Saint Petersburg State University Faculty of Physics

Department of Quantum Magnetic Phenomena

International Symposium and Summer School

in Saint Petersburg

Nuclear Magnetic Resonance in Condensed Matter

8th

meeting: “NMR in Life Sciences”

June 27 – July 1 2011

Book of Abstracts

Saint Petersburg, Russia 2011

an AMPERE event

International Symposium and Summer School in Saint Petersburg

Nuclear Magnetic Resonance in Condensed Matter

8th meeting: “NMR in Life Sciences” June 27 – July 1 2011

an

AMPERE event

ББК В334.2, Г512 М43

Department of Quantum Magnetic Phenomena Faculty of Physics Saint Petersburg State University Saint Petersburg, 198504, Russia

http://nmr.phys.spbu.ru/nmrcm/

M43 Nuclear Magnetic Resonance in Condensed Matter: abstracts of the International Symposium and Summer School, 8th meeting: “NMR in Life Sciences” – Saint Petersburg: “Solo” Publisher, 2011. – 120 p. ISBN

Symposium and Summer School are supported by:

• Saint Petersburg University • Russian Foundation for Basic Research • Dynasty Foundation

With assistance of

• Saint Petersburg Regional Public Foundation for the Development of Physical Faculty

International Advisory Board

V. Balevicius (Vilnius, Lithuania)

V. I. Chizhik (Saint Petersburg, Russia)

J. Fraissard (Paris, France)

H. Haranczyk (Kraków, Poland)

S. Jurga (Poznań, Poland)

O. B. Lapina (Novosibirsk, Russia)

D. Michel (Leipzig, Germany)

V. I. Minkin (Rostov-on-Don, Russia)

K. V. Ramanathan (Bangalore, India)

R. Z. Sagdeev (Novosibirsk, Russia)

K. M. Salikhov (Kazan, Russia)

A. V. Skripov (Ekaterinburg, Russia)

M. S. Tagirov (Kazan, Russia)

Organizing Committee Members:

S. F. Boureiko

A. S. Chirtsov

A. V. Donets

A. V. Egorov

V. V. Frolov

V. S. Kasperovich

V. V. Matveev

Layout of Abstracts Book: A. A. Levantovsky

Co-Chairmen:

V. I. Chizhik R. Z. Sagdeev (Novosibirsk)

Vice-Chairmen:

A. V. Komolkin M. G. Shelyapina

Registered names, trademarks, etc. used in this book, even without specific indication thereof, are not to be considered unprotected by law.

ISBN ББК В334.2, Г512

© Organizing Committee NMRCM 2011, Saint Petersburg, 2011. © “Solo” Publisher, Saint Petersburg, 2011. Printed in Russian Federation.

– 3 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

Contents

I. Lectures .................................................................................................................. 9

V. A. Chertkov, A. V. Chertkov, T. A. Ganina, O. I. Pokrovsky, A. A. Pushkareva, A. K. Shestakova

Ultra fast conformational dynamics as studied by vibration effects in NMR spectroscopy ............................. 11

Vladimir I. Chizhik

On the problem of the theoretical description of relaxation in a system of two identical spins ..................... 12

Sergey V. Dvinskikh

NMR imaging studies of wood moisture interaction ........................................................................................ 13

Karl Flisinski, R. V. Cherbunin, M. Yu. Petrov, M. S. Kuznetsova, I. V. Ignatiev, D. R. Yakovlev, M. Bayer

Optically detected NMR under resonant pumping of nuclear spins in self-assembled InGaAs

quantum dots .................................................................................................................................................... 14

H. Harańczyk

Tricks and traps of the NMR relaxometry of ultra dry biological systems and extremophilic organisms ........ 15

O. B. Lapina, D. F. Khabibulin, V. V. Terskikh

Multinuclear solid state NMR Study of Silica Fiberglass Modified with Zirconia ............................................. 16

S. Leclerc, M. Petryk, D. Canet, J. Fraissard

Competitive Diffusion of Gases in a Zeolite Using A Slice Selection Procedure ............................................... 17

K. V. Ramanathan

Cross-Polarization and Variable Angle Spinning Applied to Oriented Systems ................................................ 18

Tatiana N. Smekalova, Andrey V. Chudin, Aleksey E. Pasumansky

New discoveries of archaeological sites in western Crimea with help of magnetometry ................................ 19

Vitaly I. Volkov

Pulsed Field Gradient NMR for biological membranes and model systems investigations ............................. 20

II. Oral Reports ......................................................................................................... 21

Danila A. Barskiy, Kirill V. Kovtunov, Igor V. Koptyug

Strong NMR signal enhancement by Parahydrogen Induced Polarization (PHIP) for study mechanism

of heterogeneous hydrogenation ..................................................................................................................... 23

Alexey V. Donets, Vladimir I. Chizhik, Sergey V. Dvinskikh, and Dieter Michel

Solvation and hydration properties of organic molecules in complex solutions .............................................. 24

Tatiana P. Kulagina, Grigorii E. Karnaukh, Lev P. Smirnov

Line Shape NMR and Crystalliniti Degree in Biopolymers ................................................................................ 25

G. S. Kupriyanova, S. V. Molchanov, I. G. Mershiev, G. V. Mozzhukhin

The detection of NQR on the base of pattern signal ........................................................................................ 26

Dmitry A. Lysak, Alexander A. Marinin, Aleksandr F. Shestakov, Vitaly I. Volkov

Investigation of ion solvation in LiClO4 – ethylene carbonate solution ............................................................ 27

Vladimir V. Matveev, Petri Ingman

Experimental NMR indications of heterogeneous local structure of ionic liquid–water mixtures and

nonequeous solutions of tetraalkylammonium (TAA) salts .............................................................................. 28

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 4 –

A. A. Mistonov, N. A. Grigoryeva, S. V. Grigoriev, A. V. Vasilieva, K. S. Napolskii, N. A. Sapoletova,

A. A. Eliseev, A. V. Petukhov, D. V. Byelov, D. Yu. Chernyshov, H. Eckerlebe

Structural and magnetic properties of inverse opal photonic crystals studied by small-angle x-ray and

polarized neutron diffraction ............................................................................................................................ 29

Vladimir S. Neverov, Anderei V. Komolkin, Tatiana G. Volkova

Conformational structure and dynamics of two isomers, MBBA and BOBT, in liquid crystalline state ........... 30

Manuel Podrecca, Noella Taranto, Virgine Delsinne, Jean M. Colet

H-NMR based metabonomics applied to an early developmental pathology, the preeclampsia .................... 31

P. I. Polyakov, A. S. Mazur

Laws of elasticity in the physical processes influence of parameters (TPH) on the properties and

structural phase transitions .............................................................................................................................. 32

Peter M. Tolstoy, Benjamin Koeppe, Jing Guo, Erik T. J. Nibbering, Thomas Elsaesser,

Hans-Heinrich Limbach

Reaction Pathways of Proton Transfer in Anionic OHO Hydrogen Bonded Complexes Explored by

UVNMR .............................................................................................................................................................. 33

H. S. Vinay Deepak and K. V. Ramanathan

Effect of biaxiality on the measurement of molecular parameters of oriented solutes .................................. 34

Vladimir Ya. Volkov, Yury А. Vikharev, Maxim A. Kleimenov

Simultaneous measurement of FID’s and CPMG echo curves and their joint mathematical processing ........ 35

III. Poster Session ..................................................................................................... 37

Victor V. Alexandriysky, Elena V. Bobritskaya, Vladimir A. Burmistrov

13С NMR study of H-complex cyanosubstituted liquid crystal – non-mesogens ............................................... 39

Victor V. Alexandriysky, Elena V. Bobritskaya, Sofija A. Kuvshinova, Vladimir A. Burmistrov 1H NMR study of orientational ordering of LC mixtures ................................................................................... 40

Anatoly D. Alexeev, Tatyana А. Vasilenko, Andrey K. Kirillov, Alexander N. Molchanov,

Grigoriy A. Troitsky, Andrey V. Vyshnyakov

Mass transfer of methane in coal according to the 1H NMR ............................................................................ 41

Nikolay V. Anisimov, Svetlana S. Koretskaya, Kseniya L. Volkova, Mikhail V. Gulyaev,

Valery B. Petukhov, Yuri A. Pirogov

Simultaneous suppression of fat and water signals by combination of Dixon and inversion recovery

methods in MRI ................................................................................................................................................. 42

Marina L. Antipova, Alexey A. Medvedev, Valentina E. Petrenko

Hydrogen bond lifetime in water: simulation details ....................................................................................... 43

Maria I. Averina, Andrei V. Egorov

Microstructure of 13 m LiNO3 – 6.5 m Ca(NO3)2 – H2O ternary system at 25oC. A molecular dynamics

simulation study ................................................................................................................................................ 44

S. E. Belov, K. V. Ershov

Double nuclear gamma-magnetic resonance spectrometer in the “Euro-mechanics” bin .............................. 45

Yu. Bogachev, Yu. Chernenko, V. Drapkin, M. Knyazev, Ya. Marchenko, V. Frolov

Application of Double Electron-Nuclear Magnetization Transfer in Low-Field MRI ......................................... 46

Gregory V. Bondar, Victor V. Shevchenko, Peter I. Poljakov, Tatyana A. Ryumshyna

Influence of the magnetic field on indices of the blood ................................................................................... 47

