The Henryk Niewodniczaski INSTITUTE OF NUCLEAR PHYSICS
Polish Academy of Sciences ul. Radzikowskiego 152, 31-342 Krakw,
Poland
www.ifj.edu.pl/publ/reports/2010/
Krakw, December 2010
_________________________________________________________________________
Report No. 2046/AP
XLIII Polish Seminar on Nuclear Magnetic Resonance and Its
Applications. Krakw, 1-2 December 2010
ABSTRACTS
Organizing Committee:
Members:
T. Banasik Z.T. Lalowicz /v-chairman/ A. Birczyski K. Majcher J.
Blicharski M. Noga /secretary/ J. W. Hennel /chairman/ Z.
Olejniczak M. Jaboska P. Rosicka A. Jasiski /honorary chairman/ W.
Rutkowski K. Jasiski T. Skrka A. Krzyak G. Stoch P. Kulinowski U.
Tyrankiewicz S. Kwieciski W.P. Wglarz /v-chairman/ G. Woniak
Sponsors:
AMX-ARMAR AG BRUKER-POLSKA SP. Z O.O
AGILENT USA KOMITET FIZYKI POLSKIEJ AKADEMII NAUK
Addresses of the sponsors: AMX-ARMAR AG mgr Anna Potrzebowska
ul. Bugarska 12a 93-362 d tel. (042) 645 00 64 [email protected] BRUKER
POLSKA SP. Z O.O mgr Wodzimierz Leszczyski ul. Budziszyska 69
60-179 Pozna tel. (061) 868 90 08 fax. (061) 868 90 96 e-mail:
[email protected] www.bruker.pl AGILENT USA mgr in.
Wojciech Komider ul. Skarbka 21 60-348 Pozna tel. (061) 867 31 84
tel. kom. 602 287 918 e-mail: [email protected] KOMITET FIZYKI
POLSKIEJ AKADEMII NAUK Instytut Fizyki PAN Al. Lotnikw 32/46 02-668
Warszawa
mailto:[email protected]:[email protected]
CONTENTS
1. ELECTRON PARAMAGNETIC RESONANCE EXAMINATION OF VITRINITES
WITH DIFFERENT CARBON CONTENT Sylwia Bartomiejczyk, Barbara Pilawa,
Joanna Komorek
1
2. A SIMPLE ONE-DIMENSIONAL METHOD OF CHEMICAL SHIFT ANISOTROPY
DETERMINATION UNDER MAS CONDITIONS Piotr Bernatowicz
2
3. KONSTRUKCJA CEWKI RADIOWEJ CZSTOCI DO OBRAZOWANIA PIERSI W
NISKIM POLU MAGNETYCZNYM B.Basiak, V. Volotovskyy, C. Deng, B.
Tomanek
3
4. OBRAZOWANIE MOLEKULARNE MR GLEJAKW Z ZASTOSOWANIEM CELOWANYCH
RODKW KONTRASTOWYCH B.Basiak, T.Foniok, Albaghdadi, J.Landry, J. G.
Sutherland, B. Tomanek
4
5. MR IMAGING - ARTIFACTS PRODUCED BY DENTAL MATERIALS Amira
Bryll, Andrzej Urbanik, Anna Jurczak, Maria Chomyszyn-Gajewska,
Stanisaw Sztuk, Magorzata Szafirska, Barbara Sobiecka, Paulina
Karcz
5
6. STRUCTURE AND DYNAMICS CHANGES IN S100A1 PROTEINS Monika
Budziska, Micha Nowakowski, ukasz Jaremko, Mariusz Jaremko, Igor
Zhukov, Konrad Zdanowski, Agnieszka Belczyk, Andrzej Bierzyski,
Andrzej Ejchart
6
7. INFLUENCE OF STORAGE TEMPERATURE ON ANTIRADICAL PROPERTIES OF
SELECTED COSMETICS Anna Deda, Sawomir Wilczyski, Barbara Pilawa,
Ewa Pierzchaa
8
8. NOVEL DESIGN OF RF SURFACE COILS FOR MAGNETIC RESONANCE
IMAGING SYSTEM AT 0.088 T Agata Drd, Bartosz Proniewski, Henryk
Figiel, Mateusz Suchanek
9
9. NMR MEASUREMENTS IN THE GAS PHASE EMPLOYING A HOME-MADE HIGH
PRESSURE APPARATUS Piotr Garbacz, Karol Jackowski
10
10. STRUCTURE OF BARBITURIC ACID IN WATER SOLUTIONS - AN NMR/DFT
STUDY Adam Gryff-Keller, Anna Kraska-Dziadecka
12
11. BOUND WATER FREEZING IN LICHENS FROM THE GENUS UMBILICARIAE
BY PROTON RELAXATION AND BY DSC H. Haraczyk, P.Nowak, M. Bacior, M.
Marzec, M. A Olech
13
12. THE HYDRATION OF CUTICLE OF CHOSEN WEEVIL SPECIES
(COLEOPTERA: CURCULIONIDAE) AS RECORDED BY PROTON RELAXATION AND
SORPTION ISOTHERM
14
H. Haraczyk, M. Florek, P. Nowak, S. Knutelski
13. PHASE TRANSITION AND MOLECULAR MOTIONS IN [Ba(H2O)3](ClO4)2
STUDIED BY NUCLEAR MAGNETIC RESONANCE AND COMPLEMENTARY METHODS
Joanna Hetmaczyk, ukasz Hetmaczyk, Krystyna Hoderna-Natkaniec, Anna
Migda-Mikuli, Edward Mikuli
15
14. THE POSSIBILITIES OF 31P NMR SPECTROSCOPY APPLICATION IN
DETERMINATION OF PHOSPHATES ADDITIVES IN MEAT PRODUCTS Pawe B.
Hrynczyszyn, Edward Szyk
17
15. ASSESSMENT OF THE RELATION BETWEEN CARDIAC FUNCTION AND LEFT
VENTRICLE LONG-AXIS ORIENTATION IN MURINE MODEL OF HEART FAILURE
Magdalena Jaboska, Tomasz Skrka, Urszula Tyrankiewicz, Henryk
Figiel
18
16. APPLICATION OF MICROSTRIP RF COILS TO MRI MICROSCOPY
Krzysztof Jasiski, Anna Mynarczyk, Peter Latta, Vyacheslav
Volotovskyy, Wadysaw P.Wglarz, Bogusaw Tomanek
19
17. SOLID STATE NMR SPECTROSCOPY AS A PRECISE TOOL FOR ASSIGNING
THE TAUTOMERIC FORM IN CHIRAL O-HYDROXY SCHIFF BASES APPLIED AS
LIGANDS IN THE ASYMMETRIC CATALYSIS Magdalena Jaworska, Pawe B.
Hrynczyszyn, Mirosaw Weniak, Grzegorz Krasiski, Hassan Kassassir,
Wodzimierz Ciesielski, Marek J. Potrzebowski
20
18. MULTIDIMENSIONAL NMR SPECTROSCOPY WITH SPARSE RANDOM
SAMPLING Wiktor Komiski, Krzysztof Kazimierczuk, Maria Misiak, Jan
Stanek, Anna Zawadzka-Kazimierczuk
22
19. THE NMR STUDY OF SAICAR FROM BODY FLUIDS OF PATIENTS
SUFFERING FROM ADENYLOSUCCINATE LYASE DEFICIENCY Hanna Krawczyk,
Katarzyna Janowska
24
20. THE NOVEL DERIVATIVES OF STILBENES AS POTENTIALLY NEW
OPTICAL MOLECULAR SWITCHES Hanna Krawczyk, Rafa Matczak
25
21. SLOW MOTION THEORY AND ESR LINESHAPE ANALYSIS Aleksandra
Kubica, Danuta Kruk
26
22. SYNTHESIS AND DFT STUDIES OF CYCLODODECANE-1,2-DIONE AND
IT'S DERIVATIVES Dominik Kubicki, Przemysaw Szczeciski, Adam
Gryff-Keller
27
23. AN EFFICIENCY OF THE aug-cc-pVTZ-J BASIS SET IN PREDICTION
OF NMR SHIELDINGS (IN COMPARISON TO THE CLASSICAL CBS APPROACH)
28
Teobald Kupka, Micha Stachw, Marzena Nieradka, Jakub Kaminsky,
Tadeusz Pluta, Stephan P. A. Sauer
24. EFFECTS OF SIDE-CHAIN ORIENTATION ON THE BACKBONE
CONFORMATION OF DEHYDROPHENYLALANINE RESIDUE. THE NMR STUDY Teobald
Kupka, Magorzata A. Broda, Aneta M. Buczek, Tomasz Ptak
29
25. DIMERIZATION OF N-METHYLINDOLE Maria Kwasiborska, Jacek
Wjcik
30
26. DYNAMIC NUCLEAR POLARIZATION WITH TEMPO RADICAL AT 1.5 K
Grzegorz Kwiatkowski, Danuta Kruk, Walter Kckenberger
31
27. ORCA AS A TOOL TO CALCULATE ESR PARAMETERS Maciej Majka,
Aleksandra Kubica, Danuta Kruk
32
28. NMR MICROIMAGING APPLIED FOR INVESTIGATION OF THE POROSITY
OF NATURAL WOOD, WOOD-BASED MATERIALS AND A NOVEL WOOD - POLYMER
COMPOSITE Wodzimierz Masierak, Joanna Kowalczuk, Jadwiga Tritt-Goc,
Jolanta Tomaszewska, Stanisaw Zajchowski, Jacek Mirowski
33
29. MOLECULAR DYNAMICS IN TOCOPHEROL W. Medycki, J. Czaplicki,
D. Kruk
34
30. DYNAMIC NUCLEAR POLARIZATION - WHAT IT IS AND HOW IT WORKS
Artur Mielczarek, Danuta Kruk
35
31. HOW NMR AND ESR HELP TO ESTIMATE THE DYNAMIC NUCLEAR
POLARIZATION ENHANCEMENT? Agnieszka Milewska, Danuta Kruk
36
32. ANOMALOUS TEMPERATURE DEPENDENCE OF SOLID-ECHO SIGNAL IN
NANOPOROUS NATROLITE A.V. Sapiga, A.A.Sapiga, D.A.Levchenko,
M.Olszewski, N.A.Sergeev
37
33. SPIN ECHOES IN SYSTEMS WITH ANOMALOUS DIFFUSIONS
M.Olszewski, N.A.Sergeev, A.V. Sapiga, A.A.Sapiga,
D.A.Levchenko
39
34. NMR SPECTROMETRY COMBINED WITH LASER PHOTOLYSIS AS A TOOL
FOR INVESTIGATION OF THE TICT STATE Mariusz Pietrzak, Jacek
Dobkowski
41
35. FREE RADICALS IN THERMAL STERILIZED METOPROLOL Barbara
Pilawa, Pawe Ramos, Magdalena Truchan
42
36. DESIGN OF A CRYOGENIC RF COIL FOR LOW FIELD MAGNETIC
RESONANCE IMAGING
43
Bartosz Proniewski, Mateusz Krauz, Henryk Figiel
37. APPLICATION OF MRI TO ASSESSMENT THE RECOVERY AFTER SPINAL
CORD PRESSURE IMPACT INJURY IN ANIMAL MODEL P. Rosicka, K. Majcher,
W. Marcol, W. lusarczyk, T. Banasik, J.Lewin-Kowalska,
W.P.Wglarz
44
38. MONITORING OF CHELATION PROCESSES USING NMR RELAXATION
METHOD Lech Wiktor Skrski, Mateusz Synowiecki, Barbara
Blicharska
45
39. INVESTIGATION OF PAPER SAMPLES USING T1 DISPERSION PROFILES
Lech Wiktor Skrski, Barbara Blicharska
46
40. ROVIBRATIONAL CORRECTIONS TO THEORETICAL NMR PARAMETERS FROM
VPT2 METHOD Justyna Skrzewska, Teobald Kupka, Magorzata A. Broda,
Aneta M. Buczek
47
41. ITERATIVE ALGORITHM FOR ARTIFACT SUPPRESSION IN SPARSELY
SAMPLED MULTIDIMENSIONAL NMR SPECTRA Jan Stanek, Wiktor Komiski
48
42. COMPARING APPLICATION OF THE WAVELET TRANSFORM AND THE
ADAPTIVE WEIGHT SMOOTHING ALGORITHM FOR THE NOISE REDUCTION IN MRI
Joanna wiebocka-Wik, Henryk Figiel
50
43. INVERSE RECONSTRUCTION TECHNIQUES IN MAGNETIC RESONANCE
IMAGING Martin Uecker
51
44. APLICATION OF fMRI IN ESTIMATION OF HYPNOTIC SUGGESTION
DURING PAIN STIMULATION Andrzej Urbanik, Jerzy Aleksandrowicz,
Marek Binder, Barbara Sobiecka, Justyna Kozub, Paulina Karcz
52
45. NEURONAL CORRELATIONS OF WORKING MEMORY ACTIVITY -
USELFULNESS OF FMRI Andrzej Urbanik, Marek Binder, Justyna Kozub,
Barbara Sobiecka, Paulina Karcz
53
46. PROTON MAGNETIC RESONANCE SPECTROSCOPY (HMRS) OF PATIENTS
WITH DIAGNOSED DEPRESSIVE DISORDER Andrzej Urbanik, J. Kozub, B.
