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Saint Petersburg State University Faculty of Physics

International Symposium and Summer School in Saint Petersburg

Nuclear Magnetic Resonance in Condensed Matter

11th meeting: “Biomolecular NMR and related phenomena” July 7 – 11, 2014

Book of Abstracts

Saint Petersburg, Russia 2014

an AMPERE event

International Symposium and Summer Schoolin Saint Petersburg


11th meeting: “July 7 – 11,

ББК В334.2, Г512 М43 Faculty of Physics

Saint Petersburg State UniversitySaint Petersburg, 198504, Russia

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

M43 Nuclear Magnetic Resonance in Condensed Matter:School, 11th meeting: “Biomolecular NMR and related phenomena2014. – 80 p. ISBN

Symposium and Summer • Saint Petersburg State University

• Russian Foundation for Basic Resear

• Bruker Corporation

International Advisory Board A. S. Arseniev (Moscow, Russia)

V. Balevicius (Vilnius, Lithuania)

V. I. Chizhik (Saint Petersburg, Russia)

J. Fraissard (Paris, France)

H. Haranczyk (Kraków, Poland)

S. Jurga (Poznań, Poland)

M. V. Kovalchuk (Saint Petersburg, Russia)

O. B. Lapina (Novosibirsk, Russia)

Organizing Committee Co-Chairmen:

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

Vice-Chairmen:

A. V. Donets M. G. Shelyapina

Registered names, trademarks, etc. used in this book, even without specifconsidered unprotected by law.

ISBN

International Symposium and Summer School in Saint Petersburg


meeting: “Biomolecular NMR and related phenomena” 2014

Saint Petersburg State University Saint Petersburg, 198504, Russia

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

Nuclear Magnetic Resonance in Condensed Matter: abstracts of the International Symposium and SBiomolecular NMR and related phenomena” – Saint Petersburg: “Solo” Publisher,

Symposium and Summer School are supported by: Saint Petersburg State University

Russian Foundation for Basic Research

International Advisory Board A. S. Arseniev (Moscow, Russia)

V. Balevicius (Vilnius, Lithuania)

V. I. Chizhik (Saint Petersburg, Russia)

H. Haranczyk (Kraków, Poland)

M. V. Kovalchuk (Saint Petersburg, Russia)

O. B. Lapina (Novosibirsk, Russia)

D. Michel (Leipzig, Germany)

V. I. Minkin (Rostov

K. V. Ramanathan (Bangalore, India)

R. Z. Sagdeev (Novosibirsk, Russia)

K. M. Salikhov (Kazan, Russia)

A. V. Skripov (Ekaterinburg, Russia)

N. R. Skrynnikov (Purdue, USA)

M. S. Tagirov (Kazan, Russia)

Organizing Committee Members:

Yu. S. Chernyshev

A. V. Egorov

V. V. Frolov

A. V. Komolkin

V. V. Matveev

S. O. Rabdano

S. M. Sukharzhevskii

P. M. Tolstoy

Layout of Abstracts Book:A. A. Levantovsky

R. Z. Sagdeev (Novosibirsk)

Registered names, trademarks, etc. used in this book, even without specific indication thereof, are considered unprotected by law.

© Organizing Committee NMRCM 201© “Solo” Publisher, Saint Petersburg, 201Printed in Russian Federation.

an

AMPERE event

International Symposium and Summer Saint Petersburg: “Solo” Publisher,

D. Michel (Leipzig, Germany)

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

K. V. Ramanathan (Bangalore, India)

R. Z. Sagdeev (Novosibirsk, Russia)

(Kazan, Russia)

A. V. Skripov (Ekaterinburg, Russia)

N. R. Skrynnikov (Purdue, USA)

M. S. Tagirov (Kazan, Russia)

S. M. Sukharzhevskii

Layout of Abstracts Book:

ic indication thereof, are not to be

ББК В334.2, Г512

© Organizing Committee NMRCM 2014, Saint Petersburg, 2014. © “Solo” Publisher, Saint Petersburg, 2014.

– 3 – NMRCM 2014, Saint Petersburg, Russia, July 7 – 11, 2014

Contents

I. Lectures .................................................................................................................. 7

Yury Bunkov, Rasul Gazizulin

Direct observation of Majorano fermions in superfluid 3He .............................................................................. 9

Yury Bunkov, M. Tagirov

Spin superfluidity and Bose-Einstein condensation of magnons ...................................................................... 10

Vyacheslav A. Chertkov, Dmitriy A. Cheshkov, Tatiana A. Ganina, Sergey S. Nechausov,

Kirill F. Sheberstov, Alla K. Shestakova

Novel high resolution NMR techniques for elucidation of molecular solution-state structure and

dynamics ........................................................................................................................................................... 11

Dieter Michel, Farhana Gul-E-Noor, Jürgen Haase, Marko Bertmer

NMR high resolution spectroscopy and spin-lattice relaxation of Small Molecules adsorbed in metal-

organic frameworks (MOFS) ............................................................................................................................. 12

Vladislav Yu. Orekhov

Modern methods of NMR data collections and spectra processing ................................................................. 13

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

Co-diffusion of gases in a microporous solid bed: classical NMR imaging or slice selection procedure .......... 14

Yury A. Pirogov

Local NMR spectroscopy in MRI experiments with small laboratory animals .................................................. 15

Peter I. Polyakov

Laws of volume elasticity in physical processes of formation of phase states and properties ........................ 16

Vitaly I. Volkov, Irina A. Avilova, Lubov’ V. Rimareva, Ludmila D. Volkova

Water exchange in biological cells studied by pulsed NMR techniques ........................................................... 17

Tairan Yuwen, Yi Xue, Fangqiang Zhu and Nikolai R. Skrynnikov

Modeling a system with intrinsic disorder: an NMR/MD study of peptide-protein encounter complex ........ 18

II. Oral Reports ......................................................................................................... 19

A. A. Drozdov, V. M. Cheremisin, I. G. Kamyishanskaya

Magnetic Resonance features of HIV-associated opportunistic infections of the CNS .................................... 21

Sergey V. Dvinskikh

Heteronuclear Dipolar NMR Spectroscopy ....................................................................................................... 22

Egor Gerts, Andrei V. Komolkin

Structure of two cyanobiphenyl mesogens studied by molecular dynamics simulations ................................ 23

Anton Karseev, Vadim Davydov

Compact nuclear magnetic relaxometer to express - condition monitoring of liquid and viscous media ....... 24

Boris Kharkov, Sergey Dvinskikh

Molecular mobility in nanostructured mesocomposites studied by dipolar NMR spectroscopy .................... 25

T. V. Makurova, D. A. Zinkevich, V. M. Cheremisin, I. G. Kamishanskaya

Diffusion-Weighted MRI of the body in oncologic practice: method, comparison with PET/SPECT and

prospects ........................................................................................................................................................... 26

NMRCM 2014, Saint Petersburg, Russia, July 7 – 11, 2014 – 4 –

Evgeny V. Morozov, Oleg N. Martyanov

Method development to study heavy crude oils using NMR Imaging joined with Cold Finger testing

in situ ................................................................................................................................................................. 27

G. V. Mozzhukhin, J. Barras, B. Rameev, G. Kupriyanova

Two frequency nuclear quadrupole resonance for lines identifications .......................................................... 28

I. N. Petrov, V. M. Cheremisin, I. G. Kamyishanskaya

Possibilities of the MRI in a complex assessment of cardiac disaeses .............................................................. 29

Sevastyan O. Rabdano, Alexey V. Donets

The study of hydration properties of functional groups of glycine and beta-alanine amino acids by

nuclear magnetic resonance and quantum chemical calculations ................................................................... 30

V. A. Ryzhov, A. V. Lashkul, V. V. Matveev, M. V. Mokeev, P. L. Molkanov, A. I. Kurbakov, K. G. Lisunov,

I. A. Kiselev, D. Galimov, E. Lähderanta

Unusual scenario of temperature evolution of magnetic state in novel (Au, Co) doped carbon-based

nanomaterials ................................................................................................................................................... 31

Sergey Sheludiakov, Janne Ahokas, Jarno Järvinen, Otto Vainio, Denis Zvezdov, Sergey Vasiliev,

Vladimir Khmelenko, Shun Mao and David Lee

Magnetic resonance study of atomic hydrogen and deuterium stabilized in solid H2 and D2 matrices

below 1 K ........................................................................................................................................................... 32

III. Poster Session ..................................................................................................... 33

Victor V. Alexandriysky, Konstantin M. Litov, Sofija A. Kuvshinova, Vladimir A. Burmistrov 13

C NMR study of (2,2-dicyanoethenyl)-azobenzene derivatives ..................................................................... 35

Sergey I. Andronenko, Sushil K. Misra

Co2+

and Fe3+

EPR study of magnetic ZnO nanoparticles for its potential use in cancer cell treatment .......... 36

Nikolay V. Anisimov, O. Pavlova, M. Gulyaev, A. Samoylenko, Yu. Pirogov

Registration of magnetic resonance from nuclei other than protons on 0.5 Tesla MRI scanner ..................... 37

Nikolay V. Anisimov, E. Shalamova, K. Volkova, M. Gulyaev, A. Samoylenko

Whole-body NMR spectroscopy as a tool to assess human body composition ............................................... 38

Erdem Balcı, Hakkı Acar, Georgy V. Mozzhukhin, Bulat Z. Rameev, Pavel A. Kupriyanov,

Alexander V. Ievlev, Yury S. Chernyshev, Artur R. Lozovoy, Ruslan V. Archipov

Development of Earth`s field nuclear magnetic resonance (EFNMR) setup for applications in security

scanning devices ............................................................................................................................................... 39

Yu. V. Bogachev, V. A. Fokin, O. A. Cherdakov, D. Yu. Sugonyako

Application of magnetic resonance spectroscopy in the diagnostics of multiple sclerosis .............................. 40

Sergey N. Borisenko, Anna V. Lekar, Elena V. Vetrova, Sofya L. Srabionyan, Svetlana N. Sushkova,

Gennadii S. Borodkin and Nikolay I. Borisenko

NMR spectroscopy of benzimidazole derivatives synthesized in subcritical water ......................................... 41

Inna G. Borodkina, Gasan M. Abakarov, Gennadii S. Borodkin, A.-M. M. Ali, Igor S. Vasilchenko,

P. A. Ramazanova, Pavel B. Chepurnoi, Svetlana B. Zaichenko, Yuriy F. Mal’tsev, Anatolii S. Burlov,

Vladimir I. Minkin

Synthesis and NMR study of the novel class of tellurazoles – 2-sulphurfunctionalized benzotellurazoles ..... 42


Inna G. Borodkina, Anatolii S. Burlov, Valerii G. Vlasenko, Аrtem V. Dmitriev, Vasilii V. Chesnokov,

Ali I. Uraev, Dmitrii A. Garnovskii, Yan V. Zubavichus, Alexander A. Trigub, Igor S. Vasilchenko,

Pavel B. Chepurnoi, Dmitrii A. Lypenko, Еvgenii I. Mal’tsev, Тatiana V. Lifintseva, Yuriy F. Mal’tsev,

Gennadii S. Borodkin

Heteronuclear and 2D NMR Investigation of Pyrazole-Quinoline Ligand and its Zn and Cd Complexes ......... 43

Philipp Dolinenkov, Irina Korneva, Nikolay Sinyavsky

The application of the NQR relaxometry for the study of phase transitions in the molecular crystals ........... 44

Viatcheslav Frolov, Oksana Ilina

A reduction of concomitant magnetic fields effect through the optimization of the gradient magnetic

system ............................................................................................................................................................... 45

Dmitry M. Furman, Viatcheslav V. Frolov

Opportunity to enhance the contrast of MRI images using dynamic nuclear polarization in low

magnetic fields .................................................................................................................................................. 46

G. A. Gamov, S. V. Dushina, V. V. Aleksandriiskii, V. A. Sharnin

Nicotinamide solvation in aqueous ethanol: 15

N NMR study ........................................................................... 47

Ilknur Gunduz, Ivan Mershiev, Erdem Balci, Galina Kupriyanova, Georgy Mozzhukhin, Bulat Rameev

Signal Denoising in Earth’s Field Magnetic Resonance ..................................................................................... 48

Oksana Ilina, Viatcheslav V. Frolov

The structure connectome: a review ................................................................................................................ 49

V. A. Ivlev, G. A. Kalabin, V. G. Vasil’ev

Analysis of the identity and quality of peptide-based drugs by quantitative 1H NMR spectroscopy

(qNMR) .............................................................................................................................................................. 50

R. S. Каshaev, A. S. Kopilov

NMR-complex for diagnosis and control of cure of kidney scarcity decease ................................................... 51

R. S. Каshaev, A. S. Kopilov

NMR – study of the water molecules on the microbial cell surface at microbial growth process ................... 52

Ekaterina A. Krylova, Andrei V. Egorov

Water dynamics in the aqueous solution of the B1 domain of immunoglobulin-binding protein L.

A molecular dynamics simulation study ........................................................................................................... 53

Galina Kupriyanova, Aleksander Bagaychuk, Svetlana Ruzshyeva, Elena Makhno 13

C NMR relaxation in adipose tissue samples .................................................................................................. 54

Galina Kupriyanova, Ivan Mershiev, Filip Dolinenkov, Valeriy Sabirekian

Increasing signal/noise in the NQR measurements using composite pulse ..................................................... 55

Valentin V. Loskutiov, Eugene P. Petrov

Self-Diffusion in Cell Membranes in the Long Time Regime ............................................................................. 56

A. Lozovoy, N. Fatkullin, S. Stapf, C. Mattea

NMR Studies of intermolecular interaction in polymer melts .......................................................................... 57

Ivan Mershiev, Galina S. Kupriyanova

Composite pulses for 14

N NQR with minimal phase distortion ......................................................................... 58

Georgy Mozzhukhin, Galina Kupriyanova, Bulat Rameev, Bekir Aktas

Non resonance signal suppression in pulse NQR .............................................................................................. 59


Maria S. Muravyeva, Alexandr A. Khrapichev, Marina V. Shirmanova, Elena V. Zagaynova

Preclinical in vivo MR Imaging using the mouse model .................................................................................... 60

I. N. Petrov, V. M. Cheremisin, I. G. Kamyishanskaya

Possibilities of the MRI in a complex assessment of cardiac diseases .............................................................. 61

Pavel S. Popov, Ivan V. Pleshakov

Pulse magnetic field control of NMR signal in a ferrite domain walls .............................................................. 62

Kirill Sharapov, Stepan S. Dzhimak, Mihail G. Barishev, Aleksandr A. Basov, IIlya M. Bykov,

Karina I. Melkonyan, Denis I. Shashkov, Denis V. Kashaev

Determination of deuterium concentration in the biological fluids using NMR spectroscopy ........................ 63

Alla K. Shestakova, Vyacheslav A. Chertkov

Structure and stability of lanthanide cryptates in solutions ............................................................................. 64

Maxim A. Shevtsov, Boris P. Nikolaev, Ludmila Y. Yakovleva, Yaroslav Y. Marchenko,

Vyacheslav A. Ryzhov

Magnetic biosensing of experimental glioblastoma targerting with superparamagnetic nanocarriers

tagged to heat shock protein Hsp70 ................................................................................................................. 65

E. V. Shishmakova

Spin-lattice relaxation of hydrogen nuclei in dilute solutions carbosilane dendrimers of the 5th

generation with integral mesogenic groups attached by ethyleneglycol spacers ............................................ 66

A. V. Soloninin, A. V. Skripov

Hydrogen in Ti3Al: a nuclear magnetic resonance study .................................................................................. 67

Nikolay S. Vasilyev, Denis V. Kashaev

NMR research into H2O-H2O2-D2O system ........................................................................................................ 68

Vladimir Y. Volkov, Ekaterina V. Sosunova

Testing of cigarette filters by low-field NMR method ...................................................................................... 69

Author Index ............................................................................................................ 71

List of Participants ................................................................................................... 73

Part I

Lectures

Introduction The Majorana fermion, which acts as its own an

was suggested by Majorana in 1937.

particle with Majorana properties has yet been observed,

Majorana quasiparticles (QPs) was suggested at the

boundaries of topological insulators, like superfluid

Here we report the direct observation of Majorana QPs by

precise measurements of superfluid 3He-B

have succeed to separate the temperature dependence of the

bulk Bogolyubov fermions and the surface Majorana

fermions heat capacity. We have found that in the condi

of our experiments at the limit of extremely low temperature

as 0.12 mK the Majorana fermions constitute a part of about

15% of bulk 3He-B heat capacity. The heat capacity was

measured by two different methods.

Experimental results The experiments were done in the cell which consists of a

closed copper box with a small orifice. The box is immersed

in superfluid 3He-B with the temperature about 0.1 mK. The

temperature inside the box was measured by the Vibrating

Wire Resonators (VWRs) which Q-factor i

density of Bogolubov QPs. The QPs density is exponentially

related with the temperature. After some heating event the

density of QPs and temperature inside the box suddenly

rises, and then go back to its initial temperature by

thermalisation via the orifice. The extremely low specific

heat of 3He-B at ultra-low temperatures makes it possible to

measure the increase of the temperature inside the box after

the releasing the small amount of energy (down to 1 keV).

As the heating events, the neutron capture reactions with 3He and the VWR heating pulses were used. The heat

capacity of 3He-B in the box was measured by two different

methods. One was the measurements of QPs density jump

just after the calibrated heating pulse. The results are shown

in Fig. 1. The second method was the measurements of the

recovering time constant of the box [1]. In the last case the

time constant of temperature recovering depends on the full

energy, deposited on Bogolubov and Majorana QPs

Fig. 2. In a both cases we have seen the deviation of the heat

capacity from the pure Bogolubov case. This deviation

corresponds well to a predicted density of Majorana

particles.

Plans for future The existence of Majorana QPs is confirmed in a first

time in described experiments. In a future we are planning to

Direct observation of Majorano fermions in superfluid

Yury Bunkov1,2,

1MCBT, Institut Neel, Grenoble, France

E-mail: yuriy.bunkov2Kazan Federal University, Kazan, Russia

– 9 – NMRCM 2014, Saint Petersburg, Russia,

The Majorana fermion, which acts as its own antiparticle,

was suggested by Majorana in 1937. While no stable

particle with Majorana properties has yet been observed,

Majorana quasiparticles (QPs) was suggested at the

boundaries of topological insulators, like superfluid 3He-B.

t observation of Majorana QPs by

B heat capacity. We

have succeed to separate the temperature dependence of the

bulk Bogolyubov fermions and the surface Majorana

fermions heat capacity. We have found that in the conditions

of our experiments at the limit of extremely low temperature

as 0.12 mK the Majorana fermions constitute a part of about

B heat capacity. The heat capacity was

ere done in the cell which consists of a

closed copper box with a small orifice. The box is immersed

B with the temperature about 0.1 mK. The

temperature inside the box was measured by the Vibrating

factor is determined by a

density of Bogolubov QPs. The QPs density is exponentially

related with the temperature. After some heating event the

density of QPs and temperature inside the box suddenly

rises, and then go back to its initial temperature by

ion via the orifice. The extremely low specific

low temperatures makes it possible to

measure the increase of the temperature inside the box after

the releasing the small amount of energy (down to 1 keV).

eutron capture reactions with

He and the VWR heating pulses were used. The heat

B in the box was measured by two different

methods. One was the measurements of QPs density jump

just after the calibrated heating pulse. The results are shown

1. The second method was the measurements of the

recovering time constant of the box [1]. In the last case the

time constant of temperature recovering depends on the full

energy, deposited on Bogolubov and Majorana QPs, see

we have seen the deviation of the heat

capacity from the pure Bogolubov case. This deviation

corresponds well to a predicted density of Majorana

is confirmed in a first

. In a future we are planning to

investigate the Majorana QPs by a coherent magnetic

resonance. The technics of Q-ball, described in our other

lecture, will be applied.

Figure 1. The deviation of heat capacity from a bulk one.

The circles show the heat capacity, measured after a VWR

heating pulse. The boxes shows the heat capacity measured

after a neutron capture reaction which

of around 764 keV

Figure 2. The recovery time after heating pulses. The

straight line corresponds to a recovery time if only

Bogolubov QPs are involved. The covered line corresponds

to a time constant when the heat capacity of Majorana QPs,

measured by first method,

Acknowledgements This work is supported by an Agence Na

Recherche, France (project N° 099784 MajoranoPRO).

References [1] Yu. M. Bunkov, J. Low Temp. Phys.

(2014).

Direct observation of Majorano fermions in superfluid

, Rasul Gazizulin1,2

MCBT, Institut Neel, Grenoble, France

[email protected]

Kazan Federal University, Kazan, Russia

, Saint Petersburg, Russia, July 7 – 11, 2014

investigate the Majorana QPs by a coherent magnetic

ball, described in our other

The deviation of heat capacity from a bulk one.

capacity, measured after a VWR

heating pulse. The boxes shows the heat capacity measured

after a neutron capture reaction which releases energy

of around 764 keV

The recovery time after heating pulses. The

ht line corresponds to a recovery time if only

Bogolubov QPs are involved. The covered line corresponds

to a time constant when the heat capacity of Majorana QPs,

measured by first method, is included

This work is supported by an Agence National de la

Recherche, France (project N° 099784 MajoranoPRO).

Low Temp. Phys., 175, 385-394

Direct observation of Majorano fermions in superfluid 3He

NMRCM 2014, Saint Petersburg, Russia, July 7

Introduction The Spin Supercurrent and Bose-Einstein condens

(BEC) of magnons, similar to an atomic BEC, was

discovered in superfluid 3He-B, which is characterized by

absolute purity.

Later this phenomenon were observed in a few

magnetically ordered materials with differen

impurities. In this lecture we will review the propert

magnon BEC in a presence of impurities and defects.

History The conventional magnon BEC, the phase

precession of magnetization was discovered for the first

time in superfluid 3He-B in 1984 [1]. It manifests itself by a

region, where the magnetization is deflected on a large angle

and is precessing coherently even in an inhomogeneous

magnetic field. The transverse component of magnetization

is described by the single wave functi

possesses all the properties of the spin superfluidity

spatial gradient of phase ϕ leads to a spin supercurrent

which transports the magnetization. There were observed:

phase slip processes at the critical current

Josephson effect; spin current vortex; Goldstone modes

The long standing quest of nontrivial magnetic relaxation in

superfluid 3He have been resolved. The comprehensive

review of spin superfluidity in 3He-B one can find in [2

New results, Q-ball of magnonsThere are many new physical phenomena related to th

Bose condensation of magnons, which have been observed

after the discovery of Homogeneously Precessing Domain

(HPD). There was found 5 different magnon BEC states in

superfluid 3He. These include in particular compact objects

– coherently precessing states trapped by orbital texture [3

At small number N of the pumped magnons, the system is

similar to the Bose condensate of the ultracold atoms in

harmonic traps, while at larger N the analog of the

particle physics develops. The Q-ball is a rather general

physical object, which in principle can be formed in

condensed matter systems. At the quantum level, this

is a compact object formed by magnons

Spin superfluidity and Bose

Yury Bunkov1,2, M.

1MCBT, Institut Neel, Grenoble, France

E-mail: yuriy.bunkov2Kazan Federal University, Kazan, Russia

– 11, 2014 – 10 –

Einstein condensation

atomic BEC, was

B, which is characterized by

Later this phenomenon were observed in a few

rdered materials with different types of

we will review the properties of

of impurities and defects.

The conventional magnon BEC, the phase-coherent

precession of magnetization was discovered for the first

B in 1984 [1]. It manifests itself by a

is deflected on a large angle

and is precessing coherently even in an inhomogeneous

magnetic field. The transverse component of magnetization

single wave function S⊥eiωt+ϕ

. It

possesses all the properties of the spin superfluidity. The

leads to a spin supercurrent

There were observed:

sses at the critical current; spin current

ffect; spin current vortex; Goldstone modes etc.