– 5 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

I. G. Borodkina, V. V. Chesnokov, T. A. Kuz’menko, E. V. Korshunova, A. I. Uraev, I. S. Vasilchenko,

A. S. Burlov, G. S. Borodkin

Multinuclear and two-dimensional NMR spectroscopy of heterocyclic shiff bases and their zinc and

cadmium complexes ......................................................................................................................................... 48

C. Casieri and F. De Luca

Sub-diffusive dynamics of water in Nafion membrane .................................................................................... 49

A. V. Chernyak, Yu. S. Naumova 1H NMR study of proton dynamics in 12-Tungstophosphoric acid and its cesium and ammonium salts

at different environment humidity ................................................................................................................... 50

Yuri S. Chernyshev, Ekaterina S. Shemetova, Evgenia A. Safonova

Selfdiffusion of ionic liquids in water by NMR of 1H and

2H ............................................................................. 51

V. I. Chizhik, N. M. Vecherukhin, Y. S. Chernyshev

NMR detection of liquid in closed conducting cans .......................................................................................... 52

Georgy Chuiko, Vladimir Buzko, Igor Sukhno

The DFT calculations of 139

La and 19

F NMR chemical shifts in molten LaF3 ....................................................... 53

Georgy Chuiko, Denis Kashaev, Vladimir Buzko, Igor Sukhno

The 15

N NMR in 1-n-Butyl-3-Methyl-Imidazolium Chloride .............................................................................. 54

A. Danilova, E. Kurenkova, A. Vyvodceva, V. S. Kasperovich, M. G. Shelyapina, A. Ievlev,

A. G. Aleksanyan, S. K. Dolukhanyan, N. E. Skryabina

1H NMR study of hydrides of binary Ti-V disordered alloys synthesized by the SHS method .......................... 55

Sergey A. Dontsov, Alexandr V. Ievlev

To a question on correct division of relaxation contributions .......................................................................... 56

S. V. Dushina, V. А. Sharnin, G. А. Gamov, V. V. Alexandriysky

NMR study of nicotinamide-silver(I) coordination equilibrium members solvation in water-ethanol

solvent ............................................................................................................................................................... 57

Stepan S. Dzhimak, Mihail G. Barishev, Nikolay S. Vasiliev, Denis V. Kashaev, Denis I. Shashkov

Research of influence of the deuterium content in water solution NaCl on backs-spin relaxation 23

Na ......... 58

Galina N. Fedyukina, Sergey F. Biketov, Vladimir Ya. Volkov

H1-relaxation technique for diagnosticums’ testing in vitro ............................................................................. 59

Egor Gerts, Igor Kobylin, Anderei V. Komolkin, Vladimir A. Burmistrov, Viktor V. Alexandriysky

Structure of HO-6OCB liquid crystal from fully atomistic molecular dynamics simulation .............................. 60

Dariya L. Gurina, Valentina E. Petrenko, Marina L. Antipova

The structure of supercritical methanol-water solution ................................................................................... 61

H. Harańczyk, M. Florek, P. Nowak and S. Knutelski

Water bound in Donus comatus (Bohemann in Schoenherr, 1842) elytra as recorded by proton

relaxation and sorption isotherm ..................................................................................................................... 62

H. Harańczyk, J. Kobierski, D. Zalitacz, P. Nowak, A. Romanowicz, M. Marzec, and J. Nizioł

Rehydration of BA modified DNA powders by proton NMR ............................................................................. 63

H. Harańczyk, P. Nowak, M. Florek, M. A. Olech

Bound water freezing in Antarctic Cetraria aculeata (Schreb.) Fr. by proton NMR spectra ............................ 64

Oksana Ilina, Vyacheslav V. Frolov

Computer simulation of the image reconstruction using Fresnel transform ................................................... 65

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 6 –

Vladimir Karbovskii, Svitlana Smolyak, Yuriy Zagorodniy, Anatoliy Kalinichenko, Elena Kalinichenko

Studying the mechanism formation of nanosized bone apatite by the 1H MAS NMR ..................................... 66

Nikole Karlina, Konstantin Tutukin

Research of stability of a main magnetic field of a low-frequency MRI installation ........................................ 67

Nikolay S. Klekhta, Victor I. Tarkhanov

Using chirp signals to measure NMR line shape in a lithium ferrite sample .................................................... 68

K. Klyukin, M. G. Shelyapina

Hcp-bcc structural phase transformation of magnesium: ab initio calculations .............................................. 69

K. Klyukin, M. G. Shelyapina, D. Fruchart

Ab initio studies of magnesium-based alloys and their hydride: phase stability and electronic structure ...... 70

N. Krivko, M. G. Shelyapina

Electronic structure and Fe-V magnetic coupling in YFe8V4 .............................................................................. 71

Tatiana P. Kulagina, Grigorii E. Karnaukh, Anastasia N. Kuzina, Lev P. Smirnov

Diffusion Attenuation of NMR Spin Echo of Elastic Polymers........................................................................... 72

Sergey E. Kurnikov, Alexey V. Donets

Symmetry of Na+

hydration shells in electrolyte solutions by NMR-relaxation and quantum-chemical

calculations ....................................................................................................................................................... 73

Vladimir S. Kuzmin, Vladimir M. Kolesenko

Amplitude of single-pulse nuclear spin echo in magnetically ordered media in non-resonant excitation ...... 74

Mariia I. Lomovska, Stanislav I. Selivanov, Alexander A. Kasatochkin, Alexander A. Petrov

Structure elucidation of pyrazolo[1,5-a]pyrimidines fused cycloalkanes rings by NMR spectroscopy ............ 75

Ya. Yu. Marchenko, B. P. Nikolaev, L. Yu. Yakovleva, M. G. Ilyin, I. N. Voevodina

The study of magnetic porous glass microcarriers by NMR relaxometry analysis ........................................... 76

Denis A. Markelov, Maria V. Popova

Investigation of Dendrimer-Surfactant-Water Systems ................................................................................... 77

Ellina Martynchuk, Roza Aminova

Application of molecular dynamic simulations for study of 31

P chemical shifts in solutions ........................... 78

А. S. Мazur

Study of the nature of the ferromagnetic metallic phase separation in manganites

La1-xCaxMnO3 (x = 0.2, 0.3) ................................................................................................................................ 79

Aleksei A. Medvedev, Andrei V. Guryanov, Marina L. Antipova, Valentina E. Petrenko

Efficiency of conventional computer equipment for molecular dynamics simulations ................................... 80

I. G. Mershiev, G. S. Kupriyanova

Multifractal formalism applied to stochastic NQR ............................................................................................ 81

G. V. Mozzhukkin, B. Z. Rameev, R. R. Khusnutdinov, I. Kh. Khabibulin, N. Doğan, B. Aktaş

Three-frequency composite multipulse nuclear quadrupole resonance (NQR) technique for explosive

detection ........................................................................................................................................................... 82

Ivan V. Pleshakov, Stanislav I. Goloschapov, Alexandr P. Paugurt, Yuriy I. Kuzmin, Vladimir V. Matveev,

Valentin I. Dudkin, Viktor I. Tarkhanov, Artem I. Yavtushenko, Yakov A. Fofanov

Peculiarities of the spin echo behavior in a ferrite material under the moving along the magnetization

curve .................................................................................................................................................................. 83

– 7 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

A. A. Pushkareva, A. K. Shestakova, V. A. Chertkov 15

N NMR spectral parameters for structure elucidation and conformational analysis. Indole, quinoline

and substituted azobenzenes ........................................................................................................................... 84

Dmitrii F. Pyreu, Evgenii V. Kozlovskii, Matvei S. Gruzdev

NMR and thermodynamic studies of some mixed ligand lanthanide(III) ethylenediaminetetraacetate

complexes in solution ....................................................................................................................................... 85

Sevastyan O. Rabdano, Alexey V. Donets

Hydration of Alanine in aqueous solution as studied by NMR-relaxation and quantum-chemical

methods ............................................................................................................................................................ 86

Dmitriy L. Raev, Maria V. Popova

Computer Simulations of Self-Association Processes in Surfactant-Dendrimer-Water Systems ..................... 87

Boris V. Sakharov, Tatiana Kornushina, Galina Sakharova, Sergey N. Viryasov

Influence of temperature on 1H NMR relaxation parameters of agar powders with different water

contents ............................................................................................................................................................ 88

Maxim M. Senichev, Andrey S. Kuklin, Vladimir V. Matveev

NMR study of nonaqueous solutions of tetraalkylammonium (TAA) salts ....................................................... 89

Danila Sergeyev, Viacheslav Frolov

Mapping of the high-frequency magnetic field using MR imaging ................................................................... 90

Andrei N. Shishkin, Denis A. Markelov

NMR Relaxation Studies of Carbosilane Dendrimers ........................................................................................ 91

E. V. Shishmakova

Temperature dependences of proton spin-lattice relaxation rates of the carbosilane dendrimer

functional groups in the dilute chloroform solution ......................................................................................... 92

Anna Shmyreva, Aleksandr Vdovin

The 59

Co NMR study of nanostructural Co powders ......................................................................................... 93

Nikolay A. Sirotkin, Daria L. Gurina, Marina L. Antipova

Influence of technical parameters on the accuracy of density functional theory for CPMD simulations

of water ............................................................................................................................................................. 94

Vladimir V. Sizov, Stanislav V. Burov, Anastasia A. Shapovalova, Alexandr Ievlev, and