Sobiecka, A. Silczuk, T. Zyss, D. Dudek, P. Karcz
54
47. THE EFFECT OF THE ETHYL ALCOHOL ON THE CENTRAL NERVOUS
SYSTEM (CNS) - USELFULNESS OF HMRS TECHNIQUE Andrzej Urbanik,
Barbara Sobiecka, Justyna Kozub, Paulina Karcz
55
48. THE IMAGES OF THE SELECTED FRUIT OBTAINED - USABILITY OF MRI
Andrzej Urbanik, Barbara Sobiecka, Justyna Kozub, Paulina Karcz
56
49. USELFULNESS OF MR PROTON SPECTROSCOPY IN ASSESSMENT OF THE
DIAGNOSTIC OF THE DEMENTIA Andrzej Urbanik, Barbara Sobiecka,
Justyna Kozub, Paulina Karcz
57
50. ELECTRON PARAMAGNETIC RESONANCE EXAMINATION OF PPI
POLYAZOMETHINE Jan Weszka, Barbara Hajduk, Sylwia Bartomiejczyk,
Barbara Pilawa
58
51. BRAIN 1H MRS IN CHILDREN WITH LEUKODYSTROPHIES Ewa Jamroz,
Justyna Paprocka, Magdalena Wicher, Agnieszka Skorupa, Maria Sok,
Aleksandra Kietyka, Tomasz Banasik
59
52. INVESTIGATION OF GLOBULAR PROTEINS MOLECULAR DYNAMICS BY T1
DISPERSION PROFILES METHOD Dorota Wierzuchowska, Barbara
Blicharska
61
53. FREE RADICALS PROPERTIES OF GAMMA IRRADIATED PAROMOMYCIN
Sawomir Wilczyski, Barbara Pilawa, Marta Ptaszkiewicz, Jan Swako,
Pawe Olko, Robert Koprowski, Zygmunt Wrbel
62
54. DOMAIN SIZE AND MOLECULAR DYNAMICS OF POLY(BUTYLENE
TEREPHTHALATE)/DECYLAMINE_C60 NANOCOMPOSITES Aneta Woniak-Braszak,
Mikoaj Baranowski, Roman Gwodzik-Bujakowski, Kazimierz Jurga, Jan
Jurga, Krystyna Hoderna-Natkaniec
63
55. HE INFLUENCE OF CONCENTRATION OF TCNEO_C60 ADDUCT ON
MOLECULAR DYNAMICS AND DOMAIN SIZE IN PBT/TCNEO_C60 NANOCOMPOSITES
Aneta Woniak-Braszak, Mikoaj Baranowski, Roman Gwodzik-Bujakowski,
Kazimierz Jurga, Jan Jurga, Krystyna Hoderna-Natkaniec
65
56. EPR STUDIES OF PARAMAGNETIC CENTERS IN DIFFERENT MELANIN
BIOPOLIMERS Magdalena Zdybel, Barbara Pilawa, Daria Czyyk, Sawomir
Wilczyski, Anna Gondzik, Ewa Buszman, Teresa Witoszyska, Ewa
Chodurek
66
57. EPR STUDIES OF THE EFFECT OF CONCENTRATION OF COPPER(II) AND
ZINC(II) IONS ON PAMAGNETIC PROPERTIES OF THE MIXED TYPE MELANIN
BIOPOLIMER Magdalena Zdybel, Barbara Pilawa, Ewa Buszman, Teresa
Witoszyska
67
58. CONFORMATIONAL FLEXIBILITY OF BUSPIRONE ANALOGUES FROM X-RAY
IN THE SOLIDS AND NMR IN SOLUTION Anna Bielenica, Andrzej Zimniak,
Izabela Dybaa, Anna E. Kozio, Marta Struga
69
ELECTRON PARAMAGNETIC RESONANCE EXAMINATION OF VITRINITES WITH
DIFFERENT CARBON CONTENT
Sylwia Bartomiejczyk1 , Barbara Pilawa1,2,
Joanna Komorek3
1Centre of Polymer and Coal Materials, Polish Academy of
Science, Marii Curie-Skodowskiej 34, 44-100 Zabrze, 2Medical
University of Silesia in Katowice,
School of Pharmacy and Division of Laboratory Medicine,
Department of Biophysics, Jednoci 8, 41-200 Sosnowiec, Poland,
3Institute of Applied Geology, Faculty of Mining,
Silesian Technical University, Akademicka 2, 44-100 Gliwice
EPR spectroscopy was applied to analyse of four vitrinites
differ in the degree of coalification. Vitrinites are the main
constituents of coals and they are mainly responsible for their
paramagnetic properties. The aim of this work was to determine
concentration and properties of paramagnetic centres of the studied
vitrinites.
The first derivative spectra of the samples were measured by the
use of an X-band (9.3 GHz) EPR spectrometer of RADIOPAN Firm
(Pozna). Modulation of magnetic field was 100 kHz. Frequency of
microwave radiation was measured by MCM recorder produced by EPRAD
Firm (Pozna). EPR spectra were recorded with microwave power in the
range 0.7-100 mW. For the EPR spectra amplitude (A), integral
intensity (I), linewidth (Bpp) and g-factor were determined.
Changes of lineshape and parameters of EPR spectra with microwave
power were obtained. Concentration of paramagnetic centers in the
examined vitrinites was determined. Ultramarine was the reference
of the concentration. The secondary reference was a ruby crystal
permanently located in the resonance cavity.
Broad asymmetric EPR spectra were observed for all the studied
vitrinites. Linewidths in the range 0.47-0.73 mT were obtained the
studied samples. Strong dipolar interactions are responsible for
the broadening of EPR spectra. The highest amplitude of EPR line
was obtained for highest coalificated vitrinite. The highest
concentration of paramagnetic centers characterizes this sample.
Relatively lower amounts of paramagnetic centers exist in the
others examined vitrinites with the lower carbon contents. The
asymmetry of the EPR spectra strongly depends on microwave power.
The changes of lineshape with increasing of microwave power points
out that complex paramagnetic center system exist in the studied
vitrinites. Unpaired electrons in the studied vitrinites are mainly
localized on oxygen atoms, and their g-factors are 2.0034-2.0037.
The EPR lines of the examined vitrinites do not saturate in the
used microwave power up to 100 mW. Fast spin-lattice relaxation
processes exist in the vitrinite samples. The lowest spin-lattice
relaxation time characterizes vitrinite with the highest carbon
content.
1
A SIMPLE ONE-DIMENSIONAL METHOD OF CHEMICAL SHIFT ANISOTROPY
DETERMINATION UNDER MAS CONDITIONS
Piotr Bernatowicz
Institute of Physical Chemistry, Polish Academy of Sciences,
Kasprzaka 44/52, 01-224
Warsaw, Poland
A method of determination of chemical shift anisotropy (CSA)
tensor principal components under MAS condition is presented. It is
a simple, one-dimensional, and robust alternative to the commonly
exploited, but more complicated 2D-PASS. The required CSA
components are delivered by simultaneous numerical analysis of a
few regular MAS spectra acquired under different spinning rates.
Porphycene was chosen for testing of this method. It was taken as a
model molecule because standard numerical analysis of its single
slow-spinning MAS spectrum fails due to extensive spinning
sidebands overlap. Application of the new method allowed for fast
and successful determination of the chemical shift tensors with
high accuracy. The result of the simultaneous
numerical analysis of two MAS spectra of porphycene is shown in
Figure 2.
Figure 1: Porphycene.
Figure 2: The result of simultaneous numerical analysis of two
MAS spectra of porphycene. Spinning rates are 10 kHz (a) and 2 kHz
(b).
2
KONSTRUKCJA CEWKI RADIOWEJ CZSTOCI DO OBRAZOWANIA PIERSI W
NISKIM POLU MAGNETYCZNYM
B.Basiak1,2,4, V. Volotovskyy3, C. Deng4, B. Tomanek1,2,3,4
1Department of Clinical Neurosciences, University of Calgary,
Calgary, Canada; 2Instytut Fizyki Jdrowej Polskiej Akademii Nauk w
Krakowie, Polska; 3Institute for Biodiagnostics, National Research
Council, Winnipeg, Canada; 4Institute for Biodiagnostics (West),
National Research
Council, Calgary, Canada
Obrazowanie rezonansem magnetycznym jest bezinwazyjn metod
diagnostyczn pozwalajc na uzyskanie obrazw poszczeglnych czci ciaa
o wysokiej rozdzielczoci. Poniewa stosunek sygnau do szumu ronie
liniowo z nateniem pola magnetycznego obrazy rezonansowe uzyskiwane
przy zastosowaniu systemw niskopolowych (poniej 1T) charakteryzuj
si gorsz rozdzielczoci i duszym czasem akwizycji danych ni obrazy z
systemw wysokopolowych (powyej 1T). Instalacja i koszty
eksploatacji systemw wysokopolowych s jednak znacznie wysze w
porwnaniu do systemw niskopolowych. Ich wysoka cena, a co za tym
idzie cena obrazowania rezonansowego, uniemoliwia ich powszechne
zastosowanie. Jedn z metod poprawy stosunkowo niskiego SNR jest
optymalizacja cewek radiowej-czstoci. Poniewa rak piersi jest czst
chorob i przyczyn zgonw niezbdna jest ich wczesna, oglnodostpna
diagoza a dziki temu moliwoc skutecznego leczenia. W tym celu
zostaa skontruowana cewka RF skadajca si z dwch wzajemnie
odsprzganych cewek kwadraturowych typu siodowego (Rys) dziaajca w
niskopolowym systemie 0.2T. Cewka pozwolia na uzyskanie wysokiej
jakoci obrazw piersi (obu jednoczenie lub kadej osobno). Wygoda
pacjentki rwnie bya wzita pod uwag w czasie kontrukcji. Cewka
umoliwia otrzymanie obrazw piersi w przecigu niespena dwch minut
przy zastosowaniu standartowych sekwencji pomiarowych typu spin
echo. Opracowana cewka mone zwikszy dostpno dianostyki piersi i
potencjanie zastpi standardow inwazyjn mammografi.
