes) techniques. At room temperature all parameters of

magnetic resonance spectra strongly depended on thermal annealing of the prepared samples

(first four samples listed in Table 1 in Ref. 1).The composition of initialmixtures, the heating

conditions and the results of the XRD analysis of the obtained samples were presented in Ref.

2.From dc magnetization measurements it was concluded the formation of superparamagnetic

and antiferromagnetic phases with the blocking temperature and the Curie-Weiss temperature

in the low temperatures range. These two parameters were strongly dependent upon the thermal

treatment conditions of synthesised samples. At low and high temperatures the magnetic

hysteresis was observed and its parameters were dependent upon the method of thermal

treatment. The morphology of the investigated samples consisted of large magnetic

agglomerates built up from nanoclusters.This favours the possibility of formation of the

superparamagnetic phase. From the obtainedtemperature dependence of magnetic resonance

parameters it was concluded that the observed resonance line was derived from the magnetic

nanoclusters.

References 1. N. Guskos, G. Zolnierkiewicz, J. Typek, and A. Blonska-Tabero, Physica B 406, 2163 (2011).

2. A. Blonska-Tabero, M. Kurzawa, J. Therm. Anal. Calorimetry 88, 33 (2007).

18


Oral presentation

FERROMAGNETIC RESONANCE IN CdTe:Cr SINGLE CRYSTALS CONTAINING

DOPANT-RELATED MACRODEFECTS

V.D. Popovych1, M. Kuźma

2, N. Skop

2, I. Stefaniuk

3, B. Cieniek

3

1Department of Machine Science and Fundamental Technologies, Ivan Franko Drogobych State Pedagogical

University, 24 Ivan Franko str., 82100 Drogobych, Ukraine 2Faculty of Mathematics and Natural Sciences, Department of Biophysics,

University of Rzeszow, Pigonia 1, 35-959 Rzeszow, Poland 3Faculty of Mathematics and Natural Sciences, Department of Experimental Physics,

University of Rzeszow, Pigonia 1, 35-959 Rzeszow, Poland

[email protected]

The investigated CdTe:Cr single crystals were grown by the modified PVT method

from pre-synthesized charge with 2.5 and 5 at.% of Cr nominal content [1]. A number of

macrodefects were revealed by SEM patterning and EDX analysis in the crystals, both in the

form of sub-µm near-isometric particles and arranged sets of thin (less than 1 µm) polygons.

They were identified by HAADF analysis and HRTEM studies as Cr3Te4 precipitates, which

are formed during post-grown cooling due to poor solubility of Cr in CdTe [2].

Fig.1. Angular dependence of FMR spectrum of the CdTe:Cr single crystal at 300 K. The insert shows EPR

spectrum of the crystal at 350K.

Magnetic properties of the crystals were measured by EPR method using 9.43 GHz X-band

Bruker FT-EPR spectrometer ELEXSYS E580. Magnetic resonance spectra of the samples at

room and at lower temperatures are complex; its constituent lines exhibit strong angular and

temperature dependences (Fig.1). The resonance fields of the lines lies in the wide range of

magnetic field (100 – 450mT). At particular orientation of the samples in respect to the applied

field the shift of some lines to very high fields (500 – 650 mT) is observed. At higher

temperatures the spectrum is much simpler and at 350 K consists of only one Gaussian-like

line, which is attributed to the paramagnetic state of the sample (insert in Fig.1). To understand

the complex structure of the obtained spectra at room temperature and their angular

dependences, we have taken into account the contribution of ferromagnetic Cr3Te4 phase in the

form of oriented platelets embedded into CdTe:Cr matrix along its {111} planes. At room and

at lower temperatures the spectra can be described by the FMR formalism.

References [1] V.D. Popovych, P. Sagan, M. Bester, B. Cieniek, M. Kuzma, J. Cryst. Growth 426 (2015) 1733.

[2] V.D. Popovych, P.Sagan. Acta Physica Polonica, A 129 (2016) 49.

19


Oral presentation

MAGNETIC STUDY OF NANOCRYSTALLINE TiB2,TiC, B4C POWDERS DOPED

TO AISI 316L AUSTENTIC STEEL

T. Bodziony 1

, S. M. Kaczmarek1, A. Biedunkiewicz

2, G. Leniec

1, P. Figiel

2

1 Institute of Physics, West Pomeranian University of Technology, Al. Piastów 17,

70-310 Szczecin, Poland 2 West Pomeranian University of Technology, Al. Piastów 17,

70-310 Szczecin, Poland

[email protected]

The results of the EPR and magnetic susceptibility investigations of nanocrystalline

TiB2,TiC, B4C powders (3%, 5%, 7%) doped to AISI 316L austenitic steel have been

analyzed. The nanocrystalline materials offer unique chemical, structural, electrical, and

magnetic properties with wide range of potential applications. The tested five composite

samples, marked as samples 7-9, contain a number of crystalline and magnetic phases in

different proportions. The results of the EPR and magnetic susceptibility measurements of the

composites are presented for the first time. The EPR spectra are recorded from helium up to

room temperature. They reveal a structure originating from several different complex magnetic

centres. The changes of the total intensity of EPR spectra versus temperature are deeply

analysed. The temperature dependence of the total intensity of the EPR spectra of the

investigated composites reveals different magnetic phenomena like paramagnetism, ferro-

(and/or) antiferromagentism and superparamagnetism (see Fig 1). The conclusions resulting

from the EPR measurements has been verified by magnetic susceptibility measurements.

Magnetic properties of the TiB2,TiC, B4C powders doped to AISI steel may play important role

in further, possible applications many of the composite systems

Fig. 1. Temperature dependences of the total intensity for few sample AISI 316L + TiB2,TiC, B4C (7, 8, 9)

and comparison of EPR and magnetic susceptibility measurements for a sample No. 9

20


Oral presentation

FMR/EPR STUDY OF FERROMAGNETIC PROPERTIES OF PRISTINE AND

MODIFIED GRAPHENE

R. Strzelczyk1, M.A. Augustyniak-Jabłokow

1, M. Maćkowiak

1

1 Institute of Molecular Physics, Polish Academy of Sciences, Poznan, Poland

[email protected]

Theoretical predictions concerning 1D ferromagnetic order on the zig-zag edges of pristine

graphene[1] and 2D surface ferromagnetism in modified graphenes[2] has been reported in

literature. But published experimental results often show different magnitudes and temperature

dependences of these effects. This arises most likely from mismatch between relatively weak

response of the studied materials (small samples) and typical magnetometric or SQUID

measurements.

Very promising alternative present Ferromagnetic Resonance registered with Electron

Paramagnetic Resonance spectrometer. In EPR intensity of recorded signal is directly

proportional to magnetic susceptibility. Even though we cannot obtain absolute value of

susceptibility it allows us to study its temperature dependences. In addition we can analyze

separately different magnetic contributions making up total sample response.

In this report we show results of our FMR/EPR study of ferromagnetic ordering existing in

graphene and some of its derivatives. Furthermore, we determine proper conditions of its

occurrence.

Fig.1 FMR/EPR spectra of pristine graphene, graphene oxide and hydrogenated graphene registered each

at temperature of 4K.

References

[1] O. Yazyev, M. Katnelson, Phys. Rev. Lett. 100 (2008)

[2] D. Soriano, F. Muñoz-Rojas, J. Fernández-Rossier , J.J. Palacios, , Phys. Rev. B 81 (2010)

21


Invaited speaker

MOLECULAR INTERPRETATION OF EPR PARAMETERS – COMPUTATIONAL

SPECTROSCOPY APPROACHES

Z. Sojka1, P. Pietrzyk

1

1 Faculty of Chemistry, Jagiellonian University, Ingardena 3, 30-060 Krakow, Poland

[email protected]

Electronic properties and reactivity of nanostructured oxide and metallozeolite systems

are intrinsically related with their low dimensionality, reduced size. The resultant inherent

heterogeneity of such systems gives rise to low symmetry phenomena and pronounced

speciation of the paramagnetic surface species, leading often to complicated multi-component

powder CW-EPR spectra. This severely restrains recognition of individual spectral features

since the information is often unevenly distributed over broad spectral range. As a

consequence, much of useful chemical data about the investigated system can only be

recovered with the help of advanced computer analysis of the EPR spectra supported by state

of the art quantum chemical calculations of their parameters (computational spectroscopy

approach).

While analyzing EPR spectra it is often difficult to directly relate the experimentally

obtained spin Hamiltonian (sH) parameters, such as g-tensors, hyperfine (A) or fine structure

(D) tensors to molecular structure. This is especially valid for complex spectra of low

symmetry, where traditional methods of analysis based on ligand field (LFT) or angular

overlap methods (AOM) suffer from the problem of over-parameterization, despite their

undeniable merit. Currently available quantum chemical methods for calculations of EPR

parameters can, however, be very helpful to correlate experimental data with structural

information in a nearly quantitative way. Computational EPR spectroscopy is rapidly

expanding from a highly specialized research area of quantum chemistry into a versatile tool of

broad academic service, capable of reliable prediction of sH parameters and related properties

[1]. In addition, it may provide crucial missing information for their in-depth interpretation in

terms of assignment of the observed magnetic transitions, insight into their molecular nature,

structure, discrimination between alternative structural hypotheses, and assessment of the

influence of dynamical and environmental effects.

In this contribution a short outline of the spin Hamiltonian parameters and their

quantum-chemical computation methods will be provided. The applicability of principal

calculation schemes based on density functional theory (DFT) and their usefulness will be

demonstrated on the basis of selected examples. They include transition metal complexes and

their adducts with reagent molecules inside the zeolite channels. Such approach was used for

investigation of changes in the electron and spin states taking place during the interaction of

small molecules like O2 and CO with transition metals of various electron configuration (Co,

Ni, Cu i) encaged in zeolites The results provided not only an in-depth insight into the

molecular nature of the g and A tensors of the examined systems, but also allowed to account

for noncoincidence of axes, spin polarization effects as well as structure sensitivity of the

extracted magnetic parameters.

References [1] P. Pietrzyk, K. Podolska, Z. Sojka, Molecular interpretation of EPR parameters – computational spectroscopy

approaches, in: B.C. Gilbert, D.M. Murphy, V. Chechik (Eds.), Specialist Periodical Reports - Electron

Paramagnetic Resonance, RSC Publishing, (2013) pp. 264-311.

22


Oral presentation

COMPARATIVE ANALYSIS OF THE EXPERIMENTAL AND THEORETICAL

ZERO FIELD SPLITTING AND ZEEMAN ELECTRONIC PARAMETERS FOR Fe2+

IONS IN FeX2∙4H2O (X = F, Cl, Br, I) AND [Fe(H2O)6](NH4)2(SO4)2

M. Zając1, C. Rudowicz

2,3

1 Institute of Physics, West Pomeranian University of Technology, Al. Piastów 17, 70–310 Szczecin, Poland

2Faculty of Chemistry, A. Mickiewicz University (AMU), Umultowska 89B, 61-614 Poznań, Poland

3 Visiting Professor (AMU); On leave of absence from: Institute of Physics, West Pomeranian University of

Technology Szczecin, Al. Piastów 17, 70-310 Szczecin, Poland

[email protected]

The spin Hamiltonian (SH) parameters, including the zero field splitting (ZFS) and Zeeman

electronic (Ze) parameters [1, 2], have recently been modeled for Fe2+

ions in FeCl2∙4H2O and

FeF24H2O crystals, which exhibit similar crystal structure [3]. High-magnetic field and high-

frequency EMR (HMF-EMR) techniques, for references, see, e.g. [4, 5] provide nowadays

more reliable experimental ZFS and Ze parameter sets for 3d4 and 3d

6 (S = 2) ions, e.g. Fe

2+,

Mn3+

, and Cr2+

, which usually exhibit large and very large ZFS [3, 6]. Similar modeling, using

the package MSH/VBA [7, 8] is now carried out for [Fe(H2O)6](NH4)2(SO4)2 (FASH) [9-11].

The microscopic SH (MSH) approach incorporates MSH expressions for the ZFS and Ze

parameters up to fourth-order perturbation theory suitable for of 3d4 and 3d

6 ions with spin S =

2 at orthorhombic and tetragonal symmetry sites in crystals, which exhibit an orbital singlet

ground state arising from the ground 5D multiplet [7, 8].

The available data on the ground state and excited orbital states with the respective energy

levels determined or adopted for Fe2+

(S = 2) ions in FASH together with the spin-orbit

coupling (SOC) constants: c (in crystal), 0 (free ion), and the orbital reduction (or covalency)

factor defined as: c = k 0 are surveyed to obtain input for MSH/VBA calculations.

Experimental values of the ZFS parameters and energies determined for Fe2+

ions in FASH [9-

11] are reanalyzed in view of our modeling results and compared with those obtained for

FeX2∙4H2O (X = F, Cl, Br, I) compounds [3]. Investigations of the role of the fourth-rank ZFS

terms existing for S~

= 2 [1,2], which are often omitted in experimental studies, and the spin-

spin interaction contributions to the second- and fourth-rank ZFSPs are is now under progress.

Illustrative preliminary results will be presented.

Acknowledgements

This work was partially supported by the research grant # DEC-2012/04/M/ST3/00817

from the Polish National Science Center. One of us (MZ) is grateful to the Institute of Physics,

West Pomeranian University of Technology in Szczecin, for a PhD scholarship.

References [1] C. Rudowicz, M. Karbowiak, Coord. Chem. Rev. 287 (2015) 28.

[2] C. Rudowicz, S.K. Misra, Appl. Spectrosc. Rev. 36 (2001) 11.

[3] M. Zając, I. E. Lipiński, C. Rudowicz, J. Magn. Mag. Mat., 401 (2016) 1068.

[4] T. Sakurai, K. Fujimoto, R. Goto, S. Okubo, H. Ohta, Y. Uwatoko, J. Magn. Reson. 223 (2012) 41.

[5] J. Telser, J. Krzystek, A. Ozarowski, J. Biol. Inorg. Chem. 19 (2014) 297.

[6] C. Rudowicz, H.W.F. Sung, J. Phys. Soc. Japan 72 Supplement B (2003) 61.

[7] C. Rudowicz, H.W.F. Sung, Physica B 337 (2003) 204.

[8] C. Rudowicz, H.W.F. Sung, Manual for the Package MSH/VBA, unpublished (2004).

[9] J. C. Gill, P.A. Ivey, J. Phys. C: Solid State Phys. 7 (1974) 1536.

[10] R. Doerfler, et al., J. Phys. C: Solid State Phys. 19 (1986) 3005.

[11] J. Telser, et al., Magn. Reson. Chem. 43 (2005) S130.

23


Oral presentation

EFFECTIVE SPIN S~

= 2 VERSUS FICTITIOUS S' = 1 APPROACH - CONVERSIONS

OF THE 2ND

-RANK ZERO FIELD SPLITTING PARAMETERS MEASURED BY

HIGH-FREQUENCY EMR FOR Fe2+

IONS IN FORSTERITE

M. Kozanecki1, C. Rudowicz

2,3

1 Faculty of Chemistry, A. Mickiewicz University (AMU), Umultowska 89B, 61-614 Poznań, Poland

2 Visiting Professor: Faculty of Chemistry, A. Mickiewicz University, Poznań, Poland

3 On leave of absence from: Institute of Physics, West Pomeranian University of Technology Szczecin, Poland

[email protected]

Electron magnetic resonance (EMR) determination of the spin Hamiltonian parameters

for Fe2+

ions in natural and synthetic forsterite (Mg2SiO4) by Shakurov et al. [1] has been

hindered by several factors. The wide-band EMR spectrometer covered a limited frequency

region of = 65 to 850 GHz, hence only three transitions were detected in the temperature

range of 4.2 - 15 K in the magnetic field up to 9.5 kG. Importantly, these three transitions have

been described supposing that, quote [1]: 'the system of energy levels has an effective spin S =

1' instead of the effective spin S~

= 2 [2-4] most likely expected for Fe2+

ions in low symmetry

sites, see, e.g. [5].

Our analysis of the EMR data [1] reveals that the 'spin' value S = 1 has been assigned for

Fe2+

in Mg2SiO4 only due to experimental limitations, whereas the approach [1] represents, in

fact, the fictitious spin S' = 1 arising from the effective spin S~

= 2 states [2-4]. The axial (D)

and rhombic (E) second-rank zero field splitting (ZFS) parameters (ZFSPs) [2-4], obtained by

fitting the experimental EMR data using spin Hamiltonian with spin S = 1 [1], cannot be

directly compared with D and E ( S~

= 2) available in literature for Fe2+

ions [5,7]. To enable

direct comparison of (D', E') [1] and (D, E) [5,7], appropriate conversion relations have been

derived for various combinations of the possible energy level schemes for the spin S~

= 2 and

S' = 1. Illustrative preliminary results of appropriate conversions of the 2nd

-rank ZFSPs

measured by high-frequency EMR for Fe2+

in natural and synthetic forsterite [1] will be

presented. Detailed results and full analysis are provided in [6]. Investigation of the role of the

fourth-rank ZFS terms, which must be taken into account for spin S~

= 2 [2-4] is now in

progress. The results of the extended calculations will be given elsewhere.

Acknowledgments CZR acknowledges the Polish National Science Center research grant DEC-

2012/04/M/ST3/ 00817; MK is grateful to the Faculty of Chemistry, A. Mickiewicz University,

for a PhD scholarship.

References [1] G.S. Shakurov, T.A. Shcherbakova, V.A. Shustov, Appl. Magn. Reson. 40 (2011) 135.

[2] C. Rudowicz, M. Karbowiak, Coord. Chem. Rev. 287 (2015) 28.

[3] C. Rudowicz, Magn. Res. Rev. 13 (1987) 1.



[6] M. Kozanecki, C. Rudowicz, in preparation (2016).

[7] M. Zając, I. E. Lipiński, and C. Rudowicz, J. Magn. Mag. Mat. 401 (2016) 1068.

24


Oral presentation

INSIGHT INTO ELECTRONIC AND MAGNETIC STRUCTURE OF NI(II)-NO

ADDUCT INSIDE THE CHANNELS OF ZSM-5 ZEOLITE FROM MOLECULAR

MODELING, EPR AND HYSCORE MEASUREMENTS

P. Pietrzyk1, K. Podolska-Serafin

1, T. Mazur

1, M. Radoń

1, M. Chiesa

2, Z. Sojka

1


2 Dipartimento di Chimica, Università di Torino, via P. Giuria 7, 10125, Torino, Italy

[email protected]

The paramagnetic mononuclear nickel adducts with small molecules NiI/II

–XY are the

key species implicated in various important homo- and heterogeneous catalytic systems.

Incorporation of these species into the channels of zeolites allows for their stabilization,

dilution, and magnetic separation, which is beneficial from the point of view of EPR studies.

For an in-depth understanding of the fundamental chemistry of the Ni–XY units, a detailed

atomic level description of the electronic and magnetic structure of these species is of a great

cognitive value. In case where XY molecule is a non-innocent ligand, electronic structure of

the adduct results from complicated, spin and charge flow channels [1] (the case of O2

molecule), or magnetic (ferro- or antiferromagnetic) couplings as in the present case of NO.

Herein, we report the results of CW-EPR and pulsed HYSCORE spectroscopies (Fig. 1a)

corroborated by quantum chemical investigations (DFT, CASSCF) of the Ni(II)–NO adducts

inside the channels of zeolite ZSM-5. Identification of the adsorption adduct was assured by

means of IR, EPR, and HYSORE methods allowing for extraction of g tensor and 14

N

hyperfine tensor parameters, as well as 27

Al quadrupole couplings due to zeolite backbone.

CASSCF calculations showed that the dominant contribution (87%) to the electronic wave

function results from the following configuration |(dxy)2(dxz)

2(dyz)

2(dz

2)(dx

2-y

2)(x

*)0(y

*)|

(tantamount to Ni(II, S = 1) + NO (0, S = 1/2) system). It indicated that the resulting magnetic

properties results from antiferromagnetic coupling between two open shell subsystems: Ni(II)

and NO (Fig. 1b).

Fig. 1. a) HYSCORE spectrum and its simulation for Ni(II)–NO adduct inside ZSM-5 zeolite and b) DFT

optimized cluster showing structure of Ni(II)–NO along with the spin density contour in broken symmetry

state (antiferromagnetic coupling between Ni(II) and NO is shown).

Acknowledgement

This work was financially supported by National Science Center Poland based on the decision

no. DEC-2013/11/D/ST4/02838.