Yuri S. Chernyshev

Molecular dynamics simulation study of competitive solvation of Li+ and ClO4

– ions in

water/acetonitrile solutions ............................................................................................................................. 95

Nikolay S. Vasilyev, Denis V. Kashaev, Mihail G. Barishev

The spin-lattice relaxation and chemical shift of the deuterium in H2O-D2O system ....................................... 96

S. G. Vasil’ev, D. V. Mischenko, A. Yu. Rybkin, A. I. Kotelnikov, Vitaly I. Volkov

Water self-diffusion behavior in yeast cells studied by pulsed field gradient NMR ......................................... 97

S. G. Vasil’ev, Vitaly I. Volkov

Characterization of water-in-crude-oil emulsions by pulsed field gradient NMR ............................................ 98

Andrey A. Vinokurov

Ligand hyperfine structure in the EPR of superionic CaF2:Eu2+

single crystals.................................................. 99

Vladimir Ya. Volkov, Alexsei V. Stepanov

NMR method for testing of encapsulated dry medicines ............................................................................... 100

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 8 –

Mikhail A. Vovk, Mariya S. Pavlova, Vladimir I. Chizhik, and Dieter Michel

Investigation of microstructure of hydration shells of ions containing COO- group by NMR-relaxation

and quantum-chemical methods .................................................................................................................... 101

Alexander Yakimov, Kirill Nerinovski, Georgy Rychkov, Konstantin Shabalin, Alexander Dikiy

Study of the interaction between mammalian MsrB1 and Trx proteins by NMR .......................................... 102

A. I. Zhernovoy, Y. R. Rudakov

Investigation of condition formation nonmagnetic conglomerate in sol of paramagnetic nanoparticles

by NMR method .............................................................................................................................................. 103

Author Index .......................................................................................................... 105

List of Participants ................................................................................................. 107

Part I

Lectures

– 11 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

Ultra fast conformational dynamics as studied by vibration

effects in NMR spectroscopy

V. A. Chertkov1, A. V. Chertkov1, T. A. Ganina1, O. I. Pokrovsky1, A. A. Pushkareva1, A. K. Shestakova2

1Department of Chemistry, Moscow State University, 1 Leninskie Gory, Moscow, 119992, Russia 2State Research Institute of Chemistry and Technology of Organoelement Compounds, 38

Shosse Entuziastov, Moscow, 111123, Russia

E-mail: chertkov@org.chem.msu.ru

1. Introduction Dynamic behavior of molecular systems is normally

associated with some sort of chemical reactions. There are

still numerous examples of extremely rapid dynamics,

which can’t be described in terms of classical kinetic

parameters, such as reaction rates, activation parameters etc.

It even is better to consider them in terms of vibrations with

large amplitude. Accurate structure studies of saturated four-

and five-membered cycles imply solving specific problem of

quantitative description of dynamic processes with very low

barriers in them. Examples of accurate microwave studies

are known of only few simplest such systems in gaze phase.

2. Method We developed a practical method for evaluation of the

parameters of conformational dynamics in terms of

vibrations with large amplitude. The method based on: (i)

the results of complete analysis of high resolution NMR

spectra, (ii) ab’initio calculations of a reaction path and

surfaces of potential energy and spin-spin coupling

constants, (iii) a numerical solution of corresponding

vibration problem and (iv) refinement for the parameters of

the energy surface based on the best fit of experimental (see

e.g. [1-2]) and calculated spin-spin couplings.

As a starting point, the undistorted potential energy

surface (PES) of inner rotation for the compounds studied

was built by applying the scanning technique to skeletal

dihedral angles [3]. This allows us to get a trial “reaction

path” for the pseudorotation process. Conformational

dependencies for spin-spin coupling constants (SSCC) for

principal points on the reaction path were calculated using

FP DFT technique [4]. 1H NMR spectra were recorded for a

series of solvents and “Bruker AV-600” spectrometer at

room temperature, and were treated using total lineshape

analysis technique (program VALISA [1]) which allows to

get very accurate estimates of experimental SSCC values.

Finally, the reverse spectral problem was solved to adjust

experimental and calculated data and build up the “true”

potential of pseudorotation. We developed REVIBR

program [3], which solves numerically corresponding

vibration problem and models the dynamic averaging using

the technique of convolution of the spin-spin coupling

surfaces using the whole set of vibration energies and

eigenvectors (normally, 200 lowest ones). Convolution

criterion used in REVIBR program allows to get calculated

SSCC for given temperature. Nonlinear optimization

(Levenberg-Marquart techniques) of the estimated

parameters for the “true” pseudorotation PES (modeling

difference of ground states of main conformers ∆E and heights for the conformational barriers ∆E≠) used to get best fit of experimental and calculated SSCC values.

3. Results Advantages of the technique developed demonstrated on

a series of monosubstituted cyclobutanes, trans-1,2-

dihalocyclopentanes, tetrahydrofuran, tetrahydrothiophene,

tetrahydrothiophene-1-oxide, pyrrolidine, proline and

ribonucleosides. The data obtained shows, that the

pseudorotation process in every four- and five-membered

system under study is carrying out by the mechanism with

high amplitude of vibration. Major conformations of

tetrahydrofuran and terahydrothiophene are twists 4Т5 and

5Т4, for pyrrolidine – envelope Е1 with equatorial NH-

bond, for terahydrothiophene-1-oxyde – envelopes Е3 and

with axial oxygen and for proline – envelope Е5 with axial

СООН-group. Method used also for characterization of

internal rotation in acyclic systems – natural endogenic

hormone adrenaline and substituted azobenzenes.

Acknowledgement This work is supported by the RFBR (grant 09-03-

00779).

References [1] S.V. Zubkov, S.S. Golotvin, V.A. Chertkov. – Russ.

Chem. Bull., 51, 1222-1230 (2002). [2] S.V. Zubkov, V.A. Chertkov – IJMS, 4, 107-118

(2003). [3] A.V. Chertkov, O.I. Pokrovsky, A.K. Shestakova, V.А.

Chertkov – Chem. Heterocycl. Comp., 44, № 5, 782-784 (2008).

[4] T. Onak, J. Jaballas, M. Barfield, J. Am. Chem. Soc, 121, 2850 (1999).

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 12 –

On the problem of the theoretical description of relaxation

in a system of two identical spins

Vladimir I. Chizhik

Saint-Petersburg State University, Faculty of Physics

E-mail: chizhik@nmr.phys.spbu.ru

1. Introduction One of the best works in the area of the theory of the

nuclear magnetic relaxation was published by I. Solomon in

1955 relaxation in a system of two interacting spins, in

particular, so-called "Solomon's equations" were derived

namely in it. Delivering lectures on NMR-relaxation in

Saint-Petersburg State University I have disclosed the

logical error in this excellent article and would like to turn

the attention of the NMR community to this fact because

that error is still rewritten in many articles, reviews and

books (see, for example, [2-6]). Moreover many Internet

materials (including "Encyclopedia of NMR") contain it.

2. Details First, I. Solomon wrote equations for the populations ni of

energy levels of two spins (I = S = 1/2) of different kinds

(γ1≠γ2) placed in a static magnetic field. In this case there

are four energy levels which correspond to the following

orientations of the spins ("+" along the magnetic field, "–" in

the opposite direction to the magnetic field): + + (n1), + –

(n2), – + (n3), – – (n4). Then I. Solomon introduced the

macroscopic magnetizations of the I and S spins along the

magnetic field (traditionally the magnetic field is directed

along the z-axis of the laboratory coordinate system):

Iz ~ [(n1 + n2) – (n3 + n4)]; Sz ~ [(n1 + n3) – (n2 + n4)]

Using such an approach I. Solomon received the

equations:

dIz/dt= – ρ(Iz – I0) – σ(Sz – S0),

dSz/dt= – ρ1 (Sz – S0) – σ(Iz – I0),

where ρ, ρ1 and σ depend on the probabilities of

relaxation transitions.

Just to that point the Solomon's approach is quite correct.

But then I. Solomon proceeded to the consideration of the

relaxation in a system of two interacting equivalent spins

and made an error. He supposed that in this case one could

put Iz = Sz and equations turned into

dIz/dt= – (ρ + σ)(Iz – I0),

i. e. the spin-lattice relaxation time (T1) would be given by

the expression:

T1 = 1/(2w1 + 2w2),

where w1, w2 are the probabilities of one- and two- quantum

relaxation transitions.

This approach is not correct because it does not take into

account the fact that, although the dipole-dipole interaction

eliminates the degeneration of the middle energy level, one

of the new states is forbidden for the transitions from upper

and lower energy levels. It was brightly shown in the

splendid works of M.Levitt [7-12].

As a result, in the case of two equivalent spins one deals

with the three-level system.

Following the same scheme one can receive the equation

for the magnetization Iz:

dIz/dt = – (w1* + 2w2)(Iz – I0),

i.e. the spin-lattice relaxation time is

T1 = 1/ (w1* + 2w2)

that differs from the expression above. It worth noting that

w1 and w1* are different because they should be calculated

on the basis of different wave functions (incorrect or proper

ones for the middle level) but w2 is the same in both

expressions.

References [1] I. Solomon, Phys. Rev. 99, 559 (1955). [2] J. Kowalewski,in Ann. Reports NMR Spectr. 22, 307

(1989). [3] V.I. Bakhmutov, Practical NMR Relaxation for

Chemists, John Wiley and Sons, Ltd, Chichester (2004).