The long standing quest of nontrivial magnetic relaxation in

. The comprehensive

B one can find in [2].

ball of magnons re are many new physical phenomena related to the

which have been observed

Homogeneously Precessing Domain

different magnon BEC states in

lar compact objects

s trapped by orbital texture [3].

magnons, the system is

similar to the Bose condensate of the ultracold atoms in

analog of the Q-ball in

ball is a rather general

physical object, which in principle can be formed in

condensed matter systems. At the quantum level, this Q-ball

is a compact object formed by magnons – quanta of the

corresponding Ψ-field. At low temperatures the

can be formed only in a trap, similar to that in atomic gases

and the Q-balls are either formed

own trap.

Magnon BEC in solid antiferromagnetsThe magnon BEC in terms of coherent spin

has been discovered in a monocrystals of CsMnF

MnCO3. The experiments demonstrated the formation

magnon BEC as by CW NMR technics

experiments. The last one was performed b

technique. In this method the BEC is for

RF, while the single BEC state is created.

induction decay signal without beats

of the RF pulse. The details of experiments with CsMnF3

and MnCO3 one can find in Ref.

this signal strongly depends on the quality of the crystal.

The signal is 10 times longer in

quality. Definitely, the quality of the

role for observation of a BEC in solid antiferromagnets.

will present the last results of these experiments, where we

have observed the BEC signal with duration significantly

longer then the echo signals. It means that the BEC switches

of even the homogeneous broadening of the magnetic

system.

Acknowledgements The work is performed according to the Russian

Government Program of Competitive Growth of Kazan

Federal University.

References [1] A S Borovik-Romanov, Yu M Bunkov, V V Dmitriev

and Yu M Mukharskiy JETP Lett.

[2] Yu. M. Bunkov, G. E. Volovikmagnon BEC” Chapter IV of the book "Novel Superfluids", eds. K. H. Bennemann and J. B. Ketterson, Oxford University press, (2013)

[3] S. Autti, Yu. M. Bunkov, V. B. Eltsov, et al.Lett. 108, 145303 (2012).

[4] Yu. M. Bunkov, E. M. Alakshin, R. R. Gazizulin, Phys. Rev. Lett. 108, 177002 (2012).

Spin superfluidity and Bose-Einstein condensation of magnons

, M. Tagirov2

MCBT, Institut Neel, Grenoble, France

[email protected]

Kazan Federal University, Kazan, Russia

At low temperatures the condensate

formed only in a trap, similar to that in atomic gases,

balls are either formed in these traps or dig their

Magnon BEC in solid antiferromagnets The magnon BEC in terms of coherent spin precession

has been discovered in a monocrystals of CsMnF3 and

The experiments demonstrated the formation of

n BEC as by CW NMR technics so by pulsed NMR

. The last one was performed by a new

BEC is formed by a very long

BEC state is created. One can see a nice

signal without beats after the switching off

he details of experiments with CsMnF3

and MnCO3 one can find in Ref. [4]. Indeed, the length of

this signal strongly depends on the quality of the crystal.

signal is 10 times longer in a new sample of better

Definitely, the quality of the sample plays a crucial

role for observation of a BEC in solid antiferromagnets. We

last results of these experiments, where we

have observed the BEC signal with duration significantly

longer then the echo signals. It means that the BEC switches

of even the homogeneous broadening of the magnetic

med according to the Russian

Government Program of Competitive Growth of Kazan

Romanov, Yu M Bunkov, V V Dmitriev JETP Lett. 40, 1033, (1984).

G. E. Volovik “Spin superfluidity and Chapter IV of the book "Novel

Superfluids", eds. K. H. Bennemann and J. B. d University press, (2013)

S. Autti, Yu. M. Bunkov, V. B. Eltsov, et al. Phys. Rev.

Yu. M. Bunkov, E. M. Alakshin, R. R. Gazizulin, et al. , 177002 (2012).

Einstein condensation of magnons

Introduction Spin-spin coupling constants (SSCC)

parameters for structure determination nowadays

direct measurement of these parameters is

cases due to peaks overlapping, short relaxation

second order effects (see [1-2]). Theoretical description for

SSCC needs also to be developed in practical aspects. We

showed recently [3], that dynamic behavior of

important molecular systems can be described in terms of

vibrations with large amplitude. Accurate structure studies

of saturated four- and five-membered cycles

specific problem of quantitative description of

processes with very low barriers in them

application of few new effective techniques for extraction

information on the dynamic structure [3, 4] via the high

precision analysis of NMR multiplets and theoretical

description of the NMR parameters.

Methods We developed a practical method for evaluation of the

parameters of conformational dynamics

vibrations with large amplitude. The method based on: (

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

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 calcula

FP DFT technique [5]. 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

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

Novel high resolution NMR techniques for elucidamolecular solution

Vyacheslav A. ChertkovSergey S. Nechausov

1Department of Chemistry2State Research Institute of Chemistry and Technology of Or

Entuziastov, Moscow,3Faculty of Materials Science,

E-mail: [email protected].


are the key NMR

nowadays. However,

is difficult in many

relaxation times and/or

Theoretical description for

C needs also to be developed in practical aspects. We

ynamic behavior of many

can be described in terms of

vibrations with large amplitude. Accurate structure studies

ed cycles imply solving

problem of quantitative description of dynamic

in them. Here we present

effective techniques for extraction

information on the dynamic structure [3, 4] via the high

ecision analysis of NMR multiplets and theoretical

We developed a practical method for evaluation of the

parameters of conformational dynamics in terms of

The method based on: (i)

the results of complete analysis of high resolution NMR

) ab’initio calculations of a reaction path and

surfaces of potential energy and spin-spin coupling

) a numerical solution of corresponding

ment for the parameters of

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

spin couplings.

As a starting point, the undistorted potential energy

surface (PES) of inner rotation for the compounds studied

ilt by applying the scanning technique to skeletal

. This allows us to get a trial “reaction

path” for the pseudorotation process. Conformational

spin coupling constants (SSCC) for

ath were calculated using

H NMR spectra were recorded for a

600” spectrometer at

room temperature, and were treated using total lineshape

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

ery 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, 6], which solves numericall

vibration problem and models the dynamic averaging using

the technique of convolution of the spin

surfaces using the whole set of vibration energies and

eigenvectors (normally, 200 lowest ones).

criterion used in REVIBR program allows to get calculated

SSCC for given temperature. Nonlinear optimization

estimated parameters for the “true” pseudorotation PES

(modeling difference of ground states of main conformers

∆E and heights for the conformational barriers

get best fit of experimental and calculated SSCC values.

Results Advantages of the technique developed demonstrated on

a series of monosubstituted cyclobutanes, trans

dihalocyclopentanes, tetrahydrofuran

thiophene, tetrahydrothiophene-

and ribonucleosides. The data obtained shows, that

pseudorotation process in every

system under study is carrying out by the mechanism w

high amplitude of vibration. Major conformations of

tetrahydrofuran and terahydrothiophene are twists 5T4, for pyrrolidine – envelope Е

for terahydrothiophene-1-oxyde

axial oxygen and for proline

СООН-group. Method used also for characterization of

internal rotation in acyclic systems: styrene, substituted

and trans-azobenzenes, cinnamic aldehyde as well as in

natural endogenic hormones noradrenaline and adrenaline.

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

Chem. Bull., 51, 1222-1230 (2002)[2] S.V. Zubkov, V.A. Chertkov

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

Chertkov – Chem. Heterocycl. Comp.

(2008). [4] J.W. Blanchard, M.P. Ledbetter, T. Theis,

Budker, D. Budker, A. Pines, 3607-3612 (2013).

[5] W. Deng, J.R. Cheeseman, M.J. Frisch, Theory and Comput., 2, 1028

[6] A.V. Chertkov, A.K. Shestakova, V.A. Chertkov, Chem. Heterocycl. Comp., 48

Novel high resolution NMR techniques for elucidamolecular solution-state structure and dynamics

Chertkov1, Dmitriy A. Cheshkov1,2, Tatiana Nechausov1, Kirill F. Sheberstov1,3, Alla K. Shestakova

of Chemistry, Moscow State University, 1 Leninskie Gory, Moscow, 119992, Russia

State Research Institute of Chemistry and Technology of Organoelement Compounds, 38 Shosse

Moscow, 111123, Russia

Faculty of Materials Science, Moscow State University, 1 Leninskie Gory, Moscow, 119992, Russia

mail: [email protected]


, 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

program allows to get calculated

rature. Nonlinear optimization of the

estimated parameters for the “true” pseudorotation PES

(modeling difference of ground states of main conformers

or the conformational barriers ∆E≠) used to

get best fit of experimental and calculated SSCC values.

Advantages of the technique developed demonstrated on

monosubstituted cyclobutanes, trans-1,2-

ahydrofuran [3, 6], tetrahydro-

-1-oxide, pyrrolidine, proline

The data obtained shows, that the

in every four- and five-membered

is carrying out by the mechanism with

vibration. Major conformations of

tetrahydrofuran and terahydrothiophene are twists 4T5 and

Е1 with equatorial NH-bond,

oxyde – envelopes Е3 and with

axial oxygen and for proline – envelope Е5 with axial

Method used also for characterization of

internal rotation in acyclic systems: styrene, substituted cis-

azobenzenes, cinnamic aldehyde as well as in

hormones noradrenaline and adrenaline.

S.V. Zubkov, S.S. Golotvin, V.A. Chertkov. – Russ.

1230 (2002). A. Chertkov – IJMS, 4, 107-118

A.V. Chertkov, O.I. Pokrovsky, A.K. Shestakova, V.А. Heterocycl. Comp., 44, 782-784

Ledbetter, T. Theis, M.C. Pines, J. Am. Chem. Soc., 135,

W. Deng, J.R. Cheeseman, M.J. Frisch, J. Chem.

1028-37 (2006). A.V. Chertkov, A.K. Shestakova, V.A. Chertkov,

48, 412 – 421 (2012).

Novel high resolution NMR techniques for elucidation of

A. Ganina1, Shestakova2

Moscow State University, 1 Leninskie Gory, Moscow, 119992, Russia

ganoelement Compounds, 38 Shosse

Moscow State University, 1 Leninskie Gory, Moscow, 119992, Russia


Static and MAS 13C NMR techniques as well as

lattice relaxation are used to investigate the interaction of

CO and CO2 as well as water molecules with the host

structure of the MOFs Cu3(btc)2 and Cu

chemical shift anisotropy and isotropic chemical shift were

studied over a wide temperature range from 10 K to 353 K.

Above 30 K an increasing fraction of mobile carbon

monoxide is detected (isotropic line for CO) [1].

To investigate the local motion of the adsorbed molecules

in more detail, 13C nuclear spin-lattice relaxation of

and 13CO2 molecules adsorbed in the MOFs

over a wide range of temperature and at different resonance

frequencies. In all cases a single-exponential relaxation

function is observed and the 13C spin-lattice relaxation times

(T1) reveal minima in the temperature rage of our

measurements. In comparison to the results from the line

shape analysis, this suitable experimental situation allows a

more detailed analysis of local motion and the exchange

dynamics. The conclusions about the thermal motion of the

NMR high resolution spectroscopy and spinSmall Molecules

Dieter Michel, Farhana

Institute of Experimental Physics II, University of Leipzig, Linnéstr.

E-mail: [email protected]

– 11, 2014 – 12 –

C NMR techniques as well as 13C spin-

te the interaction of

as well as water molecules with the host

and Cu2.97Zn0.03(btc)2. 13C

chemical shift anisotropy and isotropic chemical shift were

studied over a wide temperature range from 10 K to 353 K.

e 30 K an increasing fraction of mobile carbon

monoxide is detected (isotropic line for CO) [1].

To investigate the local motion of the adsorbed molecules

lattice relaxation of 13CO

molecules adsorbed in the MOFs is investigated

over a wide range of temperature and at different resonance

exponential relaxation

lattice relaxation times

) reveal minima in the temperature rage of our

ents. In comparison to the results from the line

shape analysis, this suitable experimental situation allows a

more detailed analysis of local motion and the exchange

dynamics. The conclusions about the thermal motion of the

adsorbed molecules are also com

published NMR self-diffusion studies on these systems. The

results will also be discussed in relation to the structure of

the MOFs [2]. 1H MAS NMR measurements allow us to derive subtle

information about the specific interaction of wat

molecules with the Cu metal sites in the MOFs and the

intracrystalline and intercrystalline exchange dynamics [3].

References [1] F. Gul-E-Noor, M. Mendt, D. Michel, A. Pöppl, H.

Krautscheid, J. Haase, M. Bertmer,Small Molecules on Cu3(btc)as Studied by Solid-State NMR, in press.

[2] F. Gul-E-Noor, D. Michel, H. Kautscheid, J. Haase, M. Bertmer, Investigation of the Spinof 13CO and 13CO2 Adsorbed in the MOFs Cuand Cu3-xZnx(btc)2, in press.

[3] F. Gul-E-Noor, D. Michel, H. Krautscheid, J. Haase, M. Bertmer. Time Dependent Water Uptake in Cu3(btc)2 MOF, in press

NMR high resolution spectroscopy and spin-lattice relaxation of Molecules adsorbed in metal-organic frameworks (MOFS)

Farhana Gul-E-Noor, Jürgen Haase, Marko Bertmer

Institute of Experimental Physics II, University of Leipzig, Linnéstr. 5, D-


adsorbed molecules are also compared with recently

diffusion studies on these systems. The

results will also be discussed in relation to the structure of

H MAS NMR measurements allow us to derive subtle

information about the specific interaction of water

molecules with the Cu metal sites in the MOFs and the

intracrystalline and intercrystalline exchange dynamics [3].

Noor, M. Mendt, D. Michel, A. Pöppl, H. Krautscheid, J. Haase, M. Bertmer, Adsorption of

(btc)2 and Cu3-xZnx(btc)2 MOF State NMR, in press.

Noor, D. Michel, H. Kautscheid, J. Haase, M. vestigation of the Spin-Lattice Relaxation

Adsorbed in the MOFs Cu3(btc)2 , in press.

Noor, D. Michel, H. Krautscheid, J. Haase, Time Dependent Water Uptake in

lattice relaxation of organic frameworks (MOFS)

Bertmer

-04103 Leipzig, Germany

The invention of multidimensional magnetic resonance

(MR) experiments 40 years ago led to success of the modern

MRI and NMR spectroscopy in medicine, chemistry,

molecular structural biology, and other fields. The approach,

however, has an important weakness: the detailed site

specific information and ultimate resolution obtained in two

and higher dimensional experiments are contingent on the

lengthy data collection required for systematic uniform

sampling of the large multidimensional space spanned by

the indirectly detected spectral dimensions [

of measured data points increases polynomially with the

spectrometer field and the desired spectral re

exponentially with the number of dimensions. The problem

of lengthy sampling compromises or even prohibits many

applications of multidimensional spectroscopy.

Fortunately, the advent of “fast” NMR spectroscopy

offers a number of solutions. The time

systematic sampling of the signal on the entire multi

dimensional Nyquist grid describing the indirect dimensions

is replaced by acquiring FIDs for only a relatively small

number of grid points, while preserving all essential

information that would be present in the full data set. Two

distinct approaches can be traced back to the early years of

Modern methods of NMR data collections and spectra processing

Vladislav Yu. Orekhov

Swedish NMR Centre



The invention of multidimensional magnetic resonance

ccess of the modern

MRI and NMR spectroscopy in medicine, chemistry,

molecular structural biology, and other fields. The approach,

however, has an important weakness: the detailed site-

specific information and ultimate resolution obtained in two

dimensional experiments are contingent on the

lengthy data collection required for systematic uniform

sampling of the large multidimensional space spanned by

l dimensions [1]. The number

of measured data points increases polynomially with the

spectrometer field and the desired spectral resolution, and

exponentially with the number of dimensions. The problem

of lengthy sampling compromises or even prohibits many

applications of multidimensional spectroscopy.

Fortunately, the advent of “fast” NMR spectroscopy

he time-consuming

systematic sampling of the signal on the entire multi-

mensional Nyquist grid describing the indirect dimensions

is replaced by acquiring FIDs for only a relatively small

number of grid points, while preserving all essential

that would be present in the full data set. Two

distinct approaches can be traced back to the early years of

multidimensional NMR spectroscopy. The former is based

on the spectral projection theorem and Fourier Transform

[2], and applied for example in the

experiment 30 years ago [3]. In the second approach, the

positions of the measured points are not constrain

often selected randomly [4]. Both approaches require novel

analysis tools and non-standard processing methods, often

resulting in significantly increased calcula

making them only recently a practical approach.

References [1] M. Billeter and V. Y. Orekhov, in

Approaches in Higher Dimensional NMR

Billeter and V. Y. Orekhov, Springer, Heidelberg Dordrecht London New York, 2012, vol. xiv.

[2] Bracewell RN (1956) Strip integration in radio astronomy. Aust J Phys 9: 198

[3] Bodenhausen G, Ernst RR (1981) The accordion experiment, a simple approach to 3spectroscopy. J Magn Reson

[4] Barna JCJ, Laue ED, Mayger MR, Skilling J, Worrall SJP (1987) Exponential sampling, an alternative method for sampling in twoexperiments. J Magn Reson


Orekhov

Swedish NMR Centre, University of Gothenburg, Sweden

nmr.gu.se


multidimensional NMR spectroscopy. The former is based

theorem and Fourier Transform

, and applied for example in the ACCORDION

. In the second approach, the

positions of the measured points are not constrained and

. Both approaches require novel

standard processing methods, often

ignificantly increased calculations times, and

making them only recently a practical approach.

M. Billeter and V. Y. Orekhov, in Novel Sampling

in Higher Dimensional NMR, eds. M. Billeter and V. Y. Orekhov, Springer, Heidelberg

cht London New York, 2012, vol. 316, pp. ix-

Bracewell RN (1956) Strip integration in radio 198–217

Bodenhausen G, Ernst RR (1981) The accordion experiment, a simple approach to 3-dimen-sional NMR

J Magn Reson 45 (2):367–373 Barna JCJ, Laue ED, Mayger MR, Skilling J, Worrall SJP (1987) Exponential sampling, an alternative method for sampling in two-dimensional NMR

J Magn Reson 73 (1): 69–77



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 separation,

heterogeneous catalysis, etc. Classical 1H NMR imaging is

the best technique for the visualisation of these processes,

but it requires that each experiment be performed several

times under identical conditions, and each time with only

one not completely deuteriated gas. For this reason we have

devised a new NMR technique where the magnet is

displaced vertically, step by step, relative to the bed during

the adsorption 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; the variation of

the concentration of gas absorbed at the level of each layer

is obtained as a function of time.

Co-diffusion of gases in a microporous solid bed: classimaging or slice selection procedure

M. Petryk, S. Leclerc

Universite Pierre et Marie Curie Laboratoire de Physique Quantique, Paris, France


– 11, 2014 – 14 –

diffusion of gases through a

orous 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

alisation of these processes,

but it requires that each experiment be performed several

times under identical conditions, and each time with only

one not completely deuteriated gas. For this reason we have

devised a new NMR technique where the magnet is

splaced vertically, step by step, relative to the bed during

the adsorption of the gas; the detector is a very thin coil. The

very thin layers of solid, and

the region probed is limited to each layer; the variation of

centration of gas absorbed at the level of each layer

This technique allows the determination of:

• the gas diffusion coefficient profiles

against time t at each level of the zeolite bed;

• the intercrystallite concentration profiles,

versus time t for different values of the position

• the concentration profiles,

crystallites located at different positions

in the crystallites, for different time

In contrast to classical NMR imaging, this technique

gives a signal characteristic of the adsorbed gas. It can

therefore provide directly, at every moment and at every

level of the crystallite bed, the distribution of several gases

competing in diffusion and adsorption

we show the co-diffusion of benzene and hexane gases

through a bed of ZSM5 zeolite.

diffusion of gases in a microporous solid bed: classimaging or slice selection procedure

Leclerc, D. Canet, J. Fraissard



This technique allows the determination of:

the gas diffusion coefficient profiles Dintra and Dinter

at each level of the zeolite bed;

llite concentration profiles, C (z,t),

for different values of the position z in the bed;

the concentration profiles, Q(t,X,z), in zeolite

crystallites located at different positions z in the bed, and X

in the crystallites, for different times t.

In contrast to classical NMR imaging, this technique

gives a signal characteristic of the adsorbed gas. It can

therefore provide directly, at every moment and at every

level of the crystallite bed, the distribution of several gases

ion and adsorption . As a first example

diffusion of benzene and hexane gases

diffusion of gases in a microporous solid bed: classical NMR


Introduction On the base of new MRI methods,

Research Magnetic Tomography and Spectroscopy (CMTS

MSU) [1-6], some pre-clinic investigations were carried out

of small laboratory animals by 7-T biospectroscopy scanner

Bruker BioSpec 70/30 URS. The aim of that was to study

possibilities of medicine targeted delivery to oncological

and ischemia cerebral affection sites [4] and to determine

lesion power according to NMR spectrum without surgical

intervention in vivo [5, 6].

Local NMR spectroscopy Tumor experiments

First of these problems was solved with help of

containers provided with specific biomarker oriented to

tumor cells of C6 glioma and Gd ions as a contrast material.

Inside the container was developed by academician

Vladimir Chekhonin preparation suppressing C6 glioma

cells. Effectivity of preparation therapy action was

established previously by in vitro experiments. Then

next successful MRI investigations on the rats

confirmed positive medical prognosis.

Ischemia therapy by stromal cellsThe other experiment was dedicated to therapy

ischemia brain lesions with help of mesenchymal stromal

cells by academician Veronika Skvortsova’s

Ischemia formation was created by middle brain artery

occlusion. Marked (for visualization) by paramagnetic Fe

ions stromal cells were injected to the healthy brain

hemisphere. After that, the stromal cells percolated to

neighbor hemisphere and surrounded ischemia region.

Whole month MRI observation for this animal shown some

times reducing of ischemia lesion, restoration of behavior

functions and brain activity.

Multi nuclear local NMR spectroscopyInteresting results were found by combined application

MRI and NMR spectroscopy options. The last option can be

realized in the 7-T BioSpec scanner not only on protons but

on the number of heavy nuclei - 13C, 19F and

their using, interesting tissue voxel is localized

Local NMR spectroscopy in MRI experiments with small laboratory animals

Yury A. Pirogov

Faculty of Physics,



On the base of new MRI methods, developed in the

h Magnetic Tomography and Spectroscopy (CMTS

clinic investigations were carried out

T biospectroscopy scanner

Bruker BioSpec 70/30 URS. The aim of that was to study

livery to oncological

cerebral affection sites [4] and to determine

lesion power according to NMR spectrum without surgical

First of these problems was solved with help of liposome

specific biomarker oriented to

tumor cells of C6 glioma and Gd ions as a contrast material.

Inside the container was developed by academician

Vladimir Chekhonin preparation suppressing C6 glioma

ration therapy action was

experiments. Then the

next successful MRI investigations on the rats in vivo

Ischemia therapy by stromal cells The other experiment was dedicated to therapy of

ischemia brain lesions with help of mesenchymal stromal

cells by academician Veronika Skvortsova’s method [6].

Ischemia formation was created by middle brain artery

occlusion. Marked (for visualization) by paramagnetic Fe

ed to the healthy brain

hemisphere. After that, the stromal cells percolated to

neighbor hemisphere and surrounded ischemia region.