A B
Rys. 1. Cewka na piersi (A) i uzyskany obraz rezonansowy piersi
(B). (GE, FOV 7 cm, 256 x 256, warstwa 3 mm)
3
OBRAZOWANIE MOLEKULARNE MR GLEJAKW Z ZASTOSOWANIEM CELOWANYCH
RODKW KONTRASTOWYCH
B. Basiak1,2,3, T.Foniok3, Albaghdadi5,6, J.Landry1, J. G.
Sutherland1, B. Tomanek1,2,4
1Department of Clinical Neurosciences, University of Calgary,
Calgary, Canada, 2Instytut Fizyki
Jadrowej Polskiej Akademi Nauk w Krakowie, 3Institute for
Biodiagnostics (West), National Research Council, Calgary, Canada,
4Institute for Biodiagnostics, National Research Council,
Winnipeg, Canada 5Institute of Biological Sciences, National
Research Council, Ottawa, Canada, 6Faculty of Medicine, University
of Ottawa, Ottawa, Canada
Stosowane obecnie systemy RM i metody obrazowania pozwalaj
jedynie na obrazowanie duych skupisk komrek, rzdu 1 mm3.
Obrazowanie molekularne rezonansem magnetycznym pozwala na
obrazowanie na poziomie pojedynczych komrek. W celu polepszenia
kontrastu tkanki patologicznej uywa si rodkow skracajcych czasy
relaksacji. Stosowane w diagnostyce nowotworw rodki kontrastowe
opieraj si jedynie na rnym ukrwieniu tkanki normalnej i
nowotoworowej, co nie zawsze jest wyznacznikiem procesw
chorobowych. Ostatnie postpy w dziedzinie ORM, biologii
molekularnej, nano-technologii przyniosy moliwo obrazowania RM
znacznie mniejszych obiektw, takich jak pojedyncze komrki. Stao si
to moliwe dziki zastosowaniu tzw. targeted contrast agents, czyli
celowanych rodkw kontrastowych. Wspczesna nano-technologia pozwala
na syntez silnie paramagnetycznych nano-czsteczek, takich jak Fe304
z obiektami biologicznymi np. przeciwciaami. Paramagnetyczne
czsteczki zaburzajc lokalne pole magnetyczne skracaj czasy
relaksacji T2 przez co widoczne s na obrazach MRI T2 waonych.
Przeciwciaa su jako noniki dostarczajce czsteczki do komrek
nowotworowych. W ten sposb moliwe jest obrazowanie teoretycznie
nawet pojedynczych komrek nowotworowych. W zaprezentowanym
wystpieniu prezentujemy wynik dotyczce wczesnej diagnostyki glejkw
z zastosowaniem celowanych rodkw kontrastowych. Projekt
sponsorowany przez CIHR team grant in nanomedicine and regenerative
medicine.
4
MR IMAGING - ARTIFACTS PRODUCED BY DENTAL MATERIALS
Amira Bryll1, Andrzej Urbanik1, Anna Jurczak2, Maria
Chomyszyn-Gajewska2,
Stanisaw Sztuk1, Magorzata Szafirska1, Barbara Sobiecka1,
Paulina Karcz3
1Department of Radiology, Collegium Medicum, Jagiellonian
University, Krakow, Poland
2Department of Conservative Dentistry, Collegium Medicum,
Jagiellonian University, Krakow, Poland
3Division of Radiology, University Hospital in Krakow, Poland
Purpose: The aim of the study is estimation of degree of image
disturbances caused by dental materials in MR examination, and risk
of dislocation of ferromagnetic materials in magnetic field.
Material and method: 25 samples of dental materials containing
metals fixed, or present for iatrogenic reasons in oral cavity,
were examined in a gel phantom whose signal is close to the signal
of soft tissues. Signa Horizon l .5T (GEMS) unit was used with spin
echo sequences in Tl time with parameters TE: 20ms, TR: 300ms,
slice thickness: 3mm, gap: l.5mm, imaging matrix: 256x256, FOV:
20x20cm. Results: Dislocation of examined samples by magnetic field
was not noticed. All materials produced artefacts that had
different degree of intensity. Conclusions: Lac of dislocation of
dental materials in gel surrounding indicate that dislocation of
those materials fixed permanently in oral cavity of size not
exceeding the size of examined samples in l.5T will not occur.
Materials from precious alloys cause a small degree of image
disturbances, but small artefacts may occur some distance away from
them. The remaining materials produce image deformations that may
alter head MR images.
5
STRUCTURE AND DYNAMICS CHANGES IN S100A1 PROTEINS
Monika Budziska
1), Micha Nowakowski
1), ukasz Jaremko
1,2), Mariusz
Jaremko1)
, Igor Zhukov1,3,4)
, Konrad Zdanowski1,5)
, Agnieszka Belczyk1)
, Andrzej Bierzyski
1), Andrzej Ejchart
1)
1) Institute of Biochemistry and Biophysics, Polish Academy of
Sciences, [UTF-8?]Pawiskiego 5A, 02-106 Warsaw, Poland,
2) Faculty of
Chemistry, Warsaw University, Pasteura 1, 02-093, Warsaw,
Poland, 3)
Slovenian NMR Centre, National Institute of Chemistry,
Hajdrihova 19, P.O.B. 660, SI-1001 Ljubljana, Slovenia,
4) EN-FIST Center of Excellence,
Dunajska 156, SI-1000, Ljubljana, Slovenia, 5)
Institute of Chemistry, University of Podlasie, Siedlce,
Poland.
S100A1 is a homodimeric calcium binding protein built up of 93
residues per subunit. It is stabilized by noncovalent interactions
at its dimer interface; each subunit contains two EF-hand motifs
linked by a flexible linker [1].
Chemical modification of Cys 85 residue in the C-terminal part
of S100A1 protein by disulfide bond formation with small thiols
leads to a dramatic increase of the protein affinity for calcium
[2] due to conformational changes induced in the apo protein, most
probably, by an interaction of a thiol molecule attached to Cys 85
with aromatic rings of Phe 88 and Phe 89 promoting -helical
conformation in the 85-89 segment of the protein in the -helical
conformation [3].
If so, the substitution of Cys 85 by Met, with the side chain
long enough to reach Phe 88 and Phe 89 residues in the -helix
should have the similar effect on protein structure and its
calcium-binding ability as Cys 85 thionylation.
Using a number of multinuclear 3D NMR techniques applied to the
samples of
13C,
15N double labeled S100A1Cys85Met protein
measured at 11.7 T and 18.8 T we have assigned resonances of
almost all 1H,
15N,
13C. The structural information derived from chemical shifts
was
combined with dictance constrains derived from 13
C and 15
N edited NOESY spectra and used to calculate its 3D structure
with XPLOR and CYANA software.
So obtained 3D structure was compared with those for: human
apo-S100A1 protein [4], rat apo-S100A1 protein [5] and bovine
apo-
6
S100A1 protein modified by disulfide bond formation with
-mercaptoethanol [3], their backbone dynamics have been predicted
using TALOS+ software [6] which is essentially based on the
backbone chemical shifts. Acknowledgment This work was supported by
a grant N301 031234 from the Polish Ministry of Science and Higher
Education.
References [1] R. Donato, Int. J. Biochem. Cell Biol. (2001)33,
637-668. [2] G. Goch, S.Vdovenko, H. Kozowska, A. Bierzyski, FEBS
J.
(2005)272, 2557-2565. [3] I. Zhukov, A. Ejchart, A. Bierzyski,
Biochemistry (2008)47, 640-
650. [4] PDB code 2LOP [5] R.R. Rustandi, D.M. Baldisseri, K.G.
Inman, P. Nizner, S.M.
Hamilton, A. Landar, A. Landar, D.B. Zimmer and D.J. Webber,
Biochemistry (2002) 41 , 788-796.
[6] M. V. Berjanskii, D.S. Wishart JACS (2005)127,
14970-14971
7
INFLUENCE OF STORAGE TEMPERATURE ON ANTIRADICAL PROPERTIES OF
SELECTED COSMETICS
1,2Anna Deda, 1Sawomir Wilczyski, 1Barbara Pilawa, 2Ewa
Pierzchaa 1 Department of Biophysics, Medical University of Silesia
in Katowice, School of Pharmacy
and Laboratory Medicine, Jednoci 8, 41-200 Sosnowiec, Poland 2
Department of Aesthetical Medicine, Medical University of Silesia
in Katowice, School of
Pharmacy and Laboratory Medicine, Francuska 15, 40-027 Katowice,
Poland Free radicals play an important role, in both health and
disease [1-3]. Reactive oxygen
species (ROS) are implicated in many diseases and photoageing.
Some civilization disease such as diabetes, atherosclerosis,
cardiovascular diseases or the rheumatoid arthritis are linked to
damage from ROS as a result of an imbalance between
radical-generating and radical-scavenging systems - a condition
called oxidative stress [1-4].
In skin free radical cause collagen degradation and epidermis
damages [1-2]. There is a lot of evidence about antioxidants role
in disease prevention . It is supposed that application of
antioxidants in cosmetic products can delay the ageing processes
and also reduce the risk of precancerous changes [4].
The aim of work was to evaluate of antiradical properties of 8
different cosmetics after storage at increased temperature.
The EPR spectroscopy was used to define antiradical potential of
tested samples. DPPH signal intensities after cosmetics samples
adding were compared. Free radicals were studied by electron
paramagnetic resonance spectroscopy at X-band (9.3 GHz) with
magnetic modulation of 100 kHz. EPR spectra were measured by
Radiopan (Pozna) spectrometer with Rapid Scan Unit (Jagmar Firm,
Krakw). The measurements were done with microwave power in the
range 2.2-70 mW at room temperature.
Lineshape of the EPR spectra and their parameters were analysed.
Integral intensity, amplitude and linewidth of the spectra was
shown. The first derivative EPR curves were measured with the low
microwave power of 2.2 mW to avoid microwave saturation effects of
the spectra. The integral intensities (I) of the EPR spectra were
calculated by double integration of the first derivative
curves.
The preparations containing in example ascorbic acid, B3
vitamin, caffeine, flavonoids and tocopherol were stored at 50C
during 30 minutes.
Increase of temperature up to 50C during 30 minutes reduce
antiradical properties of all studied preparations.
The most distinct decrease of antiradical properties was
recorded for preparation containing ascorbic acid even though
applied temperature does not lead to thermal degradation of
ascorbic acid. [1] Bartosz G. (2006). Druga twarz tlenu. PWN,
Warszawa [2] Panickar K. S., Jayakumar A. R. & Noremberg M. D.
(2002). Differential Response of Neural Cells to Trauma-Induced
Free Radical Production In Vitro. Neurochem. Res., 27, 161-166. [3]
Stremoukhov A. A. ( 2001). Histamine-Dependent Changes in Free
Radical Processes during Coronary Heart Disease. Bull. Exp. Biol.
Med., 132, 1157 1159. [4] Czernichow S., Blacher J. & Hercberg
S. (2004). Antioxidant vitamins and blood pressure. Curr
Hypertension Rep, 6, 27-30.
8
http://vls1.icm.edu.pl/cgi-bin/sciserv.pl?collection=springer&journal=00074888
NOVEL DESIGN OF RF SURFACE COILS FOR MAGNETIC RESONANCE IMAGING
SYSTEM AT 0.088 T
Agata Drd1, Bartosz Proniewski1, Henryk Figiel1 and Mateusz
Suchanek2
1 University of Science and Technology, Faculty of Physics and
Applied Computer
Science, Al. Mickiewicza 30, 30-059 Krakow, Poland 2 Department
of Chemistry and Physics, University of Agriculture,
Balicka 122, 30-149 Krakow, Poland
Special care must be taken during the design phase of high
frequency transmit/receive coils, as the quality of images obtained
with the coil can be attributed to its parameters. Beneficial
aspects of using surface coils are high sensitivity and convenience
of application. There is a possibility to exploit the solenoid type
coils in low-field MRI scanners with permanent magnets, due to the
fact that the magnetic induction vector is perpendicular to the
patients axis. The use of solenoid or other volume coil restricts
access to the imaged region, what is especially undesirable in
head, neck and spine imaging of claustrophobic patients. One of the
advantages of low field scanners is open access to the patient that
can only be fully achieved using carefully designed, dedicated
surface coils.
