Report No xxxx - Instytut Fizyki JÄdrowej PAN

The Henryk Niewodniczański 

INSTITUTE OF NUCLEAR PHYSICS 

Polish Academy of Sciences 

ul. Radzikowskiego 152, 31-342 Kraków, Poland. 

www.ifj.edu.pl/reports/2003.html 

Kraków, listopad 2003 

Report No 1930/AP 

XXXVI Polish Seminar on Nuclear Magnetic Resonance 

and Its Applications. Kraków, 1-2 December 2003 

ABSTRACTS 

Organizing Committee: 

A. Birczyński A. Krzyżak 

P. Borowiec P. Kulinowski 

P. Filipek Z. T. Lalowicz 

S. Heinze-Paluchowska M. Noga /secretary 

J. W. Hennel /chairman/ Z. Olejniczak 

A. Jasiński /v-chairman/ T. Skórka 

J. Kibiński 

A. Korzeniowska 

Sponsors: 

Committee of Physics of the Polish Academy of Sciences 

Varian International AG 

Bruker-Service-W.L. Electronics 

AMX-ARMAR AG

Addresses of the sponsors: 

Committee of Physics of the Polish Academy of Sciences 

Wydział III PAN 

Al. Lotników 32/46 

02-668 Warszawa 

Varian International AG 

mgr inż. W. Kośmider 

ul. Skarbka 21 

60-348 Poznań 

tel. 61 867 31 84 

Bruker-Service-W.L. Electronics 

mgr W. Leszczyński 

ul. Braniborska 25 

60-179 Poznań 

tel. +48 61 868 90 08 

fax. +48 61 868 90 96 

e-mail: brukerwl@man.poznan.pl 

http://www.wlelectronics.poznan.pl 

http://www.bruker.poznan.pl 

AMX-ARMAR AG 

ul. Bułgarska 12a 

93-362 Łódź 

tel. 42 645 00 64 

2

Contents 

R. Banyś, A. Słowik, M. Pasowicz, I. Ciecko-Michalska, 

M. Motyl, M. Irzyk, A. Szczudlik, J. Bogdał 

USEFULNESS OF PROTON MAGNETIC RESONANCE SPECTROSCOPY ( 1 H MRS) 

IN DIAGNOSIS OF SUBCLINICAL HEPATIC ENCEPHALOPATY p.9 

P. Bernatowicz, I. Czerski, i S. Szymański 

FAINT LINE SHAPE EFFECTS IN LIQUID-PHASE NMR. NONCLASSICAL 

HINDERED ROTATION OF METHYL GROUPS IN 1,2,3,4-TETRACHLORO-9,10- 

DIMETHYLTRIPTYCENE p.10 

A. Bijak, B. Blicharska, M. Hyjek 

INFLUENCE OF PARAMAGNETIC IONS ON FLUORINE NMR SPECTRA p.11 

A. Birczyński, Z. T. Lalowicz, Z. Olejniczak 

LONELY DEUTERON IN NH 3 D + IONS AS A SPECTATOR OF THEIR MOBILITY p.12 

B. Blicharska 

NMR RELAXATION OF PAPER SAMPLES p.13 

J. S. Blicharski, A. Gutsze, A. M. Korzeniowska, Z. T. Lalowicz, Z. Olejniczak 

DEUTERON SPIN-LATTICE RELAXATION STUDY OF D 2 SECLUDED IN THE 

SUPERCAGES OF ZEOLITE NAY p.14 

J. S. Blicharski, A. M. Korzeniowska, Z. T. Lalowicz 

SPIN-LATTICE RELAXATION OF D 2 QUANTUM ROTORS p.15 

P. Brzegowy, A. Jasiński, T. Banasik, Z. Sułek, D. Adamek, 

K. Majcher, A. Pilc, T. Skórka, W. Węglarz 

INVESTIGATION OF NEUROPROTECTING EFFECT OF MPEP 

ON A RAT SPINAL CORD TRAUMATIC INJURY MODEL USING MR 

DIFFUSION ANISOTROPY IMAGING p.17 

K. Cieślar, K. Suchanek, M. Suchanek, Z. Olejniczak*, 

T. Pałasz, T. Dohnalik 

OPTICAL PUMPING OF 3 He p.19 

K. Dąbrowska-Balcerzak, J. Nartowska, I. Wawer 

13 C CP MAS NMR STUDIES OF STEROIDAL SAPOGENINS 

FROM CONVALLARIA MAJALIS p.20 

M. Dobies, S. Kuśmia, S. Jurga 

NMR STUDY OF GELATION PROCESS OF LOW METHOXYL PECTIN p.21 

P. Dorożyński, P. Kulinowski, A. Jasiński, R. Jachowicz 

MRI INVESTIGATIONS OF HYDROGEL FORMATION AND DIMENSIONAL CHANGES 

OCCURRING IN HBS – PRELIMINARY STUDIES p.23 

A. Ejchart 

CHEMICAL SHIFT TITRATION AT THE INTERMEDIATE EXCHANGE RATES OF HOST 

– GUEST SYSTEM p.25 

3

Z. Fojud, M. Sitarz, M. Handke, S. Jurga 

STRUCTURE AND ARRANGEMENT OF GLASSY PHOSPHO-SILICATE 

MATERIALS STUDIED BY 

23 NA, 27 AL, 31 P NMR AND FTIR METHODS p.26 

Z. Fojud, M. Kozak, S. Jurga 

LOCAL DYNAMICS AND ORGANIZATION OF N-UNDECYLAMMONIUM CHLORIDE / 

WATER SYSTEMS STUDIED BY NMR AND SAXS p.27 

J. Gabrielska, M. Soczyńska – Kordała, S. Przestalski 

ROLE OF THE CHELATING PROCESS OF FLAVONOIDS REDUCING THE 

INTERACTION BETWEEN ORGANOMETALLIC COMPOUNDS AND THE LIPID 

BILAYER - AS INFERRED FROM THE 1H-NMR STUDY p.28 

M. Grzegożek, B. Szpakiewicz 

1 H NMR DETECTION OF σ -ADDUCTS IN S N H REACTIONS OF 3-NITRO-1,5-NAPHTHY- 

RIDINES WITH CHLOROMETHYL PHENYL SULFONE p.29 

H. Harańczyk, A. Leja, K. Strzałka 

HYDRATION OF WHEAT PHOTOSYNTHETIC MEMBRANE LYOPHILIZATES 

MODIFIED BY ANTIBIOTICS OBSERVED BY PROTON MAGNETIC RELAXATION 

AND ADSORPTION ISOTHERM p.31 

H. Harańczyk, A. Ligęzowska, M. Olech 

DESICCATION RESISTANCE OF THE LICHEN TURGIDOSCULUM 

COMPLICATULUM AND ITS PHOTOBIONT PRASIOLA CRISPA BY PROTON 

MAGNETIC RELAXATION, AND SORPTION ISOTHERM p.33 

S. Heinze-Paluchowska, T. Skórka, K. Majcher, Ł. Drelicharz, 

S. Chłopicki, A. Jasiński 

ASSESSMENT OF CARDIAC FUNCTION IN MICE IN VIVO BY MRI – 

PRELIMINARY RESULTS p.34 

F. Hennel 

SEQUENCE PROGRAMMING ON BRUKER MRI SYSTEMS p.36 

J. Herold, Ł. Dobrzycki, E. Pindelska, A. Kutner, K. Woźniak, 

W. Kołodziejski 

THE MOST STABLE POLYMORPHIC FORM OF OLANZAPINE AS STUDIED BY 

13 C CP/MAS NMR AND X-RAY DIFFRACTION p.37 

M. Hyjek, B. Blicharska, M. Fornal 

ESTIMATION OF PARAMAGNETIC IONS CONTENT IN BLOOD SERUM BY 

RELAXATION MEASUREMENTS p.38 

K. Jackowski 

A DETERMINATION OF ABSOLUTE SHIELDING CONSTANTS AND SPIN-SPIN 

COUPLINGS FOR ISOLATED MOLECULES p.39 

M. Jancelewicz, M. Kempka, A. Patkowski, S. Jurga 

PROTON NMR STUDIES OF MOLECULAR DYNAMICS IN 

POLYMETHYLPHENYL SILOXANE p.40 

A. Kluczewska , E. Kluczewska, Z. Drzazga 

DIAGNOSTIC VALUE OF MRI IN CONVERSION PROCESS OF HUMAN BONE 

MORROW p.41 

4

J. Kolmas, M. Uniczko, E. Kalinowski, A. Wojtowicz, Z. Trzaska Durski, 

W. Kołodziejski 

HIGH-RESOLUTION SOLID-STATE NMR STUDIES OF HARD DENTAL TISSUES 

AND RENAL STONES p.42 

J. Krzaczkowska, Z. Fojud, S. Jurga 

NMR AND FTIR STUDY OF MOLECULAR DYNAMICS IN L-ALANINE / 

POLYETHYLENE GLYCOL COMPLEX p.43 

M. Kubiszewski 

EFFECTS OF INTERMOLECULAR INTERACTIONS 

ON THE SPIN-SPIN COUPLING CONSTANTS AND NMR CHEMICAL SHIFTS OF 

FLUOROMETHANES IN THE GAS PHASE p.45 

S. Kuśmia, E. Szcześniak, S. Jurga 

NMR STUDIES OF THE POLYETHYLENE COMPOSITES WITH ORGANIC 

FILLERS p.46 

L. Latanowicz, W. Medycki, J. Boguszyńska, E. C. Reynhardt 

LOW TEMPERATURES DYNAMICS IN SYSTEMS CONSISTING OF HYDROGEN 

BOND AND METHYL GROUPS p.48 

M. Lawenda, Ł. Popenda, N. Meyer, M. Stroinski, Z. Gdaniec, R. W. Adamiak 

VIRTUAL LABORATORY OF NMR SPECTROSCOPY p.50 

I. Łakomska, E. Szłyk, L. Pazderski, J. Reedijk 

1 H NMR STUDIES OF PLATINUM(II) CHLORIDE COMPLEXES REACTION 

WITH GUANOSINE-5’-MONOPHOSPHATE p.51 

D. Maciejewska, V. Kowalska 

STRUCTURE OF SOME ARYLAZO-2-NAPHTHYLAMINES AND THEIR N- 

ACETAMIDES p.52 

K. Makiej, B. Nogaj 

35 Cl-NQR STUDY OF ELECTRONIC STRUCTURE AND BIOLOGICAL ACTIVITY 

OF SELECTED DDT-TYPE INSECTICIDES p.53 

K. Makiej, A. Nowacka, J. Kasprzak, R. Utrecht, J. Wąsicki, B. Nogaj 

35 Cl- NQR AND 1 H-NMR STUDY OF MOLECULAR DYNAMICS OF p,p′-DDA 

INSECTICIDE p.55 

E. Michalik, A. Maślankiewicz 

THE SYNTHESIS AND NMR ANALYSIS OF THE AMIDE DERIVATIVES OF 2,3- 

DIHYDRO-1,4-DITHIINO[5,6-C]QUINOLINE p.57 

E. Mikiciuk-Olasik, B. Karwowski, M. Witczak, P. Szymański, E. Wojewoda, 

M. Studniarek 

NEW HEPATOTROPIC PREPARATIONS FOR MR IMAGING OF LIVER AND BILE 

DUCTS DISEASES p.58 

Ľ. Mucha, J. Onufer, D. Olčák 

STUDY OF MOTIONAL PROCESSES OF DRAWN I-PP/EPDM BLENDS BY 

BROAD LINE 1 H-NMR p.59 

5

J. Murín, J. Uhrin, L. Horváth, L. Ševčovič 

NMR STUDY OF STRUCTURAL CHANGES IN POLYETHYLENE – 

POLYPROPYLENE BLENDS CAUSED BY DRAWING p.60 

R. B. Nazarski 

ESTIMATION OF H2 J PH AND 2 J PH SCALAR COUPLINGS BY DFT/FPT METHOD 

TO RATIONALISE TWO DISTINCT NMR OBSERVATIONS p.62 

A. Nazirov, R. Gwoździk-Bujakowski, M. Wachowicz, S. Jurga 

SOLID STATE NMR STUDIES OF MOLECULAR MOTIONS IN THE 

BIOCOPOLYMER 

OF GLYCOLIDE/LACTIDE/CAPROLACTONE p.64 

G. Nowaczyk, M. Kempka, S. Jurga 

T 1 DISPERSION AND SELF-DIFFUSION NMR STUDY OF WATER MOLECULES IN POLY 

(ACRYLIC ACID) HYDROGELS p.65 

C. J. Oates, C. Kapusta, P. C. Riedi, M. Sikora, D. Zając, D. Rybicki, 

Ch. Martin, C. Yaicle 

AN NMR STUDY OF Pr 0.5 Ca 0.5 Mn 1-x Ga x O 3 (x=0 AND 0.03) p.66 

Z. Olejniczak, T. Pałasz, K. Cieślar, K. Suchanek, M. Suchanek, T. Dohnalik 

A LOW FIELD MRI SYSTEM FOR HYPERPOLARIZED 3 He IMAGING p.67 

B. Orozbaev, M. Wachowicz, S. Jurga 

MOLECULAR DYNAMICS IN POLY(ETHYLENE OXIDE) (PEO): 

1 H-NMR AND DIELECTRIC SPECTROSCOPY STUDIES p.68 

K. Paradowska, A. Zielińska, I. Wawer, W. Kołodziejski 

1 H MAS NMR OF FLAVONOIDS p.69 

L. Pazderski, I. Łakomska, E. Szłyk, J. Sitkowski, L. Kozerski 

15 N NMR COORDINATION SHIFTS IN STABLE AND LABILE 

d-ELECTRON METAL COMPLEXES WITH AZINES p.70 

D. Pentak, W. Korus, A. Sułkowska, W. W. Sułkowski 

EFFECT OF TEMPERATURE ON LIPOSOME STRUCTURES. 

EPR AND NMR STUDIES p.71 

A. Pietras, H. Krawczyk 

REACTIONS AND NMR STUDY OF NEW ABNORMAL METABOLITES 

IDENTIFIED IN URINE OF CANCER PATIENTS p. 72 

M. Pisklak, J. Kossakowski, I.Wawer 

1 H, 13 C NMR AND GIAO/DFT CALCULATIONS OF SUBSTITUTED N-(4-ARYL-1- 

PIPERAZINYLBUTYL) DERIVATIVES, NEW ANALOGUES OF BUSPIRONE p.73 

J. Polak, M. Bartoszek, W. W. Sułkowski 

NMR STUDY OF THE HUMIFICATION PROCESS DURING SEWAGE SLUDGE 

TREATMENT p. 74 

J. Polak, M. Bartoszek, J. Borek, W. W. Sułkowski 

NMR STUDY OF THE HUMIC ACIDS EXTRACTED FROM SEWAGE SLUDGE p.75 

6

Ł. Popenda, Z. Gdaniec, G. Dominiak, J. Milecki, R. W. Adamiak 

STRUCTURAL ANALYSIS OF RNA DUPLEXES CONTAINING ADENOSINE BULGES 

BY NMR SPECTROSCOPY p.76 

D. Rybicki , C. Kapusta, Peter Charles Riedi, Colin John Oates, D. Zając, 

M. Sikora, C. Marquina and R. Ibarra 

NMR STUDY OF LAYERED MANGANITE La 1.4 Sr 1.6 Mn 2 O 7 p.78 

M. Skarżyński, K. Krajewski, J. Krzywda and H. Fitak 

IDENTIFICATION AND DETERMINATION OF NAPROXENE ALLYL ESTERS 

DIASTEREOISOMERS WITH PROTON-NMR SPECTROSCOPY p.79 

M. Steinbauer, K. Bartušek 

MAGNETIC SUSCEPTIBILITY EVALUATION BY MEANS OF MRI TECHNIQUE p.80 

K. Suchanek, M. Suchanek, K. Cieślar, T. Pałasz, Z. Olejniczak i T. Dohnalik 

A NOVEL SOURCE OF MAGNETIC FIELD FOR IMAGING LASER-POLARIZED 3 HE p.82 

W. W. Sułkowski, B. Bojko, A. Sułkowska and J. Równicka 

THE MECHANISM OF THE DRUGS BINDING TO THE PROTEIN IN 

COMBINATION THERAPY p.83 

P. Szczeciński i D. Bartusik 

DETERMINATION OF AMINO ACIDS IN BODY FLUIDS WITH THE USE OF 19 F 

NMR SPECTROSCOPY p.84 

L. Szutkowska, B. Peplińska i S. Jurga 

MOLECULAR DYNAMICS OF TERT-BUTYL CHLORIDE CONFINED TO CPG (7.4 NM) p.86 

K. Szutkowski i S. Jurga 

NMR CHEMICAL PROTON-EXCHANGE STUDIES IN DECYl - AND 

DODECYLAMMONIUM CHLORIDE SURFACTANT-WATER SYSTEMS p.87 

M. Tanasiewicz, W. P. Węglarz, E. Machaj, T. Kupka, A. Jasiński 

MR MICROSCOPY IN COMPARISON OF YOUNG AND OLD TOOTH STRUCTURE p.88 

E. Tylek, J. Polaczek, J. Pielichowski 

STUDIES OF POLY(ASPARTIC ACID) STRUCTURE AND ITS DERIVATIVES 

USING 1 H NMR SPECTROSCOPY p.89 

M. Wachowicz, J. E. Wolak, S. Jurga, J. L. White 

SOLID-STATE NMR INVESTIGATION OF LOCAL CHAIN DYNAMICS IN 

POLYISOBUTYLENE/POLYPROPYLENE-CO-BUTENE BLENDS p.91 

A.Walczak, R.Żaguń, J.Kasprzak, B. Brycki and B.Nogaj 

35 Cl-NQR STUDY OF MOLECULAR DYNAMICS OF TETRACHLOROPHTHALIMIDE 

AND N-PHENYLTETRACHLOROPHTHALIMIDE p.92 

A.Walczak, A.Mielcarek, B.Brycki and B.Nogaj 

35 Cl-NQR STUDY OF THE SUBSTITUENT EFFECT ON THE ELECTRONIC 

STRUCTURE OF TETRACHLOROPHTHALIMIDE DERIVATIVES p.94 

M. Wilczek, K. Jackowski 

13 C AND 1 H NUCLEAR MAGNETIC SHIELDING AND SPIN-SPIN COUPLING 

CONSTANTS OF 1,2- 13 C-ENRICHED ETHYLENE IN THE GAS PHASE p.96 

J. E. Wolak, X. Jia, and Jeffery L. White 

THE GLASS TRANSITION TIME SCALE AND CONFIGURATIONAL ENTROPY IN 

POLYMERS: AN EXPERIMENTAL MOLECULAR VIEW p.97 

7

M. Wolniak, J. Oszmiański and I. Wawer 

13 C CPMAS NMR OF ANTHOCYANINS AND THEIR SUGAR DERIVATIVES p.98 

A. Woźniak-Braszak, J. Jurga, K. Jurga, S. Jurga, M. Szostek 

INVESTIGATION OF TRANSESTERIFICATION IN POLY(ETHYLENE 2,6- 

NAPHTHALATE)/POLYCARBONATE COMPOSITE USING OFF-RESONANCE 

NMR AND DMTA TECHNIQUES p.100 

T. Zalewski, S. Kuśmia, T. Trzeciak, J. Kruczyński, S. Jurga 

T 2 RELAXATION MAP OF ARTICULAR CARTILAGE IN DIFFERENT STAGE OF 

REGENERATION p.102 

A. Zielińska, K. Paradowska, T. Żołek, I. Wawer 

SOLID STATE CONFORMATION AND ANTIOXIDANT PROPERTIES OF 

COUMARIN IN 13 C CP MAS NMR, GIAO-CHF CALCULATIONS AND EPR 

STUDIES p.103 

M. Zielińska, R.Marszałek, E.Sieradzki 

MICROTOMOGRAPHY STUDIES OF TABLETS p.104 

M. Żylewski, M. Cegła, P. Kowalski, T. Kowalska, M. Paluchowska, R. Bugno, 

A. Bojarski 

CONFORMATION OF ARYLPIPERAZINES WITH LONG SIDE CHAIN – 2D NMR 

INVESTIGATIONS p.105 

T. Banasik, A. Jasiński, M. Hartel, M. Konopka, P. Pieniążek, T. Skórka, 

W.P. Węglarz 

MAPPING OF THE BI-EXPONENTIAL DIFFUSION IN HUMAN SPINAL CORD p.106 

H. Figiel, P. Filipek, P. Szczurek, A. Budziak 

DEUTERIUM NMR IN RMn 2 D 2 (R=Y, Tb, D 4 ) p.108 

N. Górska, Ł. Hetmańczyk, E. Mikuli, A. Migdał-Mikuli, K. Hołderna-Natkaniec, 

W. Kasperkowiak 

PHASE TRANSITIONS AND REORIENTATIONAL MOTIONS OF THE COMPLEX 

CATIONS AND NH 3 LIGANDS IN POLYCRYSTALLINES [Co(NH 3 ) 6 ](ClO 4 ) 3 AND 

[Zn(NH 3 ) 4 ](BF 4 ) 2 p.109 

P. Grudnik, J. Pyka, B. Turyna, R. Gurbiel, W. Froncisz 

STUDIES ON CYTOCHROME C UNFOLDING PROCESS USING ELECTRON PARAMAGNETIC 

RESONANCE SPECTROSCOPY. QUALIFICATION OF PROXYL-MTS SPIN LABEL 

IN EXAMINATION OF PROTEIN STRUCTURE p.110 

A. Zięba, K. Suwińska, A. Maślankiewicz , J. Sitkowski, B. Kamieński 

STRUCTURE OF 4-QUINOLINONES ANALYSED BY NMR STUDY AND X-RAY DATA p.111 

D. Lewandowska, T. Podoski, C.J. Lewa 

INVESTIGATION OF PROPERTIES OF FRESH AND COMMERCIAL ALOE SAP 

BY NMR SPECTROSCOPY p.112 

Jerzy S. Blicharski, Barbara Blicharska 

NMR MULTIPOLE RELAXATION IN THE ROTATING FRAME IN GASES p.113 

8

USEFULNESS OF PROTON MAGNETIC RESONANCE 

SPECTROSCOPY ( 1 H MRS) IN DIAGNOSIS OF SUBCLINICAL 

HEPATIC ENCEPHALOPATY 

1 R. Banyś, 2 A. Słowik, 1 M. Pasowicz, 3 I. Ciecko-Michalska, 2 M. Motyl, 1 M. Irzyk, 

2 A. Szczudlik, 3 J. Bogdał 

1 

Center for Diagnosis and Rehabilitation Heart and Lung Disease The John Paul II 

Hospital, Departments of 2 Neurology, and 3 Gastroenterology, Jagiellonian University, 

Kraków, Poland 

Introduction 

Subclinical hepatic encephalopathy (SHE), is a disorder of cognitive functions in 

patients with liver cirrhosis, detectable only during neuropsychological examination, 

adversely affecting daily activity, and without any deficits during standard neurological 

examination. The disorder affects up to 70% of patients with liver cirrhosis. Nuclear Magnetic 

Resonance Spectroscopy ( 1 H MRS) is a fast developing, noninvasive method allowing the in 

vivo evaluation of biochemical changes in human brain. 

Aim 

The aim of the study was to assess the usefulness of in vivo 1 H MRS detection of 

metabolic abnormalities in brains of patients with SHE. 

Method 

In this study we included 22 patients with the diagnosis of SHE and 16 healthy 

volunteers. MR imaging and 1 H MRS examinations were performed on 1.5 T Magnetom 

Vision Plus and 1.5 T Magnetom Sonata Maestro Class (Siemens, Erlangen, Germany) 

scanners with single voxel PRESS technique (TR = 1500 ms, TE = 135 ms, 256 acquistion 

with the H 2 O signal suppression). Three voxels of 8 cm 3 were positioned in: 1) 

predominantly white matter in the posteromedial parietial cortex, 2) predominantly gray 

matter in the posterior occipital cortex, 3) globus pallidus. 

Metabolite concentrations were calculated manually using integral Siemens software. 

Peaks from myo-inositol (mI), choline (Cho) and N-acetyl-asparatate (NAA) were normalized 

with respect to the creatine (Cr) peak (mI/Cr, Cho/Cr and NAA/Cr). 

Results 

Patients with SHE presented with significant reduction mI/Cr ratio as compared to 

controls (0,138 vs. 0,044, p

FAINT LINE SHAPE EFFECTS IN LIQUID-PHASE NMR. 

NONCLASSICAL HINDERED ROTATION OF METHYL GROUPS 

IN 1,2,3,4-TETRACHLORO-9,10-DIMETHYLTRIPTYCENE 

P. Bernatowicz, I. Czerski, S. Szymanski 

Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 

01-224 Warsaw, Poland (E-mail: sszym@icho.edu.pl) 

In the standard NMR spectra, the line shape patterns produced by molecular rate 

processes are often poorly structured. When alternative theoretical models of such a process 

are to be compared, the results of line shape fits may be inconclusive. Our own experience is 

that a solution may be in the use of various spin-echo techniques, where a controlled delay 

between end of the stimulating pulse sequence and start of the acquisition of the NMR signal 

is employed. An enhanced sensitivity of such echo spectra, as compared to the standard 

spectra, to even minute details of the relevant spin exchange mechanisms can be understood 

easily. In the standard experiments, the state of spin system at the start of acquisition has no 

memory of the system’s dynamical history, so that the underlying rate process will be 

reflected only in the free evolution during the acquisition. In echo experiments, such a process 

will additionally feature the spin state at the start of acquisition. Therefore, in a series of echo 

spectra measured for suitably chosen echo times the content of information about the system 

dynamics is generally much more abundant than in a single standard spectrum. 

The problem of discrimination between competing line shape models we often 

encounter in our studies on the stochastic dynamics of strongly hindered methyl groups. Here 

one has to discriminate between the Alexander-Binsch (AB) model and our own damped 

quantum rotor (DQR) model. In the AB theory, the methyl group dynamics are pictured as a 

sequence of classical jumps between the three equilibrium orientations, which is described by 

one rate constant k. In the DQR approach, this is a quantum-mechanical effect involving two 

coherence-damping processes controlled by two corresponding rate constants, k t and k K . 

When k t = k K , the DQR line shape equation becomes identical with the AB equation with k = 

k t /3 (= k K /3). However, the dynamics in question become then “classical” in an operational 

sense only, since the two coherence-damping processes never merge into a single process. 

Presently, evidence of the nonclassical character of the methyl group dynamics in 

1,2,3,4-tetrachloro-9,10-dimethyltriptycene TCDMT, is reported. In the context of our earlier 

findings for 1,2,3,4-tetrachloro-9-methyltriptycene TCMT, and 1,2,3,4-tetrabromo-9- 

methyltriptycene TBMT, the present results are remarkable in that the effect is now observed 

above 200 K. However, for TCDMT the departure from the “classical” behavior is small; 

measured in terms of the ratio c = k t / k K , it falls in the range 1.07 - 1.10, while for TCMT and 

TBMT it reaches 1.20. For TCDMT, a visualization of the effect is possible only for series of 

Carr-Purcell (CP) echo spectra subject to fits to the AB and DQR models: Evident 

deficiencies of the former are spectacularly contrasted with a virtual perfection of the latter. 

However, with the standard description of radiofrequency pulses as spin rotation 

operators, perfect fits to series of more than two CP-echo spectra cannot in general be 

achieved, even when the correct line shape model is used. On example of CP-echo spectra of 

TBMT, we demonstrate that the remedy is in the use of a more realistic description of the 

pulses, with the effective pulse strength being treated as one more adjustable parameter. This 

methodological observation is of crucial significance for the studies of faint line shape effects 

in liquid-phase NMR. 

10

INFLUENCE OF PARAMAGNETIC IONS ON FLUORINE NMR 

SPECTRA 

Antoni Bijak, Barbara Blicharska, Magdalena Hyjek 

Institute of Physics, Jagiellonian University, ul. Reymonta 4, 

30-059 Kraków, Poland 

Abstract 

Many of modern drugs contain fluorinated compounds as an active substance. These 

drugs have wide range of use in clinic therapy. It starts from fluorine salts as a component of 

toothpaste, antidepressant and anticancer drugs, to fluorinated quinole and anaesthetic agents. 

Such large variety of application of fluorinated compounds require fast and accurate methods 

of monitoring their pharmacokinetic and metabolism in the living systems. 

We have investigated the following drugs in aqueous solutions: sodium fluoride 

(osteoreconstructivum), Fevarin (thymoleptic), Ciprinol (chemotherapeutic), Flunarizinum 

(antihistamine) and 5FU (cytostatic). Some drugs were available as pure substance i.e. 

Sevoflurane (anaesthetic) and Mirenil (neuroleptic). 

In our studies we have shown also that in the presence of paramagnetic ions in 

solutions 

(i.e. iron ion in blood or polluted samples) lead to 19 F line broadening. 

11

LONELY DEUTERON IN NH 3 D + IONS AS A SPECTATOR 

OF THEIR MOBILITY 

Artur Birczyński, Zdzisław T. Lalowicz, Zbigniew Olejniczak 

MR Laboratory, H. Niewodniczański Institute of Nuclear Physics, Kraków, Poland 

Partially deuterated ammonium ions open a new field in studies of molecular mobility 

and crystal structure. Depending on the deuteration rate the sample contains NH 4 + , NH 3 D + , 

NH 2 D 2 + , NHD 3 + and ND 4 + ions with relative abundances given by the binomial distribution 

of hydrogen and deuterium. All carrying deuterons isotopomers contribute characteristic 

deuteron NMR spectra [1]. 

1 

3 

2 

4 

D H N 

Rotational tunnelling involves indistinguishable particles. Therefore for NH 3 D + only 

protons tunnel at low temperatures and deuteron is static. It can however be locked at four 

spectroscopically distinguishable positions in a crystal unit cell (see drawing). Each position 

contributes a doublet in the single crystal spectrum, with in principle, equal intensity. We can 

imagine that the local potential barriers at these positions are of different depth, say at the 

position 4 the potential appears the deepest. Such situation we met in ammonium persulphate 

[2]. In result the related doublet exhibits increased intensity. The effect is called isotope 

ordering. We may get information about mobility of protons analysing the shape of deuteron 

lines. With deuteron at position 4 we find that protons do tunnel and reorient at very high 

frequency. At other positions reorientation is absent, however tunnelling frequencies are 

measurable and different: 200kHz and 70kHz at deuteron positions 2 and 1 or 3, respectively 

[3]. At the particular orientation with magnetic field parallel to N-D(4) bond the spectrum is 

void dynamic effects. On the other hand however, its particular structure allows separate 

evaluation of dipolar deuteron-proton and deuteron-nitrogen interaction and thus precise 

measurement of their distances [2]. 

Another interesting observations were obtained in the case of ammonium perchlorate. 

Here just two doublets have been observed: from rigid deuterons at position 4 and from all 

other, reorienting already at 4K. Thermally activated transition between these two dynamic 

states is characterised by a very low activation energy 1.57meV. In this case, due to rather 

low and symmetric potential, existence of the postulated electric dipole moment of NH 3 D + 

ions [4] may be pointed out as a dominating interionic interaction and possible ordering 

mechanism. 

[1] Z.T. Lalowicz, A. Birczyński, Z. Olejniczak, and G. Stoch, Mol. Phys. Rep., 31, 108 (2001). 

[2] T. Schmidt, H. Schmitt, H. Zimmermann, U. Haeberlen, Z.T. Lalowicz, Z. Olejniczak and T. 

Oeser, Acta Crystallogr., B58, 760 (2002). 

[3] Z.Olejniczak, Z.T.Lalowicz, T.Schmidt, H.Zimmermann, U.Haeberlen, and H. Schmitt, J. 

Chem. Phys., 116, 10343 (2002). 

[4] M. Prager, P. Schiebel, M. Johnson, H. Grimm, H. Hagdorn, J. Ihringer, W. Prandl, and Z.T. 

Lalowicz, J. Phys. Condens. Matter, 11, 5483 (1999). 

12

NMR RELAXATION OF PAPER SAMPLES 

Barbara Blicharska 

Institute of Physics, Jagiellonian University, Kraków, Poland 

NMR relaxation method has been used to study water dynamics in paper samples. 

Dependence spin-lattice relaxation time T 1 on temperature and frequency can give 

information about interaction between water and cellulose protons. The parameters: activation 

energies and correlation times, describing a proposed two-motion molecular dynamics model, 

may be correlated with different origin paper structure features. We have shown that noninvasive 

NMR relaxation method can be used for an evaluation of the degree of paper 

devastation and reconstruction processes of old books and manuscripts. 

13

DEUTERON SPIN-LATTICE RELAXATION STUDY OF D 2 SECLUDED 

IN THE SUPERCAGES OF ZEOLITE NAY 

Jerzy S. Blicharski 1 , Aleksander Gutsze 2 , Agnieszka M. Korzeniowska, 

Zdzisław T. Lalowicz, Zbigniew Olejniczak 

H. Niewodniczański Institute of Nuclear Physics, Kraków, Poland; 1 Institute of Physics, Jagiellonian 

University, Kraków,Poland; 2 Biophysics Department, Medical Academy, Bydgoszcz, Poland 

Nuclear magnetic resonance provides means to study molecular dynamics in every 

state of matter. When going from solid state over liquids to gases, besides of molecular 

reorientations, also translational diffusion appears. Additionally, molecular rotation becomes 

much less quenched by intermolecular interactions. Single molecules of D 2 or CD 4 inserted 

into zeolite supercages provide new specific model system for studies of rotational and 

translational dynamics. One may have cages of different dimensions, with different wall 

features and different filling factors. 