[4] J. Keller, Understanding NMR Spectroscopy, Wiley and Sons, Ltd, Chichester (2005).

[5] G.S. Rule, T.K. Hitchens, Fundamentals of protein NMR spectroscopy, Springer, Dordrecht (2006).

[6] M. Levitt, Spin Dynamics, Wiley and Sons, Ltd, Chichester (2009).

[7] M. Carravetta, O.G. Johannessen, M.H. Levitt, Phys. Rev. Letters 92, 153003-1(2004).

[8] M. Carravetta, M.H. Levitt, J. Am. Chem. Soc. 126, 6228 (2004).

[9] M. Carravetta, M.H. Levitt, J. Chem. Phys. 122, 214505 (2005).

[10] G. Pileio, M. Carravetta, M.H. Levitt, J. Magn. Reson. 182, 353 (2006).

[11] G. Pileio, M. Carravetta, E. Hughes, M.H. Levitt, J. Am. Chem. Soc. 130, 12582(2008).

[12] G. Pileio, M.H. Levitt, J. Chem. Phys. 130, 214501 (2009).

– 13 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

NMR imaging studies of wood moisture interaction

Sergey V. Dvinskikh

Department of Chemistry and Industrial NMR Centre, Royal Institute of Technology,

SE-10044 Stockholm, Sweden

E-mail: sergey@physchem.kth.se

1. Introduction Wood has potential as a renewable material for a large

variety of applications that often call for improved

properties such as dimensional stability, moisture

insensitivity, and durability. Moisture migration in wood is a

particularly important factor in determining the cost-

effective service life of wooden construction. The primary

processes for moisture migration in wood include water

diffusion in the cell wall, adsorption to and exchange with

hydroxyl groups, and vapor diffusion in the lumen [1].

Capillary flow plays a significant role in the uptake of liquid

water. Within the present research, high and low field NMR

spectroscopy and imaging was applied for studying the

moisture spatial distribution and migration in a number of

wood specimens and under varying environmental

conditions.

2. High field MRI in wood In contrast to green or water-soaked wood, processed

construction wood at ambient condition is much less

suitable for standard MRI because of the short relaxation

times of “bound” water. Hence, a solid state MRI method -

single point imaging (SPI) [2], was applied to assess the

spatial variation of the moisture content in wood.

Moisture kinetics in wood was studied upon controlled

changing the relative humidity of the surrounding air [3, 4].

By varying the wood sample orientation with respect to

magnetic field gradient the moisture movement along three

principal directions in wood was monitored by SPI MRI, as

exemplified in Fig 1. Data were compared to multi-Fickian

numerical simulation of transient moisture transport [3].

-2 0 2 4 6 8 10 12 14

0

10

20

30

40

50

distance, mm

0

4 days

3 months

MC

x (

ρ woo

d/ρ

av

wo

od)

Figure 1: Moisture content profiles along the radial

direction in wood, obtained after changing

the relative humidity from 95 to 35 %.

The effect of wood growth rings is observed

Wood contained adsorbed heavy water (D2O) can be

studied by MRI in order to separate images due to water

(2H MRI) and macromolecular wood tissue (1H MRI). By

comparing the proton and deuterium images a linear

correlation between water and macromolecular contents in

wood is clearly demonstrated [5].

3. Low field unilateral NMR in wood We have evaluated the potential of NMR technology

based on small portable magnets for in situ studies of the

local moisture content in wood. Low field and low

resolution 1H NMR with a unilateral permanent magnet was

used to monitor the spatially resolved moisture content of

wood cladding materials [6] and for assessment of moisture

protective properties of wood coatings [7]. The method is

quick, noninvasive, simple to perform, and does not require

removing wooden parts from the structure. We also

developed an NMR sensor based on small low cost

permanent magnets for disposable multiple-sensor remote

NMR.

Acknowledgements This work was supported by Swedish Research Council

VR, Knut and Alice Wallenberg Foundation, and the

European WoodWisdom–Net project “Improved Moisture.

References [1] Skaar, C. Wood-Water Relations. Springer, Berlin,

1988.

[2] S. Emid, J. H. N. Creyghton. Physica B 128 (1) (1985)

81–83

[3] S. V. Dvinskikh, M. Henriksson, A. L. Mendicino, S.

Fortino, T. Toratti. Eng. Struct. (2011). Accepted.

[4] J. Eitelberger, K. Hofstetter, S. V. Dvinskikh.

Composites Sci. Technol. Submitted.

[5] S. V. Dvinskikh, M. Henriksson, L. A. Berglund, I.

Furó. Holzforschung 65, 103 (2011).

[6] S. V. Dvinskikh, I. Furó, D. Sandberg, O. Söderström.

Wood Mat. Sci. Eng. (2011). In press.

[7] P. Pourmand, L. Wang, S. V. Dvinskikh. J. Coat.

Technol. Res. Submitted.

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 14 –

Optically detected NMR under resonant pumping of nuclear

spins in self-assembled InGaAs quantum dots

Karl Flisinski1, R. V. Cherbunin2, M. Yu. Petrov2, M. S. Kuznetsova2, I. V. Ignatiev2, D. R. Yakovlev1,3, M. Bayer1

1Experimentelle Physik 2, Technische Universität Dortmund, 44221 Dortmund, Germany

E-mail: Karl.Flisinski@e2.physik.uni-dortmund.de 2Physics Departament, St. Petersburg State University, 198504 St. Petersburg, Russia 3Ioffe Physico-Technical Institute, Russian Academy of Sciences, 194021 St. Petersburg, Russia

1. Introduction The two main advantages of optically detected and

optically pumped NMR over common NMR measurements are (i) selective observation of nuclei in the region of electron localization e.g. in quantum dots (QD) and (ii) orders of magnitude higher sensitivity [1]. Applying optical excitation with circular polarisation modulated (PM) from right- to left-hand helicity makes it possible to pump only one isotope of nuclear spins whose frequency of Larmor precession equals to the polarisation modulation frequency. This allows one the identification of all nuclei in a QD within a quantum dot ensemble (~1013 nuclei). Present work shows how the nuclear Zeeman splitting and nuclear quadrupole splitting can be measured for InGaAs QDs using this method.

2. Theoretical overview Optical excitation with circularly polarized light transfers

an angular momentum to the resident electron of a QD. Passing on the momentum via a spin-flip to the nuclear-spin-system creates a dynamic nuclear polarisation (DNP). The DNP changes the electron spin polarisation, which can be detected by the polarisation degree of photoluminescence (PL) [2]. In the magnetic field transverse to optical pumping direction, nuclear spins can be polarized both along the magnetic field and the optical excitation [3]. The polarisation is due to the Knight field (the effective magnetic field created by polarized electrons on the nuclei), which deviates the total field affecting the nuclei from orthogonal geometry. The orientation of the Knight-field depends on helicity of excitation. Similar effect appears when additional longitudinal external magnetic field is applied to the system.

3. Experimental data Studied sample contains 20 layers of self-assembled

InGaAs QDs separated by 60 nm GaAs barriers, annealed at 980 °C. Due to n-doping each QD in average is occupied by one resident electron. A continuous RF field of about 1 mT was applied parallel to light k-vector (z-axis). Perpendicular to the z-axis an external magnetic field was swept (Voigt geometry) and the change of polarisation of QD PL was measured (Hanle effect). Figure 1 shows Hanle curves for different experimental conditions. The grey curve shows electron polarisation under influence of DNP created via continuous excitation with one helicity (CW-condition). The red curve shows electron polarisation under influence of polarisation-modulated excitation with additional in-phase RF-field (0° phase shift). The blue curve was measured with phase difference of 180°. The green curve (e-peak) was measured with additional amplitude modulation of

excitation light to suppress nuclear polarization. Its width is controlled only by the electron depolarisation in external field.

4. Discussion Signals detected outside of e-peak are due to nuclear

polarisation. Under PM conditions only nuclear isotopes can be pumped whose Larmor frequency is equal to the modulation frequency (66.7 kHz for red curve). We believe that transverse component of DNP, which precesses about the total magnetic field is pumped. Each resonant condition is marked on the red curve and fitting by the sum of Gaussians enables identification of isotopes. By measuring the Hanle curves for different PM frequencies, the dependences of the Larmor frequency for different isotopes on the magnetic field strength were measured. It was found, that their dependence is not linear. Their behaviour will be discussed.

Acknowledgements This work is supported by the Deutsche Forschungs-

gemeinschaft, the Russian Ministry of Science and Education, and the Russian Foundation for Basic Research. MYP thanks the “Dynasty” foundation.

References [1] D. Paget et al. Phys. Rev. B 25, 4444 (1982) [2] R. V. Cherbunin et al. Phys. Rev. B 80, 035326 (2009) [3] Optical Orientation, eds B. P. Zakharchenia, F. Meier

(North-Holland, Amsterdam, 1984)

0

168151.3 mW 10-08-2009F10 RFz off

0

0.04

0.08

0.12

-20 -10 0 10 20 30

113In

±5/2

113In

±3/2

71Ga

±3/2

69Ga

±3/2

113In

±5/2

71Ga

±3/2

113In

±3/2

Magnetic field, BX (mT)

Pola

risation d

eg

ree

– 15 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

Tricks and traps of the NMR relaxometry of ultra dry biological

systems and extremophilic organisms

H. Harańczyk

Institute of Physics, Jagiellonian University, Cracow,

ul. Reymonta 4, 30-059 Cracow

E-mail: hubert.haranczyk@uj.edu.pl

Some extremophilic organisms, as lichenized fungi

[1 and references therein] and insects [2, 3], can survive the

acute water stress and extremely low temperature. In

cryptobiosis the extremophile may be treated as an

amorphous system with a high porosity [4], the effect of

carbohydrates is suggested [5]. Bound water behavior is one

of crucial molecular mechanisms deciding on the ability of

living organism to survive the extreme dehydration of ice

nucleation.