References [1] P. Pietrzyk, K. Podolska, T. Mazur and Z. Sojka, J. Am. Chem. Soc., 133 (2011) 19931.

25


Plenary lecture

ULTRA-SENSITIVE IN-OPERANDO DETECTION AND IMAGING OF

PARAMAGNETIC DEFECTS IN SILICON SOLAR CELLS

K. Lips1, A. Schnegg

1, W. Akthar

1, J. Möser

1, I. Katz

2, A. Blank

2 C. Meier

3, J. Behrends

3, J.

Anders4

1 Berlin Joint EPR Lab, Helmholtz Zentrum Berlin für Materialien und Energie, Germany

2 Schulich Faculty of Chemistry, Technion, Israel

3 Berlin Joint EPR Lab, Fachbereich Physik, Freie Universität Berlin, Germany

4 Electrical Engineering, Universität Ulm, Germany

[email protected]

Almost 90% of all installed photovoltaic (PV) modules are fabricated using wafer-

based and thin-film silicon technology. The technology has reached a mature stage and current

generation costs of clearly below 0.1US$/kWh are reached. Further cost reduction can only be

achieved by further increasing module efficiency. The current efficiency record for silicon

solar cells is 26.6 % and was made possible due to excellent passivation and electrical

properties of the only 3-10 nm thin amorphous silicon (a-Si:H) layer that forms a charge

selective heterocontact with the crystalline silicon (c-Si) absorber. This then replaces the

classical silicon homo-pn junction that is achieved through phosphorus and boron doping of c-

Si. Despite the enormous success of this silicon heterojunction solar cell many open question

remain about the stability as well as the nature of the defect states of the thin a-Si:H contact

layer. Most of these defects are paramagnetic and are induced by are induced by compositional

and material disorder. These paramagnetic defects act as charge-carrier traps and

recombination centers. However, fully processed high efficiency PV devices with complex

morphologies typically do not exhibit enough paramagnetic states to be observed by EPR.

However, due to the weak spin-orbit coupling in silicon these defects can induce spin-

dependent charge carrier transport and recombination which can be detected with many orders

of magnitude higher sensitivity then EPR in pulsed and cw electrically detected magnetic

resonance experiments (pEDMR and cwEDMR, respectively).

After a short review of the status of PV technology, we will introduce the EDMR technique

and discuss the potential of combined EPR/EDMR for the study of intrinsic and light-induced

defects (LID) in a-Si:H materials [1,2] and heterojunction solar cells [3]. Structural information

obtained from pulsed multi-frequency EPR is complemented by cw and pEDMR ranging from

X-band up to 263 GHz. Benefiting from the increased resolution of multi-frequency EDMR

and the possibility to coherently manipulate coupled spins by pulsed EDMR excitation

schemes [4], a complete picture of charge carrier transport and recombination in silicon

materials and solar cells can be achieved. In addition, we will demonstrate how pEDMR in

combination with pulsed field gradients [5] provide in operando spatially resolved defect maps

of solar cells. An outlook to fascinating new applications of pEDMR using EPR-on-a-chip

concepts will be given.

References 1. M. Fehr, et al., Phys. Rev. Lett., 2014, 112, 066403

2. M. Fehr, et al., Phys. Rev B, 2011, 84, 245203/1-1

3. B.M. George, et al., Phys. Rev. Lett., 2013, 110(13), 136803

4. A. Schnegg, et al., PCCP, 2012, 14 (42), 14418-38

5. I. Katz, et al. Journal of Magnetic Resonance 251 (2015) 26–35

26


Schematic presentation of cationic

complexes [M2(μ-X)(μ-Lm)2]3+, R=H

[M2(μ-X)(μ-Lm*)2]3+,R=CH3

Invaited speaker

ISOTROPIC AND ANISOTROPIC SPIN-SPIN INTERACTIONS IN

METALLACYCLES WITH SINGLE M-X-M BRIDGES

J. Jezierska1, A. Ozarowski

2, D. L. Reger

3

1Faculty of Chemistry, Wroclaw University, Wroclaw, Poland

2National High Magnetic Field Laboratory, Florida State University, Tallahassee, Florida, USA.

3Department of Chemistry and Biochemistry, University of South Carolina, Columbia,

South Carolina, USA.

Two ligands composed of two

bis(pyrazolyl)methane units linked by a m-substituted

arene spacer; bis[bis(1-pyrazolyl)methyl]benzene, (Lm

with R=H) and m-bis[bis(3,5-dimethyl-1-pyrazolyl)-

ethyl]benzene, (Lm* with R=CH3), have become a

basis for the syntheses [1-4] of cationic binuclear

metallacycles (see Scheme) in which two metal(II)

ions (M) are held in close proximity by single M-X-M

bridges. It was shown by X-ray crystal studies that the

bulky Lm* ligand rigorously enforces the linearity of

the bridging group, while Lm allows formation of the

bent bridges.

In this presentation we intend to overview the

magnetic and EPR properties of 3d transition metal

complexes shown in the Scheme by taking into

account the effects induced by:

a) bridges X = F−, Cl

−, Br

−, OH

− in the complexes with M=CuII and Lm* [1]

b) metal ions M = MnII, FeII , CoII , NiII , CuII in the complexes with X = F− and Lm* [2]

c) ligands Lm and Lm* in the complexes with M = CuII and X = OH− [3] or CN

− (μ-1,2

bridge) or N3− (μ-1,1 bridge) [4] as well as with M = CoII and X = OH

− [3].

It is noteworthy that when the molar ratio NiII : Lm = 4 : 2 was used in the synthesis the

tetranuclear cubane-core-hydroxide-bridged cationic complex [Ni4(μ3-OH)4(μ-Lm)2]+4

was

formed, with S=4 ground state [5].

The magnetic properties of the complexes, reflected in the temperature dependence of

magnetic moments, were analyzed in terms of the isotropic spin-spin magnetic interactions

(H = -JS1S2). The anisotropic spin-spin interactions (H = S1DS2), causing splitting of S>1/2

spin states in zero magnetic field, were measured by EPR at microwave frequencies 9 - 420

GHz and at various temperatures.

DFT calculations allowed to predict the efficiency and pathways of the isotropic spin-spin

interactions ("broken symmetry") illustrating the nature of metal magnetic orbitals in the

dinuclear complexes and tetranuclear cubane with metal ions in a distorted trigonal-bipyramid

and octahedron, respectively.

References

[1] D. L. Reger, A. E. Pascui, M. D. Smith, J. Jezierska, A. Ożarowski, Inorg. Chem., 2012, 51, 7966

[2] D. L. Reger, A. E. Pascui, M. D. Smith, J. Jezierska, A.Ożarowski, Inorg. Chem., 2012, 51, 11820

[3] D. L. Reger., A. E. Pascui, E. Foley, M. D. Smith, J. Jezierska, A. Ożarowski, Inorg. Chem., 2014, 53, 1975.

[4] D. L. Reger., A. E. Pascui, E. Foley, M. D. Smith, J. Jezierska, A. Ożarowski, Inorg. Chem., 2015, 54, 1487

[5] D. L. Reger., A. E. Pascui, P. J. Pellechia, M. D. Smith, J. Jezierska, A. Ożarowski, Inorg. Chem., 2014, 53,

4325

27


Oral presentation

EPR AND DFT INSIGHT INTO INTERACTION BETWEEN O-SEMIQUINONE

RADICALS AND METAL IONS

M. Witwicki1, M. Jerzykiewicz

1, J. Jezierska

1, A. Ozarowski

2

1 Faculty of Chemistry, Wrocław Uniwersity, ul. . F. Joliot-Curie 14, 50-383 Wrocław, Poland

2 National High Magnetic Field Laboratory, Florida State University, 1800 E. Paul Dirac Drive,

Tallahassee, FL 32310, USA

Semiquinones are organic radicals being the intermediate form in the redox equilibrium

between quinones and hydroquinones. These radicals are present in all life forms as they act as

electron-transfer agents in the mitochondrial respiratory chain and in the reaction centres of

bacterial and plant photosynthesis [1,2]. Moreover, they are indigenous to natural polyphenols

(e. g. humic acids, tannins, lignin) [3,4]. o-Semiquinones are known to possess chelating ability

towards metal ions [5,6], which is particularly important for the activation of electron transfer

through interaction with cations acting as Lewis acids [6]. In this work EPR spectroscopy and

density functional theory (DFT) were used to elucidate the interaction between o-semiquinone

radicals and various diamagnetic metal ions: Mg2+

, Ca2+

, Hg2+

and Pb2+

[7-11]. The effect of

complexation on the molecular and electronic structures of the radicals were established and

correlated with the g tensor.

Fig. 1. EPR spectrum, DFT-predicted molecular structure and the singly occupied molecular orbitals of the

o-semiquinone – Hg(II) complex

References [1] S. Ohashi et al., Photosynth. Res. 104, (2010) 305.

[2] J. Barber, Chem. Soc. Rev. 38, (2009) 185.

[3] N. Senesi, Application of Electron Spin Resonance (ESR) Spectroscopy in Soil Chemistry, in B. A. Stewart

(Ed.), Advances in Soil Science Volume 14, Springer-Verlag, New York, (1990) 77-130.

[4] C. Bahrle, T. U. Nick, M. Bennati, G. Jeschke, F. Vogel, J. Phys. Chem. A 119, (2015) 6475.

[5] K.E. Vostrikova, Coord. Chem. Rev. 252, (2008) 1409.

[6] S. Fukuzumi, K. Ohkubo, Y. Morimoto, Phys. Chem. Chem. Phys. 14, (2012) 8472.

[7] M. Witwicki, M. Jerzykiewicz, A. R. Jaszewski, J. Jezierska, A. Ozarowski, J. Phys. Chem. A 113 (2009),

113, 14115.

[8] M. Witwicki, J. Jezierska, J. Phys. Chem. B 115 (2011), 3172.

[9] M. Witwicki, J. Jezierska, Theor. Chem. Acc. 132, (2013), 1383.

[10] M. Witwicki, M. Jerzykiewicz, A. Ozarowski, Chemosphere 119, (2015), 479.

[11] M. Jerzykiewicz, M. Witwicki, J. Jezierska, Chemosphere 138, (2015), 233.

28


Oral presentation

FORMATION OF REACTIVE OXYGEN SPECIES ON THE AMORPHOUS

NONREDOX MATERIALS DURING REACTION WITH H2O2

K. Sobańska,1 P. Pietrzyk

1, Z. Sojka

1


[email protected]

H2O2 decomposition is commonly catalyzed by transition-metal oxides, but also less

conventional materials of non-redox nature, such as amorphous transition-metal oxides, exhibit

activity in generation of reactive oxygen species (ROS) from H2O2. The redox active materials

show typical Fenton-like reactivity, while for the non-redox oxides formation of ROS is not

trivial and involves interfacial electroprotic reactions [1]. In this contribution reactivity of

amorphous ZrO2 oxide toward formation of ROS during interaction with H2O2 in aqueous

solutions was investigated by means of EPR spectroscopy, and auxiliary spectroscopic

techniques (Raman and UV-Vis).

The presence of superoxo groups was confirmed by EPR spectroscopy. The EPR spectra

recorded after treatment with H2O2 solution at various pH values represent a signal

characteristic of surface-stabilized O2–

species. The symmetry and shape of the signal is

insensitive to pH, while its intensity changes strongly with acidity of the reaction medium. The

obtained spin-Hamiltonian parameters values (gxx = 2.0029, gyy = 2.0095, gzz = 2.0329) are

typical of superoxides. Temperature behavior of the observed signal (10 K – 77 K) and

additional HYSCORE measurements showed that O2–

species were stabilized via H-bonding

with surface hydroxyls, on the contrary to a reference material of amorphous Nb2O5, for which

the presence of hyperfine splitting due to 93

Nb (I = 9/2) nuclei indicated direct bonding with

the metal core [1].

Generation of OH radicals in the ZrO2/H2O2 system was confirmed by means of EPR using

DMPO spin trap and additionally with the characteristic reaction involving OPD substrate.

After admission of amorphous ZrO2 to H2O2 aqueous solution in the presence of OPD, a band

in the UV-Vis spectrum located at around 440 nm appeared, proving formation of OH

radicals.

The spectral intensities of detected types of ROS changed strongly with pH of the reaction

mixture. This observation indicated that the processes leading to ROS generation must have

involved a proton transfer step. The experimental relationship between the concentration of OH and O2

– radicals versus pH showed that both types of ROS were formed simultaneously

following the electroprotic mechanism (HO2– + H2O2 = O2

– +

OH + H2O). Thus, it was

shown that amorphous ZrO2 exhibited peroxidase-type reactivity, and consequently, the nature

of ROS could effectively be controlled by varying pH of the reaction medium.

Acknowledgement

This work was financially supported by National Science Center Poland based on the decision

no. DEC-2015/17/N/ST5/01956.

References [1] M. Ziółek, I. Sobczak, P. Decyk, K. Sobańska, P. Pietrzyk and Z. Sojka, Appl. Catal. B: Environmental, 164

(2015) 288.

29


Oral presentation

RADIATION-INDUCED PARAMAGNETIC CENTERS IN SOME BORATE GLASSES

B. V. Padlyak1,2

1 Division of Spectroscopy of Functional Materials, Institute of Physics

, University of Zielona Góra,

4a Szafrana Str., 65-516 Zielona Góra, Poland 2 Sector of Spectroscopy, Vlokh Institute of Physical Optics, 23 Dragomanov Str., 79-005, Lviv, Ukraine

The undoped lithium tetraborate (Li2B4O7) and other borate single crystals are

characterized by very high radiation stability to influence of different kinds of ionizing

radiation. Only fast and thermal neutrons of high fluence (more than 1015

cm2

) leads to

generation of stable paramagnetic centers in the lattice of Li2B4O7 single crystals, which were

investigated in [1,2] by electron paramagnetic resonance (EPR) technique.

In this report the X-band ( 9.4 GHz) electron paramagnetic resonance (EPR) spectra of the

series borate glasses with LiB3O5, SrB4O7, CaB4O7, Li2B4O7, KLiB4O7, SrB6O10, and

LiCsB6O10 chemical compositions, irradiated by high dose of the - ray (107 Gy) and X - ray (1

2 · 104 R) at room temperature have been presented and analyzed. The nominally-pure borate

glasses of high chemical purity and optical quality were obtained from corresponding

polycrystalline compounds by standard glass synthesis using technological conditions

described in [3].

The analysis of EPR spectra of the - and X - irradiated borate glasses shows presence

radiation-induced paramagnetic centers stable at room temperature practically in all

investigated glasses. The most intense and well-resolved EPR spectra of the radiation-induced

centers have been observed in the Sr-contained borate glasses. Detailed analysis of the

observed EPR spectra shows that the registered spectra belong to radiation-induced

paramagnetic centers, which can be described in the framework of model of the O hole centers

in different sites of borate glass network. The 4-component EPR spectrum of the O centers are

related to the superhyperfine (SHF) structure, caused by interaction of the unpaired electron

spin with one nearest nucleus of the 11

B magnetic isotope (nuclear spin I = 3/2, natural

abundance – 80.1 %). In the irradiated borate glasses also were observed weak EPR signal with

7-component SHF structure that belong to the O centers, localized near one nucleus of the

10B

isotopes (nuclear spin I = 3, natural abundance – 19.9 %). Observed in the irradiated borate

glasses unstructured anisotropic EPR signal can be ascribed to the O hole centers, localized

near non-magnetic isotopes in the glass network. The EPR spectra of anisotropic O hole

centers without SHF structure were observed previously in the neutron-irradiated Li2B4O7

single crystals [1,2] as well as in the γ - and X - irradiated glasses of CaO-Ga2O3-GeO2 system

[4].

The features of EPR spectra, electronic and local structure and mechanisms of creation of the

radiation-induced centers in the borate glasses with different chemical composition are

discussed in comparison with available referenced data for EPR spectroscopy of the γ -, X -,

and neutron-irradiated borate crystals and glasses. Possible applications of the borate glasses

for radiation protected dosimetry as well as for different devices in space systems have been

considered.

References [1] Ya.V. Burak, B.V. Padlyak and V.M. Shevel, Nucl. Instr. Meth. Phys. Res. B 191 (2002) 633.

[2] Ya.V. Burak, B.V. Padlyak, V.M. Shevel, Radiat. Eff. Defects Solids 157 (2002) 1101.

[3] B.V. Padlyak, S.I. Mudry, Y.O. Kulyk, A. Drzewiecki, V.T. Adamiv, Y.V. Burak and I.M. Teslyuk, Mater.

Sci. Poland 30 (2012) 264.

[4] B.V. Padlyak, Radiat. Eff. Defects Solids 158 (2003) 411 .

30


Oral presentation

FATTY ACIDS BINDING SITES AND CONFORMATIONAL CHANGES BY THE

BINDING OF THEM ON BOVINE SERUM ALBUMIN

A. Oleszko1, P. Mikoda

1, K. Gałecka

1, M. Komorowska

1

1 Wrocław University of Science and Technology

Department of Biomedical Engineering

Wybrzeże Wyspiańskiego 27

50-370 Wrocław, Poland

Human serum albumin (HSA) is a major protein component of blood plasma. It serves

as a transport protein for several endogenous compounds, such as unesterified fatty acids (FA)

and bilirubin, and is also capable of binding a broad spectrum of therapeutic agents. Drug

binding to HSA (human serum albumin) can result in a prolonged in vivo half-life. Thus, the

binding property of drugs to HSA is one of the most important factors determining their

pharmacokinetics [1]. Human serum albumin, as well as bovine serum albumin (BSA)

possesses multiple fatty acid binding sites of varying affinities, but the precise locations of

these sites have remained elusive. The determination of the crystal structure of human serum

albumin complexed with myristic acid (MYR) recently revealed the positions and architecture

of six binding sites on the protein [1,2].

Fig. 1. Ribbon model of HAS, fig 1a and HSA-MYR complex fig. 1b, derived from x-ray crystallography

(PDB entry 1E7G). HSA is composed of three homologous domains I–III, each of which is divided into two

subdomains, A and B. The six MYR molecules bonding into sites are shown on the fig 1b. The FA binding

sites are numbered from 1-6. Figures 1A and 1B clearly shows a conformational change of the protein due

to binding of the fatty acids.

In presented study, two high and low affinity FA binding sites on BAS (bovine serum albumin)

were discussed, based on the results of binding spin labeled FA (X-band EPR), and possible

conformational changes of BSA by ATR-FTIR methods.

References [1] S. Curry, P. Brick, N. P. Franks, Fatty Acid Binding to Human Serum Albumin: New Insights from

Crystallographic Studies, Biochim. Biophys. Acta 1441 (1999) 131-140

[2] S. Fujiwara and T. Amisaki, Identification of High Affinity Fatty Acid Binding Sites on Human Serum

Albumin by MM-PBSA Method, Biophysical Journal 94 (2008) 95–103 H. Author, M.E. Author and H.M.

Author, Journal Name Volume, (Year) page.

31


Invaited speaker

ESR INVESTIGATION OF FUNCTIONALIZED MAGNETITE NANOPARTICLES

R. Krzyminiewski1, B. Dobosz

1, J. Kurczewska

2, G. Schroeder

2

1 Medical Physics Division, Faculty of Physics, Adam Mickiewicz University, Poznań, Poland

2 Department of Supramolecular Chemistry, Faculty of Chemistry, Adam Mickiewicz University, Poznań, Polska

[email protected]

Nanoparticles are considered as potential drug carriers in targeted therapies, e.g. anti-

cancer. Some of them can have a magnetic core e.g. magnetite or maghemite. Because of a

magnetic core, they may be controlled by appropriate magnetic fields. This would allow

directing functionalized nanoparticles to the affected area, e.g. a tumor and save the healthy

tissues. An excellent method for investigation the physical properties of functionalized

magnetite nanoparticles and their diffusion in the magnetic field is electron spin resonance

(ESR) [1-3].

In this study TEMPO-functionalized magnetite nanoparticles in water, chloroform and

toluen solutions with three different coatings: chitosan, silane or PEG, have been investigated.