Typical surface coils provide high sensitivity near the coil
windings that decreases very quickly with distance; however
conscientious design can shape the sensitivity profile to match the
desired imaging region. The winding layout of the proposed half
solenoid surface coils has been selected as a result of optimizing
coils inductance and impedance by means of the FastHenry simulation
software and subsequently using COMSOL Multiphysics 3.5 to simulate
the static magnetic field Bz. Two half solenoid surface coils with
the novel parallel-series winding scheme have been designed and
constructed, both having the same winding layout but different
cross sections, namely half circle and half ellipse. Both coils
have been tuned and matched to the Larmor frequency of hydrogen in
0.088 T magnetic field with high quality capacitors. Quality
factors have been evaluated using a spectrum analyzer. Conformity
with simulations and SNR measurements have been evaluated using MR
images of two phantoms: specifically arranged vials and a plastic
jar filled with 0.9% NaCl and water respectively.
Better coverage can be obtained with discussed coils in
comparison to typical surface coils, while providing an easy, open
access to the imaging region and comparable signal to noise ratio.
Further work is planned in order to optimize this type of
transmit/receive coils and make them viable for 0.2 T MRI systems.
Moreover, the comparison between simulation models and final
designs suggest that it is highly recommended to employ computer
simulations in a design process of more complex radiofrequency
coils.
9
NMR MEASUREMENTS IN THE GAS PHASE EMPLOYING A HOME-MADE HIGH
PRESSURE APPARATUS
Piotr Garbacz and Karol Jackowski
Laboratory of NMR Spectroscopy, Faculty of Chemistry, University
of Warsaw, Pasteura 1,
02-093 Warszawa, Poland An efficient high-pressure (HP) system
was built which permits the various NMR
studies of gaseous mixtures. The most important advantages of
the present HP system are: possibility of continuous measurements,
high degree of pressure control and easy preparation of gaseous
mixtures. Additionally, the measurement can be completed in shorter
time in comparison to measurements in glass ampoules. All parts of
high pressure apparatus are non-magnetic in order to prevent
disturbances of spectrometer magnetic filed.
The HP apparatus consists of a high pressure generator, a
pressure gauge and a high pressure cell. The high pressure
generator compresses gas mechanically. If sufficient pressure is
not reached in one stroke, the system can be recycled. Maximal
pressure which can be obtained in a HP cell was five and a half
times greater than pressure in a gas fill line. The pressure gauge
is used to measure accurately pressure inside a HP call. The high
pressure system is connected with a source of buffer gas and a
vacuum line. Gases mixtures were perpetrated in two steps. Small
amount of gas (~10 g), which resonance frequency was observed, was
transferred from a vacuum line to a HP cell. In the second step
much larger excess of buffer gas was compressed in high pressure
generator and transferred to the HP cell.
10
According to the viral equation, the shielding constant for gas
can be expanded in power series of density [1]:
(,T) = 0(T) + 1(T) +
For hydrogen mixtures with helium-4 higher order terms can be
safely neglected. The
first coefficient 0 corresponds to magnetic shielding of an
isolated molecule. The second coefficient 1 is determined by
intermolecular interactions. Both are easy to determine from
experimental data, because shielding-density dependence is linear
and provides the zero-density point (0) and a slope of straight
line (1).
The secondary isotope effect of a hydrogen molecule in helium-4
was determined. The proton chemical shifts of hydrogen and
deuterium hydride extrapolated to the zero-density point were equal
6,583(2) ppm and 6,484(1) ppm, respectively. Both values are
measured relative to liquid pure TMS. The secondary isotope effect
in hydrogen was equal -0.044 ppm. The obtained result is in good
agreement with quantum chemistry calculations [2].
References: [1] Raynes W., Buckingham A., Bernstein H., J Chem.
Phys., 36 p. 3481 (1962) [2] Jaszuski M., ach G., Strasburger K.,
Theor, Chem. Acc, in press
Acknowledgements We acknowledge financial support from the
Ministry of Science and Higher
Education, research grant N N204 244134 (2008-2011). Project
operated within the Foundation for Polish Science MPD Programme
co-
financed by the EU European Regional Development Fund.
11
STRUCTURE OF BARBITURIC ACID IN WATER SOLUTIONS AN NMR/DFT
STUDY
Adam Gryff-Keller and Anna Kraska-Dziadecka
Warsaw University of Technology, Faculty of Chemistry
Noakowskiego 3, 00-664 Warsaw
Barbituric acid (2,4,6-trioxopyrimidine) and its 5-substituted
derivatives are compounds of a high pharmacological importance. The
parent compound is a strong C-H acid occurring in water solutions
as neutral molecule (B), monoanion (B-1) and/or dianion (B-2),
dependently on the solution acidity.
NH
NH
O
O O NH
NH
O
O O N
NH
O
O O
B B-1 B-2
Figure 1. Barbituric acid, its anion and dianion.
Moreover, all these species can exist in several tautomeric
forms, although DFT calculations suggest strong preference of
triketo tautomers. Both 1H NMR and 13C NMR spectra of the
investigated compound in water solutions recorded at room
temperature exhibit dynamic line broadenings in some pH ranges. In
order to verify the beliefs concerning the solution structure of
the title compound, in this study we have looked for a
rationalization of the observed phenomena and made an effort to
reproduce theoretically the observed variations of 13C NMR chemical
shifts and spin-spin coupling constants, caused by acidity
changes.
12
BOUND WATER FREEZING IN LICHENS FROM THE GENUS UMBILICARIAE BY
PROTON RELAXATION AND BY DSC
H. Haraczyk1, P.Nowak1, M. Bacior1, M. Marzec1, and M. A
Olech2
1Institute of Physics and 2Institute of Botany, Jagiellonian
University, Cracow
Foliose lichens from the genus Umbilicariae may resist extremely
low
temperatures in their habitat [1-5]. Antarctic lichen
Umbilicaria aprina reveals the lowest detected photosynthetical
activity [1].
One of molecular mechanisms to survive extremely low temperature
is spontaneous dehydration of lichen thallus [6]. This suggests
that drought [7] and cold resistance can have similar molecular
mechanism. The formation of molecular glass may by the way for cell
to survive deep dehydration [8,9].
The understanding of the molecular mechanism of the metabolic
activity recovery during rehydration of thallus requires the
knowledge on a number and distribution of water binding sites,
sequence and kinetics of their saturation, and the formation of
tightly and loosely bound water fractions at different steps of
hydration process.
The thalli of Umbilicariae lichens were collected in Schirmacher
Oasis, Queen Maud Land, Continental Antarctics. All the reported
data were obtained in vivo, with the vitality of the photobiont no
lower than (665)%.
Proton FID is a superposition of the solid signal (described by
Abragam function with the line halfwidths equal to 38 kHz) and one
(for low hydration), or two liquid signal components coming from
tightly bound ( 80 s) and loosely bound water fraction ( 800
s).
2T2T
The freezing point of bound water detected by DSC decreases with
the increasing hydration level, suggesting that the heterogeneous
nucleation is responsible for ice nucleation in Umbilicariae
thalli. Freezing temperature is ca. 100C lower than melting
temperature. The performed freeze-thawing cycles showed that after
5th cycle the thermal response of the thallus remains unchanged.
Address for correspondence: H.Haraczyk, D. Sc., Institute of
Physics, Jagiellonian University, ul. Reymonta 4, 30-059 Cracow,
e-mail: [email protected]
References [1] H. Haraczyk On water in etremely dry biological
systems. Wyd. UJ (2003). [2] H. Haraczyk, J.Grandjean, M.Olech,
Colloids & Surfaces, B: Biointerfaces 28/4, 239, (2003). [3] H.
Haraczyk, J.Grandjean, M.Olech, M.Michalik, Colloids &
Surfaces, B: Biointerfaces 28/4, 251, (2003). [4] H. Haraczyk, A.
Pietrzyk, A. Leja, M. A. Olech, Acta Phys. Polon. 109, 411 (2006).
[5] H. Haraczyk, M. Bacior, P. Jastrzbska, M.A. Olech Acta Phys.
Polon. A115, 516-520 (2009). [6] B. Schroeter, C. Scheidegger, New
Phytologist 131, 273-285, (1995). [7] H. Haraczyk, M. Bacior, M.A.
Olech Antarctic Sci. 20, 527-535 (2008). [8] W.Q. Sun, A.C.
Leopold, Comp. Biochem. Physiol., 117A, 327 (1997). [9] T.
Kikawada, N. Minawaka, M. Watanabe, T. Okuda, Integr. Comp. Biol.
45, 710 (2003).
13
THE HYDRATION OF CUTICLE OF CHOSEN WEEVIL SPECIES (COLEOPTERA:
CURCULIONIDAE) AS RECORDED BY
PROTON RELAXATION AND SORPTION ISOTHERM
H. Haraczyk1, M. Florek1, P. Nowak1 and S. Knutelski1
1Institute of Physics and 2Institute of Zoology, Jagiellonian
University, Cracow Cuticle forms the outer shell of Arthropoda
body. It prevents the organs from environmental stresses, among
them dessication shock and decreased temperature [3]. Several
beetle genera differ in water loss through the cuticle layers, eg.
Carabidae cannot resist drying periods longer than several days,
whereas Tenebridae deal with much longer periods of water shortage
[1].
The resistivity of some beetle species for dessication stress
may be compared with those for other living organisms like
lichnized fungi [4]. As the cuticle is a multilayer composite
structure, the molecular mechanisms of water level decrease may be
connected with different layering of cuticle in different insect
genera [6].
Elytra of two Curculionidae species (Liparus glabrirostris and
Donus comatus) were collected in Southern Poland in Spring [5].
For both investigated species the hydration courses were
performed from the gaseous phase, showing: (i) a very tightly bound
water (m/m0 = 0.036 for L. glabrirostris and m/m0 = 0.044 for D.
comatus); (ii) a tightly bound water (with m/m0 = 0.03 for L.
glabrirostris, and 0.05 for D. comatus, with the hydration times
thyd = 3.1 h, and thyd = 1.7 h, respectively) and finally (iii)
loosely bound water pool (with the hydration times thyd = 25.5 h,
and thyd = 12.2 h, for L. glabrirostris and D. comatus,
respectively). The sorption isotherm is sigmoidal in form. Dent
model [2] is significantly better fitted than BET-approach. The
relative mass of water saturating primary binding sites is M/m0 =
0.036, and 0.046 for L. glabrirostris and D. comatus,
respectively.
Proton FIDs show solid component, well described by Gaussian
function, and one or two liquid, exponential, components (with 80 s
tightly bound water, and with 300-350 s loosely bound water
fraction). The sorption isotherm fittted to NMR data (with L/S, as
a measure of cuticle hydration level) shows the presence of water
sealed in pores of D. comatus elytra [6].
2T2T
Address for correspondence: H.Haraczyk, D. Sc., Institute of
Physics, Jagiellonian University, ul. Reymonta 4, 30-059 Cracow,
e-mail: [email protected]
References [1] W. Block Eur. J. Entomology, 93: 325339, (1996).
[2] R.W. Dent Textile Res. J., 47: 145-152, (1977). [3] H.Haraczyk
On water in etremely dry biological systems. Wyd. UJ (2003). [4] H.
Haraczyk, M. Bacior, M.A. Olech Antarctic Sci. 20: 527-535 (2008).
[5] S. Knutelski. Rnorodno, ekologia i chorologia ryjkowcw
rezerwatu biosfery "Tatry" ( Coleoptera: Curculionoidea [w:]
Monografie Faunistyczne 23). Polska Akademia Nauk, (2005). [6]
U.G.K. Wegst, J. F.V. Vincent. Arthropod Struct. Dev., 33: 187199,
(2004).