Even at very low overall hydration level in extremophilc

organism a small reservoirs of loosely bound water may

remain, which is not detected either by hydration kinetics or

by gravimetric sorption isotherm experiment. Only the use

of NMR sorption isotherm may reveal the presence of

additional bound water fraction which is trapped in the pores

of the dry tissue [6, 7, 8].

The initial steps of rehydration conducted from the

gaseous phase for biological macromolecules (native DNA

[9] or DNA modified by use of various surfactants) show

the swelling process (with the different values of the

swelling time).

The liquid NMR signal component hydration dependence

as detected either in time domain or in frequency domain

reveals very often a non-linear form which is well fitted by

the rational function [10-12], which is the effect of the

presence of water soluble solid fraction. For horse chestnut

bast the threshold hydration value is observed for which the

whole portion of water soluble solid fraction is dissolved

[13]. This approach enables one to calculate the saturation

hydration level and, thus, the identification of water soluble

solid fraction [13]. The solid water soluble fraction mostly

consists of sugars and/or of polyols.

Unfortunately, for majority of extremophilic organism,

the contribution of water soluble solid fraction is so

significant that the threshold hydration level is not observed

[10-12]. In such a case the detailed analysis of FID signal or

proton spectra may be helpful. If tightly bound water

component may be distinguished, it helps to identify the

water soluble solid fraction.

For Antarctic lichenized fungi (Umbilicaria aprina) the

NMR relaxometry, and the NMR spectroscopy, together

with DSC, show that for decreased temperatures the water

soluble solid fraction influences the ice nucleation process,

changing the contribution of non-cooperative bound water

immobilization compared to ice freezing [14].

References [1] H. Harańczyk „On water in etremely dry biological

systems”. Wyd. UJ 2003 pp. 276. [2] M. Watanabe, T. Kikawada, N. Minagawa, F.

Yukuhiro, T. Okuda. J. Exp. Biol., 205, 2799-2802 (2002).

[3] M. Watanabe, T. Sakashita, A. Fujita, T. Kikawada, D. D. Horikawa, Y. Nakahara, S. Wada, T. Funayama, N. Hamada, Y. Kobayashi, T. Okuda. Int. J. Radiat. Biol. 82, 587-592 (2006).

[4] F. Valladares, L.G. Sancho, C. Ascaso, Bot. Acta, 111, 99 (1997).

[5] W.Q. Sun, A.C. Leopold, Comp. Biochem. Physiol., 117A, 327 (1997).

[6] H. Harańczyk, A. Leja, K. Strzałka. Acta Physica Polonica, A109, 389-398 (2006).

[7] H. Harańczyk, M. Bacior, J. Jamróz, M. Jemioła-Rzemińska, K. Strzałka. Acta Phys. Polon. A115, 521-525 (2009).

[8] H. Harańczyk, A. Leja, M. Jemioła-Rzemińska, K. Strzałka. Acta Phys. Polon. A115, 526-532 (2009).

[9] H. Harańczyk, J. Czak, P. Nowak, J. Nizioł, Acta Phys. Polon. A117, 257 (2010)

[10] H. Harańczyk, A. Pietrzyk, A. Leja, M. A. Olech, Acta Phys. Polon. 109, 411 (2006).

[11] H. Harańczyk, M. Bacior, M.A. Olech Antarctic Science 20, 527 (2008).

[12] H. Harańczyk, M. Bacior, P. Jastrzębska, M.A. Olech Acta Phys. Polon. A115, 516 (2009).

[13] H. Harańczyk, W.P. Węglarz, S. Sojka. Holzforschung 53, 299-310 (1999).

[14] H. Harańczyk, P. Nowak, M. Bacior, M. Lisowska, M. Marzec, M. Florek, M.A. Olech, submitted to Antarctic Science (2011).

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 16 –

Multinuclear solid state NMR Study of Silica Fiberglass Modified

with Zirconia

O. B. Lapina1, D. F. Khabibulin1, V. V. Terskikh2

1Boreskov Institute of Catalysys, prospect .Lavrentieva 5, Novosibirsk, 630090, Russia 2Steacie Institute for Molecular Sciences, National Research Council Canada, Ottawa, Ontario,

Canada K1A 0R6

E-mail: olga@catalysis.ru

1. Introduction Silica fiberglass textiles are emerging as uniquely suited

supports in catalysis which offer unprecedented flexibility in designing advanced catalytic systems for chemical and auto industries. During manufacturing fiberglass materials are often modified with additives of various nature to improve glass properties. Glass network formers, such as zirconia and alumina, are known to provide the glass fibers with higher strength and to slow down undesirable devitrification processes. In this work multinuclear 1H, 23Na, 29Si, and 91Zr NMR spectroscopy was used to characterize the effect of zirconia on the molecular-level fiberglass structure. 29Si NMR results help to understand why zirconia-modified fiberglass is more stable towards devitrification comparing with pure silica glass. Internal void spaces formed in zirconia-silica glass fibers after acidic leaching correlate with sodium and water distributions in the starting bulk glass as probed by 23Na and 1H NMR. These voids spaces are important for stabilization of catalytically active species in the supported catalysts. Potentials of high-field 91Zr NMR spectroscopy to study zirconia-containing glasses and similarly disordered systems are illustrated.

2.1. Bulk Na2O-ZrO2-SiO2 glass Incorporation of zirconia into the silicon-oxygen lattice

can be considered in terms of different Sinm(Zr) (i.e. Si(OZr)m(OSi)n-m) molecular motifs, where m is the number of zirconium atoms bound to the central silicon atom via the oxygen “bridge”, n is the number of silicon atoms in the second coordination sphere, with n = 0 – 4, m ≤ n. Zirconium in zirconium-silicates is six-coordinated, with each zirconium atom linked with six silicon-oxygen tetrahedra, at the same time Zr-O-Zr linkages are never or rarely formed. The coordination number of zirconium in silicate glasses is of importance, since only octahedral Zr provides a stable glass environment; and subsequently in most true glasses Zr is not a nucleating element. From 29Si and 23Na NMR data we can conclude that sodium in zirconia-modified glass is distributed more evenly throughout the bulk, however the local sodium coordination environment appears to be more disordered than in pure silicate glass.

2.2. Na2O-ZrO2-SiO2 fiberglass 29Si, 23Na, and 1H NMR data show that the manufacturing

of glass fibers is accompanied by substantial changes in the

glass structure. In the process of spinning fiber strands from

molten glass the silicon-oxygen polyhedra are getting

slightly stretched and most likely become more aligned,

with the Si-O-Si angle increasing by about two degrees in

the zirconia-modified fibers. At the same time the extent of

silicon-oxygen tetrahedra association increases more

probable due to separation on silica enriched region and on

sodium enriched region in subsurface region. In the

zirconia-modified fibers this effect is in somewhat lesser

degree than in pure silicate glass, which may indicate better

stability of the zirconia-modified fibers towards

devitrification. In zirconia-containing fibers sodium cations

are more evenly distributed through the glass network,

which will be important during the subsequent

manufacturing step of leaching of fiberglass with acid.

Significant amounts of water are present in fiberglass.

2.3. Leached ZrO2-SiO2 fiberglass After the fiberglass threads are spun and weaved into

textiles of desired density and shapes, they then undergo a

leaching treatment in strong inorganic acids to remove

sodium and other soluble components. This leached fiber

after washing and drying, can directly be used as a support

for variety of catalysts. 29Si, 91Zr and 1H NMR data

unequivocally show that zirconium atoms are indeed being

incorporated in the silica glass lattice and, by modifying the

glass properties, zirconium is making fiberglass more robust

for practical applications. After the acid leaching treatment

the water content in fibers increases significantly, the nature

of incorporated water in leached fibers is different from

unleached fibers, According to 1H MAS NMR spectra

recorded for leached fibers, most of this water is zeolitic-like

in its character and can be easily removed at elevated

temperature. Presence of zeolitic water in fiberglass

indicates an extended network of internal microporous

voids. This microporosity becomes important when fibers

are used as catalyst supports, it also contributes to the ability

of fibers to stabilize the highly-dispersed nanoclusters of

transition-group metals in the glass bulk.

Acknowledgements This work is partly supported by the Russian Foundation

of Basic Research (grant № 10-03-00667-а).

Competitive Diffusion of Gas

Selection Procedure

S. Leclerc1, M.

1Méthodologie RMN, Univ. H2Modélisation du Transfert de Masse, University Ivan Pul’uy, Ternopil, 46001 Ukraine3LPEM - ESPCI and UPMC, 10 Rue Vauquelin, 75005 Paris cedex, France

E-mail: jacques.fraissard@upmc.fr

1. Introduction We presented in a previous paper [1] a new NMR

imaging technique which can be used

diffusion and adsorption of a gas in a microporous bed [2].