At high temperatures molecules fly freely across cages, with the life-time τ J depending 

on temperature and cage dimensions. Molecules behave as free quantum rotors and the main 

contribution to the relaxation comes from the quadrupole interaction. On decreasing 

temperature molecules become adsorbed on cage walls and undergo thermally activated 

reorientations characterized by a correlation time τ C = τ 0 exp(E/kT). This process can be 

described as surface diffusion taking place under the condition of a distribution of potential 

well depth E [1]. One may also introduce the time of residence of a molecule on the surface, 

τ ads . An adsorbed molecule may perform many translational jumps before it leaves the 

surface. 

Main contributions to the spin-lattice relaxation rate 1/T 1 come from quadrupole and 

spin-rotational terms [2] for very short τ J at high temperatures: 

1/T 1SR = (8π 2 /3) C 2 SR τ J + (3π 2 /2) C 2 Q τ J , 

and the quadrupole relaxation below about 110K: 

1/T 1Q = (3 π 2 /10) C 2 Q [J(ω 0 )+4J(2ω 0 )], where: is the mean rotational quantum 

number, and J(ω 0 ) = τ C /(1 + ω 2 0 τ 2 C ) is the spectral density function. The coupling constants 

C were obtained from molecular beam studies: C SR = 8.25 kHz, C Q = 225.04 kHz [3]. 

The observed spin-lattice relaxation rate at high temperature indicates that the lifetime 

of the free rotor state, appears to be τ J = n τ f , where τ f is the time of a single flight across 

the cage. Scattering on the walls is elastic and introduces only a weak perturbation. Factor n 

exhibits a linear temperature dependence. On the other hand, when considering the 

quadrupole relaxation below 110 K, we get highly reduced value of the effective coupling 

ef 

constant C Q = 48.3kHz. This can be explained by a very fast reorientation of D 2 molecules 

on a cone with an opening angle close to 90 o . Translational diffusion on the cage surface 

interrupts such motion by steps involving molecular turns, characterized by the time τ C . 

Measurements of the NMR line intensity and line-width provide also interesting new 

observations. The spin-conversion between ortho and para spin species of the quantum rotor, 

as well as the adsorption on cage walls, are involved processes to be studied. 

These results are just highlights of the new research project dedicated to the analysis 

of rotational effects in deuteron spin relaxation for D 2 and CD 4 molecules secluded in 

zeolites. 

This project is supported, during 2002-2005, by the State Committee for Scientific 

Research grant No 2 P03B 135 23. 

1. H.A. Resing, Advan. Mol. Relaxation Processes, 1, 109 (1967-68) 

2. J.S.Blicharski, Acta Phys. Polon. 24, 817 (1963) 

3. R.F. Code, N.F. Ramsey, Phys. Rev. A4, 1945 (1971) 

14

SPIN-LATTICE RELAXATION OF D 2 QUANTUM ROTORS 

Jerzy S. Blicharski 1 , Agnieszka M. Korzeniowska, Zdzisław T. Lalowicz, 

H. Niewodniczański Institute of Nucelar Physics, Kraków, Poland; 1 Institute of Physics, 

Jagiellonian University, Kraków,Poland 

 

We consider a system of two identical nuclear spins I 1 = I 2 = 1, total spin I = 

 

I 1 

+ I 2 

, 

and molecular angular momentum J in di-deuterium D2 molecules in gaseous state. In the 

presence of strong magnetic field B 0 the nuclear spin Hamiltonian H can be expressed as a 

sum of a dominant static Zeeman interaction H 0 , time-dependent traceless spin-rotational 

interaction H ’ SR(t), and an effective quadrupolar-dipolar interaction H ’ DQ(t) resulting from the 

nuclear quadrupole and dipole-dipole interactions under interference conditions [1]: 

' 

' 

H = H + H ( t) 

= ω I + ω J H ( ) , (1) 

where: 

H 

' 

SR 

( t) 

= C 

0 I z J z 

+ t 

' 

' 

' 

H ( t) 

= H 

SR 

( t) 

+ H 

DQ 

( t). 

R 

 

I ⋅ J ( t) 

= C 

∑ + 1 

R 

A2 

M 

( I 

M = −1 

∑ + 2 

A2 

M 

3) M = −2 

 

) A 

+ 

2M 

(2) 

 

( J ( t)) 

, (3) 

' 

∆ 

 

+ 

 

I 

H 

DQ 

( t) 

= 

( I ) A2 

M 

( J ( t)) 

. (4) 

4(2J 

−1)(2J 

+ 

 

L L 

The quantities ALM 

( P) 

= ( P ⋅∇) 

( r CLM 

( θ , φ)) 

are spherical tensors with spin operators 

 

P = ( I , J ) , where J = J (t) are random functions of time due to molecular collisions, and 

C 

LM 

( θ , φ) 

= 4π 

/ 2L + 1Y 

LM 

( θ , φ) 

are the Racah functions. Other parameters are defined as 

follows: 

2 

2 

CQ 

(11− 

3I 

− 3I) 

+ 2C 

D 

(8 + I + I) 

∆ 

I 

= 

, (5) 

(2I 

−1)(2I 

+ 3) 

with the spin-rotatinal constant C R = 55 . 10 3 rad/s, the quadrupole constant C DQ = 1413 . 10 3 rad/s 

and the dipolar constant C D = 44 . 10 3 rad/s [2]. 

The relaxation matrix elements can be calculated in a weak collision approximation from the 

following expressions [1]: 

1 +∞ 

' 

+ 

R 

jk 

= Tr T H 

~ ' 

∫ [ 

j 

, ( t)][ 

T 

j 

, H 

~ 

( t + τ )] dτ , (6) 

2 

−∞ 

where: 

iH t 

iH t 

H ~ ' 

0 0 

( t) 

e H 

' − 

= ( t) 

e . (7) 

Using (6) we can obtain the spin-lattice relaxation rate for a given total nuclear spin I, and the 

following contributions due to the spin-rotational (SR) (spin independent) and quadrupolardipolar 

(QD) interactions: 

SR 

QD 

⎛ 1 ⎞ ⎛ 1 ⎞ ⎛ 1 

T T T ⎟ ⎞ 

⎜ ⎟ = 

⎜ 

⎟ + 

⎜ , (8) 

⎝ 1 ⎠ ⎝ 1 ⎠ ⎝ 1 ⎠ 

I 

SR 

1 ⎞ 1 2 

⎟ = CR 

1 

3 

⎛ 

⎜ 

⎝ T ⎠ 

J ( J + 1) j(( 

ω −ω 

I 

I 

J 

), τ 

J 

) , (9) 

15

QD 

⎛ 1 ⎞ 3 2 

J ( J + 1) 

⎜ 

I 

(2I 

1)(2I 

3) 

f (( 

I J 

), 

J 

) 

T 

⎟ = ∆ − + 

ω −ω τ , (10) 

⎝ 1 ⎠ 400 

(2J 

−1)(2J 

+ 3) 

1 

where: 

2τ 

L 

j( 

ω, 

τ 

L 

) = , f ( ω , τ ) ( , ) 4 (2 , ) , (L=1,2) 

2 2 

L 

= j ω τ 

L 

+ j ω τ 

L 

1+ 

ω τ 

L 

The j( ω, 

τ 

L 

) is the reduced spectral density function [3] for ALM ( J (t)) and τ 

L 

are the 

correlation times due to molecular collisions. The expressions in the brackets are statistical 

averages over Boltzman population of the rotational levels with even and odd J values for ortho 

(I=2, 0) and para (I=1) species respectively [4]. 

For the total nuclear spin I=2, 1, 0 we get the respective relaxation rates: 

⎛ 1 ⎞ ⎛ 1 ⎞ 7 

2 J ( J + 1) 

⎜ ( CQ 

4C 

D 

) 

f (( 

I J 

), 

J 

) 

T 

⎟ = 

⎜ + − 

ω −ω τ 

1 

T 

⎟ 

, (11) 

⎝ ⎠ ⎝ 1 ⎠ 400 

(2J 

−1)(2J 

+ 3) 

2 

SR 

SR 

⎛ 1 ⎞ ⎛ 1 ⎞ 3 

2 J ( J + 1) 

⎜ 

( CQ 

4C 

D 

) 

f (( 

I J 

), 

J 

) 

T 

⎟ = 

⎜ + + 

ω −ω τ 

1 

T 

⎟ 

, (12) 

⎝ ⎠ 1 

80 

(2J 

−1)(2J 

+ 3) 

1 ⎝ ⎠ 

⎛ 1 ⎞ 

⎜ 

⎟ = 0 

⎝ T . (13) 

1 ⎠0 

One can see from (11) and (12) that the interference terms (cross terms) between the 

quadrupolar and dipolar interactions oppose or concur contributing to the relaxation rate for 

ortho- and para-D 2 molecules, respectively. 

In the case of the ortho-D 2 molecules with the total spin I=2 or 0 and even J, one has to take 

into account a leakage rate R L between I=2 and I=0 species, contributing to the longitudinal 

relaxation rate: 

SR 

⎛ 1 ⎞ ⎛ 1 ⎞ ⎛ 1 ⎞ 

⎜ 

T 

⎟ = 

⎜ + 

T 

⎟ 

⎜ 

T 

⎟ 

⎝ 1 ⎠ortho 

⎝ 1 ⎠ ⎝ 1 ⎠ 2 

+ RL 

. (14) 

As a result of the calculation one gets: 

1 J ( J + 1) 

R ( 2 ) 

L 

= CQ 

+ CD 

f (( ωI 

−ω 

J 

), τ 

J 

) , 

50 

(2J 

−1)(2J 

+ 3) 

(15) 

and after summing up the quadrupolar-dipolar and leakage terms we get: 

SR 

⎛ 1 ⎞ ⎛ 1 ⎞ 3 2 

2 J ( J + 1) 

⎜ 

(5CQ 

8CQC 

D 

48C 

D 

) 

T 

⎟ = 

⎜ + − + 

1 

T 

⎟ 

⎝ ⎠ ⎝ 1 ⎠ 400 

(2J 

−1)(2J 

+ 3) 

ortho 

QD 

f (( ω −ω 

I 

J 

), τ 

J 

) . (16) 

[1] Blicharski J.S., Kruk D.,: Appl. Magn. Reson. 17, 367-374 (1999) 

[2] Ramsey N.F.: Molecular Beams, p.52. Oxford University Press: Oxford 1956 

[3] Abragam A.: The Principles of Nuclear Magnetism, p.313. new York: 1961 

[4] Herzberg G.: Spectra of Diatomic Molecules, 2nd Ed., p.134 Princeton, Van Nostrand 

1950 

16

INVESTIGATION OF NEUROPROTECTING EFFECT OF MPEP 

ON A RAT SPINAL CORD TRAUMATIC INJURY MODEL USING 

MR DIFFUSION ANISOTROPY IMAGING 

Paweł Brzegowy 3 , Andrzej Jasiński 1 , Tomasz Banasik 1 , Zenon Sułek 1 , Dariusz Adamek 2 , 

Katarzyna Majcher 1 , A. Pilc 4 , Tomasz Skórka 1 , Władysław Węglarz 1 

1 

Radiospectroscopy and MRI, H. Niewodniczański Institute of Nuclear Physics PAN, Kraków; 

2 

Neuropathology, 3Radiology, Jagiellonian University Medical College, Kraków; 

4 

Neurobiology, Institute of Pharmacology PAN, Kraków, Poland 

Introduction. 

Mechanical injury creates complicated changes in structure and function of spinal cord 

tissues. Damage of nerve fibers and blood vessels give rise to ischemia, bleeding and nonequilibrium 

of different biochemical processes leading to an avalanche of secondary processes 

resulting in permanent damage of the spinal cord. Excitatory amino acids (EAA) appear in 

abundance in the intercellular space after the trauma stimulating ionotropic and metabotropic 

glutamate receptors, generating the secondary damage to GM and WM. Ionotropic glutamate 

receptors coupled to the ion channels are: NMDA, AMPA and kainate. Metabotropic 

glutamate receptors (mGluR) are linked to G-proteins. MPEP - an mGlu5 receptor antagonist 

may limit secondary excitotoxic injury after spinal cord trauma. 

In this paper we present results of our studies of MR water diffusion anisotropy 

imaging (DAI) of neuroprotecting effects of MPEP after spinal cord trauma (SCT) on a rat 

model. 

Materials and methods. 

Male Wistar rats of 250 g to 300 g weight were used. Animals were anaesthetized by 

an injection of 4% chloral hydrate intraperitoneally at 0,9 ml/100 g of body weight and 

a laminectomy at the Th12 spine level was performed and the SCT was induced using 

a dynamic weight-drop. MPEP - an mGlu5 receptor antagonist was injected intraperitoneally 

before the SCT and at 24h and 48h (30 mg/kg). Rats were anesthetized to a surgical depth 

with halothane and were maintained at 37° C using water blanket. An ECG and motion 

detector was placed on their chest to synchronize the MRI system to the animal breath rate. 

Each rat was measured 4 times at 1h, 24h, 48h and 7d after trauma. 

MR DAI experiments were done at 4.7T /31 Burker magnet with a Maran DRX 

console, using standard SE and modified FSE sequences with diffusion gradients applied 

parallel and perpendicular to the spinal cord. Dedicated inductively coupled probes were used 

to record MR images of 128 x 128 with FOV of 2 cm, slice thickness of 1.6 mm and gradient 

b-factors up to 1500 s/mm 2 . Data were analyzed using IDL based software developed inhouse. 

Longitudinal diffusion D L = D ZZ , transverse diffusion D T = (D XX +D YY )/2, isotropy 

index ID = D T /D L and anisotropy index AI = (DL-DT)/(DL+DT) were determined for selected 

regions in the white and gray matter of the spinal cord. 

Results. 

Good quality DW MR images, free from any motion artifacts were obtained from 

control and injured spinal cord of the rat in vivo. DW sagittal images delineate the traumatic 

region and its development in time very well. Axial images taken through the center of injury, 

at 2.8 mm and at 5.6 mm show development of injury in different anatomical regions. 

Average values of ID for control rats after laminectomy are: ID WM = 0.2 ± 0.05 and ID GM = 

0.5 ± 0.1. After injury ID increases depending on the extent of damage. Application of MPEP 

17

has effects in the WM and GM in the intermediate zone. These DAI results are confirmed by 

subsequent histopatology. Behavioral observations of contusion in rats based on locomotor’s 

rating scales (BBB scale and Tarlov scale) during 7 days were done. Rats treated with MPEP 

demonstrate progressive locomotor’s recovery of hind limbs from slight paresis to almost 

normal locomotion, whereas untreated rats recovered remarkably slowly. 

Conclusion. 

Diffusion anisotropy imaging (DAI) requiring 1/2 time of full DTI experiment may be 

used successfully as quantitative and noninvasive method for testing neuroprotecting drugs on 

the spinal cord injury model. 

18

OPTICAL PUMPING OF 3 He 

Katarzyna Cieślar, Katarzyna Suchanek, Mateusz Suchanek, Zbigniew Olejniczak*, 

Tadeusz Pałasz, Tomasz Dohnalik 

Institute of Physics, Jagiellonian University, Kraków; *Institute of Nuclear Physics, Kraków, Poland 

High field thermal polarization achieved in standard MRI systems is of the order 

of 10 -6 . Optical pumping techniques enable to create polarization exceeding the thermal levels 

by up to six orders of magnitude (hyperpolarization) in two stable noble gas isotopes: 3 He, 

129 Xe. As both gases are metabolically inert, they can be used as a source of NMR signal in 

the MRI lung imaging. This method, however, generates a non-equilibrium polarization, 

which has important consequences to the imaging procedures used. 

An optical pumping method called metastability exchange is used to produce the 

hyperpolarized 3 He. A glass cell containing the 3 He gas at a low pressure (1 torr) is placed in 

a magnetic field of about 30 Gs. As the optical transition between 1 1 S 0 and 2 3 S 1 states is 

strictly forbidden, a weak RF discharge is used to populate the metastable 2 3 S 1 state (Fig.1). 

3 

10 -8 [s] 

1 D 2 

2 3 P 

3 

2*10 -8 [s] 

3 D 

0 

2 3 P 

2 3 P 1 

2 1 P 5*10 -10 [s] 

1 

2 3 P 10 -7 [s] 

2 3 P 2 

2 

2*10 -2 [s] 

1 S 0 

8*10 3 [s] 

2 3 S 1 

1083 nm 

METASTABLE 

STATE 

2 3 S 1 

1 1 S 0 

Fig.1. Energy levels for 3 He atom. 

F = 

F = 

F = 

F = 

F = 

F = 

F = 

The absorption of circularly polarized (σ+) laser beam of wavelength λ = 1083nm causes a 

transition from 2 3 S 1 , m F = –1/2 to 2 3 P 0 , m F = +1/2 state (Fig.2). After excitation a spontaneous 

reemission to both m F = –1/2 and m F = +1/2 sublevels of 2 3 S 1 state takes place. However, the 

continuous depletion of the m F = –1/2 sublevel results in higher population of the 2 3 S 1 , m F = 

+1/2 state. This is equivalent to the electronic polarization of the atom. Through hyperfine 

coupling the nucleus also becomes polarized. Nuclear polarization 

of the ground state 3 He atom is achieved via 

m = - 

metastability exchange collisions in which 2 3 P 0 

a non-polarized ground state atom and a polarized 

F = 

m = 

metastable atom take part. The polarization achieved 

in that way is about 80%. One can measure the 

polarization using NMR or optical methods. 

To use the gas in the MRI lung imaging, it is 2 3 S 1 

necessary to compress it without losing the 

polarization up to atmospheric pressure for which 

purpose a compressor is being built. 

1083 nm 

σ+ 

F = 

Fig.2.Optical pumping. 

m = - 

m = 

19

13 C CP MAS NMR STUDIES OF STEROIDAL SAPOGENINS 

FROM CONVALLARIA MAJALIS L. 

Karolina Dąbrowska-Balcerzak, Jadwiga Nartowska, Iwona Wawer 

Faculty of Pharmacy, The Medical University of Warsaw, Banacha 1, 02097 Warsaw, Poland 

Convallaria majalis from the family Liliaceae is widely distributed in Europe. 

Herba Convallariae is used in the therapy of cardiological diseases. 

Steroidal sapogenins and saponins were isolated from the roots and rhizomes of 

C.majalis. Convallomarogenin was isolated by Tschasche at al. in 1973. Novel sapogenin, 

named convallanartigenin, was obtained recently. The structures of these sapogenins were 

determined by 1 H and 13 C NMR in solution and solid phase. 

13 C NMR spectra in solution were recorded on a Bruker DRX-500 spectrometer. Solid 

state 13 C CP MAS NMR spectra were recorded on a Bruker MSL-300 instrument at 

75.5 MHz, the samples were spun at 8.3 kHz in 4 mm ZrO 2 rotor (a contact time of 4 ms, 

a repetition time of 6 s, 600-800 scans). 

The assinments were made using 2D COSY, HETCOR, HMBC and NOESY 

correlations. 1 H and 13 C chemical shifts indicated that the new sapogenin, convallanartigenin, 

is a 25S spirostanol derivative with four hydroxyl groups at the ring A. These groups form 

highly polar part of this compound, their presence is confirmed by chemical shifts of the CH- 

OH carbons appearing in the range 66-75 ppm. The respective signals are easily recognized in 

13 C CP MAS spectra (in solution spectra this region is overlaped with the signals of solvent, 

CDCl 3 ). The 13 C CP MAS spectrum of convallanartigenin exhibited 18 clearly resolved 

signals for the 27 carbon atoms, the signals were assigned by comparison with solution data. 

Most solid-state chemical shifts are almost the same as for solution. 

It is worth noticing, that solid state NMR can be considered as the fast, non-destructive 

method of identification of sapogenins. The absence of sugar resonances (CHOH) confirms 

that hydrolysis was completed and the molecules studied are in the form of aglycone. 

20

NMR STUDY OF GELATION PROCESS OF LOW 

METHOXYL PECTIN 

Maria Dobies, Sławomir Kuśmia, Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, Umultowska 85, 

61-614 Poznań, Poland 

In this work the gelation process of aqueous low methoxyl pectin solution in the presence 

of divalent cations from the calcium chloride was studied by proton NMR dispersion of spinlattice 

and spin-spin relaxation times. 

Low methoxyl pectins can form gels in the presence of divalent cations (mainly Ca 2+ ), 

through associations between sequences of charged groups belonging to two different chains 

(egg-box binding) [1]. Pectin from citrus fruit (potassium salt) was obtained as dried powder 

from Sigma Chemicals (P-9311). Homogeneous samples of pectin sols and gels were prepared 

from 1% w/w aqueous pectin solution by addition of appropriate amount of calcium chloride 

solution (0,1M CaCl 2 ). The four physical stages were observed: solution (0 mM CaCl 2 ), sol 

(1.5 mM, 2.5 mM and 5 mM CaCl 2 ), homogenous gel (7.5 mM CaCl 2 ) and gel with syneresis 

(10 mM CaCl 2 ). 

Dispersions of proton spin–lattice relaxation rates R 1 were recorded with the Fast Field 

Cycling Relaxometer. The Larmor frequency was changed between 0.01 MHz and 9 MHz 

(Fig.1). Transverse relaxation times measurements (Fig. 2) were made with a 400 MHz 

spectrometer, using CPMG pulse sequence (τ CPMG =1ms). All experiments were performed at 

21 o C. 

For the low methoxyl pectin in solution the spin-lattice relaxation rate shows a slight 

frequency dependence but after addition of calcium chloride this dispersive character becomes 

more pronounced. With increasing concentration of the salts, the spin-lattice relaxation rates 

increases in the whole frequency range. The high-field behaviour appears to be not too 

sensitive to the salt content, the spin-lattice relaxation rates become strongly cation-dependent 

in the low magnetic fields. The strong differences in the magnitude of the dispersion profiles 

in the low-field range can be attributed to a decrease in the number of ionised sites on the 

pectin surface as a result of the egg-box mechanism [2]. The model-free approach [3] to the 

analysis of 1 H NMRD data was used to separate the information on the static and dynamic 

behaviour of systems. Addition of salt to the pectin solution caused a substantial modification 

of the pectin molecules structure, which is reflected by the increase of β parameter with 

increasing concentration of calcium chloride (from the value 0.61×10 7 1/s in the solution state 

up to the value 2,08×10 7 1/s in the final gel state formed at 10 mM salt concentration). The 

most pronounced changes in β were noted on varying the concentration of calcium chloride 

from 2.5 mM to 5 mM. It is expected that in this concentration range the gel network is 

created. The effect of calcium chloride addition on the τ parameter is less pronounced, but 

still shows the same tendency towards slowing down the dynamics. 

c 

21

R 1 

[1/s] 

10 

8 

6 

4 

1% LMP solution 

1% LMP sol state (2.5mM CaCl 2 

) 

1% LMP sol state (5mM CaCl 2 

) 

1% LMP gel state (7.5mM CaCl 2 

) 

1% LMP gel state (10mM CaCl 2 

) 

Fig. 1. Dispersion of the water 1 H spin-lattice 

relaxation rate in solution of 1% w/w pectin 

without added calcium chloride and after 

addition of 2,5; 5; 7.5 and 10 mM CaCl 2. 

2 

0 

10 4 10 5 10 6 10 7 

Larmor frequency [Hz] 

The existence of gelling process was confirmed by spin-spin relaxation times 

measurements. T 2 relaxation curves were bi-exponential. It can be associated with water in 

differing physical environments (away from the pectin macromolecules - long T 2 and near 

macromolecular surfaces – short T 2 ). With increasing concentration of the salts increases 

number of junction zones and sites of cross-links, due to the long component of transverse 

relaxation times decreases - around five times (from 1.13 s to over 0,23 s ). These results 

indicates that in the gelled system pectin molecules more rapidly exchange spin energy with 

water molecules [3]. 

1,2 tau CPMG 

= 1ms 

T 2 

slow 

1,0 

T 2 

fast 

0,8 

Fig. 2. The spin-spin relaxation times for 

1% w/w pectin solution without added 

calcium chloride and after addition of 1.5; 

2.5; 5; 6.5; 7.5 and 10 mM CaCl 2. 

T 2 

[s] 

0,6 

0,4 

0,2 

0,0 

0 2 4 6 8 10 

CaCl 2 

concentration [mM] 

1. G. T. Grant, E. R. Morris, D.A. Rees, P. J. C. Smith, and D. Thom, FEBS Lett., 32, (1973) 195. 

2. M. Dobies, M. Kozak, S. Jurga, Solid State NMR 25, Iss. 1-3, 2004 (in press) 

3. B. Halle, H. Johannesson, and K. Venu, J. Magn. Reson., 135, (1998) 1. 

4. W. L. Kerr, and L. Wicker, Carbohydr. Polym., 42, (2000) 133. 

22

MRI INVESTIGATIONS OF HYDROGEL FORMATION 

AND DIMENSIONAL CHANGES OCCURRING 

IN HBS – PRELIMINARY STUDIES 

Przemysław Dorożyński 1 , Piotr Kulinowski 2 , Andrzej Jasiński 2 , Renata Jachowicz 1 

1 Department of Pharmaceutical Technology and Biopharmaceutics , Pharmaceutical Faculty, 

Jagiellonian University, ul. Medyczna 9, 30-688 Kraków, Poland; 2 M.R.I. Laboratory, 

Institute of Nuclear Physics, ul. Radzikowskiego 152, Kraków, Poland 

1. Introduction 

Our aim was to set up a system for obtaining Magnetic Resonance Images 

simultaneously with the drug release profiles from Hydrodynamically Balanced Systems 

(HBS). 

HBS are the most common flotation dosage form. They are essentially composed of a drug 

mixed with gel forming hydrocolloids. In contact with gastric fluid HBS swells and forms 

hydrogel. The soft hydrogel barrier maintains a relative integrity of shape and a bulk density 

less than 1 g/cm 3 . The drug is slowly released in the stomach by diffusion through the 

gelatinous barrier and slow erosion of hydrogel on the surface of the dosage form [1]. 

The MRI is non destructive, non invasive method – it does not require sample slicing. 

Since swelling polymeric matrices are very easy to damage, Magnetic Resonance Imaging 

(MRI) can be used to observe the processes of solvent penetration inside the dosage form, 

hydrogel formation and erosion [2]. It can be done without any capsule manipulation – 

capsule remains all the time inside the flow-through cell under the flow condition. 

2. Materials and methods 

For MRI studies MR research system with digital MARAN DRX console (Resonance 

Instruments) and 4.7T/310mm horizontal bore magnet (Bruker) equipped with actively 

shielded gradient set of 200mm ID (Magnex Scientific) was used. Special flow-through cell 

for HBS systems investigations was designed. Images were obtained using modified fast spin 

echo sequence under a flow condition at flow rate 23ml/min. Imaging parameters were as 

follows: field of view – 3.5cm, number of slices – 7 (for saggital slices), 23 (for axial slices), 

slice thickness – 1mm, echo time – 19ms. Time constant of processes in investigated HBS are 

in the range of 5-6 hours. The images of HBS were taken every half an hour. Constant 

temperature of solution (37°C) was maintained during the course of the whole experiment. 

3. Results 

As an example, comparative study of HPMC 100k (Metholose 90 SH 100 000cp) with 

LDopa 3+1 in two different solutions is presented. Two HCl solutions simulating gastric fluid 

in fed and fasted state were used. Dimensional changes of the HBS capsules were detected by 

observation of changes in proton signal intensity. 

The dry cores in the HBS were observed for 5 hours. During this time the swelling in 

axial direction was clearly evident. The longitudinal dimension of the capsule immersed in 

fasted state simulated gastric fluid increased from 2,6 cm to 3,6 cm. Simultaneously the water 

content in the swollen barrier gradually increased. The weight of the system increased almost 

5 times during the experiment. The penetration of the solvent into the system was rather slow. 

The decrease of the dry core radial dimension was not significant. The hydrogel from the 

surface of the system was partially removed. In opposition, the hydrogel barrier produced in 

the fed state simulated gastric fluid remained not changed during 5 hours of experiment. 

23

4. Conclusion 

MRI could be useful in case of imaging of water penetration into the HBS and 

elucidation of the mechanisms of hydrogel formation and erosion. The erosion and swelling 

of the polymeric matrix systems appeared to play dominant role in drug release and flotation 

of the dosage form. 

5. Bibliography 

1. Singh, B.N., Kim, K.H., 2000. Floating drug delivery systems: an approach to oral 

controlled drug delivery via gastric retention. J. Contr. Rel. 63,235-259. 

2. Fyfe C.A., Gordoney H.,Blazek-Welsh A.I., Chopra S.K., Fahie B.J., NMR imaging 

investigations of drug delivery devices using a flow-through USP dissolution 

apparatus, Journal of Controlled Release, 68 (2000) 73-83 

24

CHEMICAL SHIFT TITRATION AT THE INTERMEDIATE 

EXCHANGE RATES OF HOST – GUEST SYSTEM 

Andrzej Ejchart 

Institute of Biochemistry and Biophysics, Polish Academy of Sciences, 

Pawińskiego 5A, 02-106 Warsaw, Poland; aejchart@ibb.waw.pl 

NMR spectroscopy has been widely used for the determination of association 

constants, K, observing NMR parameters, most often chemical shifts, in the titration 

experiments. Owing to the specific time scale of NMR method the appearance of the NMR 

spectrum of the host – guest mixture depends not only on association constant but also on the 

rate of the exchange of guest molecules between free and bound states. Most of the studies 

have been concerned with the case of fast exchange when only a time averaged mole fraction 

weighted spectrum of guest (and/or host) in free and bound states can be observed. 

δ obs = (1 – [C]/[G 0 ])δ G + ([C]/[G 0 ])δ C 

where δ obs is observed chemical shift of guest resonance, δ G and δ C are chemical shifts in free 

and bound states, respectively. [C] is the concentration of complex and [G 0 ] is initial 

concentration of guest. On the other hand, the equation which couples concentrations and 

association constant depends on the stoichiometry of the system. For the simplest 1 : 1 

stoichiometry one obtains: 

K = [C]/{([H 0 ]–[C])([G 0 ]–[C])} 

where [H 0 ] is initial host concentration. 

Intermediate exchange rates on the NMR time scale cause signal broadening which 

combined with the titration shifts of multiple (often superposed) resonances can preclude 

determination of their positions making such titration experiment useless. 

An approach allowing to overcome this problem is proposed. It relies on the concerted 

fit of the theoretical lineshapes determined by a number of parameters including association 

constant to the set of experimental lineshapes obtained during titration experiment. 

25

STRUCTURE AND ARRANGEMENT OF GLASSY PHOSPHO- 

SILICATE MATERIALS STUDIED BY 23 NA, 27 AL, 31 P NMR AND FTIR 

METHODS 

Zbigniew Fojud a) , Maciej Sitarz b) , Mirosław Handke b) , Stefan Jurga a) 

a) Institute of Physics, Adam Mickiewicz University, Poznań, Poland; b) Faculty of Materials 

Science and Ceramic, AGH University of Science and Technology, Kraków, Poland 

The glassy-crystalline materials obtained via direct crystallization from the glassy state 

are one of the most interesting ceramics materials [1]. The analysis of the amorphous 

materials structure due to the lack of long-distance order, is rather studied by NMR and FTIR, 

which are sensitive for short-distance order, than by x-ray methods. NMR [2] as well as FTIR 

were successfully used in studies of this problem [3, 4]. 

The main goal of the present work is detailed structure analysis of the phosphosilicate 

materials studied by NMR and FTIR methods. The 23 Na, 27 Al, and 31 P NMR chemical 

shifts are reported in ppm scale from adequate reference lines. All NMR spectra were 

recorded using a Bruker DSX 400 MHz spectrometer operating at 105.8, 104.3, 161.9 MHz 

for 23 Na, 27 Al, 31 P NMR, respectively. Samples were held in 4 mm zirconia rotors and spun at 

15 kHz. 

Our studies gave an evidence for chemically inequivalent surroundings of the studied 

nuclei. An example of this observation is given in Fig.1 for aluminium ions in the glassy 

structure. 27 Al NMR spectrum observed was non-symmetrical due to superposition of 

various intra-tetrahedral [AlO 4 ] 5- bonds, as shown in our previous work [2]. 

70 60 50 40 

Fig. 1. The selected 27 Al NMR spectrum of glassy phospho-silicate material. 

Maciej Sitarz is a scholarship holder of The Foundation For Polish Science (Scholar Grant 

2003). 

This work is supported by Polish Committee for Scientific Research under grant no. 

PBZ/KBN-013/T08/34. 

[1] H. G. Kim, T. Komatsu, J. Mat. Sci. Lett, 17, 1198, (1988). 

[2] W. Mozgawa, Z. Fojud, M. Handke, S. Jurga, J. Molec. Struc., 614, 281, (2000). 

[3] M. Sitarz, M. Rokita, M. Handke, E. Galuskin, J. Molec. Struc., 651-653, 489, (2003). 

[4] M. Handke , M. Sitarz, M. Rokita, E. Galuskin, J. Molec. Struc., 651-653, 39, (2003). 

26

LOCAL DYNAMICS AND ORGANIZATION 

OF N-UNDECYLAMMONIUM CHLORIDE / WATER SYSTEMS 

STUDIED BY NMR AND SAXS 

Zbigniew Fojud, Maciej Kozak, Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, Poznań, Poland 

The molecular dynamics in n-undecylammonium chloride (UDACl) water solution has 

been investigated by Fast Field Cycling NMR, DSC and SAXS techniques. The 

alkylammonium chlorides exhibit a number of lyotropic liquid crystalline phases [1], with 

different symmetries. Their characterization is difficult, since all the processes occurring in 

the systems are complex and involve a wide time scale. 