Whole month MRI observation for this animal shown some

times reducing of ischemia lesion, restoration of behavior

Multi nuclear local NMR spectroscopy Interesting results were found by combined application

MRI and NMR spectroscopy options. The last option can be

T BioSpec scanner not only on protons but

F and 31P. Thanks to

sting tissue voxel is localized in the

volume with 2.5-3 mm transverse size and realize

measurements of NMR spectra on protons and heavy nuclei

in this site. Positions of spectral lines

(chemical shift) correspond to characteri

tissue. Their distribution reflects the tissue ischemia power,

tumor type, allows to measure in real time

metabolite portrait and internal organs temperature [5

This approach of join MRI and NMR spectroscopy

application (that is local NMR spectroscopy) presents

noninvasive analogues of biopsy, metabolomics and intra

tissue thermometry.

Acknowledgements This work is supported by the Russian Based Research

Foundation (grant #11-04-92

President’s grant of leading scientific school financing

#4593-2008.

References [1] N. V. Anisimov, S. S. Batova, Yu. A. Pirogov

Magnetic resonance imaging: contrast control and cross-disciplinary application / Edit. Yu. A. Pirogov. Moscow: MAKS Press, 2013, 243 p.

[2] N. V. Anisimov, Yu. A. Pirogov, L. V. Gubskiy, V. V. Gladun. Contrast control and information technologies in magnetic resonance imaging / Edit. Yu. A. Pirogov. – Moscow: Moscow State Univ., 2005, 141 p.

[3] A. Yu. Yudina, A. A. Bogdanov (Jr), Yu. A. Pirogov. Magnetic resonance imaging in study of angiogenesis and its molecular markers / Edit. Yu. A. Pirogov. Moscow: Moscow State Univ., 2008, 143 p.

[4] G. M. Yusubalieva, V. P. Baklaushev,M. V. Gulyaev, Yu. A. Pirogov,Bull. Exp. Biol. Med., 153 (1)

[5] M. V. Gulyaev, L. V. Gubskiy, E. A. Cherkashova, N.V. Anisimov, Jaw Fushan, Yu. A. Pirogov. Radioelectronics, No. jre.cplire.ru/jre/jan12/9/text.pdf.

[6] M. V. Gulyaev, R. T. Tairova, L. V. Gubskiy, Yu. A. Pirogov, V. I. Skvortsova. –Congress “Medical Physics 72 (2010).

[7] D. Silachev, I. Pevzner, L. Zorova, E. Plotnikov, M. Gulyaev, Yu. Pirogov, N. Isaev, V.D. Zorov. – The FEBS Journal

Local NMR spectroscopy in MRI experiments with small laboratory animals

Pirogov

, Lomonosov Moscow State University, Russia

gmail.com


3 mm transverse size and realize

measurements of NMR spectra on protons and heavy nuclei

Positions of spectral lines in the spectrum

hemical shift) correspond to characteristic metabolites of

distribution reflects the tissue ischemia power,

tumor type, allows to measure in real time in vivo local

metabolite portrait and internal organs temperature [5-7].

oin MRI and NMR spectroscopy

application (that is local NMR spectroscopy) presents

noninvasive analogues of biopsy, metabolomics and intra-

This work is supported by the Russian Based Research

92008-HHC) and Russian

President’s grant of leading scientific school financing

N. V. Anisimov, S. S. Batova, Yu. A. Pirogov Magnetic resonance imaging: contrast control and

disciplinary application / Edit. Yu. A. Pirogov. – ow: MAKS Press, 2013, 243 p.

N. V. Anisimov, Yu. A. Pirogov, L. V. Gubskiy, V. V. Gladun. Contrast control and information technologies in magnetic resonance imaging / Edit. Yu. A. Pirogov.

Moscow: Moscow State Univ., 2005, 141 p. gdanov (Jr), Yu. A. Pirogov.

Magnetic resonance imaging in study of angiogenesis and its molecular markers / Edit. Yu. A. Pirogov. – Moscow: Moscow State Univ., 2008, 143 p.

Yusubalieva, V. P. Baklaushev, O. I. Gurina, M. V. Gulyaev, Yu. A. Pirogov, V. P. Chekhonin. –

(1), 163-169 (2012). M. V. Gulyaev, L. V. Gubskiy, E. A. Cherkashova, N. V. Anisimov, Jaw Fushan, Yu. A. Pirogov. - Journal of

1 (2013). URL http://

jre.cplire.ru/jre/jan12/9/text.pdf. . V. Gulyaev, R. T. Tairova, L. V. Gubskiy, Yu. A.

– Docl. of the 3rd EuroAsian Congress “Medical Physics – 2010”. – Moscow: MSU,

D. Silachev, I. Pevzner, L. Zorova, E. Plotnikov, M. Gulyaev, Yu. Pirogov, N. Isaev, V. Skulachev,

The FEBS Journal, 279, 364 (2012).

Local NMR spectroscopy in MRI experiments with small


Current development of science using highly sensitive

methods of the studies has resulted in division of theoretical

substantiations into a number of directions without account

of generalizing regularities of the physical processes

changing the states of the structures under the effect of

wide-ranging temperature, magnetic field a

pressure [1].

For instance, when analyzing a separated area of research

in a wide spectrum of magnetic fields H at a fixed

temperature, a statement has been made along with quantum

mechanical conception that the linear part of the presented

regularities is a result of magnetic field structure disturbance

due to magneto-elastic stresses, because even diamagnetic

structures demonstrate strictional properties. As a

consequence, a linear law is present in high fields at a fixed

temperature, together with priority of magneto

square law of evolution, competition of thermal and

magnetoelasticity.

Wide-area high-pressure testing is a determining method

of the impact on the state of the atoms within a structure

through the energy of volume elasticity that fixes a physical

process by experimental methods.

A definite mechanism of the distribution of thermal

elastic stresses takes place in physical processes of exchange

transition of the electrons of inner atom shells at the stricture

sites with participating semifree valence electrons.

A question emerges, if the process of the effect of

parameters can be analyzed, being based on the structure

state determined by the 0-temperatures, magnetic fields and

pressures? Thermal elastic expansion wea

the state from the 0-temperatures, the minimum volume,

bond energy. The process of heat supply is a weakening of

the bond of semifree valence electrons where the

conductivity is reduced and the volume and the resistance

are increased.

0-pressures at a fixed temperature evoke volume

reduction, increase in the stress of the bond energy, increase

in density. The jumps of the volume are phase transitions,

structural transformations.

0-magnetic fields provoke the magnetic uncompensated

state through the temperature and magnetoelastic stresses in

the structure that is fixed by magnetostriction. Structure

deformation and reconstruction modifies uncompensated

state of spins. The introduced stresses are additional sources

of the changes of volume, density, form of the structure,

“cooling effect” [2].

Laws of volume elasticity in physical processes of formation of phase states and properties

Peter I. Polyakov

Institute For Physics of Mining Processes, Donetsk, Ukraine


– 11, 2014 – 16 –

Current development of science using highly sensitive

has resulted in division of theoretical

substantiations into a number of directions without account

of generalizing regularities of the physical processes

changing the states of the structures under the effect of

ranging temperature, magnetic field and hydrostatic

For instance, when analyzing a separated area of research

in a wide spectrum of magnetic fields H at a fixed

temperature, a statement has been made along with quantum

mechanical conception that the linear part of the presented

regularities is a result of magnetic field structure disturbance

elastic stresses, because even diamagnetic

structures demonstrate strictional properties. As a

consequence, a linear law is present in high fields at a fixed

ther with priority of magneto-elasticity,

square law of evolution, competition of thermal and

pressure testing is a determining method

of the impact on the state of the atoms within a structure

e elasticity that fixes a physical

A definite mechanism of the distribution of thermal

elastic stresses takes place in physical processes of exchange

transition of the electrons of inner atom shells at the stricture

with participating semifree valence electrons.

A question emerges, if the process of the effect of

parameters can be analyzed, being based on the structure

temperatures, magnetic fields and

pressures? Thermal elastic expansion weakens the stress of

temperatures, the minimum volume,

bond energy. The process of heat supply is a weakening of

the bond of semifree valence electrons where the

conductivity is reduced and the volume and the resistance

pressures at a fixed temperature evoke volume

reduction, increase in the stress of the bond energy, increase

in density. The jumps of the volume are phase transitions,

magnetic fields provoke the magnetic uncompensated

through the temperature and magnetoelastic stresses in

the structure that is fixed by magnetostriction. Structure

deformation and reconstruction modifies uncompensated

state of spins. The introduced stresses are additional sources

, density, form of the structure,

The studies of simple and complex structures in physical

processes under three thermodynamical parameters are the

most demonstrative, so they expand the information basis

and allow a generalizing analysis.

The analysis of the experimental data has shown that the

impact of three parameters is revealed as linear changes in

resistive, magnetic properties and the dynamics of the

evolution of phase transition regularities.

We should take into account tha

parameters results in the volume change, so the causing role

of the volume elasticity is a determining one in cross

(thermal, magnetic, baric elasticity).

We shall estimate the energy of Coulomb interactions as

1÷10 eV, the influence of the crystal field as 0.1÷1 eV, spin

orbit relationship as 10-1÷10-2 eV, spin

as 10-4 eV, electron-nuclear bond as 10

to our estimations, the energy of elastic stresses with taking

into account the coefficient of compressibility is 1÷10 eV.

We should take into account that quantum mechanical forces

forming the magnetism are of short range in fact, so deep

understanding of the regularity if interaction is necessary for

the estimation of this process. The elas

immediate energy of long range. These are elastic stresses in

the structure that form the linearity of the magnetization

regardless of important details of microscopic interactions.

By definition, atoms and molecules have small magnetic

moments of non-compensation. The structure is the totality

of molecules and atoms brought into the sites of the

structure (several atoms and molecules) and bound in the

lattice by the compatibility of valent and free electrons.

These are the approaches of th

define the causal role of the laws of bulk elasticity in the

formation of the magnetism as well as their leading role in

the first and second order structural phase transitions.

A reversible deformation change of the state of a so

under the effect of outer parameters is a consequence of the

fundamental principles of thermodynamics and a

prerequisite of the hypothesis of the causing role of volume

elasticity in formation of the changes of properties and

phase states.

References [1] P. I. Polyakov, T. A. Ryumshina, Magnetism andlows

of bulk elasticity (Transworld research network, Kerala, 2009).

[2] P. I. Polyakov. arXiv: 1301.3327

Laws of volume elasticity in physical processes of formation of phase states and properties

Polyakov

Institute For Physics of Mining Processes, Donetsk, Ukraine


The studies of simple and complex structures in physical

processes under three thermodynamical parameters are the

most demonstrative, so they expand the information basis

lysis.

The analysis of the experimental data has shown that the

impact of three parameters is revealed as linear changes in

resistive, magnetic properties and the dynamics of the

evolution of phase transition regularities.

We should take into account that the effect of all

parameters results in the volume change, so the causing role

of the volume elasticity is a determining one in cross-effects

(thermal, magnetic, baric elasticity).

We shall estimate the energy of Coulomb interactions as

luence of the crystal field as 0.1÷1 eV, spin-

eV, spin-spin (magnetic) bond

nuclear bond as 10-4÷10-5eV. According

to our estimations, the energy of elastic stresses with taking

ent of compressibility is 1÷10 eV.

We should take into account that quantum mechanical forces

forming the magnetism are of short range in fact, so deep

understanding of the regularity if interaction is necessary for

the estimation of this process. The elastic energy is an

immediate energy of long range. These are elastic stresses in

the structure that form the linearity of the magnetization

regardless of important details of microscopic interactions.

By definition, atoms and molecules have small magnetic

compensation. The structure is the totality

of molecules and atoms brought into the sites of the

structure (several atoms and molecules) and bound in the

lattice by the compatibility of valent and free electrons.

These are the approaches of the analysis that permit to

define the causal role of the laws of bulk elasticity in the

formation of the magnetism as well as their leading role in

the first and second order structural phase transitions.

A reversible deformation change of the state of a solid

under the effect of outer parameters is a consequence of the

fundamental principles of thermodynamics and a

prerequisite of the hypothesis of the causing role of volume

elasticity in formation of the changes of properties and

Ryumshina, Magnetism andlows of bulk elasticity (Transworld research network,

1301.3327.

Laws of volume elasticity in physical processes of formation of

Introduction The self-diffusion measurement especially the techniques

using the pulsed field gradient NMR following by Fourier transforms is the he unique methods for ddynamic studies in systems with the fast ionic and moleculartransport. Water transport in biological systems is important for cellular physiological reactions, osmotic pressure of tissue and drying process of biological materials. Fordiffusional 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 10nmto its non-invasive character.

In order to interpret the experimental data correctly, the model investigations are necessary. This presentation is mainly devoted to investigations of ionic and water transport in biological cells (chlorella, yeast and erythrocytes). 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.

Synthetic membranes as model systemsSulfo-, carboxyl-, aminogroups containing ion exchange

membranes and pore track etched meinvestigated as model systems. 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 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.

Water exchange in biological cells studied by ptechniques

Vitaly I. Volkov

Institute of Problems of Chemical Physics RAS

E-mail: [email protected] Scientific Research Institute of Food Biotechnology2Russian State Agrarian University


diffusion measurement especially the techniques using the pulsed field gradient NMR following by Fourier

for direct structural and dynamic studies in systems with the fast ionic and molecular

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

NMR) spectroscopy has become the method of choice due to its remarkable sensitivity to molecular displacements in the range of 10nm–100 mm and

In order to interpret the experimental data correctly, the model investigations are necessary. This presentation is mainly devoted to investigations of ionic and water transport in biological cells (chlorella, yeast and erythrocytes). The

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,

Russia and at Laboratory ood and Biomaterial Science and Engineering,

Graduated School of Life Science and Biotechnology, Korea

Synthetic membranes as model systems , aminogroups containing ion exchange

membranes and pore track etched membranes were investigated as model systems. The hydration of fixed

earth ions were studied in details in perfluorinated Nafion membranes. The mechanism

counter ion or water molecule interactions erstood from high resolution hetero nuclear NMR

data. Microscopic ionic and water molecule mobilities were diffusion coefficients

of protonic molecules and lithium and fluorine counter ions re 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

rge 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,

behaviour in proteins and gels have been understood. It was shown that hydrogen bond is very important for proton and water molecules

Biological cell membranesWater 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 [2].

The typical spin echo PFG NMR attenuation obtained at different diffusion times td Saccharomyces cerevisiae is shown as example in the figure.

Scaling approach and two compartment exchange model were applied to calculate cell sizes and permeabilities. The values of permeability calculated by these two ways are very close to each other. The correctnessinterpretations was also demonstrated by gocell sizes obtained from PFG NMR and electron microscopic data. The permeabilities are 3.10about 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.

Acknowledgements The investigation was supported by Russian Basic

Research Foundation grant № 13

References [1] V. I. Volkov, A. A. Marinin

Reviews 82 (3) 248 - 272 (2013)[2] Cho J.H., Hong Y.S., Volkov V.I., Skirda V.D. et. al.

Magnetic Resonance Imaging

Water exchange in biological cells studied by pulsed NMR

Volkov, Irina A. Avilova, Lubov’ V. Rimareva1, Ludmila

of Problems of Chemical Physics RAS, Chernogolovka, Moscow Region,

[email protected]

Russian Scientific Research Institute of Food Biotechnology, Moscow, Russia

ian State Agrarian University-Moscow Timiryazev Agricultural Academy, Moscow, Russia


Biological cell membranes diffusion in cells of chlorella, yeast and red

was investigated. These cells were selected as model systems with different cell membrane permeabilities.

diffusion coefficients of intracellular and extracellular water were measured dependent on diffusion

f restricted diffusion and hindered

The typical spin echo PFG NMR attenuation obtained at

for water in yeast cells is shown as example in the figure.

d two compartment exchange model were applied to calculate cell sizes and permeabilities. The values of permeability calculated by these two ways are very

correctness of these theoretical interpretations was also demonstrated by good agreement of cell sizes obtained from PFG NMR and electron

The permeabilities are 3.10-6, 6.10-6 and m/s for chlorella, yeast and red blood cells, , depending on cell growing conditions and

ating. The average cell sizes are varied from 2 to 4 microns. The water exchange mechanism in

The investigation was supported by Russian Basic 13-03-00698-a

Marinin - Russian Chemical

272 (2013) Cho J.H., Hong Y.S., Volkov V.I., Skirda V.D. et. al. - Magnetic Resonance Imaging 21, 1009-1017 (2003).

ulsed NMR

, Ludmila D. Volkova2

, Chernogolovka, Moscow Region, 142432, Russia

, Moscow, Russia

Moscow Timiryazev Agricultural Academy, Moscow, Russia


Intrinsically disordered proteins (IDPs) are widely

involved in signal transduction. In this role, they bind to

their (structured) targets; in doing so they themselves

acquire a measure of structural order. The salient feature of

the binding mechanism is that it often relies on el

interactions. Initially, the IDP is pulled toward its target by

long-range electrostatic forces, forming what is termed an

electrostatic encounter complex (a transient state where the

IDP is loosely anchored in the vicinity of the binding site)

Starting from this point, it quickly finds the correct

conformation and tightly binds to the target. From this

perspective the encounter complex can be likened to a

folding intermediate on the pathway from a random state

(free IDP) to a fully structured state (bound IDP).

Fig. 1: MD snapshots representing Sos peptide in complex

with (a) wild-type and (b) Y186L/W169F mutant of c

SH3. The latter serves as a model for electrostatic

encounter complex

To obtain insight into the structure/dynamics of

electrostatic encounter complex, we choose to study the

binding of the proline-rich Sos peptide (which serves as a

minimal model for an IDP) to the c-Crk N

original system is altered by introducing two point

mutations into hydrophobic grooves of the SH3 domain,

Y186L and W169F. This abrogates tight binding and shifts

the equilibrium toward the intermediate state (i.e. the

encounter complex, which is held together by electrostatic

interactions between charged residues). The resulting

increase in the population of the encounter complex makes it

amenable to an NMR study using conventional NMR

parameters such as chemical shifts, relaxation rates, and

paramagnetic restraints.

As a first step, the experimental data have been acquired

for the complex of the Sos peptide with the wild

c-Crk N-SH3 domain. At the same time 3 µs MD trajectory

Modeling a system with intrinsic disorder: an NMR/MD study of peptide-protein

Tairan Yuwen1,

1Department of Chemistry, Purdue University, 560 Oval Drive2Current address: Department of Biochemistry, Duke Univers

27710, USA 3Department of Physics, IUPUI, 4Laboratory of Biomolecular NMR, St.

*E-mail: [email protected]

– 11, 2014 – 18 –

proteins (IDPs) are widely

involved in signal transduction. In this role, they bind to

their (structured) targets; in doing so they themselves

acquire a measure of structural order. The salient feature of

the binding mechanism is that it often relies on electrostatic

interactions. Initially, the IDP is pulled toward its target by

range electrostatic forces, forming what is termed an

electrostatic encounter complex (a transient state where the

IDP is loosely anchored in the vicinity of the binding site).

Starting from this point, it quickly finds the correct

conformation and tightly binds to the target. From this

perspective the encounter complex can be likened to a

folding intermediate on the pathway from a random state

state (bound IDP).

MD snapshots representing Sos peptide in complex

type and (b) Y186L/W169F mutant of c-Crk N-

The latter serves as a model for electrostatic

To obtain insight into the structure/dynamics of the

electrostatic encounter complex, we choose to study the

rich Sos peptide (which serves as a

Crk N-SH3 domain. The

original system is altered by introducing two point

rooves of the SH3 domain,

Y186L and W169F. This abrogates tight binding and shifts

the equilibrium toward the intermediate state (i.e. the

encounter complex, which is held together by electrostatic

interactions between charged residues). The resulting

ease in the population of the encounter complex makes it

amenable to an NMR study using conventional NMR

parameters such as chemical shifts, relaxation rates, and

As a first step, the experimental data have been acquired

omplex of the Sos peptide with the wild-type (wt)

3 µs MD trajectory

of Sos:wtSH3 complex has been

the GPU-based computers. The simulations have been

conducted in explicit solvent using Amber 11 ff99SB*

ILDN force field. The comparison of the experimental and

simulated results demonstrated that MD simulations tend to

overestimate the strength of salt

involving four Arg residues from Sos and six Glu/Asp

residues in wtSH3. As it turns out, this problem is endemic

for the modern advanced force fields. To address

we have implemented an empirical correctio

der Waals distance for nitrogen

bridge has been scaled up by 3%. The modified force field

was used to record a new 3.2 µs trajectory of Sos:wtSH3

complex, leading to an excellent agreement with

experimental data. Furthermore, using this approach we

were able to successfully simulate the entire binding process

beginning with Sos randomly placed in the vicinity of

wtSH3 and ending with the bona fide

whose coordinates are within 1.5Å of the crystallog

structure.

Armed with this improved modeling tool, we have

analyzed the experimental data from the complex between

Sos and the double mutant of SH3, which serves as a model

for the electrostatic encounter complex. The binding affinity

of the Sos·dmSH3 complex proved to be relatively low,

200 µM, reflecting the dynamic nature of the peptide

interaction. As a consequence, the NMR sample contains ca.

10% of the free Sos peptide, which has been accounted for

in our analyses. The appropriatel

data were then compared with a series of MD simulations

representing Sos·dmSH3. A number of trajectories

demonstrated excellent agreement with the experimental

results. Although the MD model in this case cannot be

deemed exhaustive, the observed dynamic scenarios are

fully consistent with the experimental data. As anticipated,

Sos hoovers over the surface of the SH3 domain, loosely

anchored via electrostatic interactions (see Fig. 1). These

results demonstrate how the protein system

degree of conformational disorder can be successfully

characterized via a combination of NMR measurements and

MD simulations.

Acknowledgement This work is supported by the NSF MCB award 105814

Modeling a system with intrinsic disorder: an NMR/MD study of protein encounter complex

, Yi Xue1,2, Fangqiang Zhu3 and Nikolai R. Skrynnikov

Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette IN

Current address: Department of Biochemistry, Duke University School of Medicine,

Department of Physics, IUPUI, Indianapolis IN 46202, USA

Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 198504, Russia


complex has been generated with the help of

The simulations have been

conducted in explicit solvent using Amber 11 ff99SB*-

ILDN force field. The comparison of the experimental and

emonstrated that MD simulations tend to

overestimate the strength of salt-bridge interactions

involving four Arg residues from Sos and six Glu/Asp

residues in wtSH3. As it turns out, this problem is endemic

for the modern advanced force fields. To address this issue

we have implemented an empirical correction whereby van

der Waals distance for nitrogen-oxygen pair across the salt

bridge has been scaled up by 3%. The modified force field

was used to record a new 3.2 µs trajectory of Sos:wtSH3

complex, leading to an excellent agreement with

urthermore, using this approach we

were able to successfully simulate the entire binding process

beginning with Sos randomly placed in the vicinity of

bona fide Sos:wtSH3 complex

whose coordinates are within 1.5Å of the crystallographic

Armed with this improved modeling tool, we have

analyzed the experimental data from the complex between

Sos and the double mutant of SH3, which serves as a model

for the electrostatic encounter complex. The binding affinity

H3 complex proved to be relatively low, Kd =

200 µM, reflecting the dynamic nature of the peptide-protein

interaction. As a consequence, the NMR sample contains ca.

10% of the free Sos peptide, which has been accounted for

in our analyses. The appropriately corrected experimental

data were then compared with a series of MD simulations

representing Sos·dmSH3. A number of trajectories

demonstrated excellent agreement with the experimental

results. Although the MD model in this case cannot be

, the observed dynamic scenarios are

fully consistent with the experimental data. As anticipated,

Sos hoovers over the surface of the SH3 domain, loosely

anchored via electrostatic interactions (see Fig. 1). These

results demonstrate how the protein system with substantial

degree of conformational disorder can be successfully

characterized via a combination of NMR measurements and

This work is supported by the NSF MCB award 105814.

