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
Transcript
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: [email protected] http://www.wlelectronics.poznan.pl http://www.bruker.poznan.pl AMX-ARMAR AG ul. Bułgarska 12a 93-362 Łódź tel. 42 645 00 64
Contents R. Banyś, A. Słowik, M. Pasowicz, I. Ciecko-Michalska, M. Motyl, M. Irzyk, A. Szczudlik, J. Bogdał USEFULNESS OF PROTON MAGNETIC RESONANCE SPECTROSCOPY (1H 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 NH3D+ 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 D2 SECLUDED IN THE SUPERCAGES OF ZEOLITE NAY p.14 J. S. Blicharski, A. M. Korzeniowska, Z. T. Lalowicz SPIN-LATTICE RELAXATION OF D2 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 3He p.19 K. Dąbrowska-Balcerzak, J. Nartowska, I. Wawer 13C 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
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Z. Fojud, M. Sitarz, M. Handke, S. Jurga STRUCTURE AND ARRANGEMENT OF GLASSY PHOSPHO-SILICATE MATERIALS STUDIED BY 23NA, 27AL, 31P 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
1H NMR DETECTION OF σ -ADDUCTS IN SN 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 13C 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
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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 1H 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 35Cl-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 35Cl- NQR AND 1H-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 1H-NMR p.59
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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 H2JPH AND 2JPH 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 T1 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 Pr0.5Ca0.5Mn1-xGaxO3 (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 3He IMAGING p.67 B. Orozbaev, M. Wachowicz, S. Jurga MOLECULAR DYNAMICS IN POLY(ETHYLENE OXIDE) (PEO): 1H-NMR AND DIELECTRIC SPECTROSCOPY STUDIES p.68 K. Paradowska, A. Zielińska, I. Wawer, W. Kołodziejski 1H MAS NMR OF FLAVONOIDS p.69 L. Pazderski, I. Łakomska, E. Szłyk, J. Sitkowski, L. Kozerski 15N 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
1H, 13C 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
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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 La1.4Sr1.6Mn2O7 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 3HE 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 19F 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 1H 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 35Cl-NQR STUDY OF MOLECULAR DYNAMICS OF TETRACHLOROPHTHALIMIDE AND N-PHENYLTETRACHLOROPHTHALIMIDE p.92 A.Walczak, A.Mielcarek, B.Brycki and B.Nogaj
35Cl-NQR STUDY OF THE SUBSTITUENT EFFECT ON THE ELECTRONIC STRUCTURE OF TETRACHLOROPHTHALIMIDE DERIVATIVES p.94 M. Wilczek, K. Jackowski 13C AND 1H NUCLEAR MAGNETIC SHIELDING AND SPIN-SPIN COUPLING CONSTANTS OF 1,2-13C-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
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M. Wolniak, J. Oszmiański and I. Wawer
13C 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 T2 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 13C 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 RMn2D2 (R=Y, Tb, D4) 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 NH3 LIGANDS IN POLYCRYSTALLINES [Co(NH3)6](ClO4)3 AND [Zn(NH3)4](BF4)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
USEFULNESS OF PROTON MAGNETIC RESONANCE SPECTROSCOPY (1H MRS) IN DIAGNOSIS OF SUBCLINICAL
1 Center for Diagnosis and Rehabilitation Heart and Lung Disease The John Paul II
Hospital, Departments of 2Neurology, and 3Gastroenterology, 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 (1H 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 1H 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 1H 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 H2O signal suppression). Three voxels of 8 cm3 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<0.05) and no significant changes between the two groups in Cho/Cr ratio (0,88 vs. 0,87) and NAA/Cr ratio (1,64 vs. 1,55).
Conclusion Proton magnetic resonance spectroscopy (1H MRS) detects in vivo neurometabolic
changes in patients with SHE. The significant reduction of mI/Cr ratio suggests the alteration of glial function.
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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: [email protected])
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, kt and kK. When kt = kK, the DQR line shape equation becomes identical with the AB equation with k = kt/3 (= kK/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 = kt / kK, 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.
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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 19F line broadening.
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LONELY DEUTERON IN NH3D+ 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 NH4
+, NH3D+, NH2D2
+, NHD3+ and ND4
+ ions with relative abundances given by the binomial distribution of hydrogen and deuterium. All carrying deuterons isotopomers contribute characteristic deuteron NMR spectra [1].
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3
2D H N
Rotational tunnelling involves indistinguishable particles. Therefore for NH3D+ 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 NH3D+ 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 T1 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 non-invasive 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 D2 SECLUDED IN THE SUPERCAGES OF ZEOLITE NAY
Jerzy S. Blicharski1, Aleksander Gutsze2, Agnieszka M. Korzeniowska,
Zdzisław T. Lalowicz, Zbigniew Olejniczak
H. Niewodniczański Institute of Nuclear Physics, Kraków, Poland; 1Institute of Physics, Jagiellonian University, Kraków,Poland; 2Biophysics 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 D2 or CD4 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 τJ 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 τC = τ0 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, τads. An adsorbed molecule may perform many translational jumps before it leaves the surface.
Main contributions to the spin-lattice relaxation rate 1/T1 come from quadrupole and spin-rotational terms [2] for very short τJ at high temperatures: 1/T1SR = (8π2/3) CSR
and the quadrupole relaxation below about 110K: 1/T1Q = (3 π2/10) CQ
2 [J(ω0)+4J(2ω0)], where: <J(J+1)> is the mean rotational quantum number, and J(ω0) = τC /(1 + ω0
2 τC2) is the spectral density function. The coupling constants C were obtained from molecular beam studies: CSR = 8.25 kHz, CQ = 225.04 kHz [3].
The observed spin-lattice relaxation rate at high temperature indicates that the life-time of the free rotor state, appears to be τJ = n τf, where τf 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 constant CQ
ef = 48.3kHz. This can be explained by a very fast reorientation of D2 molecules on a cone with an opening angle close to 90o. Translational diffusion on the cage surface interrupts such motion by steps involving molecular turns, characterized by the time τC.
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 D2 and CD4 molecules secluded in zeolites. This project is supported, during 2002-2005, by the State Committee for Scientific Research grant No 2 P03B 135 23.
Jerzy S. Blicharski1, Agnieszka M. Korzeniowska, Zdzisław T. Lalowicz,
H. Niewodniczański Institute of Nucelar Physics, Kraków, Poland; 1Institute of Physics, Jagiellonian University, Kraków,Poland
We consider a system of two identical nuclear spins I1 = I2 = 1, total spin , 21 III +=
and molecular angular momentum in di-deuterium DJ 2 molecules in gaseous state. In the presence of strong magnetic field B0 the nuclear spin Hamiltonian H can be expressed as a sum of a dominant static Zeeman interaction H0, 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]: , (1) )()( ''
0 tHJItHHH zJzI ++=+= ωω
(2) ).()()( ''' tHtHtH DQSR +=where:
, (3) ∑+
−=
+=⋅=1
122
' ))(()()()(M
MMRRSR tJAIACtJICtH
∑+
−=
+
+−∆
=2
222
' ))(()()32)(12(4
)(M
MMI
DQ tJAIAJJ
tH . (4)
The quantities are spherical tensors with spin operators , where are random functions of time due to molecular collisions, and
)),(()()( φθLMLL
LM CrPPA ∇⋅=)(tJJ =),( JIP =
),(12/ φθπ LMYL +4=),( φθLMC are the Racah functions. Other parameters are defined as follows:
)32)(12(
)8(2)3311( 22
+−
+++−−=
IIIICIIC DQ
I∆ , (5)
with the spin-rotatinal constant CR = 55.103 rad/s, the quadrupole constant CDQ = 1413.103 rad/s and the dipolar constant CD = 44.103 rad/s [2]. The relaxation matrix elements can be calculated in a weak collision approximation from the following expressions [1]:
ττ dtHTtHTTrR jjjk+
+∞
∞−
+= ∫ )](~,)][(~,[21 '' , (6)
where: . (7) tiHtiH etHetH 00 )()(~ '' −=
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 quadrupolar-dipolar (QD) interactions:
QD
I
SR
I TTT
+
=
111
111 , (8)
)),(()1(311 2
1JJIR
SR
jJJCT
τωω −+=
, (9)
15
)),(()32)(12(
)1()32)(12(40031 2
11JJII
QD
fJJ
JJIIT
τωω −+−
++−∆=
, (10)
where:
2212),(
L
LLj
τωτ
τω+
= , , (L=1,2) ),2(4),(),( LLL jjf τωτωτω +=
The is the reduced spectral density function [3] for A),( Lj τω LM ( (t)) and τ are the correlation times due to molecular collisions. The expressions in the brackets
J L
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:
)),(()32)(12(
)1()4(400711 2
121JJIDQ
SR
fJJ
JJCCTT
τωω −+−
+−+
=
, (11)
)),(()32)(12(
)1()4(80311 2
111JJIDQ
SR
fJJ
JJCCTT
τωω −+−
+++
=
, (12)
01
01
=
T
. (13)
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-D2 molecules, respectively. In the case of the ortho-D2 molecules with the total spin I=2 or 0 and even J, one has to take into account a leakage rate RL between I=2 and I=0 species, contributing to the longitudinal relaxation rate:
L
QDSR
ortho
RTTT
+
+
=
2111
111 . (14)
As a result of the calculation one gets:
)),(()32)(12(
)1()2(501 2
JJIDQL fJJ
JJCCR τωω −+−
++= , (15)
and after summing up the quadrupolar-dipolar and leakage terms we get:
)),(()32)(12(
)1()4885(400311 22
11JJIDDQQ
SR
ortho
fJJ
JJCCCCTT
τωω −+−
++−+
=
. (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 Brzegowy3, Andrzej Jasiński1, Tomasz Banasik1, Zenon Sułek1, Dariusz Adamek2, Katarzyna Majcher1, A. Pilc4, Tomasz Skórka1, Władysław Węglarz1
1Radiospectroscopy and MRI, H. Niewodniczański Institute of Nuclear Physics PAN, Kraków;
2Neuropathology, 3Radiology, Jagiellonian University Medical College, Kraków; 4Neurobiology, 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 non-equilibrium 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/mm2. Data were analyzed using IDL based software developed in-house. Longitudinal diffusion DL = DZZ, transverse diffusion DT = (DXX+DYY)/2, isotropy index ID = DT/DL 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: IDWM = 0.2 ± 0.05 and IDGM = 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 3He
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: 3He, 129Xe. 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 3He. A glass cell containing the 3He gas at a low pressure (1 torr) is placed in a magnetic field of about 30 Gs. As the optical transition between 11S0 and 23S1 states is strictly forbidden, a weak RF discharge is used to populate the metastable 23S1 state (Fig.1).