The dispersion spin-lattice relaxation times explored by field cycling method have 

been studied to elucidate the local and collective molecular dynamics, whereas the SAXS 

measurements gave us information on local conformational properties in the lyotropic 

structures. 

The study shows the existence of slow and fast contributions to the observed 

relaxation. In the smectic and nematic phases, the main contribution at low frequencies, below 

1 MHz, comes from the order director fluctuation, typical for ordered layer structures. In the 

frequency range above 1 MHz the relaxation is dominated by the rotation of the alkyl chains 

about their long axes. Simultaneously trans-gauche isomerisation as well as translational 

diffusion is taking place [2], similarly as for anhydrous n-alkylammonium chains [3, 4]. 

1 

300 K 

Relaxation Time T 1 

(s) 

0,1 

10 3 10 4 10 5 10 6 10 7 10 8 

Fig. 1. T 1 relaxation dispersion curve for 30% of UDACl in D 2 O at 300 K. 

The small angle X-ray scattering and Differential Scanning Calorimetry (DSC) 

techniques have also been used to study the kinetics of phase transformations in the binary 

systems water / n-undecylammonium chloride. The lamellar, hexagonal and isotropic phases 

of n-undecylammonium chloride in water was characterised (concentrations 20 – 70 % w/w 

and temperatures 293 – 343 K) and the structure parameters were obtained. 

[1] J. D. GAULT, M. A. LEITE, M. R. RIZZATTI, H. A. GALLARDO, J. COLLOID INTERFACE SCI., 122, 

587-590 (1988). 

[2] Z. Fojud, E. Szcześniak, S. Jurga, S. Stapf, R. Kimmich, Sol. State NMR, accepted (2003) 

[3] S. Jurga, V. Macho, B. Hüser, H. W. Spiess, Z. Phys. B., Condensed Matter, 84, 43-49 (1991). 

[4] Z. Fojud, E. Szcześniak, K. Jurga, S. Jurga, Appl. Magn. Reson., 19, 413-420 (2000). 

27

ROLE OF THE CHELATING PROCESS OF FLAVONOIDS REDUCING 

THE INTERACTION BETWEEN ORGANOMETALLIC COMPOUNDS 

AND THE LIPID BILAYER – AS INFERRED 

FROM THE 1H-NMR STUDY 

1 Janina Gabrielska, 2 Monika Soczyńska–Kordala, 1 Stanisław Przestalski 

1 Department of Physics and Biophysics, 2 Department of Food, Vegetables and Cereals, 

Agricultural University, 50-375 Wrocław, Norwida 25, Poland, jaga@ozi.ar.wroc.pl 

The toxicity of organic tin compounds (OC) with respect to biological membranes 

depends, among others, on the degree of adsorption in the lipid phase of the membrane. The 

ionic forms of organometallic compounds, once localized in the membrane bilayer, interact 

with the polar membrane region [Kaszuba and Hant, 1990; Gabrielska et al., 1997]. It seems 

possible that the interaction may decrease when the OC molecules are engaged in a donoracceptor 

interaction leading to the formation of associates. As ligands in the complexes can 

occur, e. g., natural compounds of the flavonoid family, such as kempferol, quercetin and 

mirycetin (FL) [Morel et al., 1998; Dyba et al., 1999; Cornard and Merlin, 2001]. 

The present work determines the degree of the interaction between equimolar mixtures 

of selected organometallic compounds (dichloro-diphenyltin – DPhT and chlorides of 

triphenyltin – TPhT and triphenyllead – TPhL, with kempferol, quercetin, mirycetin) and the 

phosphate grouping of the phosphatidylcholine (PC) liposome membrane. That interaction 

was compared with both FL and OC compounds interacting alone with that grouping. As a 

parameter of the interaction was assumed the competitive release of praseodymium ions (Pr 3+ ) 

from membranes induced by the compounds studied, measured with the proton nuclear 

magnetic resonance (H 1 -NMR) method. 

The results obtained allow to conclude that, as a result of chelating by FL the ionic 

forms of OC compounds, changes their coulombic interaction with phosphate group of the 

bilayer. Consequently, undergoes reduction also the degree of the competitive praseodymium 

ions release from the membrane bilayer by equimolar mixtures of FL with OC, compared with 

release of the ions effected by the compounds added separately. The decrease is especially 

conspicuous for mixtures of flavonoids with DPhT (ca. 90%), and much lower for mixtures of 

flavonoids with triphenyltin chlorides (ca. 40 %). 

Natural flavonoid compounds, such as kempferol, quercetin and mirycetin, due to their 

metal chelating properties [Cornard and Merlin, 2001; Soczyńska-Kordala et al., 2000], lead 

and tin including, constitute a good protection against the toxic forms of OC compounds 

acting on PC membranes. 

Work supported by KBN grant No 4 PO6 019 21 

1. Kaszuba M., Hunt G.R.A. (1990) A 1 H-NMR study of the influence of n-alcohols on the 

stoichiometry of melittin-induced permeability of phosphatidylcholine membrane. Biochim. Biophys. 

Acta 985, 106-110. 

2. Gabrielska J., Sarapuk J., Przestalski S. (1997) Role of hydrophobic and hydrophylic interactions of 

organotin and organolead compounds with model lipid membranes. Z. Naturforsch., 52c, 209-216. 

3. Dyba M., Solinas S, Caleddu N, Ganadu M-L, Kozłowski H. (1999) Cu(II) complexes with rutin. 

Polish J. Chem., 73, 873-878. 

4. Morel I., Cillard P., Cillard J. (1998) Flavonoid-metal interactions in biological systems. 

In:Flavonoid in health and disease. Eds. C. Rice-Evans, L. Parcker, Marcel Dekker. INC, New York, 

Basel, pp. 163-176. 

5. Cornard J.P., Merlin J.C. (2001) Structural and spectroscopic investigation of 5-hydroksyflavone 

and its complex with alumunium. J. Mol. Struc., 569, 129-138. 

6. Soczyńska-Kordala M., Gabrielska J., Bąkowska A, Przestalski S. (2000) Biochem Biophys. Mol. 

Lett. 

28

1 H NMR DETECTION OF σ-ADDUCTS IN S N H REACTIONS 

OF 3-NITRO-1,5-NAPHTHYRIDINES WITH CHLOROMETHYL 

PHENYL SULFONE 

Maria Grzegożek, Barbara Szpakiewicz 

Instytute of Organic Chemistry and Technology, 

Cracow University of Technology, PL 31155 Kraków, Poland 

3-Nitro-1,5-naphthyridines 1a-e undergo vicarious nucleophilic substitution (VNS) of 

the aromatic hydrogen when reacting with chloromethyl phenyl sulfone in basic solution. 

These S N H reactions occur very selectively, giving product of substitution of hydrogen at 

position ortho to the nitro group in nitronaphthyridines [1]. The reaction process take place 

between 3-nitro-1,5-naphthyridines and carboanion such as carboanion chloromethyl phenyl 

sulfone. In the first step addition of the carboanion to the 1 results in the formation of σ- 

adduct 2, which undergoes base induced β-elimination of HCl form carboanion which is 

subsequently protonated during the workup procedure giving product 3 [2] (Scheme). 

N 

N 

SO 2 Ph 

H CHCl 

CH 2 SO 2 Ph 

NO 2 

N 

NO 2 

N 

NO 2 

ClCH 2 SO 2 Ph 

1 ) - HCl 

− 

NaOH / DMSO 

R 

2 ) + H 3 O + 

N R 

N R 

1 2 σ-adduct 3 

. R = H, Cl, OC 2 H 5 , NHCH 3 , OH 

In order to confirm the intermediates in the above-mentioned reactions are detectable 

anionic σ-adducts like 2, we have measured the 1 H NMR spectra of 3-nitro-1,5- 

naphthyridines 1a-e in solution of NaOD in DMSO containing 1.1 equivalents of 

chloromethyl phenyl sulfone. It was observed that in the spectra nearly all signals are shifted 

upfield, particularly considerably the signals of the protons at the carbon atoms which form σ- 

adducts. Addition of carboanion of chloromethyl phenyl sulfone to the sp 2 carbon atom of 3- 

nitro-1,5-naphthyridines induces the change of its hybridization from sp 2 to sp 3 (tetrahedral 

centre of σ-adduct) which is reflected in a considerable upfield shift signal of the hydrogen 

atom attached to the particular carbon atom. This rehybridization sp 2 to sp 3 is due to the σ- 

adduct formation. The corresponding 1 H NMR data of 3-nitro-1,5-naphthyridines 1a-e and 

their (phenylsulfonyl) chloromethyl-σ-adducts 2a-e are compiled in Table. The upfield shift 

∆δ of the signals of the C-4 hydrogen atom at the tetrahedral centre of 4-(phenylsulfonyl)- 

chloromethyl-σ-adducts 2a-e lie between 2.56 - 3.51 ppm and are in the same range as those 

found for amino-σ-adducts of some 3-nitro-1,5-naphthyridines ∆δ 2.55 -3.81 [3] and for σ- 

adducts of nitroquinolines with chloromethyl phenyl sulfone ∆δ 2.90 - 4.11 [4]. 

Summing up, 1 H NMR spectroscopy is a very good method to detection of intermediary 

covalent σ-adducts, like 2 and the determination of their structures plays an important role in 

the interpretation of the mechanism of VNS reaction. 

The 1 H NMR spectra were recorded on Mercury 300 „varian”(300 MHz) spectrometer. 

29

Table. 1 H NMR data of some 3-nitro-1,5-naphthyridine (1) and their anionic σ-adducts with 

chloromethyl phenyl sulfone 

Compound Solvent Chemical shifts (δ values) 

2-H 4-H 6-H 7-H 8-H 

3-Nitro-1,5- 

naphthyridine (1a) 

4-ClCH SO 2 Ph-σadduct 

of 1a (2a) 

2-Chloro-3-nitro-1,5- 

naphthyridine (1b) 


of 1b (2b) 

2-Ethoxy-3-nitro-1,5- 

naphthyridine (1c) 


of 1c (2c) 

2-Methylamino-3-nitro- 

1,5-naphthyridine (1d) 


of 1d (2d) 

2-Hydroxy-3-Nitro-1,5- 

naphthyridine (1e) 


of 1e (2e) 

DMSO-d 6 9.66 9.17 9.21 8.01 8.60 

NaOD / 8.90 5.77 8.19 7.24 7.68 

DMSO-d 6 

∆δ 0.76 3.40 1.02 0.77 0.92 

DMSO-d 6 - 9.25 9.19 8.02 8.52 

NaOD / - 5.86 8.21 7.21 7.40 

DMSO-d 6 

∆δ - 3.39 0.98 0.81 1.12 

DMSO-d 6 - 8.46 8.79 7.68 8.16 

NaOD / - 5.80 8.13 

DMSO-d 6 

∆δ - 2.56 7.90 - 7.25 a 0.03 

DMSO-d 6 - 8.87 8.70 7.68 8.08 

NaOD / - 5.42 8.08 7.00 7.61 

DMSO-d 6 

∆δ - 3.47 0.62 0.68 0.47 

DMSO-d 6 - 8.75 8.63 7.68 7.76 

NaOD / - 5.24 7.78 7.67 7.91 

DMSO-d 6 

∆δ - 3.51 0.85 0.01 -0.15 

a The signals of these protons form a complex multiplet and can not be exactly assigned. 

References: 

[1]. M.Grzegożek, M.Woźniak, A.Barański, H.C.van der Plas, J.Heterocyclic Chem., 28, 

1075 (1991). [2]. M.Mękosza, Synthesis, 1991, 103; Pol.J.Chem., 66, 3 (1992). 

[3]. M.Woźniak, H.C.van der Plas, M.Tomula and A.Van Veldhuizen, Recl.Trav.Chim.Pays- 

Bas, 102, 511 (1983). [4]. M.A.Grzegożek, Khim.Geterocycl.Soedin., 420, 786 (2002). 

30

HYDRATION OF WHEAT PHOTOSYNTHETIC MEMBRANE 

LYOPHILIZATES MODIFIED BY ANTIBIOTICS OBSERVED BY 

PROTON MAGNETIC RELAXATION AND ADSORPTION ISOTHERM 

* H. Harańczyk, *A. Leja, **K. Strzałka 

* Institute of Physics and **Faculty of Biotechnology, Jagiellonian University, Kraków, 

Poland 

The rehydation from the gaseous phase of the wheat photosynthetic membrane 

lyophilizates was investigated using hydration kinetics, adsorption isotherm and high power 

proton free induction decays (FIDs). 

We compared the control membranes and the membranes washed out from the nonfunctional 

loosely bound manganese fraction by 1mM EDTA washing. Some membranes were 

modified by the use of chloramphenicol or actidion in the course of their growth. 

The adsorption isotherm revealed a sigmoidal form and was well fitted using Dent 

model. The obtained mass of water saturating ‘primary’ water binding sites varied depending 

on the growth protocol of the membrane, and reflect the changes in the membrane induced by 

the use of antibiotics. 

Proton FIDs distinguish (i) Gaussian component, S 0 , coming from protons of solid 

matrix of lyophilizate as well as the components increasing with the increased hydration level: 

(ii) a Gaussian component, S 1 , from water bound to the primary water binding sites; (iii) and 

exponentially decaying contribution, L 1 , from water tightly bound to lyophilizate surface, 

presumably the first hydration shell, and (iv) exponentially decaying loosely bound water 

fraction, L 2 . 

A significant contribution of ‘sealed’ water molecules belonging to the fraction S 1 and L 1 , 

already present in dry lyophilizate is detected. The sorption isotherm obtained from 

gravimetric data fits well NMR-sorption data, supporting the concept that all three FID signal 

components, S 1 , L 1 , and L 2 , come from water hydrating the photosynthetic membrane 

lyophilizate. The presence of ‘sealed’ water coincides with the non-lamellar tubular structures 

in rehydrated lyophilizate of photosynthetic membrane and presumably is the signal from 

water trapped inside this structures. 

31

DESICCATION RESISTANCE OF THE LICHEN TURGIDOSCULUM 

COMPLICATULUM AND ITS PHOTOBIONT PRASIOLA CRISPA BY 

PROTON MAGNETIC RELAXATION, AND SORPTION ISOTHERM 

* H. Harańczyk, *A. Ligęzowska, **M. Olech 

* Institute of Physics and **Institute of Botany, Jagiellonian University, Kraków, Poland 

The Antarctic lichens, as the organisms experiencing the extreme low temperatures and 

low hydration level in their habitat, are proper system in the investigations of life extremes for 

deep desiccation stress. In contrast to vascular plants they may perform active photosynthetic 

process even if their thallus is frozen. To emphasize the range of their adaptation, it is worth 

mentioning that some of lichen species survive the freezing down to the temperature of liquid 

nitrogen intependently on the freezing rate; they perform the active photosynthesis below 0 0 C 

and even below the temperature of the heterogeneous ice nucleation in their cellular fluids 

[Kappen, 1993, Kieft and Ahmadijan, 1989, Kieft and Ruscetti, 1990]; they stimulate ice 

deposition in extracellular spaces of thallus [Schroeter and Scheidegger, 1995, Harañczyk et 

al., 2003a]; and prevent the intracellular spaces from ice nucleation by transfer of the freezing 

loosely bound water to the not freezing tightly bound water pool [Harańczyk et al., 2000, 

2003b]; they reversibly dehydrate down the two dimensional percolation threshold of water 

bound on the thallus surfaces [Harañczyk, 2003]; they can hydrate from the gaseous phase up 

to the level sufficiently high to induce the photosynthetic activity; the take water directly from 

the snow up [Kappen et al, 1991]. 

Essential for understanding the molecular mechanism of the metabolic recovery during 

rehydration is knowledge about the number and distribution of water binding sites, sequence 

and kinetics of their saturation, as well as fromation of tightly and loosely bound water pools 

at different steps of hydration process. 

In our experiments we investigated the lichen Turgidosculum complicatulum and its 

free living fotobiont an alga Prasiola crispa. The relative independence of symbionts 

[Kovaeik & Pereira, 2001] makes an unique possibility to test the dessication resistance of 

both partners separately. Samples were collected in Maritime Antarctic, Antarctic Peninsula, 

King George Island, Polish Antarctic H. Arctowski Station. 

We measured the initial stages of mild rehydration from the gaseous phase of the 

lichen thallus o T. complicatulum and the separately living (in the same habitat) alga P. crispa 

using hydration kinetics, adsorption isotherm and high power proton free induction decays 

(FIDs). 

Four different water pools are differentiated: 

(i) water bound to the ‘primary’ water binding sites (∆m/m 0 = 0.020±0.005 and ∆m/m 0 = 

0.030±0.002, for P. crispa and for T. complicatulum, respectively) which was not removed by 

incubation over silica gel; 

(ii) and (iii) two fractions of tightly bound water, differentiated by hydration constant (∆m/m 0 

= 0.007±0.001 and ∆m/m 0 = 0.10±0.02 for P. crispa; and ∆m/m 0 = 0.07±0.02 and the one 

exceeding ∆m/m 0 = 0.10 for T. complicatulum); 

and (iv) loosely bound water pool. Both fractions of tightly bound water fractions are not 

differentiated by molecular mobility but only by the binding strength. 

32

References: 

1. H. Harańczyk On water in extremely dry biological systems, Wyd. Uniwersytetu 

Jagiellońskiego (2003). 

2. H.Harańczyk, S.Gaździński, M.Olech, In: New Aspects in Cryptogamic Research, 

Contribution in Honour of Ludger Kappen. Bibl. Lichenol., 75, 265 (2000). 

3. H.Harańczyk, J.Grandjean, M.Olech Colloids & Surfaces, B: Biointerfaces 28/4, 239 

(2003a). 

4. H.Harańczyk, J.Grandjean, M.Olech, M.Michalik Colloids & Surfaces, B: Biointerfaces 

28/4, 251 (2003b). 

5. L. Kappen, Arctic, 46, 297 (1993). 

6. L. Kappen, M. Breuer, M. Bölter, Polar Biology, 11, 393 (1991). 

7. T.L. Kieft, V. Ahmadjian, Lichenologist, 21, 355 (1989). 

8. T.L. Kieft, T. Ruscetti, J. Bacteriol., 172, 3519 (1990). 

9. L. Kovaeik, A.B. Pereira, Nova Hedwigia, Beiheft 123, 465 (2001). 

10. B. Schroeter, Ch. Scheidegger, New Phytol., 131, 273 (1995). 

33

ASSESSMENT OF CARDIAC FUNCTION IN MICE IN VIVO 

BY MRI – PRELIMINARY RESULTS 

S. Heinze-Paluchowska ∗ , T. Skórka ∗ , K. Majcher ∗ , Ł. Drelicharz ∗∗ , S. Chłopicki ∗∗ , 

A. Jasiński ∗ 

∗ 

H. Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences, Kraków, 

Poland; ∗∗ Chair of Pharmacology, Medical College of Jagiellonian University, Kraków, 

Poland 

Introduction 

The purpose of our study was to assess the feasibility of MRI to characterize cardiac 

function in mice in vivo. Transgenic mice are gaining widespread popularity in cardiovascular 

research. Indeed, numerous genetic models of mice with altered expression of variety of genes 

have been developed and used in studies on the physiology and pathology of cardiovascular 

system. The use of genetically-modified mice offer opportunities for better understanding of 

cardiovascular diseases [1,2] . This has provided motivation for the current study. Here we 

present our preliminary results on the measurements of cardiac function in mice in vivo. This 

technique was set-up for future assessment of functional progression of heart failure in 

transgenic mice with cardiac-specific overexpression of Glafaq protein (Mende JACC). 

Materials and Methods 

Mice were anesthetized with Avertin, injected i.p 12 mg/100g body weight. During the 

experiment, the mouse was positioned supine on a nonmagnetic pad to maintain constant 

body position and temperature throughout the MR study. Heart rates were 250-350 beats/min. 

All animal experimental procedures were in accordance with institutional guidelines. 

Experiments were performed on a 4,7T MR scanner with MARAN DRX console. The 

scanner was equipped with a gradient system (MAGNEX) capable of 10mT/m maximum 

gradient strength. For NMR signal transmission and reception an 8-rung homebuilt birdcage 

coil with inner diameter of 36mm was used. For exact ECG triggering, an ECG trigger unit 

(RAPID Biomedical ECG TRIGGER UNIT HSB) was used, allowing for multiple filtering of 

the original surface ECG signal to sufficiently isolate the QRS signal from noise generated by 

the magnet and the gradient coils. The trigger point was set on the R wave. ECG trigger unit 

was connected to the oscilloscope (Tektronix, TDS 3000). 

MR imaging was performed using an ECG triggered fast gradient echo [3] (FLASH 

with multiphase option) sequence with the following imaging parameters: Echo time (TE) 

3,8 ms; repetition time (TR) depends on the distance between R-R waves, acquisition matrix 

128×128; slice thickness 1,1 mm, number of scans (NS) 4, and a flip angle was set to achieve 

the best contrast between myocardium and blood pool (about 50 degrees). 

After the image plane orientation from saggital and coronal LV long-axis images was 

positioned, MRI data acquisition was performed in multiple contiguous short-axis slices to 

cover the entire left ventricle (LV). 

Results 

Good quality MR images of the mouse heart in vivo were obtained. Measurements of 

the multiple slice images in different phases of the cardiac cycle, with a good contrast 

between myocardium and flowing blood, give the opportunity to calculate the end-diastolic 

34

(EDV) and end-systolic (ESV) volumes. Using these parameters and their derivatives, such as 

stroke volume or cardiac output, it is possible to characterize the cardiac function. 

Fig.1. End-diastolic (left) and end-systolic (right) MR images in a midventricular 

short-axis slice. 

References: 

1. Franco F, Dubois S, Peshock RM, Shohet RV. Magnetic resonance imaging accurately 

estimates LV mass in a transgenic mouse model of cardiac hypertrophy. Am J Physiol. 

1998;274:H679–H683. 

2. Weiss RG. Imaging the Murine Cardiovascular System With Magnetic Resonance. Circ. 

Res. 2001;88:550 

3. Wiessman F, Ruff J, Englenhardt S, Hein L, Dienesh Ch, Leupold A. Dobutamine-Stress 

Magnetic Resonance Microimaging in Mice. Circ. Res. 2001;88:563-569 

35

SEQUENCE PROGRAMMING ON BRUKER MRI SYSTEMS 

Franciszek Hennel 

Bruker BioSpin MRI, D-76275 Ettlingen, Germany 

Bruker BioSpin MRI is a producer of MRI/MRS systems for clinical and biomedical 

research. The two main products – BioSpec ® and PharmaScan ® – based on the Bruker 

Avance ® spectrometer and ultra-shielded 4.7T, 7T and 9.4T horizontal magnets are controlled 

by the ParaVision ® software package running on a LINUX PC. In addition to the acquisition 

control, image/spectra reconstruction and processing components this software package 

contains an environment for the development of new experimental methods, which will be the 

topic of this presentation. 

The main feature of the ParaVision development environment is the organization of the 

experiment control at two levels. At the base level, the direct control of the pulse sequence is 

taken by a pulse program: a text file written in a very simple and intuitive language. The pulse 

program consists of a sequence of events such as RF pulses, delays, gradient pulses, etc. and 

of flow control commands (loops, conditional statements, etc.). A graphic tool is provided to 

visualize the sequence. Programming at this level is very rapid but requires some NMR skills. 

It is extremely useful for experts in the development phase, but not very practical for routine 

applications. 

The development of routine applications in ParaVision is allowed by the programming 

of "methods". Methods are independent pieces of software containing definitions of high-level 

parameters, which have no direct representation in the pulse program, but allow an intuitive 

description of the experiment. These are, e.g., geometry parameters like field-of-view, or 

contrast parameters like "diffusion b-value". The internal code of the method calculates the 

base level parameters needed by the pulse program from the high level parameters taken from 

the experiment protocol. Methods are programmed in c-language. 

A particularly interesting feature of method programming is the possibility of using 

modules. Modules are elements of pulse program which can be re-used for several 

applications. Each module comes with a group of high-level parameters which can be added to 

the method's protocol and with a group handling mechanism allowing an easy connection with 

the method's code. Elements as complex as the echo-planar acquisition, or multi-directional 

diffusion weighting, defined in ParaVision as modules, can be included in user's projects by a 

couple of lines of code. 

36

THE MOST STABLE POLYMORPHIC FORM OF OLANZAPINE 

AS STUDIED BY 13 C CP/MAS NMR AND X-RAY DIFFRACTION 

Joanna Herold, 1 Łukasz Dobrzycki, 2 Edyta Pindelska, 1 Andrzej Kutner, 3 Krzysztof Woźniak, 2 

Wacław Kołodziejski 1 

1 

Department of Inorganic and Analytical Chemistry, Medical University of Warsaw, 

ul. Banacha 1, 02-097 Warszawa, Poland; 2 Chemistry Department, Warsaw University, 

ul. Pasteura 1, 02-093 Warszawa, Poland; 3 Pharmaceutical Research Institute, 

ul. Rydygiera 8, 01-793 Warszawa, Poland 

7 

8 

6 

5a 

5 

N 

N 

H 

4 

9 9a10 10a 

1 

N 

3a 

S 

1 

2 

3 

2 

3 

4 

N 

CH 3 

CH 3 

Olanzapine, 2-methyl-4-(4-methyl-1-piperazinyl)-10H-thieno[2,3-b] [1,5] benzodiazepine, 

belongs to a new generation of antipsychotic drugs, which modulate dopaminergic 

neurotransmission by their antagonistic action on 5-HT 2A receptors. Olanzapine crystallizes in 

at least five polymorphic forms. The most stable of them, form II, is used to produce a 

pharmaceutical drug „Zyprexa” (Lilly). Various effects occurring during pharmaceutical 

processing can lead to phase transitions, which can produce other polymorhs than that applied 

to form tablets. Exposure to high pressure and temperature during compression, drying, 

milling, wet granulation or presence of additional substances, required for drug formulation, 

can affect polymorphic composition of a drug substunce inside a tablet. We confirmed by 13 C 

CP/MAS NMR that „Zyprexa” tablets contain form II of olanzapine. The assignment of 

solid-state spectra was done by comparison of chemical shifts in solid and liquid phases as 

well as by analysis of CP kinetics and dipolar-dephased spectra. The 13 C CP/MAS NMR 

spectrum of pure olanzapine II is in agreement with its crystal structure determined by 

single-crystal X-ray diffraction. 

37

ESTIMATION OF PARAMAGNETIC IONS CONTENT IN BLOOD 

SERUM BY RELAXATION MEASUREMENTS 

Magdalena Hyjek, Barbara Blicharska, Maria Fornal * 

Institute of Physics, Jagiellonian University, Kraków, Poland; * Collegium Medicum, 

Jagiellonian University, Kraków, Poland 

In certain instances as in Wilson’s disease, hemosyderosis, chronic lymphomic 

leukaemia (CLL) and others, an elevated level of paramagnetic ions (Cu +2 , Fe +3 , Zn +2 ) in 

blood serum has been observed. It is well known, that the presence of these ions shortens 

water protons relaxation times T 1 . The specific chelating agents added to solution containing 

paramagnetics cancel the metal ion effect. 

In this communication we show some examples of such a paramagnetic relaxation times 

enhancement as an alternative method of estimation and monitoring of Cu +2 , Fe +3 and Zn +2 

levels in the blood serum. 

The following model aqueous solutions will be studied: 

1) CuSO 4 and CuCl 2 , 

2) ZnSO 4 

3) FeCl 3 

in water and rabbit blood serum and in the presence of chelating agent (d-penicillamine, 

TETA, desferrioxamine). In the next step we will also examine the human blood serum 

samples from patients suspected of Wilson’s disease, hemosyderosis, leukaemia and from 

healthy volunteers. 

Proton NMR relaxation studies have been performed at 60 MHz Bruker Minispec system 

using Inversion Recovery (IR) sequence for measurements of spin-lattice relaxation times T 1 . 

We have observed a strong influence of iron and copper ions (in concentration 1 - 1×10 -5 

mol/l and 5×10 –5 – 1 mol/l respectively), and much smaller of diamagnetic zinc ions 

(concentration from 10 -5 to 6 mol/l) on relaxation time T 1 in water and serum aqueous 

solutions. An addition of suitable complexing ligand significantly narrows the range of 

changes of T 1 . 

Therefore, the differences in relaxation times in human serum before and after complexation 

can be used as a diagnostic tool in some disease. 

References: 

1.Vinken PJ, Bruyn GW. Handbook of Clinical Neurology. North-Holland PC,1976, vol.27. 

2. Kowalewski J. Paramagnetic relaxation in solution. Encyclopedia NMR 1996, 3456-3462. 

3.Greiling H, Gressner AM. Lehrbuch der Klinischen Chemie und Pathochemie. 2 nd ed. Schattauer Verlag, 

Stuttgart, New York, 1989. 

4.Kupka T, Dziegielewski JO, Pasterna G, Malecki JG. Copper-D-Penicillamine Complex as Potential Contrast 

Agent for MR. Magn. Reson. Imag. 1992,10,855-858. 

5.Bertini I, Luchinat C. Relaxation. In: Bertinti I, Luchinat, Editors. NMR of Paramagnetic Substances. 

Coordination Chemistry Reviews. Vol.150. North York: A. B. P. Lever 1996, p. 77-110. 

6.Maślicki S, Ryżewski J. Patofizjologia. Wyd. 2 Warszawa, Wydawnictwo Lekarskie PZWL,1998. pp. 445- 

458. 

7. Internet: Utility of the copper/zinc ratio in patients with lymphone. www.im.nih.gov. 

38

A DETERMINATION OF ABSOLUTE SHIELDING CONSTANTS 

AND SPIN-SPIN COUPLINGS FOR ISOLATED MOLECULES 

Karol Jackowski 

Laboratory of NMR Spectroscopy, Department of Chemistry, Warsaw University, 

ul. Pasteura 1, 02-093 Warszawa; kjack@chem.uw.edu.pl 

In a gas of low density, the nuclear magnetic shielding (σ) and spin-spin coupling (J) 

can be written as expansions in powers of density (ρ): 

σ(ρ,T) = σ 0 (T) + σ 1 (T) ρ + σ 2 (T) ρ 2 + ... (1) 

J(ρ,T) = J 0 (T) + J 1 (T) ρ + J 2 (T) ρ 2 + ... (2) 

where σ 0 (T), J 0 (T) are the shielding and coupling constants for an isolated molecule and 

σ 1 (T), σ 2 (T), J 1 (T), J 2 (T)... terms are due to intermolecular effects. The higher order terms, 

starting from σ 2 (T) and J 2 (T) are usually negligible for low-density samples. Then the 

dependence on density is linear and the spectral parameters (σ 0 (T), σ 1 (T), J 0 (T) and J 1 (T)) are 

available. According to Eqs. 1 and 2 extrapolation of gas-phase measurements to the zerodensity 

limit gives the σ 0 (T) and J 0 (T) values which are free from intermolecular interactions. 

Such results are especially attractive for ab initio studies since the calculations can actually 

model the shielding and spin-spin coupling tensors with high accuracy only for isolated 

molecules. The σ 1 (T) and J 1 (T) parameters reveal the influence of intermolecular interactions. 

The J 0 (T) values are straightforward ready for the comparison with theoretical data because 

the spin-spin couplings are independent of an external magnetic field. On the other hand the 

σ 0 (T) measurements require the determination of an absolute shielding scale for a given 

nucleus since the applied magnetic field itself cannot be measured with high precision. It can 

be done using the relationship between the paramagnetic part of shielding (σ p ) and the spinrotation 

constant measured by high-resolution microwave spectroscopy. Combined with an 

accurate calculation of the diamagnetic part of shielding (σ d ) in a molecule, the absolute 

shielding of a suitable primary reference molecule can be obtained. For 13 C and 17 O the 

primary reference molecule is CO, for 15 N and 14 N it is NH 3 , for 33 S the molecule of OCS is 

used, etc. Once the absolute shielding is determined for at least one molecule all the other 

measurements of σ 0 for the studied nucleus can be expressed as the absolute shielding 

constants suitable for the verification of ab initio results. An NMR multinuclear spectrometer 

(Varian, 500 MHz) has enabled us to observe extremely weak 17 O and 33 S spectra for a set of 

gaseous molecules: (CH 3 ) 2 CO, (CH 3 ) 2 O, (CD 3 ) 2 O, CO, CO 2 , N 2 O, OCS, SO 2 , SO 3 and SF 6 . 

Similar 1 H, 13 C, 15 N and 19 F NMR experiments were used for the investigation of other 

compounds: CH 3 13 C 15 N, 13 CH 3 13 CN, CH 3 15 NH 2 , H 13 C 13 CH, H 2 13 C 13 CH 2 , CH 3 F, CH 2 DF, 

CHD 2 F, CD 3 F, CH 2 F 2 , CHF 3 and CF 4 . Some of the molecules were exclusively studied in 

gaseous solvents (Xe, CO 2 and SF 6 ). For the first time we could measure the appropriate 

shielding and spin-spin coupling constants as the function of density. Our new results include 

NMR parameters for isolated molecules (σ 0 (T) and J 0 (T)), their isotope effects and the second 

virial coefficients (σ 1 (T) and J 1 (T)). It was shown that at least some spin-spin coupling 

constants were strongly affected by intermolecular interactions. 