Modeling a system with intrinsic disorder: an NMR/MD study of

Skrynnikov1,4*

, West Lafayette IN47907-2084, USA

ity School of Medicine, Durham, NC

Petersburg 198504, Russia

Part II

Oral Reports

Introduction The Central Nervous System (CNS) is a common site of

involvement in patients with AIDS, brain lesions are

detected in up to 90% of patients at autopsy. A variety of

infections may be diagnosed in these patients. The

common infections include HIV encephalopathy,

toxoplasmosis, cryptococcosis, mycobacterial, PML, CMV

and Herpes. Detection and differential diagnosis are

important medical problems today.

Methods At Radiology Department of Mariinsky Hospital, St.

Petersburg, Russia more than 3000 patients with HIV were

diagnosed by MRI in the last 6 years.

MRI before and then after the treatment, in goals of

treatment efficiency assessment.

HIV Encephalopathy HIV encephalopathy is the most common ne

manifestation of HIV infection. The etiologic agent is

Human Immunodeficiency Virus itself. This virus is

neurotropic and causes vacuolation of the white matter, with

areas of demyelination and multinucleated.

is the most common manifestation of HIV encephalopathy

of the brain on MR studies: a diffuse pattern of increased

signal in the deep white matter or multiple small punctate

white matter lesions on T2WIs are the most common

findings.

Toxoplasmosis Toxoplasmosis is the most common opportunistic CNS

infection in AIDS, occurring in about 1/3 of patients with

CNS complications. A necrotizing encephalitis usually

results, with the formation of thin-walled abscesses. The

typical MR appearance of CNS toxoplasmosis is that of

multiple ring-enhancing mass lesions with surrounding

vasogenic edema. The lesions are usually of increased signal

Magnetic Resonance features of HIVinfections of the CNS

A. A. Drozdov,

Saint-Petersburg State University, The Faculty of Medicine

Mariinskaya hosp. Liteyniy, 56

E-mail: a_a_drozdov@mail


The Central Nervous System (CNS) is a common site of

involvement in patients with AIDS, brain lesions are

detected in up to 90% of patients at autopsy. A variety of

infections may be diagnosed in these patients. The most

common infections include HIV encephalopathy,

toxoplasmosis, cryptococcosis, mycobacterial, PML, CMV

and Herpes. Detection and differential diagnosis are

At Radiology Department of Mariinsky Hospital, St.

ersburg, Russia more than 3000 patients with HIV were

Some patients had

MRI before and then after the treatment, in goals of

HIV encephalopathy is the most common neurologic

manifestation of HIV infection. The etiologic agent is

Human Immunodeficiency Virus itself. This virus is

neurotropic and causes vacuolation of the white matter, with

areas of demyelination and multinucleated. Diffuse atrophy

nifestation of HIV encephalopathy

of the brain on MR studies: a diffuse pattern of increased

signal in the deep white matter or multiple small punctate

white matter lesions on T2WIs are the most common

on opportunistic CNS

infection in AIDS, occurring in about 1/3 of patients with

CNS complications. A necrotizing encephalitis usually

walled abscesses. The

typical MR appearance of CNS toxoplasmosis is that of

enhancing mass lesions with surrounding

vasogenic edema. The lesions are usually of increased signal

on precontrast T2WIs. Unlike bacterial abscesses,

toxoplasmosis lesions are not high in signal on DWI.

Cryptococcosis Cryptococcosis is the most common

causing meningitis as the most common presentation.

Imaging studies are usually normal, diagnosis is made by

the CSF analysis.

Progressive multifocal leukoencephalopathyProgressive multifocal leukoencephalopathy (PML) is a

viral opportunistic infection, caused by JC virus.

incidence of PML in AIDS patients is approximately 10%.

The infection causes demyelination and necrosis, primarily

involving white matter. MR reveals focal lesions of

increased signal on TIRM and T2WI and decrease

on T1WIs within the subcortical and deep white matter.

CMV

CMV infection usually does not result in frank tissue

necrosis. MR features are divers or absent. CMV

meningoencephalitis is occasionally imaged as areas of

increased signal on T2WIs in th

matter.

Mycobacterial CNS infectionMycobacterial CNS infection is a relatively rare disease

among AIDS patients. Most of these patients are intravenous

drug abusers with pulmonary tuberculosis. Most patients

present with meningitis. Tuberculomas are present in

approximately 25% of HIV-patients with CNS tuberculosis.

Results

MRI has the highest sensitivity and specificity for detection infectious disease of the Central Nervous System in HIV-infected patients among other imaging metBrain MRI results are essential for effective pharmacological treatment of HIV

Magnetic Resonance features of HIV-associated opportunistic infections of the CNS

V. M. Cheremisin, I. G. Kamyishanskaya

Petersburg State University, The Faculty of Medicine, 21 line V.O.,


[email protected]

tersburg, Russia, July 7 – 11, 2014

on precontrast T2WIs. Unlike bacterial abscesses,

toxoplasmosis lesions are not high in signal on DWI.

Cryptococcosis is the most common fungal infection,

causing meningitis as the most common presentation.

Imaging studies are usually normal, diagnosis is made by

Progressive multifocal leukoencephalopathy Progressive multifocal leukoencephalopathy (PML) is a

unistic infection, caused by JC virus. The

incidence of PML in AIDS patients is approximately 10%.

The infection causes demyelination and necrosis, primarily

involving white matter. MR reveals focal lesions of

increased signal on TIRM and T2WI and decreased signal

on T1WIs within the subcortical and deep white matter.

CMV infection usually does not result in frank tissue

necrosis. MR features are divers or absent. CMV

meningoencephalitis is occasionally imaged as areas of

increased signal on T2WIs in the periventricular white

Mycobacterial CNS infection Mycobacterial CNS infection is a relatively rare disease

among AIDS patients. Most of these patients are intravenous

drug abusers with pulmonary tuberculosis. Most patients

s. Tuberculomas are present in

patients with CNS tuberculosis.

MRI has the highest sensitivity and specificity for detection infectious disease of the Central Nervous System

infected patients among other imaging methods. Brain MRI results are essential for effective pharmacological treatment of HIV-associated diseases.

associated opportunistic

, 8a


Valuable structural information in solids, so

anisotropic fluids such as, for example, nanostructured

composites and biological membranes,

through the determination of dipolar couplings.

Heteronuclear dipolar interactions between rare and

abundant spins are measured using Separated Local F

(SLF) experiment where dipolar coupling are correlated to

the chemical shifts of the rare nuclei [1].

Popular SLF approaches, which can be applied under

stationary and magic angle spinning sample conditions,

include (i) monitoring of the single quantum coherence

evolution of either rare or abundant spins and (ii)

observation of the polarization exchange in the rotating

frame. Latter technique typically involves

of the spin-locked magnetization components during

polarization. In another approach, multiple pulse

homonuclear decoupling sequence is applied and the

magnetization is spin-locked along the

direction. For efficient spin exchange, the same sequence is

synchronously applied in the second frequency channel

It has been demonstrated that the superior resolution in

the broad range of the dipolar coupling

with the proton detected local field (PDL

the evolution of the single quantum coherences of the

abundant spins is indirectly observed

measurements of large dipolar coupling the rotating frame

approaches are competitive [4]. In the technique based on

synchronous homonuclear decoupling in two channels the

Heteronuclear

Sergey V. Dvinskikh

Royal Institute of Technology, Stockholm, Sweden

Laboratory of Biomolecular NM

Petersburg, Russia


– 11, 2014 – 22 –

solids, soft solids and

, for example, nanostructured

, can be obtained

through the determination of dipolar couplings.

Heteronuclear dipolar interactions between rare and

Separated Local Field

(SLF) experiment where dipolar coupling are correlated to

SLF approaches, which can be applied under

onary and magic angle spinning sample conditions,

include (i) monitoring of the single quantum coherence

evolution of either rare or abundant spins and (ii)

observation of the polarization exchange in the rotating

frame. Latter technique typically involves the spin exchange

locked magnetization components during cross

. In another approach, multiple pulse

homonuclear decoupling sequence is applied and the

locked along the effective rf field

ent spin exchange, the same sequence is

synchronously applied in the second frequency channel [2].

It has been demonstrated that the superior resolution in

the broad range of the dipolar coupling values is obtained

with the proton detected local field (PDLF) technique where

the evolution of the single quantum coherences of the

[3]. For accurate

measurements of large dipolar coupling the rotating frame

In the technique based on

homonuclear decoupling in two channels the

polarization transfer can be achieved for arbitrary

magnetization component and experiment can be applied to

uniformly or partially labelled samples

In this contribution, an account will be given of recent

applications of the SLF technique to study molecular

mobility, hydrocarbon chain conformational dynamics, and

phase transformations in advanced mesocomposite

materials [5-8].

Work was supported by the Swedish Research Council

and Russian Foundation for Basic Research.

References

[1] R. K. Hester, J. L. Ackerman, B. L. Neff, J. S. Waugh. Phys. Rev. Lett., 36 1081-1083 (1976).

[2] S. V. Dvinskikh, K. Yamamoto, A. Ramamoorthy. J. Chem. Phys., 125 034507 (2006).

[3] S. V. Dvinskikh, H. Zimmermann, A. Maliniak, D. Sandström. J. Magn. Reson

[4] C. H. Wu, A. Ramamoorthy, S. J. Opella. Reson. Ser. A, 109 270-272 (1994).

[5] B. B. Kharkov, S. V. Dvinskikh. Phys., 15 18620-18626 (2013).

[6] B. B. Kharkov, S. V. Dvinskikh24511-24517 (2013).

[7] O. H. Han, Y. Paik, Y. S. Moon, S. K. Lee, et alMater., 19 3615-3623 (2007).

[8] J. Brus, M. Urbanova, I. Kelnar, J. Kotek. 39 5400-5409 (2006).

Heteronuclear Dipolar NMR Spectroscopy

Dvinskikh

Royal Institute of Technology, Stockholm, Sweden

Laboratory of Biomolecular NMR and Institute of Physics, St. Petersburg State University, St.

Petersburg, Russia

[email protected]

polarization transfer can be achieved for arbitrary

magnetization component and experiment can be applied to

uniformly or partially labelled samples [2].

In this contribution, an account will be given of recent

applications of the SLF technique to study molecular

mobility, hydrocarbon chain conformational dynamics, and

phase transformations in advanced mesocomposite

by the Swedish Research Council

sic Research.

R. K. Hester, J. L. Ackerman, B. L. Neff, J. S. Waugh. 1083 (1976).

S. V. Dvinskikh, K. Yamamoto, A. Ramamoorthy. J. 034507 (2006).

S. V. Dvinskikh, H. Zimmermann, A. Maliniak, D. J. Magn. Reson., 163 46-55 (2003).

C. H. Wu, A. Ramamoorthy, S. J. Opella. J. Magn.

272 (1994). B. B. Kharkov, S. V. Dvinskikh. Phys. Chem. Chem.

18626 (2013). B. B. Kharkov, S. V. Dvinskikh. J. Phys. Chem. C, 117

O. H. Han, Y. Paik, Y. S. Moon, S. K. Lee, et al. Chem.

3623 (2007). J. Brus, M. Urbanova, I. Kelnar, J. Kotek. Macromol.,

Institute of Physics, St. Petersburg State University, St.

Introduction ω-hydroxy-4-hexyloxy-4’-cyanobiphenyl (HO

and 4-heptyloxy-4’-cyanobiphenyl (7OCB) are two nematic

liquid crystals (Fig. 1). The first one can form hydrogen

bonds between terminal groups by the virtue of its OH

group. Another molecule was chosen for the comparison, as

it has similar length and cannot form H-bonds.

Figure 1. Structure of HO-6OCB (top) and 7OCB (

Conformational structure Fully-atomistic molecular dynamics simulations can

provide important information on the structure of the

material under study. Main results on local structure of HO

6OCB and 7OCB such as radial or cylindrical distribution

functions, hydrogen bonds formation and their lifetimes can

be found in our paper [1]. This report focuses mainly on

conformational structure of the above mentioned liquid

crystals.

Structure of two cyanobiphenyl mesogens studied by molecular dynamics simulations

Egor Gerts, Andrei

Faculty of Physics, St.

198504, Ulyanovskaya, 3, St.



cyanobiphenyl (HO-6OCB)

cyanobiphenyl (7OCB) are two nematic

ne can form hydrogen

bonds between terminal groups by the virtue of its OH-

group. Another molecule was chosen for the comparison, as

bonds.

6OCB (top) and 7OCB (bottom)

atomistic molecular dynamics simulations can

provide important information on the structure of the

material under study. Main results on local structure of HO-

6OCB and 7OCB such as radial or cylindrical distribution

unctions, hydrogen bonds formation and their lifetimes can

be found in our paper [1]. This report focuses mainly on

conformational structure of the above mentioned liquid

The analysis of dihedral angles distributions shows that

the rotational isomeric model can be applied. Odd

effect is also observed in our simulations affecting dihedral

angles distributions as well as aliphatic chains

conformations. The all trans conformation of the chain is

more typical for 7OCB liquid crystal and is the m

frequent (25.8% of all conformations), while HO

more likely to have gauch± at the end of the chain (13.2%

for each conformation). Another appearance of the odd

effect is that almost every odd carbon

central oxygen atom) is in trans

Unfortunately thesis format don’t give us the possibility

to introduce our results in sufficient manner, but all the

moments will be discussed at the conference in details.

Acknowledgements It is a pleasure to thank Saint

for the research grant 11.37.159.2014. Research

out using computational resources provided by Resource

Center ”Computer Center of SPbU”

References [1] Egor D. Gerts, Andrei V. Komolkin, Vladimir A.

Burmistrov, Victor V. Alexandriysky, and Sergey V. Dvinskikh. “Comparative study of local structure of two cyanobiphenyl liquid crystals by molecular dynamics method” (to be published).

Structure of two cyanobiphenyl mesogens studied by molecular simulations

Andrei V. Komolkin

, St. Petersburg State University,

Ulyanovskaya, 3, St. Petersburg, Russia

[email protected]


The analysis of dihedral angles distributions shows that

omeric model can be applied. Odd-even

effect is also observed in our simulations affecting dihedral

angles distributions as well as aliphatic chains

conformation of the chain is

more typical for 7OCB liquid crystal and is the most

frequent (25.8% of all conformations), while HO-6OCB is

at the end of the chain (13.2%

for each conformation). Another appearance of the odd-even

effect is that almost every odd carbon atom (counting from

position.

Unfortunately thesis format don’t give us the possibility

to introduce our results in sufficient manner, but all the

moments will be discussed at the conference in details.

It is a pleasure to thank Saint-Petersburg State University

for the research grant 11.37.159.2014. Research was carried

out using computational resources provided by Resource

Center ”Computer Center of SPbU” (http://cc.spbu.ru).

Egor D. Gerts, Andrei V. Komolkin, Vladimir A. Victor V. Alexandriysky, and Sergey V.

Dvinskikh. “Comparative study of local structure of two cyanobiphenyl liquid crystals by molecular dynamics method” (to be published).

Structure of two cyanobiphenyl mesogens studied by molecular


Introduction In the modern world there is a steady deterioration of the

ecological state of water objects. Humanity pollutes water

objects banks and the water by various hazardous

substances. Timely detection of hot spots allows for a set of

measures to clean up the coast and the water in time.

prevents more serious ecological disaster.

most effective type of environmental monitor

water objects is collecting samples and express analysis on a

place for detection of existence of pollution. Further samples

are transported in stationary laboratory and are exposed to

the full analysis. Only trials in which was

suspicion of dangerous impurities presence exposed a

complete analysis.

In such a situation, quite effective tool for express control

is compact nuclear - magnetic (NMR) relaxometer.

Moreover, this instrument can be used for quality control of

products and liquid (e.g. milk or beer) or viscous (e.g.

engine oil or linseed oil) products.

Registration of the NMR signalIn the proposed design of the portable nuclear

relaxometer the container with liquid placed into a magnet,

which also serves the function of the polarizer and analyzer.

Dimensions of the magnetic system were chosen so that the

device could be easily transported by hand. For registration

of the NMR signal in a weak magnetic field (B

we developed autodyne detector scheme

vibrations). It was based on the differential amplifier

cascade, which ensures stable operation of the device and

good suppression of common mode interference.

We developed a scheme for the control and proce

the NMR signal, which was based on a microcontroller

STM32. It allows to provide optimal conditions for the

registration of the NMR signal - high signal

(S/N), and to automate the measurements.

microcontroller controls the autodyne generation

maximize S/N ratio and automatically adjusts the frequency

Compact nuclear magnetic relaxometer to express monitoring of l

Anton Karseev,

St. Petersburg State Polytechnical University

E-mail: [email protected]: [email protected]

– 11, 2014 – 24 –

In the modern world there is a steady deterioration of the

Humanity pollutes water

e water by various hazardous

substances. Timely detection of hot spots allows for a set of

measures to clean up the coast and the water in time. This

prevents more serious ecological disaster. In most cases, the

most effective type of environmental monitoring of small

express analysis on a

place for detection of existence of pollution. Further samples

are transported in stationary laboratory and are exposed to

Only trials in which was revealed the

dangerous impurities presence exposed a

In such a situation, quite effective tool for express control

magnetic (NMR) relaxometer.

Moreover, this instrument can be used for quality control of

liquid (e.g. milk or beer) or viscous (e.g.

Registration of the NMR signal In the proposed design of the portable nuclear - magnetic

container with liquid placed into a magnet,

ction of the polarizer and analyzer.

were chosen so that the

easily transported by hand. For registration

of the NMR signal in a weak magnetic field (B0 = 0.55 mT),

we developed autodyne detector scheme (generator weak

the differential amplifier

cascade, which ensures stable operation of the device and

good suppression of common mode interference.

We developed a scheme for the control and processing of

ased on a microcontroller

provide optimal conditions for the

high signal/noise ratio

automate the measurements. The

microcontroller controls the autodyne generation level for

and automatically adjusts the frequency

of autodyne detector depending on the magnetic field

induction B0. To ensure the S / N ratio greater than 5,

microcontroller provided the signal accumulation. Using this

scheme allowed to register the NMR si

with T1> 0.005 s.

Measurement techniqueThe NMR signal from tap water at T = 17. 4

in Fig. 1.

Figure 1. NMR signal

The shape of the NMR signal decay (dotted line) is

determined by the time T2 (Fig. 1). T

performed by varying the frequency modulation of the field

B0. Comparing the T1 and T2 with the reference values

given temperature), you can instantly identify the deviation

from the natural state of the medium.

Using microcontroller allowed

modulation and modulation field amplitude. It is able to

measure the transverse relaxation time T

seconds or less. In the case of large transverse relaxation

times, the presence of impurities can be determined by

observing the NMR signal on the laptop screen, which

records the measurement results.

Compact nuclear magnetic relaxometer to express ing of liquid and viscous media

, Vadim Davydov1

rsburg State Polytechnical University

[email protected]

[email protected]

autodyne detector depending on the magnetic field

To ensure the S / N ratio greater than 5, the

the signal accumulation. Using this

scheme allowed to register the NMR signal from liquids

Measurement technique The NMR signal from tap water at T = 17. 4 0C is shown

NMR signal

The shape of the NMR signal decay (dotted line) is

(Fig. 1). T1 measurements

med by varying the frequency modulation of the field

with the reference values (at a

given temperature), you can instantly identify the deviation

from the natural state of the medium.

Using microcontroller allowed to control the frequency

modulation field amplitude. It is able to

measure the transverse relaxation time T2 of the order of 2.5

In the case of large transverse relaxation

times, the presence of impurities can be determined by

the NMR signal on the laptop screen, which

records the measurement results.

Compact nuclear magnetic relaxometer to express - condition

Introduction Nanostructured mesoporous materials have attracted

considerable interest during past decades. Unique physical

properties of these materials make them indispensable in

various industrial applications, i.e. as adsorbents for water

remediation, chemical sensors, and filters with high

sensitivity to the penetrant molecule size. Nowadays,

surfactant-templating synthesis strategies are widely

employed for mesocomposites production in both

and fundamental research applications. Studying the organic

component that is periodically arranged within inorganic

matrix of the composite can provide valuable information on

the molecular origin of the confinement effects and surface

interaction and reveal its affect on the

dynamic properties of organic molecules.

Various experimental and computational te

been applied to study dynamical and structural parameters

of organic molecules adsorbed and confined in the galleries

of mesoporous solids. Unlike diffraction and imaging

techniques, such as SAXS, TEM, and AFM, NMR spectral

and relaxation parameters are sensitive to the local

environment and are capable of delivering the structural and

dynamical information on atomic and molecular level.

dimensional 13C separated local field NMR spectroscopy

provide quantitative model-independent informati

molecular dynamics in anisotropic systems in a wide range

of molecular mobility. In a typical SLF experiment, residual

heteronuclear dipolar couplings are probed in indirect

dimension of 2D experiment, while carbon chemical shifts,

measured in the direct dimension, preserve high chemical

resolution. In the experiment, dipolar spectra with splitting

proportional to C-H bond order parameter S

for each resolved carbon position.

SLF in nanocomposites In the present work, we apply SLF spectr

nanostructured organic-inorganic mesocomposites. The

organic component often exhibits complex phase behaviour

with phases characterized by different types of molecular

motions.

Molecular mobility in nanostructured mesocomposites studied by dipolar NMR spectroscopy

Boris Kharkov1,2

1Department of Chemistry, Royal Institute of Technology 2Department of NPR3Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034, Russia



Nanostructured mesoporous materials have attracted

iderable interest during past decades. Unique physical

properties of these materials make them indispensable in

various industrial applications, i.e. as adsorbents for water

remediation, chemical sensors, and filters with high

molecule size. Nowadays,

synthesis strategies are widely

employed for mesocomposites production in both industrial

and fundamental research applications. Studying the organic

component that is periodically arranged within inorganic

trix of the composite can provide valuable information on

molecular origin of the confinement effects and surface

and reveal its affect on the structural and

.

Various experimental and computational techniques have

been applied to study dynamical and structural parameters

of organic molecules adsorbed and confined in the galleries

Unlike diffraction and imaging

techniques, such as SAXS, TEM, and AFM, NMR spectral

ameters are sensitive to the local

environment and are capable of delivering the structural and

dynamical information on atomic and molecular level. Two-

C separated local field NMR spectroscopy

independent information on

molecular dynamics in anisotropic systems in a wide range

of molecular mobility. In a typical SLF experiment, residual

heteronuclear dipolar couplings are probed in indirect

dimension of 2D experiment, while carbon chemical shifts,

rect dimension, preserve high chemical

resolution. In the experiment, dipolar spectra with splitting

H bond order parameter SCH are obtained

In the present work, we apply SLF spectroscopy to study

inorganic mesocomposites. The

organic component often exhibits complex phase behaviour

with phases characterized by different types of molecular

Figure 1. a) Schematic representation of a mesolamellar

nanocomposite; b) simulated representative C

spectra in adsorbed surfactant molecules for three motional

models: immobilized molecule, rotator phase, and rotating

molecule with fast conformational dynamics

As an example, the schematic structure of cla

layered composite is shown in Figure 1a. The organic

double layer is formed by surfactant molecules. The

composite exhibits three phases clearly distinguishable by

dipolar spectra’s shapes (Figure 1b). Motional modes were

identified from the analysis of the order parameter profiles.

Nanocomposites of different geometry [1, 2] and its

comparison to lyotropic mesophases [3, 4] will be discussed

in the presentation.

Acknowledgements This work was supported by Swedish Research Council

VR and by Russian Foundation for Basic Research.

References [1] Kharkov, B.B., Dvinskikh S.V.

24511−24517, (2013) [2] Kharkov, B.B., Dvinskikh S.V.,

Phys., 15, 18620−18626, (2013)[3] Kharkov, B.B., Chizhik, V.I., Dvinskikh S.V.