14
PHASE TRANSITION AND MOLECULAR MOTIONS IN [Ba(H2O)3](ClO4)2
STUDIED BY NUCLEAR MAGNETIC RESONANCE
AND COMPLEMENTARY METHODS Joanna Hetmaczyka, ukasz Hetmaczyka,
Krystyna Hoderna-Natkaniecb,c, Anna Migda-
Mikulia and Edward Mikulia,
a Jagiellonian University, Faculty of Chemistry, Krakw, Poland;
b A. Mickiewicz University, Institute of Physics, Pozna,
Poland;
c Frank Laboratory of Neutron Physics, JINR, Dubna, Russia
Triaquabarium chlorate(VII): [Ba(H2O)3](ClO4)2 is particularly
interesting molecular material because of the occurrence of
different reorientational motions of the complex cations, H2O
ligands and ClO4 anions. At room temperature the title compound
crystallizes in a hexagonal crystal system, within the space group
No. 176 = P63/m, with two molecules in the unit cell(Z = 2). The
following unit cell constants: a = 7.290(5) , b = 7.291(5) , c =
9.673(5) were determined by us earlier [1].
Using differential scanning calorimetry (DSC) method [1] one
solid-solid phase transition at: hCT = 210.6 K (onset on heating)
and
cCT = 204.6 K (onset on cooling) was
observed for [Ba(H2O)3](ClO4)2 in the temperature range of
90-300 K. The thermal hysteresis of the phase transition
temperature TC equal to ca. 6 K and the heat flow anomaly sharpness
suggest that the detected phase transition is a first-order one.
The relatively high entropy change (S 16.8 Jmol-1K-1) connected
with observed phase transition indicates high degree of dynamical
disorder.
The decomposition process of the title compound proceeds in the
three main stages. In stage I (330-520 K) dehydration of
[Ba(H2O)3](ClO4)2 to anhydrous Ba(ClO4)2 undergoes in two steps, in
which consecutively and of all H2O molecules per formula are
liberated. In stage II (520-740 K) anhydrous Ba(ClO4)2 has two
solid-solid phase transitions and next it melts. Stage III (above
761 K) is connected with decomposition and explosion of melted
Ba(ClO4)2 [2].
Infrared (FT-MIR) and neutron scattering (IINS/QENS)
measurements [1] show that the H2O groups do not perform fast
stochastic reorientation (within picoseconds correlation time
scale, (R10-11-10-12 s) in the temperature range of 20-270 K (even
in high temperature phase). There are possible much slower
reorientations (R 10-4-10-5 s) of the whole complex cation
[Ba(H2O)3]2+. In the FT-MIR spectra the appearing of new weak
shoulder band at ca. 1652 cm-1 at the vicinity of TC (at ca. 200
K), suggests that during phase transition changes of the crystal
structure can take place.
The temperature dependence of parameters describing 1H NMR
absorption line (slope line width (H) and second moment (M2)) was
used to propose a model of the internal dynamics of protons in
triaquabarium perchlorate. The measurements of the 1H NMR signal
were performed in the temperature range of 120-300 K on a
continuous wave 25 MHz laboratory made instrument operating in the
double modulation system [3]. Fig. 1 shows the temperature
dependence of the M2 of 1H NMR line in the studied compound. The
second moment of 1H NMR line was calculated for rigid structure
according to van Vleck formula [4], assuming O-H distance equals to
0.97 and H-O-H angle equals to 109. The M2 value corresponding to
the rigid lattice M2rigid was calculated to be equal 25.2110-8T2.
As follows from Fig. 1, we reach sufficiently low temperature
(about 120 K) to record the experimental value of M2 corresponding
to the rigid lattice. On heating the sample from 120 to 300 K we
can observe continuous, insignificant change of the M2 value from
2910-8T2 to 1910-8T2 (see
15
Fig. 1). In the temperature range of 120-180 K the second moment
value decreases from 2910-8T2 to 2410-8T2. The value of M2 remains
almost constant in the temperature range of 180-220 K. In the
vicinity of phase transition temperature, decreasing of the M2
starts and reaches value 1910-8T2 at 300 K. The absorption signal
is two-component below phase transition and reveals three
components (one is narrow) above this temperature. The analysis of
the second moment of 1H NMR line in the room temperature for
[Ba(H2O)3](ClO4)2 revealed that only one from three H2O ligands may
perform the 60 librational motion. The assumed model carried on
only small changes of M2. It confirms that reorientation of H2O
molecules is slow even at 300 K. The ratio of the area under the
narrow contribution to 1H NMR line and the whole line is close to
1/3, which suggests that at ca. 210 K switching on much faster
rotational (diffusive) motion of only one, from the three water
molecules in the formula unit of triaquabarium perchlorate, takes
place. This observation is in a good agreement with the results of
the thermal analysis (TG/DTG/SDTA) [2] of title compound.
100 200 3000
10
20
30
T cc
M2 [
10-8 T
2 ]
T [K]
T hc
Fig. 1. Temperature dependence of the second moment (M2) of the
1H NMR line for
[Ba(H2O)3](ClO4)2 [1] . Hetmaczyk, J. Hetmaczyk, A.
Migda-Mikuli, E. Mikuli, EUCMOS 2008 XXIX
European Congress on Molecular Spectroscopy, Opatija, Croatia,
31 August-5 September 2008. Poster P1-29. Book of Abstracts, page
64. ISBN 978-953-6690-76-3.
[2] A. Migda-Mikuli, J. Hetmaczyk, E. Mikuli, . Hetmaczyk,
Thermochimica Acta 487 (2009) 43-48.
[3] K. Hoderna-Matuszkiewicz, Fizyka dielektrykw i
radiospektroskopia XV, PWN, Warszawa-Pozna 1989, p. 95.
[4] J.H. van Vleck, Phys. Rev. 74 (1948) 1168.
16
THE POSSIBILITIES OF 31P NMR SPECTROSCOPY APPLICATION IN
DETERMINATION OF PHOSPHATES ADDITIVES IN MEAT
PRODUCTS
Moliwoci zastosowania spektroskopii 31P NMR w oznaczaniu dodatkw
fosforanowych w produktach misnych
Pawe B. Hrynczyszyn, Edward Szyk
Faculty of Chemistry, Nicolaus Copernicus University, 7 Gagarina
Str., 87-100 Toru
Currently, the Nuclear Magnetic Resonance spectroscopy is one
the most important
method of the compounds identification. This non-invasive
technique is used not only in chemistry, physics or medicine, but
also in the other experimental sciences. The wide possibilities of
NMR spectroscopy and high technological progress in this discipline
create good conditions to the application of this technique in
analytical chemistry.
Due to the increase of additives applications, such as
polyphosphates (Na3P3O9, Na5P3O10, Na2H2P2O7, Na4P2O7,) in food
industry, we decided to prepare new analytic methods. In this case
the best solution was to develop the new method that was very
sensitive, non-invasive and without any influence on the studied
matrix. The NMR technique is one of the most appropriate in this
case. Our previous researches about the possibilities of NMR
spectroscopy application as analytical method with external
reference standard MDPA (Methylenediphosphonic Acid) was very
successful. High recovery, accuracy and precision parameters
allowed using this method in routine polyphosphates analyses1. The
aim of the presented here study was to elaborate new analytical
method using a short preparation time and a simpler procedure. We
also applied our new method in the other matrices. The use of
internal standard method with HMPA (Hexamethylphosphoramide)
allowed shortening the time of analysis procedure with good
analytical parameters. However, ideal situation will be the use of
this method without the special procedure of sample preparation.
Therefore, the first optimistic tests were also made using 31P CP
MAS NMR experiments in 7 mm rotors with rotation speed 4.5 kHz on
Bruker Avance 300 MHz.
31P NMR spectrum of meat extract with Na3P3O9 CP MAS 31P NMR
spectrum of laboratory sample with K4P2O7
Acknowledgements: The author wishes to thank the Ministry of
Science and Higher Education for the financial support: grant No N
N204 150838.
1 Hrynczyszyn, P.; Jastrzbska, A.; Szyk, E. Anal. Chim. Acta,
2010, 673, 73-78.
17
ASSESSMENT OF THE RELATION BETWEEN CARDIAC FUNCTION AND LEFT
VENTRICLE LONG-AXIS ORIENTATION IN MURINE
MODEL OF HEART FAILURE
Magdalena Jaboska1,2, Tomasz Skrka1, Urszula Tyrankiewicz1,
Henryk Figiel2
1H. Niewodniczanski Institute of Nuclear Physics PAN, Department
of Magnetic Resonance Imaging, Krakow, Poland
2AGH University of Science and Technology, Faculty of Physics
and Applied Computer Science, Department of Medical Physics and
Biophysics, Krakow, Poland
Purpose and introduction The aim of his work was to assess
changes in left ventricle (LV) long-axis orientation in TgGq*44
mice model of heart failure. In this model cardiac pathology mimics
human non-ischemic dilated cardiomiopathy and develops in
age-dependent manner. Motivation of this retrospective study was
observed variability of LV long-axis orientation during MRI
measurements. The secondary aim was to characterize mice cardiac
function using separate functional condition stages witch
differentiate mice during pathology development. Material and
methods LV long-axis orientation was assessed from MR scout images
and was described using two angles: horizontal angle (HA), from
images in the coronal projection, and the vertical angle (VA), from
the images in the sagittal plane, including long axis of the heart.
LV function was estimated from series of short-axis cine images of
one midventricular slice (at the papillary muscles level). For
cardiac function assessment FAC parameter was used (calculated as
EDA-ESA/EDA, where EDA End-Diastolic Area, ESA End-Systolic Area).
The segmentation problem with respect to the LV long-axis
orientation was solved using unsupervised cluster analysis (CA)
with k-means algorithm. The same technique was used for heart
function segmentation (FAC). In order to find proper number of
clusters, v-fold cross-validation method was used. Results Six
homogeneous clusters were found as an optimal number for CA with
respect to HA and VA. In order to assess relation between long-axis
orientation and mouse age, age-interval contributing to the cluster
and contribution of the clusters to each interval were evaluated.
Similar analysis were performed for the FAC parameter. Population
was divided into groups under eight functional condition stages:
starting from very poor contractility (35%
APPLICATION OF MICROSTRIP RF COILS TO MRI MICROSCOPY Krzysztof
Jasiski1, Anna Mynarczyk1, Peter Latta2, Vyacheslav Volotovskyy2,
Wadysaw
P.Wglarz1, Bogusaw Tomanek1,2
1Instytut Fizyki Jdrowej Polskiej Akademii Nauk,ul.
Radzikowskiego 152, 31-342 Krakw, Poland, 2Institute for
Biodiagnostics, National Research Council of Canada, 435 Ellice
Avenue, Winnipeg, Manitoba R3B 1Y6, Canada
Quantitative MRI studies of mass limited samples require
application of appropriate RF coils to ensure homogenous B1 field
distribution within the sample. To facilitate imaging of
submillimetre object with sufficient SNR, the RF coil has to be
scaled down to match the size of the sample. The two
straightforward RF microcoil designs are micro solenoid and planar
helix. Fabrication of submillimetre coils according to those
patterns is challenging as it requires application of
micromachining and other complicated microtechnologies such as
X-ray or optical lithography, electroplating and
electrodeposition.
There are several concepts of MRI RF coils such as TEM
resonators or surface coils exploiting microstrip line. However
application of microstrip to MRI microimaging was not reported so
far. We present a novel design of MRI RF volume microcoil, based on
a microstrip structure. The coil consists of two parallel
microstrip elements conducting RF currents in opposite direction
thus creating a homogenous RF field in the space between the
microstrips.
Theoretical calculations and FEM electromagnetic virtual
prototyping were used to optimize the coil geometry in order to
achieve optimal SNR distribution within the sample volume, high Q
factor and predict electric properties (tuning and matching) of the
coil.
Results of B1 RF field distribution obtained from FEM simulation
and MRI B1 field mapping experiment are presented. MRI images of
capillary phantoms and biological objects obtained with use of the
double microstrip RF microcoil on an 11.7T Bruker scanner are
presented as well. The double microstrip RF microcoil presents an
interesting alternative to commercially available MRI microcoils as
its construction is cost effective and efficient. MRI results agree
with theoretical calculations and FEM simulations. Acknowledgments:
This work was partially supported by grant from European Community
(EuroCanMRI, PIRSES-GA-2008-230863)
19
SOLID STATE NMR SPECTROSCOPY AS A PRECISE TOOL FOR ASSIGNING THE
TAUTOMERIC FORM IN CHIRAL O-HYDROXY
SCHIFF BASES APPLIED AS LIGANDS IN THE ASYMMETRIC CATALYSIS.
