The Henryk Niewodniczański INSTITUTE OF NUCLEAR PHYSICS

Polish Academy of Sciences ul. Radzikowskiego 152, 31-342 Kraków, Poland

www.ifj.edu.pl/publ/reports/2010/

Kraków, December 2010

_________________________________________________________________________

Report No. 2046/AP

XLIII Polish Seminar on Nuclear Magnetic Resonance and Its Applications. Kraków, 1-2 December 2010

ABSTRACTS

Organizing Committee:

Members:

T. Banasik Z.T. Lalowicz /v-chairman/ A. Birczyński K. Majcher J. Blicharski M. Noga /secretary/ J. W. Hennel /chairman/ Z. Olejniczak M. Jabłońska P. Rosicka A. Jasiński /honorary chairman/ W. Rutkowski K. Jasiński T. Skórka A. Krzyżak G. Stoch P. Kulinowski U. Tyrankiewicz S. Kwieciński W.P. Węglarz /v-chairman/ G. Woźniak

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. Bułgarska 12a 93-362 Łódź tel. (042) 645 00 64 amx@amx.pl.pl BRUKER POLSKA SP. Z O.O mgr Włodzimierz Leszczyński ul. Budziszyńska 69 60-179 Poznań tel. (061) 868 90 08 fax. (061) 868 90 96 e-mail: sekretariat@bruker.poznan.pl www.bruker.pl AGILENT USA mgr inż. Wojciech Kośmider ul. Skarbka 21 60-348 Poznań tel. (061) 867 31 84 tel. kom. 602 287 918 e-mail: woko@eranet.com KOMITET FIZYKI POLSKIEJ AKADEMII NAUK Instytut Fizyki PAN Al. Lotników 32/46 02-668 Warszawa

mailto:amx@amx.pl.plmailto:woko@eranet.com

CONTENTS

1. ELECTRON PARAMAGNETIC RESONANCE EXAMINATION OF VITRINITES WITH DIFFERENT CARBON CONTENT Sylwia Bartłomiejczyk, 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 CZĘSTOŚCI DO OBRAZOWANIA PIERSI W NISKIM POLU MAGNETYCZNYM B.Błasiak, V. Volotovskyy, C. Deng, B. Tomanek

3

4. OBRAZOWANIE MOLEKULARNE MR GLEJAKÓW Z ZASTOSOWANIEM CELOWANYCH ŚRODKÓW KONTRASTOWYCH B.Błasiak, 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, Stanisław Sztuk, Małgorzata Szafirska, Barbara Sobiecka, Paulina Karcz

5

6. STRUCTURE AND DYNAMICS CHANGES IN S100A1 PROTEINS Monika Budzińska, Michał Nowakowski, Łukasz Jaremko, Mariusz Jaremko, Igor Zhukov, Konrad Zdanowski, Agnieszka Belczyk, Andrzej Bierzyński, Andrzej Ejchart

6

7. INFLUENCE OF STORAGE TEMPERATURE ON ANTIRADICAL PROPERTIES OF SELECTED COSMETICS Anna Deda, Sławomir Wilczyński, Barbara Pilawa, Ewa Pierzchała

8

8. NOVEL DESIGN OF RF SURFACE COILS FOR MAGNETIC RESONANCE IMAGING SYSTEM AT 0.088 T Agata Dróżdż, 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. Harańczyk, 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. Harańczyk, 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 Hetmańczyk, Łukasz Hetmańczyk, Krystyna Hołderna-Natkaniec, Anna Migdał-Mikuli, Edward Mikuli

15

14. THE POSSIBILITIES OF 31P NMR SPECTROSCOPY APPLICATION IN DETERMINATION OF PHOSPHATES ADDITIVES IN MEAT PRODUCTS Paweł B. Hrynczyszyn, Edward Szłyk

17

15. ASSESSMENT OF THE RELATION BETWEEN CARDIAC FUNCTION AND LEFT VENTRICLE LONG-AXIS ORIENTATION IN MURINE MODEL OF HEART FAILURE Magdalena Jabłońska, Tomasz Skórka, Urszula Tyrankiewicz, Henryk Figiel