39

PROTON NMR STUDIES OF MOLECULAR DYNAMICS 

IN POLYMETHYLPHENYL SILOXANE 

Mariusz Jancelewicz, Marek Kempka, Adam Patkowski, Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, Umultowska 85, 

PL- 61614 Poznań, Poland 

Polymethylphenyl siloxane belongs to the family of silicon elastomers, which have 

been employed for many years in the manufacture of medical devices, medical devices 

components and medical tubing. Introduction of aromatic groups raises thermal stability to 

greater than 300 C. The phenyl groups also introduce rigidity in the silicon chain [1]. 

In this paper we present dispersion of the magnetic relaxation times T 1 (Fig.1.), 

relaxation time T 1 at 9, 16.5, 30,2 and 200 MHz (Fig.2.), and the second moment M 2 of the 

proton relaxation line (Fig.3.) measured for polymethylphenyl siloxane ( PMPS, M w =23360 

D) as a function temperature. The proton dispersion measurements have been performed in 

the range of the Larmor frequencies from 3 kHz to 20 MHz using Fast Field Cycling 

experiment. Results of dispersion measurements indicate the T 1 dependence according to 

Rouse model (T 1 ~υ 0.35 ) [2]. 

POLYMETHYLPHENYLSILOXANE 

POLYMETHYLPHENYLSILOXANE 

[s] 

1 

T 

0,1 

T 1 

[ms] 

10 3 

I 

0,01 

1E-3 

υ~ 0.35 

υ ~ 0.35 

0,01 0,1 1 10 

Larmor frequency [MHz] 

20[°C] 

35[°C] 

55[°C] 

75[°C] 

10 2 

10 1 

III 

9 MHz 

16.5 MHz 

30.2 MHz 

200 MHz 

0 2 4 6 8 10 12 14 

10 3 /T [K -1 ] 

Fig. 1. 1 H T 1 relaxation times vs. Larmor frequency Fig. 2. Temperature dependence of the T 1 

for PMPS at different temperatures 

relaxation times for PMPS 

10 

9 

M 2 

[Gs 2 ] 

8 

7 

6 

5 

4 

3 

2 

1 

I 

II 

rotation of rotation of 

methyl groups methyl groups 

and flip-flop 

of C 6 

H 5 

groups 

2α = 46° 

III 

∆H=1Gs 2 

glass transition 

0 

12.5 

10.0 

8.0 

6.6 

5.7 

50 75 100 125 150 175 200 225 250 275 300 

T[K] 

Fig. 3. Second moment M 2 versus temperature for PMPS 

[1] Cai WZ, Schmidtrohr K, Egger N, Gerharz B, Spiess HW, A solid-state NMR study of microphase structure 

and segmental dynamic of poly (styrene-B-methylphenylsiloxane) diblock copolymers, Polymer 34 (2) 1993 

[2] N. Fatkullin, R. Kimmich, Nuclear spin-lattice relaxation dispersion and segment diffusion in entangled 

polymers. Renormalized Rouse formalism, J. Chem. Phys. 101 (1), 1 July 1994. 

5.0 

4.4 

4.0 

40

DIAGNOTIC VALUE OF MRI IN CONVERSION PROCESS 

OF HUMAN BONE MORROW 

Kluczewska Aneta 1 , Kluczewska Ewa 2 , Drzazga Zofia 1 

1 Institute of Physic, Department of Medical Physics, Silesian University, 

40-007 Katowice, Uniwersytecka 4, Poland; 2 Silesian Medical Academy, Department 

of Radiology, 40-000 Katowice, Poniatowskiego 15, Poland 

Bone morrow plays important physiologic roles in the both health and disease. In 

healthy individuals its function is to provide a continual supply of red cells, platelets and 

white cells to meet the body’s demands for oxygenation, coagulation and immunity. 

The diagnostic value of various sequences in MR imaging of the healthy and pathological 

lumbar spine was studied. In those structures conversion processes and age-related changes 

were observed. The natural conversion is a changes process of red to yellow bone morrow 

fraction. The conversion’s patterns of bone morrow were derivated. 

Larger fraction of cellular morrow is present throughout the vertebral body resulting in an 

overall lowering of signal intensity on T1-weight images. Conversion from red to yellow 

morrow is observed around the central venous plexus. This pattern is seen most commonly in 

younger patients, especially at children of above seventh year of life. The second pattern 

reflects the effects of mechanical stress on vertebral morrow subjacent to end plates where 

conversion of cellular to fatty morrow was observed (at adults above fortieth years of life with 

intensification above sixties). The third pattern is diffusely distributed throughout the 

vertebral body. These foci range from little to larger area in spine based. 

Moreover ascertained, that all illness changes vertebras of spine inseparably join with changes 

in bone morrow. 

The results were elaborated in nonparametric Kruskall-Wallis’s, ANOVA Friedman’s, 

Wilcoxon’s and tau Kendall’s tests. 

The statistical analysis showed, that the largest differences in intensity signal between red and 

yellow were observed in SE/T1 and SE/T2 sequences for the all patterns of conversion bone 

morrow. The most useful diagnostic sequence seems to be the SE/T1 one. In this sequence all 

illness – changes and normal structures in bone morrow of lumbar spine are the best visible. 

With progressive T2-weighting, the signal intensity of red morrow slowly increase while that 

of yellow morrow slowly declines making it more difficult to discriminate between two. 

Differences between SE/T1 and SE/T1iv were not detected statistical essential. 

41

HIGH-RESOLUTION SOLID-STATE NMR STUDIES OF HARD 

DENTAL TISSUES AND RENAL STONES 

Joanna Kolmas, 1 Monika Uniczko, 2 Emil Kalinowski, 2 Andrzej Wojtowicz, 2 Zygmunt 

Trzaska Durski, 3 Wacław Kołodziejski 1 

1 

Department of Inorganic and Analytical Chemistry, Medical University of Warsaw, 

ul. Banacha 1, 02-097 Warszawa, Poland; 2 Department of Dental Surgery, Medical 

University of Warsaw, ul. Nowogrodzka 59, 02-006 Warszawa, Poland; 3 Department 

of Inorganic Chemistry, Technical University of Warsaw, ul. Noakowskiego 3, 00-664 

Warszawa, Poland 

High-resolution 1 H, 31 P and 13 C solid-state NMR spectra of enamel, dentin, cement 

and renal stones containing apatite mineral were assigned and compared. Structure and 

composition of the materials were discussed. 

42

NMR AND FTIR STUDY OF MOLECULAR DYNAMICS 

IN L-ALANINE / POLYETHYLENE GLYCOL COMPLEX 

Justyna Krzaczkowska, Zbigniew Fojud, Stefan Jurga 

Department of Macromolecular Physics, Adam Mickiewicz University, Poznań, Poland 

and Markus Antonietti Max-Planck Institute of Colloids and Interfaces, Research Campus 

Golm-Potsdam, Germany 

Study of conjugation process of complexes proteins with biocompatible polymers is 

very important with regard on pharmaceutical and biomedical application especially for drugs 

distribution. Polymer properly linked to amino acid modifies some of protein’s properties like 

molecular size, solubility but also protect them from enzymatic degradation [1]. 

Determination of the molecular dynamic of polymer chain and amino acid can yield 

information about site and way of binding polymer. Polyethylene Glycol (PEG) is widely 

used polymer in these field because of its outstanding physico-chemical properties: 

hydrophilicity, solubility in water and in organic solvents, non-toxicity, non-immunogenicity. 

In this paper we report proton NMR T 1 spin-lattice relaxation for L-Alanine / 

Polyethylene Glycol complex at 200 MHz using Bruker CXP 200 NMR spectrometer. The 

measurements performed in the temperature range from 100K to 285K allowed to determine 

an activation energy of the NH 3 group reorientation, E a = 5.16 kcal/mol (Fig.1). This value is 

lower then activation energy for pure L-Alanine, E a ≈ 8 kcal/mol [2]. Observed difference 

suggested that PEG are conjugated into L-Alanine structure probably by the amine group. 

100000 

10000 

E a =5.16 kcal/mol 

T 1 

[ms] 

1000 

100 

2 4 6 8 10 12 

1000/T [K] 

001) 1907-1912 

Fig.1. Temperature dependence of T 1 spin-lattice 

relaxation times for L-Alanine / Polyethylene Glycol 

complex 

43

DSC measurements confirm existing of L-alanine / Polyethylene Glycol complex. 

Melting temperature for the complex (578K) is lower then that for pure L-Alanine (588K), 

and in the DSC diagram, due to low concentration, is not observed a melting peak for the pure 

Polyethylene Glycol. 

The infrared spectra for L-Alanine / Polyethylene Glycol in KBr matrix were recorded 

on BRUKER IFS 66/s FTIR Spectrometer in the temperature range from 143K to 547K. 

Characteristic Polyethylene Glycol absorption band is observed at ~1115 cm -1 – C-O-C 

symmetric stretching vibration (Fig.2) [3]. 

0,8 

Mobility of this molecular group increases 

0,7 

with increasing temperature. 

Bands at ~1650 and ~1550 cm -1 are due to 

0,6 

symmetric stretching C=O (Fig.3) and 

0,5 

143K 

stretching CO-NH (Fig.4) vibrations, 

163K 

0,4 

183K 

ν 

203K 

s 

(C-O-C) 

respectively. It corresponds to formation 

0,3 

223K 

253K 

273K 

of L-Alanine / Polyethylene Glycol 

0,2 

293K 

313K 

complex [3]. Mobility of the C=O group 

333K 

0,1 

353K 

373K 

increases with increasing temperature, 

0,0 

whereas CO-NH bond, which links 

1130 1120 1110 1100 

Wavenumber [cm 

Polyethylene Glycol part with L-Alanine 

-1 ] 

part of complex, is very stiff. Shifting of Fig.2. Polyethylene Glycol absorption 

the absorption maximum as a function 

band of νs(C-O-C) vibration 

temperature is not observed. 

Transmittance [a.u.] 


0,2 

0,1 

ν s 

(C=O) 

0,0 

1670 1660 1650 1640 1630 

Wavenumber [cm -1 ] 

143K 

163K 

183K 

203K 

223K 

253K 

273K 

293K 

313K 

333K 

353K 

373K 

Fig.3. L-Alanine/Polyethylene Glycol 

absorption band of νs(C=O) vibration 


0,4 

0,3 

0,2 

ν(CO-NH) 

143K 

163K 

183K 

203K 

223K 

253K 

273K 

293K 

313K 

333K 

353K 

373K 

0,1 

1560 1550 1540 1530 

Wavenumber [cm -1 ] 

Fig.4. L-Alanine/Polyethylene Glycol 

absorption band of ν(CO-NH) vibration 

References: 

[1] Guiotto A., Pozzobon M., Sanavio C., Schiavon O., Orsolini P.; Veronese F.M., Bioorganic 

&Medicinal Chemistry Letters 12 (2002) 177-180 

[2] Andrew E.R., Hinshaw W.S., Hutchins M.G., Sjoblom R.O.I., Canepa P.C., Molecular Physics 32 

(1975) 795 

[3] Yuan M., Deng X.; European Polymer Journal 37 (2001) 1907-1912 

44

EFFECTS OF INTERMOLECULAR INTERACTIONS 

ON THE SPIN-SPIN COUPLING CONSTANTS AND NMR CHEMICAL 

SHIFTS OF FLUOROMETHANES IN THE GAS PHASE 

Marek Kubiszewski 


ul. Pasteura 1, 02-093 Warsaw, Poland; kubisz@chem.uw.edu.pl 

Fluoromethanes (CH 4-n Fn, where n = 1, 2, 3 and 4) have been studied using 

multinuclear advanced NMR spectra in the gas phase [1,2]. All the 19 F, 13 C and 1 H shielding 

constants of the studied compounds have been determined and analyzed with high accuracy. 

After extrapolation of the experimental results to the zero-density limit it was possible to 

determine the shielding constants of isolated molecules. Similar procedure has successfully 

been applied for the investigations of spin-spin coupling constants. The spin-spin coupling 

constants are generally less dependent on intermolecular interactions than shielding constants 

for the same nuclei. This problem has recently been reviewed [3] and many new examples of 

density-dependent spin-spin coupling constants have been reported. It seems that there is only 

a problem of precision during NMR measurements because every coupling constant is more 

or less dependent on intermolecular interactions. The molecules of fluoromethanes have 

delivered many new excellent examples showing the strong density-dependence on density 

for many one-bond coupling constants. Deuterium isotopomers of fluoromethanes (CD 3 F, 

CD 2 HF, CDH 2 F, CHDF 2 and CDF 3 ) were also included in our investigations. For the first 

time the 13 C and 19 F magnetic shielding and spin-spin coupling of the isotopomers were 

measured as functions of density. All the new experimental data were analyzed as a function 

of the structural changes in studied molecules after fluorine substitution. It was shown that all 

the new NMR parameters are suitable for comparison with the results of recent ab initio 

calculations. 

References: 

[1] K. Jackowski, M. Kubiszewski, W. Makulski, J. Mol. Struct., 358 (2002) 267. 

[2] M. Kubiszewski, W. Makulski, K. Jackowski, J. Mol. Struct., to be published. 

[3] K. Jackowski, Int. J. Mol. Sci., 4 (2003) 135. 

45

NMR STUDIES OF THE POLYETHYLENE COMPOSITES 

WITH ORGANIC FILLERS 

Sławomir Kuśmia, Eugeniusz Szcześniak, Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, 

Umultowska 85, PL - 61614 Poznań, Poland 

During recent years a great deal of effort has been made in solving of polymer waste 

problem. One of the ways used to tackle the issue consists in introducing organic fillers into 

polymer matrix. The presence of fillers should promote the biodegradation process, but do not 

affect significantly mechanical properties of polymer composites [1]. The fillers make the 

water penetration into polymer matrix possible, which results in weakening of the material 

structure and leads to its degradation [2,3]. 

The object of the present study is LDPE filled with 20 wt. % of calcium lactate and 

LDPE filled with 30 wt. % of starch. We investigated the proton NMR spectra and the spinlattice 

relaxation times vs. temperature of the “virgin” samples before subjecting them to 

water penetration. 

We found that the water uptake process features an exponential time dependence and reaches 

the saturation level characterized by a time constant of about 2 days for LDPE-20 wt. % of 

calcium lactate and of about 13 days for LDPE-30 wt. % of starch. 

We also studied the composites undergoing degradation in environmental-like circumstances 

and noticed the loss in weight of LDPE-20 wt. % calcium lactate amounting to about 7% 

after twelve months of treatment. 

Some selected results of our studies are shown in Figs 1 and 2. The data are compared with 

our previous results obtained by NMR microimaging techniques [4]. 

1,4 

Relaxation times T 1 

[ s ] 

1,3 

1,2 

1,1 

1,0 

0,9 

0,8 

LDPE 

LDPE-20 wt. % of calcium lactate 

LDPE-30 wt. % of starch 

0,7 

0,6 

2,6 2,8 3,0 3,2 3,4 3,6 3,8 4,0 

1000/T [ 1/K ] 

Fig.1. 

Spin-lattice relaxation times T 1 of the “virgin” samples: LDPE, LDPE-20 wt. % of calcium 

lactate and LDPE-30 wt. % of starch vs. temperature. 

46

600000 

Integral of 1D MRI profils [ a.u.] 

500000 

400000 

300000 

200000 

100000 

LDPE-20 wt. % of calcium lactate 

LDPE-30 wt. % of starch 

0 

0 2 4 6 8 10 12 14 16 18 20 22 24 

Time of soaking [ days ] 

Fig.2. 

Integral of 1D profiles obtained by magnetic resonance imaging spin echo technique vs. time 

of soaking of the samples. 

References: 

1. Katz H.S. and Milewski J.V., Handbook of fillers for plastics, Van Nostrand Reinhold, 

New York, (1987) 

2. “Biodegradable Polymers and Plastics” The Proceeding of the Seceond International 

Scientific Workshop on Biodegradable Polymers and Plastics, Montpellier, France, 25- 

27.11.1991 

3. D. Bikiaris, E. Pavlidou, J. Prinos, J. Aburto, I. Alric, E. Borredon, C. Panayioton, Polym. 

Degrad. Stabil., 60, 437-447, 1998 

4. S. Kuśmia, E. Szcześniak and S. Jurga, Solid State NMR, 25, iss. 1-3, 2004 (in press). 

47

LOW TEMPERATURES DYNAMICS IN SYSTEMS CONSISTING 

OF HYDROGEN BOND AND METHYL GROUPS 

L. Latanowicz, W. Medycki*, J. Boguszyńska*, E. C. Reynhardt** 

Department of Biophysics, Institute of Biotechnology and Environmental Sciences, Zielona Góra University, 

Monte Cassino 21 B, 65-561 Zielona Gora, Poland; *Institute of Molecular Physics, Polish Academy of 

Sciences, Smoluchowskiego 17, 60-179 Poznań, Poland; **Department of Physics, University of South Africa, 

P O Box 392, Pretoria, 0003, SA 

The paper deals with the two different approaches to the spectral densities functions of 

proton transfer and methyl group rotation. 

The transfer of a hydrogen atom in a hydrogen bond is due to classical jumps over the 

potential barrier and incoherent tunnelling. The concerted jumps of two hydrogen bonded 

protons (or deuterons) along a hydrogen bond of benzoic acid can be visualised as an 

exchange motion between potential energy minima associated with tautomers A and B with 

different sets of rate constants, the first set obeying Arrhenius' law (rate constants of the 

jumps over the barrier) and the second set given by Skinner and Trommsdorff [1] or Nagaoka 

et al [2] (rate constants of the incoherent tunnelling). The preexponential factor of the rate of 

tunneling jumps (k tu 0 ) is usually in range 10 8 Hz for hydrogen (10 6 Hz for deuterium) while 

this of the rate of jumps over the barrier (k ov 0 ) is in range 10 12 Hz (10 10 Hz). If the interaction 

Hamiltonian is modulated by a series of independent stochastic processes, the total correlation 

function of such a complex motion should be calculated [3]. The equations for spectral 

densities functions of complex motion, which consists of jumps over the barrier and 

incoherent tunnelling were derived by Reynhardt and Latanowicz [4]. That the spectral 

density of incoherent tunnelling is eliminated above a certain temperature, leaving only the 

spectral density of the classical jump motion contributing to spin-lattice relaxation at higher 

temperatures has been revealed in the paper [5]. A comparison (Fig. 1) of measured (open 

circles [2]) and calculated T 1 (theory [4] - #1, jumps over the barrier - #2) for benzoic acid 

confirms this discovery. We have found that this event has justification in the quantum 

mechanics. Quantum mechanics involves probability of transfer of the particle through the 

barrier, which is serious different then probability of jumps over the barrier. This probability 

can be defined as D = I / I 0 , where I is intensity of de Broglie's wave (which describe the 

particle) outside of the potential wall and I 0 is this intensity inside the potential wall. The 

formula, which describes a coefficient D depends on the shape of the potential barrier. For the 

2L 

rectangular barrier D = D exp[ − 2m( E E ) ] , where E AB and L are height and width 

0 AB 

− 

 

of the barrier, E and m are energy and mass of the particle. The value (E AB - E) under square 

root is negative for E > E AB and the probability D is lost. The thermal energy of the Avogadro 

number of particles equals E = C p T [kJ/mol] where C p is molar heat capacity and T is 

temperature in the Kelvin scale. When C p T = E AB this should be the last value of coefficient D 

in the temperature dependence. 

In opposition to presented equations, the expression for spectral density functions of single 

motion with total rate constant, approximated by two exponents k AB = k ov tu 

0 exp(-H/RT) + k 0 

exp(-∆/RT) (H and ∆ are the high and low temperature slopes of T 1 ) has been used in number 

of papers. This last one theoretical approach assumes the smooth transition between the over 

the barrier rate constant and incoherent tunneling rate constant. Here the question appears 

how this is possible that the Arrhenius rate constant k ov = k 0 exp(-H/RT), goes to zero value 

above temperature zero Kelvin and classical motion ceases? Moreover, when "single motion 

approach" to the total spectral density functions is applied then T 1 looses the frequency 

dependence at minimum value for low resonance frequencies of spectrometer. The 

48

simultaneous analyse of the temperature dependences of the spin-lattice relaxation times in 

rotating frame (T 1ρ ) and in laboratory frame (T 1 ) is impossible. The theoretical temperature 

dependences of T 1 (15 MHz) and T 1ρ (B 1 - different values ) are not distinguished. 

Haupt proposed the spin–lattice relaxation theory of methyl group [6]. In this theory, the 

stochastic motion related to coherent tunneling is assumed as a modulation of the hindering 

potential (torsional coordinate) ћω mm' about its average value ћ

VIRTUAL LABORATORY OF NMR SPECTROSCOPY 

Marcin Lawenda 1 , Łukasz Popenda 2 , Norbert Meyer 1 , Maciej Stroinski 1 , Zofia Gdaniec 2 , 

Ryszard W. Adamiak 2 

1 Poznań Supercomputing and Networking Center (PSNC), Z. Noskowskiego 10, 

61-704 Poznań, Poland; 2 Institute of Bioorganic Chemistry, Polish Academy of Sciences, 

Z. Noskowskiego 12/14, 61 704 Poznań, Poland 

Virtual laboratories are now among the front activities of academic research groups 

and companies, which are working on new solutions for remote access to very expensive 

laboratory devices. The Virtual Laboratory (VLab) project is being developed by the Poznań 

Supercomputing and Networking Center in collaboration with the Institute of Bioorganic 

Chemistry PAS [1,2]. The primary goal of the VLab was to create within grid architecture the 

VLab of NMR spectroscopy based on access to Bruker Avance 600 MHz and Varian Unity+ 

300 MHz spectrometers. This is not only to make remote access to this facilities but, through 

the VLab broker, to assist researcher in finding necessary basic information for educational 

purposes (e-learning, digital library, communication), to show details how to run an 

experiments and how to do experiment using concept of dynamic scenarios. The latter 

include: pre-processing, executing the experiment, and the post-processing. VLab is giving an 

unique opportunity to complex visualization tasks. Users would be also allowed to add their 

own module as a part of the dynamic scenario. Actual stage of our work on the VLab project 

concerning NMR spectrocopy will presented. All interested are invited to visit an active VLab 

domain (http://vlab.psnc.pl). Currently works are advanced on the VLab project concerning 

applications of radiotelescope (with A. Kus, Centre for Astronomy, Nicolas Copernicus 

University, Toruń) and supercomputing (with K. Kulinska, Institute of Bioorganic Chemistry 

PAS, Poznań). 

[1] KBN project no. 6 T11 0052 2002 C/05836, part of the project co-funded by KBN and 

SGI: "High Performance Computations and Visualisation for Virtual Laboratory Purposes 

with the Usage of SGI Cluster" (based on decision number 03282/C.T11-6/2002 of 

December 9th 2002), WP 3.1 task: Virtual Laboratory and Teleimersion 

[2] KBN project no. 4 T11 F 010 24: “Building of Universal Architecture for Virtual 

Laboratory” 

50

1 H NMR STUDIES OF PLATINUM(II) CHLORIDE COMPLEXES 

REACTION WITH GUANOSINE-5’-MONOPHOSPHATE 

Iwona Łakomska 1 , Edward Szłyk 1 , Leszek Pazderski, 1 Jan Reedijk 2 

1 Faculty of Chemisty, Nicolas Copernicus University, 87-100 Toruń, Poland, email: 

dziubek@umk.pl; 2 Gorlaeus Laboratories, Leiden University of Chemistry, P.O. Box 9502, 

2300 RA Leiden, The Netherlands 

Studies on the binding of cis-[PtCl 2 (dmtp)(NH) 3 ] and cis-[PtCl 2 (tmtp)(NH) 3 ] to model 

nucleotide guanosine- 5’-monophosphate (5’-GMP) are important for the explanation of the 

molecular interaction between antitumor platinum complex and DNA. The Pt binding 

to 5’-GMP has been studied by 1 H NMR, using a fourfold excess of guanosino-5’- 

monophoshate. The Pt-GMP interaction can be followed, by observing the formation and 

disappearance of several platinum-GMP species. The chemical shift of the H(8) proton of 

GMP is very sensitive to the geometry and the composition of the complex. 

The reactions of cis-[PtCl 2 (dmtp)(NH) 3 ], cis-[PtCl 2 (tmtp)(NH) 3 ] were very slow for 

NMR time scale, and therefore we decided to study the reaction between monoaquaspieces: 

[PtCl(D 2 O)(dmtp)(NH 3 )] + , [PtCl(D 2 O)(tmtp)(NH 3 )] + . In all cases, the typical downfield shift 

of H8 of 5’-GMP (8.19 ppm for H(8) of free 5’-GMP; 8.5 ppm for H(8) of bis-bound and 8.8- 

8.7 ppm for H(8) of mono-bound 5’-GMP) was observed, indicating that the platination site 

of in N(7) position 5’-GMP for all complexes. For the 1:1 adduct of platinum(II) complexes 

two H(8) resonance peaks would be expected in 1 H NMR spectra, as the 5’-GMP in each 

intermediate has a slightly different chemical magnetic environment. 

Acknowledgements 

Financial support from Polish Committee for Scientific Research (KBN) the grant No: 

4 T09A 11623 is gratefully acknowledgment. 

51

STRUCTURE OF SOME ARYLAZO-2-NAPHTHYLAMINES 

AND THEIR N-ACETAMIDES 

Dorota Maciejewska 1 , Violetta Kowalska 2 

1 Department of Organic Chemistry, 2 Department of Drug Technology, Faculty of Pharmacy, 

Medical University of Warsaw, 1 Banacha St., 02-097 Warsaw, Poland 

The aminoazodyes exist almost completely in appropriate azo forms, in contrary to azo 

dyes with ortho and para hydroxy substituents to azo linker, which revealed azo-hydrazone 

tautomerism. In spite of this, we have observed a complicated pattern of signals in the 

13 CP/MAS NMR spectra of the polycrystalline powdered sample of the N-acetyl 

aminoazonapthalene 2. Some peaks are double in the spectrum of compound 2, but not in the 

spectra of remained three title aminoazodyes 1, 3, 4 (Fig.1). In the papers [1,2] authors have 

concluded on the basis of the detailed studies of the 15 N NMR and X-ray diffraction 

measurements data of azobenzenes that the azo group N=N is seen to be disordered between 

the two trans conformations. It is, therefore, expected that similar process would also occur in 

solid azoaminonaphthalenes. Considering that we have decided to analyze the structures of 

the arylazo-2-naphthylamine and its N-acetamides 1-4 using solid-state 13 C CP/MAS NMR, 

1D and 2D solution-state 1 H and 13 C NMR, X-ray diffraction and theoretical DFT calculations 

in an attempt to understand their conformational interconversion. 

4 

10 

5 

3 

R 2' 3' 

1 2 1' R R 1 

= o-NH 2 

, R 2 

= m-CH 2 

3 (1) 

1 

N N 4' R 1 

= o-NHCOCH 3 

, R 2 

= m-CH 3 (2) 

R 1 

= o-NHCOCH 3 

, R 2 

= p-NO 

9 6' 

2 (3) 

5' 

R 1 

= o-NHCOCH 3 

, R 2 

= p-COCH 

8 

3 (4) 

6 7 

Figure 1. Studied arylazo-2-naphthylamine derivatives with atoms numbering. 

[1] 

[2] 

G. McGeorge, R.K. Harris, A.M. Chippendale, J.F. Bullock, J. Chem. Soc. Perkin Trans 

2, (1996) 1773. 

G. McGeorge, R.K. Harris, A.S. Batsanov, A.V. Churakov, J. Phys. Chem. A 102 (1998) 

3505. 

52

35 Cl-NQR STUDY OF ELECTRONIC STRUCTURE AND BIOLOGICAL 

ACTIVITY OF SELECTED DDT-TYPE INSECTICIDES 

K. Makiej, B. Nogaj 

Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, 

Poland 

INTRODUCTION 

Insecticides belong to pesticides being a large group of compounds toxic to pests. 

They are synthetic compounds and do not occur in the natural environment. An important 

criterion of classification of pesticides is the acute toxicity defined as the lethal dose LD 50 per 

os, so the dose causing death of a half of the number of target animals, expressed in mg/kg of 

body weight [1]. Insecticides are characterised by low molecular mass and high biological 

activity in insects. One of the best known insecticide is DDT – 1,1,1-trichloro-2,2-bis-(pchlorophenyl)ethane 

[2,3]. It was commonly used in agriculture in the 40s through to the 60s 

of the last century because of its high and selective toxicity. Its use was eventually abandoned 

because of its exceptionally high stability in the environment and in living organisms, 

following from its resistance to the effect of enzymes. 

In this study an attempt was made to find a correlation between the chemical structure 

and biological activity of selected DDT-type insecticides. 

EXPERIMENTAL 

The NQR spectra provide the information on NQR line frequency, quadrupole 

coupling constant and asymmetry of the tensor of electric field gradient and on the basis of 

them on the electron density in the vicinity of a given nucleus. 

The electronic structure of the following DDT type insecticides has been studied by 

35 Cl-NQR: DDT, DDD, DDE, DDA. The molecules of these compounds have the shape of a 

wedge with the base of phenyl rings with Cl atoms at para positions (Fig.1). 

Cl 

R 

Cl 

Fig.1. The structural formula of DDT-type insecticides 

RESULTS AND DISCUSSION 

Table 1 presents the structural formula, 35 Cl-NQR frequencies and biological activity of the 

insecticides studied (LD 50 for rats [4]). The two phenyl rings are constant elements of the 

compounds differing only in the substituent R joining the rings. The mean 35 Cl-NQR ( ν 1, 2 ) 

frequency characterising the two Cl atoms at the para positions of the phenyl rings was 

calculated for particular insecticides. This value was correlated with the parameter LD 50 

obtaining a linear relation. The LD 50 parameter decreases with increasing mean frequency 

ν 1,2 (Fig.2), which means that the biological activity of the insecticides increases with 

increasing 35 Cl-NQR frequency on chlorine atoms at the phenyl rings. 

53

Table 1. The structural formulae, 35 Cl-NQR frequencies at 77K, mean frequencies ν 1, 2 and LD 50 values for 

rats, characterising particular insecticides. 

COMPOUND R STRUCTURAL FORMULA ν Q [MHz] 

ν 1,2 

[MHz] 

LD 50 (mg/ 

kg) [4] 

p,p’-DDE CCCl 2 

(ν 1 )Cl C Cl(ν 2 ) 

34.6220 a) 

34.6580 

34.66 

880 

CCl 2 

35.1312 

34.620 

p,p’-DDA HCCO(OH) H 

(ν 1 )Cl C Cl(ν 2 ) 

34.656 b) 

34.923 

34.79 

590 

CO(OH) 

p,p’-DDT HCCCl 3 H 

34.8670 a) 

34.9732 

(ν 1 )Cl C Cl(ν 2 ) 

38.4845 

CCl 3 

38.8115 

39.0362 

34.92 

250 

p,p’-DDD HCCHCl 2 H 

( ν 1 )Cl C Cl(ν 2 ) 

CHCl 2 

a) Ref. [5] b) Ref. [6] 

34.9363 a) 

34.9805 

35.9743 

37.1310 

34.96 

113 

Higher 35 Cl-NQR frequencies imply lower electron density on a given nucleus, so in order to 

design a new more active insecticide the two phenyl rings should be joined through a group R causing 

a decrease in the electron density on the chlorine atoms at the phenyl rings. 

LD 50 

[mg/kg] 

900 

800 

700 

600 

500 

400 

300 

200 

100 

p,p'-DDE 

p,p'-DDA 

p,p'-DDT 

p,p'-DDD 

34.6 34.7 34.8 34.9 35.0 35.1 

ν 1,2 

[MHz] 

Fig. 2. The value of LD 50 versus the 35 Cl-NQR frequency for selected DDT-type insecticides. 

REFERENCES: 

1. L.Różański, Przemiany pestycydów w organizmach żywych i środowisku, Państwowe Wydawnictwo 

Rolnicze i Leśne, Warszawa (1992). 

2. B.Nogaj, J. Phys. Chem., 91, 1241 (1987). 

3. B.Nogaj, J. Phys. Chem., 91, 1236 (1987). 

4. Analytical reference standards and supplemental data: The pesticidies and industral chemicals repository, 

U.S. Environmental Protection Agency, Las Vegas (1984). 

5. J.Komasa, J.Rychlewski, B.Nogaj, J. Chem. Soc., Faraday Trans. 2, 84(8), 1197 (1988). 

R.Rzepka, Badanie struktury elektronowej i dynamiki molekularnej wybranych insektycydów typu DD 

54

35 Cl- NQR AND 1 H-NMR STUDY OF MOLECULAR DYNAMICS OF 

p,p′-DDA INSECTICIDE 

K. Makiej, A. Nowacka, J. Kasprzak, R. Utrecht, J. Wąsick, B. Nogaj 

Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, 

Poland 

INTRODUCTION 

The method of Nuclear Quadrupole Resonance (NQR) brings information not only on the 

electronic structure of molecules, but also on the motions of the molecules or certain atomic groups. 

This method along with the 1 H-NMR have been applied to study molecular dynamics of the insecticide 

p,p`-DDA ( 1,1-bis(p-chlorophenyl) acetic acid) [1], belonging to DDT type compounds [2]. The 

molecule of this compound takes the shape of a wedge with the base of phenyl rings with chlorine 

atoms at the para positions and the COOH group at the top. 

EXPERIMENTAL 

The compound studied p,p`-DDA was purchased at Polish Chemical Reagents – Gliwice. 

35 Cl-NQR measurements were performed on a lab-made pulse Fourier transform NQR spectrometer 

operating in the frequency range 20-40 MHz. The 35 Cl-NQR frequencies (ν Q ) and nuclear quadrupole 

spin-lattice relaxation times (T 1Q ) were determined in the temperature range 77K- 350.5K. 