Reson., 223, 73, (2012) [4] Kharkov, B.B., Chizhik, V.I.,

Phys., 137, 234902, (2012)

Molecular mobility in nanostructured mesocomposites studied by dipolar NMR spectroscopy

1,2, Sergey Dvinskikh1,2,3

Department of Chemistry, Royal Institute of Technology - KTH, SE-10044 Stockholm, Sweden

Department of NPRM, St. Petersburg State University, St. Petersburg 199034, Russia


[email protected]


chematic representation of a mesolamellar

omposite; b) simulated representative C-H dipolar

spectra in adsorbed surfactant molecules for three motional

: immobilized molecule, rotator phase, and rotating

molecule with fast conformational dynamics

As an example, the schematic structure of clay-based

layered composite is shown in Figure 1a. The organic

double layer is formed by surfactant molecules. The

composite exhibits three phases clearly distinguishable by

dipolar spectra’s shapes (Figure 1b). Motional modes were

is of the order parameter profiles.

Nanocomposites of different geometry [1, 2] and its

comparison to lyotropic mesophases [3, 4] will be discussed

This work was supported by Swedish Research Council

Foundation for Basic Research.

ov, B.B., Dvinskikh S.V., J. Phys. Chem. C, 117,

Kharkov, B.B., Dvinskikh S.V., Phys. Chem. Chem.

, (2013) , Chizhik, V.I., Dvinskikh S.V., J. Magn.

Kharkov, B.B., Chizhik, V.I., Dvinskikh S.V., J. Chem.

Molecular mobility in nanostructured mesocomposites studied by

10044 Stockholm, Sweden

St. Petersburg 199034, Russia



The number of patients with cancer has increased significantly for the last 10 years. In 2012, cancabout 8.2 million people according to WHO [1]. In Russia, each year 20.8 new malignancies are diagnosed per 100 thousand population [1]. Unfortunately, in 60% of cases neglected tumors on III – IV stage are detected [Therefore, early diagnosis of the primary tumor and visualization of metastases are essential for the timely and proper patient management.

Nowadays the special place among modern methods of radiation diagnostic imaging of cancer is occupying by CT and MRI.

However, functional and metabolic pathological changes are not usually conjoined with anatomic changes, thus standard CT imaging can’t identify them. Furthermore, using CT isn’t enough for assessing results of the therapy, that is why functional methods of visualization suchSPECT and PET are used to supplement anatomic methods of visualization [2].

In the early 90s diffusion-weighted MRI (DWI) had appeared in medicine, being used to diagnose the cerebrovascular accident. [2] With the advent of superconducting MR- tomographs, it became possible to conduct whole-body DWI [2, 3].

Not only pathologically high glucose uptake characterizes cancer cells, but also high cellularity, so the restriction of water diffusion is hallmark of tumor cells. Modification of the H2O diffusion, caused by the pathophysiological processes leading to impairment of cell membrane permeability, can be detected by DWI and characterized by maps of apparent diffusion coefficient (ADC). The last notion reflects the mean square distance that molecule of water passes per unit time [3, 4].

Signal intensity on DWI reflects the extent of freedom of the H2O diffusion in the voxel of the object. In terms of scale relativity it means that tissue with limited diffusion will give hyperintensive signal, while tissue limited diffusion will be hypointensive. The reverse is true for ADC map: if diffusion is more limited, the meaning of ADC will be lower and accordingly the intensity will be also lower [5].

Recent years usual DWI has been evolved into whole body DWI (WB-DWI), which becomes comparable with PET-CT.

DWI is hold as well as SPECT-CT and PETsame scanner without unnecessary patient’s shifting, that reduces the chance of a mismatch slices.

PET-CT and SPECT-CT are associated with Xexposure and patient’s gamma irradiation, the tracer

Diffusion-Weighted MRI of the body in oncologic practice: method, comparison with PET/SPECT and prospects

T. V. MakurovaI. G. Kamyishanskaya

1Faculty of Medicine, 2Mariinskaya Hospital, MRI Department

– 11, 2014 – 26 –

The number of patients with cancer has increased significantly for the last 10 years. In 2012, cancer has killed about 8.2 million people according to WHO [1]. In Russia, each year 20.8 new malignancies are diagnosed per 100

Unfortunately, in 60% of cases IV stage are detected [1].

nosis of the primary tumor and visualization of metastases are essential for the timely and

Nowadays the special place among modern methods of radiation diagnostic imaging of cancer is occupying by CT

and metabolic pathological changes are not usually conjoined with anatomic changes, thus standard CT imaging can’t identify them. Furthermore, using CT isn’t enough for assessing results of the therapy, that is why functional methods of visualization such as SPECT and PET are used to supplement anatomic methods

weighted MRI (DWI) had appeared in medicine, being used to diagnose the

] With the advent of hs, it became possible to

Not only pathologically high glucose uptake characterizes cancer cells, but also high cellularity, so the restriction of water diffusion is hallmark of tumor cells. Modification of

caused by the pathophysiological processes leading to impairment of cell membrane permeability, can be detected by DWI and characterized by maps of apparent diffusion coefficient (ADC). The last notion reflects the mean square distance that molecule of

Signal intensity on DWI reflects the extent of freedom of O diffusion in the voxel of the object. In terms of

scale relativity it means that tissue with limited diffusion will give hyperintensive signal, while tissue with less limited diffusion will be hypointensive. The reverse is true for ADC map: if diffusion is more limited, the meaning of ADC will be lower and accordingly the intensity will be also

Recent years usual DWI has been evolved into whole DWI), which becomes comparable with

CT and PET-CT using the same scanner without unnecessary patient’s shifting, that

CT are associated with X-ray

ure and patient’s gamma irradiation, the tracer

production. They are more timemethods. Moreover, sensitivity and specificity of isotope tomographic methods depend on tumor’s histologradiopharmaceuticals [6].

With reference to WB-DWI, this method allows to assess either on the molecular level, and using inverted scale by type “negative” are visually similar to PETDWI method isn’t required opacifying injection or using radiopharm drugs, being cheaper than SPE

Simultaneously with the advantages of this technique, there are a number of drawbacks and limitatinfluence of values T2 and T1 (limited opportunities for focuses with short T2 values, with short T1 values focuses visualized as a high-intensity zones); motion and streams artifacts; insufficient resolution, which reduces sensitivity to small focuses [6].

Almost one of the major drawbacks of DWI associated with occurrence of artifacts in breathing, is eliminated with using the program DWIBS, which eliminatmotion of water [2].

Prospectively, early made DWI (after 1chemotherapy), supplemented by accounting and modification values of ADC before and after, permits to predict tumor response at the end of tre

In conclusion, WB-DWI can be good alternative in searching for the primary tumors and more important, for metastases, their number and location, the extent of the positive response to treatment. WBdiagnosis and can be used repeatedly for monitoring chemoand radiotherapy.

References [1] Kaprin A.D., Starinsky V.V., Petrova G.V.

Malignancies in Russia 2012 // Moscow, 2014.[2] Karelskaya N.A., Karmazanovsky G.G. Diffusion

weight whole-body MRI // Moscow, Khirurgia Vol.8, № 57, 2010, p.57-60.

[3] Bakhtiozin R., Safiullin R. Wholeweighted imagining in diagnosis and monitoring of malignant neoplasm treatment. // journal of radiology, №1, 2011, p.13

[4] Horujik S.A., Javrid E.A., Karman A.V., Diffusionweighted MRI in oncology. // Minsk, 2013, p.66.

[5] Graessner J. Frequently asked questions: diffusionweighted imaging.// Magnetom flash

87 [6] Lichy M.Ph., Aschoff Ph., Pfannenberg C. Tumor

detection by diffusion-weighted MRI and ADCmapping with correlationMagnetom flash, №3, 2009, p.47

Weighted MRI of the body in oncologic practice: method, comparison with PET/SPECT and prospects

Makurova1, D. A. Zinkevich1, V. M. Cheremisin1,2, Kamyishanskaya1,2

Medicine, Saint-Petersburg State University, 21 Liniya 8a, Saint Petersburg

ospital, MRI Department, Liteinii prospect 56, Saint Petersburg

production. They are more time-consuming and costly methods. Moreover, sensitivity and specificity of isotope tomographic methods depend on tumor’s histology and used

DWI, this method allows to assess either on the molecular level, and using inverted scale by type “negative” are visually similar to PET-CT. In addition, DWI method isn’t required opacifying injection or using radiopharm drugs, being cheaper than SPECT and PET.

Simultaneously with the advantages of this technique, there are a number of drawbacks and limitations: the

T2 and T1 (limited opportunities for focuses with short T2 values, with short T1 values focuses

intensity zones); motion and streams artifacts; insufficient resolution, which reduces sensitivity to

Almost one of the major drawbacks of DWI associated with occurrence of artifacts in breathing, is eliminated with

IBS, which eliminates the coherent

Prospectively, early made DWI (after 1st or 2nd course of chemotherapy), supplemented by accounting and modification values of ADC before and after, permits to predict tumor response at the end of treatment.

DWI can be good alternative in searching for the primary tumors and more important, for metastases, their number and location, the extent of the positive response to treatment. WB-DWI is a safe method of

repeatedly for monitoring chemo-

Kaprin A.D., Starinsky V.V., Petrova G.V. Malignancies in Russia 2012 // Moscow, 2014. Karelskaya N.A., Karmazanovsky G.G. Diffusion

body MRI // Moscow, Khirurgia Vol.8,

Bakhtiozin R., Safiullin R. Whole-body diffusion-weighted imagining in diagnosis and monitoring of malignant neoplasm treatment. // Russian electronic

, 2011, p.13-18. Horujik S.A., Javrid E.A., Karman A.V., Diffusion-

hted MRI in oncology. // Minsk, 2013, p.66. Graessner J. Frequently asked questions: diffusion-

Magnetom flash, №1, 2011, p.84-

Lichy M.Ph., Aschoff Ph., Pfannenberg C. Tumor weighted MRI and ADC-

orrelation to PET/CT results.// , 2009, p.47-51.

Weighted MRI of the body in oncologic practice: method, comparison with PET/SPECT and prospects

, Saint Petersburg

, Liteinii prospect 56, Saint Petersburg

Introduction One of the most critical challenges facing

today is assuring crude oil flow through complex long

pipelines. Pipeline failures are extremely costly and

potentially disastrous to the environment. Failures can

in for a variety of reasons, but the most widely spread is n

paraffin (wax) deposition [1]. It occurs along the pipe walls

when the temperature of produced fluids falls below the

cloud point (the point at which the first wax crystals start to

precipitate out of solution [2]). The most commonly used

method to study wax deposition tendency in crude oil is

Cold Finger testing. The basic concept of this

a surface (cold finger) is placed in a sample of heated crude

oil, and cooling fluid is circulated through the interior of the

cold finger. Wax deposition on cold surface is measured

against the time (it’s accompanied by cold finger removin

and weighting).

The deep inside into the mechanisms of deposit formation

could be provided by NMR Imaging application to Cold

Finger testing, making it possible to visualize the deposits

and temperature distribution as well as measurement rates of

growth in non destructive manner (in situ). Therefore the

aim of this work was to develop the methodology of MRI

application to Cold Finger testing including equipment

implementation and conducting the model experiments.

Experimental Experimental installation was consisted of

system based on Bruker AVANCE DPX 200

probe PH MINI 0.75, RF coil diameter being 38 mm) and

homemade Cold Finger device adjusted into the magnet

system (Fig.1).

Figure 1. Scheme of device adjusted into the RF

and photo of cold finger filled by model sample (right)

To prove workability and efficiency the installation

tested on model sample (glycerol) and two samples of heavy

crude oils (Mongolian [3] and Tatarskaya).

Method development to study heavy crude oils using NMR Imaging joined with Cold Finger testing

Evgeny V. Morozov

Kirensky Institute of Physics SB RAS, 660036 Akademgorodok 38/50, Krasnoyarsk, Russia

E-mail: morozov_if1Boreskov Institute of Catalysis SB RAS, 630090


One of the most critical challenges facing oil industry

oil flow through complex long

Pipeline failures are extremely costly and

. Failures can occur

but the most widely spread is n-

deposition [1]. It occurs along the pipe walls

produced fluids falls below the

cloud point (the point at which the first wax crystals start to

precipitate out of solution [2]). The most commonly used

method to study wax deposition tendency in crude oil is

Cold Finger testing. The basic concept of this testing is that

a surface (cold finger) is placed in a sample of heated crude

oil, and cooling fluid is circulated through the interior of the

Wax deposition on cold surface is measured

against the time (it’s accompanied by cold finger removing

The deep inside into the mechanisms of deposit formation

could be provided by NMR Imaging application to Cold

Finger testing, making it possible to visualize the deposits

temperature distribution as well as measurement rates of

in non destructive manner (in situ). Therefore the

aim of this work was to develop the methodology of MRI

application to Cold Finger testing including equipment

implementation and conducting the model experiments.

as consisted of NMR imaging

system based on Bruker AVANCE DPX 200 (field 4.7 T,

probe PH MINI 0.75, RF coil diameter being 38 mm) and

homemade Cold Finger device adjusted into the magnet

Scheme of device adjusted into the RF probe (left)

and photo of cold finger filled by model sample (right)

and efficiency the installation was

tested on model sample (glycerol) and two samples of heavy

crude oils (Mongolian [3] and Tatarskaya).

Results and discussionIn results the experimental installation was implemented

and successfully tested on model samples. The temperature

profiles measured along the radius (t

using calibration curves T2=f(t) measured previously) for

model glycerol sample revealed a good agreement with

theoretically predicted t-profiles based on

equations.

Installation is able to generate wide range of steady

temperature gradients (the strongest is 10/80°C where 10°C

– the temperature of cold walls and 8

of hot ones). Given temperature gradients were visualized

(Fig.2, T2-weighted images are presented) and the action of

these gradients on oil samples was studied. So, crude oil

stratification and light fractions transport were observed

deposit outgrowth formation was visualized directly.

Figure 2. NMR images of Cold Finger device with glycerol

(left, transverse slice) and crude oil (right, vertical slice)

Conclusion New method developed seems to be promising for study

heat and mass transfer in crude oils, providing the deep

insight into the mechanisms of deposit formation.

Acknowledgements This research was performed under the UNIHEAT

project. The authors wish to acknowledge the Skolkovo

Foundation and BP for financial support

References [1] J.S.T. Santos et al. – J.

Engineering, 45, 47-60 (2004).[2] V.R. Kruka et al. – JPT, Aug. 1995, [3] E.V. Morozov et al. – Mater. Sci. Eng. A

551 (2011).

Method development to study heavy crude oils using NMR Imaging joined with Cold Finger testing in situ

Morozov, Oleg N. Martyanov1


[email protected]

Boreskov Institute of Catalysis SB RAS, 630090 Pr. Akad. Lavrentieva 5, Novosibirsk, , Russia


and discussion esults the experimental installation was implemented

and successfully tested on model samples. The temperature

profiles measured along the radius (t-profiles were evaluated

=f(t) measured previously) for

ealed a good agreement with

profiles based on heat conduction

is able to generate wide range of steady-state

temperature gradients (the strongest is 10/80°C where 10°C

the temperature of cold walls and 80°C – the temperature

of hot ones). Given temperature gradients were visualized

weighted images are presented) and the action of

these gradients on oil samples was studied. So, crude oil

stratification and light fractions transport were observed;

deposit outgrowth formation was visualized directly.

NMR images of Cold Finger device with glycerol

(left, transverse slice) and crude oil (right, vertical slice)

New method developed seems to be promising for study

ss transfer in crude oils, providing the deep

insight into the mechanisms of deposit formation.

This research was performed under the UNIHEAT

project. The authors wish to acknowledge the Skolkovo

on and BP for financial support.

J. Petroleum Science and

60 (2004). Aug. 1995, 681-687.

Mater. Sci. Eng. A, 1 No. 4, 545-

Method development to study heavy crude oils using NMR


Pr. Akad. Lavrentieva 5, Novosibirsk, , Russia


Introduction In single crystal the preferred direction in nuclear

quadrupole resonance(NQR) is defined by quadrupole principal axis, but in powder there is no preferred direction for one frequency NQR. However in the case of two and three frequencies signals the relative directions of the coihave important meaning, because the maximum probabilities of the signal on ν+, ν- and associated with quadrupole principal axiswork we study two and three frequencies signals for one coil multifrequencies probe and for case of different angles between exciting coils. We also studied the exciting of two transition by one pulse in the system with small parameter η≤0.2 and for high asymmetry

Modeling and experiments Our theory is based on following approach: the

of pulses are considered to be much shorter than therelaxation time of the quadrupole system.density approach for calculations of transition NQR signal,neglecting the relaxation terms [1].

Firstly we studied the application of the case of small asymmetry parameter η of excitation pulse is enough to excite both transitions). This pulse produces the signal on transitions ν+ and ν-. We carried out calculations of the case of excitation two transitions by two pulse on different transitions. The results for a single crystal for different orientation of coils to principal axis EFG were carried out. We modeled the behavior of the signal for different polar angle θ and ϕ. The results of the modeling show that there are two- and threefrequency signals for one coil excitation. Although the signal on the third frequency is smallest, the probability of the detection of this signal is comparable to other signals. In this situation, we suppose that the range of resonance of coil circuit is very wide including all resonance frequencies. However, in powder, there is no unique direction in the laboratory frame defining the quantization axis of the sample, but the axis of the radiofrequency coil defines the preferred direction in the sample. For instance, in work [2] the effective radiofrequency component is defined by the projection of radiofrequency magnetic field on the axis of spin quantization. Some results presen

The average value of zI projection on

is equal to zero. Also, we studied the case of two coils with different

resonance frequencies ν+ and ν- in powder and variable angle between these coils.

NQR experiments have been performed on Apollo NQR/NMR console (0.1-100 MHz)

Two frequency nuclear quadrupole resonance for lineidentifications

G. V. Mozzhukhin

1Gebze Institute of Technology, Istanbul Str. 101, P.B. 141, 41400 Gebze2Kazan State Power Engineering University, 420066 Kazan, Russian Federation 3Department of Mechanical Engineering, King’s College London, Strand, London WC2R 2LS, UK4Kazan Physical-Technical Institute (KPhTI), 420029 Kazan, Russia 5Baltic Federal State University, 320014 Kaliningrad, Russian Federation

– 11, 2014 – 28 –

eferred direction in nuclear quadrupole resonance(NQR) is defined by quadrupole principal axis, but in powder there is no preferred direction for one frequency NQR. However in the case of two and three frequencies signals the relative directions of the coils have important meaning, because the maximum

and ν0 frequencies are quadrupole principal axis X, Y and Z. In our

work we study two and three frequencies signals for one coil for case of different angles

between exciting coils. We also studied the exciting of two transition by one pulse in the system with small asymmetry

and for high asymmetry parameter η ≥ 0.2.

following approach: the durations

considered to be much shorter than the he quadrupole system. We use the matrix

for calculations of transition NQR signal,

the application of the single pulse in (i.e. the bandwidth

of excitation pulse is enough to excite both ν+ and ν- the signal on both

ulations of the case of excitation two transitions by two pulse on different transitions. The results for a single crystal for different orientation of coils to principal axis EFG were carried out. We modeled the behavior of the signal for different polar

. The results of the modeling show that there frequency signals for one coil excitation.

Although the signal on the third frequency is smallest, the probability of the detection of this signal is comparable to

. In this situation, we suppose that the range of resonance of coil circuit is very wide including all resonance

n powder, there is no unique direction in the laboratory frame defining the quantization

radiofrequency coil defines the preferred direction in the sample. For instance, in

the effective radiofrequency component is defined projection of radiofrequency magnetic field on the

. Some results presented in fig.1.

projection on one coil in powder

Also, we studied the case of two coils with different in powder and variable

iments have been performed on Tecmag

MHz) (with two-

channel transmitter and one-channel receiver modulesGIT (Gebze Institute of Technology) group and channel for King’s college group)studies was carbamazepine (CDibenz[b,f]azepine-5-carboxamideAldrich Company Ltd.

Figure 1. One frequency (blue) and two frequencies (red

experiments for carbamazepine at room temperature

in one coil. F1 =

Conclusion We investigated some aspects of two frequency method

for application in one and two coil experimental setup. The first important conclusion is following: in the case of one coil probe and two coils probe the signal at third frequency after two-frequency excitation is not observable in powder. We need two coils for excitation and third coil for receiving the signal on the third frequency. Thus, use of threefrequency signal for detection of the compounds requires three orthogonal coils experimental setup in second important conclusion includes the application of two-frequency method for line identification of NQR spectra in one coil probe. We showed that both one coil probe and two coils probe are effective for line identification in the case of carbamazepine.

Acknowledgements

This work is supported by the Scientific and Research Council of Turkey (TUBITAK) (grant #212T131).

References [1] G.V.Mozzhukkin, B.Z.Rameev, R.R.Khusnutdinov,

N.Doğan, B. Aktas, Appl. Magn. Reson.

547-556 [2] M.Bloom, E.L.Hahn and B.Herzog,

(1955) 1699-1714.

Two frequency nuclear quadrupole resonance for lineidentifications

Mozzhukhin1,2, J. Barras3, B. Rameev1,4, G. Kupriyanova

Gebze Institute of Technology, Istanbul Str. 101, P.B. 141, 41400 Gebze

Kazan State Power Engineering University, 420066 Kazan, Russian Federation

Mechanical Engineering, King’s College London, Strand, London WC2R 2LS, UK

Technical Institute (KPhTI), 420029 Kazan, Russia

Baltic Federal State University, 320014 Kaliningrad, Russian Federation

channel receiver modules for GIT (Gebze Institute of Technology) group and single

King’s college group). The sample of our as carbamazepine (C15H12N2O, 5H-

carboxamide) produced by Sigma-

quency (blue) and two frequencies (red)

for carbamazepine at room temperature

F1 = ν+, F2 = ν–

We investigated some aspects of two frequency method for application in one and two coil experimental setup. The first important conclusion is following: in the case of one coil probe and two coils probe the signal at third frequency

citation is not observable in powder. We need two coils for excitation and third coil for receiving the signal on the third frequency. Thus, use of three-frequency signal for detection of the compounds requires three orthogonal coils experimental setup in powder. The second important conclusion includes the application of

frequency method for line identification of NQR spectra in one coil probe. We showed that both one coil probe and two coils probe are effective for line identification in the

This work is supported by the Scientific and Research Council of Turkey (TUBITAK) (grant #212T131).

G.V.Mozzhukkin, B.Z.Rameev, R.R.Khusnutdinov, Appl. Magn. Reson. 43 (4) (2012)

M.Bloom, E.L.Hahn and B.Herzog, Phys.Rev., 97 (6)

Two frequency nuclear quadrupole resonance for lines

Kupriyanova5

Gebze Institute of Technology, Istanbul Str. 101, P.B. 141, 41400 Gebze-Kocaeli, Turkey


Mechanical Engineering, King’s College London, Strand, London WC2R 2LS, UK


The cardiac MRI, commonly used

specialized centers, is rarely applied in general hospitals.

While the percentage of cardiac pathology is one of the

biggest among other diseases. That is why

problem for a cardiology and radiology. Together with other

modalities, cardiac MRI has a large field for research and

scientific work. It caused by the fact that the MRI is one of

the most accurate and least invasive methods in cardiac

imaging. Sometimes the MRI is an irreplaceable modality in

a difficult diagnostic case, when other

enough or related with unjustified risk for the pati

provides the detailed assessment of the cardiac morphology

and function. The using of ECG-gating gives a possibility to

avoid the artifacts, caused by cardiac motion. And the right

slice positioning due to oblique (in relation to body axes)

cardiac axes – gives anatomically-correct pattern of the

cardiac structures.

Historically, there are two principal types of sequences.