F = F =
F =
F =
F = F =
F =
23P
23S1
23P2
23P1
23P0
1083 nm METASTABLE
STATE
10-8 [s]
2*10-2 [s]
2*10-8 [s]
10-7 [s]
8*103 [s]
33D
23P
23S1
21P15*10-10 [s]
11S0
21S0
31D2
Fig.1. Energy levels for 3He atom.
The absorption of circularly polarized (σ+) laser beam of wavelength λ = 1083nm causes a transition from 23S1 , mF = –1/2 to 23P0, mF = +1/2 state (Fig.2). After excitation a spontaneous reemission to both mF = –1/2 and mF = +1/2 sublevels of 23S1 state takes place. However, the continuous depletion of the mF = –1/2 sublevel results in higher population of the 23S1, mF = +1/2 state. This is equivalent to the electronic polarization of the atom. Through hyperfine coupling the nucleus also becomes polarized. Nuclear polarization m = -of the ground state 3He atom is achieved via metastability exchange collisions in which a non-polarized ground state atom and a polarized metastable atom take part. The polarization achieved
1083 nm
σ+
F =
23P0 F =
m =
in that way is about 80%. One can measure the m = -polarization using NMR or optical methods.
To use the gas in the MRI lung imaging, it is 23S1necessary to compress it without losing the m = polarization up to atmospheric pressure for which
purpose a compressor is being built. Fig.2.Optical pumping.
19
13C CP MAS NMR STUDIES OF STEROIDAL SAPOGENINS FROM CONVALLARIA MAJALIS L.
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 1H and 13C NMR in solution and solid phase.
13C NMR spectra in solution were recorded on a Bruker DRX-500 spectrometer. Solid
state 13C 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 ZrO2 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. 1H and 13C 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 13C CP MAS spectra (in solution spectra this region is overlaped with the signals of solvent, CDCl3 ). The 13C 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 spin-lattice and spin-spin relaxation times. Low methoxyl pectins can form gels in the presence of divalent cations (mainly Ca2+), 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 CaCl2). The four physical stages were observed: solution (0 mM CaCl2), sol (1.5 mM, 2.5 mM and 5 mM CaCl2), homogenous gel (7.5 mM CaCl2) and gel with syneresis (10 mM CaCl2). Dispersions of proton spin–lattice relaxation rates R1 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 (τCPMG =1ms). All experiments were performed at 21 oC.
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 1H 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 0.61×107 1/s in the solution state up to the value 2,08×107 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 cτ parameter is less pronounced, but still shows the same tendency towards slowing down the dynamics.
21
104 105 106 1070
2
4
6
8
10
1% LMP solution 1% LMP sol state (2.5mM CaCl2) 1% LMP sol state (5mM CaCl2) 1% LMP gel state (7.5mM CaCl2) 1% LMP gel state (10mM CaCl2)
R 1 [1
/s]
Larmor frequency [Hz]
Fig. 1. Dispersion of the water 1H 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 CaCl2.
The existence of gelling process was confirmed by spin-spin relaxation times measurements. T2 relaxation curves were bi-exponential. It can be associated with water in differing physical environments (away from the pectin macromolecules - long T2 and near macromolecular surfaces – short T2). 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].
0 2 4 6 8 100,0
0,2
0,4
0,6
0,8
1,0
1,2
tauCPMG = 1ms T2 slow T2 fast
T 2 [s
]
CaCl2 concentration [mM]
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 CaCl2.
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 Dorożyński1, Piotr Kulinowski2, Andrzej Jasiński2, Renata Jachowicz1
1Department 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/cm3. 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,
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. δobs = (1 – [C]/[G0])δG + ([C]/[G0])δC where δobs is observed chemical shift of guest resonance, δG and δC are chemical shifts in free and bound states, respectively. [C] is the concentration of complex and [G0] 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]/{([H0]–[C])([G0]–[C])} where [H0] 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 23NA, 27AL, 31P 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 phospho-silicate materials studied by NMR and FTIR methods. The 23Na, 27Al, and 31P 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 23Na, 27Al, 31P 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. 27Al NMR spectrum observed was non-symmetrical due to superposition of various intra-tetrahedral [AlO4]5- bonds, as shown in our previous work [2].
70 60 50 40
Fig. 1. The selected 27Al 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].
103 104 105 106 107 108
0,1
1 300 K
Rel
axat
ion
Tim
e T 1 (
s)
Fig. 1. T1 relaxation dispersion curve for 30% of UDACl in D2O 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
1Department of Physics and Biophysics, 2Department of Food, Vegetables and Cereals, Agricultural University, 50-375 Wrocław, Norwida 25, Poland, [email protected]
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 donor-acceptor 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 (Pr3+) from membranes induced by the compounds studied, measured with the proton nuclear magnetic resonance (H1-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 1H-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.
1H NMR DETECTION OF σ-ADDUCTS IN SNH 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 SNH 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
N
N
NO2 NO2��� ���ClCH2SO2Ph ����
RR
HCl1
2
)
)
-
+ H3O+
CH2SO2Ph
NaOH / DMSO−
H CHCl
RRRRR
NO2
SO2Ph
N
N 1 2 σ-adduct 3 . R = H, Cl, OC2H5, NHCH3, OH
In order to confirm the intermediates in the above-mentioned reactions are detectable anionic σ-adducts like 2, we have measured the 1H 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 sp2 carbon atom of 3-nitro-1,5-naphthyridines induces the change of its hybridization from sp2 to sp3 (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 sp2 to sp3 is due to the σ- adduct formation. The corresponding 1H 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, 1H 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 1H 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)
DMSO-d6 9.66 9.17 9.21 8.01 8.60
4-ClCH SO2Ph-σ-adduct of 1a (2a)
NaOD / DMSO-d6
8.90 5.77 8.19 7.24 7.68
∆δ 0.76 3.40 1.02 0.77 0.92
2-Chloro-3-nitro-1,5-naphthyridine (1b)
DMSO-d6 - 9.25 9.19 8.02 8.52
4-ClCH SO2Ph-σ-adduct of 1b (2b)
NaOD / DMSO-d6
- 5.86 8.21 7.21 7.40
∆δ - 3.39 0.98 0.81 1.12
2-Ethoxy-3-nitro-1,5-naphthyridine (1c)
DMSO-d6 - 8.46 8.79 7.68 8.16
4-ClCH SO2Ph-σ-adduct of 1c (2c)
NaOD / DMSO-d6
- 5.80 8.13
∆δ - 2.56 7.90 - 7.25a 0.03
2-Methylamino-3-nitro-1,5-naphthyridine (1d)
DMSO-d6 - 8.87 8.70 7.68 8.08
4-ClCH SO2Ph-σ-adduct of 1d (2d)
NaOD / DMSO-d6
- 5.42 8.08 7.00 7.61
∆δ - 3.47 0.62 0.68 0.47
2-Hydroxy-3-Nitro-1,5-naphthyridine (1e)
DMSO-d6 - 8.75 8.63 7.68 7.76
4-ClCH SO2Ph-σ-adduct of 1e (2e)
NaOD / DMSO-d6
- 5.24 7.78 7.67 7.91
∆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 non-functional 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, S0, coming from protons of solid matrix of lyophilizate as well as the components increasing with the increased hydration level: (ii) a Gaussian component, S1, from water bound to the primary water binding sites; (iii) and exponentially decaying contribution, L1, from water tightly bound to lyophilizate surface, presumably the first hydration shell, and (iv) exponentially decaying loosely bound water fraction, L2. A significant contribution of ‘sealed’ water molecules belonging to the fraction S1 and L1, 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, S1, L1, and L2 , 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 00C 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/m0 = 0.020±0.005 and ∆m/m0 = 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/m0 = 0.007±0.001 and ∆m/m0 = 0.10±0.02 for P. crispa; and ∆m/m0 = 0.07±0.02 and the one exceeding ∆m/m0 = 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).
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.
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 13C CP/MAS NMR AND X-RAY DIFFRACTION
Joanna Herold,1 Łukasz Dobrzycki,2 Edyta Pindelska,1 Andrzej Kutner,3 Krzysztof Woźniak,2
Wacław Kołodziejski1
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
belongs to a new generation of antipsychotic drugs, which modulate dopaminergic neurotransmission by their antagonistic action on 5-HT2A 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 13C 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 13C 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 T1. 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) CuSO4 and CuCl2, 2) ZnSO4 3) FeCl3
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 T1. 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 T1 in water and serum aqueous solutions. An addition of suitable complexing ligand significantly narrows the range of changes of T1. 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. 2nd 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,
where σ0(T), J0(T) are the shielding and coupling constants for an isolated molecule and σ1(T), σ2(T), J1(T), J2(T)... terms are due to intermolecular effects. The higher order terms, starting from σ2(T) and J2(T) are usually negligible for low-density samples. Then the dependence on density is linear and the spectral parameters (σ0(T), σ1(T), J0(T) and J1(T)) are available. According to Eqs. 1 and 2 extrapolation of gas-phase measurements to the zero-density limit gives the σ0(T) and J0(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 σ1(T) and J1(T) parameters reveal the influence of intermolecular interactions. The J0(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 σ0(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 (σp) and the spin-rotation constant measured by high-resolution microwave spectroscopy. Combined with an accurate calculation of the diamagnetic part of shielding (σd) in a molecule, the absolute shielding of a suitable primary reference molecule can be obtained. For 13C and 17O the primary reference molecule is CO, for 15N and 14N it is NH3, for 33S the molecule of OCS is used, etc. Once the absolute shielding is determined for at least one molecule all the other measurements of σ0 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 17O and 33S spectra for a set of gaseous molecules: (CH3)2CO, (CH3)2O, (CD3)2O, CO, CO2, N2O, OCS, SO2, SO3 and SF6. Similar 1H, 13C, 15N and 19F NMR experiments were used for the investigation of other compounds: CH3
13C15N, 13CH313CN, CH3
15NH2, H13C13CH, H213C13CH2, CH3F, CH2DF,
CHD2F, CD3F, CH2F2, CHF3 and CF4. Some of the molecules were exclusively studied in gaseous solvents (Xe, CO2 and SF6). 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 (σ0(T) and J0(T)), their isotope effects and the second virial coefficients (σ1(T) and J1(T)). It was shown that at least some spin-spin coupling constants were strongly affected by intermolecular interactions.