Measurements of 1 H-NMR spin-lattice relaxation times (T 1 ) were made in the range 100K - 299K on a 

laboratory-made pulse spectrometer operating at 60 MHz. 

RESULTS AND DISCUSSION 

The NQR spectrum of p,p`-DDA shows two 35 Cl-NQR lines assigned to the two chlorine 

atoms in the molecule. The frequencies of these lines decrease with increasing temperature, Fig.1. 

35.0 

34.8 

ν Q 

[MHz] 

34.6 

34.4 

34.2 

34.0 

50 100 150 200 250 300 350 400 

T [K] 

Fig.1. Temperature dependence of 35 Cl-NQR frequency in p,p’-DDA. 

The difference in the slope of the ν Q (T) dependencies obtained for the two lines suggests a 

dynamical inequivalence of the two phenyl rings in the p,p′-DDA molecule. The values of the nuclear 

quadrupole spin-lattice relaxation times (T 1Q ) increase with increasing temperature (Fig.2). From the 

slopes of the T 1Q (T) dependencies the activation energies have been found as 3.5kJmol -1 and 

3.9kJmol -1 . A similar dependence has been obtained for the nuclear magnetic spin-lattice relaxation 

times (T 1 ). It should be noticed, that these values are very high and reach 214 s at room temperature 

(Fig. 3). From the slope of the T 1 (T) the activation energy has been calculated as 4 kJmol -1 . 

55

ln T 1Q 

3 

2 

1 

0 

100 200 300 400 

7 

3 

1 

T 1 

[ms] 

-1 

ν Q2 

ν Q1 

-2 

12 10 8 6 4 2 

10 3 /T [K -1 ] 

Fig.2. Temperature dependence of 35 Cl-NQR spin-lattice relaxation time in p,p′-DDA. 

ln T 1 

6 

5 

4 

3 

T [K] 

100 200 300 400 

200 

150 

100 

50 

T 1 

[s] 

2 

12 10 8 6 4 2 

10 3 /T [K -1 ] 

Fig.3. Temperature dependence of 1 H-NMR spin-lattice relaxation time in p,p′-DDA. 

At the present stage of the study it is difficult to unambiguously conclude about the dominant 

relaxation mechanism and the dominant molecular motion in p,p`-DDA. It is expected that the 

problem will be solved in further study. Perhaps, as it has been established by Pajzderska et al., [3] for 

tetraphenyltin [Sn(C 6 H 5 ) 4 ], also in p,p′-DDA the motions are small amplitude 

reorientations/oscillations of phenyl rings. 

REFERENCES: 

1. A.Nowacka, Badanie struktury elektronowej i dynamiki molekularnej insektycydu p,p`-DDA metodą 

spektroskopii jądrowego rezonansu kwadrupolowego, praca magisterska, UAM (2001). 

2. L.Różański, Przemiany pestycydów w organizmach żywych i środowisku, Państwowe Wydawnictwo 

Rolnicze i Leśne, Warszawa (1992). 

3. A.Pajzderska, J.Wąsicki, S.Lewicki, Z.Naturforsch. 54a, 488-494 (1999). 

0 

56

THE SYNTHESIS AND NMR ANALYSIS OF THE AMIDE 

DERIVATIVES OF 2,3-DIHYDRO-1,4-DITHIINO[5,6-c]QUINOLINE 

Ewa Michalik, Andrzej Maślankiewicz 

Department of Organic Chemistry, The Medical University of Silesian, 

ul. Jagiellońska 4, 41-100 Sosnowiec, Poland; Email: emichalik@slam.katowice.pl 

Interesting spectral properties of the amide derivatives of 3,4-quinolinediyl bissulfides 

A, B [1-3] prompted us to study the reaction of 2,3-dihydro-1,4-dithiino[5,6- 

c]quinoline 1, as partially alicyclic analog of A and B, with DMF / hydroxylamine-Osulfonic 

acid / Fe++ ion system, i.e. under the condition of Minisci reaction [4]. The 

reaction gave 2-(N,N-dimethylcarbamoyl)-2,3-dihydro-1,4-dithiino[5,6-c]quinoline 2 

(30.5%), 2-(N-methyl-N-formylaminomethyl)-2,3-dihydro-1,4-dithiino[5,6-c]quinoline 3 

(12.2%) and 2,3-dihydro-1,4-dithiino[5,6-c]quinoline-4-oxide (12.2%) calculated to the 

55% converted substrate 1. 

Scheme 

S 

S 

S 

S 

A, 

= 

2 

R 

N 

3 4 

R 1 =CON(CH 3 ) 2 , R 2 =H 

N 

N 

A, B 

R 

1 

B, 

= 

4 3 

N 

R 2 

R 1 =CH 2 N(CH 3 )CHO, R 2 =H 

R 1 =R 2 =CON(CH 3 ) 2 

10 

1 

S 

N 

S 

DMF-H 2 O 

HSA - FeSO 4 

S 

N 

S 

R 

3. R=CON(CH 3 ) 2 

4. R= CH 2 N(CH 3 )CHO 

The structure of the compounds 2 and 3 has been completely assigned by means of 

1D and 2D 1 H and 13 C nmr spectra. The key-part in this methodology were long-range proton 

carbon correlation. The 1 H and 13 C spectra of compound 2 show the lines of the same 

functional groups of two species with the similar intensities and two ABMX systems. This 

observation was interpreted in terms of restricted rotation about the C(O)-N bond in 

unsymmetrical which can give rise to cis- and trans- rotational isomers 3a and 3b. 

The transmission of the steric effect induced by N-methyl-N-formylaminomethyl substituent 

in compound 3 is comparable with those observed for unsymmetrical amide of A and B 

types. It affects quinoline moiety, but especially the environment of the C-10 and H-10 

positions. For compound 2 difference in chemical shift of methyl protons (∆δ(CH 3 ) = 

0.25ppm) is smaller then that observed for amides A and B. 

References: 

[1] A. Maślankiewicz, E. Michalik, J. Heterocyclic Chem., 34, 401 (1997) 

[2] A. Maślankiewicz, E. Michalik, T. Głowiak, J. Chem.Crystallography, 28, 1, 35 (1998) 

[3] A. Maślankiewicz, E. Michalik, A. Kowalski, J.Heterocyclic Chem., 40, 201 (2003) 

[4] F. Minisci, Synthesis, 1, 1 (1973) 

CH 3 

O 

N 

C 

3a 

CH 2 R 

H 

CH 3 

H 

N 

C 

3b 

CH 2 R 

O 

57

NEW HEPATOTROPIC PREPARATIONS FOR MR IMAGING 

OF LIVER AND BILE DUCTS DISEASES 

Elżbieta Mikiciuk-Olasik*, Bolesław Karwowski*, Małgorzata Witczak*, Paweł Szymański*, 

EmiliaWojewoda ** , Michał Studniarek # 

* Zakład Chemii Farmaceutycznej i Analizy Leków Uniwersytet Medyczny, Łódź, Poland; 

** Zakład Biofarmacji Katedra Biofarmacji Uniwersytet Medyczny, Łódź, Poland; 

# Instytut Radiologii i Medycyny Nuklearnej Akademii Medycznej, Gdańsk, Poland 

Problems in NMR diagnosis of liver and biliary ducts diseases can be divided into the 

problems related to morphology as well as the problems related to function of these organs. 

Morphological assay can be useful in identification and distinction of focal changes in 

liver and in finding the reasons of cholestasia. Application of hepatotropic contrast agents in 

both fields could have remarkable influence on the effectiveness of NMR diagnosis. In that 

case the increase of relationship: the signal to the noise versus contrast agent to the noise can 

be observed in pathological changes. Actually there is no possibility for non-invasive 

estimation of the morphology and function of the biliary ducts. 

There is no literature data for gadoline complexes that are subject of our study. 

Preliminary investigation of that compounds showed up strong affinity to hepatocytes. After 

injections of gadolinium complexes into the rats considerable increase of signal intensity was 

observed in NMR tomography. The knowledge of difference between signal intensity before 

and after application of the contrast agent gives the possibilities of quantitative analyses for 

the degree of its accumulation in liver cell. In the consequence we can receive the valuable 

diagnostic tool for investigation of pathological changes in the liver. 

58

STUDY OF MOTIONAL PROCESSES OF DRAWN I-PP/EPDM 

BLENDS BY BROAD LINE 1 H-NMR 

Ľubomír Mucha, Józef Onufer, Dušan Olčák 

Department of Physics, Technical University of Košice, 042 00 Košice, Slovakia 

E-mail:lubomir.mucha@tuke.sk 

The broad line 1 H NMR study of polymer blend composed of isotactic polypropylene 

(iPP) and ethylene – propylene - diene monomer (EPDM) rubber was carried out. The NMR 

measurements were performed on the samples of undrawn and drawn polymer blend in the 

temperature range covering the glass transition regions of all studied polymers. The molecular 

processes of iPP, EPDM rubber and blend of iPP and EPDM rubber (i-PP/EPDM) were 

investigated in our previous works [1,2]. In this paper, the effect of drawing and effect of 

drawing temperature on motional and relaxation processes related to the glass transitions 

of i-PP/EPDM blend is studied. 

iPP is a commercial partially crystalline polymer Mosten 58.142. The EPDM rubber 

Keltan 512, product of DSM, is an amorphous polymer, which contains 55, 41, and 4 % of 

carbon atoms in ethylene, propylene and diene units, respectively. The i-PP/EPDM blend 

contains 22,5 % of the EPDM rubber. A drawing of 4 x 20 mm thick plates of i-PP/EPDM 

blend was done at 293 K and 373 K, respectively. The maximum reachable drawn ratio for 

both blends was about 3,5. The i-PP/EPDM blend was cut into small pieces from drawn 

materials to prepare non – oriented samples for NMR measurements. The broad line 1 H NMR 

measurements were performed in the temperature range 160 – 370 K. 

The shape and width of broad line 1 H NMR spectra depend on the magnetic dipole – 

dipole interactions that depend on the spatial configuration of hydrogen protons and their 

motions. To obtain information about structure and molecular motions of investigated 

polymers the second moment M 2 was calculated from measured NMR spectra. Furthermore, 

to get information about molecular motions in particular phases of drawn blends, a 

decomposition of spectra into elementary components according to Bergmann [3] was done. 

Conclusions were drawn from the temperature dependences of the second moment and the 

parameters that were derived from decomposition of the NMR spectra. These temperature 

dependences reflect the changes in the structure, molecular mobility and glass transition 

behavior caused by drawing. 

References: 

[1] Olčák, D., Mucha, Ľ., Onufer, J., Raab, M., Spěváček, J.: Acta Electrotechnica et 

Informatica 2, 2002, 31. 

[2] Dušan Olčák, Jozef Onufer, Ľubomír Mucha, Miroslav Raab, Jiří Spěváček, Journal of 

Applied Polymer Science, 91, 2004, 247 - 252. 

[3] Bergmann, K.: J. Polym. Sci. Polym. Phys. Ed. 16, 1978,1611. 

59

NMR STUDY OF STRUCTURAL CHANGES IN POLYETHYLENE – 

POLYPROPYLENE BLENDS CAUSED BY DRAWING 

Jozef Murín, Ján Uhrin, Ladislav Horváth, Ladislav Ševčovič 

Department of Physics, Technical University of Košice, Park Komenského 2, 042 00 Košice, 

Slovak Republic 

Introduction 

The macroscopic properties of polymer blends are determined by their composition, 

properties of the components, mixing conditions and further processing. Uniaxial drawing of 

such materials is currently used in the plastics industry to achieve an improvement of 

mechanical properties, especially in the direction of drawing. The structural changes at 

different levels of deformation may be experimentally studied by several methods including 

also nuclear magnetic resonance (NMR), which provides important information concerning 

the phase structure and macromolecular mobility in polymeric materials. 

In this article materials based on low-density polyethylene (LDPE) and isotactic 

polypropylene (PP) are studied by means of a broad-line NMR spectroscopy. This work 

follows our previous ones [1, 2, 3] where macromolecular orientation in particular LDPE / PP 

blends have been studied. 

Materials and methods 

Blends of LDPE / PP with different compositions of components have been prepared 

at mixing temperature of 190 0 C and then were compression moulded at the same temperature 

in the form of a small slabs. After their solidification two kinds of drawn samples (B, A) have 

been prepared: B-type – are slabs deformed up to neck formation and A-type – are samples 

drawn up to their failure. Undrawn samples (denoted as C) are also studied. Drawing was 

realized at room temperature (22 0 C) with the clamps speed of 10 mm/min. 

NMR spectra in a derivative form were recorded at temperature of 22 0 C by means of 

BL-NMR spectrometer operating at the fixed magnetic field B 0 = 0,247 T, using frequency 

sweep. The broad-line NMR spectra were decomposed into three elementary components: 

narrow (n) – related to the amorphous, intermediate (m) – related to regions with hindered 

motion and broad (b) – related to crystalline or rigid phase. Each phase is characterized by the 

relative mass fraction w i (i = n, m, b) and by the line-width parameters [4]. 

In this paper the NMR spectra for drawn samples (B and A) are compared with the ones for 

undrawn samples (C) for pure LDPE and PP and for two blends with compositions 

70 LDPE / 30 PP and 30 LDPE / 70 PP, respectively. 

Results and discussion 

As we can see from Fig.1 there is a great difference between NMR spectra for 

undrawn samples (C) and drawn samples (B and A). On the other hand the differences 

between drawn samples (B and A) are less pronounced at first sight. This suggests that the 

most significant changes in the material structure and properties take place at the first steps of 

deformation up to so called yielding point. After neck formation up to the state of ultimate 

strength changes in NMR spectra are not so pronounced as in the former case. From these 

observations we may conclude that the transformation of structure from originally spherulitic 

into fibrilar one is realized mainly at the first stages of drawing. Further information on 

changes in structure and macromolecular mobility may be obtained from analysis of 

parameters of NMR spectra obtained by their decomposition. 

60

intensity (arb. units) 

0,20 

0,15 

0,10 

0,05 

LDPE / PP 

70 / 30 (C) 

0,05 

0,04 

0,03 

0,02 

0,01 

70 / 30 (B) 

0,05 

0,04 

0,03 

0,02 

0,01 

70 / 30 (A) 

0,00 

0 2 4 6 8 10 12 14 16 

0,00 

0 2 4 6 8 10 12 14 16 

B - B 0 

[10 - 8 T] 

0,00 

0 2 4 6 8 10 12 14 16 


0,07 

0,06 

0,05 

0,04 

0,03 

0,02 

LDPE / PP 

30 / 70 (C) 

0,03 

0,02 

0,01 

30 / 70 (B) 

0,03 30 / 70 (A) 

0,02 

0,01 

0,01 

0,00 

0 2 4 6 8 10 12 14 16 

0,00 

0 2 4 6 8 10 12 14 16 

B - B 0 

[10 - 8 T] 

0,00 

0 2 4 6 8 10 12 14 16 

0,30 

0,25 

LDPE (C) 

0,10 LDPE (B) 

0,10 LDPE (A) 


0,20 

0,15 

0,10 

0,05 

0,08 

0,06 

0,04 

0,02 

0,08 

0,06 

0,04 

0,02 

0,00 

0 2 4 6 8 10 12 14 

0,035 

0,030 

PP (C) 

0,00 

0 2 4 6 8 10 12 14 

0,035 

0,030 

B - B 0 

[10 - 8 T] 

PP (B) 

0,00 

0 2 4 6 8 10 12 14 

0,035 

0,030 

PP (A) 


0,025 

0,020 

0,015 

0,010 

0,025 

0,020 

0,015 

0,010 

0,025 

0,020 

0,015 

0,010 

0,005 

0,005 

0,005 

0,000 

0 2 4 6 8 10 12 14 

0,000 

0,000 

0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14 

B - B 0 

[10 - 8 T] 

Fig.1. Halves of normalized NMR spectra for studied samples and the component spectra 

(n, m, b) are shown. The solid lines drawn through experimental points are the weighted sums 

of component spectra. 

Acknowledgement 

The authors are indebted to DrSc. I. Chodák and to Ing. Z. Nógellová (Polymer Institute, 

Slovak Academy of Sciences, Bratislava) for providing us polymer materials for this study. 

References: 

[1] Murín J., Uhrin J., Horváth L., Ševčovič L.: Molecular Physics Reports 33 (2001) 118 

[2] Murín J., Uhrin J., Chodák I.: Macromolecular Symposia 170 (2001) 115 

[3] Uhrin J., Murín J., Ševčovič L., Chodák I.: Macromolecular Symposia 170 (2001) 123 

[4] Uhrin J., Murín J., Olčák D.: Acta Physica Slovaca 34 (1984) 209 

61

ESTIMATION OF h2 J PH AND 2 J PH SCALAR COUPLINGS 

BY DFT/FPT METHOD TO RATIONALISE TWO DISTINCT 

NMR OBSERVATIONS 

Ryszard B. Nazarski 

Department of Organic Chemistry, Institute of Chemistry, University of Łódź, 

90-950 Łódź 1, P.O. Box 376, Poland. E-mail: rynaz@chemul.uni.lodz.pl 

Four years ago, our report appeared [1] about first probable observation of two-bond scalar 

31 P− 1 H coupling constants J across the N−H···O − −P + intramolecular hydrogen bond (H 

bond) in the Z forms of four O,O-dialkyl 1-oxoalkanephosphonate hydrazones 1 (R = Me, t- 

Bu, CH 2 Ph, Ph; J PH 2.9 ± 0.5 Hz, from 1 H and/or 31 P proton-coupled NMR spectra), investigated 

previously by NMR [2]. Our work was subsequently followed by two experimental 

findings of similar H-bond-mediated interactions involving a P nucleus in protein-DNA complexes 

[3] or D. vulgaris flavodoxin (flavoprotein) [4], supported later by deMon-NMR code 

based DFT computations [5] for the models of aforementioned biological systems. In addition, 

other related papers were published (see e.g., refs 68-72 in recent review on J-coupling 

calculations [6]). In the case of compounds (Z)-1, two possibilities exist for explaining the observed 

heteronuclear J PH coupling, namely, the P↔H interaction across the N−H···O − −P + 

hydrogen bond ( h2 J) in the formed 6-membered ring, or traditional coupling along a longrange 

pathway via the molecular backbone ( 4 J). The best simple method to choose between 

these two pathways was a theoretical study. Results of presented DFT/FPT computations suggest 

that the foregoing interactions in 1 are in fact due to an across-H-bond J coupling. As the 

h2 J PH coupling seems to be a sensitive probe of the H-bond angle and distance [5], an interesting 

question of its sign will be discussed in detail in the poster version of this communication. 

The second problem related to this issue concerns our recent NMR study on phosphonium 

Ph 

N 

N 

R 

H 

P 

O 

O-iPr 

O-iPr 

Ph 

Ph 

Pα 

Ph 

C 

1 2 

Hβ' 

ylide 2 [7], i.e. a proper assignment of the 1 H-spectra observable 2 J PH coupling (≅ 5.2 Hz) and 

tentative explanation of an “absence” of the second coupling of this type in terms of fast pyramidalisation 

of the Cβ-anionic site. Thus, it was possible to arrange a large variety of ϕ- 

constrained conformers of the small-sized model 3 to simulate reversible inversion of the geometry 

at its β-carbon, and then to estimate 2 J PH for each arrangement. The simplest ylide 3 

was thoroughly examined before, including the J-sign determination ( 2 J PH +6.5 Hz, in C 6 D 6 ) 

[8,9]. In this way, we can test the reliability of such computations for 2 and 3 and, at the same 

time, answer the question of which orientation of the β-proton in such systems gives a minimal 

magnitude of vicinal J PH coupling. Gas-phase DFT/FPT data for 2 J PH in ylide 3 plotted as 

a function of the X–P α –C β –H torsion angle (ϕ), where X is dummy atom lying on an axis perpendicular 

to the C S symmetry plane, are shown in Fig. 1 (squares); the related DFT-energy 

well is also pictured (circles). These results drive us to the conclusion that for 3 only qualitative 

agreement of calculations is observed with 2 J PH data in solution (13.8 vs 6.5 Hz) and that 

for ϕ near 28 o this more than twice overestimated NMR parameter most likely is of a negligible 

value in P-ylides. Obviously, various motional processes (e.g. pyramidalisation or rotation 

around the P α –C β bond) can modify these values of ϕ and J, for the reason that all low-energy 

forms of such carbanionic systems exist only part of the time (Boltzmann averaging). Above 

Pγ 

O 

OPh 

OPh 

Me 

Me 

Me 

Pα 

X 

Cβ 

trans-bent conformation [9] 

3 

H 

H' 

62

data for Cβ-nonplanar model 3 are in agreement with 2 J PαHβ’ = 12.1 and 2 J PγHβ’ = 1.3 Hz evaluated 

analogously for the lowest found energy conformer of the near Cβ-planar ylide 2 [7]; an 

opposite J assignment would be practically impossible, see Fig. 1. The lacking small coupling 

2 J PγHβ’ ≅ 0.5 Hz was determined very recently [10]. 

∆E DFT 

FC term 

energy 

minimum 

-50 -30 -10 10 30 50 

-10 

Torsion angle X-P-C-H, ϕ ( o ) 

-20 

Fig. 1 DFT/FPT results for 2 J PH in 3 

50 

40 

30 

20 

10 

0 

Relative DFT energy (kJ/mol) and 

the FC contribution to 2 J PH (Hz) 

Calculational Details. Fermi-contact (FC) 

terms are usually dominant contributors to total 

J couplings, including interactions with a P 

nucleus [11]. According to works by Del 

Bene et al. [12], the trans-H bond hn J AB (n = 2, 

3) coupling is also dominated by the distance 

dependent FC term, at least for N−N, N−O, 

O−O, Cl−N and N−P(V) systems of the type 

A−H···B and A−H···O−B, respectively. So, to 

economically recover these most probably 

leading FC contributions to J couplings discussed 

here, a finite perturbation theory (FPT) 

method of Pople et al. [13] was solely used, 

which has been reintroduced recently by 

Barfield and co-workers [14]. All DFT/FPTcomputed 

J values are based on the FC output 

of the FIELD option of Gaussian 98W, obtained for free molecules of (Z)-1, 2 and 3 at the 

UB3LYP/6-31G**//B3LYP/6-31G** level of theory. The parameter λ = 0.01 and the tight 

SCF convergence criterion were applied as giving calculational results in a reasonable agreement 

with the n J XY (XY = CH, PC or PP) couplings measured for above compounds in 

solution. Differently designed conformers of 3 were geometrically optimised under the C S 

symmetry constraint. 

References 

1. Nazarski, RB; Gralak, DK; Kudzin, ZH Bull. Pol. Acad. Sci., Chem. 2000, 48, 27-33. 

2. (a) Gralak, DK; Kudzin, ZH; Nazarski, RB, poster presented at the Symposium on Application 

of Magnetic Resonance in Chemistry and Related Areas, Warszawa, June 25-27, 1997; abstract 

P-35. (b) Gralak, DK, Master Thesis, University of Łódź, 1997. 

3. Mishima, M; Hatanaka, M; Yokoyama, S; Ikegami, T; Wälchli, M; Ito, Y; Shirakawa, M. 

J. Am. Chem. Soc. 2000, 122, 5883-5884. 

4. Löhr, F; Mayhew, SG; Rüterjans, H J. Am. Chem. Soc. 2000, 122, 9289-9295. 

5. Czernek, J; Brüschweiler, R J. Am. Chem. Soc. 2001, 123, 11079-11080. 

6. Alkorta, I; Elguero, J Int. J. Mol. Sci. 2003, 4, 64-92. 

7. Chęcińska, L; Kudzin, ZH; Małecka, M.; Nazarski, RB; Okruszek, A Tetrahedron, 2003, 59, 

7681-7693. 

8. Schmidbaur, H; Buchner, W; Scheutzow, D Chem. Ber. 1973, 106, 1251-1255. 

9. Mitzel, NW; Brown, DH; Parsons, S; Brain, PT; Pulham, CR; Rankin, DWH Angew. Chem. Int. 

Ed. 1998, 37, 1670-1672 and refs therein. 

10. Nazarski, RB, unpublished results. 

11. Malkina, OL; Salahub, DR; Malkin, VG J. Chem. Phys. 1996, 105, 8793-8800 and refs therein. 

12. Del Bene, JE; Perera, SA; Bartlett, RJ, Elguero, J; Alkorta, I; López-Leonardo, C; Alajarin, M. 

J. Am. Chem. Soc. 2002, 124, 6393-6397 and refs therein. 

13. Pople, JA; McIver, JW Jr.; Ostlund, NS J. Chem. Phys. 1968, 49, 2960-2964, 2965-2970. 

14. Onak, T; Jaballas, J; Barfield, M. J. Am. Chem. Soc. 1999, 121, 2850-2856. 

63

SOLID STATE NMR STUDIES OF MOLECULAR MOTIONS IN THE 

BIOCOPOLYMER OF GLYCOLIDE/LACTIDE/CAPROLACTONE 

Alovidin Nazirov, Roman Gwoździk-Bujakowski, Marcin Wachowicz , Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland 

Solid biodegradable copolymers poly(glycolide-co-lactide-co-caprolactone) (PGLC) 

[1-3] containing various proportions of these three monomers were investigated by proton 

NMR second moment (M 2 ) and spin-lattice relaxation times (T 1 ) in the temperature range 

from 120 to 373 K. The proportions of monomers used in the studies were following 

10/70/20, 30/50/20 and 30/0/20. The glass transition temperatures were determined by 

Differential Scanning Calorimetry and it was observed that T g increases with the increase of 

the lactide content. 

The second moment technique was used to monitor the molecular dynamics in the 

solid–state copolymers and to determine the kind of molecular motions. The results of M 2 

obtained for copolymers (Fig. 1) were compared with calculated values for different motional 

modes and in addition confronted with the M 2 results obtained for pure components of PGLC: 

glycol, lactide and caprolactone. 

The activation energies and the correlation times of the copolymer motions were 

determined from T 1 measurements as a function of temperature. The T 1 minimum detected at 

low temperatures was attributed to methyl group rotation (Fig. 2). The only component of 

PGLC copolymer containing methyl groups was lactide, and consequently the variations in 

lactide contents were reflected in T 1 results. The increase of lactide content makes the 

copolymer more stiff. 

Polymer, 39, 267 (1998) 

Second moment [mT 2 10 2 ] 

20 

18 

16 

14 

12 

10 

8 

6 

4 

2 

M 2 

= 10.7 

M 2 

= 7,29 

M 2 

17.99 

T g 

= 232 K 

25MHz 

M 2 

= 10,18 

M 2 

=0,52 

0 

50 100 150 200 250 300 350 400 450 

Temperature [K] 

Relaxation time T 1 

(ms) 

10000 

1413 PGLC(10/70/20) 

1000 

T g 

=294K 

100 

2 3 4 5 6 7 8 9 

1000/T 

Fig.1. Temperature dependence of proton 

second moment of PGLC(30/20/50) 

Fig. 2. Arrhenius plot of 1 H-NMR spinlattice 

relaxation time of PGLC(10/70/20) 

[1] Qing Cai, Jianzhong Bei and Shenguo Wang, Polym Adv Technol 13,105 (2002) 

[2] Hans R. Kricheldorf and Soo-Ran Lee, Macromolecules 29,8689 (1996) 

[3] G.Kister, G.Cassanas and M.Vert, Polymer, 39, 267 (1998) 

64

T 1 DISPERSION AND SELF-DIFFUSION NMR STUDY 

OF WATER MOLECULES IN POLY(ACRYLIC ACID) HYDROGELS 

Grzegorz Nowaczyk, Marek Kempka, Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, Umultowska 85,PL-61614 Poznań, Poland 

A detailed understanding of the structure of hydrogels and the dynamics of molecular 

motions of water in gels is very important for biomedical drug delivery processes that use 

hydrogels as carriers (1). 

One of the most extensively used and studied hydrogels is poly(acrylic acid) gel. Here 

we report studies of water molecules in poly(acrylic acid) microgels (carbopol ® 971) by means 

of Fast Field Cycling Realaxometry and NMR diffusion methods. 

Carbopol ® 971 was provided by Noveon, Inc. The polymer powder was dispersed in 

distillated water with or without surfactants. The polymer content of gels was 0,5 and 1%. 

10% NaOH was added to neutralize the sample to pH 3. 

T 1 dispersion of water was measured in the frequency range from 10 kHz to 9 MHz at 

293 and 281K, whereas the self-diffusion measurements were performed using homemade 

spin-echo NMR spectrometer operating at 16,5 MHz at temperature range from 297 to 323K. 

Proton NMR data shows decreasing of T 1 spin-lattice relaxation time with the decrease 

of Larmor frequency down to 1,5 Mhz. The slopes, determined for this dependence, are equal 

υ~0,51 (293K) and υ~0,22 (281K) (Fig. 1.). Below 1 MHz T 1 is frequency independent. 

The diffusion coefficients for systems containing 1% of carbopol are very similar to 

unrestricted water (2). It was found that an addition of surfactants to gels leads to a slowing 

down of the diffusion of water molecules (Fig. 2.). 

5 

T 1 

(s) 

293K 

281K 

ν∼0.51 

10 0 ν∼0.22 

10k 100k 1M 10M 

Larmor frequency (Hz) 

Fig. 1. 1 H spin-lattice relaxation times versus Larmor 

frequency for Carbopol (0,5%) at 281 and 293K. 

D(10 -5 cm 2 /s) 

4 

3 

Carbopol 1% 

Carbopol 1%+surfactant (Brij 58) 1% 

E a 

=4,1 (kcal/mol) 

E a 

=3,9 (kcal/mol) 

2 

3,05 3,10 3,15 3,20 3,25 3,30 3,35 3,40 

1000/T 

Fig. 2. Water diffusion in Carbopol hydrogels. 

[1] M. Dittgen, M. Durrani, K. Lehmann, Acrylic polymers. A review of pharmaceutical applications, 

Stp Pharma Sci. 7 (1997) 403-437 

[2] B. Peneke, S. Kinsey, S. J. Gibbs, T. S. Moerland, B. R. Locke, Proton diffusion and T 1 relaxation 

in polyacrylamide gels: A unified approach using volume averaging, J Magn Reson 132 (1998) 240-254 

65

AN NMR STUDY OF Pr 0.5 Ca 0.5 Mn 1-x Ga x O 3 (x=0 AND 0.03) 

Colin John Oates 1 , Czesław Kapusta 1,2 , Peter Charles Riedi 2 , Marcin Sikora 1 , Dariusz Zając 1 , 

Damian Rybicki 1 , Christine Martin 3 , Cedric Yaicle 3 

1 Department of Solid State Physics, Faculty of Physics & Nuclear Techniques, AGH 

University of Science and Technology, Kraków, Poland; 2 School of Physics and Astronomy, 

University of St. Andrews, St. Andrews, KY16 9SS, Scotland, United Kingdom; 3 Laboratoire 

CRISMAT – UMR 6508, ISMRA et Universite de Caen, 6 Boulevard du Marechal JUIN, 

14050 Caen Cedex, France 

A NMR study of polycrystalline Pr 0.5 Ca 0.5 Mn 1-x Ga x O 3 (x=0 and 0.03) at 3 K is 

presented. Zero field spin-echo spectra of the Ga doped compound consist of a overlapping 

69,71 Ga signal at 74 MHz (hyperfine field of 5.3T), a 55 Mn double exchange (DE) line at 

375MHz (35.5T) and a weak Mn 3+ signal between 400 to 550MHz. Measurements in an 

applied field show a step-like increase in the DE line intensity, which corresponds to an 

increase of the amount of the ferromagnetic metallic phase. This coincides with a step-like 

feature in the bulk magnetization measurements. The effect is similar to that in the previous 

field dependent 55 Mn NMR measurements of Pr 0.67 Ca 0.33 MnO 3 . At the demagnetized and 

remanent state, a variation of spin-spin relaxation time, T 2 , across the 55 Mn line, due to Suhl – 

Nakamura interaction is observed, which suggests that the ferromagnetic metallic (FMM) DE 

regions, at liquid helium temperatures, are at least 4nm in size. 

66

A LOW FIELD MRI SYSTEM 

FOR HYPERPOLARIZED 3 He IMAGING 

Zbigniew Olejniczak*, Tadeusz Pałasz, Katarzyna Cieślar, Katarzyna Suchanek, 

Mateusz Suchanek, Tomasz Dohnalik 

* Institute of Nuclear Physics, Radzikowskiego 152, 31-342 Kraków, Poland; 

Institute of Physics, Jagiellonian University, Reymonta 4, 30-059 Kraków, Poland 

The design and construction of a low field MRI system for imaging small animal lungs 

using hyperpolarized helium-3 will be described. It is based on a permanent magnet of unique 

geometry, built from a new generation Nd-B-Fe magnetic material, which provides very high 

magnetic energy density. The magnet generates a field of 0.088 Tesla, with the initial inhomogeneity 

of 360 ppm in the 10 cm diameter sphere. The inhomogeneity was reduced by a factor 

of ten by passive shimming , using steel pieces attached to the magnet poles. It is expected to 

improve by another factor of four in the second iteration of shimming. The temperature dependence 

of the magnetic field is about -836 ppm/°C, which made it necessary to stabilize the 

temperature of the magnet to 0.1°C inside the Faraday cage. The Faraday cage simultaneously 

provides sufficient electromagnetic shielding at the resonance frequency of 2.8 MHz for 3 He. 

The final temperature compensation is achieved by using a current feedback system and the 

temperature sensor anchored to the magnet pole. 