The sample is displaced vertically, step by step, relative to

the detector during the adsorption of the gas; the detector is

a very thin coil. The bed is assumed to consist of

layers of solid, and the region probed is limited to each

layer; so the variation of the concentration of gas absorbed

at the level of each layer is obtained as

This technique allows the calculation of all the parameters

of the system at every moment, at every position in the solid

and in each crystallite. But the most interesting thing is that

this technique is now able to visualize directly

diffusion of several gases [2].

The study of the co-diffusion of gases through a

microporous solid and the resulting instantaneous

distribution (out of equilibrium) of the adsorbed phases is

particularly important in many fields, such as gas separa

heterogeneous catalysis, etc. Classical 1H NMR imaging is a

good technique for the visualisation of these processes

since the signal obtained is not specific

requires that each experiment be performed several times

under identical conditions, and each time with only one

incompletely deuteriated gas. In contrast, our new technique

gives a signal characteristic of the adsorbed gas.

therefore provide directly, at every moment and at every

level of the crystallite bed, the distribution of several gases

competing in diffusion and adsorption.

2. Experimental results

Figure 1: left: Sample-holder bulb containing the liquid

phase in equilibrium with the gas phase;

the narrow zone monitored

– 17 – NMRCM 2011, Saint Petersburg, Russia

Competitive Diffusion of Gases in a Zeolite Using

Selection Procedure

, M. Petryk2, D. Canet1, J. Fraissard3

Méthodologie RMN, Univ. H. Poincaré, 54506 Vandoeuvre-les-Nancy cedex, France

Modélisation du Transfert de Masse, University Ivan Pul’uy, Ternopil, 46001 Ukraine

ESPCI and UPMC, 10 Rue Vauquelin, 75005 Paris cedex, France

mail: jacques.fraissard@upmc.fr

We presented in a previous paper [1] a new NMR

for following the

diffusion and adsorption of a gas in a microporous bed [2].

The sample is displaced vertically, step by step, relative to

tion of the gas; the detector is

a very thin coil. The bed is assumed to consist of n very thin

layers of solid, and the region probed is limited to each

layer; so the variation of the concentration of gas absorbed

a function of time.

the calculation of all the parameters

of the system at every moment, at every position in the solid

But the most interesting thing is that

this technique is now able to visualize directly the co-

diffusion of gases through a

microporous solid and the resulting instantaneous

distribution (out of equilibrium) of the adsorbed phases is

particularly important in many fields, such as gas separation,

H NMR imaging is a

good technique for the visualisation of these processes but,

since the signal obtained is not specific for each gas, this

requires that each experiment be performed several times

ical conditions, and each time with only one

completely deuteriated gas. In contrast, our new technique

gives a signal characteristic of the adsorbed gas. It can

at every moment and at every

istribution of several gases

containing the liquid

equilibrium with the gas phase; right: Schema of

the narrow zone monitored

As a first example we have studied the co

benzene and hexane through

15 mm).

Figure 1 shows the sample-holder tube

vertically, up or down, opposite the very thin detector. The

homogeneous liquid phase consists of two equal volu

benzene and hexane. It is in equilibrium with its gas phase at

25°C. The two gases begin to diffuse in the zeolite when the

glass partition is broken.

Figure 2 compares the evolution, as a function of time, of

the benzene and hexane concentrations,

the sample. It reveals particularly well, under the chosen

experimental conditions, the negative effect of benzene on

the diffusion of hexane, and this at every moment.

Figure 2: Time variation of the benzene and hexane

concentrations at different levels of the sample

More precise results will be presented at the meeting.

3. Conclusion The choice of the two diffusing ga

hexane, and of the ZSM5 zeolite

important. The main result is the possibilit

time, of following at every moment the concomitant

distribution of several gases co

environment.

References [1] S. Leclerc, G. Trausch, B.

Retournard , J. Fraissard and D.Chem., 44, 311-317 (2006)

[2] Michel Petryk, Sebastien Leclerc, Daniel Canet, Jacques Fraissard, Catalysis Today(2008)

, Saint Petersburg, Russia, June 27 – July 1, 2011

in a Zeolite Using A Slice

Nancy cedex, France

Modélisation du Transfert de Masse, University Ivan Pul’uy, Ternopil, 46001 Ukraine

ESPCI and UPMC, 10 Rue Vauquelin, 75005 Paris cedex, France

have studied the co-diffusion of

through a bed of ZSM5 (length

holder tube which is moved

vertically, up or down, opposite the very thin detector. The

homogeneous liquid phase consists of two equal volumes of

benzene and hexane. It is in equilibrium with its gas phase at

25°C. The two gases begin to diffuse in the zeolite when the

compares the evolution, as a function of time, of

the benzene and hexane concentrations, at different levels of

the sample. It reveals particularly well, under the chosen

experimental conditions, the negative effect of benzene on

the diffusion of hexane, and this at every moment.

Figure 2: Time variation of the benzene and hexane

ions at different levels of the sample

More precise results will be presented at the meeting.

two diffusing gases, benzene and

and of the ZSM5 zeolite is not what is most

important. The main result is the possibility, for the first

time, of following at every moment the concomitant

distribution of several gases co-diffusing in a physical

Cordier, D. Grandclaude, A. , J. Fraissard and D. Canet, Magn. Reson.

Michel Petryk, Sebastien Leclerc, Daniel Canet,

Catalysis Today, 139, 234 – 240

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 18 –

Cross-Polarization and Variable Angle Spinning Applied to

Oriented Systems

K. V. Ramanathan

NMR Research Centre, Indian Institute of Science, Bangalore 560012, India

E-mail: kvr@nrc.iisc.ernet.in

1. Introduction Cross-Polarisation (CP) and Magic Angle /Variable

Angle Spinning (MAS/VAS) are techniques well-known in

NMR and are being used extensively to study a variety of

organic, inorganic, polymeric and biological systems in the

solid state. When applied to partially ordered systems that

orient in a magnetic field, these techniques yield results that

have features which are different from the ones obtained

from rigid solid powder samples. The properties of the

systems lend themselves to be exploited with these

techniques and yield parameters that are useful for structure

and dynamics studies. We will elaborate here on the above

methodologies applied to nematic liquid crystals and cover

particularly topics such as development of new pulse

schemes for polarization transfer, improved SLF pulse

sequences and variable angle spinning studies. Such studies

provide an ideal test-bed for developing methodologies

which have applications to other similar systems such as

biological membranes.

2. Separated Local Field Spectroscopy NMR provides several parameters that can be used to

obtain information about the liquid crystalline phase. Of

these, the measurement of dipolar couplings between nuclei

has proved to be a convenient way of obtaining the ordering

of the dipolar vector in the magnetic field. The measurement

of the dipolar coupling between a pair of nuclei is

conveniently carried out by the use of the separated local

field (SLF) 2D NMR technique, which can be used for

extracting dipolar couplings for several sites simultaneously.

There are many SLF-2D techniques that are available for

this purpose. We have employed SLF techniques based on

Hartmann-Hahn cross-polarization (HHCP) extensively for

measuring the dipolar couplings of many novel liquid

crystal systems. The liquid crystalline phase represents a

unique state of matter where partial order exists on

molecular and supramolecular levels and is responsible for

several interesting properties observed in this phase. Hence

a detailed study of ordering and topology in liquid crystals is

of significant scientific and technological interest. The SLF

techniques, however, have a few limitations such as

sensitivity to r.f. inhomogeniety and carrier frequency off-

set and the presence of undesirable zero-frequency peaks.

We have proposed a number of modifications to address

these problems and have devised techniques that provide

accurate dipolar couplings in a sensitive fashion and free of

dependence on experimental conditions [1,2].

We have also explored an approach different from HHCP

for polarization transfer [3]. This approach is similar to the

INEPT technique used in solution NMR. Magnetization

evolution of the I spin in a tilted rotating frame under

heteronuclear I-S dipolar Hamiltonian gives rise to anti-

phase two spin order terms. This can be converted into a

single spin order term of S spin by a 900 pulse on the S spin

followed by subsequent magnetization evolution under bi-

linear operator terms. We have shown that this approach can

be used not only for polarization transfer from I to S spin,

but also for measuring I-S dipolar couplings. The technique

can be used for polarization transfer between spin 1/2 nuclei

and also between a spin 1 and a spin 1/2 nucleus [4]. It has

also been demonstrated that the technique can be used for

polarization transfer from protons to the overtone transition

of 14N nucleus, thus reducing the spectral window for 14N

studies from MHz to kHz [5]. These experiments provide

correlation as well coupling information.

3. Variable Angle Spinning The experiments are based on the orientation of the

nematic directors in a spinning liquid crystal in a magnetic

field. Due to the interplay of the interactions between the

magnetic and the viscous forces in a spinning sample,

different orientational behavious are observed. Depending

on the magnetic susceptibility anisotropy of the sample, it is

observed that spinning the sample about an axis making an

angle less than or greater than the magic angle results in the

alignment of the major or the minor directors along the

spinning axis. This gives rise to characteristic NMR line

splittings, that depend on factors such as the symmetry of

the phase and the sign of the diamagnetic susceptibility

anisotropy of the system. This orientational behaviour can

be used for a number of applications and a few examples

will be illustrated [6].

References [1] Nitin P. Lobo and K.V. Ramanathan, J. Phys. Chem.