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 T1 (Fig.1.), relaxation time T1 at 9, 16.5, 30,2 and 200 MHz (Fig.2.), and the second moment M2 of the proton relaxation line (Fig.3.) measured for polymethylphenyl siloxane ( PMPS, Mw=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 T1 dependence according to Rouse model (T1~υ0.35 ) [2].
[s
]
T
0,01 0,1 1 10
1E-3
0,01
0,1
υ~ 0.35
υ~ 0.35
POLYMETHYLPHENYLSILOXANE
20[°C] 35[°C] 55[°C] 75[°C]
1
Larmor frequency [MHz]0 2 4 6 8 10 12 14
101
102
103
III
9 MHz 16.5 MHz 30.2 MHz 200 MHz
I
T1
[ms]
POLYMETHYLPHENYLSILOXANE
103/T [K-1]
Fig. 1. 1H T1 relaxation times vs. Larmor frequency Fig. 2. Temperature dependence of the T1 for PMPS at different temperatures relaxation times for PMPS
Fig. 3. Second moment M2 versus temperature for PMPS
50 75 100 125 150 175 200 225 250 275 300
0
1
2
3
4
5
6
7
8
9
10
glass transition
rotation of methyl groups and flip-flopof C6H5 groups 2α = 46°
rotation ofmethyl groups
4.04.45.05.76.68.010.012.5
III
III∆H=1Gs2
M2 [
Gs2 ]
T[K]
[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.
40
DIAGNOTIC VALUE OF MRI IN CONVERSION PROCESS OF HUMAN BONE MORROW
1Institute of Physic, Department of Medical Physics, Silesian University, 40-007 Katowice, Uniwersytecka 4, Poland; 2Silesian 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 Kołodziejski1
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 1H, 31P and 13C 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 T1 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 NH3 group reorientation, Ea = 5.16 kcal/mol (Fig.1). This value is lower then activation energy for pure L-Alanine, Ea ≈ 8 kcal/mol [2]. Observed difference suggested that PEG are conjugated into L-Alanine structure probably by the amine group.
2 4 6 8 10 12100
1000
10000
100000
Ea=5.16 kcal/mol
T 1 [m
s]
1000/T [K]
r
001) 1907-1912
Fig.1. Temperature dependence of T1 spin-lattice
elaxation times for L-Alanine / Polyethylene Glycolcomplex
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]. Mobility of this molecular group increases with increasing temperature. Bands at ~1650 and ~1550 cm-1 are due to symmetric stretching C=O (Fig.3) and stretching CO-NH (Fig.4) vibrations, respectively. It corresponds to formation of L-Alanine / Polyethylene Glycol complex [3]. Mobility of the C=O group increases with increasing temperature, whereas CO-NH bond, which links Polyethylene Glycol part with L-Alanine part of complex, is very stiff. Shifting of the absorption maximum as a function temperature is not observed.
[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
Laboratory of NMR Spectroscopy, Department of Chemistry, Warsaw University, ul. Pasteura 1, 02-093 Warsaw, Poland; [email protected]
Fluoromethanes (CH4-nFn, where n = 1, 2, 3 and 4) have been studied using
multinuclear advanced NMR spectra in the gas phase [1,2]. All the 19F, 13C and 1H 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 (CD3F, CD2HF, CDH2F, CHDF2 and CDF3) were also included in our investigations. For the first time the 13C and 19F 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.
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 spin-lattice 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].
2,6 2,8 3,0 3,2 3,4 3,6 3,8 4,00,6
0,7
0,8
0,9
1,0
1,1
1,2
1,3
1,4
LDPE LDPE-20 wt. % of calcium lactate LDPE-30 wt. % of starch
Rel
axat
ion
times
T1 [
s ]
1000/T [ 1/K ]
Fig.1. Spin-lattice relaxation times T1 of the “virgin” samples: LDPE, LDPE-20 wt. % of calcium lactate and LDPE-30 wt. % of starch vs. temperature.
46
0 2 4 6 8 10 12 14 16 18 20 22 240
100000
200000
300000
400000
500000
600000
LDPE-20 wt. % of calcium lactate LDPE-30 wt. % of starch
Inte
gral
of 1
D M
RI p
rofil
s [ a
.u.]
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 (k0
tu) is usually in range 108 Hz for hydrogen (106 Hz for deuterium) while this of the rate of jumps over the barrier (k0
ov) is in range 1012 Hz (1010 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 T1 (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 / I0, where I is intensity of de Broglie's wave (which describe the particle) outside of the potential wall and I0 is this intensity inside the potential wall. The formula, which describes a coefficient D depends on the shape of the potential barrier. For the
rectangular barrier ])EE(m2L2exp[DD AB0 −−= , where EAB and L are height and width
of the barrier, E and m are energy and mass of the particle. The value (EAB - E) under square root is negative for E > EAB and the probability D is lost. The thermal energy of the Avogadro number of particles equals E = CpT [kJ/mol] where Cp is molar heat capacity and T is temperature in the Kelvin scale. When CpT = EAB 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 kAB = k0
ov exp(-H/RT) + k0
tu
exp(-∆/RT) (H and ∆ are the high and low temperature slopes of T1) 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 kov
= k0exp(-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 T1 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 (T1ρ) and in laboratory frame (T1) is impossible. The theoretical temperature dependences of T1 (15 MHz) and T1ρ (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) ћωmm' about its average value ћ<ωmm'>, which make the energies of methyl spins in magnetic field random function of time. The single potassium acetate molecule has protons in the methyl group only. Therefore the (1/T1)AE term governs the proton relaxation process in the CH3COOK molecule. The lack of a frequency dependence of T1 [7] indicates that ωT > ωI, and the observed T1 temperature dependence correspond to the resonance frequency equal ωT -tunnel splitting frequency. A theory of magnetic nuclear relaxation, providing a calculation of the spectral density functions of complex motion of methyl group is reported in present paper. The complex motion consists of jumps over the barrier (correlation timeτc3
(H)), incoherent tunnelling (correlation time τc3(T)) and motion
related to the coherent tunneling (correlation time τc(ω)) of methyl protons. In the temperature
dependence of T1 , shown in Fig. 2, the temperature intervals in which particular mechanisms of motion are dominant in the process of proton relaxation in CH3COOK can be estimated. In the high-temperature range the only one mechanism is the classical motion leading to the spin-lattice relaxation (line #3). Line #2 represents the T1 relaxation time due to classical motion and motion related to coherent tunneling. The motion related to coherent tunneling in the temperature regime (25 K-1 ≥ 1000/T ≥ 50 K-1) seems to be dominated mechanism of relaxation (activation energy E01 = 0.12 kJ/mol) . The lowest slope (1000/T > 60 K-1) of the whole temperature dependence of T1 (line #1) corresponds to the activation energy of incoherent tunneling ET = 0.04 kJ/mol. It is impossible to conclude about a smooth transition from classical dynamics (characterized by τc3
(H)) to quantum dynamics (characterized by τc(ω)
and ,τc3(T)), on the basis of the temperature dependencies of the spectral densities functions.
Such smooth transition is predicted in the number of papers at intermediate temperatures. In these papers the stochastic motion of methyl group is treated as a single motion with the total rate constant, which is usually assumed as two-exponential temperature dependence (incoherent tunnelling of methyl group is not expected).
[1] J. L. Skinner and H. P. Trommsdorff, J. Chem. P
0 20 40 60 80
1
10
100
BAC-d5(59.53 MHz)
#2
#1
1000/T (K-1)
PROT
ON T
1 (s)
Fig. 1
0 20 40 60 80 100 120
0,1
1
10
(52 MHz) (30 MHz) (15 MHz)
#3 #2
#1
1000/T (K-1)
PRO
TON
T1 (
s)
CH3COOK
2
[2] S. Nagaoka, T. Terao, F. Imashiro, A. Saika, N. H[3] D. E Woessner, J. Chem. Phys. 36, 1 (1962). [4] E. C. Reynhardt and L. Latanowicz, J. Magn. Res[5] L. Latanowicz and E. C. Reynhardt, Chem. Phys.[6] J. Haupt, Z. Naturforsch. 26a, 1578 (1971). [7] F. Köksal, E. Rössler and H. Sillescu J. Phys : So
Fig.
hys. 89, (1988), 897 - 906. irota, and S. Hayashi, J. Chem. Phys. 79, 4694 (1983).
on. 130, 195 (1998). Lett. 341, 561 (2001).
lid State. 15, 5821 (1982).
49
VIRTUAL LABORATORY OF NMR SPECTROSCOPY
Marcin Lawenda1, Łukasz Popenda2, Norbert Meyer1, Maciej Stroinski1, Zofia Gdaniec2, Ryszard W. Adamiak2
1Poznań Supercomputing and Networking Center (PSNC), Z. Noskowskiego 10,
61-704 Poznań, Poland; 2Institute 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
1H NMR STUDIES OF PLATINUM(II) CHLORIDE COMPLEXES REACTION WITH GUANOSINE-5’-MONOPHOSPHATE
Iwona Łakomska1, Edward Szłyk1, Leszek Pazderski,1 Jan Reedijk2
1Faculty of Chemisty, Nicolas Copernicus University, 87-100 Toruń, Poland, email:
[email protected]; 2Gorlaeus Laboratories, Leiden University of Chemistry, P.O. Box 9502, 2300 RA Leiden, The Netherlands
Studies on the binding of cis-[PtCl2(dmtp)(NH)3] and cis-[PtCl2(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 1H 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-[PtCl2(dmtp)(NH)3], cis-[PtCl2(tmtp)(NH)3] were very slow for NMR time scale, and therefore we decided to study the reaction between monoaquaspieces: [PtCl(D2O)(dmtp)(NH3)]+, [PtCl(D2O)(tmtp)(NH3)]+. 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 1H 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.
STRUCTURE OF SOME ARYLAZO-2-NAPHTHYLAMINES AND THEIR N-ACETAMIDES
Dorota Maciejewska1, Violetta Kowalska2
1Department of Organic Chemistry, 2Department 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 13CP/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 15N 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 13C CP/MAS NMR, 1D and 2D solution-state 1H and 13C NMR, X-ray diffraction and theoretical DFT calculations in an attempt to understand their conformational interconversion.
NN
R1 = o-NH2, R2 = m-CH3R2R1 (1)
R1 = o-NHCOCH3, R2 = m-CH3
R1 = o-NHCOCH3, R2 = p-NO2
R1 = o-NHCOCH3, R2 = p-COCH3
(2)(3)(4)
123
4
5
6 7
8
910
1'2' 3'
4'
5'6'
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
35Cl-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 LD50 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-(p-chlorophenyl)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 35Cl-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).