The “dark-blood” sequences are based on the spine echo,

where the contrast between the myocardium and the blood is

low, but a good visibility of the myocardial edema, whereas

the “bight-blood” sequences are based on the gradient echo

and have the best contrast to noise ratio and the most clearly

view of the endocardial border. Unlike the geometrical

assumption in Echocardiography, the evaluation of the

cardiac function by MRI allows an accurate

the cardiac chambers volumes, the ejection fraction and

other most important indicators of the myocardial function.

Furthermore, even the moderate decrease of the local (

global) contractility can be visualized by the myocardium

tagging technique with the inversion pre-pulses.

Possibilities of the MRI in a complex assessment of cardiac disaeses

I. N. Petrov, V.

Saint-Petersburg State University, Medical faculty




The cardiac MRI, commonly used in cardiology-

in general hospitals.

rcentage of cardiac pathology is one of the

biggest among other diseases. That is why it is a significant

cardiology and radiology. Together with other

has a large field for research and

he fact that the MRI is one of



a difficult diagnostic case, when others are not reliable

enough or related with unjustified risk for the patient. MRI


gating gives a possibility to



correct pattern of the


blood” sequences are based on the spine echo,


good visibility of the myocardial edema, whereas

blood” sequences are based on the gradient echo



, the evaluation of the

rdiac function by MRI allows an accurate quantification of



Furthermore, even the moderate decrease of the local (or


pulses.

Quantification of the blood flow

other intracardiac hemodynamic

phase-encoding technique. It is

indications for surgery in patients with congenital heart

disease.

In spite of the higher resolution given by CT in coronary

angiography, MRI is an alternative for patients with allergy

to the iodine contrast agents. MR

improving and probably will be able to compete with CT

angiography soon.

MRI is a great modality in visualization of the myocardial

ischemia and infarction. MR-perfusion has the best tissue

sensitivity. Combined with the

results in detecting ischemia zones, myocardial necrosis and,

which is particularly important, hibernating/stunning

myocardium and determines the need of the

revascularization.

Delayed contrast-enhanced MRI gives a possibility to

reveal myocarditis, sarcoidosis, hypertrophic

cardiomyopathy, myocardial scar. Moreover, myocardial

mapping enables to quantify these lesions.

Despite of high sensitivity, specificity and accuracy of the

abovementioned MR-methods, occasionally the real clinical

situation is so difficult, that even MRI don’t enables to

determine the right diagnosis. It forces to use the complex

examination of the patient, from physical examination

tech modalities and to improve the current

imaging techniques

Possibilities of the MRI in a complex assessment of cardiac disaeses


Petersburg State University, Medical faculty, 21 line V.O., 8a


[email protected]


flow volumes, velocities and

hemodynamic values are enable via the

encoding technique. It is actively used to determine


higher resolution given by CT in coronary


MR-coronary angiography is

improving and probably will be able to compete with CT-


perfusion has the best tissue

the stress-test, it gives accurate



determines the need of the

enhanced MRI gives a possibility to

tis, sarcoidosis, hypertrophic

cardiomyopathy, myocardial scar. Moreover, myocardial

mapping enables to quantify these lesions.


methods, occasionally the real clinical

is so difficult, that even MRI don’t enables to


examination of the patient, from physical examination to hi-

to improve the current diagnostic

Possibilities of the MRI in a complex assessment of


Most of organic molecules adapted to function

exclusively in aqueous environment. Protein

interactions shape the free energy surface that governs

structure, backbone dynamics and protein folding. Functions

like enzymatic catalysis, recognition and binding

accompanied with specific interactions involving individual

water molecules in hydration of solute. Kinetics of these

processes constrained by mobility of water in hydration

spheres. Hence the study of microstructure and dynamics of

solvent is an important question because the primary events

in most biological processes take place at the protein

interface.

Detailed elaboration of present hydration models is not

sufficient to capture the hydration of hydrophilic and

hydrophobic functional groups of organic molecules.

approach of study of distinct hydrations of functional groups

is necessary to correctly describe the solvation of

amphiphilic molecules.

We report the technique for study of hydration properties

of distinct fragments of organic molecules by nuclear

magnetic resonance on 2H nuclei. It is based on model of

additive contributions from hydrations of functional groups

in observed nuclear magnetic relaxation rate.

of the solvent nuclei should be calculated as a sum of

contributions of each substructure. In t

exchange of deuterons between all substructures, t

lattice relaxation of the solvent nuclei in the investigated

system is given by simple formula.

With use of new technique it was established that

rotational correlation times of water molecules near

methylene group of glycine and β-alanine is 2.8

lower, than one for pure solvent. Ratio of correlation times

is remain unchanged in wide temperature range and don’t

The study of hydration properties of functional groups of glycine and beta-alanine amino acids by nuclear magnetic resonance and quantum chemical calculations

Sevastyan O. Rabdano

1Faculty of Physics, 2Laboratory of Biomolecular NMR, St. Petersburg State U


– 11, 2014 – 30 –

Most of organic molecules adapted to function

exclusively in aqueous environment. Protein-water

tions shape the free energy surface that governs

structure, backbone dynamics and protein folding. Functions

like enzymatic catalysis, recognition and binding

accompanied with specific interactions involving individual

e. Kinetics of these

processes constrained by mobility of water in hydration

spheres. Hence the study of microstructure and dynamics of

solvent is an important question because the primary events

in most biological processes take place at the protein-water

Detailed elaboration of present hydration models is not

sufficient to capture the hydration of hydrophilic and

hydrophobic functional groups of organic molecules. New

of distinct hydrations of functional groups

correctly describe the solvation of

technique for study of hydration properties

of distinct fragments of organic molecules by nuclear

It is based on model of

hydrations of functional groups

in observed nuclear magnetic relaxation rate. Relaxation rate

of the solvent nuclei should be calculated as a sum of

contributions of each substructure. In the case of fast

between all substructures, the spin-

lattice relaxation of the solvent nuclei in the investigated

technique it was established that

rotational correlation times of water molecules near

alanine is 2.8-3 times

, than one for pure solvent. Ratio of correlation times

is remain unchanged in wide temperature range and don’t

depends on solution concentration. The increase of water

molecules mobility in hydration of amino and carboxylic

groups versus pure solvent is observed. At low temperatures

difference in mobility is maximum. At high temperatures

mobility of water molecules in hydration of amino and

carboxylic groups is the same as in pure solvent. Moreover

it was established that energy of activation o

water molecules in hydration of methylene group is almost

equal to activation energy for bulk water. Activation

energies of motion of water molecules in hydration of

hydrophilic carboxylic and amino groups is 1.2 times lower

than in bulk water.

The study of chemical exchange of water and glycine

amide deuterons was made. Also quantum chemical

calculations of clusters constructed from amino acids and

large number of water molecules were performed. The

coordination numbers of functional groups, pr

orientation of water molecules with respect to organic

molecules fragments, hydrogen bond length, Mulliken

partial charges of atoms of solute molecule, Mayer bond

orders and quadrupole coupling constants of deuterons of

water in solutions of glycine and β

Acknowledgements NMR studies were performed at the Centre for Magnetic

Resonance, St. Petersburg State University. pH

measurements were performed at the Centre for diagnosis of

functional materials in medicine, pharmacology a

nanoelectronics, St. Petersburg State University. Quantum

chemical calculations were performed at the Resource

Center “Computer Center SPbU

University.

y of hydration properties of functional groups of glycine alanine amino acids by nuclear magnetic resonance and

quantum chemical calculations

Rabdano1,2, Alexey V. Donets1

, St. Petersburg State University, St. Petersburg, Russia

Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg


depends on solution concentration. The increase of water

molecules mobility in hydration of amino and carboxylic

solvent is observed. At low temperatures

difference in mobility is maximum. At high temperatures

mobility of water molecules in hydration of amino and

carboxylic groups is the same as in pure solvent. Moreover

established that energy of activation of motion of

water molecules in hydration of methylene group is almost

equal to activation energy for bulk water. Activation

energies of motion of water molecules in hydration of

hydrophilic carboxylic and amino groups is 1.2 times lower

The study of chemical exchange of water and glycine

amide deuterons was made. Also quantum chemical

calculations of clusters constructed from amino acids and

large number of water molecules were performed. The

coordination numbers of functional groups, primary

orientation of water molecules with respect to organic

molecules fragments, hydrogen bond length, Mulliken

partial charges of atoms of solute molecule, Mayer bond

orders and quadrupole coupling constants of deuterons of

and β-alanine were calculated.

NMR studies were performed at the Centre for Magnetic

Resonance, St. Petersburg State University. pH

measurements were performed at the Centre for diagnosis of

functional materials in medicine, pharmacology and

nanoelectronics, St. Petersburg State University. Quantum

chemical calculations were performed at the Resource

Computer Center SPbU”, St. Petersburg State

y of hydration properties of functional groups of glycine alanine amino acids by nuclear magnetic resonance and

Russia

niversity, St. Petersburg, Russia

Carbon-based nanomaterials are a novel exciting class of

ferromagnetic (F) materials which do not contain any

metals [1]. They attract considerable interest in recent years

due to high-temperature F behavior accompanied by a field

hysteresis and a remanent magnetization

catching for applications not only in techniques

biology and medicine due to their low toxicity

concentrations of metallic elements [1,

properties of a few carbon-based compounds

by magnetization measurements in [3]. Nevertheless, many

important details (local and long-range structures, character

of F ordering over samples) remain unclear. In this work we

have studied carbon-based compounds doped by Au (

and Co (S-Co), which have been prepared and studied

earlier in [3]. We have obtained data on their structure and

magnetic properties using a few independent physical

techniques, which clarify some above mentioned details.

Neutron diffraction data reveal amorphous character of

the structure in the both samples that correspond to the well

known conceptions on organization of

nanocomposites, having nanoporosity. T

exhibits a more regular distribution of pores and probably

larger average size of material between them

with that in the S-Au sample. This is accompanied by more

homogeneous short-range magnetic arrangement

formation of ground state with long-range F order.

NMR data indicate that both samples are the products of

partial carbonization of initial aromatic compounds and

these products did not reach the state of glassy carbon.

The main result of the magnetic investigations

composite samples doped with Au and Co is establishing of

their inhomogeneous phase-separated magnetic state, which

depends on temperature. This state contains the system of

the FM clusters and the magnetic matrix. The latter is

Unusual scenario of temperature evolution of magnetic state in novel (Au, Co) doped carbon

V. A. Ryzhov1,2, P. L. Molkanov1

D. Galimov2,5, E.

1Petersburg Nuclear Physics Institute, NRC “Kurchatov

Leningrad province, 188300, Russia1E-mail: [email protected] of Mathematics and Physics, Lappeenranta University of Technology, PO Box 20, FIN

53851 Lappeenranta, Finland2E-mail: erkki.lahderanta3Faculty of Physics, 3E-mail: [email protected] of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia5South Ural State University, 454080 6Institute of Applied Physics ASM, Academiei Str., 5, MD 2028 Kishinev, Moldova


nanomaterials are a novel exciting class of

materials which do not contain any F

erest in recent years

temperature F behavior accompanied by a field

hysteresis and a remanent magnetization. This makes them

ions not only in techniques but in

toxicity through small

ations of metallic elements [1, 2]. Magnetic

compounds were studied

]. Nevertheless, many

range structures, character

main unclear. In this work we

based compounds doped by Au (S-Au)

, which have been prepared and studied

]. We have obtained data on their structure and

magnetic properties using a few independent physical

iques, which clarify some above mentioned details.

Neutron diffraction data reveal amorphous character of

the structure in the both samples that correspond to the well

s on organization of carbon-metal

. The S-Co sample

exhibits a more regular distribution of pores and probably

larger average size of material between them in comparison

Au sample. This is accompanied by more

range magnetic arrangement and by

range F order.

samples are the products of

partial carbonization of initial aromatic compounds and

these products did not reach the state of glassy carbon.

The main result of the magnetic investigations of the

composite samples doped with Au and Co is establishing of

separated magnetic state, which

depends on temperature. This state contains the system of

the FM clusters and the magnetic matrix. The latter is

formed by paramagnetic cente

clusters. The magnetic characteristics and their temperature

behavior, as well as structure of the compounds depend

appreciably on the doping material. In the sample doped by

nonmagnetic Au, the onset of the matrix orderin

lower temperature (TC ≈ 210 K

sample such ordering takes place at higher temperature

above 350 K. The S-Co sample exhibits the

magnetization and the coercive force

considerably those of the S-Au s

doped sample displays inhomogeneous

on the long-range spatial scale

magnitude of the mean magnetic moment. The complex

temperature behavior of the magnetization in the Au

sample suggests changing of a mutual arrangement of

magnetic moments of the matrix and the FM cluster system

from an almost opposite orientation below

parallel one at low temperatures. Only the last stage of this

process has been observed in the S

investigated temperature interval. This stage is accompanied

probably by formation of an almost homogeneous

as follows from the neutron diffraction investigations.

Generally, the results obtained

permit us to clarify the peculiarities

obtain important information about

magnetic arrangement of carbon

nanomaterials doped by Au and Co

References [1] T. Makarova and F. Palacio (eds.). Carbon

Magnetism. North-Holland, Elsevier, 2006. [2] T. Makarova. Frontiers in Magnetic Materials

Narlikar (ed.), p. 5, Berlin, [3] E. Lähderanta, A. V. Lashkul,

Materials Science and Engineering

Unusual scenario of temperature evolution of magnetic state in , Co) doped carbon-based nanomaterials

, A. V. Lashkul2, V. V. Matveev3, M. V. Mokeev1, A. I. Kurbakov1,3, K. G. Lisunov2,6, I. A. KiselevE. Lähderanta2

Petersburg Nuclear Physics Institute, NRC “Kurchatov Institute”, Orlova Coppice, Gatchina,

Leningrad province, 188300, Russia

[email protected]

Department of Mathematics and Physics, Lappeenranta University of Technology, PO Box 20, FIN

53851 Lappeenranta, Finland

[email protected]

Faculty of Physics, Saint Petersburg State University, Saint Petersburg, Russia

[email protected]

Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia

University, 454080 Chelyabinsk, Russia

Institute of Applied Physics ASM, Academiei Str., 5, MD 2028 Kishinev, Moldova


ers located outside the FM

. The magnetic characteristics and their temperature

behavior, as well as structure of the compounds depend

on the doping material. In the sample doped by

nonmagnetic Au, the onset of the matrix ordering occurs at

210 K) whereas in the Co-doped

sample such ordering takes place at higher temperature

Co sample exhibits the remanent

coercive force, which exceed

Au sample. In addition, the Co-

doped sample displays inhomogeneous magnetic properties

spatial scale, characterized by larger

magnitude of the mean magnetic moment. The complex

temperature behavior of the magnetization in the Au-doped

suggests changing of a mutual arrangement of

magnetic moments of the matrix and the FM cluster system

from an almost opposite orientation below TC to an almost

parallel one at low temperatures. Only the last stage of this

process has been observed in the S-Co sample within the

investigated temperature interval. This stage is accompanied

probably by formation of an almost homogeneous FM state,

as follows from the neutron diffraction investigations.

the results obtained by different techniques

clarify the peculiarities of the structure and to

obtain important information about delicate processes of the

magnetic arrangement of carbon-based porous

nanomaterials doped by Au and Co.

T. Makarova and F. Palacio (eds.). Carbon-Based Holland, Elsevier, 2006.

Frontiers in Magnetic Materials. A.V. Springer, 2005.

Lashkul, et al. IOP Conf. Series: Materials Science and Engineering 38 (2012) 012010.

Unusual scenario of temperature evolution of magnetic state in based nanomaterials

Mokeev4, Kiselev1,

Orlova Coppice, Gatchina,

Department of Mathematics and Physics, Lappeenranta University of Technology, PO Box 20, FIN-

Petersburg, Russia

Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia

Institute of Applied Physics ASM, Academiei Str., 5, MD 2028 Kishinev, Moldova


Introduction Hydrogen and deuterium solids at low temperatures

represent a special class of quantum crystals, where due to

the large zero point oscillations and light mass, the effects of

quantum tunnelling play an important role. Light impuriti

such as atomic H or D stabilized in solid H

move through the lattice by means of tunnelling and at low

enough temperatures behave similar to an ideal gas where

collective quantum phenomena related to Bose

Condensation (BEC) can be observed. On the other hand,

effects of exchange interaction in the system are expected

appear at high enough densities of H atoms.

work [1] we succeeded in reaching record high densities of

atoms: nH= 4·1019 cm-3.

In this work we present our results of electron spin

resonance (ESR) and electron nuclear double resonance

(ENDOR) experiments with atomic hydrogen and deuterium

stabilized in solid H2 and D2 films in 4.6 T magnetic field at

temperatures below 1 K.

Figure 1: ESR spectra of D and H atoms stabilized in solid

H2;D2 matrix at 300mK. Solid line corresponds to thermal

population of the hyperfine levels, dashed line:

polarized sample

Experimental setup Samples of H and/or D in solid H

created in two stages: 1) we deposited a thin film of solid

molecular para-H2 (ortho-D2) onto a cold (<

Magnetic resonance study of atomic hydrogen and deuterium stabilized in solid H

Sergey SheludiakovDenis Zvezdov1,2

David Lee3

1Department of Physics and Astronomy

E-mail: [email protected] Federal University, 420008, 18 Kremlyovskaya St, Kazan, Russia3Department of Physics and Astronomy and Institute for Quantum Sci

A&M University, College Station, Texas 778

– 11, 2014 – 32 –

Hydrogen and deuterium solids at low temperatures

represent a special class of quantum crystals, where due to

the large zero point oscillations and light mass, the effects of

quantum tunnelling play an important role. Light impurities

such as atomic H or D stabilized in solid H2 and D2 may

move through the lattice by means of tunnelling and at low

enough temperatures behave similar to an ideal gas where

collective quantum phenomena related to Bose-Einstein

bserved. On the other hand,

effects of exchange interaction in the system are expected to

appear at high enough densities of H atoms. In our recent

work [1] we succeeded in reaching record high densities of

ur results of electron spin

resonance (ESR) and electron nuclear double resonance

(ENDOR) experiments with atomic hydrogen and deuterium

films in 4.6 T magnetic field at

ESR spectra of D and H atoms stabilized in solid

matrix at 300mK. Solid line corresponds to thermal

population of the hyperfine levels, dashed line:

H and/or D in solid H2/D2 crystals were

in two stages: 1) we deposited a thin film of solid

) onto a cold (< 1 K) surface of

a quartz microbalance, which served also as a mirror of

128-GHz Fabry-Perot resonator;

the molecules in the film by running an RF discharge in the

miniature helical resonator located nearby

study was performed using a cryogenic 128

spectrometer [3] which is optimized for reaching highest

sensitivity at very low (in the pW range) excitation po

Helical resonator placed near the sample was used for

making ENDOR of H atoms (f=910 MHz) and running RF

discharge in the sample cell. An additional varactor

coil (f=140 MHz) was arranged near the sample to carry out

ENDOR studies of D atoms.

Results We observed quantum isotopic exchange reactions

D+H2=H+HD and D+HD=H+D

the concentration of atomic hydrogen in H;D; H

films. ENDOR measurement provided information on the

trapping condition of the H and D atom

matrix. The presence of D2 molecules in vicinity of H and D

atoms was supported by observation of the holes in both

ESR spectra of H and D atoms during pumping the p

of the satellite lines. These satellite lines appear when

simultaneous spin flips of the electron of the atom and the

deuteron spin on a neighbouring D

found efficient dynamic nuclear polarization (DNP) of H in

D2 matrices via both Overhauser and solid effects.

suggest that interaction of electrons of the H atoms with

magnetic moments of ortho-D2

probabilities of forbidden transitions. In addition, pumping

the center of the H spectrum created negative DNP, the

effect not seen before in magnetic resonance experiment

We anticipate that this phenomenon may be related with

strong exchange effects of H atoms.

References [1] J.Ahokas, O.Vainio, S.Novotny, V.V.Khmelenko,

D.M. Lee and S.Vasiliev, Phys. Rev.B,

(2010) [2] S.Sheludiakov, J.Ahokas,

D.Zvezdov, S.Vasiliev, V.V.Khmelenko, S.Mao, and D.M.Lee, Rev. Sci. Instrum.

[3] S. Vasilyev, J. Järvinen, E. Tjukanoff, A. Kharitonov, and S. Jaakkola, Rev. Sci. Instrum.

Magnetic resonance study of atomic hydrogen and deuterium stabilized in solid H2 and D2 matrices below 1 K

Sheludiakov1, Janne Ahokas1, Jarno Järvinen1, Otto1,2, Sergey Vasiliev1, Vladimir Khmelenko3, Shun

Department of Physics and Astronomy, University of Turku, Finland

[email protected]

Kazan Federal University, 420008, 18 Kremlyovskaya St, Kazan, Russia

Department of Physics and Astronomy and Institute for Quantum Science and Engineering, Texas

University, College Station, Texas 77843, USA

quartz microbalance, which served also as a mirror of a

Perot resonator; 2) we dissociated part of

running an RF discharge in the

miniature helical resonator located nearby [2]. The ESR

study was performed using a cryogenic 128-GHz heterodyne

[3] which is optimized for reaching highest

sensitivity at very low (in the pW range) excitation powers.

Helical resonator placed near the sample was used for

making ENDOR of H atoms (f=910 MHz) and running RF-

discharge in the sample cell. An additional varactor-tuned

coil (f=140 MHz) was arranged near the sample to carry out

We observed quantum isotopic exchange reactions

=H+HD and D+HD=H+D2 which effectively increase

the concentration of atomic hydrogen in H;D; H2;D2 mixture

films. ENDOR measurement provided information on the

trapping condition of the H and D atoms in the molecular

molecules in vicinity of H and D

atoms was supported by observation of the holes in both

ESR spectra of H and D atoms during pumping the positions

of the satellite lines. These satellite lines appear when

taneous spin flips of the electron of the atom and the

deuteron spin on a neighbouring D2 molecule take place. We

found efficient dynamic nuclear polarization (DNP) of H in

matrices via both Overhauser and solid effects. We

lectrons of the H atoms with

molecules greatly enhances

probabilities of forbidden transitions. In addition, pumping

the center of the H spectrum created negative DNP, the

effect not seen before in magnetic resonance experiments.

We anticipate that this phenomenon may be related with

strong exchange effects of H atoms.

J.Ahokas, O.Vainio, S.Novotny, V.V.Khmelenko, Phys. Rev.B, vol. 81, 104516,

.Sheludiakov, J.Ahokas, O.Vainio, J.Järvinen, D.Zvezdov, S.Vasiliev, V.V.Khmelenko, S.Mao, and

Instrum. vol. 85, 053902, (2014) S. Vasilyev, J. Järvinen, E. Tjukanoff, A. Kharitonov,

Rev. Sci. Instrum. vol. 75, 94 (2004).

Magnetic resonance study of atomic hydrogen and deuterium

, Otto Vainio1, , Shun Mao3 and

Kazan Federal University, 420008, 18 Kremlyovskaya St, Kazan, Russia

ence and Engineering, Texas

Part III

Poster Session

Introduction Liquid crystalline compounds with strong polar

fragments are of great interest for electro

Earlier the 4-hexyloxy-(I) and 4-(ω-

4’(2,2-dicyanoethenyl)azobenzenes (II) were synthesized

and studied [1,2].

Two strong polar cyano groups result in increase in

dipole moment in comparison with monocyanosubstituted

azobenzenes and biphenyls. Moreover hydroxyl group in

molecule II can result in intermolecular H

formation and physicochemical properties modification. The

both compounds (I,II) are the monotropic liquid crystals.

This work was devoted to theoretical and experimental

study of these compounds structure by

spectroscopy and quantum-chemical calculations.

Experimental and computationalThe computations were carried out in the frame of density

functional by program PCGAMESS/Firefly.