18

16. APPLICATION OF MICROSTRIP RF COILS TO MRI MICROSCOPY Krzysztof Jasiński, Anna Młynarczyk, Peter Latta, Vyacheslav Volotovskyy, Władysław P.Węglarz, Bogusław 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, Paweł B. Hrynczyszyn, Mirosław Wełniak, Grzegorz Krasiński, Hassan Kassassir, Włodzimierz Ciesielski, Marek J. Potrzebowski

20

18. MULTIDIMENSIONAL NMR SPECTROSCOPY WITH SPARSE RANDOM SAMPLING Wiktor Koźmiński, 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, Rafał 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, Przemysław Szczeciński, 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, Michał Stachów, 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, Małgorzata A. Broda, Aneta M. Buczek, Tomasz Ptak

29

25. DIMERIZATION OF N-METHYLINDOLE Maria Kwasiborska, Jacek Wójcik

30

26. DYNAMIC NUCLEAR POLARIZATION WITH TEMPO RADICAL AT 1.5 K Grzegorz Kwiatkowski, Danuta Kruk, Walter Köckenberger

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 Włodzimierz Masierak, Joanna Kowalczuk, Jadwiga Tritt-Goc, Jolanta Tomaszewska, Stanisław 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, Paweł 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. Ślusarczyk, T. Banasik, J.Lewin-Kowalska, W.P.Węglarz

44

38. MONITORING OF CHELATION PROCESSES USING NMR RELAXATION METHOD Lech Wiktor Skórski, Mateusz Synowiecki, Barbara Blicharska

45

39. INVESTIGATION OF PAPER SAMPLES USING T1ρ DISPERSION PROFILES Lech Wiktor Skórski, Barbara Blicharska

46

40. ROVIBRATIONAL CORRECTIONS TO THEORETICAL NMR PARAMETERS FROM VPT2 METHOD Justyna Skórzewska, Teobald Kupka, Małgorzata A. Broda, Aneta M. Buczek

47

41. ITERATIVE ALGORITHM FOR ARTIFACT SUPPRESSION IN SPARSELY SAMPLED MULTIDIMENSIONAL NMR SPECTRA Jan Stanek, Wiktor Koźmiński

48

42. COMPARING APPLICATION OF THE WAVELET TRANSFORM AND THE ADAPTIVE WEIGHT SMOOTHING ALGORITHM FOR THE NOISE REDUCTION IN MRI Joanna Świebocka-Więk, 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 Bartłomiejczyk, Barbara Pilawa

58

51. BRAIN 1H MRS IN CHILDREN WITH LEUKODYSTROPHIES Ewa Jamroz, Justyna Paprocka, Magdalena Wicher, Agnieszka Skorupa, Maria Sokół, Aleksandra Kiełtyka, Tomasz Banasik

59

52. INVESTIGATION OF GLOBULAR PROTEINS MOLECULAR DYNAMICS BY T1ρ DISPERSION PROFILES METHOD Dorota Wierzuchowska, Barbara Blicharska

61

53. FREE RADICALS PROPERTIES OF GAMMA IRRADIATED PAROMOMYCIN Sławomir Wilczyński, Barbara Pilawa, Marta Ptaszkiewicz, Jan Swakoń, Paweł Olko, Robert Koprowski, Zygmunt Wróbel

62

54. DOMAIN SIZE AND MOLECULAR DYNAMICS OF POLY(BUTYLENE TEREPHTHALATE)/DECYLAMINE_C60 NANOCOMPOSITES Aneta Woźniak-Braszak, Mikołaj Baranowski, Roman Gwoździk-Bujakowski, Kazimierz Jurga, Jan Jurga, Krystyna Hołderna-Natkaniec

63

55. HE INFLUENCE OF CONCENTRATION OF TCNEO_C60 ADDUCT ON MOLECULAR DYNAMICS AND DOMAIN SIZE IN PBT/TCNEO_C60 NANOCOMPOSITES Aneta Woźniak-Braszak, Mikołaj Baranowski, Roman Gwoździk-Bujakowski, Kazimierz Jurga, Jan Jurga, Krystyna Hołderna-Natkaniec