R Cl Cl Fig.1. The structural formula of DDT-type insecticides RESULTS AND DISCUSSION Table 1 presents the structural formula, 35Cl-NQR frequencies and biological activity of the insecticides studied (LD50 for rats [4]). The two phenyl rings are constant elements of the compounds differing only in the substituent R joining the rings. The mean 35Cl-NQR ( 2,1ν ) 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 LD50 obtaining a linear relation. The LD50 parameter decreases with increasing mean frequency
2,1ν (Fig.2), which means that the biological activity of the insecticides increases with increasing 35Cl-NQR frequency on chlorine atoms at the phenyl rings.
53
Table 1. The structural formulae, 35Cl-NQR frequencies at 77K, mean frequencies 2,1ν and LD50 values for rats, characterising particular insecticides. COMPOUND
R
STRUCTURAL FORMULA
νQ [MHz]
2,1ν [MHz]
LD50(mg/kg) [4]
p,p’-DDE
CCCl2
(ν1)Cl C Cl(ν2) CCl2
34.6220 a)
34.6580
35.1312 34.620
34.66
880
p,p’-DDA
HCCO(OH)
H (ν1)Cl C Cl(ν2) CO(OH)
34.656 b)
34.923
34.79
590
p,p’-DDT
HCCCl3
H (ν1)Cl C Cl(ν2) CCl3
34.8670 a) 34.9732
38.4845 38.8115 39.0362
34.92
250
p,p’-DDD
HCCHCl2
H ( ν1)Cl C Cl(ν2) CHCl2
34.9363 a)
34.9805
35.9743 37.1310
34.96
113
a) Ref. [5] b) Ref. [6] Higher 35Cl-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. Fig. 2. The value of LD50 versus the 35Cl-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
35Cl- NQR AND 1H-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 1H-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. 35Cl-NQR measurements were performed on a lab-made pulse Fourier transform NQR spectrometer operating in the frequency range 20-40 MHz. The 35Cl-NQR frequencies (νQ) and nuclear quadrupole spin-lattice relaxation times (T1Q) were determined in the temperature range 77K- 350.5K. Measurements of 1H-NMR spin-lattice relaxation times (T1) 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 35Cl-NQR lines assigned to the two chlorine atoms in the molecule. The frequencies of these lines decrease with increasing temperature, Fig.1.
50 100 150 200 250 300 350 40034.0
34.2
34.4
34.6
34.8
35.0
ν Q[M
Hz]
T [K]
Fig.1. Temperature dependence of 35Cl-NQR frequency in p,p’-DDA.
The difference in the slope of the νQ(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 (T1Q) increase with increasing temperature (Fig.2). From the slopes of the T1Q(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 (T1). It should be noticed, that these values are very high and reach 214 s at room temperature (Fig. 3). From the slope of the T1(T) the activation energy has been calculated as 4 kJmol-1.
55
12 10 8 6 4 2-2
-1
0
1
2
3
νQ2 νQ1
ln T
1Q
103/T [K-1]
1
3
7
T 1 [ms]
100 200 300 400
Fig.2. Temperature dependence of 35Cl-NQR spin-lattice relaxation time in p,p′-DDA.
12 10 8 6 4 22
3
4
5
6
ln T
1
103/T [K-1]
0
50
100
150
200
T 1 [s]
100 200 300 400T [K]
Fig.3. Temperature dependence of 1H-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(C6H5)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).
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: [email protected]
Interesting spectral properties of the amide derivatives of 3,4-quinolinediyl bis-sulfides 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-O-sulfonic 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.
The structure of the compounds 2 and 3 has been completely assigned by means of 1D and 2D 1H and 13C nmr spectra. The key-part in this methodology were long-range proton carbon correlation. The 1H and 13C 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(CH3) = 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)
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 1H-NMR
Ľubomír Mucha, Józef Onufer, Dušan Olčák
Department of Physics, Technical University of Košice, 042 00 Košice, Slovakia
The broad line 1H 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 1H NMR measurements were performed in the temperature range 160 – 370 K. The shape and width of broad line 1H 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 M2 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
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 0C 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 0C) with the clamps speed of 10 mm/min. NMR spectra in a derivative form were recorded at temperature of 22 0C by means of BL-NMR spectrometer operating at the fixed magnetic field B0 = 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 wi (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
0 2 4 6 8 10 12 14 160,00
0,05
0,10
0,15
0,20
LDPE / PP70 / 30 (C)
inte
nsity
(ar
b. u
nits
)
B - B0 [10 - 8 T]0 2 4 6 8 10 12 14 16
0,00
0,01
0,02
0,03
0,04
0,05
70 / 30 (B)
0 2 4 6 8 10 12 14 160,00
0,01
0,02
0,03
0,04
0,05
70 / 30 (A)
0 2 4 6 8 10 12 14 160,00
0,01
0,02
0,03
0,04
0,05
0,06
0,07 LDPE / PP30 / 70 (C)
inte
nsity
(ar
b. u
nits
)
0 2 4 6 8 10 12 14 160,00
0,01
0,02
0,0330 / 70 (B)
B - B0 [10 - 8 T]
0 2 4 6 8 10 12 14 160,00
0,01
0,02
0,03 30 / 70 (A)
0 2 4 6 8 10 12 140,00
0,05
0,10
0,15
0,20
0,25
0,30
LDPE (C)
inte
nsity
(ar
b. u
nits
)
B - B0 [10 - 8 T]0 2 4 6 8 10 12 14
0,00
0,02
0,04
0,06
0,08
0,10 LDPE (B)
0 2 4 6 8 10 12 140,00
0,02
0,04
0,06
0,08
0,10
LDPE (A)
0 2 4 6 8 10 12 140,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035PP (C)
inte
nsity
(ar
b. u
nits
)
0 2 4 6 8 10 12 140,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035PP (B)
B - B0 [10 - 8 T]0 2 4 6 8 10 12 14
0,000
0,005
0,010
0,015
0,020
0,025
0,030
0,035PP (A)
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 h2JPH AND 2JPH 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: [email protected]
Four years ago, our report appeared [1] about first probable observation of two-bond sca-lar 31P−1H 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, CH2Ph, Ph; JPH 2.9 ± 0.5 Hz, from 1H and/or 31P proton-coupled NMR spectra), investi-gated 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 com-plexes [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 addi-tion, 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 ob-served heteronuclear JPH coupling, namely, the P↔H interaction across the N−H···O−−P+ hydrogen bond (h2J) in the formed 6-membered ring, or traditional coupling along a long-range pathway via the molecular backbone (4J). The best simple method to choose between these two pathways was a theoretical study. Results of presented DFT/FPT computations sug-gest that the foregoing interactions in 1 are in fact due to an across-H-bond J coupling. As the h2JPH coupling seems to be a sensitive probe of the H-bond angle and distance [5], an interest-ing 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
ylide 2 [7], i.e. a proper assignment of the 1H-spectra observable 2JPH coupling (≅ 5.2 Hz) and tentative explanation of an “absence” of the second coupling of this type in terms of fast pyra-midalisation 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 ge-ometry at its β-carbon, and then to estimate 2JPH for each arrangement. The simplest ylide 3 was thoroughly examined before, including the J-sign determination (2JPH +6.5 Hz, in C6D6) [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 mini-mal magnitude of vicinal JPH coupling. Gas-phase DFT/FPT data for 2JPH in ylide 3 plotted as a function of the X–Pα–Cβ–H torsion angle (ϕ), where X is dummy atom lying on an axis per-pendicular to the CS 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 qualita-tive agreement of calculations is observed with 2JPH data in solution (13.8 vs 6.5 Hz) and that for ϕ near 28o this more than twice overestimated NMR parameter most likely is of a negligi-ble value in P-ylides. Obviously, various motional processes (e.g. pyramidalisation or rotation around the Pα–Cβ 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
data for Cβ-nonplanar model 3 are in agreement with 2JPαHβ’ = 12.1 and 2JPγHβ’ = 1.3 Hz evalu-
ated 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 2JPγHβ’ ≅ 0.5 Hz was determined very recently [10].
Calculational Details. Fermi-contact (FC) terms are usually dominant contributors to to-tal J couplings, including interactions with a P nucleus [11]. According to works by Del Bene et al. [12], the trans-H bond hnJAB (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 dis-cussed 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/FPT-computed 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 agree-ment with the nJXY (XY = CH, PC or PP) couplings measured for above compounds in solution. Differently designed conformers of 3 were geometrically optimised under the CS symmetry constraint.
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,
[1-3] containing various proportions of these three monomers were investigated by proton NMR second moment (M2) and spin-lattice relaxation times (T1) 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 Tg 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 M2 obtained for copolymers (Fig. 1) were compared with calculated values for different motional modes and in addition confronted with the M2 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 T1 measurements as a function of temperature. The T1 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 T1 results. The increase of lactide content makes the copolymer more stiff. Polymer, 39, 267 (1998)
50 100 150 200 250 300 350 400 4500
2
4
6
8
10
12
14
16
18
20
M2= 10,18
M2=0,52
Tg= 232 K
M2= 7,29
M2= 10.7
M217.9925MHz
Seco
nd m
omen
t [m
T2 10
2 ]
Temperature [K]2 3 4 5 6 7 8 9
100
1000
100001413 PGLC(10/70/20)
Tg=294K
Rela
xatio
n tim
e T
1 (m
s)
1000/T
Fig.1. Temperature dependence of proton second moment of PGLC(30/20/50)
Fig. 2. Arrhenius plot of 1H-NMR spin-lattice 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
T1 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.
T1 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 T1 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 T1 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.).