In order to examine differences in the diffusion rates they were also added to human blood or

human serum. The ESR measurements were performed using X-band (9.4 GHz) Bruker

ESR/ENDOR EMX-10 spectrometer. The ESR spectra were recorded in the temperature range

of 115 K– 300 K in a magnetic field sweep width of 650 mT and 20 mT [1,3]. So called field

cooling method FC was also used for calculation magnetic properties of magnetic core and

dynamics of spin labels attached to the core. To investigate the diffusion rate the sample was

kept in the inhomogeneous magnetic field which source was a neodymium magnet. In this part

of experiment the sample was measured in 230 K. Ten positions of a sample in a resonator

were measured and then using a special own software the concentration of nanoparticles in

particular layers was determined giving the information about the previously diffusion [2].

For all ESR spectra typical spectroscopic parameters like g-factor value, peak-to-peak

line width (ΔHpp) and for TEMPO correlation time (τ) have been determined. On the basis of

these results for functionalized nanoparticles two types of information can been obtained: one

about the magnetite core and the second one about the dynamics of TEMPO [1]. The results of

nanoparticles diffusion in different solvents (water, human blood or human serum) were shown

that the rate of this process depends on the solvent and the time during which the sample is

kept in the inhomogeneous magnetic field [2]. The advanced CREM method of increasing

resolution of experimental spectra was used. Thanks to this analysis the narrow central line was

detected with isotropic g-value and amplitude increasing with increasing temperature. Probably

this line is connected to the amorphous surface of nanoparticle magnetic core [3].

References [1] B. Dobosz, R. Krzyminiewski, G. Schroeder and J. Kurczewska, Journal of Physics and Chemistry of Solids

75 (2014) 594–598.

[2] B. Dobosz, R. Krzyminiewski, G. Schroeder and J. Kurczewska, Current Applied Physics 16 (2016) 562–567.

[3] B. Dobosz, R.Krzyminiewski, M.Koralewski and M.Hałupka-Bryl, Journal of Magnetism and Magnetic

Materials 407 (2016) 114–121.


32


Oral presentation

APPLICATION OF QUALITATIVE STANDARDS TO INTERPRETATION OF EPR

SPECTRA OF PLANT MATERIAL

M. Kurdziel1, M. Łabanowska

1, M.Filek

2

1Faculty of Chemistry, Jagiellonian University, Kraków, Poland

2The Franciszek Górski Institute of Plant Physiology, Polish Academy of Sciences, Kraków, Poland

[email protected]

EPR spectra of native plant material are often very complex and their interpretation is

sometimes uncertain. In order to improve the scientific reliability of attribution of signals to

defined species, the standard samples of particular compounds found in plant tissues have been

applied. As biological material grains of various cereals as well as their parts have been used.

The signals found in their spectra have been preliminary ascribed to transition metal ions, such

as Fe(III), Mn(II) in organic and inorganic surroundings. Moreover, several types of organic

radicals’ signals have also been detected. It has been assumed that they originated from carbon

centered radicals and radicals of phenoxyl type.

Mn(II) signal present in the spectra consisted of two lines with the g factor about 2.0. Well

resolved six lines of hyperfine structure with A 9.2 mT were overlapped on a broad signal.

The g value has suggested the oxide surroundings of Mn ions. Therefore, the samples of Mn(II)

ions in low and high concentration, dispersed in MgO matrix, have been chosen as standards.

The spectrum of a sample containing low Mn(II) concentration has shown characteristic hfs

typical for isolated Mn species. With the increasing amount of Mn(II) in the samples the signal

broadened and lost its hf structure, which was caused by increasing dipole – dipole

interactions.

Signals of Fe(III) with g in the range of 2.2 - 2.3 recorded at room temperature disappeared at

77 K, indicating that paramagnetic ions Fe(III) were antiferromagnetically coupled.

Simultaneously, the broad signal at g about 2.4 - 2.6 grew with lowering temperature. It has

been known, that in plant material iron species are accumulated in the inorganic “iron-core” of

ferritin as well as in the ferritin protein shell. Therefore, the sample of ferritin of biological

origin was registered as a standard. The parameters of standard spectrum and its temperature

characteristics were similar to those observed in grains spectra.

The structures of the spectra of some radical species recorded in grains suggested their origin

from carbon centered radicals. Such radicals can be formed in carbohydrate and protein

biomolecules, hence, the samples of saccharose, starch and albumine with radicals generated

by UV-irradiation and thermal treatment were used as standards. Character of their signals and

EPR parameters confirmed our supposition.

The origin of the second type of organic radicals was proved by comparing their signals with

those found in the spectra of samples of hydroquinone and tyrosine subjected to UV treatment.

33


Oral presentation

ELECTRON DONOR-ACCEPTOR PROPERTIES OF MELANIN STUDIED BY EPR

AND REDOX POTENTIOMETRY

Z. Matuszak1

1Department of Medical Physics and Biophysics, Faculty of Physics and Applied Computer Science, Academy of

Mining and Metallurgy, AGH-UST, Cracow, Poland

[email protected]

Melanins are natural pigments of polymeric character, widespread in virtually all living

organisms, both in animal and plant kingdoms. In mammals these polymers are found

principally in the skin, hair, in the eye, the brain and in the inner ear. Melanin has many

functions: it can act as radicals scavenger, chelating agent, binds many organic compounds,

xenobiotics etc. The most known function of these pigments are their photoprotective

properties. Light absorption by the polymer is accompanied by redox reactions and electron

transfer processes within its granules. Protection against the oxidative and nitrosative stress by

melanin is also related to its redox activity. Melanin itself is paramagnetic. The intensity of

EPR signal of melanin is often used as measure of its redox activity. Despite many studies of

the redox interactions of melanins with various oxidizing and reducing agents, only few

investigations were focused on the fundamental redox properties of these polymers, e.g. the

redox potential E0 of melanin remains unknown.

In this communication a series of redox titration of DOPA-melanin (DM) in acidic

solution with various strong oxidants such as KMnO4, CeSO4, K2Cr2O7 etc. is reported. Changes

in redox potential values of DM/oxidant solution during titration were monitored using

platinized platinum electrode. EPR spectroscopy was used for additional control of progress of

reaction (detection of paramagnetic products of redox reaction).

A direct electron transfer (ET) between DM redox active groups (quinones) and oxidant

was confirmed in separated SE-EPR (Simultaneous Electrochemical EPR) experiment, in

which reaction between KMnO4 and DM was conducted on electrochemical way i.e. with

spatially separated reagents. Reduction of Mn(VII) to Mn(II) on helical platinum electrode

placed in EPR cavity was observed.

The redox titration curves of melanin are strongly asymmetric and the measured redox

potential remains practically constant during titration. These facts indicate that ET reactions of

melanin have a cooperative character, and that melanin itself demonstrates a huge redox

capacity. An apparent redox potential E0 for DM was estimated, E0≈700 mV (vrs. NHE).

In order to explain the cooperative character of ET processes in melanins (linear

dependence of melanin E0 on oxidation degree), a simple theory of ET equilibria based on

theory of lattice gases (Ising model) in mean-filed approximation was formulated and tested.

34


Invaited speaker

GRAPHENE OXIDE – EPR AND IMPEDANCE NEW INTERPRETATION

S. Łoś1, W. Kempiński

1, T. Bandosz

2, M. Kempiński

3

1Institute of Molecular Physics Polish Academy of Sciences, ul. M. Smoluchowskiego 17,

60-179 Poznań, Poland 2Department of Chemistry, The City College of New York, 160 Convent Ave,

New York, 10031, USA 3Faculty of Physics and NanoBioMedical Centre, Adam Mickiewicz University,

Umultowska 85, 61-614 Poznań.

[email protected]

The granular carbon materials became important as they can be used in devices for

energy storage and conversion [1-3]. Discovering the graphene results in increase of the

interest in carbon physical and chemical properties. It is supposed that a surface

functionalization allow to achieve materials for water dissociation reaction [4, 5]. We repot an

EPR and an impedance characterization of modified carbon materials. The EPR method is

excellent for testing the electronic states localized on the surface. The spectrum of common

granular active carbons consists of one slightly asymmetric line [6]. Its deconvolution reveal

three different electron states. However, EPR of graphene oxides of similar granular

distribution is characterized by the dysonian line-shape. It reveals a much higher density of

electrons delocalized within conducting band. The impedance spectroscopy is a

complementary method, which allow to investigate conductive properties of the sample. The

EPR double integral follow to temperature increase of the impedance. Such relation reveal that

localized state observed in EPR signal can be originated from electronic states located on the

interface between carbon grains and adsorbed molecules.

Acknowledgment

This work has been partially supported by grants: DEC-2013/09/B/ST4/03711 and DEC-

2013/11/B/ST3/041900.

References [1]. E. Frackowiak, F. Béguin “Carbon materials for the electrochemical storage of energy in

Capacitors” Carbon 39 (2001) 937–950

[2]. J. R. Miller and P. Simon “Electrochemical capacitors for energy management”. Science Magazine. 321

(2008) 651-652

[3]. D. Wang, F. Li, M. Liu, G. Q. Lu, and H. Cheng “3D Aperiodic Hierarchical Porous Graphitic Carbon

Material for High-Rate Electrochemical Capacitive Energy Storage” Angew. Chem. Int. Ed. 47 (2008) 373 –376

[4]. Y. A. Shaban, S.U.M. Khan “Visible light active carbon modified n-TiO2 for efficient hydrogen production by

photoelectrochemical splitting of water” Int. J. Hydrogen Energ. 33 (2008) 1118 – 1126

[5]. J. H. Park, S. Kim, and A. J. Bard “Novel Carbon-Doped TiO2 Nanotube Arrays with High Aspect Ratios for

Efficient Solar Water Splitting” Nano Letters 6 (2006) 24-28

[6]. Sz. Łoś, M. Letellier, Ph. Azaïs, L. Duclaux “Li doped carbon (activated microporous carbons and

graphite):characterization by resonance spectroscopies (ESR and 7Li NMR) and their potentiality for hydrogen

adsorption” J. Phys. Chem. Solid. 67 (2006) 1181-1185


35


Oral presentation

DIELECTRIC AND EPR STUDIES ON FULLERENES: C60 AND C70

Z. Trybuła1, S. Łoś

1,W. Kempiński

1, M. Trybuła

1

1 Institute of Molecular Physics, Polish Academy of Sciences,

Smoluchowskiego 17, 60-179 Poznań, Poland

[email protected]

The influence of absorbed oxygen from the air on the physical properties of fullerenes:

C60 and C70 will be presented. We will report dielectric and EPR studies of the C60

monocrystalline sample and C60 and C70 thin films [1-7]. The monocrystal of the virgin,

oxygen free C60 exhibits typical first order structural phase transition behavior: There is a

discontinuous change in real part of electric permittivity at the phase transition temperature

[1, 7]. The symmetry is lowered from fcc to sc phase and the lattice parameter changs

by0.005nm [8]. Such alternations implies changes in polarizability of the C60 lattice. However,

the absorbed oxygen affects the mechanism of the structural phase transition at Tc=260K in the

monocrystal of C60. This is the reason of the experimental evidence for the drastic change in

the temperature dependence of the real part of electric permittivity. During the cooling run in

the vicinity of phase transition, the real part of electric permittivity jumps down for oxygen free

C60 monocrystal [1, 3, 7]. For crystal exposure to oxygen [1, 9-11] there is observed an

opposite effect.

The fullerene materials (C60 or C70) with no oxygen contact is EPR silent.

Measurements revealed that light – air exposure causes an increase of the number of C60+ and

C70+ [2, 6] paramagnetic defects. This effect was related to oxygen diffusion into pristine

fullerene samples. If the oxygen is removed by sample vacuum pumping, the amplitude of the

EPR signal decreases. Once again exposure of these materials to the air results in signal

restoring in a very short time. Repeating this procedure in inert atmosphere e.g. with nitrogen

N2 gives no EPR effect.

References [1] Z. Trybuła, Sz. Łoś, W. Kempiński, M. Trybuła and L. Piekara-Sady, J. Phys.: Condens. Matter 21, (2009)

435402.

[2] W. Kempiński, Sz. Łoś, Z. Trybuła, L. Piekara-Sady, A. I. Shames, S. Shutina and E. A. Katz, Karbo 4-5,

(2000) 141.

[3] Z. Trybuła, Sz. Łoś, W. Kempiński, M. Trybuła, S. Shutina, A. I. Shames and E. A. Katz, Karbo 4-5, (2000)

139.

[4] Z. Trybuła and M. Krupski, Acta Phys. Pol. A 98, (2000) 389.

[5] Z. Trybuła, W. Kempiński, Sz. Łoś, I. Shames, S. Shutina and E. A. Katz, Molecular Physics Reports 34/2,

(2001) 154.

[6] W. Kempiński, L. Piekara-Sady, E. A. Katz, A. I. Shames and S. Shutina, Solid State Commun. 114, (2000)

173.

[7] J. Stankowski, W. Kempiński, Z. Trybuła, P. Byszewski and W. Krätschmer, Ferroelectrics 155, (1994) 109.

[8] W. I. F. David, R. M. Ibberson, T. J. S. Dennis, J. P. Hare, K. Prassides, Europhys. Lett. 18, (1992) 219.

[9] B. Pevzner, A. F. Hebard, M. S. Dresselhaus, Phys. Rev. B 55, 1(1997) 6 439.

[10] A. Fartash, Phys. Rev. B 54, (1996) 17215.

[11] T. B. Tang and M. Gu, Fiz. Tverdogo Tela 44, (2002) 607.

36


Oral presentation

STRUCTURAL AND MAGNETIC ORDER AND DISORDER IN METAMAGNETIC

SHAPE MEMORY ALLOYS Ni2Mn1+xIn1-x

M. Kuźma1

1 Biophysics Chair, Rzeszow University , 35 959 Rzeszow , Rejtana 16a , Poland

Shape memory effect (SME) in ferromagnetic shape memory alloys (SMA) based on

Heusler alloys of X-Y-Z type (X = Ni; Y = Mn, Co, Fe; Z = Ga, Sb, Sn, In) is attributed to the

structural transition from high-temperature austenitic phase to low-temperature martensitic

phase and to the combination of ferromagnetic properties of the martensite and thermoplastic

properties of the martensite transformation. There are two groups of the classical SMA :

Ni2MnGa-type and Ni2MnZ-type (Z = Ge, Sn In). The first family shows the SME strongly

enhanced by off-stoichiometric composition of the material, whereas the second family shows

martensitic transition, and therefore the SME, only at off-stoichiometric conditions. It was

observed experimentally that a giant SME was detected when magnetic phase transition at

Curie temperature TC occurs simultaneously with structural austenite-martensite transition at

temperature TM [1]. Merging of these temperatures can be achieved by changing the

stoichiometry. Therefore, the off-stoichiometry is the principal reason of structural disorder

which drives magnetic properties of the SMA. The typical tendency in off-stoichiometric Ni2-

Mn-Ga systems is that martensitic transformation temperature is increased, while Curie

temperature is decreased by deviation from stoichiometry. The increase of Tm is explained by

increase of electron concentration e/a in the system . The lowering of the Curie temperature

arises from decrease of the exchange interaction between Mn atoms.

Fig. 1. An EPR signal of Ni2Mn1+x In1-x (x =0.41) measured at T = 300K (a ) and temperature dependence of

the integral intensity (b).

Magnetic properties of the Ni2Mn1+x In1-x differs from that for Ni-Mn-Ga Heusler alloys, while

magnetization in the austenitic phase (cubic L21) increases with Mn content increasing [2]. It

means that the excess of Mn on In sublattice should be ferromagnetically coupled instead of

antiferromagnetically. Our electron paramagnetic resonance measurements (Fig.1) confirm the

paramagnetic-antiferromagnetic transition in the Ni50Mn35.5In14.5 (x = 0.41) alloy at room

temperature.

References [1] V.V. Khovailo, T. Takagi, A.N. Vasilev, H. Miki, M. Matsumoto, R. Kainuma, Phys. Rev. B 72, 224408

(2005).

[2] C.-M. Li, H.-B. Luo, Q.-M. Hu, R. Yang, B. Johansson, L/ Vitos, Phys. Rev. B 86, 214205 (2012).

37


Oral presentation

ELECTRON PARAMAGNETIC RESONANCE AND OPTICAL STUDY OF

Ca4GdO(BO3)3 SINGLE CRYSTALS AFTER IRRADIATION BY BISMUTH IONS

I. Stefaniuk1, P. Potera

1 A. Badyła

1

1 Faculty of Mathematics and Natural Sciences,

University of Rzeszow1 Pigonia Str., 35-959 Rzeszow Poland

[email protected]

Gadolinium calcium oxoborate Ca4GdO(BO3)3 (GdCOB) crystals are of great interest

due to their excellent nonlinear optical properties [1]. GdCOB has the monoclinic noncentro-

symmetric structure with two molecules per unit cell and space group symmetry Cm [2]. The

EPR measurements were performed at room temperature and in the temperature range from 95

K up to 300 K . The selected EPR spectra are presented in Figs 1 The aim of this paper is to

determine the nature of centers produced in the GdCOB crystal after irradiation by bismuth

ions. Quantitative analysis of EPR spectra has been carried out using the program EMR_NMR

assuming spin Hamiltonian for triclinic site symmetry. The fundamental absorption edge of the

GdCOB crystal is above 47000 cm-1

, in the region below the crystal is transparent. After

irradiation by bismuth ions with energy 11.4 MeV/u (MeV per nucleon) and a fluence 51011

cm-1

at room temperature the growth of absorption of the crystal was observed. We note, that

unstructured absorption growth was early observed in lithium niobate crystal for irradiation by

high energy gadolinium ions with similarity fluency [3]

Fig. 1. Angular dependence of the EPR spectra of GdCOB crystal after irradiation by bismuth ions

References [1] A.Brenier, A.Majchrowski, E.Michalski, T.Łukasiewicz, Opt. Commun., 217, (2003) 395.

[2] F. Mougel, A. Kahn-Harari, G. Aka, D. Pelenc, J. Mater. Chem. 8 (1998) 1619.

[3] B. Canut, R. Brenier, A. Meftah, P. Moretti, S. Ould, S.M.M. Ramos, P. Thevenard, M. Toulemonde, Nucl.

Instr. Meth. B 91, (1994) 312-316.

0 1000 2000 3000 4000 5000 6000 7000

Inte

nsi

ty [

arb

. u.]

Magnetic field [Gs]

Angle [ ] 0 510 1520 2530 3540 4550 5560 6570 7580 8590 95100 105110 115120 125130 135140 145150 155160 165170 175180 185190 195200 205210 215220 225230 235240 245250 255260 265270 275280 285290 295300 305310 315320 325330 335340 345350 355

38


Plenary speaker

MAGNETIC TRANSITION-METAL AND RARE-EARTH ADATOMS ON SURFACES

– EMR PERSPECTIVE

C. Rudowicz1,2

, K. Tadyszak3, M. Karbowiak

4



3 NanoBioMedical Centre, Adam Mickiewicz University, Poznań, Poland

4 Faculty of Chemistry, University of Wrocław, ul. F. Joliot-Curie 14, 50-383 Wrocław, Poland

[email protected]

The atomic scale and low-dimensional magnets based on transition-metal (TM) and

rare-earth (RE) adatoms on surfaces [1,2] have attracted huge interest in view of potential

applications for high-bit density of data storage [3-5]. Due to recent advances in

nanotechnology it is now possible to build magnetic lattices using vertical atom manipulation

and to probe them locally. This gave tremendous boost to scanning tunneling microscopy

(STM) and inelastic tunneling spectroscopy (ITS) studies and opened avenue for realizing

quantum systems and study transitions to classical limit. Extracting experimental quantities

from density functional theory (DFT) and/or ab-initio calculations for adatoms on surfaces

presents significant difficulties. This is partially due to the gap between the DFT/ab-initio

techniques and the semi-empirical ones employed in optical spectroscopy, electron magnetic

resonance (EMR/EPR) spectroscopy, and magnetism. The concepts underlying these areas

form nowadays an intricate web of interrelated notions at the interface between the physical

Hamiltonians and the effective (spin) Hamiltonians [6,7], which are often confused [6-8].

Description of adatoms properties crucially depends on proper interpretation of experimental

STM/ITS data and their meaningful comparison with DFT/ab-initio results [9,10].