Spektroskopia NMR w ciele staym jako precyzyjne narzdzie do
opisu form tautomerycznych chiralnych o-hydroksy zasad Schiffa
stosowanych
jako ligandy w asymetrycznej katalizie.
Magdalena Jaworska1, Pawe B. Hrynczyszyn1, Mirosaw Weniak1,
Grzegorz Krasiski2, Hassan Kassassir2, Wodzimierz Ciesielski2,
Marek J. Potrzebowski2
1 Wydzia Chemii, Uniwersytet Mikoaja Kopernika, ul. Gagarina 7,
87-100 Toru 2 Centrum Bada Molekularnych i Makromolekularnych,
Polska Akademia Nauk,
ul. Sienkiewicza 112, 90-363 d e-mail: [email protected]
Chiral Schiff bases can be obtained using aldehydes and primary
amines. Schiff base
metal complexes are broadly applied as catalysts in homogenous
catalysis1 or after immobilization on solid support in
heterogeneous catalysis2, biologically active compounds3, chemical
sensors in spectrophotometric method4 and luminescent
materials5.
(S)-Diphenylvalinol was obtained from L-valine according to
method previously reported by Itsuno6. Tridentate Schiff bases (8
compounds) were prepared in the reaction with different
salicylaldehydes and 2-hydroxy-1-naphtaldehyde in ethanol solutions
at room temperature. All compounds were yellow or orange
crystalline solids. Two analogous Schiff bases,
(S,E)-2-((1-hydroxy-3-methyl-1,1-diphenylbutan-2-ylimino)methyl)phenol
1 and
(S,Z)-2-hydroxy-6-((1-hydroxy-3-methyl-1,1-diphenylbutan-2-ylamino)methylene)cyclohexa-2,4-dienone
2, exist in the solid state as phenol-imine and keto-amine
tautomers, respectively. 1D and 2D SS NMR techniques were used for
structure assignment and for inspection of the 13C and 15N ii of
the chemical shift tensor (CST) values (Fig. 1).
Figure 1. 15N CP MAS spectra of 1 and 2 recorded at different
spinning rates: (A, B) 8 kHz, (C, D) 1 and 2 kHz. The best-fitting
simulated 1D spinning CSA sideband patterns obtained using the
TOPSPIN program are presented in (E) and (F). NMR study indicates
that the span () and the skew (22iso) are extremely sensitive to
change in the tautomeric form of the Schiff bases. The experimental
data were confirmed by the theoretical calculations of NMR
shielding parameters for 1 and 2
20
using GIAO method with B3LYP functional and 6-311++g(d,p) basis
sets. It was concluded that the position of hydrogen in the
intra-molecular bridge has tremendous influence on 13C and 15N CST
parameters.
The tridentate Schiff bases were applied as chiral ligands in
the asymmetric diethylzinc addition to aldehydes. When ligands 2
and 8 were examined the enantioselectivity of the tested reaction
was the most remarkable subject to an electronic effect. When
ligand 2 was applied, the substrates with the electron-donating
groups in the para-positions (methoxy groups in examined aryl
aldehydes) led to the increase of enantioselectivity in comparison
with non-substituted benzaldehyde, but those with the
electron-withdrawing groups afforded enantioselectivity at the
lower rate. The opposite phenomenon was observed for other ligands.
Probably, the tautomerization phenomenon affected the formation of
catalytic active complex with zinc and the occurrence of two
different kinds of electronic effects. 1. Katsuki, T. Chem. Soc.
Rev. 2004, 33, 437. 2. Fraile, J. M.; Garca, J. I.; Mayoral, J. A.
Chem. Rev. 2009, 109, 360. 3. Rehder, D.; Santoni, G.; Licini, G.
M.; Schulzke, C.; Meier, B. Coord. Chem. Rev. 2003, 237, 53. 4.
Khatua, S.; Choi, S. H.; Lee, J.; Kim, K.; Do, Y.; Churchill, D. G.
Inorg. Chem. 2009, 48, 2993. 5. Binnemans, K. Chem. Rev. 2009, 109,
4283. 6. Itsuno, S.; Ito, K.; Hirao, A.; Nakahama, S. J. Org. Chem.
1984, 49, 555.
21
MULTIDIMENSIONAL NMR SPECTROSCOPY WITH SPARSE RANDOM
SAMPLING
Wiktor Komiski, Krzysztof Kazimierczuk, Maria Misiak, Jan
Stanek, Anna Zawadzka-Kazimierczuk
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093
Warszawa, Poland
Nuclear Magnetic Resonance is nowadays one of the most efficient
spectroscopic
techniques, providing insight into molecular structure and
dynamics. The observed frequencies of oscillatory Free Induction
Decay signal are sensitive indicators of electron surroundings of
nuclei and their, often very subtle, changes caused by inter- and
intramolecular interactions. However, especially in studies of
biomolecules, complexity of NMR spectra often causes difficulties
in their interpretation. This problem may be solved by acquisition
of multidimensional spectra which increases resolution and enables
identification of nuclei connected by mutual interactions.
The conventional approach to recording multidimensional NMR
experiments is limited by the need for fulfilling of the Nyquist
Theorem to avoid aliasing. It determines the sampling rate to be
twice higher than the highest frequency expected in the signal. In
consequence, this is an implicit limit for the maximum evolution
time and therefore obtainable resolution.
A truncated time domain signal results in broadened spectral
peaks, according to the Fourier Uncertainty Principle. Since the
above limitation is valid for all indirectly sampled dimensions
separately, the overall measurement time grows rapidly with the
number of dimensions and the desired resolution. Measurement of an
N-dimensional experiment requires acquisition of 2N-1k1k2kN-1
single FID signals (where ki, equal to switmaxi, is the number of
points in the i dimension, swi and tmaxi are the required spectral
width and maximum evolution time respectively, and the 2N-1 factor
is necessary because of the quadrature detection requirement).
Because of this, for spectra of higher dimensionality, it is
practically impossible to reach the relaxation limits in indirectly
sampled dimensions. The problem of effective acquisition of
multidimensional NMR spectra is getting relatively more important
at high fields, where the required Nyquist rate increases together
with spectral width.
A number of different approaches have been proposed to
circumvent the sampling limitation. Among them random sampling of
evolution time space and Multidimensional Fourier Transform,
enables to obtain, spectra at a very small fraction of number of
data points required conventionally. Moreover, the relative level
of artifacts caused by random sampling does not depend on this
fraction, and could be effectively removed. The new applications of
high dimensionality experiments will be shown and discussed.
References:
1. K. Kazimierczuk, W. Komiski, I. Zhukov, J. Magn. Reson. 179,
323-328 (2006). 2. K. Kazimierczuk, A. Zawadzka, W. Komiski, I.
Zhukov, J. Biomol. NMR, 36, 157-
168 (2006) 3. M. Misiak, W. Komiski, Magn. Res Chem., 45,
171-174 (2007) 4. K. Kazimierczuk, A. Zawadzka, W. Komiski, I.
Zhukov, J. Magn. Reson., 188, 344-
356 (2007) 5. K. Kazimierczuk, A. Zawadzka, W. Komiski, J. Magn.
Reson. 192, 123-130 (2008)
22
6. K. Kazimierczuk, A. Zawadzka, W. Komiski, I. Zhukov, J. Am.
Chem. Soc., 130, 5404-5405 (2008)
7. M. Misiak, W. Komiski, Magn. Res. Chem., 47, 205-209 (2009)
8. K. Kazimierczuk, A. Zawadzka, W. Komiski, J. Magn. Reson., 197,
219-228 (2009) 9. M. Misiak, W. Komiski, M. Kwasiborska, J. Wjcik,
E. Ciepichal, E. Swiezewska,
Magn. Res. Chem., 47, 825829 (2009) 10. Zawadzka-Kazimierczuk,
K. Kazimierczuk, W. Komiski, J. Magn. Reson., 202,
109-116 (2010) 11. J. Stanek, W. Komiski, J. Biomol. NMR, 47,
65-77 (2010) 12. K. Kazimierczuk, A. Zawadzka-Kazimierczuk, W.
Komiski, J. Magn. Reson., 205,
286292 (2010) 13. V. Motkov, J. Novek, A. Zawadzka-Kazimierczuk,
K. Kazimierczuk, L. dek,
H. anderov, L. Krsn, W. Komiski, V. Sklen, J. Biomol. NMR, 48,
169-177 (2010)
14. K. Kazimierczuk, J. Stanek, A. Zawadzka-Kazimierczuk, W.
Komiski, Prog. Nucl. Mag. Res. Sp., 57, 420434 (2010)
23
THE NMR STUDY OF SAICAR FROM BODY FLUIDS OF PATIENTS SUFFERING
FROM ADENYLOSUCCINATE LYASE
DEFICIENCY
Hanna Krawczyk and Katarzyna Janowska
Faculty of Chemistry, Warsaw University of Technology,
Noakowskiego 3,
00-664 Warsaw, Poland, [email protected]
The de novo purine biosynthesis pathway involves 10 steps that
lead from 5-phosphoribosylpyrophosphate (PRPP) to inosine
monophosphate (IMP), from which the adenine and guanine nucleotides
are formed. Adenylosuccinate lyase (ADSL) catalyzes two reactions
in the biosynthesis of purine nucleotides. This concerns the
conversion of SAICA-ribotide into aminoimidasole carboxamide
ribotide and the conversion of adenylosuccinate into AMP. Marie et
al. [1] noted that deficiency of adenylosuccinate lyase (ADSL) was
the first inborn deficiency of purine synthesis to be identified in
humans. This disorder is characterized by the presence of
succinyl-5-amino-4-imidazolecarboxamide riboside (SAICA-riboside)
and succinyladenosine (S-Ado) in urine and cerebrospinal fluid. In
case of patients with ADSL deficiency, the lower was the
S-Ado:SAICAr ratio in CSF, the more severe the phenotype was.
Patients with neonatal fatal disease have a ratio less than 1,
those who suffer in the first months of life from severe form of
the disorder have a ratio of about 1, whereas those with a
relatively milder phenotype have ratios equal to or greater than 2
[2]. In our investigation the NMR measurements were performed on
samples of SAICAR, which were obtained after separation of urine of
patients suffering from this disease. The structures of this
compound have been designated with the use of NMR spectra and
theoretical GIAO - DFT calculations (Gaussian 03W). All these
results will be presented in the poster. [1] Marie S., Heron B.,
Bitoun P., Timmerman T., Van Den Berghe G., Vincent MF., Am. J.
Hum. Genet. (2004) 74, 1276. [2] Jurecka A., Zikanova M.,
Tylki-Szymanska A., Krijt J., Bogdanska A., Gradowska W., Mullerova
K., Sykut-Cegielska J., Kmoch S., Pronicka E., Mol Genet Metab.
(2008) 94(4) 435.
24
THE NOVEL DERIVATIVES OF STILBENES AS POTENTIALLY NEW OPTICAL
MOLECULAR SWITCHES
Hanna Krawczyk and Rafa Matczak
Faculty of Chemistry, Warsaw University of Technology,
Noakowskiego 3,
00-664 Warsaw, Poland, [email protected]
Stimulated by the success of digital optical data systems, in
which recording of information is carried out by light, and
realizing the demand for high storage densities, high switching
rates, and all optical devices, the search for molecular memory
elements for data processing by light has gained great impetus in
the past decade [1]. The use of organic materials offers the
advantage of easy fabrication, the possibility to shape organic
compounds into the desired structures by molecular engineering, the
fine-tuning of a large variety of physical properties by small
changes in the structure, and the characterization of single
isolated structures to allow the study of fundamental problems. The
design of molecular switches and trigger elements offer a
formidable challenge on the road toward miniaturization in future
technology. The basic requirement for a molecular switch is
bistability, i.e., the occurrence of two different forms of a
molecule, which can be interconverted by means of an external
stimulus. The molecules may be shifted between the states in
response to changes in e.g. pH, light, temperature, an electrical
current, microenvironment, or the presence of a ligand. A widely
studied class are photochromic compounds which are able to switch
between electronic configurations when irradiated by light of a
specific wavelength. For this class of compounds belong to
stilbenes. We synthetized new derivatives of stilbenes that may be
potentially new optical molecular switches. The structures of this
compounds have been designated with the use of NMR spectra and
theoretical GIAO - DFT calculations (Gaussian 03W). All these
results will be presented in the poster. [1] P. A. Lewis, C. E.