10k 100k 1M 10M100
ν∼ 0 .22
ν∼ 0 .51
T 1(s)
Larmor frequency (Hz)
293K 281K
3,05 3,10 3,15 3,20 3,25 3,30 3,35 3,40
2
3
4
5
Ea=3,9 (kcal/mol)
Ea=4,1 (kcal/mol)
D(1
0-5 c
m2 /s
)
1000/T
Carbopol 1% Carbopol 1%+surfactant (Brij 58) 1%
Fig. 1. 1H spin-lattice relaxation times versus Larmor Fig. 2. Water diffusion in Carbopol hydrogels. frequency for Carbopol (0,5%) at 281 and 293K. [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 T1 relaxation in polyacrylamide gels: A unified approach using volume averaging, J Magn Reson 132 (1998) 240-254
65
AN NMR STUDY OF Pr0.5Ca0.5Mn1-xGaxO3 (x=0 AND 0.03)
Colin John Oates1, Czesław Kapusta1,2, Peter Charles Riedi2, Marcin Sikora1, Dariusz Zając1, Damian Rybicki1, Christine Martin3, Cedric Yaicle3
1Department of Solid State Physics, Faculty of Physics & Nuclear Techniques, AGH
University of Science and Technology, Kraków, Poland; 2School of Physics and Astronomy, University of St. Andrews, St. Andrews, KY16 9SS, Scotland, United Kingdom; 3Laboratoire
CRISMAT – UMR 6508, ISMRA et Universite de Caen, 6 Boulevard du Marechal JUIN, 14050 Caen Cedex, France
A NMR study of polycrystalline Pr0.5Ca0.5Mn1-xGaxO3 (x=0 and 0.03) at 3 K is
presented. Zero field spin-echo spectra of the Ga doped compound consist of a overlapping 69,71Ga signal at 74 MHz (hyperfine field of 5.3T), a 55Mn double exchange (DE) line at 375MHz (35.5T) and a weak Mn3+ 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 55Mn NMR measurements of Pr0.67Ca0.33MnO3. At the demagnetized and remanent state, a variation of spin-spin relaxation time, T2, across the 55Mn 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 3He 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 inhomo-geneity 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 dep-endence 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 3He. 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 grad-ient 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 B1 field within the wor-king volume of better than 1% homogeneity. The coil can be tuned to both 3He and 1H reson-ance 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 hyper-polarized helium-3. The first images obtained in the described system will be presented.
67
MOLECULAR DYNAMICS IN POLY(ETHYLENE OXIDE) (PEO): 1H-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⋅106
and M=1⋅105 were studied by T1 Dispersion NMR and Dielectric Spectroscopy. T1 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⋅106 and M=1⋅105 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⋅106 and M=8.4⋅105 [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.
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5
-2
0
2
4
6
8
10
γ '- process
β - process
γ - process
186 kJ/mol
22 kJ/mol
13 kJ/mol
27 kJ/mol
PEO 2E6
log(
f) [H
z]
1000/Tmax [1/K]
0.01 0.1 1 101E-3
0.01
0.1
1
ω 0.27PEO_2E6
ω 1.23
45 °C 65 °C 90 °C
T 1 [s]
Larmor frequency ω [MHz]
Fig. 1. Larmor frequency dependence of 1H-NMR T1 relaxation time for PEO (M=2⋅106) Fig. 2. Arrhenius plot correlation times for PEO (M=2⋅106)
68
1H 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. 1H and 13C 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. 13C 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 1H NMR study of solid flawonoids. Large dipolar coupling for 1H- 1H 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].
1H 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 ZrO2 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, 1H 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
15N 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 15N NMR coordination shift, i.e. the difference between the chemical shift of the same nitrogen atom within the complex and ligand molecules (∆coord = δcompl - δlig), 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 1H NMR measurements of their equimolar mixtures with the ligands. In the case of platinides two distinct sets of 1H 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 Pentak1, Wioletta Korus1, Anna Sułkowska2, Wiesław W. Sułkowski1
1Department of Environmental Chemistry and Technology, University of Silesia,
Szkolna 9, 40-006 Katowice, Poland; 2Department 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 1H-NMR, 13C-NMR and 31P-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.
N
N
O
NH2RO
Me1
2
34
5
R = CH3, C2H5, NH2 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
1H, 13C NMR AND GIAO/DFT CALCULATIONS OF SUBSTITUTED N-(4-ARYL-1-PIPERAZINYLBUTYL) DERIVATIVES,
NEW ANALOGUES OF BUSPIRONE
Maciej Pisklaka, Jerzy Kossakowskib, Iwona Wawera
aDepartment of Physical Chemistry, Faculty of Pharmacy, The Medical University
of Warsaw, Banacha 1, 02097 Warsaw, Poland; bDepartment 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).
N NN
O
OH
H
R
R
Ar
1
2
3
4 5 6
7
8
9
1213
1415
11
16
17
18
19
20
21
22
23
24 25
26
10
13C NMR spectra of a series of compounds were recorded for CDCl3solution 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 13C CP MAS NMR techniques and reasonable assignment of carbon resonances was made with the aid of theoretical studies.
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, [email protected]
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 1H 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 1H 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
Humic acids isolated from sludge from biologic-mechanical sewage treatment plant in Sosnowiec Zagórze were characterised by using 13C NMR and 1H NMR spectroscopy.
The 1H NMR spectra were recorded with Bruker 400 MHz spectrometer at room temperature. The 13C 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 13C 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 1H 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 1H 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 Popenda1, Zofia Gdaniec1, Grażyna Dominiak1, Jan Milecki2, Ryszard W. Adamiak1
1Institute of Bioorganic Chemistry, Polish Academy of Sciences, Z. Noskowskiego 12/14,
61 704 Poznań, Poland; 2Department 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, 1H-13C HSQC, 1H-31P 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 La1.4Sr1.6Mn2O7
Damian Rybickia , Czesław Kapustaa,b, Peter Charles Riedib, Colin John Oatesa,
Dariusz Zająca, Marcin Sikoraa, Clara Marquinac, Ricardo Ibarrac
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 55Mn nuclear magnetic resonance study of a layered perovskite La1.4Sr1.6Mn2O7 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) Mn3+, Mn4+ 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 Steinbauer1, Ing. Karel Bartušek, DrSc2
1Faculty of Electrical Engineering and Communication, Brno University of Technology,
Purkyňova 464/118, 612 00 Brno, [email protected]; 2Institute of Scientific Instruments, Academy of Sciences of the Czech Republic, Královopolská 147, 612 00 Brno,
[email protected] 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 material. In our example the paramagnetic specimen of thickness x0 is inserted in homogeneous magnetic field with induction B0 parallel with z-axis. Magnetic induction in the specimen with susceptibility χs increases to . When material of the specimen gives no MR signal, the indirect method of induction B
(0 1sB B χ= ⋅ +
.const=
)s
0-6 T.m. Relative deviation 9 % from initial
s computation can be used. Assuming constant magnetic flux Φ thru normal area of cross-section S of the magnet working space
. Suppose the specimen has enough
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 , what means that sum of hatched areas bounded by curve in Fig. 1 with respect to the base value of induction B
S
B dSφ = ⋅∫∫
( )0B x∆
( )0 0B x dx∆ ⋅ =∫0 is
zero. If substance surrounding the specimen gives MR signal and we can determine the course of , we also can compute the value Bs and χs values of the investigated specimen. Several numerical tests were carried to verify the method 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 B0 = 4,700 T in z-axes direction. Module of magnetic induction B along the “path” is depicted in Fig. 2. The data set from graph shown in Fig. 2 was numerically integrated and area bounded by the curve B and base level B0 = 4.700 T was evaluated. Founded difference between areas over and below B0 level was 9.16·1
χ1
Bs x0
B0
∆B0(x)
z χ2
x
Fig. 1. Local deformation of magnetic field due to weakly
χs
χ2 χ1
estimation was caused due to numerical error.
79
Fig. 2. The course of magnetic induction slony the path marked in Fig. 2 χ1 = -9·10-4,χs = 3·10-3, χ2 = 0
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 (χH2O = -9.04·10-6) filled into cube vessel. The field echo method with echotime TE = 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 B0 = 4.7 T. Position of the specimen is depicted in Fig. 3A. Obtained image with phase-contrast 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
0B ∆Θ
ETγ ⋅∆ =
gyromagnetic ratio of water. In this way we can identify the course of magnetic induction
, where γ is
change in water nearby the clay specimen.
0 d measured area ∆B0 from, the suscept
From known thickness x of the specimen anon water filled vessel 40×35 mm. Processed in Matlab. Fig. 3. Images obtain from MR experiment with 7 mm thick clay specimen placed
ibility of clay specimen was finally calculated 0 2.B dxB B − ∆ ⋅− ∫ -6
-50-3
0 0
656 10 8.07 104.7 7 10
SS B B x
χ⋅
= = = = ⋅⋅ ∆ ⋅ ⋅
.
Conclusion: ethod designed for magnetic susceptibility measurement based on MRI
tomogrThe maphy 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
80
A NOVEL SOURCE OF MAGNETIC FIELD
Katarzyna Suchanek, Mateusz Suchanek
FOR IMAGING LASER-POLARIZED 3HE
, Katarzyna Cieślar, Tadeusz Pałasz,
Marian Smoluchowski Institute of Physics
The development of the system for NMR imaging of the laser-polarized helium-3 is present
Zbigniew Olejniczak*, Tomasz Dohnalik , Jagiellonian University, Kraków, Poland;
*Henryk Niewodniczański Institute of Nuclear Physics, Kraków, Poland
ed. 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 work e for imaging small animal lungs.
is used for spatial
ing volumA 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 inho-mogeneity 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 shimm-ing).Using this method a homogeneity of 56 ppm within the sphere was achieved.
A system of actively shielded gradient coils mounted between the poles 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
1Wiesław W. Sułkowski, 2Barbara Bojko, 2Anna Sułkowska, 2Joanna Równicka
1University of Silesia, Department of Environmental Chemistry and Technology, Szkolna 9,
40-006 Katowice, Poland; 2Medical 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 1HNMR 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 13CNMR 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
1 13
sitions. 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.
Scheme 2
E OF 19F 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 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 multi-component 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 19F NMR spectroscopy has been developed. Investigated compounds are transformed into fluoro derivatives (see Scheme 1) and then identified on the basis of their 19F chemical shifts.
Cl
CF3NO2H2ONaHC
NH
CH RCOOH
+ R CH COOH 2 3EtOH
NH2NO2 Scheme1
NO2
O3 NO CF
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 po
3CF
Cl Cl
CF3
SO3H
Cl
CF3
SO3 H
N2OfumingH 2SO4
65 %
4SO2H
fuming
30 %fuming
HNO 3
83
To obtain model derivatives, prepared compound was used in the nucleophilicth several a
substitution reaction wi rse of the reaction has been strongly affected by the conditions applied (Scheme 3) leading to N-phenyl substituted amino acids or to benzoimidazole derivarives. t was found that in both cases the differences in fluorine chemical shift h to use new marker in discussed investigations (Table 1).