In this presentation the following topics will be covered. (1) Introduction to physics behind

adatoms studies, with focus on relationships between the classical magnetic anisotropy energy

(MAE), single-ion anisotropy (SIA), zero-field splitting (ZFS), and spin-flip energy of

tunneling electrons. (2) Links between adatoms studies and EMR techniques based on ZFS

Hamiltonians. (3) Clarifications concerning the MA=ZFS and MA=CF confusion, i.e. labelling

the true ZFS quantities and the true CF (crystal or ligand field) quantities as purportedly the

MA (SIA) quantities [6,10], prevalent in TM and RE adatoms studies, respectively. (4)

Implications of the incorrect relations between MAE (SIA) and ZFS quantities identified in

adatoms literature. (5) Standardization of non-standard ZFSP sets used in adatoms studies.

Finally, we mention the 'ZFS terms' recently introduced for spin S=1/2 'contrary to common

belief' [11,12] and adopted for Cu2+

systems [13].

References [1] H. Brune, P. Gambardella, Surface Science 603, 1812 (2009).

[2] J.-P. Gauyacq, N. Lorente, F. D. Novaes, Progress in Surface Science 87, 63 (2012).

[3] A. Spinelli, M. P. Rebergen, A. F. Otte, J. Physics: Condensed Matter 27, 243203 (2015).

[4] J. Dreiser, J. Physics: Cond. Matter 27, 183203 (2015).

[5] A. Caneschi, D. Gatteschi, F. Totti, Coordination Chemistry Reviews 289–290, 357 (2015).

[6] C. Rudowicz, M. Karbowiak, Coordination Chemistry Reviews 287, 28 (2015).

[7] C. Rudowicz, S. K. Misra, Applied Spectroscopy Reviews 36, 11 (2001).

[8] C. Rudowicz, M. Karbowiak, Physica B: 451, 134 (2014); ibidem 456, 330 (2015).

[9] C. Rudowicz, M. Karbowiak, Phys. Rev. B 93, 184415 (2016).

[10] C. Rudowicz, K. Tadyszak, submitted April (2016).

[11] J. Liu, et al., J. Chem. Phys. 141, 124113 (2014).

[12] H. J. Xiang, et al., Phys. Rev. B 83, 174402 (2011).

[13] A. T. Apostolov, et al., Modern Physics Letters B 29, 1550086 (2015).

39


Invaited speaker

THE EPR SPECTRA OF BULK ANTHRACITE UNDER STRONG COUPLING OF A

SPIN ENSEMBLE TO RESONATOR

R. Fedaruk1, K. Tadyszak

2,3, R. Strzelczyk

3, M.A. Augustyniak-Jabłokow

3

1 Institute of Physics, University of Szczecin, Szczecin, Poland


3 Institute of Molecular Physics PAS, Poznań, Poland

[email protected]

The strong photon-matter coupling, including coupling between a microwave resonator

and an ensemble of electron spins, has attracted increasing attention in quantum information

processing [1,2]. A quantum effect called vacuum Rabi splitting is the signature of this

coupling. Its solid-state analog can be realized in EPR studies of materials with high spin

density and a narrow EPR line. Recently this effect was shown for large samples of anthracite

[3]. But the size- and temperature- dependent anomaly of the EPR signals of anthracite can be

due to the skin effect [4].

In this report we present the temperature dependences of the EPR signal of bulk anthracite. At

low temperatures the strong spin-resonator coupling is revealed by bistability and hysteresis of

EPR signals (Fig. 1 a and b). The weaker coupling results in the super-Lorentzian EPR

lineshape (Fig. 1c). Changes of microwave frequency during EPR signal recording were used

to estimate the spin-resonator coupling strength.

Our results allow discrimination of the strong spin-resonator coupling from other reasons of the

EPR line distortion and correct interpretation of the EPR signals of materials with high spin

density, especially at low temperatures.

Fig. 1. EPR spectra and the microwave oscillator frequency recorded for the large (25 mg) and small (1.4

mg) samples. The microwave power was 0.5 mW. Black and grey lines in (a) and (b) show spectra recorded

with increasing and decreasing magnetic field, respectively. Grey lines in the bottom part of (c) depict two

branches of the microwave frequency due to the Rabi splitting.

References [1] E. Abe, H. Wu, A. Ardavan and J.J.L. Morton, Appl. Phys. Lett. 98, (2011) 251108.

[2] I. Chiorescu, N. Groll, S. Bertaina, T. Mori and S. Miyashita, Phys. Rev. B 82, (2010) 024413.

[3] R. Fedaruk, S.V. Adashkevich, J. Appl. Spectroscopy 81, (2014) 355.

[4] K. Tadyszak, R. Strzelczyk, E. Coy, M. Maćkowiak, M.A. Augustyniak-Jabłokow, Magnetic Resonance in Chemistry 54, (2016) 239.

320,2 320,4 320,6

8,9772

8,9776

8,9780

Mic

row

ave

fre

qu

en

cy,

GH

z

B, mT

(a) T = 4.2 K

EP

R s

ign

al

320,6 320,8 321,0

8,9878

8,9879

8,9880

8,9881

B, mT

(b) T = 25 K

320,6 320,8 321,0

8,9928

8,9930

8,9932

B, mT

(c)

Lorentz line

T = 4.2 K


40


Oral presentation

INTERPRETATION OF “ANOMALOUS” TEMPERATURE DEPENDENCIES OF

EPR SIGNAL INTENSITY IN VARIOUS SYSTEMS

M.A. Augustyniak-Jabłokow1

1 Institute of Molecular Physics, Polish Academy of Sciences, Poznań, Poland

[email protected]

EPR signal intensity is proportional to paramagnetic susceptibility. Therefore, the

signal intensity is expected to be either reversibly proportional to temperature (I~1/T) or, in a

case of conduction electrons, independent of temperature. In practice, one meets a number of

anomalous I(T) dependencies resulting from various factors, such as gradual localization of

conduction electrons [1], thermal exciting to the paramagnetic state [2, 3], changes of the

magnetic order [4] or complicated and conformation dependent structure of energetic levels in

the systems with total spin S>1/2 [5, 6]. There are cases, when similar I(T) dependencies are

due to very different reasons. Analysis of such dependences requires special attention and deep

knowledge about properties of the studied material, but can yield significant information

concerning properties of the studied material

In the present report various approaches to several “anomalous” I(T) dependencies are shown

and discussed.

Fig. 1. Examples of the “anomalous” I(T) dependencies due to: transition to antiferromagnetic state in

graphene – 1; temperature induced changes of conformation of structural fragments in the amorphous

carbon – 2; structural phase transition, which influences order of the energetic levels in the mixed valence

cluster of [V4IV

V2VO7(OCH3)12] crystal – 3 down (temperature) and 3 up. For comparison the Curie–type

dependence is shown – 4.

References [1] K. Tadyszak, M.A. Augustyniak-Jabłokow, A.B. Więckowski, L. Najder-Kozdrowska, R. Strzelczyk, B.

Andrzejewski, Carbon, 94, (2015) 53.

[2] G. Wagoner, Physical Review 118 (1960), 647.

[3] K.Lewandowska, W. Bednarski, G. Milczarek, S. Waplak, A. Graja, A., E.Y. Park, T.D. Kim,K.S. Lee,

Synthetic Metals 161 (2011). 1640.

[4] M.A. Augustyniak-Jabłokow, K. Tadyszak, M. Maćkowiak, Y.V. Yablokov, physica status solidi (RRL), 5(8),

(2011) 271-273.

[5] M.A. Augustyniak-Jabłokow, S.A. Borshch, C. Daniel, H. Hartl, Y.V. Yablokov, New Journal of Chemistry

29, (2005) 1064.

[6] Khavryuchenko, M.A. Augustyniak, Submitted to Inorganic Chemistry (2016).


41

Poster contributions

42


Poster I

EUPHORBIA TURKESTANICA TANNINS – ANTIRADICAL ACTIVITY,

INTERACTION WITH ALPHA-HEMOLYSIN AND ERYTHROCYTES LIPIDS

M. Bitiucki1, S. Sękowski

1, E. Olchowik-Grabarek

1, N. Abdullajanova

2, M. Zamaraeva

1

1 Institute of Biology, University of Bialystok, Bialystok, Poland

2 Institute of Bioorganic Chemistry, Academy of Science of Uzbekistan, Tashkent, Uzbekistan

[email protected]

Oxidative damage of erythrocytes cause eryptosis and cells elimination from blood

result in anemia. It was found that polyphenols like flavonoids can reduce the oxidative stress

level and protect erythrocytes from damage [1]. Tannins as a group of polyphenolic

compounds [2] may exhibit similar activity. In this study tannins isolated from an Asian plant

Euphorbia Turkestanica (1,2-di-O-galloyl-4,6-valoneoyl-β-D-glucose; 2-O-galloyl-4,6-

valoneoyl-β-D-glucose and 3-O-galloyl-4,6-valoneoyl-β-D-glucose) have been investigated

using EPR spectroscopy to analyze the scavenging activity against stable free radicals DPPH

(2,2-diphenyl-1-picrylhydrazyl). We have found that studied tannins possess the antiradical

activity against DPPH in the range 0.5-20 µM. By using fluorescence spectroscopy we have

measured fluorescence quenching of alpha-toxin’s tryptophans, caused by 3-O-galloyl-4,6-

valoneoyl-β-D-glucose, which previously showed antihemolytic activity against the bacteria

Staphylococcus aureus. It has been shown that tannins, depending on the concentration,

significantly reduces the fluorescence signal which indicates its strong binding to alpha-

hemolysin.

Using the same method and Laurdan (fluorescent label), we investigated the influence of

tannins on the liposomes fluidity prepared from human erythrocytes lipids, as a model of cell

membranes. Results of membrane fluidity investigation show that all three tannins cause the

decrease of membrane stiffness.

References [1] F. An, S. Wang, D. Yuan, Y. Gong, S. Wang, Attenuation of Oxidative Stress of Erythrocytes by Plant-

Derived Flavonoids, Orientin and Luteolin, Evid Based Complement Alternat Med., 2016, 2016:3401269

[2] K.T. Chung, T.Y. Wong, C.I. Wei, Y.W. Huang, Y. Lin, Tannins and human health: a review, Critical

Reviews in Food Science and Nutrition, Volume 38, Issue 6 (1998)

43


Poster II

MAGNETIC INVESTIGATIONS OF Nb6Sb3VO25

J. Typek1, G. Zolnierkiewicz

1, M. Bobrowska

1, E. Filipek

2, M. Piz

2

1Institute of Physics, West Pomeranian University of Technology, Szczecin, Poland

2Department of Inorganic and Analytical Chemistry, West Pomeranian University of Technology, Szczecin,

Poland

[email protected]

The compound of the formula Nb6VSb3O25 in the Nb-V-Sb-O system was obtained by

solid state reaction method [1]. EPR and dc magnetisation techniques were used to characterise

magnetically this phase (Fig. 1). Although the nominal valence of the constituting ions

indicated on a non-magnetic substance, Nb6VSb3O25 displayed rich and interesting magnetic

behavior due to numerous defects. The number of magnetic defects was calculated to be

equivalent to roughly of a quarter of vanadium ions in non-nominal +4 oxidation state (3d1,

S=1/2). Dc isothermal magnetisation study indicated that part of other ions may be also in non-

nominal states forming pairs and clusters of magnetic ions.

2.5 3.0 3.5 4.0 4.5

-8

-6

-4

-2

0

2

4

6

8

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0 5 10 15 20 25 30 35 40 450

20

40

60

80

100

120

140

160

180

Magnetic field [T]

EP

R a

mplit

ud

e [a

rb.u

nits]

Magnetic field [kOe]

4 K

290 K

(A)

0 1 2 3 4 5 6 7

0.00

0.05

0.10

0.15

0.20

0.25

290 K

60 K

10 K

Ma

gn

etiza

tio

n [B

/f.u

.]

2 K

(C)

0 50 100 150 200 250 3000.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

EP

R in

teg

rate

d in

ten

sity [a

rb.u

nits]

Temperature [K]

(B)

0 50 100 150 200 250 300

0

10

20

30

40

50

60

70

80

Temperature [K]

Temperature [K]

[1

0-3

em

u/m

olO

e]

FC10 Oe

(D)

Re

cip

rocal E

PR

inte

gra

ted

in

ten

sity [a

rb.u

nits]

[m

olO

e/e

mu

]

Fig. 1. (A) EPR spectra of Nb6Sb3VO25 recorded at 4 and 290 K; (B) Temperature dependence of EPR

integrated intensity (left axis) and reciprocal EPR integrated intensity (right axis); (C) Isothermal

magnetisation registered at four different temperatures; (D) Temperature dependence of magnetic dc

susceptibility, insert shows low-temperature part of the inverse magnetic dc susceptibility.

References

1. E. Filipek, M. Piz, J. Alloy. Compd. 661 (2016) 141.

44


Poster III

SPATIAL- AND SPECTRAL-SPATIAL IMAGING - AN APPLICATION TO EPRI

OXIMETRY

A. Boś-Liedke 1,3

, K. Tadyszak 3, T. Czechowski

3,4, M. Walawender

1,2, Z. Kabacińska

1, S.

Jurga 2,3

1 Department of Medical Physics, Faculty of Physics, Adam Mickiewicz University,

ul. Umultowska 85, PL 61614 Poznan, Poland 2 Department of Macromolecular Physics, Faculty of Physics, Adam Mickiewicz University,

ul. Umultowska 85, PL 61614 Poznan, Poland 3 NanoBioMedical Centre, Adam Mickiewicz University, ul. Umultowska 85, 61-614 Poznań, Poland

4 noviLET ul. Piotrowo 3, 61-138 Poznań

[email protected]

The history of Electron Paramagnetic Resonance Imaging (EPRI) started in 1979 when

this phenomenon was published by Hoch and Day [1]. At that time it was demonstrated that it

is possible to reveal the spatial distribution of paramagnetic centers in diamond. This fact

became a starting point in development of methodology and new equipment for EPR imaging.

There are three widely used techniques in EPRI: Continuous Wave (CW), Pulse, and Rapid

Scan Technique, where CW is the most widely used. There are two ways to perform an

imaging experiment – by the spatial imaging and by the spectral-spatial imaging (SSI). The

first one gives an information about the position of unpaired spins, whereas the second one

about the line width of each point of the image [2]. Moreover the SSI approach determines the

interactions of spin probes with paramagnetic molecules that is used e.g. in imaging of tissue

oxygenation. Therefore, the result of SSI in the case of O2 molecules is an oxygenation map of

the selected tissues.

In the standard SSI, each projection is recorded multiple times with different gradient

amplitudes. Unfortunately, such a procedure cause the 3D and 4D SSI measurements too long

for animal applications.

The following study shows the results of spatial and spectral-spatial image reconstruction

technique (2D, 3D, 2D SSI, 3D SSI), with some signal to noise ratio improvements, allowing

for the shortening of the measurement time.

Acknowledgements

Financial support from the National Science Centre (UMO-2014/15/B/ST4/04946), is

gratefully acknowledged.

References [1] M.J.R. Hoch, A. R. Day, Solid State Communications, 1979, 30, 211 – 213.

[2] T. Czechowski et al. Journal of Magnetic Resonance 248 (2014) 126–130


45


Poster IV

EMR SPECTRA OF ZNO THIN FILMS DOPED WITH HIGH CONCENTRACTION

OF CO AND CR ON QUARTZ AND SAPPHIRE SUBSTRATES

B. Cieniek1, I. Stefaniuk

1, I.Virt

1,2

1Faculty of Mathematics and Natural Sciences, University of Rzeszow, Pigonia 1, 35-959 Rzeszow, Poland

2Ivan Franko Drohobych State Pedagogical University, 24, I. Franko Str., 82100 Drohobych, Ukraine

[email protected]

Diluted Magnetic Semiconductors (DMS) and their properties have potential

applications in the spin-dependent semiconductor electronics [1] due to the spin-spin exchange

interaction between the localized magnetic moments and the band electrons [2]. We have

studied magnetic properties of zinc-oxide composite doped with high concentrations (20%) of

Co and Cr ions. The pulsed laser deposition (PLD) method were used to obtain samples on two

different substrates, quartz glass and sapphire. Samples were annealed in 100 – 250 C for ZnO

with quartz substrate, and 300 - 700 C with sapphire substrate. Electron paramagnetic

resonance (EPR) measurements were carried out and temperature dependence of the EPR

spectra was obtained. The angular dependence in two samples orientation were also obtained.

Analysis of the temperature dependences of the integral intensity of EPR spectra was carried

out using the Curie-Weiss law.

Fig. 1. ZnO:Cr annealed, with Curie temperature equal to 166,6 °C

Fig. 2. ZnO:Cr not annealed, angular dependence with horizontal orientation

References [1] D.D. Awshalom, D. Loss and N. Samarth (Eds.), Semiconductors Spintronics and Quantum Computation,

Springer, Berlin, (2002).

[2] W. Dobrowolski, J. Kossut, Handbook of Magnetic Materials, 15, (Ed. K.H.J. Bushow), Elsevier, (2003).


46


Poster V

EPR STUDY OF Cu-Mn-Zn SPINELS SUPPORTED ON DEALUMINATED HY(–Al)

ZEOLITE

P. Decyk1, A. B. Więckowski

2,3, L. Najder-Kozdrowska

3, M. Ziółek

1, I. Bilkova

1

1 Faculty of Chemistry, Adam Mickiewicz University, Poznań, Poland


3 Institute of Physics, Faculty of Physics and Astronomy, University of Zielona Góra, Zielona Góra, Poland

[email protected], [email protected]

Dealuminated HY(–Al) zeolite has been modified by supporting of Cu-Mn-Zn spinels

according to the procedure given by Fei et al. [1]. The loading of spinels in the HY(–Al)

zeolite was in the range of 0.5-25 wt%. The EPR spectra of samples with 10 wt% loading were

recorded at temperatures from 77 K to 403 K, whereas the spectra of materials with loading of

0.5 to 25 wt% were taken of at 77 K and 293 K. For all samples, independent of loading, three

types of lines were observed in the EPR spectra. The first line is a broad one, which originated

from the spinels on the surface of the zeolite. The second one is an anisotropic line that can be

attributed to four-component hyperfine structure (hfs) from isolated Cu2+

cations (S = 1/2, 63

Cu, 65

Cu, I = 3/2 both). The third signal, an isotropic line comes from six-component hfs of

isolated Mn2+

cations (S = 1/2, 55

Mn, I = 5/2). With the increase in the concentration of spinels

phase individual hfs lines from Cu2+

and Mn2+

undergo broadening due to spin-spin

interactions what causes the reducing of the resolution of spectra measured at 293 K. For all

samples regardless of spinels loading, the spectra recorded at 77 K have shown only a single

nearly symmetric EPR line. The linewidth of these lines growths with increasing the

concentration of the spinels in HY(–Al) zeolite. The analysis of

250 300 350 400

a

b

Inte

nsit

y [

a.u

.]

Magnetic field [mT]

the main values of g and A tensors show that Cu2+

complexes posses the form of elongated octahedra

[2]. The linewidth of individual hfs lines of Mn2+

complexes is strongly dependent on the

temperature, what is illustrated in Fig. 1. This

indicates the role of dynamic processes (e.g.

random tumbling) occurring in the Mn2+

complexes.

Fig. 1. EPR spectra of dealuminated HY(–Al) zeolite doped

with Cu-Mn-Zn spinels (10 wt%) recorded at 273 K (a)

and 373 K (b).

Additionally dealuminated HY(–Al) zeolite doped with Cu-Mn-Zn spinels was also evacuated

at different temperatures. It is worth noting that EPR spectra recorded at 77 K for evacuated

catalyst to 573 K do not show significant changes of the lineshape and the line intensity. Only

evacuation at 673 K caused a dramatic reduction of the signal intensity. This may indicate on

the transformations that took place in the spinels deposited on HY(–Al) zeolite.

References [1] J. Fei, Z. Hou, B. Zhu, H. Lou, X. Zheng, Appl. Catal. A-Gen., 304, (2006) 49.

[2] P. Decyk, A.B. Więckowski, L. Najder-Kozdrowska, I. Bilkova, Nukleonika 60, (2015) 423.