Inman, F. Maya, J. M. Tour, J. E. Hutchison, and P. S. Weiss,
Molecular Engineering of the Polarity and Interactions of Molecular
Electronic Switches, J. Am. Chem. Soc., (2005) 127,
17421-17426.
25
SLOW MOTION THEORY AND ESR LINESHAPE ANALYSIS Aleksandra Kubica,
Danuta Kruk
Institute of Physics, Jagiellonian University, Reymonta 4,
30-059 Krakow, Poland
The main theoretical difficulties in Electron Spin Resonance
(ESR) spectroscopy are caused by the fact that the electron spin
system is outside of the Redfield limit [1, 2]. To describe ESR
spectra beyond validity regimes of the perturbation theory we use
the slow-motion theory [1,2,3,4,5-8]. This theory can handle
complexes of any symmetry, for any electron spin S, at various
magnetic fields, and with arbitrary magnitudes of the zero field
splitting (ZFS). The primary mechanism for the electron spin
relaxation is by distortional modulation of a transient ZFS
interaction due to collisions with solvent molecules. The approach
is based on expressing all relevant interactions and dynamic
processes [1,5] as a (super)matrix in a complete orthonormal basis
set [3-4,], including all relevant interactions and degrees of
freedom of the system. The computationally heavy step is finding a
small number of elements of the inverse of this complex matrix. ESR
lineshape is determined by one element of the inverted matrix. The
method has been extended to include other interactions, like higher
terms of the zero field splitting and the anisotropy of the
g-tensor. This work presents a description of a general theory of
ESR lineshape analysis and some examples of ESR spectra calculated
by this method. Acknowledgement This work has been financed by
Polish Ministry of Science and Education, grant No N N202 105936
References: [1] Freed J.H., Bruno G.V., Polnaszek C. J. Phys. Chem.
75, 3385-3399, (1971) [2] Nilsson T., Kowalewski J.: Slow-Motion
Theory of Nuclear Spin Relaxation in Paramagnetic Low-Symmetry
Complexes: A Generalization to High Electron Spin, Journal of
Magnetic Resonance 146, 345-358 (2000) [3] Kowalewski J., Kruk D.,
Parigi G. Advances in Inorganic Chemistry, 57, 41- 104, (2005) [4]
Kruk D.: Theory of Evolution and Relaxation of Multi-spin Systems.
Application to Nuclear Magnetic Resonance (NMR) and Electron Spin
Resonance (ESR), Abramis Academic, Arima Publishing UK, (2007) [5]
Freed J.H., Bruno G.V., Polnaszek C. J. Phys. Chem. 55, 5270-5281,
(1971) [6] Nilsson T.: Nuclear Spin Relaxation in Paramagnetic
Comples in Solution, Division of Physical Chemistry Arrehenius
Labolatory Stockholm University, (2000) [7] Nilsson T., Svoboda J.,
Westlund P.-O., Kowalewski J.: Slow-Motion Theory of Nuclear Spin
Relaxation in Paramagnetic Complexes (S=1) of Arbitrary Symmetry,
Journal of Chemical Physics, 15 (1998) [8] Benetis N., Kowalewski
J., Nordenskild L, Wennerstrm H., Westlund P.-O.: Nuclear Spin
Relaxation in paramagnetic systems: The slow motion problem for the
electreon spin relaxation, Molecular Physics, 48, 329-346
(1983)
26
SYNTHESIS AND DFT STUDIES OF CYCLODODECANE-1,2-DIONE AND ITS
DERIVATIVES
Dominik Kubicki, Przemysaw Szczeciski, Adam Gryff-Keller
Warsaw University of Technology
Faculty of Chemistry, Noakowskiego 3, 00-664 Warsaw
Conformational analysis of chemical compounds has always been a
subject of vital importance for profound understanding of how
molecules interact with each other. Though notably interesting for
organic chemists, yet it is even more essential for studies in
physiological systems where everything is controlled through
geometry of reaction sites. In these studies we made an effort to
thoroughly analyze the complex nature of geometry-related phenomena
in alicyclic, ten-carbon -diketone and its derivatives. We
addressed this problem by means of liquid-state NMR as well as
quantum chemical methods.
27
AN EFFICIENCY OF THE aug-cc-pVTZ-J BASIS SET IN PREDICTION OF
NMR SHIELDINGS (IN COMPARISON TO THE CLASSICAL
CBS APPROACH)
Teobald Kupka1, Micha Stachw1, Marzena Nieradka1, Jakub
Kaminsky2, Tadeusz Pluta3 and Stephan P. A. Sauer4
1Faculty of Chemistry, University of Opole, Poland; 2Department
of Molecular Spectroscopy,
Institute of Organic Chemistry and Biochemistry, Prague, Czech
Republic; 3University of Silesia, Institute of Chemistry, Katowice,
Poland; 4Department of Chemistry, University of
Copenhagen, Copenhagen, Denmark Linear correlation between
nuclear shieldings obtained with aug-cc-pVTZ-J basis set for
several small inorganic and organic molecules and the corresponding
Kohn-Sham results, approximated from polarization-consistent pcS-n
basis set family calculations were observed. A significant saving
of computational efforts using inexpensive calculations of nuclear
isotropic shieldings with aug-cc-pVTZ-J basis set by scaling toward
CCSD(T) calculated complete basis set limit (CBS) using pcS-n basis
set family is proposed. The proposed aug-cc-pVTZ-J basis sets is
significantly smaller and allows prediction of nuclear shieldings
of nearly similar accuracy as those, obtained by fitting of
computationally demanding individual pcS-n calculations to the
Kohn-Sham, Hartree-Fock, MP2 or CCSD(T) limit. This simply approach
is feasible for several molecules of small and medium size in
comparison to very expensive CCSD(T) calculations.
-200 -180 -160 -140 -120 -100 -80 -60 -40 -20 0 20
-220
-200
-180
-160
-140
-120
-100
-80
-60
-40
-20
0
N2 linearfitChi^2/DoF = 3.32679R^2 = 0.99421 P1 1.00398 0.0113P2
-10.41353 0.95456
CBS
CB
S [p
pm]
aug-cc-pVTZ-J [ppm]
Fig. 1. Linear correlation between nitrogen shieldings in N2
estimated in the complete basis set limit (pcS-n basis set,
two-parameter fit to results obtained with 47 methods) and
inexpensive calculations with aVTZJ basis set. 1. T. Kupka, M.
Stachw, M. Nieradka, J. Kaminsky, T. Pluta, Convergence of Nuclear
Magnetic Shieldings in the Kohn-Sham Limit for Several Small
Molecules, J. Chem. Theory Comput., 6 (2010) 1580-1589.
28
EFFECTS OF SIDE-CHAIN ORIENTATION ON THE BACKBONE CONFORMATION
OF DEHYDROPHENYLALANINE RESIDUE. THE
NMR STUDY.
Teobald Kupkaa, Magorzata A. Brodaa, Aneta M. Buczeka, Tomasz
Ptakb
aFaculty of Chemistry, University of Opole, Opole bChair and
Department of Basic Medical Sciences, Silesian Piasts University of
Medicine in
Wrocaw, Wrocaw
The discovery of peptide hormones, growth factors and
neuropeptides implicated in biological functions of our organism
has increased interest in therapeutic use of short peptides.
However, the development of peptides as clinically useful drugs is
greatly limited by their poor metabolic stability and low
bioavailability, which is due in part to their inability to readily
cross membrane barriers such as the intestinal and blood-brain
barriers.
The aim of peptide medicinal chemistry is, therefore, to develop
strategies to overcome these problems. One simple approach to
stabilize a peptide is to modify the side-chains of some of the
amino acids involved in the protease recognition site. An essential
point in the strategy for peptide targeted molecular design is the
introduction of conformationally constrained amino acid residues
into bioactive peptides. It is a useful and frequently applied
modification method for studying resulting active conformation and
to design new potent analogs.
One group of such residues, found in naturally occurring
peptides, is ,-dehydro-amino acids. The C=C double bond of
dehydroamino acids makes the rotation of the side chain impossible
and only two positions (Z) or (E) can be adopted. Receptor
proteins
frequently discriminate quite precisely between the (Z) and (E)
disposition of the double bond C=C in their bioligands. Much more
is known about the conformational preferences of
(Z)--dehydropeptides than those of their (E)-analogues, because
most of the preparative procedures yield exclusively or
predominately the former isomers.
N-Alkylation of biologically active peptide is the next strategy
which can also results
in anal
rmational properties betwee
ogues with improved pharmacological properties, such as
resistance to enzymatic degradation, receptor selectivity, enhanced
potency and bioavailability.
The aim of this article is to provide a comparison of the confon
the E and Z isomers of the model dehydropeptide Ac-Phe-NMe2, by
NMR
spectroscopy and theoretical calculations. In order to
experimentally determine the preferred conformation in solution
several 1D and 2D NMR experiments were performed. The obtained
spectral features were compared with theoretically calculated
nuclear magnetic shieldings (recalculated to theoretical chemical
shifts) and indirect nuclear spin-spin coupling constants
calculated at B3LYP/aug-cc-pVTZ-J level of theory and with
inclusion of solvent effect via PCM model.
R R C C
C C
(E) (Z)
29
DIMERIZATION OF N-METHYLINDOLE
Maria Kwasiborska, Jacek WjcikInstitute of Biochemistry and
Biophysics, PAS, Laboratory of Biological NMR, Warszawa,
Poland;
The analysis of X-ray and NMR structures of biological systems
revealed that many of them are stabilized with the C-H type
hydrogen bonds. Lipid-protein complexes are good examples of such
interactions. One of the most interesting interaction is that
involving methyl protons of 7-methylguanine from the cap in
cap-protein complexes [1].
In our studies of C-H... interactions we have used
N-methylindole (Figure) as a model compound and studied it with 1D
and 2D heteronuclear NMR experiments. The exact values of chemical
shifts have been measured in respect to the external reference.It
was found that some of the proton and carbon chemical shifts of
N-methylindole measured in nonpolar solvent depend on the solute
concentration. This suggests the occurrence of the self-association
process. Moreover, we have measured a full set of
direct one-bond proton-carbon couplings at each concentration
used. Some of them demonstrate meaningful concentration dependence.
The significant amount of long-range protoncarbon J-couplings has
been also measured.In order to assign the dimer geometry the ab
initio calculations have been carried out with Gaussian09 program
[2].
References1. Berman, H. M., Westbrook, J., Feng, Z., Gilliland,
G., Bhat, T. N., Weissig, H., Shindyalov, I. N., Bourne, P. E.,
Nucleic Acids Research, 28, 235-242 (2000).2. Frisch, M. J., et
al., Gaussian 09, Revision C 02, Gaussian, Inc., Wallingford, CT
(2009).
Figure Chemical formula of N-methylindole
30
DYNAMIC NUCLEAR POLARIZATION WITH TEMPO RADICAL AT 1.5 K
Grzegorz Kwiatkowski1, Danuta Kruk1 and Walter Kckenberger2
1) Institute of Physics, Jagiellonian Institute of Physics,
Jagiellonian University,
Krakow, Poland 2) The sir Peter Mansfield MagneticResonance
Centre, University of Nottingham, UK
Dynamic nuclear polarization (DNP) transfers the large
polarization of unpaired electrons to
nuclei and thus significantly enhances the NMR signal strength.