Institute of Physics, A. Mickiewicz University, ul. Umultowska 85, 61-614 Poznań, Poland
he paper reports the proton and deuteron NMR study of molecular dynamics of tert-butyl chloride confined in CPG with pore diameter of 7.4 nm here denoted as TBCC. he 1H and 2H NMR lineshapes and spin-lattice relaxation times were measured in the tem erature range 70 K ≤ T ≤ 292 K, thus covering all the phases which occur in the bulk state of TBC.
he phase transition from liquid to solid phase I of the TBCC is invisible in temperature dependences of 1H and 2H 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 1H, 2H relaxation times T1 are reduced indicating that the confinement strongly restricts molecular reorientation.
wo 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].
phase III, the temperature dependences of 1H and 2H 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 ted ation
es of bulk-like phase obtained from both 1H and 2H T1 data are given in Table I.
at 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
phase of TBCC. This effect can be explained by the surface to volume ratio, increasing with the reduction of the pore diameters, where a
cti c c x ces direct interaction with pore walls. The slowing down of the motion can be also due to geometrical restrictions and depends on the
f re n p e
able 1. Activation energies and the preexponential factors of the C3’ motion of bulk-like phase of TBC
onfined to 7.4 nm pore diameters CPG obtained from 1H, 2H T1. 1H T1 2H T1
ECULAR DYNAMICS OF TERT-BUTYL CHLORIDE CONFINED TO CPG (7.4 NM)
Lidia Szutkowska, Barbara Peplińska, Stefan Jurga
T
Tp
T
T
In
of the tert-butyl group, as the consequence of confinement. The calcula activenergies and preexponential factors for C3
’ rotation in two dynamically different stat
The fact th
the intermolecular interactions in the bulk liquid
large fra on of onfining mole ules e perien
degree o ductio of the ore siz .
Tc
Ea (kJ/mol) 4.2 4.6 Subphase I τ0 (s) 1.4 E-11 2.2E-11
Ea (kJ/mol) 4.2 4.6 Subphase II τ0 (s) 1E-10 1E-10
Ea (kJ/mol) 15.5 TBC in bulk [2] τ0 (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,
g from 18% to 63% wt. by means of the transverse spin-spin relaxation time T rela
n chemical exchange (Fig. 1) from the proton transverse relaxat
Poland
This paper reports NMR relaxation study of interfacial properties of water molecules in lyotropic decylammonium chloride and dodecylammonium chloride in the solutions rangin
2 xometry [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 of the protob
ion T2 data and measured T2 dependence on the FT-CPMG 2/π -π pulse delay cpτ (Fig. 2).
Obtained activation energies for exchange rates Cb 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.
cp
Fig 1. Proton-exchange rate Cb versus temperature for DDACl with water 33% wt.
Fig 2. Relaxation rate 1/T2 of water molecules vs. Carr-Purcell pulse spacing τ in FT-CPMG
1. D. E. Woessner, Journal of Chemical Physics 3 3-& (1963). 2. G. Paradossi, Cavalieri F., and Crescenzi V., Carbohydrate Research 3. J. D. Gault, M. A. Leite, M. R. Rizzatti, and H. Gallardo, Journal of Colloid and Interface Science 1 88). 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).
Literature
9, 278300, 77 .
22, 587 (19
86
MR MICROSCOPY IN COMPARISON OF YOUNG AND OLD TOOTH
Marta Tanasiewicz*, Władysław P. Węglarz**, Edyta Machaj**, Tomasz Kupka*,
*
**Department of Nuclear Radiospectroscopy, H. Niewodniczański Institute of Nuclear Physics Polish Academy of Sciences, Kraków, Poland
ere a DLrch Systems) based software. The structure (thick, density) of the tooth from young p
[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.
ng of nal vo ssue 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.
STRUCTURE
Andrzej Jasiński**.
Department of Preclinical Dentistry, Silesian Medical Academy, Zabrze, 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 H2O 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 w an lysed using I 5.5 (Reseaand older atients were compared. Results indicate the possibility of use MRM as the original method of visualization and tooth structure registration.
[5] M. Tanasiewicz, T.W. Kupka, W.P. Węgtooth surface. An in vitro study, Jour
larz, A. Jasiński, M. Gibas, 3D SE geometry imagiof Dental Research 2003, l. 82, special i
87
STUDIES OF POLY(ASPARTIC ACID) STRUCTURE AND ITS ING 1H NMR SDERIVATIVES US PECTROSCOPY
Elżbieta Tylek, Jolanta Polaczek, Jan Pielichowski
Department of Chemistry and Technology oh Polymers Technical University, Kraków, Poland
Poly(aspartic acid) ( could be have a
neal or cyclic structure (figure 1). Poli(aspartates) have different proprieties depending on eir
s can be characterized using some uclear magnetic resonance methods; especially H NMR and 13C NMR spectroscopy. The ain chain of PAA include α - and β - peptide bonds, where the ratio α:β peptide units can be
and C NMR. Application H NMR
here: PAA) belongs to biodegradable polymers, which lith chemical construction [1,2].
Figure 1. Structure poly(aspartic acid)
The structure of poly(aspartic acid) and its derivative
1
N
O
O
NH CH
COOH
CH2 CO NH CH
CH2
COOH
CO
mq n
q ≥ n+m
nmdetermined by NMR spectroscopy; particularly important are signals methane in 1H NMR
signals methylene in 13 1 spectroscopy can observe local branches and opening peptide ring in PAA structure. Using 13C NMR spectroscopy in PAA
its derivatives to make possible can be determined local branches, characteristic ormation and irregular structure. trum 1H NMR of poly(succinimide) characterized signals of th
and confSpec e methine proton in
obse
Procβ-as
open
char otons methine CH-) and methylene (-CH2-) of the succinimide unit disappeard and appear signals of rotons methine at 4,7 and 4,2 ppm and methylene at 2.8, 2.7 and 2.4 ppm. Two different hemical 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].
5,3 ppm and smaller signal at 4,6 ppm succinimide units. Two very board resonance are rved 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]. ess hydrolysis of the polymerization products leads to poly(aspartates) containing α- and 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 ing in position β- is more prefer.
In result of hydrolysis can be obtained salts of poly(aspartic acid). On figure 2 shows acteristic spectrum 1H NMR of sodium polyaspartate in D2O. Signals of pr
(-pc
88
NH CH CH2 NH CH CO
References: 1. E. Dziki, J. Pielichowski:2. E. Dziki, J. Pielichowski:3. E. Dziki, J. Pielichowski:4.K.Matsubara, T. Nakato: „
ONa
CH2n mCOONa
CO
89
“Polimery”, (2003), 48, nr 1 „Inżynieria biomateriałów”, (2003), nr 28 „Inżynieria biomateriałów”, (2003), 27, 6 Macromolecules”, (1998), 31, 1466-1472
SOLID-STATE NMR INVESTIGATION OF LOCAL CHAIN DYNAMICS IN
POLYISOBUTYLENE/POLYPROPYLENE-CO-BUTENE BLENDS
Marcin Wachowicz1,2, Justyna E. Wolak2, Stefan Jurga1, Jeffery L. White2
1Institute of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland; 2Department 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 2H- and 129Xe-
ds. The pure PIB and 50/50 mixtures of PIB and PEB, where the butane ed (23 or 66 wt %), were studied. The
n and vacuum drying [1]. ted PIB (Fig. 1) and for two
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 129Xe-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)
NMR methomonomer concentration in PEB copolymer was variblends were prepared by dissolution in toluene, solvent evaporatio The quadrupolar echo 2H-NMR spectra for pure perdeuteraPIB/PEB blends were acquired in the temperature range from 210 to 294 K. In the blend
2 Fig. 1. H-NMR spectra of pure
perdeuterated PIB.
129Fig.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
35Cl-NQR STUDY OF MOLECULAR DYNAMICS OF TETRACHLOROPHTHALIMIDE
AND N-PHENYLTETRACHLOROPHTHALIMIDE
A. Walcza 1 R. Żaguń1, J. Kasprzak1, B. Brycki2, B. Nogaj1
1 Department of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań,
Introduction
The information on molecular dynam cs can be obtained from the temperature
cs of
e
35
k ,
Poland; 2 Department of Chemistry, Adam Mickiewicz University,Grunwaldzka 6, 60-780 Poznań, Poland
idependencies of the nuclear quadrupole resonance (NQR) frequency.
In this work the NQR method was applied to study molecular dynamitetrachlorophthalimide (C6HCl4NO2) and N-phenyltetrachlophthalimide (C12H9Cl4NO2). 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 thlast stages of digestion of carbohydrates [1]. Experimental
The compounds studied were synthesized at the Faculty of Chemistry, A. Mickiewicz University, Poznań. 35Cl-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 35Cl-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-phenyl- tetrachlorophthalimide. Results and discussion
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 νQ decreases with increasing temperature (Figs.1 and 2). Using the least-squares approximation the theoretical functions νQ(T) [2] were fitted to the experimental dependencies.
50 100 150 200
37.4
37.6
37.8
38.0
38.2
N
O
O
ClCl
ClCl
H
ν3
ν4
ν2
ν Q [M
Hz]
T [K]
35
250 300 350 40037.2
ν1
Fig.1. Temperature dependence of Cl-NQR frequency in tetrachlorophthalimide.
Solid line - fit with the Brown function.
91
50 100 150 200 250 300 350 40037.2
OCl
Cl 2
ν1
T [K]
37.4 NCl
ν
37.6
38.0
OCl ν3 ν4
ν Q [M
35
37.8Hz]
38.2
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 esonance frequency and taking into regard anharmonicity of the crystal lattice vibrations.
in the slopes of the temperature dependencies of the 35Cl-NQR frequen
ed for the lines ν3 and ν4 on the plots of νQ(T). References: 1. S.Sou, H.Takahashi, R.Yamasaki, H.Kagechika, Y.Endo, Y.Hashimoto, Chem.Pharm.Bull. 49, 791
rThe differences cies permitted assignment of individual lines to particular chlorine atoms in the
molecules studied (Figs.1 and 2). In tetrachlorophthalimide and in N-phenyltetrachloro- phtalimide, 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 observ
92
93
35Cl-NQR STUDY OF THE SUBSTITUENT EFFECT ON THE ELECTRONIC STRUCTURE
OF TETRACHLOROPHTHALIMIDE DERIVATIVES
A. Walczak1, A. Mielcarek1, B. Brycki2, B. Nogaj1
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 35Cl-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 NQR spectrometer type NQS-300 (0. nics (Poland). Cl-NQR frequencies were measured at 77K. Results
1. With i
ity, Poznań. All measurements were performed on a pulse Fourier transform355-300 MHz) from MBC Electro
and discussion The spectra of all tetrachlorophthalimide salts revealed four lines, which proves the crystalline inequivalence of chlorine atoms in these compounds. The 35Cl-NQR frequencies and line widths obtained at the liquid nitrogen temperature (77K) are collected in Table
ncreasing ionic radius R of the substituent M the mean resonance frequency Qν decreases, which means that the electron density on the chlorine atoms increases (Fig.1).