The magnetic field gradients are generated by a set of biplanar, actively shielded gradient 

coils. The gradient strengths are about 30 mTesla/m at the current of 40 A, for all three 

directions. The minimum rise time for the gradient pulses is 200 µsec. The gradient coils are 

cooled with temperature stabilized water circulating in the closed loop. The gradients linearity 

within the working volume is better than 1%. The residual time dependent fields due to eddy 

currents generated in the magnet poles are of the order of 40 ppm and decay with the time 

constant of 20 msec, when the maximum amplitude gradient pulse with a minimum rise time 

is used, and no preemphasis is applied. 

The radiofrequency coil is a solenoid supplemented by an additional pair of paraxial 

coils, which compensates the field up to the 6-th order, providing the B 1 field within the working 

volume of better than 1% homogeneity. The coil can be tuned to both 3 He and 1 H resonance 

frequency. 

The NMR spectrometer consists of a commercial MR Research Systems (previously 

SMIS) MR4200 Narrow Band console, with an additional home-built frequency converter 

which enables to perform the experiments on either helium-3 or proton frequencies. All 

magnetic field and gradient coils tests were performed on water samples. The console is 

supplemented by the Dressler 1 kW rf power amplifier, and three Resonance Research 40 A / 

100 V gradient amplifiers. The standard library of imaging sequences has been enhanced by 

special imaging protocols that are suitable for imaging small animal lungs using hyperpolarized 

helium-3. 

The first images obtained in the described system will be presented. 

67

MOLECULAR DYNAMICS IN POLY(ETHYLENE OXIDE) (PEO): 

1 H-NMR AND DIELECTRIC SPECTROSCOPY STUDIES 

Bakyt Orozbaev, Marcin Wachowicz, Stefan Jurga 

Institute of Physics, A. Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland 

Molecular dynamics in poly(ethylene oxide) (PEO) with molecular weights M=2⋅10 6 

and M=1⋅10 5 were studied by T 1 Dispersion NMR and Dielectric Spectroscopy. 

T 1 spin-lattice relaxation times were measured by Fast Field Cycling technique in the 

frequency range from 10 kHz to 16 MHz for selected temperatures below and above melting 

points of 67°C and 63°C, for M=2⋅10 6 and M=1⋅10 5 samples, respectively (Fig. 1). Two 

different slopes observed in our experiment are interpreted in terms of the Rouse dynamics of 

chain segmental motion [1]. 

Dielectric relaxation spectra were collected using a Novocontrol BDS-80 broadband 

dielectric spectrometer. Experiments were performed in the frequency domain (0.01 Hz – 1.8 

GHz) and between –140 and 60 °C with 5 °C increments. Dielectric specimens were 0.4-0.6 

mm thick, and were coated on both sides with a thin layer of gold to optimize electrical 

contact, then sandwiched between two electrodes having a diameter of 20 mm and 10 mm. 

Two relaxation processes, β and γ, were observed, and are similar to those observed in PEO 

with molecular weights M=2.8⋅10 6 and M=8.4⋅10 5 [2]. The relaxation process detected at low 

temperature and high frequency called β relaxation, is due to the local motions of amorphous 

PEO segments. The β process is independent of molecular weight (M) and degree of 

crystallinity ( Χ c ). The γ-process was assigned to local twisting in the main chains of PEO 

molecule and refers to both crystalline and non-crystalline regions, including amorphous 

segments of the folded molecules. 

From the temperature shift of β and γ maximum observed in the ε”(T) plot the 

activation energies for these two processes were evaluated (Fig. 2) and compared with NMR 

data. 

1 

10 

8 

22 kJ/mol 

PEO 2E6 

PEO_2E6 ω 0.27 

ω 1.23 

6 

0.1 

log(f) [Hz] 

4 

γ - process 

2 

13 kJ/mol 

β - process 

0 186 kJ/mol 

γ '- process 

27 kJ/mol 

-2 

3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 

1000/T max 

[1/K] 

T 1 

[s] 

0.01 

45 °C 

65 °C 

90 °C 

1E-3 

0.01 0.1 1 10 

Larmor frequency ω [MHz] 

Fig. 1. Larmor frequency dependence of 1 H-NMR T 1 relaxation time for PEO (M=2⋅10 6 ) 

Fig. 2. Arrhenius plot correlation times for PEO (M=2⋅10 6 ) 

68

1 H MAS NMR OF FLAVONOIDS 

Katarzyna Paradowska*, Agnieszka Zielińska*, Iwona Wawer*, Wacław Kołodziejski** 

*Department of Physical Chemistry , Faculty of Pharmacy, Medical University of Warsaw, 

Banacha 1, 02-097 Warsaw, Poland; **Department of Inorganic and Analytical Chemistry, 

Faculty of Pharmacy, Medical University of Warsaw, Banacha 1, 02097 Warsaw, Poland 

Flavonoids, polyphenol-type compounds with several OH groups are widely 

distributed in plants. 1 H and 13 C NMR solution spectra of naturally occurring flavonoids and 

flavonoid glycosides are routinely used for their identification in plant material. Since 

antioxidant and radical scavenging activity of flavonoids depends on their molecular 

structure, it is important to collect data on the preferred conformation and the intramolecular 

and intermolecular interactions. There are only few X-ray crystallographic data, because 

suitable single crystals of flavonoids are difficult to obtain. Therefore, solid state NMR can be 

a complementary source of information. 13 C CPMAS NMR spectra for a series of flavonoids 

were studied previously [1], enabling the conclusions as to the orientation of OH groups in the 

solids. According to our knowledge there was no 1 H NMR study of solid flawonoids. Large 

dipolar coupling for 1 H- 1 H interaction of 20-50 kHz cause that this interaction cannot be 

averaged out fully in standard MAS experiment. Usually, the spectra of organic solids 

obtained with low rotational speed give broad signals covering whole spectral region [2]. 

1 H MAS spectra of flavonoids: chrisin, kaempferol, morin and quercetin were recorded on 

a Bruker DSX-400 wide bore spectrometer equipped with a BL 2.5 mm probehead enabling 

high speed rotation. The samples were spun at 32 kHz in a ZrO 2 rotor. 

The spectra recorded with rotational speed of 32 kHz exhibited broad signal with 

maximum at ca. 7 ppm, however the resonances of protons involved in an intramolecular 

hydrogen bond C5-OH…O=C at ca. 10.5 ppm can be distinguished. 

Keywords: flavonoids, 1 H MAS NMR, hydrogen bonds 

1. I. Wawer and A. Zielinska, Magn. Reson. Chem., 39 (2001) 374-380 

2. A.Temeriusz, M.Rowińska, K.Paradowska, I.Wawer, Carbohydr. Res., 338 (2003) 183-188 

69

15 N NMR COORDINATION SHIFTS IN STABLE AND LABILE 

d-ELECTRON METAL COMPLEXES WITH AZINES 

Leszek Pazderski, Iwona Łakomska, Edward Szłyk 

Faculty of Chemistry, Nicholas Copernicus University, Toruń, Poland 

Jerzy Sitkowski, Lech Kozerski 

Institute of Organic Chemistry, Polish Academy of Sciences, Warsaw, Poland 

National Institute for Public Health, Warsaw, Poland 

The 15 N NMR coordination shift, i.e. the difference between the chemical shift of the 

same nitrogen atom within the complex and ligand molecules (∆ coord = δ compl - δ lig ), is a useful 

tool indicating the metallation site in many N-donors. For azines, possessing the pyridine-type 

nitrogens, the coordination shifts induced by binding of diamagnetic transition metal ions are 

usually negative (shielding effect being observed). Their absolute values seem to depend 

primarily on the stability/lability of the formed metal-nitrogen bondings. ∆ coord can reach 70- 

100 ppm for stable Pd(II), Pt(II), Pt(IV) complexes and does not exceed 10 ppm for labile 

Zn(II) species. 

The stability of the coordination compounds in commonly used NMR solvents can be 

easily tested by 1 H NMR measurements of their equimolar mixtures with the ligands. In the 

case of platinides two distinct sets of 1 H signals appear, the deshielding of protons being 

usually observed upon metal coordination. For zinc compounds an average spectrum is 

detected, with the chemical shifts intermediate between those characteristic for the pure 

complex and the free ligand. Hence one can assume that in the solution the changes of δ 

values can be regarded rather as the result of temporary Zn-N interactions than the real 

bonding formation (although the latter is present in the solid phase). 

The studied examples concern Pd(II), Pt(II), Pt(IV) and Zn(II) chloride complexes with such 

azines as: pyridine, pyridazine, purine and 1,2,4-triazolo-[1,5a]-pyrimidine. 

70

EFFECT OF TEMPERATURE ON LIPOSOME STRUCTURES. 

EPR AND NMR STUDIES 

Danuta Pentak 1 , Wioletta Korus 1 , Anna Sułkowska 2 , Wiesław W. Sułkowski 1 

1 Department of Environmental Chemistry and Technology, University of Silesia, 

Szkolna 9, 40-006 Katowice, Poland; 2 Department of Physical Pharmacy, Medical University 

of Silesia, Jagiellońska 4, 41-200 Sosnowiec, Poland 

The effect of temperature on liposomes structures has been investigated by means of 

electron paramagnetic resonance spectroscopy using spin labeling technique and NMR 

spectroscopy. The EPR spectra were recorded on a Bruker EMX spectrometer in the 

temperature range 300 – 340K. The 1 H-NMR, 13 C-NMR and 31 P-NMR spectra were recorded 

on a Bruker 400 MHz spectrometer in the same temperatures. Liposomes were prepared from 

L-α-phosphatidylcholine dipalmitoyl (1,2-dihexadecanoyl-sn-glycerol-3-phosphocholine) 

(DPPC) and cholesterol (5-cholesten-3β-ol) as main component of a membrane. Liposomes 

contained variable quantity of cholesterol. Molar ratio of DPPC to cholesterol was: 4:1, 4:0,5, 

4:0. The spin marker, 2-(3carboxypropyl)-4,4-dimethyl-2-tridecyl-3-oxazolidinyloxyl free 

radical (5-DOXYL), placed in a liposome membrane, allows to observe the structural changes 

in liposomes with temperature increasing. The correlation time and an order parameter of the 

5-DOXYL spin marker placed in liposomes membranes were determined. The changes of 

rotational correlation time and order parameter values with increasing temperature result from 

the motion rise of the spin probe. The intensity of the EPR signal of 5-DOXYL and NMR 

spectroscopy give information about structure of liposomes. 

71

REACTIONS AND NMR STUDY OF NEW ABNORMAL 

METABOLITES IDENTIFIED IN URINE OF CANCER PATIENTS 

Agnieszka Pietras, Hanna Krawczyk 

Warsaw University of Technology, Faculty of Chemistry, Noakowskiego 3, 00-664 Warsaw, 

Poland 

Free creatinine is a natural by-product of cellular metabolism related to muscular mass 

and it is always present in human urine. In 1997 Aruna Arakali et.al. [1], during the course of 

investigation of the urine of cancer patients, found new tumor markers, 5-methoxycreatinine 

and 5- ethoxycreatinine, abnormal metabolites of creatinine. 

In the present study 5-methoxycreatinine, 5-ethoxycreatinine and 5-aminocreatinine 

were synthesised. These molecules are chiral molecules, they may occur in urine in one or 

two enantiomeric forms, which may be important for medical diagnostics. 

Me 

RO 

5 

N 

1 

2 

NH 2 

O 

4 

3 

N 

R = CH 3 

, C 2 

H 5 

, NH 2 

We obtained diastereomeric derivatives of investigated compounds, recorded their 

NMR spectra, optimised geometries and calculated NMR shielding tensors for carbon nuclei 

by DFT (B3LYP) method in 6-311++ G(2d,p) basis. In the poster all these results will be 

presented. 

[1] A.V. Arakali, J. McCloskey, R. Parthasarathy, J.L. Alderfer, G.B. Chheda and 

T. Srikrishanan , NUCLEOS NUCLEOT, 16 (12): 2193-2218 1997. 

72

1 H, 13 C NMR AND GIAO/DFT CALCULATIONS OF SUBSTITUTED 

N-(4-ARYL-1-PIPERAZINYLBUTYL) DERIVATIVES, 

NEW ANALOGUES OF BUSPIRONE 

Maciej Pisklak a , Jerzy Kossakowski b , Iwona Wawer a 

a Department of Physical Chemistry, Faculty of Pharmacy, The Medical University 

of Warsaw, Banacha 1, 02097 Warsaw, Poland; b Department of Medicinal Chemistry, 

The Medical University of Warsaw, Oczki 3, 02007 Warsaw, Poland 

Buspirone was a first of the anxiolytics of second generation, with high affinity to 

5-HT1A and D2 receptors. The ligands for the 5-HT1A receptors are of special interest since 

they may be important in treating psychiatric disorders (anxiety, depressions). Several groups 

of ligands have been synthesised and tested for pharmacological activity with the task to find 

a compound with better selectivity and higher affinity. Continuing our studies on potential 

anxiolytics we have designed a series of compounds, the N-(4-aryl-1-piperazinylbutyl) 

derivatives with bulky imide moiety (see the structures with carbon numbering). 

2 

3 

1 

11 

H 

15 

R 

10 

18 

14 

O 

N 

16 13 

12 

H 

4 5 17 6 

9 

8 

7 

19 

20 

21 

22 

N 

23 

26 

24 25 

N 

R O 

13 C NMR spectra of a series of compounds were recorded for CDCl 3 solution and solid state. 

NMR shielding constants were calculated using GIAO/DFT approach for selected model 

fragment. Reliable assignment of carbon resonances was made with the aid of theoretical 

data. 

Considering the interaction of a ligand with 5-HT1A receptor, it was supposed that the 

distances between the aromatic substituent, nitrogen atom of piperazine and carbonyl group of 

imide moiety are important for binding of buspirone-like compounds. Therefore, the data 

concerning the structure, conformational flexibility and properties of functional groups are of 

interest. Main interest was placed on the configuration of piperazine nitrogen attached to the 

aromatic moiety. The combined NMR and theoretical studies enable for improvement of the 

model of pharmacophore. 

Additionally, little research has been done on solid state structures of buspirone 

analogues applying 13 C CP MAS NMR techniques and reasonable assignment of carbon 

resonances was made with the aid of theoretical studies. 

Ar 

73

NMR STUDY OF THE HUMIFICATION PROCESS DURING SEWAGE 

SLUDGE TREATMENT 

Justyna Polak, Mariola Bartoszek, Wiesław W. Sułkowski 

Department of Environmental Chemistry and Technology, Institute of Chemistry,University 

of Silesia, Szkolna 9, 40-006 Katowice, Poland, wsulkows@uranos.cto.us.edu.pl 

The aim of this work was to study the humic acids, extracted from sludge from 

biologic-mechanical sewage treatment plant Ruptawa in Jastrzębie Zdrój by NMR 

spectroscopy. Sludge samples for studies were sampled according to Polish standards (in 

a wide range in agreement with ISO/5667/3 standard) from a primary settling tank, from 

a sludge nitrification and denitrification chamber, a sludge digestion chamber and from a 

sludge drying bed. Humic acids were extracted from sludge by means of conventional 

methods by Stevenson [1]. 

The 1 H NMR spectra were recorded with Bruker 400 MHz spectrometer at room 

temperature. The humic acids spectra showed basically the same signals, although changes in 

their relative intensities were observed. This fact indicate the presence of the same species in 

different concentrations in the studied humic acids. 

The most interesting is to compare the intensity of aliphatic and aromatic region for 

samples extracted from each stage of sewage treatment. The percentage of total intensity for 

each region were estimated by integrating the 1 H NMR spectrum within each region. The 

increasing of the signals intensity in the aromatic region and decreasing in the aliphatic one 

were observed. This points to the increase of aromatisation of humic acids during the sewage 

treatment and confirms the humification process during sewage sludge treatment. 

The obtained results are consistent with the results of elementary analysis and EPR 

spectroscopy [2]. 

[1] F.J. Stevenson, Humus Chemistry: Genesis, Composition, Reaction, Willey-Interscience, 

New York, 1982 

[2] J. Pajączkowska, A. Sułkowska, W.W. Sułkowski, M. Jędrzejczyk, Journal of Molecular 

structure, 2003: 651-653; 141-149 

74

NMR STUDY OF THE HUMIC ACIDS 

EXTRACTED FROM SEWAGE SLUDGE 

Justyna Polak, Mariola Bartoszek, Jerzy Borek, Wiesław W. Sułkowski 

Department of Environmental Chemistry and Technology,Institute of Chemistry, University 

of Silesia, Szkolna 9, 40-006 Katowice, Poland, wsulkows@uranos.cto.us.edu.pl 

Humic acids isolated from sludge from biologic-mechanical sewage treatment plant in 

Sosnowiec Zagórze were characterised by using 13 C NMR and 1 H NMR spectroscopy. 

The 1 H NMR spectra were recorded with Bruker 400 MHz spectrometer at room 

temperature. The 13 C NMR spectra were recorded with Varian 300 MHz spectrometer at room 

temperature. Sludge samples for studies were sampled from: a primary settling tank, a sludge 

recirculate chamber, a sludge digestion chamber and a sludge drying bed. 

The 13 C NMR method was used to define the position of the characteristic function 

groups in spectra and to estimate aromatisation of humic acids, extracted from particular 

stages of sewage treatment. The total aromaticity (106 –165 ppm) was calculated by 

expressing aromatic C as percentage of aliphatic C (0 – 105 ppm) + aromatic C (106 – 165 

ppm). The increase of the aromatisation of humic acids during the sewage treatment was 

observed. 

The structure of humic acids was changed mainly in the digestion chamber. Results of EPR 

spectroscopy, elementary analysis and decrease of H/C value of humic acid extracted from 

sludge from the digestion chamber confirms this hypothesis [1]. Hence, the analysis of the 1 H 

NMR spectra humic acids, extracted from sludge from the primary settling tank (the initial 

stage of sewage sludge treatment) and from the digestion chamber (stage with mesophil 

digestion), was carry out. 

The humic acids spectra showed basically the same signals, although changes in their 

relative intensities were observed. Investigation of the peaks in 1 H NMR spectra gives 

information on the details of the chemical structure of humic acids and its change during 

sewage sludge treatment. 

[1] J. Pajączkowska, A. Sułkowska, W.W. Sułkowski, M. Jędrzejczyk, Journal of Molecular 

structure, 2003: 651-653; 141-149 

75

STRUCTURAL ANALYSIS OF RNA DUPLEXES CONTAINING 

ADENOSINE BULGES BY NMR SPECTROSCOPY 

Łukasz Popenda 1 , Zofia Gdaniec 1 , Grażyna Dominiak 1 , Jan Milecki 2 , Ryszard W. Adamiak 1 

1 Institute of Bioorganic Chemistry, Polish Academy of Sciences, Z. Noskowskiego 12/14, 

61 704 Poznań, Poland; 2 Department of Chemistry, Adam Mickiewicz University 

Grunwaldzka 6, 60-780 Poznań, Poland 

Double stranded regions of RNA molecules contain structural motifs, in which one or 

more residues in one strand does not have the pairing residue in the opposite strand. Bulges 

are the simplest as well as the most abundant structural motifs that play a crucial structural 

and functional role in many RNAs [1]. At present, bulges are known to participate in the 

process of RNA folding, RNA-RNA and RNA-protein interactions [2]. 

Previous thermodynamic studies on the influence of bulges on RNA duplexes stability 

[3] has resulted in the following observations: (i) all the bulges destabilise the duplexes, (ii) 

bulges containing the same number of A and U residues destabilise RNA duplexes to the 

same extent, (iii) long bulges not necessarily destabilise the duplex more than the shorter 

ones. Up to now, no systematic structural studies on the preferable conformation of these 

RNA motifs have been done. This is important to emphasize that very often bulged structures 

that are obtained from X-ray analysis differ from those determined in solution by NMR 

spectroscopy. This fact is an additional reason for doing the structural studies in solution. 

The subject of our research are bulged RNA duplexes containing unpaired adenine 

residues. Analysis of homo- and heteronuclear NMR spectra (2D NOESY, DQF-COSY, 1 H- 

13 C HSQC, 1 H- 31 P HSQC) let us to conclude about the structure and dynamics of RNA 

duplexes with single- and trinucleotide bulges. Our data show that the bulged residues within 

RNA duplexes containing single bulged adenosine, tend to stack into the helix. The 

experimental data reveal that the accommodation of bulged adenine residue between the 

neighbouring base pairs, does not disturbe the regular A-RNA structure. Analysis of NMR 

spectra and the thermodynamic data obtained for the duplex with three bulged adenine 

residues show that the presence of additional residues within the bulged region causes a 

considerable destabilisation of the duplex structure. 

Literature: 

[1] M. E. Burkard, D. H.Turner, I. Tinoco Jr. in: RNA World II, R. Gesteland, T. Cech, and J. 

Atkins (ed), Cold Spring Harbor Press, 1999, str. 233 

[2] T. Hermann, D. J. Patel, Structure, 8 (2000), 47 

[3] C. E. Longfellow, R. Kierzek, D. H. Turner, Biochemistry, 29 (1990) 278 

76

NMR STUDY OF LAYERED ANGANITE La 1.4 Sr 1.6 Mn 2 O 7 

Damian Rybicki a , Czesław Kapusta a,b , Peter Charles Riedi b , Colin John Oates a , 

Dariusz Zając a , Marcin Sikora a , Clara Marquina c , Ricardo Ibarra c 

a 

Department of Solid State Physics, Faculty of Physics & Nuclear Techniques, AGH 

University of Science and Technology, Kraków, Poland; b Department of Physics & 

Astronomy, University of St. Andrews, St. Andrews, KY16 9SS Scotland, United Kingdom; 

c 

Instituto de Ciencias de Materiales de Aragon, Universidad de Zaragoza CSIC, 50009 

Zaragoza, Spain 

A 55 Mn nuclear magnetic resonance study of a layered perovskite La 1.4 Sr 1.6 Mn 2 O 7 is 

reported. Between 4.2K and the magnetic ordering temperature, 100K, zero field spin echo 

spectra consist of signals corresponding to the double-exchange (DE) states and charge 

localised (CL) Mn 3+ , Mn 4+ states. This indicates occurrence of electronic and magnetic phase 

segregation into ferromagnetic metallic and ferromagnetic insulating regions. Above 100K a 

DE line is observed, revealing the presence of long lived metallic clusters. The relation of 

results to magnetoresistive properties of the compound is discussed. 

77

IDENTIFICATION AND DETERMINATION OF NAPROXENE ALLYL 

ESTERS DIASTEREOISOMERS WITH PROTON-NMR 

SPECTROSCOPY 

Maciej Skarżyński, Krzysztof Krajewski, Jerzy Krzywda, Hanna Fitak 

Pharmaceutical Research Institute, Warsaw, Poland 

The work is an example of the use of NMR spectroscopy for the identification and 

determination of particular diastereoisomers in their mixtures. The diastereoisomers of 

naproxene allyl esters can be fast and easily distinguished and determined with proton-NMR 

spectra. 

Results of the series of PMR analyses performed in various solvents are presented and 

compared with those obtained with high-pressure liquid chromatography and with optical 

rotation measurements. Sources of error as well as limits of the detection and the 

determination and accuracy of the determination are discussed. 

78

MAGNETIC SUSCEPTIBILITY EVALUATION BY MEANS OF MRI 

TECHNIQUE 

Ing. Miloslav Steinbauer 1 , Ing. Karel Bartušek, DrSc 2 

1 Faculty of Electrical Engineering and Communication, Brno University of Technology, 

Purkyňova 464/118, 612 00 Brno, steinbau@feec.vutbr.cz; 2 Institute of Scientific 

Instruments, Academy of Sciences of the Czech Republic, Královopolská 147, 612 00 Brno, 

bar@isibrno.cz 

The determination of magnetic susceptibility of weakly magnetic materials is simple 

for substances giving MR signal by comparison with substance, whose susceptibility is 

known [2]. In this paper we will discuss measuring technique suitable for substances with no 

signal in MR tomography. 

This method is based on constant magnetic flux in working space superconducting 

magnet. Inserting of the specimen with different value of magnetic susceptibility causes local 

deformation of homogeneous magnetic field – idealized example see Fig. 1. Using MRI field 

echo technique we can acquire image of the magnetic field homogeneity in measured volume 

of specimen. From this image we derived a course of 

the magnetic induction module in the measured 

z χ 2 

χ 1 

material. In our example the paramagnetic specimen 

of thickness x 0 is inserted in homogeneous magnetic 

B s 

field with induction B 0 parallel with z-axis. Magnetic 

x 0 

induction in the specimen with susceptibility χ s B 0 

increases to Bs 

= B0 ⋅ ( 1+ 

χs) 

. When material of the 

x 

specimen gives no MR signal, the indirect method of ∆B 0 (x) 

induction Bs computation can be used. Assuming 

constant magnetic flux Φ thru normal area of crosssection 

S of the magnet working space 

φ = B ⋅dS 

=const. 

Fig. 1. Local deformation of 

∫∫ 

. Suppose the specimen has enough 

S 

magnetic field due to weakly 

large length in y-axes direction, so we can neglect boundary effect and for z-x cross-section in 

the middle of the specimen Fig. 1 we can write ∫ ∆ B0 ( x) 

⋅ dx = 0 , what means that sum of 

hatched areas bounded by curve in Fig. 1 with respect to the base value of induction B0 is 

zero. If substance surrounding the specimen gives MR signal and we can determine the course 

of ∆B0 

( x) 

, we also can compute the value B s and χ s 

values of the investigated specimen. Several 

numerical tests were carried to verify the method 

χ s 

mentioned above. Numerical modelling was provided 

in Ansys 6.1 software. Model was meshed with 31642 

nodes and 49775 elements of Solid96 type. Boundary 

conditions were adjusted so that induction 

B 0 = 4,700 T in z-axes direction. Module of magnetic 

χ 2 

induction B along the “path” is depicted in Fig. 2. The 

χ 1 

data set from graph shown in Fig. 2 was numerically 

integrated and area bounded by the curve B and base 

level B 0 = 4.700 T was evaluated. Founded difference 

between areas over and below B 0 level was Fig. 2. The course of magnetic induction 

9.16·10 -6 T.m. Relative deviation 9 % from initial slony the path marked in Fig. 2 χ 1 = -9·10 -4 , 

estimation was caused due to numerical error. 

χ s = 3·10 -3 , χ 2 = 0 

79

The method was experimentally verified with clay specimen on 200 MHz 

MR tomograph in ISI AS Brno. Reference substance giving the MR signal was water 

(χ H2O = -9.04·10 -6 ) filled into cube vessel. The field echo method with echotime T E = 5.56 ms 

[3] was used to acquire MR image with contrast corresponding to the magnetic field 

inhomogeneity. Experiment was treated one time with clay specimen of 7 mm thickness 

(Fig. 3A) and next only with water reference (Fig. 3B); basic field has magnetic induction 

B 0 = 4.7 T. Position of the specimen is depicted in Fig. 3A. Obtained image with phasecontrast 

was processed in Matlab. After de-noising by the limitation of signal the spatial 

deformation evoked by magnetic field inhomogeneity in specimen vicinity was eliminated. 

Acquired phase images were consequently subtracted to eliminate inhomogeneity of the basic 

field - Fig. 3C. By properly selected slice of this image we have the curve of phase change ∆Θ 

of the water MR signal in the specimen vicinity, Fig. 3D. For the used MR technique the 

phase change ∆Θ = 2π rad response to magnetic induction change ∆Θ , where γ is 

B 0 

∆ = 

γ ⋅T E 

gyromagnetic ratio of water. In this way we can identify the course of magnetic induction 

change in water nearby the clay specimen. 

Fig. 3. Images obtain from MR experiment with 7 mm thick clay specimen placed 

on water filled vessel 40×35 mm. Processed in Matlab. 

From known thickness x 0 of the specimen and measured area ∆B 0 from, the 

susceptibility of clay specimen was finally calculated 

B B − ∆B0 ⋅dx 

-6 

S 

− 

0 ∫ 2. 656⋅10 

χS 

= = = = 8.07 ⋅10 

-3 

B B ⋅∆x 

4.7 ⋅7 ⋅10 

0 0 

Conclusion: 

The method designed for magnetic susceptibility measurement based on MRI 

tomography techniques is simple and enables to determine the magnetic susceptibility of such 

materials, which give no MR signal. After an optimization this method can be used for 

investigation of the materials used in MR tomography as well as of biological tissues 

affecting quality of MR images. The paper was prepared within the framework of 

N°IAA2065201 project of the Grant Agency of the Academy of Sciences of the Czech 

Republic and with the support of the grant agency of Czech Republic 103/03/Z048. 

[1] Starčuk jr., Z.: NMR-compatibility of the dental alloy, ISI AS CR, Brno 2003 

[2] Zeman, V.: Magnetic susceptibility measurement by NMR. Tesla Brno, 1981 

[3] Blumlich B.: NMR Imaging of Materials. Clarenton Press, Oxford, 2000 

-5 

. 

80

A NOVEL SOURCE OF MAGNETIC FIELD 

FOR IMAGING LASER-POLARIZED 3 HE 

Katarzyna Suchanek, Mateusz Suchanek, Katarzyna Cieślar, Tadeusz Pałasz, 

Zbigniew Olejniczak*, Tomasz Dohnalik 

Marian Smoluchowski Institute of Physics, Jagiellonian University, Kraków, Poland; 

*Henryk Niewodniczański Institute of Nuclear Physics, Kraków, Poland 

The development of the system for NMR imaging of the laser-polarized helium-3 is 

presented. The source of magnetic field is a permanent Nd-Fe-B magnet characterized by high 

saturation induction. Since the magnetic field exhibits a large temperature coefficient, the 

magnet is placed in an air-conditioned Faraday cage, in which the temperature is stabilized 

with accuracy of +/- 0.1 °C. 

A 10 cm diameter sphere is a suitable working volume for imaging small animal lungs. 

A specially designed positioning device was used to precisely measure the magnetic field map 

on a sphere of radius 5 cm. The initial inhomogeneity of the magnetic field was 361 ppm 

within the sphere. In order to obtain good quality images, it was necessary to reduce this inhomogeneity 

by an order of magnitude. The method of improving the homogeneity relies on 

placing precisely distributed pieces of steel on the poles of the magnet (passive shimming).Using 

this method a homogeneity of 56 ppm within the sphere was achieved. 

A system of actively shielded gradient coils mounted between the poles is used for 

spatial encoding of the NMR signal. The linearity and efficiency of the gradient coils were 

tested. In addition, the magnitude and the time constant of the eddy currents generated in the 

magnet poles was estimated. 

81

THE MECHANISM OF THE DRUGS BINDING TO THE PROTEIN 

IN COMBINATION THERAPY 

1 Wiesław W. Sułkowski, 2 Barbara Bojko, 2 Anna Sułkowska, 2 Joanna Równicka 

1 University of Silesia, Department of Environmental Chemistry and Technology, Szkolna 9, 

40-006 Katowice, Poland; 2 Medical University of Silesia, Department of Physical Pharmacy, 

Jagiellońska 4, 41-200 Sosnowiec, Poland 

The co-admnistration of cytarabine (ara-C) and 5-fluorouracil (5FU) in combination 

aticancer therapy enhances the therapeutical effect of 5FU. It can cause also increase risk of 

appearance of side effects of both drugs. 

The aim of this study was to investigate the mechanism of interaction between 5FU and ara-C 

in the binding with bovine serum albumin (BSA) using NMR method. 

The 1 HNMR spectra of pure cytarabine and ara-C in presence of BSA and/or 5FU were 

compared. We found that chemical shifts of all aromatic protons of both drugs in presence of 

BSA were changed. Moreover, presence of the second drug involves changes in chemical 

shifts of the first one. Neither BSA nor 5FU did not change the position of the signals of the 

sugar ring of cytarabine. 

Similar results were observed in 13 CNMR spectra. The chemical shift of aromatic signals of 

5FU or ara-C were changed in presence of BSA and second drug. The position of those 

resonance lines was shifted upfield or downfield. The changes in chemical shift of aromatic 

signals of ara-C and 5FU can be a result of π-π interactions between pyrimidine ring of the 

drugs and the aromatic ring of aminoacides present in BSA. 

The chemical shifts of carbon signals of ara-C sugar ring didn’t change in presence of 5FU 

and BSA. 

The alteration of environment of aromatic protons and carbons of ara-C and 5FU suggests a 

participation of pyrimidine ring of both drugs in forming a drug-albumin complex. 

The sugar ring of ara-C probably does not take a part in the forming a complex with serum 

albumin. 

The competition between 5-fluorouracil and cytarabine observed in the binding of drugs to 

transporting protein (albumin) can be one of the mechanisms causing the presence of the side 

effect of those drugs. 

82

DETERMINATION OF AMINO ACIDS IN BODY FLUIDS WITH THE 

US E OF 19 F NMR SPECTROSCOPY 

Przemysław Szczeciński, Dorota Bartusik 

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

00-664 Warsaw, Poland 

It is commonly known that amino acids play a very important role in living organisms. 

They are reactants as well as products of many biological processes and therefore their 

qualitative and quantitative determination in body fluids, e.g. urine or blood, is essential for 

1 13 

the diagnosis of numerous metabolic diseases. The usefulness of the H and C NMR 

spectroscopy for such determinations is well documented. However, body fluids, being multicomponent 

mixtures, give complex spectra, in which identification of the interesting signals 

may be often difficult. To avoid this problem the method of determination of amino acids 

with the use of 19 F NMR spectroscopy has been developed. Investigated compounds are 

transformed into fluoro derivatives (see Scheme 1) and then identified on the basis of their 19 F 

chemical shifts. 