65

56. EPR STUDIES OF PARAMAGNETIC CENTERS IN DIFFERENT MELANIN BIOPOLIMERS Magdalena Zdybel, Barbara Pilawa, Daria Czyżyk, Sławomir Wilczyński, Anna Gondzik, Ewa Buszman, Teresa Witoszyńska, 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 Witoszyńska

67

58. CONFORMATIONAL FLEXIBILITY OF BUSPIRONE ANALOGUES FROM X-RAY IN THE SOLIDS AND NMR IN SOLUTION Anna Bielenica, Andrzej Zimniak, Izabela Dybała, Anna E. Kozioł, Marta Struga

69

ELECTRON PARAMAGNETIC RESONANCE EXAMINATION OF VITRINITES WITH DIFFERENT CARBON CONTENT

Sylwia Bartłomiejczyk1 , Barbara Pilawa1,2,

Joanna Komorek3

1Centre of Polymer and Coal Materials, Polish Academy of Science, Marii Curie-Skłodowskiej 34, 44-100 Zabrze, 2Medical University of Silesia in Katowice,

School of Pharmacy and Division of Laboratory Medicine, Department of Biophysics, Jedności 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 (Poznań). Modulation of magnetic field was 100 kHz. Frequency of microwave radiation was measured by MCM recorder produced by EPRAD Firm (Poznań). EPR spectra were recorded with microwave power in the range 0.7-100 mW. For the EPR spectra amplitude (A), integral intensity (I), linewidth (ΔBpp) 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 CZĘSTOŚCI DO OBRAZOWANIA PIERSI W NISKIM POLU MAGNETYCZNYM

B.Błasiak1,2,4, V. Volotovskyy3, C. Deng4, B. Tomanek1,2,3,4

1Department of Clinical Neurosciences, University of Calgary, Calgary, Canada; 2Instytut Fizyki Jądrowej 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 bezinwazyjną metodą diagnostyczną pozwalającą na uzyskanie obrazόw poszczegόlnych części ciała o wysokiej rozdzielczości. Ponieważ stosunek sygnału do szumu rośnie liniowo z natężeniem pola magnetycznego obrazy rezonansowe uzyskiwane przy zastosowaniu systemόw niskopolowych (poniżej 1T) charakteryzują się gorszą rozdzielczością i dłuższym czasem akwizycji danych niż obrazy z systemów wysokopolowych (powyżej 1T). Instalacja i koszty eksploatacji systemów wysokopolowych są jednak znacznie wyższe w porównaniu do systemów niskopolowych. Ich wysoka cena, a co za tym idzie cena obrazowania rezonansowego, uniemożliwia ich powszechne zastosowanie. Jedną z metod poprawy stosunkowo niskiego SNR jest optymalizacja cewek radiowej-częstości. Ponieważ rak piersi jest częstą chorobą i przyczyną zgonόw niezbędna jest ich wczesna, ogólnodostępna diagoza a dzięki temu możliwośc skutecznego leczenia. W tym celu została skontruowana cewka RF składająca się z dwóch wzajemnie odsprzęganych cewek kwadraturowych typu siodłowego (Rys) działająca w niskopolowym systemie 0.2T. Cewka pozwoliła na uzyskanie wysokiej jakości obrazόw piersi (obu jednocześnie lub każdej osobno). Wygoda pacjentki również była wzięta pod uwagę w czasie kontrukcji. Cewka umożliwiła otrzymanie obrazów piersi w przeciągu niespełna dwόch minut przy zastosowaniu standartowych sekwencji pomiarowych typu spin echo. Opracowana cewka możne zwiększyć dostępność dianostyki piersi i potencjanie zastąpić standardową inwazyjną mammografię.