B3LYP/6-311G(d, p) was used. The shielding terms

were calculated by GIAO method. Chemical shifts were

obtained from shielding terms. Chemical shifts of rapidly

exchanging 13C nuclei were averaged out. The

spectra of I,II solutions in CDCl3 were obtained with use of

spectrometer Bruker Avance III-500.

Results The optimization of molecular geometry

out, dipole moments, polarizability, its

theoretical 13C NMR spectra were calculated

13C NMR study of (2,2

Victor V. AlexandriVladimir A. Burmistrov

1Research Institute of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and

Technology, 153000 Ivanovo, Russia

E-mail: [email protected] of Solution Chemistry of Russian Academy of Sciences, 153045 Ivanovo, Russia


ne compounds with strong polar

fragments are of great interest for electro-optic materials.

-hydroxyhexyloxy)-

dicyanoethenyl)azobenzenes (II) were synthesized

I

II

oups result in increase in

dipole moment in comparison with monocyanosubstituted

azobenzenes and biphenyls. Moreover hydroxyl group in

molecule II can result in intermolecular H-bonded complex

formation and physicochemical properties modification. The

compounds (I,II) are the monotropic liquid crystals.

This work was devoted to theoretical and experimental

study of these compounds structure by 13C NMR

chemical calculations.

computational carried out in the frame of density

PCGAMESS/Firefly. The method

The shielding terms 13C

Chemical shifts were

obtained from shielding terms. Chemical shifts of rapidly

C nuclei were averaged out. The 13C NMR

were obtained with use of

geometry I,II was carried

its anisotropy and

calculated.

Figure 1

The durable correlation between calculated and

experimental data was observed in the case of trans

conformation of aliphatic substituents (Fig. 1).

Acknowledgements

This work was supported by The Russian Foundation for

Basic Research, project 12-03

RAS Presidium N 24.

References [1] Litov К.М. et al. // Liquid crystals and their

applications, 2013, No. 2, pp[2] Litov К.М. et al. // Liquid crystals and their

applications, 2013, No. 3, pp

y = 0,985x - 4,4198

R² = 0,9957

0

50

100

150

200

0 50 100

δδδδexp

y = 0,9872x - 4,3238

R² = 0,9945

0

50

100

150

200

0 50 100

δδδδexp

study of (2,2-dicyanoethenyl)-azobenzene derivatives

Alexandriysky1,2, Konstantin M. Litov1, Sofija A. KuvshinovaBurmistrov1,2

tute of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and

Technology, 153000 Ivanovo, Russia

[email protected]

Institute of Solution Chemistry of Russian Academy of Sciences, 153045 Ivanovo, Russia


I

II

Figure 1

durable correlation between calculated and

experimental data was observed in the case of trans-

conformation of aliphatic substituents (Fig. 1).

supported by The Russian Foundation for

03-00370-а, and Program of

Liquid crystals and their

pp. 5-12. Liquid crystals and their

pp. 5-13.

150 200

δδδδтеор

150 200

δδδδтеор

zobenzene derivatives

Kuvshinova1,

tute of Macroheterocyclic Compounds, Ivanovo State University of Chemistry and

Institute of Solution Chemistry of Russian Academy of Sciences, 153045 Ivanovo, Russia


Introduction Nanoparticles are being increasingly recognized for their

potential use in biological applications including

nanomedicine for cancer treatment. The response of normal

human cells to ZnO nanoparticles under different signaling

environments was investigated previously and compared to

the response of cancerous cells. As a result, ZnO

nanoparticles exhibit a strong preferential ability to kill

cancerous T cells, compared to normal cells [1,

ability is enhanced with transition metal ions doping.

Therefore careful investigation of local environment and

magnetic state of these ions is very important in the study of

potential use of ZnO nanoparticles for cancer cell treatment.

Experimental results An EPR study of ZnO nanoparticles, doped with Fe ions,

prepared using acetate method, was recently carried out [3].

Here we present the results of EPR investigations on two

types of ZnO nanoparticles, prepared using chemical

hydrolysis methods, in diethylene glyco

denatured ethanol solutions (QJ), respectively, doped with

0.5 – 10 % Fe3+ and Co2+, which were carried out at X

(9.5 GHz) at 5 K. To interpret the experimental results. EPR

spectra were simulated by exact diagonalization of the spin

Hamiltonian matrix, in order to identify the presence of Fe

and Co2+ ions at different magnetically active sites in these

samples. The simulation of EPR spectra for NL samples

revealed that they contained (i) Fe3+ and Co

substituted for Zn2+ ions, exhibiting axial Co

spectrum in crystalline ZnO; (ii) low intense EPR signals in

the samples with Co concentration more than 0.5% and less

that 5%; (iii) EPR spectrum due to surface oxygen defects;

and (iv) FMR (ferromagnetic resonance) from

ferromagnetically (FM) ordered area in ZnO nanoparticles

The EPR spectra for QJ samples are similar to those for NL

samples, however FMR signal is found more intense. No

EPR signals due to surface oxygen defects were observed in

QJ samples, as well no low intence EPR signals. The

ferromagnetism and EPR spectra are found to vary with

differences in the surface morphology of nanoparticles.

Origin of ferromagnetism Recently, Coey et al. [4] suggested new mechanism for

ferromagnetism nature, based on charge tra

oxides. They involved the model of Stoner ferromagnetism

Co2+ and Fe3+

potential use in cancer cell treatment

Sergey I. Androne

Institute of Physics

E-mail: [email protected] Department, Concordia University, Montreal, QC, H3G 1M8, Canada1E-mail: [email protected]

– 11, 2014 – 36 –

Nanoparticles are being increasingly recognized for their

potential use in biological applications including

nanomedicine for cancer treatment. The response of normal

r different signaling

environments was investigated previously and compared to

the response of cancerous cells. As a result, ZnO

nanoparticles exhibit a strong preferential ability to kill

cancerous T cells, compared to normal cells [1, 2]. This

enhanced with transition metal ions doping.

Therefore careful investigation of local environment and

magnetic state of these ions is very important in the study of

potential use of ZnO nanoparticles for cancer cell treatment.

tudy of ZnO nanoparticles, doped with Fe ions,

prepared using acetate method, was recently carried out [3].

EPR investigations on two

types of ZnO nanoparticles, prepared using chemical

hydrolysis methods, in diethylene glycol (NL), and in

denatured ethanol solutions (QJ), respectively, doped with

, which were carried out at X-band

(9.5 GHz) at 5 K. To interpret the experimental results. EPR

spectra were simulated by exact diagonalization of the spin-

miltonian matrix, in order to identify the presence of Fe3+

ions at different magnetically active sites in these

samples. The simulation of EPR spectra for NL samples

and Co2+ ions, which

ions, exhibiting axial Co2+ EPR

spectrum in crystalline ZnO; (ii) low intense EPR signals in

the samples with Co concentration more than 0.5% and less

that 5%; (iii) EPR spectrum due to surface oxygen defects;

and (iv) FMR (ferromagnetic resonance) from

rromagnetically (FM) ordered area in ZnO nanoparticles.

The EPR spectra for QJ samples are similar to those for NL

samples, however FMR signal is found more intense. No

EPR signals due to surface oxygen defects were observed in

ntence EPR signals. The

ferromagnetism and EPR spectra are found to vary with

differences in the surface morphology of nanoparticles.

Recently, Coey et al. [4] suggested new mechanism for

ferromagnetism nature, based on charge transfer in defected

oxides. They involved the model of Stoner ferromagnetism

for explanation of ferromagnetism origin. In this model

paramagnetic impurity ions are not ordered and

ferromagnetism arises due to defect band electron structure

of semiconducting ZnO. In this model, Fe

and ferromagnetically ordered area exist separately. This

model can be applied to semiconducting ZnO.

Conclusion The main conclusions of our EPR investigations of ZnO

nanoparticles are as follows:

(i) The observed EPR spectra provide clear evidence for

the presence of both paramagnetic localized Fe

ions exhibiting sharp lines, as well as FMR lines, due to

ferromagnetically coupled area, producing very broad

signal. Fe3+ and Co2+ EPR lines are broadened due t

distribution of oxygen defects near surface. Both the

paramagnetic Fe3+ and Co2+ ions and the ferromagnetic

components are present in NL and QJ samples. EPR

linewidth of Co2+ in QJ samples is much larger, than in NL

samples.

(ii) EPR signal, due to surface oxygen defects, was

clearly observed in NL samples, but not in QJ samples. This

explains the smaller magnetic moment observed in NL

samples, where not all oxygen defects involved in

ferromagnetic ordering. QJ samples, on the other hand,

exhibit intense FM resonance signals, suggesting that all

oxygen defects in them are magnetically coupled. This

accounts for their stronger ferromagnetism.

Acknowledgements This work is supported by the Natural Science and

Engineering Research Council of Canada (NSE

SIA thanks the Ministry of Education and Science (RNP

for support.

References [1] A. Thurber, D. G. Wingett, J. W. Rasmussen, J. Layne,

L. Johnson, D. A. Tenne, J. Zhang, C. B. Hanna, A. Punnoose. – Nanotoxycology,

[2] C. Hanley, J. Layne, A. Punnoose, K.M. Reddy, I. Coobs, A. Coobs, K. Feris, D. Wingett. Nanotechnology, 19, 295103 (2008).

[3] S.K. Misra, S.I. Andronenko, A. Thurber, A. Punnoose, A. Nalepa. – J. Magn. Magn Mater.

[4] J. M. D. Coey, P. Stamenov, P. D. GVenkatesan, K. Paul. – New.

(2010).

3+ EPR study of magnetic ZnO nanoparticles for its potential use in cancer cell treatment

Andronenko, Sushil K. Misra1

Institute of Physics, Kazan Federal University, Kazan, 420008, Russia


Physics Department, Concordia University, Montreal, QC, H3G 1M8, Canada


for explanation of ferromagnetism origin. In this model

paramagnetic impurity ions are not ordered and

ferromagnetism arises due to defect band electron structure

ZnO. In this model, Fe3+ and Co2+ ions

and ferromagnetically ordered area exist separately. This

model can be applied to semiconducting ZnO.

The main conclusions of our EPR investigations of ZnO

spectra provide clear evidence for

the presence of both paramagnetic localized Fe3+ and Co2+

ions exhibiting sharp lines, as well as FMR lines, due to

ferromagnetically coupled area, producing very broad

EPR lines are broadened due to wide

distribution of oxygen defects near surface. Both the

ions and the ferromagnetic

components are present in NL and QJ samples. EPR

in QJ samples is much larger, than in NL

surface oxygen defects, was

clearly observed in NL samples, but not in QJ samples. This

explains the smaller magnetic moment observed in NL

samples, where not all oxygen defects involved in

ferromagnetic ordering. QJ samples, on the other hand,

ense FM resonance signals, suggesting that all

oxygen defects in them are magnetically coupled. This

accounts for their stronger ferromagnetism.

This work is supported by the Natural Science and

Engineering Research Council of Canada (NSERC, SKM).

SIA thanks the Ministry of Education and Science (RNP-31)

A. Thurber, D. G. Wingett, J. W. Rasmussen, J. Layne, L. Johnson, D. A. Tenne, J. Zhang, C. B. Hanna, A.

Nanotoxycology, 6, 440-452 (2012). . Layne, A. Punnoose, K.M. Reddy, I.

Coobs, A. Coobs, K. Feris, D. Wingett. – , 295103 (2008).

S.K. Misra, S.I. Andronenko, A. Thurber, A. Punnoose, J. Magn. Magn Mater., 363, 82-87 (2014).

J. M. D. Coey, P. Stamenov, P. D. Gunning, M. New. J. Phys., 12, 053025

dy of magnetic ZnO nanoparticles for its

Physics Department, Concordia University, Montreal, QC, H3G 1M8, Canada

Introduction In this paper we report on additional technical capabilities

that were found in a typical MRI scannerS50 (0.5 T). These may be employed for a wide range of NMR applications – high resolution NMR (MRS), MRI and NQR. The main attention idetecting fluorine (19F) signals. Interest in this nucleus consists in prospects to use perfluorocarbonssubstitutes and MRI contrast in medicine

Materials and methods This study was initially focused on registering fluorine

nuclei. It turned out that the resonant circuit, which includes a built-in magnet gap transmitter coil, is proton NMR frequency (21.08 MHz). It on the fluorine NMR frequency (19.83 MHz)were looking for other options for the transmitter coiladopted firm resonator intended for the study of the knee.By modifying its electronic components it has been transformed to work as a transceiver. Measurements were preceded by experiments using the homemade transceiver probeheads. As a result we have gained experience registering MRS not only from the proton 19F, but other nuclei - phosphorus 31P, carbon 2D. Their resonant frequencies are respectively, 8.53, 5.30 and 3.24 MHz. For some nuclei other than protons (31P), technique to obtain MRI images was debuggedaddition, 35Cl NQR signal from powdered KClOoutside of the polarizing magnet was successfully

Results By optimizing the parameters of the

(design and location), MRS is possible without the longterm accumulation of signals. A large number of scans (~10or more) is required only for nuclei with low natural abundance - 13C, 2D. The MRS and NQR from other above mentioned nuclei were recorded with a single scan. The same applies to isotopically enriched nuclei.MRS and MRI are shown in Figure 1.

Left: the 19F MRS and MRI (one of 5 slices in two projections) from a cylindrical vessel (H/

Figure 1. MRI, MRS and NQR specta which

Registration of magnetic resonance from nuclei other than protons on 0.5 Tesla MRI scanner

Nikolay V. Anisimov

Faculty of Fundamental Medicine, Lomonosov Moscow State University, Moscow, Russia


19F


In this paper we report on additional technical capabilities that were found in a typical MRI scanner – Bruker Tomikon

. These may be employed for a wide range of NMR spectroscopy

NQR. The main attention is directed to signals. Interest in this nucleus

luorocarbons as blood [1].

This study was initially focused on registering fluorine It turned out that the resonant circuit, which includes

is tuned only on the (21.08 MHz). It can be not retuned

frequency (19.83 MHz). Therefore, we were looking for other options for the transmitter coil and adopted firm resonator intended for the study of the knee.

electronic components it has been . Measurements were

preceded by experiments using the homemade transceiver s a result we have gained experience

not only from the proton 1H and fluorine P, carbon 13C, deuterium

D. Their resonant frequencies are respectively, 8.53, 5.30 or some nuclei other than protons (19F and

), technique to obtain MRI images was debugged. In Cl NQR signal from powdered KClO3 placed

successfully registered.

parameters of the transceiver coils possible without the long-large number of scans (~103

or more) is required only for nuclei with low natural and NQR from other above

mentioned nuclei were recorded with a single scan. The same applies to isotopically enriched nuclei. Examples of

(one of 5 slices in two from a cylindrical vessel (H/Ø = 4/2 cm) filled

with perfluorocarbon. These MR images were obtained in 1 minute using multiple spin-echo ETL=8, (in-plane resolution 1 mm, slice thickness 1 cm.

Center: 13C MRS of ethanol after 1.5 hours signal accumulation, Right: 35Cl NQR spectrum from from powdered KClO3 after one scan.

Discussion It is interesting that according to firm documentation

MRI transceiver tract is not suitableother than protons. Indeed, an output RF amplifier LPPA 2120 (Dressler) and a preamplifier with filter X-BB31P have the bandwidthsand 12-32 MHz respectively. Really their bandwidths are much broader. Probably the MRI manufactureronly in narrowly targeted use of its products. declares only those characteristics that lead away from the temptations to use the equipment for questionapplications. May be that’s whyspecially designed so that it cannot be

Conclusion We revealed significant potential for use of the MR

scanner for multi-nuclear magnetic resonance applications. The results obtained by MRI and MRS fluorine nuclei give reason to hope that the registration of these nuclei can be carried out and not only in studies of laboratory animals , but also man. Obvious the registration of the NMR spectra in weak fields (0.5 T) is of only MRI is of interest in any field. But registration of nuclei other than protons and fluorine in weak fields is while not widespread due to insufficiently high sensitivity of the method. As for NQR, this method is now little used in structural studies, not at least because of the lack of specialized equipment. MRI and NMR spectroscopy equipment can be adapted to solve this problem.

References [1] G. Schnur, R. Kimmich, R. Lietzenmayer.

Reson. Med., 13 (3), 478-489 (1990).[2] Tomikon - Avance System. Technical Description.

Doc. No.: T2J-1122, T4-J1133

specta which were obtained using 0.5 T MRI scanner. Spectrum widths are 3.2, 2, 40 kHz

Registration of magnetic resonance from nuclei other than protons on 0.5 Tesla MRI scanner

Anisimov, O. Pavlova, M. Gulyaev, A. Samoylenko



35Cl

13C


These MR images were obtained in 1 echo - TR/TEmin=470/12.5 ms,

plane resolution 1 mm, slice thickness 1 cm. C MRS of ethanol after 1.5 hours signal

Cl NQR spectrum from from

according to firm documentation, the suitable for registration of nuclei

other than protons. Indeed, an output RF amplifier LPPA preamplifier HPPR (Bruker) equipped

BB31P have the bandwidths declared: 19-22 ely. Really their bandwidths are

MRI manufacturer is interested only in narrowly targeted use of its products. Therefore it declares only those characteristics that lead away from the temptations to use the equipment for questionable

May be that’s why transmitter coil was specially designed so that it cannot be tuned to 19.83 MHz.

We revealed significant potential for use of the MR nuclear magnetic resonance applications.

ined by MRI and MRS fluorine nuclei give reason to hope that the registration of these nuclei can be carried out and not only in studies of laboratory animals ,

stration of the NMR spectra (0.5 T) is of only methodological interest.

MRI is of interest in any field. But registration of nuclei other than protons and fluorine in weak fields is while not widespread due to insufficiently high sensitivity of the method. As for NQR, this method is now little used in

uctural studies, not at least because of the lack of specialized equipment. MRI and NMR spectroscopy equipment can be adapted to solve this problem.

G. Schnur, R. Kimmich, R. Lietzenmayer. - Magn.

489 (1990). vance System. Technical Description.

J1133 (1996).

Spectrum widths are 3.2, 2, 40 kHz

Registration of magnetic resonance from nuclei other than protons

Samoylenko, Yu. Pirogov



Introduction Methods for evaluating the content of

human body are described. They are based on the analysis of MR images and recording the NMR spectra of the body. Particular attention is paid to the spectroscopic method, where the evaluation is made by intensities ratio of water and fat peaks. Early measwere performed on mice by a high field [1]. Interest in such measurements is due to the fact tare easy to implement and take little time. thing is that there is correlation between the of peaks and the content of fat in the body of an animalaim of our work was to adapt the method laboratory animals to human studies.

Materials and methods The measurements were performed on a standard

(horizontal bore magnet) 0.5 Tesla MRTomikon S50). NMR spectra were recorded the body, and then summed. In the total spectrumwater and fat were defined - figure 1. The analysis of intensities (IW and IF) gave information aboutfat in the human body.

Figure 1: Left: arrangement of scanned slices;

Center: NMR spectra from each slice;

Right: total (whole-body) NMR sp

Registration of the NMR spectra from all parts of the human body was carried out in a homogeneous field. To do this, the patient's body was along the horizontal axis of the magnet. Scanning area limited by slice thickness of 20 cm. Slice direction was perpendicular to the mentioned axis.

Whole-body NMR spectroscopy as a tocomposition

Nikolay V. Anisimov


E-mail: [email protected] Institute of Chemical Physics, Moscow, Russia

– 11, 2014 – 38 –

ds for evaluating the content of fatty tissue in the They are based on the analysis of

and recording the NMR spectra of the whole s paid to the spectroscopic

method, where the evaluation is made by analysis of the ks. Early measurements

high field NMR spectrometer due to the fact that they

plement and take little time. But the main correlation between the intensity ratio

fat in the body of an animal. The pt the method used on small

he measurements were performed on a standard (horizontal bore magnet) 0.5 Tesla MR scanner (Bruker

spectra were recorded from all parts of summed. In the total spectrum, peaks of

he analysis of peak about the content of

Figure 1: Left: arrangement of scanned slices;

each slice;

NMR spectrum

the NMR spectra from all parts of the homogeneous magnetic

was moved stepwise . Scanning area was Slice direction was

axis. Local NMR

spectroscopy scanning methods were usedlocation and its thickness. Theseinhomogeneous (gradient) fielsynchronous with exciting RF pulses [2]

NMR data were compared with the average density of the body ρ=m/V, where m and V are body mass (kg) and volume (m3) for each object of research accordingly, as well as the volume of fat VF determined by MR images. There were T1 and T2-FSE weighted images (in0.23 mm, slice thickness 10 mm). Abdominsubcutaneous fat areas were determined visually by anatomical landmarks [3]. Segmentation of these areas and areas inside hypodermic fat was carried out [4]. It gave possibility to count the volume of body fat and the volume of whole body respectively.

Results The measurement results for the

and 2 males) are presented in the table below.

Table 1

f1 f2 f3 f4 ρ 960 985 997 1000

IF/IW 0.97 0.84 0.93 0.77VF/V - 0.46 0.42 -

One can notice that both parameters approximately linearly dependent on average density of the body. In particular it indicates to correlation between fat content in human body and intensity of fat peak in the whole body NMR spectrum.

The problem connected withwas revealed. Width of the lines appeared to be comparablewith the distance between them. It leads to the difficulties not only of measuring integrals of spectral lines but also the differentiation of peaks. Because of this in low field one can obtain a doubtful result for a very lean subject IF/IW for m8 (marked with an asterix) in the table

Conclusion Measurements indicate a correlation between the average

density of body and fat in it. It of work [1]. It is preferable measurements at a stronger magnetic field (to obtain whole body high resolution NMR spectra.

References [1] P. Mystkowski, et al. - Int J Obes Relat Metab Disord

2000, 24 (6), 719-724. [2] A. N. Garroway, P. K. Grannell,

C7, 1974, 457-462. [3] E. L. Thomas, et al. - J Appl P

85. [4] N. V. Anisimov, et al. - Proc. EUROMAR

body NMR spectroscopy as a tool to assess human body

nisimov, E. Shalamova, K. Volkova, M. Gulyaev


[email protected]

tute of Chemical Physics, Moscow, Russia

IW

IF

spectroscopy scanning methods were used to fix the slice location and its thickness. These methods use inhomogeneous (gradient) fields which are applied synchronous with exciting RF pulses [2].

NMR data were compared with the average density of the =m/V, where m and V are body mass (kg) and

) for each object of research accordingly, as well determined by MR images. There

FSE weighted images (in-plane resolution 0.23 mm, slice thickness 10 mm). Abdominal and subcutaneous fat areas were determined visually by

Segmentation of these areas and areas inside hypodermic fat was carried out [4]. It gave possibility to count the volume of body fat and the volume

the 8 test subjects (6 females are presented in the table below.

f5 f6 m7 m8 1000 1014 1016 1045 1175 0.77 0.63 0.61 0.31 0.42*

0.32 - - 0.27

One can notice that both parameters IF/IW and VF/V are approximately linearly dependent on average density of the

it indicates to correlation between fat content in human body and intensity of fat peak in the whole

The problem connected with low magnetic field (0.5 T) idth of the lines appeared to be comparable

een them. It leads to the difficulties s of spectral lines but also the

differentiation of peaks. Because of this in low field one can obtain a doubtful result for a very lean subject – see value

sterix) in the table.

indicate a correlation between the average is consistent with the results

s preferable to perform spectroscopic measurements at a stronger magnetic field (1.5 T and more) to obtain whole body high resolution NMR spectra.