47


Poster VI

FERROMAGNETIC RESONANCE IN NiCoMnIn LAYERS OBTAINED BY PULSED

LASER DEPOSITION

Ł. Dubiel1, M. Kuźma

1, W. Maziarz

2, I. Stefaniuk

3, P. Sagan

1, G. Wisz

4, A. Wal

1

1Faculty of Mathematics and Natural Sciences, Department of Biophysics, University of Rzeszow, Pigonia 1, 35-

959 Rzeszow, Poland 2Institute of Metallurgy and Materials Science of the Polish Academy of Science, 25 Reymonta Str., 30-059

Krakow, Poland 3Faculty of Mathematics and Natural Sciences, Center for Microelectronics and Nanotechnology, University of

Rzeszow, Pigonia 1, 35-959 Rzeszow, Poland 4Faculty of Mathematics and Natural Sciences, Department of Experimental Physics, University of Rzeszow,

Pigonia 1, 35-959 Rzeszow, Poland

[email protected]

The alloys of the type Ni-Mn-Z (Z = Ga, Sb, Sn, In) are potential candidates as

materials for spintronics technology. Depending on composition and temperature these alloys

exhibit ferromagnetic semimetal properties. In the case of the Ni50-xCox Mn50-yIny the Curie

temperature is above room temperature, therefore these alloys may have practical interest. The

layers of Ni50-xCox Mn50-yIny have been grown by means of pulsed laser deposition (PLD) on

(100) Si substrate. The target was bulk Ni50-xCox Mn50-yIny (x=5,y = 14.5) alloy prepared by

induction melting of pure elements under argon atmosphere [1]. The morphology of the layers

and composition were studied by electron microscopy TESCAN Vega3 equipped with EDS

spectrometer Bruker (10 mm2, 133 eV). The layers were grown in PREVAC PLD system using

YAG Nd3+

LITRON laser operating at second harmonic. In Fig.1a. the typical morphology of

the layers is presented .

Fig.1. SEM image of a layer deposited on (100) Si substrate (a), angular dependence of a resonance field (b).

Magnetic properties were investigated on Bruker X band EPR spectrometer (9.36GHz) at room

temperature. The magnetic resonance spectrum consists of one non-symmetric line with

resonance field within wide field range (250-500 mT). The resonance field depends strongly on

a position of the layer in respect to magnetic field (in plane, out of plane). The angular

dependence is addressed according to ferromagnetic resonance.

References

[1] W. Maziarz , Solid State Phenomena 186, (2012) 251


48


Poster VII

WIDE TEMPERATURE RANGE SYSTEM FOR EPR MEASUREMENTS

UP TO 1300 K

Z. J. Frączek1, M. Wencka

1, S. Turczyński

2

1Institute of Molecular Physics Polish Academy of Sciences, Poznań, Poland

2Institute of Electronic Materials Technology, Warszawa, Poland

[email protected]

Heating system for spectroscopic measurements in temperature range from 5 K up to

1300 K is presented. Hardware together with software possibilities contain: X-band

RADIOPAN SE/X 2547 Spectrometer, resonator, quartz cryostat, temperature controller,

temperature sensor, nitrogen dewar, flow meter, nitrogen heating subsystem and control PC

computer. For tests of high temperature EPR measurements we performed experiments of

Y4Al2O7 (YAM) doped by europium that is a new laser, scintillating and sensing material. At

heating run we detected Eu2+

(S=7/2) that exhibit broad EPR spectrum. EPR signal intensities

show two maxima at 425 K and 700 K that are related with oxidation/reduction processes

between Eu2+

and Eu3+

.

Fig. 1. To avoid over heating consecutive measure points are reached in small steps.

49


Poster VIII

MAGNETIC PROPERTIES OF STEEL BALLS INVESTIGATED BEFORE AND

AFTER NITRIDING PROCESS

H. Fuks1, S.M. Kaczmarek

1, G. Leniec

1, J. Michalski

2,3, B. Kucharska

4, P. Wach

2

1 Zachodniopomorski Uniwersytet Technologiczny w Szczecinie

2 Instytut Mechaniki Precyzyjnej

3 Szkoła Główna Gospodarstwa Wiejskiego w Warszawie

4 Politechnika Częstochowska

[email protected]

Nitriding is a thermo-chemical treatment of the steel improves its wear resistance,

corrosion resistance and hardness. Nitrided layer affects the magnetic and electric properties of

the steel. The article presents the results of magnetic and electric studies of nitrided steel balls.

Samples, as well as before and after thermal treatment, were investigated with using EPR and

SQUID techniques. The aim of presented work was to find general connections between

different chemical composition of steel, different procedure of thermal treatment and magnetic

properties concluded from EPR and SQUID investigation.

EPR spectra revealed wide and intense signals visible at whole accessible temperature range.

Position of each signal, far from geff≈ 2 expected for Fe magnetic ions, indicates on complex

nature of responsible magnetic centers. Another feature confirming existence of complex

magnetic sites arises from unusual increasing of the intensity of EPR signal as a function of

temperature.

From the point of view of EPR experiment, magnetic centers are better distinguished for higher

carbon containing materials, whereas low carbonated samples usually gives EPR signal

strongly disturbed and far from expected Lorentzian shape.

Similar situation is observed if one compares the resonance signal before and after thermal

treatment. When nitrogen inclusions appear on the steel surface, the EPR signal becomes more

symmetric and close to standard Lorentzian line.

Well defined thermal processes, described as Nx1021 and Nx1025 also gives significantly

different EPR resonance signal, which indicates that, as well as temperature and time of staying

in nitrogen atmosphere have influence on magnetic properties of presented steel materials.

Results obtained from SQUID experiment confirmed unusual behavior of magnetic

susceptibility as a function of temperature and generally are consistent with EPR results.

In presented work we find out and describe connections between some mechanical, electric and

magnetic properties of investigated steel materials. According to presented results, such

properties could be controlled with using of very sensitive techniques as EPR and SQUID

methods.


50


Poster IX

MONITORING OF PLATELET MEMBRANE FLUIDITY DURING DIALYSIS OF

SHEEP

K. Gałecka1, T. Walski

1, J. Bujok

2, K. Grzeszczuk-Kuć

1, J. Detyna

3, M. Komorowska

1

1 Department of Biomedical Engineering, Wrocław University of Science and Technology, Poland

2 Department of Animal Physiology and Biostructure, Wrocław University of Environmental and Life Sciences,

Poland 3 Department of Mechanics, Materials Science and Engineering, Wrocław University of Science and Technology,

Poland

[email protected]

Platelet plasma membrane is thought to participate in mediating signal transduction

processes. The changes of platelet membrane fluidity is one of the signs of the activation

process or pathological states [1-8]. Among the methods to monitor molecular membrane

organization is the spin probe method where paramagnetic molecules diffusing into a

membrane and reflecting its rigidity states are used. Here we demonstrated a simple way which

provides information on alterations in the membrane fluidity of blood platelets. In this method

platelets in platelet-rich plasma (PRP) samples were studied to avoid washing procedures that

activate cells. The glass surface was employed as an activator by placing the PRP samples in

glass capillaries. Surface-induced platelet activation and accompanied membrane changes were

analyzed by electron paramagnetic resonance (EPR) measurements. The EPR spectra of the 16-

doxylstearic acid labeled platelets were recorded as a function of time and a parameter of the

membrane fluidity were calculated. Activation of platelets was associated with an increase of

fluidity of the membrane to the equilibrium state which was reached after 10 min. contact with

a glass surface that correspond to taking the fully spread form by platelets.

The method was tested on sheep platelets upon haemodialysis (HD) procedures which is

known to promote haemostasis disorders, activate immune cells or impair blood elements [9-

10]. For each animal procedures were repeated ten times as short daily HD sessions. During

each procedure blood was drawn prior to, after ca. 15 minutes and at the end of HD from the

arterial and venous lines and were used as research material. In addition, blood of half sheep

(five) flowing via dialyzer were exposed to near infrared (NIR) radiation. It has been

demonstrated that NIR light can produce a beneficial effects on cells, therefore were applied to

study its protective action during HD.

EPR spectra indicated the reduction of the membrane fluidity of platelets from blood exposed

to NIR radiation. The results of experiments corresponded with better aggregability of

irradiated platelets investigated by impedance aggregometer.

References [1] M. Steiner and E.F. Lüscher, Biochemistry, 23(2), (1984) 247–252

[2] A. Kantar et al., Mediators Inflamm., 1(2), (1992) 127–131

[3] I. Nathan et al., J. Biol. Chem., 254, (1979) 9822–9828

[4] S. Kitagawa, T. Shinohara and F. Kametani, J. Membr. Biol., 79(1), (1984) 97–102

[5] R.D. Sauerheber et al., J. Membr. Biol., 52(3), (1980) 201–219

[6] S.J. Shatti, D.B. Cines and A.D Schreiber., J. Clin. Invest., 61(3), (1978) 582–589

[7] G.S. Zubenko et al., Psychopharmacology (Berl), 145(2), (1999) 175–180

[8] C. Watala et al., Eur. J. Haematol., 61(5), (1998) 319–326

[9] M. Olszewska, Ann. Acad. Med. Stetin, 50, (2004) 41-52

[10] V. Sirolli et al., Int. J. Artif. Organs, 25, (2002) 529-537

51


Poster X

SPIN LABELING STUDIES OF ERYTHROCYTES PROPERTIES IN VARICOSE

VEINS PATIENTS

L. Gwoździński1,2

, A. Pieniążek3, J. Bernasińska

4, M. Grabowski

1, E. Kowalczyk

4, K.

Gwoździński4

1General Surgery Ward, K. Jonscher Municipal Medical Center, Lodz, Poland.

2Department of Pharmacology and Toxicology, Medical University of Lodz, Lodz, Poland.

3Department of Medical Biophysics, Faculty of Biology and Evironmental Protection, University of Lodz, Lodz,

Poland. 4Department of Molecular Biophysics, Faculty of Biology and Evironmental Protection, University of Lodz, Lodz,

Poland.

[email protected]

Introduction: Varicose veins are enlarged veins of the subcutaneous tissue occurring

most commonly on the superficial veins of the lower limb. They are usually caused by faulty

or damaged venous valves leading to impaired blood flow. Blood stasis, excessive clotting

disorder and alterations in the vein walls are symptoms of Virchow’s triad which may affect

the morphotic elements of blood, such as erythrocytes.

Purpose: The aim of this study was to investigate alterations in erythrocytes properties

in varicose veins in comparison to the antecubital vein of patients with chronic venous disease.

The investigation was conducted in whole erythrocytes using spin labeling method in EPR

spectroscopy.

The plasma membrane fluidity was measured using two spin labeled fatty acids (5-DS and and

16-DS). The internal viscosity of cells was determined by Tempamine. The conformation state

of internal proteins, mainly hemoglobin was determined by maleimide spin labels.

Methods: Venous blood samples in EDTA from eight patients with chronic venous disease

(age: 45-55 years) were taken from the antecubital vein and varicose veins. Blood was

centrifuged and erythrocytes were washed thrice with cold PBS solution. The hematocrite was

50%. Erythrocytes were labelled with 5- and 16-doxylstearic acids. The internal viscosity

of cells was determined with Tempamine using Morse method [1]. The state of internal

proteins, mainly hemoglobin, was estimated by maleimide spin label-MSL [2].

Results: A significant increase in lipid membrane fluidity indicated by 5-DS and 12-DS was

observed in varicose vein erythrocytes in comparison to the erythrocytes from the antecubital

vein. The internal viscosity of varicose vein erythrocytes was significantly lower than in the

erythrocytes taken from antecubital vein. However, we did not find changes in the state of

internal proteins in the erythrocytes from varicose and antecubital vein measured using a

maleimide spin label.

Conclusion: The erythrocytes from varicose veins show lower lipid membrane fluidity and

lower internal viscosity than the erythrocytes obtained from antecubital non-varicose veins.

These alterations can result in an increased risk of varicose veins erythrocytes structure

deformations as compared to the erythrocytes from antecubital veins.

References [1] P.D. Morse, Methods in Enzymology, 127, 1986, 239–249.

[2] K. Gwozdzinski, Toxicology, 65, 1991, 315-323.

52


Poster XI

RADIATION DEFECTS IN CALCITE AND THEIR INFLUENCE

ON MECHANICAL PROPERTIES

Z. Kabacińska1*, L. E. Coy

2, R. Krzyminiewski

1, M. Wencka

3

1 Medical Physics Division, Faculty of Physics, Adam Mickiewicz University,

Umultowska 85, 61-614 Poznań, Poland

2 NanoBioMedical Centre, Adam Mickiewicz University, Umultowska 85, 61-614 Poznan, Poland

3 Department of Solid State Radiospectroscopy, Institute of Molecular Physics, Polish Academy of Sciences,

Smoluchowskiego 17, 60-179 Poznań, Poland

[email protected]

Generation and recombination of defects generated by γ, X- and UV radiation in calcite

(CaCO3) and their influence on mechanical properties were investigated [1]. Calcium carbonate

is one of the most abundant minerals in the nature, and it has wide applications in many

branches of industry e.g. as a filler in plastics, rubber and paper [2]. Its property to accumulate

some structural defects, often referred to as the time effects, that appear under the effect of

natural radiation has been used in EPR dating of e.g. cultural objects or constructions [3]. EPR

studies were performed on the X-band (9.7 GHz) Bruker EPR spectrometer (EMX-10 type).

Measurements of mechanical properties were conducted by means of the nanoindentation

technique. Additionally, X-ray diffraction and Scanning Electron Microscopy were used for

sample characterisation. We examined natural and synthetic calcite, subjected to UV irradiation

from a low pressure Hg lamp and to γ irradiation from a Co60 source. Analysis of EPR

measurements has shown that UV light generates similar defects in calcite as γ radiation.

Moreover, our observations confirm a strong correlation between the morphology and size of

crystals and the presence of particular types of defects with characteristic geometries generated

by a particular radiation. Namely, the isotropic symmetry of CO2- defect (g-factor 2.0007) is

favoured in the samples with a less regular morphology of spherical and ‘cigar-like’ aggregates

of smaller crystals, while the orthorhombic CO2- defects (gx = 2.0030, gy = 2.0017, gz =

1.9973) are more abundant in the samples of well-defined rhombohedral crystals. In the less

regular synthetic calcite the UV-induced defects occur in a relatively small concentration.

Measurements of mechanical properties of the natural calcite single crystal revealed a decrease

in hardness and Young modulus after γ, X-ray and UV irradiation. A correlation between these

changes and the type and number of radiation defects was established on the basis of EPR

measurements of a powdered single crystal.

Acknowledgements This work was supported by the Operational Program ’Human Capital’ - PO KL 4.1.1,

’Proinnowacyjne kształcenie, kompetentna kadra, absolwenci przyszłości’.

References [1] Z. Kabacińska, R. Krzyminiewski andB. Dobosz, Rad. Prot. Dos., 159, (2014) 1-6.

[2] H.S. Katz, and J.V. Milewski, Handbook of fillers for plastics, Van Nostrand Reinhold, New York, (1987).

[3] M. Ikeya, New applications of electron spin resonance: dating, dosimetry and microscopy, World Scientifc,

Singapore, (1993).


53


Poster XII

EPR INVESTIGATIONS INTO FORMATION OF NITROSYL COMPLEXES

OF PALLADIUM CATIONS IN ZEOLITES Y AND ZSM-5

A. Krasowska1, K. Podolska-Serafin

1, P. Pietrzyk

1


[email protected]

Nitrogen oxides (NOx) are among the most harmful air polluting compounds. Their

removal requires a catalyst which incorporates selected transition metal ions. One of them is

palladium, which plays an important role in catalytic reduction of NOx. In this context metallo-

zeolites are extensively studied as model systems exhibiting required catalytic activity. The use

of zeolite as a support allows for the generation of isolated cationic centers whose valence

state, being a key factor for interaction with NO, can be controlled to a certain degree.

Owing to its electronic properties, NO molecule (*1) can be studied by means of electron

paramagnetic resonance (EPR) spectroscopy. In fact, EPR is sensitive both to the gas-phase

reactant as well as to the palladium active sites (Pd3+

, 4d7 and Pd

+, 4d

9), whose valence state is

decisive for the EPR parameters or lack of EPR signal (4d8 electron configuration, Pd

2+).

Chemical nature of the active sites depend on the thermal treatment of the samples. When

activated in dioxygen (Fig. 1a), isotropic EPR signal shows formation of Pd(III) cations (giso =

2.23) [1], while reduction in H2 (Fig. 1b) leads to a more complicated, multicomponent signal

(g|| ≈ 2.90 – 2.74 and g ≈ 2.13 – 2.11), characteristic of Pd(I) [1].

Both in the case of oxidized and reduced zeolite, reaction with NO results in an EPR signal

with a characteristic hyperfine structure. It comes from the coupling with the magnetic moment

of nucleus 105

Pd (22.3%, I = 5/2). In addition, in the case of interaction with Pd(I), the

superhyperfine structure can be observed, which was assigned to two nuclei of nitrogen (14

N, I

= 1) coming from dinitrosyl species Pd+(NO)2. While in the case of Pd(I) they are formed by

simple addition reaction 2Pd + 2

2NO =

2{Pd

+(NO)2}, for the oxidized centers reactive

adsorption is observed which leads first to a reduction of Pd3+

to Pd2+

and Pd+, and subsequent

formation of the paramagnetic mono- Pd2+

NO and dinitrosyls Pd+(NO)2.

Fig. 1. EPR spectra (X band, T = 77 K) recorded before and after adsorption of NO on Pd-Y sample after a)

activation in dioxygen and b) reduction in hydrogen.

Acknowledgement

This work was financed by National Science Center Poland based on the decision no. DEC-

2013/11/D/ST4/02838

References [1] L.S. Stokes, D.M. Murphy, R.D, Farley, C.C. Rowlands, S. Bailey, Phys. Chem. Chem. Phys., 1 (1999) 621.

54


Poster XIII

EPR STUDY OF PARAMAGNETIC CENTERS ON A SURFACE OF MODIFIED

NANODIAMONDS

A. Krupska1, R. Strzelczyk

1, M.A. Augustyniak-Jabłokow

1


[email protected]

EPR studies of nanodiamonds [1-2] showed that the observed EPR spectrum is

dependent on the method of production and processing. Nanodiamonds can be obtained by

various method, both static and dynamic ones such as chemical vapor deposition (CVD),

technique of high temperature and pressure (HPHT), detonation of materials containing carbon

and others. In this report we describe results obtained for the detonation nanodiamonds,

separated into individual crystallites and ultrasonically dispersed, to form a stable suspension

in water [3]. The concentration of paramagnetic centers reaches 4x1020 spin/g. Obtained results

indicate presence of both, localized and delocalized centers. We discuss the origin of the signal

and its stability. The possible sources of the EPR signal of nanodiamonds are: dangling bonds

due to broken on a surface sp3 bonds, conduction electron, defects of the bulk and surface

structure of nanodiamonds, paramagnetic impurities eg. NV-, Fe

3+, forbidden transition S=2)

for triplet states. Annealing of nanodiamonds at 500 oC in air removes the graphitized surface

layer and the EPR signal disappears. Annealing thus prepared nanodiamonds in vacuum at a

temperature of ~200 C removes the functional groups and exposes the dangling bonds. EPR

spectrum of such sample is composed of two broad, signals of high intensity, which quickly

disappear with time leaving a weak, broad signal.

Fig.1 EPR spectrum of nanodiamonds; 1 – with graphitized surface; 2 – annealed at 500°C and cleaned in

vacuum at ~200 °C; 3 – the same sample as 2, but after 24 hours; 4 – signal of resonator

References [1] A.I. Shames, A.M. Panich, W. Kempiński et al., Journal of Physics and Chemistry of Solids 63, (2002) 1993-

2001.

[2] A.I. Shames, V.Yu. Osipov, H.J. von Bardeleben and A.Ya. Vul, J. Phys.: Condens. Matter 24, (2012) 225302-

225400.

[3] E.D. Eidelman, V.I. Siklitsky, L.V. Sharonova et al., Diamond & Related Materials 14, (2005) 1765 – 1769.

55


Poster XIV

EPR STUDY OF THE MAGNETIC PROPERTIES OF IRON OXIDE

NANOPARTICLES IN HUMAN BLOOD AND SERUM

T. Kubiak1, R. Krzyminiewski

1, B. Dobosz

1, J. Kurczewska

2, G. Schroeder

2

1 Medical Physics Division, Faculty of Physics, Adam Mickiewicz University in Poznań

2 Department of Supramolecular Chemistry, Faculty of Chemistry, Adam Mickiewicz University in Poznań

[email protected]

Fe3O4 nanoparticles are perfect candidates for drug carriers due to a number of

favorable properties such as biodegradability, chemical stability, low toxicity and

superparamagnetic behavior. However, the research on the properties of functionalized

magnetite nanoparticles and their interaction with human serum and whole blood is crucial

prior to the introduction of nanoparticles into clinical practice.