40
46
OCl
0.6 0.8 1.0 1.2 1.4 1.6 1.836
37
38
39
*
(3)
(2)
(4)
N
OClCl
ClM
Cs
K
Na
Li
ν Q [M
Hz
2.0
(1) OCl
]2O
ClCl
0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.836
38
4
44N
ClM
ν [M
Hz]
Cs
KNa
Li
40Q
Fig.1. The mean 35Cl-NQR frequency versus the Fig.2. The mean 35Cl-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.
94
Table 1. 35C νQ – full width a a
p. COMPOUND STRUCTURAL FORMULA νQ [MHz] δνQ [kHz]
l – NQR results for tetrachlorophthalmide salts at 77K (νQ – 35Cl-NQR frequency, δt h lf-intensity).
L
1 Lithium salt of tetrachlorophthalimide
N
O
Cl
ClCl
Li 38.748 39.484
31 12
OCl
OCl
Cl
N
OClCl
K
Nl
ClCs
38.483
39.556
19
18
2 Sodium salt of tetrachlorophthalimide
N
OCl
Cl
Na
37.547 37.582 37.613
31 10 11
37.412 19
3 Potassium salt of tetrachlorophthalimide
OCl
Cl
38.077 38.102
24 22
Cesium salt of OCl
C 35.701 15
36.928 37.205
14 14
4 tetrachlorophthalimide OCl 38.504 18
On the basis of [1,2] the experimental dependence Qν (R) was approximated by a
theoretical function of the form:
36.932 37.021
10 24
−+=
cRbaQ expν (1)
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 35Cl-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).
95
13C AND 1H NUCLEAR MAGNETIC SHIELDING AND SPIN-SPIN COUPLING CONSTANTS OF 1,2-13C-ENRICHED ETHYLENE
IN THE GAS PHASE
Marcin Wilczek
, Karol Jackowski
La R Spectroscopy, Department of Chemistr w Universi 02-093 Warsaw, Poland; [email protected]
boratory of NMul. Pasteura 1,
y, Warsa ty,
In this study we present gas phase measurements of the 1H and 13 chemical s and spin-spin coupling constants for 1,2-13C-ethylene (13C2H4). This isotopomer of ethylene gives an AA´XX´X´´X´´´ NMR spectrum of which the XX´X´´X´´´ and AA´ parts can be separately 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 1,2-13C-ethylene (i.e. 1JCH, CH, 2JHH, 3JHH(cis) and 3
(tran
C NMR hifts
1 13
1JCC, 2JJHH s)) C NMR spectra. The 13C2H4 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 13C NMR spectra of 13
4 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 1,2-13C-ethylene. T eous solvents were additionally cor r ethylene- lene inter and this way we could also de the reliab MR parameters for an isolated 13C2H4 molecule. It was especially im or the 1JCC spin-spin coupling and for both the 1H and 13C shielding constants which were distinctly dependent on density. The other spin-spin couplings (1JCH, 2JCH, 2JHH, 3JHH(cis) and 3JHH(trans)) in a 1,2-13C-ethylen
estigations performed for 1,2-13C-acetylene [2] where the density dependence was also found only for the spin-spin coupling between carbon nuclei, 1JCC. References:
in the 1H and 13
H and C2H
he values measured in gasmolecular interactions
rected fotermine
ethyle N
portant f
e molecule were almost independent of density in the studied systems. This result is consistent with our previous inv
[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.
96
THE GLASS TRANSITION TIME SCALE AND CONFIGURATIONAL ENTROPY IN POLYMERS: AN EXPERIMENTAL MOLECULAR
J
VIEW
. E. Wolak, X. Jia, Jeffery L. White
Department of Chemistry, North Carolina State University, Campus Box 8204, Raleigh,
, we use a miscible blend, PIB with PEB66 (polyethylene-co-1-), to
emonstrate 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 Tg timescale are directly relevant to fundamental understanding of the Tg length-scale, i.e., the dimension of cooperatively rearranging regions.
North Carolina 27695-8204
We report direct experimental observation of local conformational dynamics in a polymer chain at the calorimetric glass transition temperature Tg. 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 Tg 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 importantlybutene in which the concentration of 1-butene comonomer units is 66 weight %d
Banacha 1, 02-097 Warsaw, Poland; 2Department of Fruit and Vegetable Processing,
hocyanins 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, cyanidingalactoside and cyanidin rutinoside were obtained from Agricultural University, Wrocław. NMR spectrometers
: cross-polarization (CP) magic-angle spinning (MAS) solid-state 13C NMR spectra were recorded on a Bruker AVANCE DSX-400 instrument at 100.61 MHz. The samples were spun at 8 kHz in 4mm ZrO2 rotor. 13C Chemical shifts were calibrated indirectly
rough the glycine CO signal recorded at 176.03ppm relative to TMS. 1H and 13C NMR pectra for the samples in acetone and methanol were recorded on a Bruker Avance 500 MHz pectrometer equipped with an inverse detection probe. The experiments were run using tandard Bruker software.
he structure of cyanidin and its derivatives:
thsss T
6
OH
OR45310
6'
.R=H cyanidin; 2.R=galactose, cyanidin galactoside; 3.R=rutinose, c
OH
HO
OH
78
29O
Cl
1'
2'3'
4'
5'
1 yanidin rutinoside. 13C NMR spectra of 1-3 were recorded for solution and solid state. Unfortunately, the orrect assignment of the signals is not an easy task. Positive charge at oxygen atom of avylium 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.
cfl
97
98
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.
Re 1. Kong, Jin-M rd, R. (2003).
Analysis and biological activities of anthocyanins. Phytochemistry, 64, 923-933.
INVESTIGATION OF TRANSESTERIFICATION IN POLY(ETHYLENE 2,6-NAPHTHALATE)/POLYCARBONATE
A. Woźniak-Braszaka)
COMPOSITE USING OFF-RESONANCE NMR AND DMTA TECHNIQUES
, J. Jurgab), K. Jurgaa), S. Jurgac), M. Szostekb)
Processing Division, Institute of Materials Technology, Poznan University of Technology, Piotrowo 3, 61-138 Poznań, Poland, e-mail:[email protected]; c)Macromolecular
Physics Division, Institute of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland
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 T1ρ
off . The dynamic-mechanical properties of the blends were investigated by dynamic-
mechanical 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.
a)High Pressure Physics Division, Institute of Physics, Adam Mickiewicz University, Umultowska 85, 61-614 Poznań, Poland, e-mail:[email protected]; b)Polymer
2. J. Jurga, A. Woźniak-Braszak, Z. Fojud and K. Jurga, Proton longitudinal NMR relaxation of pNuclear3.W. J. behavior of poly(ethylene naphthalat ) 4933-4942.
.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.
ol(p-phenylene sulfide) in the laboratory and the rotating frames reference, Solid State Magnetic Resonance, in print. Yoon, H. S. Myung, B. C. Kim, S. S. Im, Effect of shearing on crystallization
e), Polymer 41 (20004
T2 RELAXATION MAP OF ARTICULAR CARTILAGE IN DIFFERENT STAGE OF REGENERATION
Tomasz Zalewski, Sławomir Kuśmia, Tomasz Trzeciak*, Jacek Kruczyński*, Stefan Jurga
ań, nce 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 T2 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 T2 relaxations times to make the assessment of different methods of therapy.
Institute of Physics, Adam Mickiewicz University, Umultowska 85, PL-61614, Pozn
Poland; * Department of Orthopaedics University of Medical Scie
Articular cartilage with out scaffold T2 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
102
Fig.1 Simple coumarins
R1 R2
OCH3 OH
herniarin H OCH3 esculetin OH OH
scopoletin
R3 R4 bergaptene OCH3 H
umbelliferone H OH
xanthotoxin H OCH3
Fig .2 Furanocoumarin
OF COUMARIN IN CALCULATIONS AND EPR STUDIES
ńska*, 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
ake up an important part of the human diet.
R 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, 13C CP MAS NMR, GIAO-CHF calculations, EPR
SOLID STATE CONFORMATION AND ANTIOXIDANT PROPERTIES 13C CP MAS NMR, GIAO-CHF
Agnieszka Zieli
Abstract: Coumarins are widely distributed in nature and are found in all parts of plants. These compounds m
13C 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 (R2=0.9845) can be used to obtain structural information for coumarins, for which solid state NM
O OO
R3
R4O O
R1
R2
103
MICROTOMOGRAPHY STUDIES OF TABLETS
lińska, R. Marszałek, E. SieM. Zie radzki
02-097 Warsaw, Poland
ing small The ellulose derivates, which form gel and swell on contact with water, were of special interest,
polymers are mainly used for controlled drug delivery[1,2].
as pH-independent permeability.
]. Bowtell R., Sharp J.C., Peters A., Mansfield P., Rajabi-Siahboomi A.R., Davies M.C.,
Faculty of Pharmacy, The Medical University of Warsaw, Banacha 1,
Magnetic resonance imaging (microtomography) is a unique method for study objects. MRI has been widely used to monitor the diffusion of water into polymers.
csince these
Different behaviour on contact with water demonstrated copolymers of metacrylic acids, such as Eudragit RL. It is water insoluble and hTherefore 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.
CONFORMATION OF ARYLPIPERAZINES WITH LONG SIDE CHAIN – 2D NMR INVESTIGATIONS
Marek Żylewski1, Marek Cegła1, Piotr Kowalski2, Teresa Kowalska2, Maria Paluchowska3,
Departament of Organic Chemistry, Medical College, Jagiellonian University, 9 Medyczna
Str. 2
ified class of 5-HT1A serotonin recepto
a of various arylpiperazines containing flexible 4-carbon chain showed that small changes in the structure can express in large changes in conformation. Also
We have found that arylpiperazines can exist in solution in two different types of
on, between protons of the two ending
ethylene 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.
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.