        

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 GLEJAKÓW Z ZASTOSOWANIEM CELOWANYCH ŚRODKÓW KONTRASTOWYCH

B. Błasiak1,2,3, 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 pozwalają jedynie na obrazowanie dużych skupisk komórek, rzędu 1 mm3. Obrazowanie molekularne rezonansem magnetycznym pozwala na obrazowanie na poziomie pojedynczych komórek. W celu polepszenia kontrastu tkanki patologicznej używa się środkow skracających czasy relaksacji. Stosowane w diagnostyce nowotworów środki kontrastowe opierają się jedynie na różnym ukrwieniu tkanki normalnej i nowotoworowej, co nie zawsze jest wyznacznikiem procesów chorobowych. Ostatnie postępy w dziedzinie ORM, biologii molekularnej, nano-technologii przyniosły możliwość obrazowania RM znacznie mniejszych obiektów, takich jak pojedyncze komórki. Stało się to możliwe dzięki zastosowaniu tzw. targeted contrast agents, czyli celowanych środków kontrastowych. Współczesna nano-technologia pozwala na syntezę silnie paramagnetycznych nano-cząsteczek, takich jak Fe304 z obiektami biologicznymi np. przeciwciałami. Paramagnetyczne cząsteczki zaburzając lokalne pole magnetyczne skracają czasy relaksacji T2 przez co widoczne są na obrazach MRI T2 ważonych. Przeciwciała służą jako nośniki dostarczające cząsteczki do komórek nowotworowych. W ten sposób możliwe jest obrazowanie teoretycznie nawet pojedynczych komórek nowotworowych. W zaprezentowanym wystąpieniu prezentujemy wynik dotyczące wczesnej diagnostyki glejków z zastosowaniem celowanych środkόw 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,

Stanisław Sztuk1, Małgorzata 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 Budzińska

1), Michał Nowakowski

1), Łukasz Jaremko

1,2), Mariusz

Jaremko1)

, Igor Zhukov1,3,4)

, Konrad Zdanowski1,5)

, Agnieszka Belczyk1)

, Andrzej Bierzyński

1), Andrzej Ejchart

1)

1) Institute of Biochemistry and Biophysics, Polish Academy of Sciences, [UTF-8?]Pawińskiego 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 α-helical conformation in the 85-89 segment of the protein in the α-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 α-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 β-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. Kozłowska, A. Bierzyński, FEBS J.

(2005)272, 2557-2565. [3] I. Zhukov, A. Ejchart, A. Bierzyński, 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, 1Sławomir Wilczyński, 1Barbara Pilawa, 2Ewa Pierzchała 1 Department of Biophysics, Medical University of Silesia in Katowice, School of Pharmacy

and Laboratory Medicine, Jedności 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 (Poznań) spectrometer with Rapid Scan Unit (Jagmar Firm, Kraków). 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 50°C during 30 minutes.

Increase of temperature up to 50°C 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 Dróżdż1, 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 patient’s 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 coil’s 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] Jaszuński M., Łach 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. Harańczyk1, 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 (66±5)%.

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.Harańczyk, D. Sc., Institute of Physics, Jagiellonian University, ul. Reymonta 4, 30-059 Cracow, e-mail: hubert.haranczyk@uj.edu.pl

References [1] H. Harańczyk „On water in etremely dry biological systems”. Wyd. UJ (2003). [2] H. Harańczyk, J.Grandjean, M.Olech, Colloids & Surfaces, B: Biointerfaces 28/4, 239, (2003). [3] H. Harańczyk, J.Grandjean, M.Olech, M.Michalik, Colloids & Surfaces, B: Biointerfaces 28/4, 251, (2003). [4] H. Harańczyk, A. Pietrzyk, A. Leja, M. A. Olech, Acta Phys. Polon. 109, 411 (2006). [5] H. Harańczyk, M. Bacior, P. Jastrzębska, M.A. Olech Acta Phys. Polon. A115, 516-520 (2009). [6] B. Schroeter, C. Scheidegger, New Phytologist 131, 273-285, (1995). [7] H. Harańczyk, 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. Harańczyk1, 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 (Δm/m0 = 0.036 for L. glabrirostris and Δm/m0 = 0.044 for D. comatus); (ii) a tightly bound water (with Δm/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 ΔM/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.Harańczyk, D. Sc., Institute of Physics, Jagiellonian University, ul. Reymonta 4, 30-059 Cracow, e-mail: hubert.haranczyk@uj.edu.pl

References [1] W. Block Eur. J. Entomology, 93: 325–339, (1996). [2] R.W. Dent Textile Res. J., 47: 145-152, (1977). [3] H.Harańczyk “On water in etremely dry biological systems”. Wyd. UJ (2003). [4] H. Harańczyk, M. Bacior, M.A. Olech Antarctic Sci. 20: 527-535 (2008). [5] S. Knutelski. „Różnorodność, ekologia i chorologia ryjkowców 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: 187–199, (2004).