Functionalized magnetite nanoparticles with a core diameter of 5 nm were investigated in

aqueous solution, human serum and whole human blood by means of X-band (9,4 GHz)

Bruker EPR/ENDOR EMX-10 spectrometer. The measurements were carried at room

temperature and in the temperature range 125-265K. Paramagnetic centers naturally occurring

in the blood (Fe3+

ions in transferrin and methemoglobin; Cu2+

ions in ceruloplasmin) were

identified prior to the addition of nanoparticles. The EPR spectrum of magnetite nanoparticles

has a form of a broad line. The values of EPR line parameters were different for nanoparticles

in water, serum and blood, which indicated the influence of the environment on the properties

and interactions of nanoparticles. Field cooling (FC) experiment showed that the value of g

factor for the orientation 0o is greater than for 90

o, so the external resonance field is higher for

the angle of 90o. The use of computer resolution enhancement method (CREM) allowed to

separate an additional narrow spectral component (g = 1.99) from the EPR spectra of magnetite

nanoparticles. The presence of this line might be related to the phenomena occurring on the

surface of the nanoparticle core.

Fig. 1. The CREM analysis (Lorentz, core width 20 pt.) of EPR signal of magnetite nanoparticles in whole

human blood at temp 230K.

References [1] T. Kubiak, R. Krzyminiewski, B. Dobosz, G. Schroeder, J. Kurczewska, M. Hałupka-Bryl, Acta Bio-Optica et

Informatica Medica Biomedical Engineering 21, (2015), 9-15.

[2] T. Kubiak, R. Krzyminiewski, B. Dobosz, Current Topics in Biophysics 36 (2013), 7-13.

[3] R Krzyminiewski, T Kubiak, B Dobosz, G Schroeder, J Kurczewska, Current Applied Physics 14 (2014), 798-

804.

[4] B. Dobosz, R. Krzyminiewski, M. Koralewski, M. Hałupka-Bryl, Journal of Magnetism and Magnetic

Materials, 40 (2016), 114-121.

56


Poster XV

OPTIMIZATION OF ANTIOXIDANT PROPERTIES OF WATER-IN-OIL AND OIL-

IN-WATER CREAMS WITH BILBERRY, CHOKEBERRY AND ELDERBERRY

EXTRACTS BY ARTIFICIAL NEURAL NETWORKS

K. Makarova1, K. Zawada

1, D. Wagner

1, J. Skowyra

1, M. Trębińska

1, I. Wawer

1

1 Department of Physical Chemistry, Faculty of Pharmacy, The Medical University of Warsaw, Banacha 1, 02-

097 Warsaw, Poland

[email protected]

Oxidative stress and the excess of free radicals accelerate the aging process of human

skin. The application of skin cream with antioxidant compounds could reduce the damage

caused by free radicals. In this work we studied two types of skin creams with extracts from

chokeberry (Aronia melanocarpa), elderberry (Sambucus nigra) and bilberry (Vaccinium

myrtillus) due to their high content of anthocyanins, which are strong natural antioxidants. The

DPPH (2,2-diphenyl-1-picrylhydrazyl) radical scavenging ability of the skin creams with berry

extracts was studied with Electron Spin Resonance (ESR) spectroscopy. The Artificial Neural

Networks (ANN) were applied to optimize the berry extract concentration and storage time for

oil-in-water and water-in-oil creams [1]. Based on experimental results, chokeberry and

elderberry extracts in oil-in-water cream base revealed higher DPPH radical scavenging ability

than corresponding water-in-oil samples. ANN predicted maximum of DPPH radical

scavenging of oil-in-water creams for elderberry (2.23 mg DPPH/ml) cream stored for 1 week

and freshly prepared chokeberry (5.37 mg DPPH/ml) and bilberry (5.26 mg DPPH/ml) creams

with the 0.76% concentration of extract. The maximum of DPPH radical scavenging for water-

in-oil creams was predicted for the 0.8% Aronia extract cream stored for 6 weeks, the freshly

prepared cream with 0.76% bilberry extract and the cream with 0.56% elderberry extract stored

for 1 week. The ANN predicted values are in good agreement with experimental values. Thus,

DPPH-EPR could be combined with ANN in order to optimize the extract concentration, type

of cream base and to predict the effect of storage based on limited number of experiments and

samples.

References [1] S. Haykin, Neural Networks: A Comprehensive Foundation (2nd Edition), Prentice Hall PTR, Upper Saddle

River, NJ, USA, (1998).


57


Poster XVI

HYPERFINE STRUCTURE OF VANADIUM IONS IN LIQUIDS AND SOLIDS

I. Mrówka1, B. Pytel

1, D. Man

1

1 Institute of Physics, University of Opole, Opole, Poland

[email protected]

Vanadium is a silver-gray, ductile metal with high hardness and high melting point. For

an element with an atomic number 23 there is known 26 isotopes with mass numbers of 40 to

63. Only one stable isotope is the one with mass number 51. Chemically not very active at

room temperature, vanadium at high temperature react with oxygen, hydrogen, nitrogen

dioxide and water vapor . The presence of vanadium in nature is quite common and widely

used in industry. His most important minerals are: patronit VS4 and vanadinite Pb5[Cl(VO4)]3,

in terms of prevalence in the earth's crust occupies 23th place. The atmosphere appears

primarily as a component of continental dust, sea spray and volcanic emissions. The main

source of vanadium in surface waters are waste. It is used mainly for the production of non-

ferrous alloys, highly resistant carbon steel, as well as in the chemical, glass, ceramics, paint

and photo industries.

Vanadium is a component of living organisms, important for their proper functioning. In higher

concentrations reveals the toxic properties leading to poisoning and damaging biological

structures. There exists also reports of potential anticancer activity. Because vanadium has a

paramagnetic properties may be examined by electron paramagnetic resonance. In the course

of the research to date, the following substances were used: vanadium (III) chloride VCl3,

vanadium III acetylacetonate C15H21O6V and vanadyl (IV) acetylacetonate VO (C5H7O2)2, also

were used sodium benzoate and water and methanol as solvents. Presented here vanadium

compounds are powders - spectra of pure powders have a total domination of the fine structure

of the hyperfine structure, thus demonstrating a much greater intensity of interaction between

the spins of electrons than the interaction of spins of electrons with spins of nuclei. Completely

different situation, we have in the solutions. The weakening of intermolecular interactions in

liquids influences the narrowing of the energy levels and the disclosure in the spectra hyperfine

structure. In the case of powders produced based on sodium benzoate, in which the vanadium

ions are an admixture we have dealing with the indirect situation. In these substances revealed

hyperfine structure, however, the ratio of intensities of individual lines is greatly disturbed and

suffer the same lines move on the axis of the magnetic induction - which leads to a narrowing

of the whole spectrum.Within the theoretical analysis of results attempted to use for this

purpose the package Mathematica. So far, interesting results were obtained with the measuring

liquid samples, further work in this area are carried on.

Conclusion - commonly found in nature vanadium on the one hand there is an essential

element for the functioning of living organisms (it may even have therapeutic properties),

on the other hand, there are risks associated with dissemination of its manufacturing. The fact

that the element exhibits paramagnetic properties allows to apply the method of electron

paramagnetic resonance to study its compounds. The authors of this work are interested in the

influence of the vanadium on the biological structures, with respect to this there exists plans to

undertake in the near future studies on the effects of vanadium on the durability of membranes

model.


58


Poster XVII

SPECIFICITY OF FREE RADICAL-SCAVENGING PROPERTIES OF SUMAC

TANNINS IN PROTECTION OF ERYTHROCYTES AGAINST OXIDATIVE STRESS

E. Olchowik-Grabarek1, S. Mavlyanov

2, N. Abdullajanova

2,

R. Gieniusz3, M. Zamaraeva

1

1Department of Biophysics, University of Bialystok, K. Ciolkowskiego 1J, 15-245 Bialystok, Poland

2Institute of Bioorganic Chemistry, Academy of Science of Uzbekistan, Abdullaev 83,

100125 Tashkent, Uzbekistan 3Laboratory of Magnetism, University of Bialystok, K. Ciolkowskiego 1L., 15-245 Bialystok, Poland

[email protected]

Tannins, polyphenoles with the molecular mass ranging between 500 and 3000 Da, are

characterized by high chemical activity and a variety of biological effects, such as antitumor,

antimutagen, antimicrobial, and anti-inflammatory [1,2].

In this study, we show using EPR method that extract and 3,6 bis-O-di-O-galloyl-1,2,4-

tri-O-galloyl-β- D-glucose (C55H40O34) displayed a strong antiradical activity against the

synthetic DPPH radical in homogenous (solution) and hetereogeneous systems (suspension

of DPPH containing liposomes).

We also examined the antioxidant activity of extract from sumac leaves containing

tannins (98%) and flavonoids (2%) and also its main component - 3,6 bis-O-di-O-galloyl-1,2,4-

tri-O-galloyl-β- D-glucose (C55H40O34) against reactive oxygen and nitrogen species (RONS),

such as hydroxyl radical (.OH), superoxide radical (O

.-2), singlet oxygen (

1O2) and nitric oxide

(NO.) in the model system and RONS generated by tert-butyl hydroperoxide (tBuOOH),

peroxynitrate (ONOO-) and hypochlorous acid (HClO) in erythrocytes.

We found that the effectiveness of scavenging of RONS in relative to oxidants can be

represented by following order: tBuOOH > ONOO- > HClO. It is closely associated with

a specificity of neutralization of various RONS in model systems (O.-

2 ≥ NO > .OH>

1O2 ).

The extract from sumac was significantly more effective in comparison with 3,6 bis-O-

di-O-galloyl-1,2,4-tri-O-galloyl-β- D-glucose against RONS in all models.

References [1]. S. Rayne and G. Mazza, Biological activities of extracts from sumac (Rhus spp.): a review. Plant Foods for

Human Nutrition, 62 (2007) 165-175.

[2]. V. Koleckar, K. Kubikova, Z. Rehakova, K. Kuca, D. Jun, L. Jahodar and L. Opletal, Condensed and

hydrolysable tannins as antioxidants influencing the health. Mini Reviews in Medicinal Chemistry, 8 (2008) 436–

447.

59


Poster XVIII

MICROWAVE X-BAND RESONANCES IN DOPED Cd2Nb2O7 MONOCRYSTALS

S. Waplak1, A. Ostrowski

1, M. Wencka

1, W. Bednarski

1

1 Institute of Molecular Physics, Smoluchowskiego 17, PL-60179 Poznan, Poland

Cadmium pyroniobiate Cd2Nb2O7 (CNO) is a ferroic material with unusual diffuse

phase transition (PT) despite the absence of compositional fluctuations, unlike the conventional

relaxors PbMg1/3Nb2/3O3 (PMN), where a frequency-dependent broad dielectric peak is brought

about by nanoscopic polar clusters, but macroscopic ferroelectric ordering does not appear [1,

2]. We will present data strongly suggesting that both the ferroelectric/ferroelastic and local

order do coexist in Cd2Nb2O7 compounds and the interplay between them leads to a rich phase

diagram and relaxation [3-5].

Recently, attention has been paid to the possibility of electronic ferroelectricity based

on charge-ordering phenomena in complex oxides like perovskite structure manganites [6, 7].

An intriguing behavior of dielectric permittivity versus external electric field [8] stimulated us

to look closely on this problem by means of EPR spectra of doped Cd2Nb2O7.

Some EPR papers with the aim to study the molecular mechanism of the phase

transitions in Cd2Nb2O7 crystals have been published [9, 10]. Our papers [11,12] concerned

especially EPR of Cr3+

and Gd3+

ion dopants under the influence of temperature and/or external

electric field. The dielectric behaviour of cadmium pyroniobiate Cd2Nb2O7 shows “unusual

properties” around PT and strongly suggests the presence of polar clusters carrying additional

polarization. However, no molecular origin of such a behavior has been yet elucidated [8, 13].

The most striking effects observed in current study represent anomalies in the

microwave resonator quality parameter Q versus temperature in zero external magnetic field.

In Cd2Nb2O7, this effect appears only in the X-band ( 9.5 GHz) and is absent from the S-band

( 3.5 GHz). The details of the dependence Q = Q(T) rely on the type and concentration of the

doping (paramagnetic) ions Mn

2+, Cr

3+, Fe

3+ introduced. Currently, mainly electric (Q) data,

complemented with the EPR ones in case of necessity, will be discussed.

References [1] L. E. Cross, Ferroelectrics 76, (1987) 241.

[2] R. Blinc, Advanced Ferroelectricity, Oxford University Press Inc., New York, (2011).

[3] V. A. Isupov, Phys. Solid State 47, (2005) 2119.

[4] M.Tachibana, H. Kawaji, and T. Atake, Phys. Rev. B 70, (2004) 064103.

[5] N. N. Kolpakova, I. L. Shulpina, M. P. Shcheglov, S. Waplak, W. Bednarski, W. Nawrocik, and M. Wisner,

Ferroelectrics 240, (2005) 265.

[6] M. Falicov, and J. C. Kimball, Phys. Rev. Lett. 22, (1969) 997.

[7] N. Ikeda, H. Ohsumi, K. Ohwada, K. Ishii, T. Inami, K. Kakurai ,Y. Murakami, K. Yoshii, S. Mori, Y. Horibe,

and H. Kito, Nature 436, (2005) 1136.

[8] Chen Ang, L. E. Cross, Ruyan Guo, and A. Bhalla, Appl. Phys. Lett. 77, (2000) 732.

[9] I. N. Geifman, G. W. Sirotkin, and E. S. Sher, Fiz. Tverd. Tela 25, (1983) 3606.

[10] I. N. Geifman, Solid State Physics 21, (1979) 2251.

[11] N. N. Kolpakova, S. Waplak, and W. Bednarski, J. Phys. Cond. Matter 10, (1998) 9309.

[12] S. Waplak, and N. N. Kolpakova, phys. stat. sol.(a) 117, (1990) 461.

[13] R. Pirc, R. Blinc, and Z. Kutniak, Ferroelectrics 267, (2002) 139.

60


Poster XIX

POTENTIAL ROLE OF SUPEROXIDE ANION IN HOMOCYSTEINE-INDUCED

FLUIDIZATION OF PLATELET MEMBRANES – EVIDENCE FROM

PRELIMINARY EPR MEASUREMENTS

K. Karolczak1, P. Danielska

1, A. Pieniążek

2

1Department of Haemostatic Disorders, Faculty of Health Sciences, Medical University of Lodz, Lodz, Poland.

2Department of Medical Biophysics, Faculty of Biology and Evironmental Protection, University of Lodz, Lodz,

Poland.

[email protected]

Introduction: Homocysteine (Hcy) is a sulphur, non-protein amino acid, considered as

an important factor contributing to enhanced atherogenesis. The exact mechanism of Hcy-

dependent atherogenesis remained poorly understood, however, increased activation of blood

platelets by Hcy is thought to be a key factor in Hcy-driven atherosclerosis. Since Hcy is known

as potent oxidant we presumed that superoxide anion generated by Hcy during thiols oxidation

may act as mediator of Hcy-dependent changes in membranę fluidity.

Methods: The platelets were isolated from blood obtained from a forearm vein from healthy,

non-smoking donors, not taking any drugs or diet supplements. Platelets were isolated by

differential centrifugation.

Isolated blood platelets were labeled with 5-DOXYL-stearic acid (5-DS) or 12-DOXYL-stearic

acid (12-DS). Doxyl-stearic acids-stained platelets were incubated with Hcy (at final

concentrations of 10, 25 or 50 μmol/l), PBS (solvent for Hcy) hypoxanthine/xanthine oxidase,

NaOH and PBS (solvents for hypoxanthine and xanthine oxidase, respectively). After

incubations, EPR spectra were performed at room temperature and correlation time of rotational

diffusion c was calculated. ESR measurements were performed on ESP 300E X-band

spectrometer microwave frequency of 9.5 GHz; center field 337.5 mT; scan range 10 m;

modulation frequency 100 kHz; modulation amplitude 0.1 mT.

The isolated platelets were preincubated with Hcy (or PBS). Bovine heart cytochrome c was

added immediately after initiating of the incubation with Hcy in order to trap short-living oxygen

peroxide molecules. The concentration of generated superoxide anion radicals was estimated on

the basis of the molar extinction coefficient.

Results: Decrease of values of correlation time for rotational diffusion (τc) estimated for

membranes of intact homocysteinylaeted blood platelets stained with 5-DS spin has been

observed for all tested Hcy concentrations. However, the statistically significant reduction in τc

has been noted only for platelets treated with Hcy at concentration of 25 μmol/l.

Values of τc after incubation with Hcy were reduced in the case of platelets stained with 12-DS

spin tracer. Hcy at 10 μmol/l concentration reduced the mean value of τc 1.7, whereas 25 and 50

μmol/l concentrations decreased rotational time of correlation 1.8 and 1.5 times to control probes.

Hcy appeared as potent superoxide anion inducer only when used at concentration of 25 µmol/l

in comparison to PBS-treated platelets. At all other tested concentration Hcy-induced changes in

the concentration of superoxide anion remained statistically insignificant.

Conclusions: Hcy action on blood platelets is associated with membrane fluidization, especially

in deeper, hydrophobic regions of platelet membrane. On the base of preliminary, ongoing

experiments we preclude that superoxide anion generated during homocysteinylation of blood

platelets is probable mediator membrane fluidization.

Funding:This research was supported by the grant from the National Science Center (Cracow,

Poland), No. UMO 2012/07/N/NZ1/03140, funds from the Medical University of Lodz (Poland),

No. 502-03/6-020 01/502-64-058 and partially by the funds from the Polish Society of Metabolic

Diseases (Lodz, Poland).

61


Poster XX

THEORETICAL INVESTIGATIONS OF THE SPIN HAMILTONIAN PARAMETERS

AND THE LOCAL STRUCTURE OF Co2+

IONS IN PbMoO4 CRYSTAL

D. Piwowarska1, P. Gnutek

1, C. Rudowicz

1

1 Institute of Physics, West Pomeranian University of Technology, Al. Piastów 17, 70–310 Szczecin, Poland

[email protected]

In the present work, we employ the superposition model (SPM) analysis [1] for

determination of the zero-field splitting parameters (ZFSPs) [2] as well as the crystal field

parameters (CFPs) [3,4] for Co2+

ions doped into PbMoO4 crystal. The SPM calculations

utilize the structural data on the local environment around the dopant ions. Two structural

models are considered to predict CFPs and independently ZFSPs for Co2+

ions in PbMoO4 in

order to better to match the calculated ZFSPs with experimental ones measured by electron

paramagnetic resonance (EPR). The results enable to confirm the structural distortions in the

PbMoO4 lattice induced by doping Co2+

ions and discern between different environments: (i)

deformed dodecahedral 8-fold coordinated sites (Co2+

ions substituting for Pb2+

sites in the

host crystal) and (ii) deformed tetrahedral 4-fold coordinated sites (Co2+

ions replacing Mo6+

ions). The local distortion angles Δθ1 and Δθ2 in the vicinity ion Co2+

doped in PbMoO4 are

obtained. The experimental data are analyzed within the framework of the CF (or ligand field)

theory for the two Co2+

complexes in PbMoO4. Illustrative preliminary results are presented in

Table 1.

Table 1. Parameters for the 4-fold coordinated Co

2+ complexes in PbMoO4 crystal.

Calculated ZFSPs (This work ) Experimental spin

Hamiltonian parameters [5]

HS S=3/2 S=1/2

Complex Principal g-tensor

values (gx, gy, gz) D [cm

-1] E [cm

-1]

Principal g-tensor values

(g’x, g’y, g’z)

Co2+(α)

(1.99, 2.84, 2.51) 41.95 2.89

(6.26, 4.47, 1.97)

Co2+(β)

(1.72, 3.30, 1.79) 41.05 3.53

(7.41, 3.10, 1.69)

Calculated ZFSPs [6] Experimental spin

Hamiltonian parameters [6]

Co2+

doped

PbWO4 (2.10, 2.82, 2.52)

41.37

2.87 (6.20, 4.50, 2.07)

Acknowledgments We gratefully acknowledge the research grants from the Polish National Science Center: DEC-

2012/04/M/ST3/00817.

References [1] D.J. Newman, B. Ng, Superposition model, in: D.J. Newman, B. Ng (Eds.), Crystal Field Handbook,

Cambridge University Press, Cambridge (2000), 83-120.