HOOC CH R 

Cl 

N O 2 

NH 

CF H 3 

2 O 

NaHCO 3 O N 

CF 

+ R CH COOH 2 3 

EtOH 

NO 2 

NH 2 

Scheme1 

NO 2 

Because marker used is insoluble in water the reaction has to be performed in water-ethanol 

mixture. It was found that the presence of alcohol in measured sample noticeably influenced 

the fluorine signal positions. Therefore, to obtain reproducible results, ethanol has to be 

effectively removed prior to resonance measurement. It undesirably complicates the 

procedure of sample preparation. To overcome this problem we decided to use a marker 

soluble in water. We assumed that 4-chloro-3-nitro-5-trifluoromethylbenzenesufonic acid 

should fulfil this demand. Its synthesis is shown in Scheme 2. 

Cl 

Cl 

Cl 

CF 

3 

65 % 

fuming 

H 2 

SO 4 

CF 3 

fuming 

HNO 3 

O 

2 

N 

CF 3 

Scheme 2 

SO 3 

H 

30 % 

fuming 

H SO 

2 4 

SO 3 

H 

83

To obtain model derivatives, prepared compound was used in the nucleophilic 

substitution reaction with several amino acids. It appeared that the course of the reaction has 

been strongly affected by the conditions applied (Scheme 3) leading to N-phenyl substituted 

amino acids or to benzoimidazole derivarives. It was found that in both cases the differences 

in fluorine chemical shifts for different amino acids are large enough to use new marker in 

discussed investigations (Table 1). 

O N 

2 

Cl 

CF 

3 

+ 

R 

CH 

COOH 

H 2 O 

NaHCO 

3 

HOOC 

O 2 

N 

CH 

NH 

R 

CF 

3 

SO 3 

Na 

NH 

2 

SO 3 

Na 

(1) 

Cl 

O N 

CF 2 3 

+ R CH COOH 

NH 

SO Na 

2 

3 

H 2 

O 

NaHCO 3 

NaO S 

3 

CF 3 

N 

N 

ONa 

R 

(2) 

Scheme 3 

Aminoacid Ala Gab Ser Phe Glh Tyr Thr Ile Leu Val 

1 derivs. 17.05 17.15 17.56 17.72 17.79 17.84 17.86 17.78 17.97 18.25 

2 derivs. 16.39 16.64 16.54 16.51 16.36 16.53 16.57 16.50 16.59 16.42 

Table 1 

84

MOLECULAR DYNAMICS OF TERT-BUTYL CHLORIDE CONFINED 

TO CPG (7.4 NM) 

Lidia Szutkowska, Barbara Peplińska, Stefan Jurga 

Institute of Physics, A. Mickiewicz University, ul. Umultowska 85, 61-614 Poznań, Poland 

The paper reports the proton and deuteron NMR study of molecular dynamics of tertbutyl 

chloride confined in CPG with pore diameter of 7.4 nm here denoted as TBCC. 

The 1 H and 2 H NMR lineshapes and spin-lattice relaxation times were measured in 

the temperature range 70 K ≤ T ≤ 292 K, thus covering all the phases which occur in the bulk 

state of TBC. 

The phase transition from liquid to solid phase I of the TBCC is invisible in 

temperature dependences of 1 H and 2 H spin-lattice relaxation times. The temperatures of the 

other phase transitions of TBCC are depressed, by about 23 K in comparison with bulk TBC. 

The values of 1 H, 2 H relaxation times T 1 are reduced indicating that the confinement strongly 

restricts molecular reorientation. 

Two exponential magnetization recoveries are observed in the temperature range 

corresponding to the solid phase II and III. The dynamical behaviour of the TBCC can be 

explained by assuming that the guest molecules form two distinct phases: the surface-affected 

phase, composed of molecules located at the pore surface, and the bulk-like phase located at 

the center of the pores. The relative amount of the surface-affected phase is significantly 

larger than the bulk-like phase compared to the results obtained for larger pore diameters of 

CPG [1- 3]. 

In phase III, the temperature dependences of 1 H and 2 H spin-lattice relaxation times of 

the bulk-like component of TBCC exhibit higher, shallower and wider minimum. This is 

attributed to the coexistence of subphases with different correlation times characterizing 

rotation of the tert-butyl group, as the consequence of confinement. The calculated activation 

energies and preexponential factors for C ’ 3 rotation in two dynamically different states of 

bulk-like phase obtained from both 1 H and 2 H T 1 data are given in Table I. 

The fact that the energies of the tert-butyl reorientation are much lower than in bulk 

TBC and lower than for TBCC with larger pore diameters [2,3], may result from a decrease of 

the intermolecular interactions in the bulk liquid phase of TBCC. This effect can be explained 

by the surface to volume ratio, increasing with the reduction of the pore diameters, where a 

large fraction of confining molecules experiences direct interaction with pore walls. The 

slowing down of the motion can be also due to geometrical restrictions and depends on the 

degree of reductio n of the pore siz e. 

’ 

Table 1. Activation energies and the preexponential factors of the C 3 

confined to 7.4 nm pore diameters CPG obtained from 1 H, 2 H T 1 . 

motion of bulk-like phase of TBC 

Subphase I 

Subphase II 

TBC in bulk [2] 

1 H T 1 

2 H T 1 

E a (kJ/mol) 4.2 4.6 

τ 0 (s) 1.4 E-11 2.2E-11 

E a (kJ/mol) 4.2 4.6 

τ 0 (s) 1E-10 1E-10 

E a (kJ/mol) 15.5 

τ 0 (s) 1E-14 

1. L. Wasyluk, B. Peplinska, J. Klinowski, and S. Jurga, Phys. Chem. Chem. Phys. 4, 2392 (2002). 

2. L. Wasyluk, B. Peplinska, S. Jurga, Solid State NMR 25, Iss.1-3, 2004 (in press) 

3. L. Wasyluk, B. Peplinska, S. Jurga, Abstracts, XX International Seminar RAMIS 2003, P-68 

85

NMR CHEMICAL PROTON-EXCHANGE STUDIES IN DECYl – 

AND DODECYLAMMONIUM CHLORIDE SURFACTANT-WATER 

SYSTEMS 

Kosma Szutkowski, Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, Umultowska 85, PL-61614 Poznań, 

Poland 

This paper reports NMR relaxation study of interfacial properties of water 

molecules in lyotropic decylammonium chloride and dodecylammonium chloride in the 

solutions ranging from 18% to 63% wt. by means of the transverse spin-spin relaxation time 

T 2 relaxometry [1,2]. N-alkylammonium chlorides salts in the presence of water make a 

number of lyotropic phase transitions: micellar (ISO-isotropic), nematic (NEM) lamellar, 

micellar (HEX-hexagonal)[3-5]. Water properties were directly monitored at the presence of 

hydrated surfactant micelles and bilayers. We have calculated the temperature dependence of 

the exchange rate C b of the proton chemical exchange (Fig. 1) from the proton transverse 

relaxation T 2 data and measured T 2 dependence on the FT-CPMG π / 2 -π pulse delay τ cp 

(Fig. 2). 

Obtained activation energies for exchange rates C b are close to the hydration 

energy of water molecules at the interface. In turn dispersion of the relaxation time is 

characteristic for the chemical exchange phenomena. 

Fig 1. Proton-exchange rate C b versus 

temperature for DDACl with water 33% wt. 

Fig 2. Relaxation rate 1/T 2 of water molecules vs. 

Carr-Purcell pulse spacing τ in FT-CPMG 

cp 

Literature 

1. D. E. Woessner, Journal of Chemical Physics 39, 2783-& (1963). 

2. G. Paradossi, Cavalieri F., and Crescenzi V., Carbohydrate Research 300, 77 . 

3. J. D. Gault, M. A. Leite, M. R. Rizzatti, and H. Gallardo, Journal of Colloid and Interface 

Science 122, 587 (1988). 

4. M. R. Rizzatti and J. D. Gault, Journal of Colloid and Interface Science 110, 258 (1986). 

5. K. Szutkowski , J. Klinowski, and S. Jurga, Solid State NMR 22, 394 (2002). 

86

MR MICROSCOPY IN COMPARISON OF YOUNG AND OLD TOOTH 

STRUCTURE 

Marta Tanasiewicz*, Władysław P. Węglarz ** , Edyta Machaj**, Tomasz Kupka * , 

Andrzej Jasiński**. 

* Department of Preclinical Dentistry, Silesian Medical Academy, Zabrze, Poland; 

**Department of Nuclear Radiospectroscopy, H. Niewodniczański Institute of Nuclear 

Physics Polish Academy of Sciences, Kraków, Poland 

MR Microscopy may be used for quantitative analysis of root canal shape and volume 

[1-6]. MR images using 4.7 T research MR system (Resonance Instruments Ltd.) were made 

to compare shape, thick and density of first upper premolar’s walls structure of young (before 

16 years old) and older (over 60 years old) patients. Prior to the experiment, the samples 

were placed in H 2 O bath and degassed to minimize magnetic susceptibility artifacts. 

A multislice Spin Echo based pulse sequence was used to produce images 128x128 pixels, 

with in plane resolution about 200 µm and slice thickness of 1.2 mm. The echo time TE was 

28 ms and repetition time 2 s. The transverse slices through teeth were analysed using I DL 

5.5 (Research Systems) based software. The structure (thick, density) of the tooth from young 

and older patients were compared. Results indicate the possibility of use MRM as the original 

method of visualization and tooth structure registration. 

[1] M. Tanasiewicz, W.P. Węglarz, T. Kupka, Z. Sułek, M. Gibas, A. Jasiński, Stomatologia 

Współczesna,V, 2002. 

[2] W.P. Węglarz, T. Kupka, M. Tanasiewicz, T. Banasik, Z. Sułek, M. Gibas, A. Jasiński. 

Zastosowanie mikroskopii MR do określenia kształtu i objętości kanalów korzeniowych zębów w 

warunkach in vitro,Valetudinaria, Postępy Medycyny Klinicznej i Wojskowej. IV Zjazd Polskiego 

Medycznego Towarzystwa Rezonansu Magnetycznego, Bydgoszcz 2002. 

[3] M. Tanasiewicz, W.P. Węglarz, T. Kupka, Z. Sułek, M. Gibas, A. Jasiński, Nieimpresyjne 

odwzorowanie jam zębowych z wykorzystaniem mikroskopii MR, XXXV Ogólnopolskie 

Seminarium na Temat Magnetycznego Rezonansu Jądrowego i Jego Zastosowań, Kraków 2002. 

[4] M. Tanasiewicz -Mikroskopia rezonansu magnetycznego w diagnostyce endodontycznej. 

Możliwości nieimpresyjnego obrazowania jam zębowych dla potrzeb dentystyki odtwórczej, 

Magazyn Stomatologiczny, 2003, XIII, 3, 64-68. 

[5] M. Tanasiewicz, T.W. Kupka, W.P. Węglarz, A. Jasiński, M. Gibas, 3D SE geometry imaging of 

tooth surface. An in vitro study, Journal of Dental Research 2003, vol. 82, special issue B, 3047. 

[6] W.P. Węglarz, T. Kupka, M. Tanasiewicz, T. Banasik, Z. Sułek, M. Gibas, A. Jasiński, 3D MR 

Microscopy of dental cavities. An in vitro study, Solid State NMR, accepted 2003. 

87

STUDIES OF POLY(ASPARTIC ACID) STRUCTURE AND ITS 

DERIVATIVES USING 1 H NMR SPECTROSCOPY 

Elżbieta Tylek, Jolanta Polaczek, Jan Pielichowski 

Department of Chemistry and Technology oh Polymers Technical University, Kraków, Poland 

Poly(aspartic acid) ( here: PAA) belongs to biodegradable polymers, which could be have a 

lineal or cyclic structure (figure 1). Poli(aspartates) have different proprieties depending on 

th eir chemical construction [1,2]. 

O 

N 

NH 

CH 

CH 2 

CO NH CH 

CO 

O 

q 

COOH 

n 

CH 2 

m 

q ≥ n+m 

COOH 

Figure 1. Structure poly(aspartic acid) 

The structure of poly(aspartic acid) and its derivatives can be characterized using some 

1 

nuclear magnetic resonance methods; especially H NMR and 13 C NMR spectroscopy. The 

main chain of PAA include α - and β - peptide bonds, where the ratio α:β peptide units can be 

determined by NMR spectroscopy; particularly important are signals methane in 1 H NMR 

and signals methylene in 13 C NMR. Application 1 H NMR spectroscopy can observe local 

branches and opening peptide ring in PAA structure. Using 13 C NMR spectroscopy in PAA 

and its derivatives to make possible can be determined local branches, characteristic 

conformation and irregular structure. 

Spectrum 1 H NMR of poly(succinimide) characterized signals of the methine proton in 

5,3 ppm and smaller signal at 4,6 ppm succinimide units. Two very board resonance are 

observed at 12,48 ppm and 13,22 ppm. The broad peaks between 8,0 and 9,5 ppm are 

consistent with amide protons of branches or ring-open sites [3]. 

Process hydrolysis of the polymerization products leads to poly(aspartates) containing α- and 

β-as partic acid units. This can be caused by attack of nucleophilic factor on bond C-N 

in ring of succinimide. Possible is opening of ring succinoimide in position α- and β- what 

opening in position β- is more prefer. 

In result of hydrolysis can be obtained salts of poly(aspartic acid). On figure 2 shows 

characteristic spectrum 1 H NMR of sodium polyaspartate in D 2 O. Signals of protons methine 

(-CH-) and methylene (-CH 2 -) of the succinimide unit disappeard and appear signals of 

protons methine at 4,7 and 4,2 ppm and methylene at 2.8, 2.7 and 2.4 ppm. Two different 

chemical shifts have shown different openings of ring succinimide. The α/β ratio can be 

determined by nuclear magnetic resonance spectroscopy and carries out 26 / 74 [4]. 

88

NH CH CH 2 NH CH CO 

COONa 

n 

CH 2 

m 

COONa 

References: 

1. E. Dziki, J. Pielichowski: “Polimery”, (2003), 48, nr 1 

2. E. Dziki, J. Pielichowski: „Inżynieria biomateriałów”, (2003), nr 28 

3. E. Dziki, J. Pielichowski: „Inżynieria biomateriałów”, (2003), 27, 6 

4.K.Matsubara, T. Nakato: „Macromolecules”, (1998), 31, 1466-1472 

89

SOLID-STATE NMR INVESTIGATION 

OF LOCAL CHAIN DYNAMICS IN 

POLYISOBUTYLENE/POLYPROPYLENE-CO-BUTENE BLENDS 

Marcin Wachowicz 1,2 , Justyna E. Wolak 2 , Stefan Jurga 1 , Jeffery L. White 2 

1 Institute of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland; 

2 Department of Chemistry, Campus Box 8204, North Carolina State University, Raleigh, NC 

27695, United States of America 

Changes in local dynamics of polyisobutylene (PIB) upon blending with different poly- 

(ethylene-co-1-butene) copolymers (PEB) were investigated by solid-state 2 H- and 129 Xe- 

The pure PIB and 50/50 mixtures of PIB and PEB, where the butane 

NMR methods. 

monomer concentration in PEB copolymer was varied (23 or 66 wt %), were studied. The 

blends were prepared by dissolution in toluene, solvent evaporation and vacuum drying [1]. 

The quadrupolar echo 2 H-NMR spectra for pure perdeuterated PIB (Fig. 1) and for two 

PIB/PEB blends were acquired in the temperature range from 210 to 294 K. In the blend 

samples only the PIB was perdeuterated. The line shapes contained the contribution from 

methyl and methylene groups and at lower temperatures they were clearly distinguished due 

to the different quadrupolar splittings. The deuteron line shape analysis demonstrated that the 

molecular dynamics of PIB molecules (the conformational exchange along PIB backbone) 

have the same character in all the samples investigated. However, the rate of molecular 

dynamics of PIB chains is increased in the blends in comparison to the pure PIB as evidenced 

by the shift of a temperature at which coalescence of the deuteron spectra occurs. The 

difference between the coalescence temperatures of pure PIB and the blend containing the 

highest butene monomer (PIB/PEB-66) content was ~10 K. 

The 129 Xe-NMR experiments involved the investigation of Xe gas absorbed by the 

polymer. The xenon chemical shift is sensitive to subtle changes in the electronic environment 

and can be successfully utilized to probe the homogeneity of the blend. For the PIB/PEB-23 

polymer two peaks were observed (Fig. 2b) corresponding to the chemical shifts of pure 

polymers indicating phase separation. In contrast, PIB/PEB-66 blend was found to be 

homogeneously mixed, as indicated by a single peak with an intermediate chemical 

shift (Fig.2a) 

2 

Fig. 1. H-NMR spectra of pure 

perdeuterated PIB. 

129 

Fig.2. Xe-NMR spectra of Xe gas absorbed in 

(a) PIB/PEB-66 blend 

and in (b) PIB/PEB-23 blend. 

[1] Wolak J., Jia X., Gracz H., Stejskal E.O., White J.L., Wachowicz M., Jurga S., 

Macromolecules 36(13), 4844-4850 

90

35 Cl-NQR STUDY OF MOLECULAR DYNAMICS 

OF TETRACHLOROPHTHALIMIDE 

AND N-PHENYLTETRACHLOROPHTHALIMIDE 

A. Walczak 1 , R. Żaguń 1 , J. Kasprzak 1 , B. Brycki 2 , B. Nogaj 1 

1 Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, 

Poland; 2 Department of Chemistry, Adam Mickiewicz University,Grunwaldzka 6, 


Introduction 

The information on molecular dynamics can be obtained from the temperature 

dependencies of the nuclear quadrupole resonance (NQR) frequency. 

In this work the NQR method was applied to study molecular dynamics of 

tetrachlorophthalimide (C 6 HCl 4 NO 2 ) and N-phenyltetrachlophthalimide (C 12 H 9 Cl 4 NO 2 ). 

These compounds show biological activity and are used as bactericidal, antiviral and 

fungicidal agents as well as inhibitors of different enzymes, e.g. α-glucosidase, active in the 

last stages of digestion of carbohydrates [1]. 

Experimental 

The compounds studied were synthesized at the Faculty of Chemistry, A. Mickiewicz 

University, Poznań. 35 Cl-NQR measurements were performed on a lab-made pulse Fourier 

transform NQR spectrometer operating in the frequency range 20-40 MHz. 

Temperature measurements of the 35 Cl-NQR frequency were performed in the range 

176.4 - 341.9 K for tetrachlorophthalimide and in the range 156.5 - 324.5 K for N-phenyltetrachlorophthalimide. 


35 

In the entire temperature ranges studied, for both compounds the Cl-NQR spectra 

revealed four lines, which indicates the presence of crystallographically inequivalent chlorine 

atoms. The NQR frequency ν Q decreases with increasing temperature (Figs.1 and 2). Using 

the least-squares approximation the theoretical functions ν Q (T) [2] were fitted to the 

experimental dependencies. 

38.2 

38.0 

ν Q 

[MHz] 

37.8 

37.6 

37.4 

Cl 

Cl 

Cl 

Cl 

37.2 

50 100 150 200 

ν 4 

O 

N H 

ν 3 

ν 2 

O 

ν 1 

T [K] 

250 300 350 400 

35 

Fig.1. Temperature dependence of Cl-NQR frequency in tetrachlorophthalimide. 

Solid line - fit with the Brown function. 

91

38.2 

38.0 

Hz] 

ν Q 

[M 

37.8 

37.6 

37.4 

Cl 

Cl 

Cl 

Cl 

O 

O 

N 

2 

ν 1 

37.2 

50 100 150 200 250 300 350 400 

T [K] 

ν 4 

ν 3 

ν 

35 

Fig.2. Temperature dependence of Cl-NQR frequency in N-phenyltetrachlorophthalimide. 

Solid line - fit with the Brown function. 

Analysis of the standard deviations and correlation coefficients has shown that the 

experimental dependencies are the best approximated by the functions derived from the 

Brown theory [3], assuming the negligible effect of thermal expansion of the crystal on the 

resonance frequency and taking into regard anharmonicity of the crystal lattice vibrations. 

The differences in the slopes of the temperature dependencies of the 35 Cl-NQR 

frequencies permitted assignment of individual lines to particular chlorine atoms in the 

molecules studied (Figs.1 and 2). In tetrachlorophthalimide and in N-phenyltetrachlorophtalimide, 

the coupling of strongly polarised oxygen atoms with the nearest chlorine atoms 

hinders the atom librations, which is manifested as a smaller averaging of the electric field 

gradient. This effect is observed for the lines ν 3 and ν 4 on the plots of ν Q (T). 

References: 

1. S.Sou, H.Takahashi, R.Yamasaki, H.Kagechika, Y.Endo, Y.Hashimoto, Chem.Pharm.Bull. 49, 791 

(2001). 

2. B.Nogaj, Bull.Chem.Soc.Jpn 61, 2615 (1988). 

3. R.J.C.Brown, J.Chem.Phys. 32, 116 (1960). 

92

35 Cl-NQR STUDY OF THE SUBSTITUENT EFFECT 

ON THE ELECTRONIC STRUCTURE 

OF TETRACHLOROPHTHALIMIDE DERIVATIVES 

A. Walczak 1 , A. Mielcarek 1 , B. Brycki 2 , B. Nogaj 1 

1 Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, 

Poland; 2 Department of Chemistry, Adam Mickiewicz University,Grunwaldzka 6, 60-780 

Poznań, Poland 

Introduction 

Using the 35 Cl-NQR method the effect of the following substituents Li, Na, K, Cs on 

the electron density distribution in tetrachlorophthalmide derivatives has been studied. The 

compounds are interesting because of their biological activity and bactericidal, antiviral and 

fungicidal properties. 

Experimental 

The compounds studied were synthesized at the Faculty of Chemistry, A. Mickiewicz 

Univers ity, Poznań. All measurements were performed on a pulse Fourier transform NQR 

35 

spectrometer type NQS-300 (0. 5-300 MHz) from MBC Electronics (Poland). Cl-NQR 

frequencies were measured at 77K. 


The spectra of all tetrachlorophthalimide salts revealed four lines, which proves the 

crystalline inequivalence of chlorine atoms in these compounds. The 35 Cl-NQR frequencies 

and line widths obtained at the liquid nitrogen temperature (77K) are collected in Table 1. 

With increasing ionic radius R of the substituent M the mean resonance frequency ν Q 

decreases, which means that the electron density on the chlorine atoms increases (Fig.1). 

ν [MHz] 

Q 

46 

44 

42 

Cl O 

Cl 

N M 

Cl 

Cl 

O 

40 

Li 

38 

K 

Na 

Cs 

36 

0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 

ν Q 

[MHz 

* 

2.0 

] 

40 

39 

38 

37 

Li 

Na 

Cl(3) 

Cl(2) 

Cl(4) 

Cs 

36 

0.6 0.8 1.0 1.2 1.4 1.6 1.8 

K 

O 

Cl (1) O 

N 

M 

Fig.1. The mean 35 Cl-NQR frequency versus the Fig.2. The mean 35 Cl-NQR frequency of chlorine 

ionic radius of the substituent M. 

atom pairs: Cl (1) and Cl (4); Cl(2) and Cl(3) 

Solid line - the fit by function (1). versus the ionic radius of the substituent M. 

93

Table 1. 35 Cl – NQR results for tetrachlorophthalmide salts at 77K (ν Q – 35 Cl-NQR frequency, δν Q – full width 

at half-intensity). 

Lp. COMPOUND STRUCTURAL FORMULA ν Q [MHz] δν Q [kHz] 

1 

2 

3 

4 

Lithium salt of 

tetrachlorophthalimide 

Sodium salt of 


Potassium salt of 


Cesium salt of 


Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

Cl 

O 

N 

O 

O 

N 

O 

O 

N 

O 

O 

N 

O 

38.483 

38.748 

Li 

39.484 

39.556 

K 

Cs 

19 

31 

12 

18 

37.412 19 

37.547 

31 

Na 

37.582 

10 

37.613 

11 

36.928 

37.205 

38.077 

38.102 

14 

14 

24 

22 

35.701 15 

36.932 

10 

37.021 

24 

38.504 18 

On the basis of [1,2] the experimental dependence ν Q 

(R) was approximated by a 

theoretical function of the form: 

⎛ R ⎞ 

ν Q = a + b exp⎜ 

− ⎟ 

(1) 

⎝ c ⎠ 

where a,b,c – constants; R –the ionic radius of the substituent. 

The coupling of the strongly polar oxygen atoms with the chlorine atoms Cl(1) and 

Cl(4) leads to a decrease in the electron density on the nuclei of these atoms, so to an increase 

in the observed 35 Cl-NQR frequencies (Fig.2). 

The correlation of the data obtained in this study with the bactericidal activity of the 

compounds studied could help search for the derivatives of tetrachlorophtalimide showing 

higher effectiveness. 

References: 

1. E.B.Bryll, J. Chem. Phys., 61, 424 (1974). 

2. A.Walczak, Struktura elektronowa i dynamika molekularna chloranów ołowiu i cezu, badane za pomocą 

spektroskopii jądrowego rezonansu kwadrupolowego, praca magisterska, Wydział Fizyki UAM (2000). 

94

13 C AND 1 H NUCLEAR MAGNETIC SHIELDING AND SPIN-SPIN 

COUPLING CONSTANTS OF 1,2- 13 C-ENRICHED ETHYLENE 

IN THE GAS PHASE 

Marcin Wilczek, Karol Jackowski 


ul. Pasteura 1, 02-093 Warsaw, Poland; wilczek@chem.uw.edu.pl 

In this study we present gas phase measurements of the 1 H and 13 C NMR chemical s hifts and 

spin-spin coupling constants for 1,2- 13 C-ethylene ( 13 C 2 H 4 ). This isotopomer of ethylene gives 

an AA´XX´X´´X´´´ NMR spectrum of which the XX´X´´X´´´ and AA´ parts can be separately 

1 13 

monitored by the H and C NMR methods. The latter spectra are rather complex and in our 

laboratory they have been analyzed using the PERCH program [1]. It has enabled us to 

measure all the coupling constants of 1,2- 13 C-ethylene (i.e. 1 J CH , 

1 J CH, 2 J HH , 3 CC , 2 J J HH(cis) and 

3 

J HH (tran s) ) in the 1 H and 13 C NMR spectra . The 13 C 2 H 4 compound has been investigated as the 

pure gas and as the solute in gaseous solutions where xenon and carbon dioxide have been 

used as gaseous solvents. We have observed the 1 H and 13 C NMR spectra of 13 C 2 H4 as 

functions of density and after extrapolation to zero density it was possible to determine all the 

shielding and spin-spin coupling constants independent of density for pure 1,2- 13 C-ethylene. 

T he values measured in gaseous solvents were additionally corrected for ethylene-ethylene 

intermolecular interactions and this way we could also determine 

the reliable NMR 

parameters for an isolated 13 C 2 H 4 molecule. It was especially important for the 1 J CC spin-spin 

coupling and for both the 1 H and 13 C shielding constants which were distinctly dependent on 

density. The other spin-spin couplings ( 1 J CH , 2 J CH , 2 J HH , 3 J HH(cis) and 3 J HH(trans) ) in a 1,2- 13 C- 

ethylene molecule were almost independent of density in the studied systems. This result is 

consistent with our previous investigations performed for 1,2- 13 C-acetylene [2] where the 

density dependence was also found only for the spin-spin coupling between carbon nuclei, 

1 J CC . 

References: 

[1] R. Laatikainen, M. Niemitz, U. Weber, J. Sundelin, T. Hassinen, J. Vepsäläinen, J. Magn. 

Reson. A, 120 (1996) 1. 

[2] K. Jackowski, M. Wilczek, M. Pecul, J. Sadlej, J. Phys. Chem. A, 104 (2000) 5955. 

95

THE GLASS TRANSITION TIME SCALE AND CONFIGURATIONAL 

ENTROPY IN POLYMERS: AN EXPERIMENTAL MOLECULAR 

VIEW 

J. E. Wolak, X. Jia, Jeffery L. White 

Department of Chemistry, North Carolina State University, Campus Box 8204, Raleigh, 

North Carolina 27695-8204 

We report direct experimental observation of local conformational dynamics in a 

polymer chain at the calorimetric glass transition temperature T g . Variable-temperature 2D 

solid-state exchange NMR, at natural abundance, reveals segmental dynamics in pure 

polyisobutylene (PIB) occurring on a timescale of several seconds over the T g range observed 

by DSC (203-208 K). To our knowledge, this is the first direct observation of molecular-level 

conformer interchange (trans-trans/trans-gauche/gauche-gauche) at the caloric glass 

transition temperature. Our results provide a chronologically accurate and pedagogically 

advantageous demonstration of molecular processes during a polymer phase transition, 

relative to traditional bulk mechanical and calorimetric techniques. 

tt tg/gt gg 

More importantly, we use a miscible blend, PIB with PEB66 (polyethylene-co-1- 

butene in which the concentration of 1-butene comonomer units is 66 weight %), to 

demonstrate 

a general strategy for quantitative evaluation of configurational entropy changes 

via combination of temperature-dependent 2D exchange NMR and Adams-Gibbs theory. Our 

results on the T g timescale are directly relevant to fundamental understanding of the T g 

length-scale, i.e., the dimension of cooperatively rearranging regions. 

96

13 C CPMAS NMR OF ANTHOCYANINS AND THEIR SUGAR 

DERIVATIVES 

Michał Wolniak 1 , * Jan Oszmiański 2 , Iwona Wawer 1 

1 Department of Physical Chemistry, Faculty of Pharmacy, Medical University of Warsaw, 

Banacha 1, 02-097 Warsaw, Poland; 2 Department of Fruit and Vegetable Processing, 

Agricultural University, Norwida 25, 50-375 Wrocław, Poland 

Anthocyanins are water-soluble pigments, widely distributed in the plant kingdom. They are 

second order metabolites and are responsible for a great variety of colors that occur in petals, 

fruits and vegetables [1]. Unfortunately, unlike flavonoids, anthocyanins received much less 

attention. It seemed interesting to examine the structure of anthocyanins in the solid state. 

The studied compounds: cyanidin chloride was purchased from Carl-Roth, cyanidin 

galactoside and cyanidin rutinoside were obtained from Agricultural University, Wrocław. 

NMR spectrometers: cross-polarization (CP) magic-angle spinning (MAS) solid-state 13 C 

NMR spectra were recorded on a Bruker AVANCE DSX-400 instrument at 100.61 MHz. The 

samples were spun at 8 kHz in 4mm ZrO 2 rotor. 13 C Chemical shifts were calibrated indirectly 

through the glycine CO signal recorded at 176.03ppm relative to TMS. 1 H and 13 C NMR 

spectra for the samples in acetone and methanol were recorded on a Bruker Avance 500 MHz 

spectrometer equipped with an inverse detection probe. The experiments were run using 

standard Bruker software. 

The structure of cyanidin and its derivatives: 

OH 

Cl 2' 

3' 

4' 

HO 

8 

O 1' 

7 9 2 

6' 

5' 

6 10 3 

5 4 

OH 

OR 

OH 

1.R=H cyanidin; 2.R=galactose, cyanidin galactoside; 3.R=rutinose, cyanidin rutinoside. 

13 C NMR spectra of 1-3 were recorded for solution and solid state. Unfortunately, the 

correct assignment of the signals is not an easy task. Positive charge at oxygen atom of 

flavylium cation and the presence of chloride anion makes the comparison of cyanidin 

chloride with similar compounds somewhat difficult. The signals in CPMAS spectra were 

assigned with the aid of solution data. Some signals were identified using dipolar dephasing 

and short contact time sequences. NMR shielding constants were calculated using GIAO 

DFT method, as an aid in the reliable spectra assignment. 

97

The computers & program: the calculations were run on Cray SV1ex-1-32 supercomputer 

using Gaussian 98 package. 

Satisfactory correlations between calculated shielding constants and experimental chemical 

shifts were found. The analyses of shielding tensors are in progress. 

Reference: 

1. Kong, Jin-Ming; Chia, Lian-Sai; Goh, Ngoh-Khang; Chia, Tet-Fatt; Brouillard, 

R. (2003). 

Analysis and biological activities of anthocyanins. Phytochemistry, 64, 923-933. 

98

INVESTIGATION OF TRANSESTERIFICATION 

IN POLY(ETHYLENE 2,6-NAPHTHALATE)/POLYCARBONATE 

COMPOSITE USING OFF-RESONANCE NMR AND DMTA 

TECHNIQUES 

A. Woźniak-Braszak a) , J. Jurga b) , K. Jurga a) , S. Jurga c) , M. Szostek b) 

a) High Pressure Physics Division, Institute of Physics, Adam Mickiewicz University, 

Umultowska 85, 61-614 Poznań, Poland, e-mail:abraszak@hoth.amu.edu.pl; b) Polymer 

Processing Division, Institute of Materials Technology, Poznan University of Technology, 

Piotrowo 3, 61-138 Poznań, Poland, e-mail:jan.jurga@put.poznan.pl; c) Macromolecular 

Physics Division, Institute of Physics, Adam Mickiewicz University, Umultowska 85, 


The work presents the study of molecular dynamics of the series of poly(ethhylene 

2,6-naphthalate)(PEN)/polycarbonate (PC) blends with a changing weight ratio of 

homopolymers by off-resonance NMR and dynamic-mechanical thermal analysis DMTA. 

These investigations concern new polymer materials based on polyesters and 

polycarbonates which have recently received wide commercial and industrial application. 

Two series of blends were prepared by injection moulded using the Engel machine ES, 

one without the compatibilizer and the second with the compatibilizer SMAC (Samarium 

acetylacetonate hydrate). 