Solid-state dynamic nuclear polarization experiments are commonly
performed by irradiating a sample that contains dilute paramagnetic
species with a saturating microwave field oscillating with, or
close to, the electron Larmor frequency.
Using chemically-stable radical (4-amino-TEMPO) diluted in
D2O/Glycerol glass matrix, for wide range of concentration (10-100
mM) process of nuclear polarization was studied at very low
temperature (1.55K) and magnetic field of 3.35 T. To compare
experimental result with theoretical predictions all crucial
parameters were collected: nuclear and electronic relaxation rates,
enhancement and SNR factor and ESR line shape. Because of broad ESR
line the thermal mixing theoretical approach was used to explain
experimental results. A Brief description of hardware is included.
Acknowledgement This work has partially been financed by Polish
Ministry of Science and Education, grant No N N202 105936
References: [1] T. Maly, G. T. Debelouchina, V. S. Bajaj, K.-N.,
Hu, C.-G. Joo, M. L. Mak-Jurkauskas, J. R. Sirigiri, P. C. A. van
der Wel, J. Herzfeld, R. J. Temkin and R. G. Griffin J. Chem. Phys.
128(5) (2008) [2] J. Granwehr , J. Leggett and W. Kckenberger,
Journal of Magnetic Resonance 187 (2007) 266276 [3] J. H.
Ardenkjaer-Larsen, S. Macholl and H. Jhannesson, Applied Magnetic
Resonance 34( 3-4), 509-522, [4] F Kurdzesau, B van den Brandt, A
Comment, P Hautle1, S Jannin, J J van der Klink and J A Konter, J.
Phys. D: Appl. Phys. 41 (2008) 155506
31
ORCA AS A TOOL TO CALCULATE ESR PARAMETERS Maciej Majka,
Aleksandra Kubica, Danuta Kruk
1 Institute of Physics, Jagiellonian University, Reymonta 4,
30-059 Krakow, Poland
The main difficulties in Electron Spin Resonance (ESR) lineshape
simulations are caused by the fact that parameters used in
calculations are from a "reasonable" range. ESR lineshape for high
electron spin quantum numbers are determined by such parameters as
g-tensor anisotropy [1-3] and zero field splitting (ZFS) [4-6].
These parameters could be calculated using advanced quantum
chemistry methods [7]. We have chosen ORCA package to run such
calculations. ORCA allows using advanced quantum chemistry methods
and calculating parameters at different levels of theory. The
package consists of several separate programs that call each other
during a run and it contains modules, which are useful to calculate
the g-tensor and ZFS. This work presents the main idea of ORCA
simulations and some examples. Acknowledgement This work has been
financed by Polish Ministry of Science and Education, grant No N
N202 105936 References: [1] Orton J.W.: Electron Paramagnetic
Resonance. An Introduction to Transition Group Ions in Crystals,
London Iliffe Books LTD, (1968) [2] Poole Ch. P. Jr.: Electron Spin
Resonance, A Comprehensive Treatise on Experimental Techniques,
Dover Publications, INC., New York, 2000 [3] Stoll S: Spectral
Simulations in Solid-State Electron Paramagnetic Resonance, 2003
[4] Kruk D.: Theory of Evolution and Relaxation of Multi-spin
System, Arima Publishing, 2007 [5] Nilsson T., Kowalewski J.:
Slow-Motion Theory of Nuclear Spin Relaxation in Paramagnetic
Low-Symmetry Complexes: A Generalization to High Electron Spin,
Journal of Magnetic Resonance 146, 345-358 (2000) [6] Kruk D.,
Nilsson T., Kowalewski J.: Nuclear Spin Relaxation in Paramagnetic
Systems with Zero-Field Splitting and Arbitrary Electron Spin,
Phys. Chem. Chem. Phys., 3, 4907-4917 (2001) [7] Piela L.: Ideas of
Quantum Chemistry, Elsevier B.V. (2007) [8] Neese F: ORCA- An ab
initio, DFT and semiempirical SCF-MO package This work has been
financed by Polish Ministry of Science and Education, grant No N
N202 105936
32
NMR MICROIMAGING APPLIED FOR INVESTIGATION OF THE POROSITY OF
NATURAL WOOD, WOOD-BASED MATERIALS
AND A NOVEL WOOD POLYMER COMPOSITE
Wodzimierz Masierak1, Joanna Kowalczuk2, Jadwiga Tritt-Goc2,
Jolanta Tomaszewska3, Stanisaw Zajchowski3, Jacek Mirowski3
1. Department of physics and material research, University of
Economy in Bydgoscz, ul. Garbary 2, 85-229 Bydgoszcz
2. Institute of Molecular Physics, Polish Academy of Sciences,
ul. M.Smoluchowskiego 17, 60-179 Pozna
3. Faculty of Chemical Technology and Engineering, University of
Technology and Life Sciences, ul. Seminaryjna 3, 85-326
Bydgoszcz
Numerous wood-based materials are still widely applied in modern
building technology. Natural wood is used mainly for creating these
parts which must have a relatively low mass and should be easy to
processing. Wooden rafter framing is durable, easy to fabricate
even in case of very difficult shapes of the roof. Nowadays
application of pure natural wood is restricted mainly by its
rapidly increasing price and restrictions caused by the dimensions
of the available material. That is why more often the wood-based
materials such as oriented strand boards (OSB) are used. It is easy
to fabricate plates with the desired dimensions and thickness from
8 mm up to more than 30 mm. They are used not only for the interior
but quite often also as construction panels for outside walls and
even for small roofs (later covered by waterproof materials like
ceramic tiles). Such an application demands high durability and
resistance for water penetration. Recently novel wood-based
materials based on the polypropylene and wooden fibers have been
introduced. The aim of this work is to investigate the influence of
water on such materials and compare it to the behavior of natural
wood and OSB. As first example the mixture of pine-tree fibers with
dimensions between 0.25 mm and 0.5 mm and a polypropylene was used.
A cubic piece of this material (10 mm x 10 mm x 10 mm) was placed
in a water and such a sample was examined by NMR imaging after
increasing periods of imbibition. The Single Slice Multi Echo
(SSME) technique was employed using Bruker AVANCE 300 MHz
spectrometer. This led to the tomographic pictures with resolution
0.19 x 0.19 mm and a slice thickness of 1 mm. Additionally proton
density profiles were obtained from the pictures. Similar cubic
samples of natural pine-tree wood and commercial OSB were examined
in exactly the same conditions. Obtained results clearly show that
this novel material is much more waterproof than natural wood and
OSB. The resolution of obtained pictures is sufficient to reveal
that water which diffuses through the surface of OSB later is
accumulated inside internal cavities between the strands. Such a
bulk water can play an important role in the degradation of this
material especially in case of cyclic freezing and unfreezing.
Obtained results may lead to draw a conclusion that
wood-polypropylene composites can be used for fabricating various
parts used in the building even those which are subjects of the
influence of water and wide range of temperatures.
33
MOLECULAR DYNAMICS IN TOCOPHEROL
W. Medycki1, J. Czaplicki2 and D. Kruk3
1Institute of Molecular Physics, Polish Academy of Sciences,
Pozna, Poland;
2Institute of Pharmacology and Structural Biology (IPBS),
Universite de Toulouse, Universite Paul Sabatier (UPS), 205 route
de Narbonne, 31077 Toulouse, France
3Institute of Physics, Jagiellonian University, Krakw, Poland;
3Faculty of Chemistry
Dynamical properties of -tocopherol acetate (commonly known as
vitamin E) have been
investigated in a broad temperature range (over the glass
transition) by means of proton spin-
lattice relaxation and molecular dynamics (MD) simulations. Two
distinct relaxation
processes have been detected in the studied temperature range in
the proton relaxation
experiment. One of them, present in the solid phase, has been
attributed to reorientation of
methyl groups. Second, in glassy and liquid state, is visible
above the glass transition
temperature (Tg). In order to identify the motional process, the
molecular dynamics (MD)
simulations of correlation functions for several internuclear
vectors in the tocopherol have
been performed. In conclusion we may recognize the observed
relaxation process as caused
by the dynamics of the aromatic rings of the tocopherol
molecule.
This work has been financed by Polish Ministry of Science and
Education, grant No N N202
172135
Reference
W. Medycki, J. Czaplicki, D. Kruk, C. Uniszkiewicz, A.
Mielczarek, Applied Magnetic Resonance, 39(3) (2010) 273-283
34
http://www.springerlink.com/content/0937-9347/http://www.springerlink.com/content/0937-9347/http://www.springerlink.com/content/0937-9347/39/3/
DYNAMIC NUCLEAR POLARIZATION WHAT IT IS AND HOW IT WORKS
Artur Mielczareka,b, Danuta Krukb
aInstitute of Nuclear Physics PAS, Radzikowskiego 152, 31-342
Krakow, Poland
bInstitute of Physics, Jagiellonian University, Reymonta 4,
30-059 Krakow, Poland
Dynamic Nuclear Polarization (DNP) is a way to enhance the
polarization of nuclei coupled to electrons due to the transfer of
the electron polarization. Theoretically, the enhancement can reach
as much as about 660, which is the ratio of electronic to nuclear
gyromagnetic factors. Several effects can cause the enhancement in
solids [1, 2, 3, 4]..
The effects are classified by the number of spins partaking in
an elementary polarization transfer phenomenon and their relative
EPR/NMR characteristics. If there are two spins considered
(electron and a nucleus), and EPR linewidth is lower than nuclear
Larmor frequency the effect is called solid effect (SE). If three
(two electrons and a nucleus) and NMR Larmor frequency falls
between the homogeneous and inhomogeneous EPR line broadening the
DNP mechanism is referred to as cross effect (CE). The exchange of
magnetization between particles is due to their coupling which
results in the mixing of Zeeman states. The mixing enables
transitions between levels isolated in case of noninteracting spins
[3, 5].
Here we explain the mechanisms of these effects and describe
them quantitatively using the density operator approach within the
framework of perturbation theory, with the spin interactions and
the molecular structure treated as input. Acknowledgement This work
has been financed by Polish Ministry of Science and Education,
grant No N N202 105936. Literature: [1] N. Chandrakumar Dynamic
Nuclear Polarization in NMR, Journal of the Indian Institute of
Science 90:1 (2010), 133. [2] T. Maly at al. Dynamic nuclear
polarization at high magnetic fields, Journal of Chemical Physics
128 (2008), 052211. [3] Kan-Nian Hu Polarizing Agents for
High-Frequency Dynamic Nuclear Polarization, PhD Thesis,
Massachusetts Institute of Technology 2006. [4] A. Abragam, M.
Goldman Principles of dynamic nuclear polarisation, Reports on
Progress in Physics 41 (1978) 395. [5] St. Goertz et al. Polarized
H, D and 3He Targets for Particle Physics Experiments, Progress in
Particle and Nuclear Physics 49 (2002), 403
35
HOW NMR AND ESR HELP TO ESTIMATE THE DYNAMIC NUCLEAR
POLARIZATION ENHANCEMENT?
Agnieszka Milewska, Danuta Kruk
Institute of Physics, Jagiellonian University, Krakow,
Poland
The NMR signal intensities can be enhanced in many ways. One of
them is Dynamic Nuclear Polarization. The enhancement results from
polarization that transfers from unpaired electrons to the nuclei.
In practice this is achieved by irradiating the sample with diluted
paramagnetic species with a saturating microwave field oscillating
close to the electron Larmor frequency. However as long as DNP
enhancement measurements are done, still their interpretations are
difiicult. The enhancement that is achieved depends on many factors
and processes.
In thsi work dynamics of selected radicals in solution will be
discussed. Field dependent proton spin-lattice relaxation studies
and ESR spectra of 4-carboxy-TEMPO in water solution have been
performed. The relaxation data have been collected in a broad
frequency rang