[2] C. Rudowicz, M. Karbowiak, Coord. Chem. Rev., 287, (2015) 28.

[3] C. Rudowicz, Magn. Res. Rev. 13 (1987) 1.

[4] C. Rudowicz, S.K. Misra, Appl. Spectrosc. Rev. 36, 11 (2001).

[5] D. Piwowarska, A. Ostrowski, I. Stefaniuk, S. M. Kaczmarek, C. Rudowicz, Optical Materials 35 (2013) 2296.

[6] M.C. Chen, J.O. Artman, Phys. Rev. B 187 (1969) 723.


62


Poster XXI

THE STUDY OF FREE RADICALS IN THE ENRICHED PEAT OF SPENT OIL – EPR

TECHNIQUE

B. Pytel1, K. Najwer

2, I. Pisarek

2, R. Szatanik

1, I. Mrówka

1

1Institute of Physics, Opole University, Opole, Poland

2Department of Land Protection, Opole University, Opole, Poland

[email protected]

The aim of the study was to determine the amount of free radicals and to understand the

role of Pleurotus ostreatus in the transformation of organic compounds in peat contaminated

with spent oil. An important part of our study was also to determine the degree of oyster

growing as a function of the effect of contamination in time. The technique of electron

paramagnetic resonance (EPR) was used, which is a non-invasive technique that requires a

small amount of the biological material for measurements. Tests were made at a constant

temperature of 22 ± 10C. Operating parameters of EPR spectrometer were: sweep range

ΔH=20mT, amplitude modulation ΔH=0.08mT, time constant Δt = 0.3s, sweep time t = 128s,

the center of the field H0 = 339.0 mT. The weight of each sample was 0.08 ± 0.002 g.

Fig. 1. Changes of the amplitude spectra: a) peat (without contaminants) with Pleurotus ostreatus, b) peat

contaminated of spent oil with Pleurotus ostreatus

Based on the study, the coefficient g for the measurements ranged close to a value of 2, which

indicates the presence of unbound free radical compounds. After 49 days of the experiment,

samples containing peat and Pleurotus ostreatus, the number of free radicals was slightly

decreased. This may show the possibility of organic matter transformation by Pleurotus

ostreatus and the involvement of free radicals in the structure of humic substances. At the same

time, in the samples containing peat contaminated with spent oil the opposite trend was

observed. A significant increase of free radicals in the analyzed samples can confirm the

degradation of Pleurotus ostreatus and the harmful effects of pollution from spent oil on the

growth of oyster and the effect of biological activity reduction in used peat. In the case of

control samples containing peat contaminated with spent oil (without Pleurotus ostreatus),

after 49 days of the experiment, no significant changes in the content of free radicals was

observed, which indicates that the Pleurotus ostreatus can be involved in transformation

processes of the organic matter contaminated with xenobiotics, including spent oil.

a) b)

63


Poster XXII

FERROMAGNETIC RESONANCE STUDY OF HIGHLY CHROMIUM DOPED CdTe

ALLOY

I. Stefaniuk1, I. Rogalska

1 B. Cieniek

1

1 Faculty of Mathematics and Natural Sciences, University of Rzeszow, 1 Pigonia Str., 35-959 Rzeszow, Poland

[email protected]

The Cr- based DMS are also attractive for study due to the interesting connection, both

for semiconductor and magnetic physics resulting in future applications in spintronics [1]. In

the present work a CdTe alloy doped with relatively high concentration of chromium (8%) was

studied. This paper is extension of the work [2]. The EMR measurements at temperature range

from 95 K up to 380 K using the X-band ELEXSYS Bruker E 580 spectrometer were

performed. In addition, the measurements of ED EPR were also performed. The obtained

representative FMR spectra are shown in Fig. 1. The most interesting magnetic properties were

noticed for the sample in the vicinity of room temperature.

Ferromagnetism and probably antiferromagnetism properties correlated to changes induced by

temperature were observed simultaneously.

Fig. 1. Representative FMR spectra of Cd1-xCrxTe alloy at various temperatures in K

References [1]. W. Dobrowolski, J. Kossut, T. Story, II-VI and IV-VI diluted magnetic semiconductors–new bulk materials

and low-dimensional quantum structures, in K.H.J. Buschov (ed), Handbook of magnetic materials, Amsterdam

2003

[2]. I. Stefaniuk, M. Bester, I.E. Lipiński, Journal of Physics: Conference Series 30, (2006) 339 – 343

0 1000 2000 3000 4000 5000 6000

EPR

sig

nal

[arb

.u.]

Magnetic field [Gs]

220

225

230

235

240

245

250

255

260

265

270

275

280

285

290

295

300

305

315

320

64


Poster XXIII

RELATION OF TOTAL POLYPHENOL AND FLAVONOID CONTENTS TO

ANTI-RADICAL PROPERTIES AND STABILITY OF TINCTURES OF

GEISSOSPERMUM RETICULATUM: CHEMOMETRIC ANALYSIS

AND LAG PHASE EPR

J.J. Sajkowska-Kozielewicz1, K. Gulik, K. Makarova

1, K. Paradowska

1

1 Department of Physical Chemistry, Medical University of Warsaw, Warsaw, Poland

[email protected]

Native people of Amazon region widely use tinctures from the bark of Geissospermum

species for numerous medicinal purposes. These tinctures exhibit antioxidant, anti-tumoral,

anti-malarial, anti-bacterial and nociceptive activities. [1] However, there is a lack of

physicochemical description of traditional remedies of Geissospermum reticulatum.

The aim of this research was to determine total phenolic and flavonoid contents of three

tinctures of G. reticulatum barks and evaluate their anti-radical activities and stability.

Three samples of barks were collected in Peruvian Amazonia. Total polyphenol (TP) and

flavonoid (TF) contents were defined by spectrophotometric methods. The obtained values

were interpreted by artificial neural networks (ANN) to find the most beneficial conditions for

tinctures. Their stability were assessed using lag phase electron paramagnetic resonance (EPR)

with α-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) spin trap. The ferric reducing ability of

plasma (FRAP) assay, the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging test using

EPR spectroscopy and the fluometric oxygen radical absorbance capacity (ORAC) assay were

applied to study anti-radical properties of tinctures. The Principal Component Analysis (PCA)

was employed to relate contents and properties.

All tinctures have shown the maximum of TP between 14-20 weeks of maceration, whereas the

maximum of TF was between 25-30. However, our data suggest that TP and TF contents do

not explain completely anti-radical activities. Results from the lag phase studies at 60 C

demonstrated that the stability of tinctures were related to TP content. Thus, samples with 550-

800 mg GAE/kg were more stable than those with higher TP contents.

The most beneficial conditions for tinctures from bark depends on aimed final products, i.e.

maximum of polyphenols or flavonoids and long-term stability. Further studied about content

and storage conditions are needed.

References [1] M. Reina, W. Ruiz-Mesia, M. López-Rodríguez, L. Ruiz-Mesia, A. González-Coloma and R. Martínez-Díaz,

Journal of natural products 75(5), (2012) 928-934.

65


Poster XXIV

EMR DATA ON HIGH-SPIN Mn3+

(S = 2) IONS IN MnTPPCl COMPLEX

MODELLED BY MICROSCOPIC SPIN HAMILTONIAN APPROACH

K. Tadyszak1, C. Rudowicz

2,3




[email protected]

Due to the recent advances in the high-magnetic field and high-frequency EMR (HMF-

EMR) techniques, for references, see, e.g.[1,2]

an increasing number of experimental zero field

splitting (ZFS) and Zeeman electronic (Ze) parameter sets[1,2]

for 3d4 and 3d

6 (S=2) ions have

become available in literature in recent decades. The S = 2 ions, e.g. Fe2+

, Mn3+

, and Cr2+

,

usually exhibit large and very large ZFS[3,4]

, hence the HMF-EMR techniques are indispensable.

The availability of HMF-EMR data offers a comprehensive testing of the reliability of the

package MSH/VBA[3,4]

, which enables modelling of the spin Hamiltonian (SH) parameters

based on the microscopic SH (MSH) approach. The MSH expressions for the ZFS and Ze

parameters were developed up to fourth-order perturbation theory for studies of 3d4 and 3d

6

ions with spin S = 2 at orthorhombic and tetragonal symmetry sites in crystals, which exhibit

an orbital singlet ground state arising from the ground 5D multiplet

[7,8].

The SH parameters experimentally determined by HMF-EMR may be corroborated or

otherwise by theoretical modelling using either semiempirical methods or the density

functional theory (DFT) and ab initio methods. By bridging the gap between the two types of

methods the predictive power of model calculations may be increased. To this end

semiempirical modeling utilizing the package MSH/VBA is carried out for high-spin (S = 2)

manganese (III) 3d4

ion in complex of tetraphenylporphyrinato manganese (III) chloride

(MnTPPCl)[9]

. Calculations of the ZFS and Ze parameters are carried out for wide ranges of

values of the microscopic parameters. This enables to examine the dependence of the

theoretically determined ZFS parameters q

kb (in the Stevens notation) and the Zeeman factors

gi on the spin-orbit (λ), spin-spin () coupling constants, and the ligand-field energy levels (Δi)

within the 5D multiplet. The results are presented in suitable tables and graphs. The values of λ,

, and Δi best describing Mn(III) ions in MnTPPCl are determined by matching the theoretical

SH parameters and the experimental ones. Investigations of the role of the fourth-rank ZFS

parameters qb4 existing for S

~= 2

[5-7], which are often omitted in experimental studies, and the

(spin-spin) - related contributions to ZFSPs are now under progress. Illustrative preliminary

results will be presented.

Acknowledgments We gratefully acknowledge the research grants from the Polish National Science Center: DEC-

2012/04/M/ST3/00817 (CZR) and UMO-2014/15/B/ST4/04946 (KT).

References [1] T. Sakurai, K. Fujimoto, R. Goto, S. Okubo, H. Ohta, Y. Uwatoko, J. Magn. Reson. 223 (2012) 41.

[2] J. Telser, J. Krzystek, A. Ozarowski, J. Biol. Inorg. Chem. 19 (2014) 297.

[3] C. Rudowicz, M. Karbowiak, Coord. Chem. Rev. 287 (2015) 28.



[6] M. Zając, I. E. Lipiński, and C. Rudowicz, J. Magn. Mag. Mat. 401 (2016) 1068.

[7] C. Rudowicz, H.W.F. Sung, Physica B 337 (2003) 204.

[8] C. Rudowicz, H.W.F. Sung, Manual for the Package MSH/VBA, unpublished (2004).

[9] J. Krzystek, J. Telser, et. al., Inorg. Chem., 31 (1999) 6121.

66


Poster XXV

MAGNETIC DEFECTS IN Nb2SbVO10

J. Typek1, G. Zolnierkiewicz

1, M. Bobrowska

1, M. Piz

2, E. Filipek

2

1 Institute of Physics, West Pomeranian University of Technology, Szczecin, Poland

2 Department of Inorganic and Analytical Chemistry, West Pomeranian University of Technology, Szczecin,

Poland [email protected]

Nb2VSbO10 in powder form has been synthesized by a standard solid-state reaction

method [1]. To study its magnetic properties the dc magnetisation measurements using an

MPMS-7 SQUID magnetometer and EPR measurements performed on a conventional X–band

Bruker E 500 spectrometer were carried out (Fig. 1). From the nominal valence of ions forming

the Nb2VSbO10 structure it follows that the compound should display only diamagnetic

properties. Surprisingly, various types of magnetic defects (isolated ions, pairs and clusters)

have been detected. Comparison with reference sample allowed to calculate the equivalent

number of defect V4+

ions to reach 5% of all vanadium ions (EPR method) or 6.7 %

(isothermal magnetisation). The last method points out to the presence of other paramagnetic

ions in Nb2VSbO10 as well as pairs and clusters of ions.

3.0 3.5 4.0

-8

-6

-4

-2

0

2

4

6

8

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

40

60

80

100

120

140

160

180

200

EP

R a

mplit

ude [arb

.units]

Magnetic field [kOe]

4 K

290 K

(A)

0 1 2 3 4

0.00

0.02

0.04

0.06

0.08

0.10

Temperature [K]

Magnetic field [T]

290 K

60 K

10 K

Magnetization [

/f.u

.]

2 K

(C)

0 50 100 150 200 250 3000

1

2

3

4

5

EP

R inte

gra

ted inte

nsity [arb

. units]

T0L=-1.1 K

T0H=-85 K

(B)

0 50 100 150 200 250 3004

6

8

10

12

14

16

18

20

700 Oe 1 kOe

70 kOe

70 kOe

1 kOe

700 Oe

Temperature [K]

(D)

[10

3m

olO

e/e

mu]

[10-6

em

u/m

olO

e]

Recip

rocal E

PR

inte

gra

ted inte

nsity [arb

. units]

Fig. 1. (A) EPR spectra of Nb6Sb3VO25 recorded at 4 and 290 K; (B) Temperature dependence of EPR

integrated intensity (left axis) and reciprocal integrated intensity (right axis); (C) Isothermal magnetisation

registered at four different temperatures; (D) Temperature dependence of magnetic dc susceptibility (left

axis) and reciprocal dc magnetic susceptibility (right axis).

References [1] E. Filipek, M. Piz, J. Therm. Anal. Calorim. 101 (2010) 447.

67


Poster XXVI

INTERACTION BETWEEN SPIN – LABELED Fe3O4 NANOPARTICLES AND

HUMAN BLOOD STUDIED BY EPR METHOD

K. Urbaniak1, B. Dobosz

1, R. Krzyminiewski

1, T. Kubiak

1, J. Kurczewska

2,

G. Schroeder2

1 Faculty of Physics, Adam Mickiewicz University, Poznań, Polska

2 Faculty of Chemistry, Adam Mickiewicz University, Poznań, Polska

[email protected]

Magnetic nanoparticles because of their specific structure give many medical

applications based mostly on functionalization of their surface. Usually such processes are

carried out with help of medicines or spin labels which can be successfully used in clinical

therapy and diagnostics. Nanoparticles are covered with biodegradable polymers with low

toxicity. Polymers increase biocompatibility of nanoparticles, improve stability in solutions,

prevent agglomeration and make possible to attach different ligands. Nanoparticles can serve

as a contrast in magnetic resonance imaging, they also give prospects for cancer therapy with

hyperthermia method or for use as medicines in targeted drug delivery.

The subject of research was the behavior of functionalized magnetite nanoparticles

Fe3O4 in aqueous solution, human blood and human blood serum. Magnetite nanoparticles

were labeled with 4-Amino-TEMPO and coated with chitosan. Measurements were conducted

using electron paramagnetic resonance EPR with spectrometer working on X-band. Samples

containing magnetite nanoparticles in different conditions were subjected to field cooling

process and frozen in the temperature of 130 K. Next EPR spectra for each of three samples

were recorded in the temperatures from 130 to 230 K in two orientations of samples in the

magnetic field: 0O and 90

O.

From EPR spectra of such nanoparticles it is possible to obtain two sources of

information. First is the broad line from magnetic core, second one is received from TEMPO

attached to the core. For each spectrum characteristic spectroscopic parameters have been

calculated (g factor and peak to peak line width ∆H) and the dependence between them and

temperature was shown in the appropriate graphs. For TEMPO spectra was determined so

called correlation time which gives the information about the dynamics.

References [1] B. Dobosz, R. Krzyminiewski, G. Schroeder, J. Kurczewska, Journal of Physics and Chemistry of Solids 75

(2014) 594-59

[2] R. Krzyminiewski, T. Kubiak, B. Dobosz, G. Schroeder, J. Kurczewska, Current Applied Physics 14 (2014)

798-804

[3] T. Kubiak, R. Krzyminiewski, B. Dobosz, G. Schroeder, J. Kruczewska, M. Hałupka-Bryl, Acta Bio-Optica et

Informatica Medica Inżynieria Biomedyczna, vol.21, nr1 (2015) 9-15

[4] J. Chomoucka, J. Drbohlavova, D. Huska, V. Adam, R. Kizek, J. Hubalek, Pharmacol, Res. 62 (2010) 144-149

68


Poster XXVII

UV-INDUCED RADICALS IN STATINES – LIPID-LOWERING MEDICATIONS

M. Wencka1, S. van Doorslaer

2, J. Mielcarek

3


2 Department of Physics, University of Antwerp, Wilrijk, Belgium

3 Department of Inorganic and Analytical Chemistry, Poznań University of Medical Sciences, Poznań, Poland,

[email protected]

Statins act by competitive inhibition of the reductase, 3-hydroxy-3-methylglutaryl-

coenzyme A (HMG-CoA), an enzyme regulating of cholesterol synthesis in the cell. As a result

of their action is blocked conversion of HMG-CoA to mevalonic acid, which leads to a

reduction of the intracellular synthesis of cholesterol and low density lipoprotein (LDL).

Statins reduce LDL cholesterol by 30-50%, triglycerides by 10-15% and increase the

concentration of cholesterol in HDL by 5-8%. Statins are not a homogenous group of drugs

have different properties lipo- and hydrophilic, which determine the selectivity, affinity and

tissue penetration. Pravastatin and fluvastatin are characterized by a special hydrophilicity,

while lovastatin, simvastatin and atorvastatin, are characterized by a relative lipophilic. Statins

possess different pharmacological and pharmacokinetic properties. In recent years, statins have

been widely used in the prevention and treatment of atherosclerosis and its complications and

currently represent the most widely used group of drugs modifying blood lipids. The basic

mechanism of action has been very well understood. But today, statins are no longer seen as a

lipid-lowering drugs. Recent reports also indicate their pleiotropic properties and great

potential use of statins in the treatment of other diseases. Proven and observed for several

years, the process of expanding the indications for their administration - make that statins are a

very fast growing group of drugs. For inhibition of HMG-CoA is required the presence of

certain chemical moieties, spatially distributed in a well-defined distance; the remaining part of

the molecule may exhibit a large variation in the structure, without affecting the effectiveness

of the drug. This allows a broad modification of the molecule and the synthesis of new

compounds, leading to a drugs more and more targeted properties. Currently on the polish

pharmaceutical market there are seven statins differing in chemical structure, potency and

pharmacokinetic profile.

The aim of our studies was to investigate the photochemical stability of selected HMG-CoA

reductase inhibitors including atorvastatin, fluvastatin, lovastatin, pitavastatin, pravastatin,

rosuvastatin and simvastatin. Photodegradation of drugs was monitored by means of the EPR

method (X- and W- band Bruker EPR spectrometers). Photochemical experiments were

conducted according to the Document International Conference on Harmonization (ICH Q1B)

recommendations, currently in force in studies of photochemical stability of drugs and drug

products. Statins in crystalline form were irradiated using high pressure UV Hg-lamp equipped

with Wood’s filter of 365 nm at the maximum of wavelength. For 60 min of irradiation that

corresponds to 750 J of energy we created 1015

light-generated radicals in one gram of

lovastatin that is the most light-stable statin. The easiest degradable statin is the pitavastatin

with 6 1016

radicals/g. We were able to distinguish three types of UV-induced radicals in

pitavastatin and fluvastatin. The first Lorentzian-type radical is characterised by gII =

2.00195(5) and g = 2.0050(1) with BppII

= 0.65 mT and Bpp

= 1.05 mT, the second – with

less precisely assessed parameters of gII = 2.0080(10) and g = 2.0022(5) and the third one

with gII = 2.0021(5) and g = 2.0043(5) with BppII

= 1.2 mT and Bpp

= 1.05 mT. Relatively

big anisotropies of g-factor without hyperfine structure might be a signature confirming

interaction without protons. Considering our results supported by crystal structure of statins we

suggest that UV-generated radicals are localized on oxygen atoms.

https://en.wikipedia.org/wiki/Atorvastatin

https://en.wikipedia.org/wiki/Fluvastatin

https://en.wikipedia.org/wiki/Lovastatin

https://en.wikipedia.org/wiki/Pitavastatin

https://en.wikipedia.org/wiki/Pravastatin

https://en.wikipedia.org/wiki/Rosuvastatin

https://en.wikipedia.org/wiki/Simvastatin

69


Poster XXVIII

Cu2+

DOPED MOLECULAR SIEVES FOR MONITORING STRUCTURAL CHANGES

AND GUEST-HOST INTERACTIONS

A. Zalewska1, A. Jankowska

1, A. Skalska

1, A. Ostrowski

2, S. K. Hoffmann

2, S. Kowalak

1

1 Faculty of Chemistry, Adam Mickiewicz University, Poznań, Poland


[email protected]

The molecular sieves consist of various families of porous materials (zeolites, zeotypes,

ordered mesoporous materials, MOF etc.) indicating an uniform pore system in given type,

regardless of different chemical composition. During recent decades they attained enormous

importance in many practical applications. The composites comprising the host (molecular

sieve) – guest (entrapped molecules) systems are particularly interesting and promising for

numerous applications (e.g. sensors, optical, microelectronic devices, etc.). The advanced and

detailed study of these systems require whole arsenal of modern scientific tools and ESR

spectroscopy is one of the most sensitive and efficient. However, many types of the molecular

sieves and the incorporated guest compounds do not show any paramagnetic properties and

cannot be directly studied by means of this technique. Nevertheless, a doping of the studied

material with paramagnetic agent such as Cu2+

either to guest or to host allows to investigate

the interaction between them and the structural details of resulted species.