Lett., (In Press). [2] S. Jayanthi and K.V. Ramanathan, J. Chem. Phys., 132,

134501 (2010). [3] S.Jayanthi, P K Madhu, N.D Kurur; and K V

Ramanathan, Chem. Phys. Lett., 439, 407 (2007). [4] S.Jayanthi and K.V. Ramanathan, Chem. Phys. Lett.

487, 122, (2010). [5] S. Jayanthi and K.V. Ramanathan, Chem. Phys. Lett.

502, 121 (2011). [6] H.S.Vinay Deepak, Anu Joy, N. Suryaprakash and

K.V.Ramanathan, Magn. Reson. Chem. 42, 409, (2004).

– 19 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

New discoveries of archaeological sites in western Crimea with

help of magnetometry

Tatiana N. Smekalova, Andrey V. Chudin, Aleksey E. Pasumansky

Saint-Petersburg State University, Faculty of Physics

E-mail: tnsmek@mail.ru

This report presents the results of recent investigations of ancient Greek and late Scythian sites in north-western Crimea. This region played an important role in the history of the northern Black Sea littoral in antiquity.

In terms of its landscape, economy, and cultural history, this region was unusual; it was the main agricultural base for both ancient Greek Chersonesos and the Late Scythian kingdom. The north-western Crimea was a focus of the interests of the Chersonesean state in the second half and the end of the 4th century BC. The whole maritime zone of north-western Crimea and the inland areas of the Tarkhankut Peninsula was controlled by Chersonesos, which founded a net of settlements here.

In contrast to Late-Scythian townsites of the Crimean foothills, the Late-Scythian settlements in western Crimea are a special phenomenon; this is because they were established at fortified and unfortified settlements in the Chersonesean rural hinterland. These settlements were founded between the beginning and the second half of the 2nd century BC. Therefore, the defensive system of these settlements was based on the fortifications of the Chersonesean period.

Until recently, a generally accepted axiom was that, during the Greek period, only the maritime zone was occupied in north-western Crimea. This supposition must now be revised because of recent discoveries in the inner part of the Tarkhankut Peninsula. The investigation of the ancient settlement-sites on the Tarkhankut Peninsula was carried out by means of the interdisciplinary method including remote techniques (analysis of space photographs and aerial shots), examination of detailed maps, viewshed analysis, magnetic surveys and visual explorations.

Remote sensing methods, such as electric resistivity surveys and magnetic surveys, have proved to be effective non-destructive techniques for exploration of Greek and “aboriginal” sites in the north-western Crimea. Magnetic surveys have been used over many seasons in the region under consideration, and have proved an indispensable tool in investigations of settlement structures. Indeed, it is this technique that allows the identification of household pits or pit houses, not normally visible on photographs. In addition, the magnetic maps show very clearly the rectangular layout of the antique farmhouses, which makes it easy to identify this class of archaeological site and so distinguish the Greek settlements from the “aboriginal” villages.

Magnetic surveying involves the measurement of the Earth’s magnetic field over small intervals close to the surface of the site under investigation. Variations in the magnetic field of an identified area may be due to the contrasts in the magnetic properties of the archaeological objects and their environment. For instance, the ashy and ceramic-rich fills of household pits are, as a rule, more strongly magnetic compared with the loam in which they are often found. Therefore, pits and dugout dwellings create

weak positive magnetic anomalies with magnitudes from a few nT (nT or nanotesla is a unit for measuring the intensity of the magnetic field) to 20 nT. Stone walls, by contrast, produce weak (several nT) negative anomalies because they are constructed of nonmagnetic limestone within the weak-magnetic environment of the cultural deposits. The strongest positive anomalies (hundreds or even thousands of nT) are produced by manufacturing items associated with fire, such as hearths and ovens, particularly potters’ or iron-making kilns. A more detailed description of the physical principles of magnetic surveying with examples of its application in investigations of various archaeological sites is presented in the book “Magnitorazvedka v arkheologii” (Magnetic surveys in archaeology), 2010.

At the sites under investigation, a grid of rectangular plots that covered the entire area of the site and some of the surrounding space was made for the purposes of the survey. Magnetic surveys were then conducted with a step of 0.5 m, and the sensor positioned so it was never higher than 0.3 m above the surface. The data were stored in the computer memory of the magnetometer. Every 15 s, control measurements were carried out with a second magnetometer located in a zone of normal field. The latter measurements were later used in data analysis to determine and then subtract the temporary variations in the Earth’s magnetic field. Using the Surfer software, the magnetic maps were drawn in the form of shadowgraphs or colour contour maps. In these images, positive anomalies were represented in dark and blue colours, while the lighter and red colours marked the negative anomalies.

Among the important results of the studies in 2009-2011 was the discovery of previously unknown Greek-period settlement-sites (Kunan, Southern Ocheretay, Kipchak 1, Kipchak 2, and Dzhangul?-Mysovoe) in the inland and maritime zone of northwestern Tarkhankut. The surface finds of the Hellenistic period and the rectangular architectural plan, revealed by means of magnetic surveys, allow us to identify these sites as ancient Greek rural estates typical of northwestern Crimea.

These studies resulted in the compilation of a catalogue of twenty four Greek and Late-Scythian settlement-sites, some known before and some discovered recently. This catalogue shows their exact positions in detailed maps, topographic plans, and excavation drawings. The catalogue also includes descriptions of previous studies, high resolution space photos, plans of unexcavated building remains (based on the interpretation of magnetic maps) and photographs of the sites.

The emphasis of this lecture is on the results of remote sensing and archaeological and geophysical surveys which were conducted during the field campaign of 2009-2011 as part of the Aarhus University project and with the financial support from Russian Humanitarian Foundation (grant # 11-01-00546а).

NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011 – 20 –

Pulsed Field Gradient NMR for biological membranes and model

systems investigations

Vitaly I. Volkov

Institute of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region, 142432, Russia

E-mail: vitwolf@mail.ru

1. Introduction The self-diffusion measurements especially the

techniques using the pulsed field gradient NMR following by Fourier transforms are the he unique methods for direct structural and dynamic studies in systems with the fast ionic and molecular transport. Water transport in biological systems is important for cellular physiological reactions, osmotic pressure of tissue and drying process of biological materials. For diffusional water permeability in biological systems, pulsed field gradient NMR (PFG-NMR) spectroscopy has become the method of choice due to its remarkable sensitivity to molecular displacements in the range of 10nm–100 mm and to its non-invasive character.

In order to interpret the experimental data correctly, the model investigations are necessary.

The results were obtained at the Laboratory of Membrane Processes, Karpov Institute of Physical Chemistry, Moscow, Russia; Laboratory of NMR, Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region Russia and at Laboratory of Food and Biomaterial Science and Engineering, Graduated School of Life Science and Biotechnology, Korea University, Seoul, Korea.

This presentation devotes to investigations of ionic and water transport in biological cells (chlorella, yeast and erythrocytes) and in cation-exchange and pore membranes as model systems. Well known perfluorinated cation-exchange memdranes, sulfocation-exchange styrene bivinyl benzene resin CU-2 with different amount of crosslinked agent and aromatic bi sulfocontaining polyamides were stidied. The sulfocontaining polyamides allows varying chemical structure widely. Two isomer compositions iso (µPA) and tere (πPA) were investigated.

2. Synthetic membranes as model

systems Sulfo-, carboxyl-, aminogroups containing ion exchange

membranes and pore track etched membranes were investigated as model systems. The structure of ionic channels was observed by porometry, small-angle X-ray scattering, ESR, ENDOR and electrochemistry methods. The hydration of fixed groups and alkaline and alkaline – earth ions were studied in details in perfluorinated Nafion membranes. The mechanism of charge group – counter ion or water molecule interactions were understood from high resolution hetero nuclear NMR data. Microscopic ionic and water molecule mobilities were determined by NMR relaxations. Self-diffusion coefficients of protonic molecules and lithium and fluorine counter ions in different spatial scales were measured directly by PFG NMR. It was

concluded that the macroscopic electro – mass transfer is controlled by local ion and molecule jumps between adjacent charge groups. The interconnection between ionogenic channel structure, mobile ion or molecule-charge groups binding and translational ionic and molecular mobility was determined [1]. The quantitative relations of structural and motion parameters were derived from the percolation theory. On the basic of this knowledge, the main particularities of water behaviour in proteins and gels have been understood. It was shown that hydrogen bond is very important for proton and water molecules motions in biological ionic channels.

3. Biological cell membranes. Emulsions Water self-diffusion in cells of chlorella, yeast and red

blood cell was investigated. These cells were selected as model systems with different cell membrane permeabilities. The apparent self-diffusion coefficients of intracellular and extracellular water were measured dependent on diffusion time. The regions of restricted diffusion and hindered diffusion were observed. Scaling approach and two compartment exchange model were applied to calculate cell sizes and permeabilities [2, 3]. The values of permeability calculated by these two ways are very close to each other. The correctness of these theoretical interpretations was also demonstrated by good agreement of cell sizes obtained from PFG NMR and electron microscopic data. The permeabilities are 3.10-6, 6.10-6 and about 10-4 m/s for chlorella, yeast and red blood cells, respectively, depending on cell growing conditions and physical chemistry treating. The average cell sizes are varied from 2 to 4 microns. The water exchange mechanism in biological cells is discussed.

Surfactant emulsions in water were studied by PFG NMR. The phenomenon of restriction diffusion was observed. The protonic exchange rate between water molecules and micelle surface as well as micelle size and water layer thickness were determined [4].