14

PHASE TRANSITION AND MOLECULAR MOTIONS IN [Ba(H2O)3](ClO4)2 STUDIED BY NUCLEAR MAGNETIC RESONANCE

AND COMPLEMENTARY METHODS Joanna Hetmańczyka, Łukasz Hetmańczyka, Krystyna Hołderna-Natkaniecb,c, Anna Migdał-

Mikulia and Edward Mikulia,

a Jagiellonian University, Faculty of Chemistry, Kraków, Poland; b A. Mickiewicz University, Institute of Physics, Poznań, 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) Å, b = 7.291(5) Å, c = 9.673(5) Å 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 ⅓ and ⅔ 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 Å and H-O-H angle equals to 109. The M2 value corresponding to the rigid lattice M2rigid was calculated to be equal 25.21·10-8T2. 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 29·10-8T2 to 19·10-8T2 (see

15

Fig. 1). In the temperature range of 120-180 K the second moment value decreases from 29·10-8T2 to 24·10-8T2. 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 19·10-8T2 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] Ł. Hetmańczyk, J. Hetmańczyk, A. Migdał-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. Migdał-Mikuli, J. Hetmańczyk, E. Mikuli, Ł. Hetmańczyk, Thermochimica Acta 487 (2009) 43-48.

[3] K. Hołderna-Matuszkiewicz, Fizyka dielektryków i radiospektroskopia XV, PWN, Warszawa-Poznań 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

Możliwości zastosowania spektroskopii 31P NMR w oznaczaniu dodatków fosforanowych w produktach mięsnych

Paweł B. Hrynczyszyn, Edward Szłyk

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

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.; Jastrzębska, A.; Szłyk, 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 Jabłońska1,2, Tomasz Skórka1, 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 TgGαq*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 Jasiński1, Anna Młynarczyk1, Peter Latta2, Vyacheslav Volotovskyy2, Władysław

P.Węglarz1, Bogusław Tomanek1,2

1Instytut Fizyki Jądrowej Polskiej Akademii Nauk,ul. Radzikowskiego 152, 31-342 Kraków, 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 stałym jako precyzyjne narzędzie do opisu form tautomerycznych chiralnych o-hydroksy zasad Schiffa stosowanych

jako ligandy w asymetrycznej katalizie.

Magdalena Jaworska1, Paweł B. Hrynczyszyn1, Mirosław Wełniak1, Grzegorz Krasiński2, Hassan Kassassir2, Włodzimierz Ciesielski2, Marek J. Potrzebowski2

1 Wydział Chemii, Uniwersytet Mikołaja Kopernika, ul. Gagarina 7, 87-100 Toruń 2 Centrum Badań Molekularnych i Makromolekularnych, Polska Akademia Nauk,

ul. Sienkiewicza 112, 90-363 Łódź e-mail: magdajaworska@vp.pl

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.; García, 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 Koźmiński, 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-1×k1×k2×…×kN-1 single FID signals (where ki, equal to swi×tmaxi, 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. Koźmiński, I. Zhukov, J. Magn. Reson. 179, 323-328 (2006). 2. K. Kazimierczuk, A. Zawadzka, W. Koźmiński, I. Zhukov, J. Biomol. NMR, 36, 157-

168 (2006) 3. M. Misiak, W. Koźmiński, Magn. Res Chem., 45, 171-174 (2007) 4. K. Kazimierczuk, A. Zawadzka, W. Koźmiński, I. Zhukov, J. Magn. Reson., 188, 344-