The following study presents the ESR study on imidazole (Him) embedded into

zeolites, zeotypes, and ZIF materials in order to assess the proton electric conductivity of

resulted composites. The applied diamagnetic matrices were doped with Cu2+

cations either

upon their synthesis or by means of post–synthesis modification. The ESR signals due to Cu2+

are very sensitive and they clearly reflect the interaction with the guest Him molecules. For

instance the spectra indicate a significant difference in spectroscopic parameters gII and AII in

the Cu2+

doped material [Zn(im)2]n before (A) and after (B) replacing of the initial guest –

pyridine with imidazole. The above spectral changes reflect the structural matrix

transformations resulted from the guest replacement and illustrated in XRD.

70


Poster XXIX

SPIN TRAP AND SPIN PROBE ESR FOR THE OPTIMIZATION OF ANTIOXIDANT

PROPERTIES OF HERBAL BATHING SALTS

K. Zawada1, K. Makarova

1, D. Kowalska

1

1 Faculty of Pharmacy with the Laboratory Medicine Division, Medical University of Warsaw, Warsaw, Poland

[email protected]

Traditionally, bathing with salts has been viewed as relaxing and healing. Herbal

extracts have been added to the salts in order to increase their therapeutic properties. This

increase is partly due to the antioxidant properties of herbs. In this work we optimized the

extraction condition of 3 herbal materials (lavender flower, melissa and birch leaf) in order to

achieve maximum antioxidant properties. The lipid membrane permeability of herbal extracts

with the highest antioxidant activity was also determined. Then we prepared bathing salts

(from Dead Sea or Bochnia Salt Mine) based on optimized extracts, and determined their

antioxidant properties and the influence on lipid membrane permeability.

The antioxidant activity was studied with DPPH–ESR test as well as by spin trap ESR using

Fenton reaction both in the absence and in the presence of model lipids (DOPC), with PBN as

a spin trap. The influence on lipid membrane permeability of herbal extracts and herbal salts

was studied with the spin probe ESR in the range of 293-323 K. DOPC liposomes were used as

a model lipid bilayer, and DTBN as a spin probe.

The optimal conditions for the extraction of herbal materials were: 15 minutes extraction time

and temperature of 333 K. The order of antioxidant activity of herbal salts depended on the

presence or absence of lipids. The lowest permeability was observed for extracts of melissa and

birch leaf, followed by corresponding herbal salts based on Bochnia Salt Mine salt, and it was

lower than in the reference system. On the other hand, lavender extract increased the

permeability of the model membrane, and lavender salts decreased the permeability. Thus,

even though the lavender extract did not show the highest antioxidant activity in the Fenton

reaction and DPPH test, due to better permeability it showed the highest antioxidant activity in

the lipid phase which is desired for cosmetic use.

In conclusion, combination of permeability studies with antioxidant studies in the presence of

model lipids could be potentially used for optimization of other types of herbal bath salts.

71


Poster XXX

EPR STUDIES OF THE FREE RADICAL SCAVENGING ACTIVITY

OF SIMVASTATIN

M. Zdybel1, B. Pilawa

1, E. Chodurek

2

Medical University of Silesia, School of Pharmacy with the Division of Laboratory Medicine in Sosnowiec,

1Department of Biophysics,

2Department of Biopharmacy, Jedności 8, 41-200 Sosnowiec, Poland

[email protected]

The interactions of simvastatin with free radicals were examined by an X-band (9.3

GHz) EPR spectrometer. The influence of temperature and UV-irradiation on the free radical

scavenging activity of simvastatin was determined. The model DPPH (1,1-diphenyl-2-

picrylhydrazyl) free radicals with unpaired electrons localized on nitrogen (N) atom [1,2] were

used in this study. DPPH is the standard in EPR studies of the antioxidative samples [3,4]. EPR

spectra of DPPH in contact with simvastatin were compared with those of DPPH - the

reference. The samples were prepared in ethyl alcohol solution. The drug storage at room

temperature, and it was heated in the hot air oven with air circulation of Memmert Firm

(Germany) at temperatures: 37 oC, 40

oC, and 42

oC. UVA-irradiation (λ: 315-400 nm) was

done by the Medisun 250 lamp (Germany) equipped with 4 radiators with power of 20 W. The

spectra of DPPH were measured by EPR spectrometer of Radiopan Firm (Poznań, Poland) and

by the data acquisition system - the Rapid Scan Unit of Jagmar Firm (Kraków, Poland).

The antioxidative character was stated for the original - untreated simvastatin, the heated

and UV-irradiated samples. The tested drug quenched the EPR lines of DPPH free radicals.

The kinetics of the interactions free radicals - simvastatin were tested as the correlations

between amplitudes (A) of DPPH EPR lines and contact time of DPPH with the drug samples.

The changes of the scavenging activity of simvastatin treated by the higher temperatures and

UV-irradiation were evaluated. The kinetic modification by the physical factors was obtained.

The practical applications of the results in medicine of tumors were discussed.

Acknowledgements

This study was financially supported by Medical University of Silesia in Katowice.

References [1] G. Bartosz, Druga twarz tlenu. Wolne rodniki w przyrodzie, PWN, Warszawa, (2006).

[2] G. Tirzitis and G. Bartosz, Acta Biochimica Polonica 57, (2010) 139-142.

[3] N.D. Yordanov and A. Christova, Applied Magnetic Resonance 6, (1994) 341-345.

[4] P. Molyneux, Songklanakarin Journal of Science of Technology 26, (2004) 211-219.

72


PosterXXXI

THE INFLUENCE OF SIMVASTATIN ON FREE RADICALS IN HUMAN

MELANOMA MALIGNUM CELLS – EPR EXAMINATION

M. Zdybel1, E. Chodurek

2, B. Pilawa

1

Medical University of Silesia, School of Pharmacy with the Division of Laboratory Medicine in Sosnowiec,

1Department of Biophysics,

2Department of Biopharmacy, Jedności 8, 41-200 Sosnowiec, Poland

[email protected]

Free radicals in different types of human melanotic cells (Fig. 1) exposed to simvastatin

were examined by electron paramagnetic resonance (EPR) spectroscopy. Simvastatin showed

cytotoxic and cytostatic effect in numerous cancer cell lines [1]. The effect of simvastatin

doses on properties and concentration of free radicals in the human melanoma cells was

determined. The human melanoma malignum cells were purchased from LGC Promochem

(Łomianki, Poland). Simvastatin was obtained from Sigma-Aldrich.

Fig. 1. A-2058 cell lines. Magnification 200x.

Melanoma malignum cells contain paramagnetic melanin polymer [2]. Paramagnetic centers of

melanin are mainly responsible for the EPR spectra of melanotic cells [2-4].

o-Semiquinone free radicals were found in the tested tumor cells. All the EPR spectra of the

cells were the very broad lines.

The simvastatin changed the free radical concentration in the melanotic tumor cells. Probably

o-semiquinone melanin free radicals take a part in the formation of the complexes between

simvastatin and the melanin polymer in the pathological cells. The role of o-semiquinone free

radicals in binding of different drugs to melanin was stated earlier [5,6]. The changes in free

radical system of human melanoma malignum cells after treatment by simvastatin depended on

type of cells and dose of this drug. The practical application of the EPR results in therapy of

tumor were discussed.

Acknowledgements

This study was financially supported by Medical University of Silesia in Katowice.

References [1] A. Saito, N. Saito, W. Mol, H. Furukawa, A. Tsutsumida, A. Oyama, M. Sekido, S. Sasaki and Y. Yamamoto,

Melanoma Research 18, (2008) 85-94.

[2] M. Zdybel, E. Chodurek and B. Pilawa, Acta Poloniae Pharmaceutica – Drug Research 71, (2014) 1066-1072.

[3] E. Chodurek, M. Zdybel, B. Pilawa and Z. Dzierżewicz, Acta Poloniae Pharmaceutica – Drug Research 69,

(2012) 1334-1341.

[4] E. Chodurek, M. Zdybel and B. Pilawa, Journal of Applied Biomedicine 11, (2013) 173-185.

[5] M. Otręba, M. Zdybel, B. Pilawa, A. Beberok, D. Wrześniok, J. Rok and E. Buszman, European Biophysics

Journal 44, (2015) 359-365.

[6] B. Wiernek, B. Pilawa, M. Zdybel, E. Buszman and D. Wrześniok, Journal of Applied Biomedicine 12, (2014)

161-169.

http://213.227.100.63/scripts/expertus3e3.exe?KAT=c%3A%5Cexpertus.cd%5Cbib%5Cpar%5C&FST=data.fst&FDT=data.fdt&ekran=ISO&lnkmsk=2&cond=AND&mask=2&F_00=02&V_00=Otr%EAba+Micha%B3+

http://213.227.100.63/scripts/expertus3e3.exe?KAT=c%3A%5Cexpertus.cd%5Cbib%5Cpar%5C&FST=data.fst&FDT=data.fdt&ekran=ISO&lnkmsk=2&cond=AND&mask=2&F_00=02&V_00=Zdybel+Magdalena+

http://213.227.100.63/scripts/expertus3e3.exe?KAT=c%3A%5Cexpertus.cd%5Cbib%5Cpar%5C&FST=data.fst&FDT=data.fdt&ekran=ISO&lnkmsk=2&cond=AND&mask=2&F_00=02&V_00=Pilawa+Barbara+

http://213.227.100.63/scripts/expertus3e3.exe?KAT=c%3A%5Cexpertus.cd%5Cbib%5Cpar%5C&FST=data.fst&FDT=data.fdt&ekran=ISO&lnkmsk=2&cond=AND&mask=2&F_00=02&V_00=Beberok+Artur+

http://213.227.100.63/scripts/expertus3e3.exe?KAT=c%3A%5Cexpertus.cd%5Cbib%5Cpar%5C&FST=data.fst&FDT=data.fdt&ekran=ISO&lnkmsk=2&cond=AND&mask=2&F_00=02&V_00=Wrze%B6niok+Dorota+

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73


Poster XXXII

EPR/FMR STUDY OF nCoO/(1-n)ZnO (n=0.4, 0.5, 0.6 AND 0.7) NANOCOMPOSITES

N. Guskos1, G. Zolnierkiewicz

1, J. Typek

1, D. Sibera

2, U. Narkiewicz

2

1Institute of Physics, West Pomeranian University of Technology, Al.Piastow 48,70-311 Szczecin, Poland

2Institute of Chemical and Environment Engineering, West Pomeranian University of Technology, ul. Pulaskiego

10, 70-322 Szczecin, Poland

[email protected]

The EPR/FMR spectra of the nCoO/(1-n)ZnO nanocomposites (where the composition

index n=0.4, 0.5, 0.6 and 0.7) prepared by hydrothermal synthesis have been investigated.

XRD measurements of the obtained nanocomposites displayed peaks from ZnO, ZnCo2O4 and

weak lines attributed to Co(OH)2 phase containing Co2+

ions. With an increase of the index n

the decrease of ZnO phase was observed and the reflections from ZnCo2O4 compound were

more intense. SEM picture of 0.7CoO/0.3ZnO nanocomposite confirmed the presence of large

agglomerates of magnetic nanoparticles. Figure 1 presents FMR/EPR spectra taken at different

temperatures and the insets show EPR spectra of Co2+ ions at low temperatures. In general,

magnetic resonance spectra consists of two components, one derived from the Co2 +

ions (EPR)

which form a narrow resonance line at low magnetic fields and the other arising from magnetic

agglomerates (FMR) with appears as a very broad line. The former component is due to

Co(OH)2 phase and the later to ZnCo2O4 phase. In case of 0.6CoO/0.4ZnO nanocomposite the

FMR line is so broad it couldn’t be registered at our spectrometer (Fig. 1c).

0 2000 4000 6000 8000

-4

-2

0

2

4

0 500 1000 1500 2000 2500-40

0

40

80

120

160a)

d"/d

H [

Arb

. u

nit

s]

Magnetic field H [G]

60 K

70 K100 K

n = 0.4

17 K

13 K

7 K

4 K

0 2000 4000 6000 8000

-6

-5

-4

-3

-2

-1

0

0 1000 2000 3000

-10

0

10

20

30

40

b)

d"/d

H [

Arb

. u

nit

s]


90 K

60 K

50 K

n = 0.5

4 K

7 K

13 K

17 K

0 500 1000 1500 2000 2500 3000-6

-3

0

3

6

9

12

15c)

d"/

dH

[A

rb.

un

its

]


4 K

7 K

13 K

17 K

n=0.6

0 2000 4000 6000 8000-10

-8

-6

-4

-2

0

0 1000 2000

-4

-2

0

2

4

6

8

10

d)

d"/

dH

[A

rb.

un

its]


70 K

55 K

45 K

35 K

n = 0.7

4 K

7 K

13 K

17 K

Fig. 1 FMR/EPR spectra of the nCoO/(1-n)ZnO nanocomposites: (a) n=0.4; (b) n=0.5; (c) n=0.6; (d) n=0.7.

The insets in (a), (b), and (d) show EPR spectra of Co2+

ions registered at low temperatures.

74


Names index

A

Abdullajanova, N., 42, 58

Akthar, W., 25

Anders, J., 25

Augustyniak-Jabłokow, M. A.,

20, 39, 40, 54

B

Badyła, A., 37

Bandosz, T., 34

Baranowski, M., 15, 16

Bednarski, W., 59

Behrends, J., 25

Bernasińska, J., 51

Biedunkiewicz, A., 19

Bilkova, I., 46

Bitiucki, M., 42

Blank, A., 25

Blonska-Tabero, A., 17

Bobrowska, M., 43, 66

Bodziony, T., 19

Boś-Liedke, A., 16, 44

Bujok, J., 50

C

Chiesa, M., 24

Chlewicki, W., 15, 16

Chodurek, E., 71, 72

Cieniek, B., 18, 45, 63

Coy, L. E., 52

Czechowski, T., 15, 16, 44

D

Danielska, P., 60

Decyk, P., 46

Detyna, J., 50

Dobosz, B., 31, 55, 67

Doorslaer, S., 68

Dubiel, Ł., 47

F

Fedaruk, R., 39

Figiel, P., 19

Filek, M., 32

Filipek, E., 43, 66

Frączek, Z. J., 48

Fuks, H., 49

G

Gałecka, K., 30, 50

Gieniusz, R., 58

Gnutek, P., 61

Grabowski, M., 51

Grzeszczuk-Kuć, K., 50

Gulik, K., 64

Guskos, N., 17, 73

Gwoździński, K., 51

Gwoździński, L., 51

H

Hara, S., 14

Hoffmann, S. K., 69

J

Jancelewicz, M., 16

Jankowska, A., 69

Jerzykiewicz, M., 27

Jezierska, J., 26, 27

Jurga, J., 15, 16

Jurga, K., 15

Jurga, S., 44

K

Kabacińska, Z., 16, 44, 52

Kaczmarek, S. M., 19, 49

Karbowiak, M., 38

Karolczak, K., 60

Katz, I., 25

Kedzia, P., 15

Kempiński, M., 34

Kempiński, W., 34, 35

Komorowska, M., 30, 50

Kowalak, S., 69

Kowalczyk, E., 51

Kowalska, D., 70

Kozanecki, M., 23

Krasowska, A., 53

Krupska, A., 54

Krzyminiewski, R., 31, 52, 55,

67

Kubiak, T., 55, 67

Kucharska, B., 49

Kurczewska, J., 31, 55, 67

Kurdziel, M., 32

Kuźma, M., 18, 36, 47

L

Łabanowska, M., 32

Leniec, G., 19, 49

Lips, K., 25

Łoś, S., 34, 35

M

Maćkowiak, M., 20

Makarova, K., 56, 64, 70

Malinowski, P., 15

Man, D., 57

Matuszak, Z., 33

Mavlyanov, S., 58

Maziarz, W., 47

Mazur, T., 24

Meier, C., 25

Michalski, J., 49

Mielcarek, J., 68

Mikoda, P., 30

Möser, J., 25

Mrówka, I., 57, 62

N

Najder-Kozdrowska, L., 46

Najwer, K., 62

Narkiewicz, U., 73

O

Ohmichi, E., 14

Ohta, H., 14

Okubo, S., 14

Olchowik-Grabarek, E., 42, 58

Oleszko, A., 30

Ostrowski, A., 59, 69

Ozarowski, A., 26, 27

P

Padlyak, B.V., 29

Paradowska, K., 64

Pieniążek, A., 51, 60

Pietrzyk, P., 21, 24, 28, 53

Pilarska, M., 17

Pilawa, B., 71, 72

Pisarek, I., 62

Piwowarska, D., 61

75


Piz, M., 43, 66

Podolska-Serafin, K., 53

Popovych, V. D., 18

Potera, P., 37

Pytel, B., 57, 62

R

Radoń, M., 24

Reger, D. L., 26

Rogalska, I., 63

Rudowicz, C., 22, 23, 38, 61,

65

S

Sagan, P., 47

Sajkowska-Kozielewicz, J. J.,

64

Sakurai, T., 14

Samolej, A., 16

Schnegg, A., 25

Schroeder, G., 31, 55, 67

Sękowski, S., 42

Sibera, D., 73

Skalska, A., 69

Skop, N., 18

Skowyra, J., 56

Sobańska, K., 28

Sojka, Z., 21, 24, 28

Stefaniuk, I., 18, 37, 45, 47, 63

Strzelczyk, R., 20, 39, 54

Szatanik, R., 62

Szczepanik, P., 15

Szulc, P., 15

T

Tadyszak, K., 15, 16, 38, 39,

44, 65

Takahashi, H., 14

Trębińska, M., 56

Trybuła, M., 35

Trybuła, Z., 35

Turczyński, S., 48

Typek, J., 17, 43, 66

U

Urbaniak, K., 67

V

Virt, I., 45

W

Wach, P., 49

Wagner, D., 56

Wal, A., 47

Walawender, M., 44

Walski, T., 50

Waplak, S., 59

Wawer, I., 56

Wencka, M., 48, 52, 59, 68

Więckowski, A. B., 46

Wisz, G., 47

Witwicki, M., 27

Z

Zając, M., 22

Zalewska, A., 69

Zamaraeva, M., 42, 58

Zawada, K., 56, 70

Zdybel, M., 71, 72

Ziółek, M., 46

Zolnierkiewicz, G., 17, 43, 66,

73

76


Important places

Campus of the A. Mickiewicz University with marked route to the Faculty of Physics

The Campus Morasko (Campus of the A. Mickiewicz University) is located on the

north site of Poznań. The easiest way to get to the Faculty of Physics from the city centre is to

take tram (no. 12, 14, 15, or 16) in the direction ‘Sobieskiego’. The final stop (Osiedle

Sobieskiego) is marked at the plan above as Tramway terminal. Then take approximately 1 km

walk to the Faculty (entrance B), marked with red dots.

Faculty of Physics, Campus Morasko AMU

77


Działyński Palace (PL - Pałac Działyńskich) is located on the old marked squere

Conference Dinner will be held in Działyński Palace in Poznań, a baroque palace built in 1773

– 1776.

The way to Działyński palace from Kupiec Poznański shoping centre

Direct conection between Campus Morasko and the city centre is made by the tram no

16. On the figure above the way to the Dzialyński palace is marked with red dots.

78


79


80


81


82


NOTES

83


NOTES

84


NOTES

85


NOTES

86


NOTES

Documents

PG EMRpgemr.org/sites/default/files/Book of abstracts IV Forum...3 Scientific Committee Julia Jezierska – University of Wroclaw, Wrocław Kazimierz Dziliński – University of Technology,