Acknowledgements The investigation was supported by Russian Basic

Research Foundation, grant № 10-03-00862-a.

References [1] V.I. Volkov, A.A. Pavlov, E.A. Sanginov

Solid State Ionics 188 (2011) 124–128 [2] Suh K.J., Hong Y.S., Volkov V.I., Skirda V.D. et.al

Biophys. Chem. 104, 121-130, (2003). [3] Cho J.H., Hong Y.S., Volkov V.I., Skirda V.D. et. al. -

Magnetic Resonance Imaging 21,1009-1017 (2003). [4] Y.S. Hong, K.C. Kim, V.I. Volkov, V.D. Skirda, et.al. -

Appl. Magn. Reson. (2005) 105-112

Part II

Oral Reports

– 23 – NMRCM 2011, Saint Petersburg, Russia, June 27 – July 1, 2011

Strong NMR signal enhancement by Parahydrogen Induced

Polarization (PHIP) for study mechanism of heterogeneous

hydrogenation

Danila A. Barskiy1,2, Kirill V. Kovtunov1, Igor V. Koptyug1

1International Tomography Center, SB RAS, Institutskaya St. 3A, 630090 2Novosibirsk State University, Novosibirsk, Pirogova St. 2, 630090

E-mail: barskiy@tomo.nsc.ru

PHIP is a powerful tool for investigation of catalytic

reactions involving molecular hydrogen. By virtue of its

signal enhancing capabilities, PHIP has been used in

homogeneous hydrogenation catalysis to observe and

identify catalytic intermediates, determine hydrogen

position in product molecules and, hence, establish reaction

mechanism. Heterogeneous catalysts were not expected to

produce PHIP since the reaction mechanism involved should

destroy the original correlation of the two nuclear spins of

parahydrogen. However, it was recently demonstrated [1],

contrary to these expectations, that supported metal catalysts

do exhibit PHIP effect. This fact can be used for the

production of spin-polarized fluids for MRI applications [2]

and for developing new research tools for mechanistic and

kinetic studies on heterogeneous hydrogenation processes

by NMR.

In the present work we focus our attention on the study of

1,3-butadiene and 1-butyne hydrogenation reactions over Pt

supported catalysts with the use of parahydrogen. It was

noted that in case of heterogeneous catalysis the main route

of reaction pass through the dissociation of molecular

hydrogen to the atoms on the catalyst’s surface. At the same

time one of the most important features of PHIP is that it

can be observed just in the case of pairwise addition of two

H atoms to the same product molecule. It means that, first,

conventional mechanism including dissociative way of H

addition for heterogeneous hydrogenation is not completely

understood and, second, information extracted from the

PHIP NMR spectrum may be successfully utilized for

establishing of reaction mechanism.

Reaction of 1,3-butadiene and 1-butine were studied over

Pt supported catalysts. Polarization is observed for all

reaction products. It proves the presence of pairwise

addition route in the reaction mechanism. For the purpose to

examine the effect of particle size to the enhancement of

polarized NMR signal, platinum catalysts with different

particle sizes were used. Also, it was shown that intensity of

polarized peaks and, hence, percentage of pairwise addition

is in the strong dependence of support nature (Figure 1). We

have also analyzed the position of parahydrogen atoms in

the reaction products (such as 1-, 2-butenes and butane) and

reaction mechanisms including the stage of pairwise

addition of molecular hydrogen were suggested.

It should be remarked, that by reason of rapid gas flow

rate from Earth magnetic field to the strong field of NMR

magnet (flow rate is approximately 7 ml/s), there is not

enough time for the full spin relaxation of gas molecules.

Thus, the NMR signal is very low when spectrum is

acquired in the gas flow regime. For the purpose to increase

relaxation rate we used tube with paramagnetic substance –

activated charcoal. When coal tube was put in the path of

gas flow while in high field of magnet, signal intensity

became the same order of magnitude with the signal

obtained in the simple NMR experiment (in the stopped

flow).

Figure 1: 1H NMR PHIP spectra of 1,3-butadiene

hydrogenation reaction products over Pt catalysts with

different support nature

Conclusions • For the first time it was demonstrated that PHIP can be

obtained for all reaction products in the catalytic

hydrogenation reaction of 1,3-butadiene and 1-butyne over

supported Pt catalysts.

• Mechanisms of 1,3-butadiene and 1-butyne hydrogenation over Pt supported catalysts were suggested

taking into account the stage of pairwise addition of

hydrogen.

• Influence of support nature and Pt particle size to the NMR PHIP signal intensity were investigated.

Acknowledgements This work is supported by the RFBR 11-03-93995-

CSIC_a, RFBR 11-03-00248-а, RAS (5.1.1), SB RAS (67,

88), NSh-7643.2010.3, ERC (02.740.11.0262) and Grant of

President of Russian Federation (MK-1284.2010.3).

References [1] K. V. Kovtunov, I. E. Beck, V. I. Bukhtiyarov, I. V.

Koptyug, Angew. Chem. Int. Ed. 2008, 47, 1492. [2] L.-S. Bouchard, S. R. Burt, M. S. Anwar, K. V.

Kovtunov, I. V. Koptyug, A. Pines, Science 2008, 319, 442

Pt / TiO2

Pt / Al2O3

Pt / SiO2

Pt / C

Pt / ZrO2

Pt / TiO2

Pt / Al2O3

Pt / SiO2

Pt / C

Pt / ZrO2

Pt / TiO2

Pt / Al2O3

Pt / SiO2

Pt / C

Pt / ZrO2

Pt / TiO2

Pt / Al2O3

Pt / SiO2

Pt / C

Pt / ZrO2

NMRCM 2011, Saint Petersburg, Russia, June 27

Solvation and hydration properties of organic molecules in

complex solutions

Alexey V. Donetsand Dieter Michel

Faculty of Physics

E-mail: aldonets@mail.ru1Department of Chemistry and Industrial NMR Centre, Royal Institute of Technology SE

Stockholm, Sweden2Faculty of Physics and Geosciences, University of Leipzig, Germany

1. Introduction The effects of hydration and solvation of organic

molecules are the points at fundamental issues of modern

biochemistry. The investigation of inte

biomolecules and solvation shells is usually quite difficult,

because the solute-solvent interactions must be treated on

the molecular level.

Approach developed in the Department of Q

Magnetic Phenomena (SPbSU) is based on

and complementary research methods: NMR

quantum chemical calculation. This approach allows

get the solvation and hydration properties of the

molecules in salt solutions.

2. NMR-relaxation method The method of investigation of the microstructure of

ionic solutions using measurements of the NMR

rates of solvent and solute nuclei as function of the

concentration and temperatures was earlier developed [1]. It

was found, that the ions can be used as probes in the st

of complex solutions. Researches of the NMR ion

useful for studying the hydration environment of organic

molecules. It was determined [2] that the

the Cl-, Br- , I- can change due to temperature variations

the relatively narrow interval: between 30 and 35

effect, initially observed for simple salt solutions, also exists

in ternary systems. Temperature studies of the relaxation of

the anion nuclei allow the determination of

hydration properties of organic molecules

spin-lattice and spin-spin relaxation gives information on the

mechanisms of exchange in solution and the protein surface

The investigation of the aqueous solutions of salts,

containing the Na+, Cl-, surfactants (SDS)

organic compounds, has been carried out in a wide range of

concentration and temperature.

Hydrophobic properties of surface of some amino

were studied. The results of NMR investigation suggest that

there are two classes of chlorine-bindi

molecules: a small number of strong binding sites, where the

chloride binding can be inhibited by stoichiometric amount

of the sodium dodecyl sulphate (SDS), and weak (SDS

insensitive) binding sites (see Fig. 1).

, June 27 – July 1, 2011 – 24 –

Solvation and hydration properties of organic molecules in

complex solutions

Donets, Vladimir I. Chizhik, Sergey V. DvinskikhMichel2

Physics, Saint-Petersburg State University, Russia

aldonets@mail.ru

Department of Chemistry and Industrial NMR Centre, Royal Institute of Technology SE

Stockholm, Sweden

Faculty of Physics and Geosciences, University of Leipzig, Germany

The effects of hydration and solvation of organic

fundamental issues of modern

interactions between

biomolecules and solvation shells is usually quite difficult,

solvent interactions must be treated on

Approach developed in the Department of Quantum

U) is based on two independent

and complementary research methods: NMR-relaxation and

quantum chemical calculation. This approach allows us to

get the solvation and hydration properties of the organic

the microstructure of

solutions using measurements of the NMR-relaxation

rates of solvent and solute nuclei as function of the

concentration and temperatures was earlier developed [1]. It

be used as probes in the study

NMR ion nuclei are

useful for studying the hydration environment of organic

hydration shells of

can change due to temperature variations in

: between 30 and 35oC. The

effect, initially observed for simple salt solutions, also exists

of the relaxation of

of the solvation and

f organic molecules. Comparison of

spin relaxation gives information on the

and the protein surface.

The investigation of the aqueous solutions of salts,

, surfactants (SDS) and different

organic compounds, has been carried out in a wide range of

surface of some amino-acids

. The results of NMR investigation suggest that

binding sites on BSA

molecules: a small number of strong binding sites, where the

chloride binding can be inhibited by stoichiometric amount

of the sodium dodecyl sulphate (SDS), and weak (SDS-

Figure 1: Concentration dependences of the