356 (2007) 5. K. Kazimierczuk, A. Zawadzka, W. Koźmiński, J. Magn. Reson. 192, 123-130 (2008)

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6. K. Kazimierczuk, A. Zawadzka, W. Koźmiński, I. Zhukov, J. Am. Chem. Soc., 130, 5404-5405 (2008)

7. M. Misiak, W. Koźmiński, Magn. Res. Chem., 47, 205-209 (2009) 8. K. Kazimierczuk, A. Zawadzka, W. Koźmiński, J. Magn. Reson., 197, 219-228 (2009) 9. M. Misiak, W. Koźmiński, M. Kwasiborska, J. Wójcik, E. Ciepichal, E. Swiezewska,

Magn. Res. Chem., 47, 825–829 (2009) 10. Zawadzka-Kazimierczuk, K. Kazimierczuk, W. Koźmiński, J. Magn. Reson., 202,

109-116 (2010) 11. J. Stanek, W. Koźmiński, J. Biomol. NMR, 47, 65-77 (2010) 12. K. Kazimierczuk, A. Zawadzka-Kazimierczuk, W. Koźmiński, J. Magn. Reson., 205,

286–292 (2010) 13. V. Motáčková, J. Nováček, A. Zawadzka-Kazimierczuk, K. Kazimierczuk, L. Žídek,

H. Šanderová, L. Krásný, W. Koźmiński, V. Sklenář, J. Biomol. NMR, 48, 169-177 (2010)

14. K. Kazimierczuk, J. Stanek, A. Zawadzka-Kazimierczuk, W. Koźmiński, Prog. Nucl. Mag. Res. Sp., 57, 420–434 (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, hkraw@ch.pw.edu.pl

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.

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THE NOVEL DERIVATIVES OF STILBENES AS POTENTIALLY NEW OPTICAL MOLECULAR SWITCHES

Hanna Krawczyk and Rafał Matczak

Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3,

00-664 Warsaw, Poland, hkraw@ch.pw.edu.pl

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.

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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., Nordenskiöld L, Wennerström 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)

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SYNTHESIS AND DFT STUDIES OF CYCLODODECANE-1,2-DIONE AND IT’S DERIVATIVES

Dominik Kubicki, Przemysław Szczeciński, 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 α-diketone and it’s derivatives. We addressed this problem by means of liquid-state NMR as well as quantum chemical methods.

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AN EFFICIENCY OF THE aug-cc-pVTZ-J BASIS SET IN PREDICTION OF NMR SHIELDINGS (IN COMPARISON TO THE CLASSICAL

CBS APPROACH)

Teobald Kupka1, Michał Stachów1, 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. Stachów, 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.

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EFFECTS OF SIDE-CHAIN ORIENTATION ON THE BACKBONE CONFORMATION OF DEHYDROPHENYLALANINE RESIDUE. THE

NMR STUDY.

Teobald Kupkaa, Małgorzata 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

Wrocław, Wrocław

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)

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DIMERIZATION OF N-METHYLINDOLE

Maria Kwasiborska, Jacek WójcikInstitute 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…π 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...π 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 proton–carbon 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

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DYNAMIC NUCLEAR POLARIZATION WITH TEMPO RADICAL AT 1.5 K

Grzegorz Kwiatkowski1, Danuta Kruk1 and Walter Köckenberger2

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. Köckenberger, Journal of Magnetic Resonance 187 (2007) 266–276 [3] J. H. Ardenkjaer-Larsen, S. Macholl and H. Jóhannesson, 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

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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

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NMR MICROIMAGING APPLIED FOR INVESTIGATION OF THE POROSITY OF NATURAL WOOD, WOOD-BASED MATERIALS

AND A NOVEL WOOD – POLYMER COMPOSITE

Włodzimierz Masierak1, Joanna Kowalczuk2, Jadwiga Tritt-Goc2, Jolanta Tomaszewska3, Stanisław 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 Poznań

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.

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MOLECULAR DYNAMICS IN TOCOPHEROL

W. Medycki1, J. Czaplicki2 and D. Kruk3

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

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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