Ryszard Bugno3, Andrzej Bojarski3
1
, 30-688 Kraków, Poland; Institute of Organic Chemistry and Technology, Cracow University of Technology, 24 Warszawska Street, 31-155 Kraków, Poland; 3Department 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 divers
r 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 spectr
protonation of the piperazine moiety and change of the solvent can lead to conformation'schange.conformations. First is, the most expected for alkyl chain, maximally extended conformatiin which we can not observe any NOE interactions m
R2NH
H
H
HH
H
HH N
NCH2
CH2Ph
104
MAPPING OF THE BI-EXPONENTIAL DIFFUSION IN HUMAN SPINAL CORD
T. Banasik, A. Jasiński, M. Hartel1, M. Konopka1, P. Pieniążek1, T. Skórka, W.P. Węglarz
H. Niewodniczański Institute of Nuclear Physics, 31-342 Kraków, Poland; 1Silesian
InDif rs.
owever, it has a limite difficulties. Recently, a mber of studies reported successful diffusion imaging of the cervical spinal cord (CSC)
using s
ies in the CSC at high b–
of 1200, 2000, 3000, 4000, 6000 and 7000 s/mm2. Echo time varied from 84 ms for b=450 s/mm2 to TE=155 ms for b=7000 s/mm2. 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
(1) here, the subscripts f and s refer to fast and slow diffusion components respectively. Due to
esults:
adient intensity for a ROI in the Ventral Horn Left (VHL) in GM nd 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
Diagnostic Imaging Center Helimed, 40-752 Katowice, Poland
troduction: fusion weighted imag neurological disordeing (DWI) is used routinely to evaluate
d role in the spinal cord due to technical Hnu
pin-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 studvalues of up to 7000 s/mm2, 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/mm2, and NEX = 16 for b-values
).exp().exp( ssff DbADbAS −+−=wlow S/N of DWI in Z direction at high b values, only transverse diffusion images were analyzed.
RGood quality DW images were recorded for diffusion gradient in transverse direction (X, Y) for b-values up to 7000 s/mm2, as shown in Fig. 1. Fig.2 presents dependence of DW signal ntensity on X diffusion gri
a
105
selec rior Funiculus Right (PFR) for diffusion directions. The average values of diffusion components in the Ventral Horn in GM are: Df=(1.11±0.17) 10-3 mm2/s, Af=0.54±0.07 and D =(0.14±0.03) 10-3 mm2 , A M in the Posterior FunDs=(0.08±0.02) 10-3 mm2/s, A =0.26±0.07. Our results are within the limits of human brain data [1
Conclusion: We have demonstrated the existence of non-m oexponential diffusion in the human CSC
ximated by fast and slow diffusion components.
ted in GM in VHL and Ventral Horn Right (VHR), in WM in PFL and Poste gradient along X, Y
s s=0.46±0.07. For Wiculus the corresponding values are: Df=(1.35±0.55) 10-3 mm2/s, Af=0.74±0.07 and
/s
s0] and full DTI data for the rat spinal cord at Th7 [11].
onthat can be appro
b=450 s/mm2
b=900 s/mm2
b=5000 s/mm2
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/mm2. Fig. 2. Dependence of signal amplitude on diffusion 0 1000 2000 3000 4000 5000 6000 700
0,1
1
A
GM-VHR WM-FCR
0 8000
b [s/mm2]
weighting along X direction in CSC at C5 level in GM – VHR, in WM – FCR. Solid lines represent the biexponential fit. 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).
106
DEUTERIUM NMR IN RMn2D2 (R = Y, Tb, Dy)
Henryk Figiel1), Paweł Filipek2), Paweł Szczurek1), Andrzej Budziak1,2)
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
2
ts 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 TN. Above TN the spin fluctuations are strongly influenced by hydrogen (deuterium). Measurements of the 2D spin-lattice relaxation time T1 and the Knight shift in function temperature above TN gives valuable insight into magnetic interactions and their dynamics. The longitudinal (T1) relaxation was mea ree d echo technique for YMn2D2 [1] and
r DyMn2D2. On approaching TN a resonant line shift δν are observed.
changes are caused by the spin fluctuations related ibution of nonmagnetic Y atoms [1]. tion to the T1 relaxation rate from r relaxation with divergence similar to
In the DyMn2D2 deuteride the T1 relaxation is even faster than that for bMn2D2 but the divergence is of the same character. The observed enhancement of the
DyMn2D2 deuteride reflects interaction with Dy of higher magnetic moment tharem
theTbMdeu
The analysed behaviour of T1 and the resonant line shift δν brought us to the conclusion that the exchange of the rare earth element in RMn2D2 deuterides strongly influences dynamics of spin fluctuations as monitored by 2D 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
The Laves phase type compounds of Manganese with Yttrium and rare earths (RMn ) easily adsorb hydrogen or deuterium atoms. These light elemen
sured using th -pulse stimulateTbMn2D2 [2], and by saturation recovery method focharacteristic critical type divergences of T1 and of theFor the YMn2Dx deuterides the observedwith Mn magnetic moments only, because of no contrFor the TbMn2D2 deuteride the significant contribufluctuating Tb moments is visible [2], what causes fastethat in YMn2D2. Trelaxation for
n Tb, whereas the same character of spin fluctuations due to Mn magnetic moments ains.
The Knight shifts for the investigated deuterides are negative. For DyMn2D2 deuteride temperature shift of the resonant line δν is less pronouncing than for YMn2D2 and
n2D2 deuterides what well corresponds to the faster relaxation observed in DyMn2D2 teride.
107
PHASE TRANSITIONS AND REORIENTATIONAL MOTIONS OF THE COMPLEX CATIONS AND NH3 LIGANDS IN POLYCRYSTALLINES
3
[Co(NH3)6](ClO4) AND [Zn(NH3)4](BF4)2
Natalia Górskaa, Łukasz Hetmańczyka, Edward Mikulia, Anna Migdał-Mikulia, Krystyna Hołderna-Natkaniecb, Weronika Kasperkowiakb
a Jagiellonian University, Faculty of Chemistry, Department of Chemical Physics,
30-0
p
60 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(NH3)6](ClO4)3 and ([Zn(NH3)4](BF4)2), respectively) are articularly interesting molecular materials because of different reorientational motions of the
complex cation and NH3 ligands. In [Co(NH3)6]2+ cation the Co3+ ion occupies the center of an octahedron, while in [Zn(NH3)4]2+ the Zn2+ ion occupies the center of a tetrahedron of the NH3 ligands. The ClO4
- and BF4- 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 TC [K] ∆H [J·mol-1] ∆S [J·mol-1·K-1
The proton magnetic resonance H NMR measurements were performed on a lab-
made 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 )
f NMR line in the studied compounds. In order to propose a model of inter
1
2nal dynamics, the
ent value was calculated from the van Vleck formula [4]. The onset of the rientations was taken into account during the heating of these compounds: the
o of octahedral or tetr were of 1.00 Å and ct to the Zn-N bonds, or oct d tance Zn-N and Co-N takes the value of 2.01 and 2.28 Å, respectively. The M2
Rigid obtained the value of 47.3 and 43.8 G2, for [Zn(NH3)4](BF4)2 and [Co(NH3)6](ClO4)3, respectively. The observed value of the second moment of 1H NMR line for [Zn(NH3)4](BF4)2 close to 15 G2 at 90 K can be interpreted as resulting from the NH3 ligands reorientation. On heating at TC1 also the reorientations of tetrahedral [Zn(NH3)4]2+ cation set on. The observed value of the second moment of 1H NMR line for [Co(NH3)6](ClO4)3 close to 17 G2 at 90 K can be interpreted also as resulting from the NH3 ligands reorientation. On heating the reorientations of octahedral [Co(NH3)6]3+ cation set on, too
osecond momollowing reof
re rientation of NH3 ligands about the M-N axis and the reorientation ahe assumed that the N-H bond distancesdral cation, respectively. It was all the N-H bonds were tetrahedraly directed with respeahe -N bonds, and the disrally directed with respect to the Co
.
108
The neutron scattering (IINS, QNS, NPD) study [3,5] in the temperature range of 20–77 K give also evidence of the fast stochastic reorientational motions of NH3 in all phases of
d [Co(NH2 [Zn(NH3)4](BF4)2,an ve NMR studies. 3)6](ClO4)3 measured by us in presented abo
100 150 200 250 3000 0
5
Tc3Tc2 Tc1
Temperature [K] 100 150 200 250 300
0
5
0
5
Tc= 103.25K
T [K]
Fig. 1. Temperature dependence of the slope line width (δH) - open symbols - and the second
moment (M2) - full symbols - of the 1H NMR line in [Zn(NH3)4](BF4)2 and [Co(NH3)6](ClO4)3
5
15
1H δH
(
[Zn(NH ) ](BF )
1H M
2 (10-8
T
10
20
dH
[10-4
Co(NH3)6(ClO4)3
M2 [
10
15
A
20
3 4 4 2
15 15
10 10
2 ) T]
10-4T)
10-8 T
2 ]
References: [1] A kuli, E. Miku tmańczyk, E Ściesińs
l. Struct. 5 1) 123. igdał-Mikuli, N. Górska, S. Wróbel, siński, E. Ściesińska, J. Mol.
Struct. (2003) 519. [3] A. Migdał-Mikuli, E. Mikul tmańczyk, I. Natkaniec, K. Hołdern-Natkaniec,
W. Łasocha, J. Solid St. Chem. 174 (2003) 357. ] J.H
. Migdał-Mi li, Ł. He . Ściesińska, J. ki, S. Wróbel, N. Górska, J. Mo 96 (200
[2] E. Mikuli, A. M J. Ście651-653
i, Ł. He
[4 . 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.
STRUCTURE OF 4-QUINOLINONES ANALYSED BY NMR STUDY AND X-RAY DATA
Andrzej Ziębaa, Andrzej Maślankiewicza , Jerzy Sitkowski b, Bohdan Kamieńskic ,
Kinga Suwińskad
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; cInstitute of
Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw; dInstitute 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 14N NMR spectroscopy (in CDCl3 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
N
O
RN
O
R
_
+
14N NMR spectral data (in CDCl3 solution) of 1-methyl-4(1H)-quinolinone 3 reveals nitrogen atom signal (δ=-220 ppm) with half-height of linewidths ∆v1/2=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 sp2 hybridization of nitrogen N1. 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 1H,13C,15N 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)
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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 so- called 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.
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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 I1 = I2 = 7, with a total spin I = I1 + I2 in gaseous state, in the presence of electric quadrupole and magnetic dipole - dipole interactions in a rotating tilted frame. The multipole relaxation times TLMρ are calculated for a maximal multipole order L = Lmax = 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 Bo and effective field Be in the rotating frame. These calculations are also extended for two spin systems of 176Lu2O3 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).