The reaction taking place between the polyester and polycarbonate is known as 

transesterification. It provides novel materials with varying degree of randomness, 

composition and physical properties. The product obtained is a copolymer consisting of two 

polymers. The properties of this product are a mixture of the properties of the these two 

homopolymers. Transesterification affects the melting behaviour. It also has a strong impact 

on properties determined by kinetic process as the glass transition of the blend and the 

crystalization rate of PEN. The change of glass transition temperature and that of melting 

temperature of blends with changing weight of homopolymers were investigated. 

The influence of the compatibilizer on the course of transesterification was 

investigated as well. 

The molecular dynamics of the blends was studied by off-resonance NMR. The 

correlation times of the internal motions and the spectral density function amplitudes were 

estimated on the basis of the dispersion of the spin-lattice relaxation time off-resonance T 1ρ 

off 

. 

The dynamic-mechanical properties of the blends were investigated by dynamicmechanical 

thermal analysis DMTA. By this method, some important characteristics such as 

the glass transition temperatures and frequency-temperature characteristics, expressed in 

terms of master curves, were obtained. 

The comparative analysis of the DMTA and NMR results led to the explanation of the 

transesterification on the compatibility of PEN and PC. 

Acnowledgement 

This work was supported by KBN 7T0BE 004 21. 

References: 

1. J. Jurga, A. Woźniak-Braszak, Z. Fojud, K. Jurga, Proton Magnetic Relaxation in Polymer 

Materials, Solid State Nuclear Magnetic Resonance, in print. 

99

2. J. Jurga, A. Woźniak-Braszak, Z. Fojud and K. Jurga, Proton longitudinal NMR relaxation 

of pol(p-phenylene sulfide) in the laboratory and the rotating frames reference, Solid State 

Nuclear Magnetic Resonance, in print. 

3.W. J. Yoon, H. S. Myung, B. C. Kim, S. S. Im, Effect of shearing on crystallization 

behavior of poly(ethylene naphthalat e), Polymer 41 (2000) 4933-4942. 

4.H. 

J. Bang, J. K. Lee, K. H. Lee, Phase behavior and structure development in extruded 

poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blend, Journal of Polymer 

Science Part B: Polymer Physics V.38, Issue 20 (2000) 2625-2633. 

100

T 2 RELAXATION MAP OF ARTICULAR CARTILAGE IN DIFFERENT 

STAGE OF REGENERATION 

Tomasz Zalewski, Sławomir Kuśmia, Tomasz Trzeciak*, Jacek Kruczyński*, Stefan Jurga 

Institute of Physics, Adam Mickiewicz University, Umultowska 85, PL-61614, Poznań, 

Poland; * Department of Orthopaedics University of Medical Science in Poznań, Poland 

28 June 1956 no 135/147 

The high incidence of cartilage lesion, have necessitated the development of 

techniques for accurate treatment and monitoring of these lesions. Magnetic resonance 

imaging has made it possible to analyse the structure of cartilage more completely than 

arthroscopy. 

The aim of this study was a non-invasive assessment of regeneration of articular 

cartilage with scaffold (PLGA) properties. Rabbit specimens were studied only by MR 

microscopy. We obtained NMR images for all specimens. Maps of proton relaxation times T 2 

were obtained on cartilage-bone plug samples [1,2], cartilage-bone plug samples with scaffold 

and cartilage-bone plug sample with chondrocytes within scaffold. We used the observed 

changes of T 2 relaxations times to make the assessment of different methods of therapy. 

Articular cartilage with out scaffold 

T 2 map of articular cartilage 

[1] Y. Xia, T. Farquhar, N. Burton-Wurster, E. Ray, L. W. Jelinski, Diffusion and Relaxation Mapping of 

Cartilage-Bone Plugs and Excised Disks Using Microscopic Magnetic Resonance Imaging, Magn Reson Med 

31(1994): 273-282 

[2] Y. Xia, J.B. Moody, H. Alhadlaq, J. Hu, Imaging the Physical and Morphological Properties of a Multi-Zone 

Young Articular Cartilage at Microscopic Resolution, J Magn Reson Imaging 17 (2003):365-374 

101

SOLID STATE CONFORMATION AND ANTIOXIDANT PROPERTIES 

OF COUMARIN IN 

13 C CP MAS NMR, GIAO-CHF CALCULATIONS 

AND EPR STUDIES 

Agnieszka Zielińska*, Katarzyna Paradowska*, Teresa Żołek**, Iwona Wawer* 

*Department of Physical Chemistry , Faculty of Pharmacy, Medical University of Warsaw, 

Banacha 1, 02-097 Warsaw, Poland; **Department of Organic Chemistry, Faculty 

of Pharmacy, Medical University of Warsaw, Banacha 1, 02-097 Warsaw, Poland 

Abstract: 

Coumarins are widely distributed in nature and are found in all parts of plants. These 

compounds make up an important part of the human diet. 

13 C cross-polarization (CP) magic angle spinning (MAS) NMR spectra were recorded 

for a series of solid coumarins (bergapten, herniarin, xanthotoxin, esculetin, scopoletin). Ab 

initio calculations of shielding constants were performed with the use of GIAO-CHF method. 

The combined CP MAS NMR and theoretical approach was successful in characterizing 

solid-state conformationsof coumarins; a relationship σ (ppm)= -1.032·δ+205.28 (R 2 =0.9845) 

can be used to obtain structural information for coumarins, for which solid state NMR or 

crystal structure data are not available. 

We tested scavenging effect of series of coumarin by react with DPPH radical, using 

EPR spectroscopy. The results obtained by EPR show, that the presence of hydroxyl group is 

important for antioxidation activity of those compounds. 

Keywords: coumarins, 13 C CP MAS NMR, GIAO-CHF calculations, EPR 

R3 

R1 

R2 

O 

O 

O 

R4 

O 

O 

R1 R2 

herniarin H OCH 3 

esculetin OH OH 

scopoletin OCH 3 OH 

umbelliferone H OH 

R3 R4 

bergaptene OCH 3 H 

xanthotoxin H OCH 3 

Fig.1 Simple coumarins 

Fig .2 Furanocoumarin 

102

MICROTOMOGRAPHY STUDIES OF TABLETS 

M. Zielińska, R. Marszałek, E. Sieradzki 

Faculty of Pharmacy, The Medical University of Warsaw, Banacha 1, 

02-097 Warsaw, Poland 

Magnetic resonance imaging (microtomography) is a unique method for studying 

small objects. MRI has been widely used to monitor the diffusion of water into polymers. The 

cellulose derivates, which form gel and swell on contact with water, were of special interest, 

since these polymers are mainly used for controlled drug delivery[1,2]. 

Different behaviour on contact with water demonstrated copolymers of metacrylic 

acids, such as Eudragit RL. It is water insoluble and has pH-independent permeability. 

Therefore it is widely used in controlled release dosage forms which provide drug liberation 

on entire gastrointestinal passage where different pH- values exist. MRI allows to monitor 

water penetration into individual Eudragit RL matrix tablet. 

The measurements were performed on a Bruker AVANCE 400 MHz NMR wide bore 

spectrometer equipped with micro imaging probehead 20mm. The kinetic of water penetration 

was followed using gradient echo fast imaging (mgefiortho) sequence with repetition time 

100ms and echo time 2,5 ms. 

[1]. Melia C.D., Rajabi-Siahboomi A.R., Bowtell R.W.: Pharm. Sci. Technol. Today 1, 32-39 

(1998) 

[2]. Bowtell R., Sharp J.C., Peters A., Mansfield P., Rajabi-Siahboomi A.R., Davies M.C., 

Melia C.D.: Magn. Reson. Imaging 12, 361-364 (1994) 

103

CONFORMATION OF ARYLPIPERAZINES WITH LONG SIDE 

CHAIN – 2D NMR INVESTIGATIONS 

Marek Żylewski 1 , Marek Cegła 1 , Piotr Kowalski 2 , Teresa Kowalska 2 , Maria Paluchowska 3 , 

Ryszard Bugno 3 , Andrzej Bojarski 3 

1 

Departament of Organic Chemistry, Medical College, Jagiellonian University, 9 Medyczna 

2 

Str. , 30-688 Kraków, Poland; Institute of Organic Chemistry and Technology, Cracow 

University of Technology, 24 Warszawska Street, 31-155 Kraków, Poland; 3 Department 

of Medicinal Chemistry, Institute of Pharmacology of the Polish Academy of Sciences, 

12 Smętna Street, 31-343 Kraków, Poland 

NMR spectroscopy is one of the most powerful techniques for the conformational 

analysis of small organic compounds. Recently it was applied to study a flexible, complex 

arylpiperazine derivatives to determine how structural features influenced their conformation 

in solution. Arylpiperazines constitute functionally diversified class of 5-HT 1A serotonin 

receptor ligands, since among them, agonists, partial agonists or antagonists can be found. We 

hope that the results of extensive NMR investigations together with biological data may help 

in determination of bioactive conformation of studied compounds. 

Analysis of 2D NOESY spectra of various arylpiperazines containing flexible 4-carbon chain 

showed that small changes in the structure can express in large changes in conformation. Also 

protonation of the piperazine moiety and change of the solvent can lead to conformation's 

change. We have found that arylpiperazines can exist in solution in two different types of 

conformations. First is, the most expected for alkyl chain, maximally extended conformation, 

in which we can not observe any NOE interactions between protons of the two ending 

methylene groups. Further the plane of the aryl moiety connected to piperazine is twisted 

against the plane of piperazine ring. This situation is rather rare. The second, which is the 

most often observed, is characterised by strong NOE interactions between all protons in alkyl 

chain. Such set of signals indicate that these protons have to be much closer in space than it 

can be achieved in extended conformation. Therefore we have proposed “kinked” or folded 

conformation to explain spectral properties of these derivatives. 

R 2 N 

H 

H 

H 

H 

H 

H 

H 

H 

N 

CH 2 

CH 2 

N 

Ph 

Fig. Proposed folded conformation of investigated arylpiperazine derivatives. Arrows indicate 

important NOE interactions observed for this structure. 

This study was supported by the Polish State Committee for Scientific Research (KBN), 

Grant No 3-P05F-012-23. 

104

MAPPING OF THE BI-EXPONENTIAL DIFFUSION IN HUMAN 

SPINAL CORD 

T. Banasik, A. Jasiński, M. Hartel 1 , M. Konopka 1 , P. Pieniążek 1 , T. Skórka, W.P. Węglarz 

H. Niewodniczański Institute of Nuclear Physics, 31-342 Kraków, Poland; 1 Silesian 

Diagnostic Imaging Center Helimed, 40-752 Katowice, Poland 

Introduction: 

Diffusion weighted imag ing (DWI) is used routinely to evaluate neurological disorders. 

However, it has a limited role in the spinal cord due to technical difficulties. Recently, a 

number of studies reported successful diffusion imaging of the cervical spinal cord (CSC) 

using spin-echo (1), FSE (2), non-CPMG FSE (3), interleaved EPI (4,5), single-shot EPI (6) 

and single-shot axial EPI (7,8). Recent studies have shown that at high b-values diffusion is 

non-monoexponential in the brain (9) and in the animal spinal cord (10,11). It can be 

approximated by a biexponential decay corresponding to fast and slow diffusion components. 

These two components may elucidate water properties in various compartments of the 

nervous tissue. To the best of our knowledge DWI of human CSC at high b-values has not 

been published so far. We report results of transverse diffusion studies in the CSC at high b– 

values of up to 7000 s/mm 2 , using single shot axial DW-EPI (8) on a group of volunteers. 

Mmaterials and Methods: 

This study was conducted on 8 healthy volunteers, 4 woman and 4 man, aged from 23 to 39, 

average 32. All volunteers gave their informed consent. All volunteers underwent a basic high 

resolution sagittal FSE scan before DWI measurements. Imaging was performed on a GE 

SIGNA LX Echo-Speed with maximum gradient strength of 33 mT/m, equipped with 

Research Mode at Helimed in Katowice. Standard DW EPI supplied by GEMS was used to 

measure diffusion in along X, Y, Z directions. A peripheral pulse trigger with minimal delay 

gated all DWI scans. Saturation bands were put in three directions to reduce aliasing artifacts 

and reduce the FOV. DW images were acquired with a 64 x 64 matrix, FOV = 7 cm, slice 

thickness = 7 mm, slice separation = 2 mm, number of slices 4, TR = 2 RR, NEX = 8 for b 

factor of 450, 600, 750, 900 s/mm 2 , and NEX = 16 for b-values of 1200, 2000, 3000, 4000, 

6000 and 7000 s/mm 2 . Echo time varied from 84 ms for b=450 s/mm 2 to TE=155 ms for 

b=7000 s/mm 2 . Axial slices were positioned at intervertebral discs and at the center of the 

vertebra. Full DWI scan for all b-values took around 70 min. Data were analyzed off-line 

using IDL based software developed in-house. Motion and eddy current corrections were 

applied for all DW images. Values of ADT were determined for different ROI in the white 

(WM) and gray matter (GM) by fitting the signal decay for different b after TE correction. 

The fitting was constrained to a biexponential function 

S = Af 

exp( −b. 

Df 

) + Asexp( 

−b. 

Ds) 

(1) 

where, the subscripts f and s refer to fast and slow diffusion components respectively. Due to 

low S/N of DWI in Z direction at high b values, only transverse diffusion images were 

analyzed. 

Results: 

Good quality DW images were recorded for diffusion gradient in transverse direction (X, Y) 

for b-values up to 7000 s/mm 2 , as shown in Fig. 1. Fig.2 presents dependence of DW signal 

intensity on X diffusion gradient intensity for a ROI in the Ventral Horn Left (VHL) in GM 

and in the Posterior Funiculus Left (PFL) in WM. The non-monoexponential dependence on b 

is easily seen. The data were fitted to a biexponential function given by equation (1) for ROI’s 

105

selected in GM in VHL and Ventral Horn Right (VHR), in WM in PFL and Posterior 

Funiculus Right (PFR) for diffusion gradient along X, Y directions. The average values of 

diffusion components in the Ventral Horn in GM are: D f =(1.11±0.17) 10 -3 mm 2 /s, 

A f =0.54±0.07 and D s=(0.14±0.03) 10 -3 mm 2 /s, As=0.46±0.07. For WM in the Posterior 

Funiculus the corresponding values are: D f =(1.35±0.55) 10 -3 mm 2 /s, A f =0.74±0.07 and 

D s =(0.08±0.02) 10 -3 mm 2 /s, A s=0.26±0.07. Our results are within the limits of human brain 

data [10] and full DTI data for the rat spinal cord at Th7 [11]. 

Conclusion: 

We have demonstrated the existence of non-monoexponential diffusion in the human CSC 

that can be approximated by fast and slow diffusion components. 

1 

b=450 s/mm 2 

b=900 s/mm 2 b=5000 s/mm 2 

Fig. 1. DW images from a slice through the center of 

C5 for different b values. Note increasing contrast 

between GM and WM at b=5000 s/mm 2 . 

Fig. 2. Dependence of signal amplitude on diffusion 

0 1000 2000 3000 4000 5000 6000 700 

A 

0,1 

GM-VHR 

WM-FCR 

weighting along X direction in CSC at C5 level in 

GM – VHR, in WM – FCR. Solid lines represent the 

biexponential fit. 

b [s/mm 2 ] 

References: 

1) Clark, et al., MRM 41:1269-1273 (1999); 2) Alsop, MRM 38:527-533 (1997); 3) Le 

Roux et al., MAGMA 14:243-247 (2002); 4) Ries et al., MRM 44:884-892 (2000); 5) 

Bammer et al., JMRI 15:364-373 (2002); 6) Shimony et al., Proc. 8 ISMRM 773 (2000); 

7) Wheeler-Kingshott et al., NeuroImage 16:93-102 (2002), 8) Jasinski et al., Proc. 11 

ISMRM 2462 (2003), 9) Clark, et al., MRM 44:852-859 (2000), 10) Inglis et al., MRM 

45:580-587 (2001), 11) Elshafiey et al., MRI 20:243-247 (2002). 

0 8000 

106

DEUTERIUM NMR IN RMn 2 D 2 (R = Y, Tb, Dy) 

Henryk Figiel 1) , Paweł Filipek 2) , Paweł Szczurek 1) , Andrzej Budziak 1,2) 

1) Faculty of Physics and Nuclear Techniques, AGH University of Science and Technology 

Al. Mickiewicza 30, 30-059 Kraków, Poland; 2) H. Niewodniczański Nuclear Physics Institute, 

ul. Radzikowskiego 152, 31-342 Kraków, Poland 

The Laves phase type compounds of Manganese with Yttrium and rare earths (RMn 2) 

easily adsorb hydrogen or deuterium atoms. These light elements locate in the tetrahedral 

type A2B2 interstitial positions with 2 Mn and 2 RE (Y) NN atoms, cause noticeable lattice 

expansion and very significant increase of the magnetic ordering temperature T N . Above T N 

the spin fluctuations are strongly influenced by hydrogen (deuterium). Measurements of the 

2 D spin-lattice relaxation time T 1 and the Knight shift in function temperature above T N gives 

valuable insight into magnetic interactions and their dynamics. The longitudinal (T 1 ) 

relaxation was measured using three-pulse stimulated echo technique for YMn 2 D 2 [1] and 

TbMn 2 D 2 [2], and by saturation recovery method for DyMn 2 D 2 . On approaching T N a 

characteristic critical type divergences of T 1 and of the resonant line shift δν are observed. 

For the YMn 2 D x deuterides the observed changes are caused by the spin fluctuations related 

with Mn magnetic moments only, because of no contribution of nonmagnetic Y atoms [1]. 

For the TbMn 2 D 2 deuteride the significant contribution to the T 1 relaxation rate from 

fluctuating Tb moments is visible [2], what causes faster relaxation with divergence similar to 

that in YMn 2 D 2 . In the DyMn 2 D 2 deuteride the T 1 relaxation is even faster than that for 

TbMn 2 D 2 but the divergence is of the same character. The observed enhancement of the 

relaxation for DyMn 2 D 2 deuteride reflects interaction with Dy of higher magnetic moment 

than Tb, whereas the same character of spin fluctuations due to Mn magnetic moments 

remains. 

The Knight shifts for the investigated deuterides are negative. For DyMn 2 D 2 deuteride 

the temperature shift of the resonant line δν is less pronouncing than for YMn 2 D 2 and 

TbMn 2 D 2 deuterides what well corresponds to the faster relaxation observed in DyMn 2 D 2 

deuteride. 

The analysed behaviour of T 1 and the resonant line shift δν brought us to the 

conclusion that the exchange of the rare earth element in RMn 2 D 2 deuterides strongly 

influences dynamics of spin fluctuations as monitored by 2 D NMR method. 

References: 

1. H. Figiel, A. Budziak, P. Mietniowski, M.T. Kelemen, E. Dormann, 

Phys. Rev. B, 63 (2001)104403 

2. S. Leyer, G. Fischer, E. Dormann, A. Budziak, H. Figiel, 

J. Phys. Cond. Matt., 13 (2001)6115 

107

PHASE TRANSITIONS AND REORIENTATIONAL MOTIONS OF THE 

COMPLEX CATIONS AND NH 3 LIGANDS IN POLYCRYSTALLINES 

[Co(NH 3 ) 6 ](ClO 4 ) 3 AND [Zn(NH 3 ) 4 ](BF 4 ) 2 

Natalia Górska a , Łukasz Hetmańczyk a , Edward Mikuli a , Anna Migdał-Mikuli a , Krystyna 

Hołderna-Natkaniec b , Weronika Kasperkowiak b 

a Jagiellonian University, Faculty of Chemistry, Department of Chemical Physics, 

30-060 Kraków, ul. Ingardena 3, Poland; b A. Mickiewicz University, Institute of Physics, 

61-606 Poznań, ul. Umultowska 85, Poland 

Hexaaminecobal(III) chlorate(VII) and tetraaminezinck(II) tetrafluoroborate 

compounds (chemical formula: [Co(NH 3 ) 6 ](ClO 4 ) 3 and ([Zn(NH 3 ) 4 ](BF 4 ) 2 ), respectively) are 

particularly interesting molecular materials because of different reorientational motions of the 

complex cation and NH 3 ligands. In [Co(NH 3 ) 6 ] 2+ cation the Co 3+ ion occupies the center of 

an octahedron, while in [Zn(NH 3 ) 4 ] 2+ the Zn 2+ ion occupies the center of a tetrahedron of the 

NH 3 ligands. The ClO - 4 and BF - 4 anions have a tetrahedral structure and also perform fast 

reorientational motions. Both substances undergo a several solid-solid phase transitions which 

are attributed to the changes in the molecular groups arrangements as well as in their 

reorientational dynamics. The DSC measurements [1,2] performed in the temperature range 

90-300 K detected the phase transitions which thermodynamic parameters are presented in 

Table. 1. 

Table. 1. Thermodynamics parameters of the phase transitions on heating 

Compound T C [K] ∆H [J·mol -1 ] 

-1 

∆S [J·mol 

-1·K 

[Co(NH 3 ) 6 ](ClO 4 ) 3 103.2 137 1.4 

[Zn(NH 3 ) 4 ](BF 4 ) 2 179.4 

120.6 

106.5 

1370 

930 

80 

7.6 

7.7 

0.7 

1 

The proton magnetic resonance H NMR measurements were performed on a labmade 

spectrometer operating in the double modulation system at 25 MHz [3]. Fig. 1a and 1b 

show the temperature dependencies of the slope line width (δH) and the second moment (M 2) 

of NMR line in the studied compounds. In order to propose a model of internal dynamics, the 

second moment value was calculated from the van Vleck formula [4]. The onset of the 

following reorientations was taken into account during the heating of these compounds: the 

reorientation of NH 3 ligands about the M-N axis and the reorientation of octahedral or 

tetr ahedral cation, respectively. It was assumed that the N-H bond distances were of 1.00 Å 

and all the N-H bonds were tetrahedraly directed with respect to the Zn-N bonds, or 

octahedrally directed with respect to the Co-N bonds, and the distance Zn-N and Co-N takes 

the value of 2.01 and 2.28 Å, respectively. The M Rigid 2 obtained the value of 47.3 and 43.8 G 2 , 

for [Zn(NH 3 ) 4 ](BF 4 ) 2 and [Co(NH 3 ) 6 ](ClO 4 ) 3 , respectively. The observed value of the second 

moment of 1 H NMR line for [Zn(NH 3 ) 4 ](BF 4 ) 2 close to 15 G 2 at 90 K can be interpreted as 

resulting from the NH 3 ligands reorientation. On heating at T C1 also the reorientations of 

tetrahedral [Zn(NH 3 ) 4 ] 2+ cation set on. The observed value of the second moment of 1 H NMR 

line for [Co(NH 3 ) 6 ](ClO 4 ) 3 close to 17 G 2 at 90 K can be interpreted also as resulting from the 

NH 3 ligands reorientation. On heating the reorientations of octahedral [Co(NH 3 ) 6 ] 3+ cation set 

on, too. 

108

The neutron scattering (IINS, QNS, NPD) study [3,5] in the temperature range of 20– 

277 K give also evidence of the fast stochastic reorientational motions of NH 3 in all phases of 

[Zn(NH 3 ) 4 ](BF 4 ) 2 ,and [Co(NH3) 6 ](ClO 4 ) 3 measured by us in presented above NMR studies. 

A 

15 

15 

20 

Co(NH 3 

) 6 

(ClO 4 

) 3 

20 

[Zn(NH ) ](BF ) 

3 4 4 2 

2 

) 

T] 

M 2 

(10 -8 T 

1H 

10 10 

5 

5 

10 -4 T) 

-8 2 

T ] 

1H 

δH ( 

M 2 

[10 

15 15 

10 

5 

5 

10 

dH [10 -4 

T c3 

T c2 T c1 

0 0 

100 150 200 250 300 

Temperature [K] 

0 

T c 

= 103.25K 

0 

100 150 200 250 300 

T [K] 

Fig. 1. Temperature dependence of the slope line width (δH) - open symbols - and the second 

moment (M 2 ) - full symbols - of the 1 H NMR line in [Zn(NH 3 ) 4 ](BF 4 ) 2 and 

[Co(NH 3 ) 6 ](ClO 4 ) 3 

References: 

[1] A. Migdał-Mikuli, E. Miku li, Ł. He tmańczyk, E . Ściesińska, J. Ściesiński, S. Wróbel, 

N. Górska, J. Mol. Struct. 596 (2001) 123. 

[2] E. Mikuli, A. M igdał-Mikuli, N. Górska, S. Wróbel, J. Ściesiński, E. Ściesińska, J. Mol. 

Struct. 651-653 (2003) 519. 

[3] A. Migdał-Mikuli, E. Mikuli, Ł. Hetmańczyk, I. Natkaniec, K. Hołdern-Natkaniec, 

W. Łasocha, J. Solid St. Chem. 174 (2003) 357. 

[4] J.H. van Vleck, Phys. Rev. 74 (1948) 1168. 

[5] N. Górska, E. Mikuli, I. Natkaniec, K. Hołderna-Natkaniec, to be published. 

109

STUDIES ON CYTOCHROME C UNFOLDING PROCESS USING 

ELECTRON PARAMAGNETIC RESONANCE SPECTROSCOPY. 

QUALIFICATION OF PROXYL-MTS SPIN LABEL IN EXAMINATION 

OF PROTEIN STRUCTURE 

Przemysław Grudnik + , Janusz Pyka, Bohdan Turyna, Ryszard Gurbiel, Wojciech Froncisz 

Department of Biophysics, Faculty of Biotechnology, Jagiellonian University, 

ul. Gronostajowa 7, 30-387 Kraków, Poland 

Yeast iso-1-cytochrome c was labeled by two different spin labels: MTSL ((1-Oxyl-2,2,5,5- 

tetramethyl-∆ 3 -pyrrolin-3-yl) methanethiosulfonate)) and proxyl-MTS ((1-oxyl-2,2,5,5- 

tetramethylpyrrolidin-3-yl) methyl methanethiosulfonate). Proteins were denaturized in 

guanidinium hydrochloride. EPR spectroscopy was used to qualify protein unfolding degree. 

Continuous wave (CW) EPR spectrum of cytochromes c was registered in different 

concentration of guanidinium hydrochloride. Comparison of our results shows that proxyl- 

MTS spin label influence on protein structure stability has comparable grade like influence of 

MTSL spin label. 

+ pgrudnik@op.pl 

110

STRUCTURE OF 4-QUINOLINONES ANALYSED BY NMR STUDY 

AND X-RAY DATA 

Andrzej Zięba a , Andrzej Maślankiewicz a , Jerzy Sitkowski b , Bohdan Kamieński c , 

Kinga Suwińska d 

a Department of Organic Chemistry, The Medical University of Silesia, Jagiellońska 4, 

41-200 Sosnowiec; b Institute of Drugs, 30/34 Chełmska, 00-725 Warsaw; c Institute of 

Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw; d Institute 

of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw 

The previous study on 1-ethyl-3-methylthio-4(1H)-quinolinethione 1 and 1-methyl- 

4(1H)-pyridinethione 2 performed with the use of 14 N NMR spectroscopy (in CDCl 3 solution) 

and with X-ray examination led us to the conclusion that the compounds 1 and 2 do not exist 

in the form of azinethiones, but they exist as 1-alkylazinium-4-thiolates 4 or 5. 1,2 

O 

_ 

O 

N 

R 

N 

R 

+ 

14 N NMR spectral data (in CDCl 3 solution) of 1-methyl-4(1H)-quinolinone 3 reveals nitrogen 

atom signal (δ=-220 ppm) with half-height of linewidths ∆v 1/2 =286 Hz. It suggests for 

pyridinium-type resonance form 4 as the major contributor to the real molecular structure of 

3. X-ray examination of 3 shows the planarity of pyridine ring in 3 including the planarity 

around the endocyclic-nitrogen indicating for sp 2 hybridization of nitrogen N 1 . Planar 

tricoordinated nitrogen should bear a positive charge, and pyridinium-type resonance form 4 

should be major contributor to the real molecular structure of 3. The same structural features 

of pyridine unit (as concluded from CCDB) were observed also in the case of numerous 

compounds with 4-quinolinone formula including potent antibacterial drugs. The 1 H, 13 C, 15 N 

NMR study in the solid state and the solution of 3 in DMSO and those of ciprofloxacine 

confirmed the mentioned above conclusion. 

1. A.Maślankiewicz, A.Zięba, K.Suwińska, J.Chem.Crystallogr., 28, 701 (1998). 

2. A.Zięba, A.Maślankiewicz, K.Suwińska, Acta Crystallogr., C58, 32 (2002). 

3. A.Zięba, A.Maślankiewicz, V.Milata, J.Sitkowski, Magn. Reson. Chem., 41, 639, (2003) 

111

INVESTIGATION OF PROPERTIES OF FRESH 

AND COMMERCIAL ALOE SAP BY NMR SPECTROSCOPY 

D. Lewandowska, T. Podoski*, C.J. Lewa 

Institute of Experimental Physics, University of Gdańsk, ul. Wita Stwosza 57, 80-952 

Gdańsk; * Maritime Academy, ul. Morska 83, 81-225 Gdynia 

Abstract 

Aloe, as a medicinal plant, is well known to man since time immemorial. Aloe (Liliaceae 

Juss) is a perennial evergreen succulent from the lillaceous family with an extraordinarily 

rich composition. An aloe vera leaf contains more than 200 biologically active compounds 

that have anti-inflammatory, wound healing, analgesic and anti-arthritic activity. The three 

main components are glucose and/or mannose (a monomeric sugar constituent), malic acid 

(a preliminary stage for sugar in the plant’s organism), and the polysaccharide acemannan, 

the core of aloe. After the aloe leaves have been harvested, the lactobacillus causes lactic 

acid fermentation to occur. During this process lactic acid – not a natural component of aloe 

– is produced. Further substances that are produced by enzymes typical of aloe in the socalled 

citric acid cycle are fumaric acid , succinic acid and pyruvate. 

The citric acid cycle is interrupted after the harvest takes place but some of enzymes 

continue to work on, thus enriching these compounds. Besides the enzymatic decomposition 

and fermentation, there is also a chemical decomposition, during which the polysaccharide 

releases acetate groups and producing acetic acid. Preservatives should be added to liquid 

aloe products to guarantee their stability and avoid chemical and enzymatic degradation. 

These additives should be declared in the list of constituents on the product label. 

Earlier preliminary investigations of the changes in viscosity and relaxation times of aloe 

tissues and juice demonstrated the usefulness of the nuclear resonance method in 

observation of time effects and hypothermia. 

The present work comprises the results of time and temperature studies of 1H NMR 

spectra of fresh and commercial aloe juices . The aim of the studies was to determinate the 

effect of selected physical factors on the stability of the fresh and commercial aloe sap. 

For fresh aloe saps some distinctions in the NMR spectra have been observed. The results 

have shown biological, chemical and enzymatic degradation of the natural aloe juice. In 

opposition to fresh sap the spectra of commercial liquids not to be altered during the time 

and temperature measurements. 

Most of preservatives, sweeteners and fillers added to aloe sap were detectable in NMR 

spectra. Spectroscopic data allow the identification of the auxiliary substances added to 

commercial products. The method of analysis of 1H NMR spectra seems to be fruitful in 

detection of any non-aloe constituents and also in purity and quality control of aloe products. 

112

NMR MULTIPOLE RELAXATION 

IN THE ROTATING FRAME 

IN GASES 

Jerzy S. Blicharski, Barbara Blicharska 

M. Smoluchowski Institute of Physics, Jagellonian University, Kraków, Poland 

We consider NMR multipole relaxation for a system of two identical nuclear 

quadrupole spins I 1 = I 2 = 7, with a total spin I = I 1 + I 2 in gaseous state, in the presence of 

electric quadrupole and magnetic dipole - dipole interactions in a rotating tilted frame. The 

multipole relaxation times T LMρ are calculated for a maximal multipole order L = L max = 2I 

= 28 and M-quantum coherences, with M = 28 and 0, in a weak collision approximation 

[1-3], as a function of temperature, frequency and the tilt angle β between the external 

magnetic field B o and effective field B e in the rotating frame. These calculations are also 

extended for two spin systems of 176 Lu 2 O 3 in a liquid and solid state. The multipole 

relaxation times in the rotating frame are compared with relaxation times for dipolar orders 

[4-9] and they may be used for investigations of slow molecular motions in gases, liquids 

and solids. 

REFERENCES: 

[1] R.R. Ernst, G. Bodenhausen, A. Vokaun, Principles of Nuclear Magnetic 

Resonance in One and Two Dimensions, Clarendon Press, Oxford, 1987. 

[2] B. Blicharska, Physica, 147A, 601 (1988). 

[3] J. S. Blicharski, D. Kruk, Appl. Magn. Reson. 17, 367 (1999). 

[4] J. S. Blicharski, Report No 1885/AP, 12, INP, Cracow, 2001. 

[5] J. S. Blicharski, Proc. XXXI Comgress AMPERE, Poznań, 10 (2002). 

[6] J.S. Blicharski, Acta Phys. Polon. A41, 223 (1972), ibid. A74, 743 (1988). 

[7] J.S. Blicharski, Z.Naturforsch. 27A, 1359 (1972), ibid. 27A, 1456 (1972). 

[8] J. S. Blicharski, Proc. XXVI Congress AMPERE, Athens, 203 (1992). 

Proc.AMPERE Summer School, Nafplion, 78 (2000). 

[9 ] K. Kuwata, T. Schleich, J. Magn. Reson. A111, 43 (1994). 

113

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