Int J Obes Relat Metab Disord,

Grannell, P. Mansfield - J Phys

J Appl Physiol, 1998, 85, 1778-

Proc. EUROMAR-2008, 254.

ol to assess human body

Gulyaev, A. Samoylenko1


Introduction Recently, there has been a renewed interest in the Earth’s field

nuclear magnetic resonance spectroscopy (EFNMR), whicbeen known for more than 60 years [1, 2]. It has attracted an attention of researchers as inexpensive alternative to the high resolution NMR spectrometers in a number of applications. As early as in 1965, G. Bene et al. showed that it is possible to measure heteronuclear J-couplings in the Earth’s field NMR [3]. It has also been stressed that some information accessible in low fields is hard to obtain in high fields [4], e.g. there are the benefits in the relaxation measurements made at low fields [5important fields for potential EFNMR applications are security scanning devices [8, 9], and the MRI imaging combined with MEG in medicine [10]. However, improvement of the signal to noise ratio (SNR) and spectral resolution (SR) are the crucialorder to use this technique effectively. Thus, new effective approaches and ideas must be developed in order to increase the low SNR and SR in the EFNMR measurements.

Figure 1. Shimming coils attached to a wood box

Experimental setup Our EFNMR setup consists of Magritek

MHz) KEA-2 NMR console. A pulse current source has been constructed to apply the DC current pulses to the polarizing coil. Serially-connected active and passive filters have been developed to filter the low/high frequency noise (i.e., 50 Hz harmonics) and to increase the SNR. The active filter works at a 200 Hz (narrow) band. The cut-off frequency of passive filter (high pass) is 1

Experimental results The transmitting/receiving probe has been constructed

gradiometer coil. The probe is composed of two coils wound on opposite directions in order to mitigate the noise effect of radiofrequency interference (RFI). The probe was placed in the 7 mm thick aluminium box and additionally a double copperaluminium metal folio was wrapped around the probe to decrease further the SNR. All these measures have resulted in about 65 dB of the RFI. As additional measure to increase the SNR, the prepolarization technique has been used. In this technique, a polarizing magnetic field of 100 Oe, orthogonal to the Earth’s field, is applied to the sample. As result of pretechnique the SNR is increased by factor of 250. The prepolarization coil consists of 3 layers, each of 125 turns wounded with 1 mm thick copper wire on a teflon cylindrical frame. In the standard laboratory conditions the uniformity of Earth’s magnetic

Development of (EFNMR) setup

Erdem Balcı, HakkıPavel A. KupriyanovArtur R. Lozovoy

Gebze Institute of Technology, 41400, Gebze

E-mail: erdembalcı[email protected] Petersburg State Univer2Kazan Federal Volga


Recently, there has been a renewed interest in the Earth’s field nuclear magnetic resonance spectroscopy (EFNMR), which has been known for more than 60 years [1, 2]. It has attracted an attention of researchers as inexpensive alternative to the high resolution NMR spectrometers in a number of applications. As early as in 1965, G. Bene et al. showed that it is possible to

couplings in the Earth’s field NMR [3]. It has also been stressed that some information accessible in low fields is hard to obtain in high fields [4], e.g. there are the benefits in the relaxation measurements made at low fields [5-7]. Another important fields for potential EFNMR applications are security

9], and the MRI imaging combined with MEG in medicine [10]. However, improvement of the signal to noise ratio (SNR) and spectral resolution (SR) are the crucial points in order to use this technique effectively. Thus, new effective approaches and ideas must be developed in order to increase the low SNR and SR in the EFNMR measurements.

ng coils attached to a wood box

Magritek low-frequency (0-1 NMR console. A pulse current source has been

constructed to apply the DC current pulses to the polarizing coil. connected active and passive filters have been developed

gh frequency noise (i.e., 50 Hz harmonics) and to increase the SNR. The active filter works at a 200 Hz (narrow)

off frequency of passive filter (high pass) is 1 kHz.

The transmitting/receiving probe has been constructed as the gradiometer coil. The probe is composed of two coils wound on opposite directions in order to mitigate the noise effect of radiofrequency interference (RFI). The probe was placed in the 7 mm thick aluminium box and additionally a double copper-

inium metal folio was wrapped around the probe to decrease further the SNR. All these measures have resulted in about 65 dB of the RFI. As additional measure to increase the SNR, the pre-polarization technique has been used. In this technique, a

magnetic field of 100 Oe, orthogonal to the Earth’s field, is applied to the sample. As result of pre-polarization technique the SNR is increased by factor of 250. The pre-polarization coil consists of 3 layers, each of 125 turns wounded

opper wire on a teflon cylindrical frame. In the standard laboratory conditions the uniformity of Earth’s magnetic

field is usually low due to presence of magnetic materials around the EFNMR setup (e.g. due to iron items in the lab and in the construction wall). Therefore, the shimming should be applied to compensate the gradient of the Earth’s magnetic field and to obtain the better SR. For that we constructed a shimming system, consisting of a 3 sets of paired coils for each orthogonal axes of x, y and z. A wood box of cubical shape (outside of aluminium shielding box) has been used as a fixture for the coils (Fig. 1).

Experimental tests of the EFNMR setup have been performed on H2O and Fluorine samples. The long decay time of free induction decay signal of the H2O sample reveals rather good homogeneity of the Earth’s magnetic field (Fig.

Figure 2. Free Induction Decay (FID) signal of the H

Conclusions We have developed and tested the EFNMR system, consisting

of KEA-2 NMR unit, polarizing coil, the gradiometer RF probe, RF shield box, a metal folio wounded around coil and shimming coils. It has been demonstrated that the system improves the SNR and the SR for several orders of magnitude. Further research is planned to apply the constructed EFNMR setup in the studies of various compounds and to develop the security scanning system.

Acknowledgements This work is supported by the TÜBĐTAK/RFBR joint project

programme, grant No. 212T131/13-

References [1] M. Packard, R. Varian. Phys. Rev.

[2] P.M. Borodin, A.V. Melnikov, A.A. Morozov, Yu.S. Chernyshev. Nuclear Magnetic Resonance in EUniversity, 1967 (in Russian).

[3] Duval E, Ranft J, Bene G. J. Mol.

[4] Aleš Mohorič, Janez Stepišnik, Prog. Nucl. Magn. Reson. Spectros.54 (3) (2009) 166-182.

[5] S.H. Koenig, D. Adams, D. Emerson, C.G. HarrRC 10116, IBM Research division, 1983.

[6] G.J. Bene, B. Borgard, E. Hiltbrand, P. Magnin. Lond. B 289 (1980) 501–502.

[7] G. Planinšič, J. Stepišnik, M. Kos. 170–174.

[8] H. Sato-Akaba, H. Itozaki. Appl. Magn. Reson.

[9] Espy M, Flynn M, Gomez J, et al. Supercond. Sci. Technol. 23 (2010) 034023.

[10] V.S. Zotev, A.N. Matlachov, P.L. Volegov, et al.Supercon. 17 (2) (2007) 839–842.

Development of Earth`s field nuclear magnetic resonance setup for applications in security scanning devices

, Hakkı Acar, Georgy V. Mozzhukhin, Bulat Z. Kupriyanov1, Alexander V. Ievlev1, Yury S. ChernyshevLozovoy2, Ruslan V. Archipov2

Gebze Institute of Technology, 41400, Gebze-Kocaeli, Turkey

mail: erdembalcı[email protected]

Saint Petersburg State University, 198504 Saint Petersburg, Russian Federation

Kazan Federal Volga-region University, 420009 Kazan, Russian Federation


field is usually low due to presence of magnetic materials around the EFNMR setup (e.g. due to iron items in the lab and in the

wall). Therefore, the shimming should be applied to compensate the gradient of the Earth’s magnetic field and to obtain the better SR. For that we constructed a shimming system, consisting of a 3 sets of paired coils for each orthogonal axes of x,

A wood box of cubical shape (outside of aluminium shielding box) has been used as a fixture for the coils (Fig. 1).

Experimental tests of the EFNMR setup have been performed O and Fluorine samples. The long decay time of free

O sample reveals rather good homogeneity of the Earth’s magnetic field (Fig. 2).

Free Induction Decay (FID) signal of the H2O sample

We have developed and tested the EFNMR system, consisting coil, the gradiometer RF probe,

RF shield box, a metal folio wounded around coil and shimming coils. It has been demonstrated that the system improves the SNR and the SR for several orders of magnitude. Further research is

EFNMR setup in the studies of various compounds and to develop the security scanning system.

This work is supported by the TÜBĐTAK/RFBR joint project -03-91372_CT_a.

Phys. Rev. 93 (1954) 941. P.M. Borodin, A.V. Melnikov, A.A. Morozov, Yu.S. Chernyshev. Nuclear Magnetic Resonance in Earth’s field. 232 p., Leningrad State

J. Mol. Phys. 9 (1965) 427. Prog. Nucl. Magn. Reson. Spectros.

S.H. Koenig, D. Adams, D. Emerson, C.G. Harrison, Research report RC 10116, IBM Research division, 1983. G.J. Bene, B. Borgard, E. Hiltbrand, P. Magnin. Phil. Trans. R. Soc.

G. Planinšič, J. Stepišnik, M. Kos. J. Magn. Reson. A 110 (1994)

Appl. Magn. Reson. 43 (2012) 579. Espy M, Flynn M, Gomez J, et al. Supercond. Sci. Technol. 23

V.S. Zotev, A.N. Matlachov, P.L. Volegov, et al. IEEE T. Appl.

field nuclear magnetic resonance applications in security scanning devices

Rameev, ernyshev1,

sity, 198504 Saint Petersburg, Russian Federation

region University, 420009 Kazan, Russian Federation


Introduction The modern development of MR

provided an opportunity to study

compounds or metabolites in a variety of

processes affecting CNS in vivo. In addition t

MRI proton MR-spectroscopy (1H-MRS)

shed light on understanding of the pathophysiology of

multiple sclerosis (MS) and response to therapeutic

treatment. With the help of MRS biochemical

their course in time can be analyzed.

choline and lactate increase at demyelinating process

reflecting inflammation and demyelination,

followed by reduction of NAA in most foci. That

damage or loss of axons (Dong-Hyun Kim

of NAA is perhaps the most informative spectral value

the level of losses in NAA reflects severity o

axons and correlates with the level of disability

phase (Ponnada A. Narayana, 2005).

restoration of NAA might happen with time

Experimental Methods Proton MR-spectroscopy of the brain was performed on a

MR scanner Siemens «Magnetom Symphony»

magnetic field strength of 1.5 Tesla. MRI examination

included following steps:

• positioning the patient under examination;

• performing of traditional MRI;

• conducting MR spectroscopy on hydrogen;

• performing of MRI of the brain after intravenous

administration of contrast agent;

• spectrogram analysis, constructing

colored maps of metabolite distribution and their

In this paper we have analyzed data of 6 pat

suffering from multiple sclerosis. Thus, changes in

metabolites in 16 MS plaques were studied.

In order to get MR spectra the methodology

Volume Spectroscopy (MVS) was used.

were obtained for each patient.

Results and Discussion The following metabolites were determined in the MR

spectrum: N – acetylaspartate (NAA)

creatine (Cr) (Fig. 1).

In all patients, the lactate peak (Lac) and lipids (Lipid)

were not detected in the spectrum.

Additionally, according to the data provided by

contrast enhancement only one plaque out

accumulated the contrast agent as on the diffuse type.

Application of magnetic resonance spectrosof multiple sclero

Yu. V. Bogachev

Department of Physics1S.M. Kirov Military Medical Academy

– 11, 2014 – 40 –

MR-spectroscopy has

certain chemical

compounds or metabolites in a variety of pathologic

. In addition to traditional

MRS) has significantly

understanding of the pathophysiology of

and response to therapeutic

biochemical changes and

their course in time can be analyzed. In acute plaques

inating process early,

reflecting inflammation and demyelination, which is

NAA in most foci. That reflects

Kim, 2012). The peak

most informative spectral value, and

severity of damage of

the level of disability in the late

A partial or full

with time [1].

the brain was performed on a

«Magnetom Symphony» with a

. MRI examination

positioning the patient under examination;

opy on hydrogen;

MRI of the brain after intravenous

of parametric and

distribution and their ratios.

data of 6 patients

multiple sclerosis. Thus, changes in

metabolites in 16 MS plaques were studied.

methodology of Multi

(MVS) was used. 64 MR-spectra

were determined in the MR-

(NAA), choline (Cho),

peak (Lac) and lipids (Lipid)

provided by MRI with

contrast enhancement only one plaque out of 16 investigated

diffuse type.

Figure 1. MR spectrum of ill

of the brain

The results show that average concentration

MS plaques decreased by 14.5% compared with the norm

The average concentration of Cho in

by 9.9% compared to the norm.

The ratio of NAA / Cr in the plaque of multiple sclerosis

decreased compared to the same area in the heal

hemisphere by 15.5%. At the same time the ratio of Cho / Cr

increased by 2.3% in the demyelination

Figure 2. The ratios of metabolites in the site of

demyelination and normal white matter of the brain

Subsequent MRS showed changes in

relative concentrations of the metabolites in plaques of

multiple sclerosis in a patient. The

demyelination focus increased

initial examination. In the second

in the third – by 38%.

In this paper, we confirmed

spectroscopy on hydrogen one

of the MS disease and determine

References [1] Yu. V. Bogachev, O.A. Cherdakov, V.A. Fokin.

Magnetic resonance imaginmultiple sclerosis // Izvestia SPbSETU “LETI”

No.3. P. 7 – 15.

0,00

1,00

2,00

3,00

NAA/Cr Cho/Cr

Application of magnetic resonance spectroscopy in the diagnostics of multiple sclerosis

Bogachev, V. A. Fokin1, O. A. Cherdakov, D. Yu. Sugonyako

Department of Physics, Saint Petersburg Electrotechnical University “LETI”

Military Medical Academy

Figure 1. MR spectrum of ill portion of white matter

of the brain

average concentration of NAA in

by 14.5% compared with the norm.

he average concentration of Cho in MS plaques increased

The ratio of NAA / Cr in the plaque of multiple sclerosis

decreased compared to the same area in the healthy

At the same time the ratio of Cho / Cr

increased by 2.3% in the demyelination sector (Fig. 2).

The ratios of metabolites in the site of

ormal white matter of the brain

Subsequent MRS showed changes in absolute and

relative concentrations of the metabolites in plaques of

The ratio NAA/Cr in the first

by 77% compared to the

second focus it increased by 52%,

confirmed that according to MR

can follow the development

determine therapeutic effect.

Yu. V. Bogachev, O.A. Cherdakov, V.A. Fokin. Magnetic resonance imaging in the diagnostics of

Izvestia SPbSETU “LETI”. 2014.

Cho/Cr

Норма

РС

copy in the diagnostics

Sugonyako

“LETI”

Introduction The purpose of this study was to develop

experimental schemes of organic synthesis

water to give a yield of the comparable

with traditional methods of synthesis. As a test

chosen synthesis of 2 - (2-pyridyl) benzimidozol

from 1,2-phenylenediamine, and pyridine

Experiment Sub-and supercritical water (t ≤ 350

subcritical water; t > 350 °C, p > 218

water) has recently attracted attention as a universa

for chemical reactions. A characteristic

reactions is that the sub-and supercritical

non-toxic solvent with good varying

properties (due to changes in pressure and temperature

In the present study we explored the possibility of using

the synthesis as static installations and flow diagrams,

consisting of a high-pressure pump (up to 300 atm).

Especially constructed for the purpose of high

- stainless steel extractor, a pressure regulator

providing temperature control with temperature range up to

320 °C [2].

The effect of reaction parameters, such as temperature

pressure, flow rate and the reaction time of the reaction

studies.

NMR spectroscopy subcritical water

Sergey N. BorisenkoSvetlana N. Sushkova

1Research Institute

Russia, Rostov-on-2Ecological-Analytical Center, South Federal Un



velop and study of

of organic synthesis in subcritical

or better compared

As a test reaction was

benzimidozole started

phenylenediamine, and pyridine-2-carboxylic acid.

°C, p ≤ 218 bar -

bar - supercritical

has recently attracted attention as a universal medium

A characteristic feature of these

supercritical water acts as a

varying physicochemical

and temperature) [1].

In the present study we explored the possibility of using

the synthesis as static installations and flow diagrams,

pressure pump (up to 300 atm).

Especially constructed for the purpose of high-pressure cell

, a pressure regulator, a stove,

h temperature range up to

, such as temperature,

, flow rate and the reaction time of the reaction was

NH2

NH2

N

HOOC+

1 2

Analysis of the reaction products was performed by

spectroscopy. Depending on conditions of synthesis in the

reaction product observed the

various proportions.

These results indicate that the proposed pilot scheme may be

used for environmentally friendly (Green

synthesis of benzimidozole derivatives in

The benzimidozole derivatives synthesized in the subcritical

water could used for created the new

on glycyrrhizic acid [3].

Acknowledgements This work is supported financially by the RFBR grants

13-03-12275 (OFI-M) and 13-03

All measurements were performed on the equipment of

the Joint Science Centre of SFU “Molecular Spectroscopy”.

References [1] A.A. Galkin, and V.V. Lunin.

Reviews, 74 (1), 21-40 (2005).[2] A.V. Lekar, S.N. Borisenko, E.V.

Sushkova, and N.I. BorisenkoAgricultural and Biological Science

[3] S. N. Borisenko, A. V. Lekar_, E. V. Vetrova, and N. I. Borisenko.- Chemistry of Natural Compounds, Vol. 49 (5), 969-971, (2013).

NMR spectroscopy of benzimidazole derivatives subcritical water

Borisenko1, Anna V. Lekar1, Elena V. Vetrova1, SofyaSushkova1, Gennadii S. Borodkin1 and Nikolay

Institute of Physical and Organic Chemistry, South Federal University,

-Don

Analytical Center, South Federal University, Russia, Rostov-on

[email protected]


NH

N NH2O

3

Analysis of the reaction products was performed by NMR

. Depending on conditions of synthesis in the

the compounds 1, 2 and 3 in

These results indicate that the proposed pilot scheme may be

used for environmentally friendly (Green chemistry) organic

synthesis of benzimidozole derivatives in subcritical water.

atives synthesized in the subcritical

water could used for created the new “low-dose drug” based

This work is supported financially by the RFBR grants

03-01318А.

rformed on the equipment of


A.A. Galkin, and V.V. Lunin. - Russian Chemical

40 (2005). Borisenko, E.V. Vetrova, S.N.

N.I. Borisenko. - American Journal of

Agricultural and Biological Science, 9 (1), 1-5 (2013). S. N. Borisenko, A. V. Lekar_, E. V. Vetrova, and N. I.

Chemistry of Natural Compounds, Vol.

benzimidazole derivatives synthesized in

, Sofya L. Srabionyan, and Nikolay I. Borisenko2

South Federal University,

on-Don


Introduction Chalcogen containing compounds are a matter of the

great interest [1, 2]. From the other hand modern data on the hetercyclic tellurium-containing are comparatively sca[3]. In continuation of our investigations of organoselenium and organotellurium derivatives we have obtained and studied by NMR novel sulphurbenzotelluroazoles 1-3.

Results and Discussion Compound 1 was synthesized according to the fol

Scheme 1:

NaBH4, CS2

Te TeNH2NH2

HMPA

Scheme 1

This derivative can exist in two forms (Scheme 2):

Te

N

SH

1a

Scheme 2

IR spectrum of the solid sample of 1 demonstrates bands at 1315 and 3105 cm-1 which may be assigned to the stretching of C=S and N-H groups respectively. It may point to the realization of the form 1b in the solid state.

NMR spectra of 1 registered on the AVANCEspectrometer in DMSO-d6 show (ppm) the next signals (atom labeling see on Fig. 1): 1H - 7.09 (1H, dd, H7.27 (1H, dd, H-C6), 7.36 (1H, dd, H-C4), 7.73 (1H, dd, HC7), 13.36 (1H, s, HN); 13C - 114.73 (C4), 120.78 (C8), 123.86 (C5), 127.21 (C7), 132.14 (C6), 146.64 (C9), 195.41 (C2); 15N - 199.40; 125Te - 990.15.

Te

N

S

H

1

2

34

5

6

78

9

10

Figure 1

The final conclusion on the existence of the form 1a was made on the base of the correlation spectrum 1H-15N HMBC demonstrating distinct cross1H-15N.

Alkylation of 1 may occurs by two pathways (Scheme 3):

Synthesis and NMR 2-sulphurfunctionalized

Inna G. BorodkinaIgor S. VasilchenkoSvetlana B. ZaichenkoVladimir I. Minkin

1Institute of Physical and Organic Chemistry

344090, Rostov-on2Dagestan State Technical University, Shamilya str. 70, 3Dagestan State University4Physical Faculty of

– 11, 2014 – 42 –

Chalcogen containing compounds are a matter of the great interest [1, 2]. From the other hand modern data on the

containing are comparatively scarce [3]. In continuation of our investigations of organoselenium and organotellurium derivatives we have obtained and studied by NMR novel sulphur-functionalized

Compound 1 was synthesized according to the following

Te

N

SH

1

This derivative can exist in two forms (Scheme 2):

Te

N

S

H

1b

IR spectrum of the solid sample of 1 demonstrates bands 1 which may be assigned to the H groups respectively. It may point

to the realization of the form 1b in the solid state. NMR spectra of 1 registered on the AVANCE-600

d6 show (ppm) the next signals 7.09 (1H, dd, H-C5), C4), 7.73 (1H, dd, H-

114.73 (C4), 120.78 (C8), 123.86 (C5), 127.21 (C7), 132.14 (C6), 146.64 (C9), 195.41

n on the existence of 1 in solution in was made on the base of the correlation N HMBC demonstrating distinct cross-peak

may occurs by two pathways (Scheme 3):

Te

N

S

H

1

XR

- HX

Scheme 31H, 13C, 15N and 125Te spectra of compounds

labeling see on Fig. 2) demonstrate next ppm): 2 1H - 2.67 (3H, s, CH3), 7.08 (1H, dd, Hdd, H-C6), 7.80 (1H, dd, H-C4), 7.97 (1H, dd, H(C11), 123.30 (C5), 123.59 (C7), 123.60 (C133.16 (C8), 160.29 (C9), 168.64 (C986.05; 3 1H - 3.95 (2H, s, CH2

7.67 (2H, s+s, NH2), 7.35 (1H, dd, H7.97 (1H, dd, H-C7); 13C - 37.31 (C126.50 (C6), 131.92 (C7), 133.87 (C(C12), 169.13 (C2); 15N - 109.14 (N

Te

N

S

CH31

2

34

5

6

78

9

10

11

2

5

6

Figure 2

Interesting feature of the 1H NMR spectrum of inequality of proton signals of aminogroup that may be caused by participation of one proton in the formation of hydrogen bond.

1H-15N HMBC spectra of 2 and cross-peaks of N3 atom and alkyl hydrogens; it may mean that alkylation occurs by the sulfur atom (path

So, we have shown that unsubstituted 2mercaptobenzotellurazole exists as thione form alkylation proceeds to the sulfur atom.

Acknowledgements All measurements were performed on the equipment of


References [1] A. Panda. – Coord. Chem. Rev.

(2009). [2] A. Panda. – Coord. Chem. Rev.

(2009). [3] A.D. Garnovskii, G.S.Borodkin, A.S.

G.G. Sadikov, I.D. Sadekov,Maksimenko, I.S. Vasil'chenko, Sergienko, V.I. Minkin. – 767-773 (1999).

Synthesis and NMR study of the novel class of tellurazoles ulphurfunctionalized benzotellurazoles

Borodkina1, Gasan M. Abakarov2, Gennadii S. BorodkinVasilchenko1, P. A. Ramazanova3, Pavel B. Chepurnoi

Zaichenko1, Yuriy F. Mal’tsev4, Anatolii S. BurlovMinkin1

of Physical and Organic Chemistry, Southern Federal University, Stachki pr. 194/2,

on-Don, Russia, E-mail: [email protected]

Technical University, Shamilya str. 70, 367015, Dagestan Republic,

University, Gadjieva str. 43a, 367000 Makhachkala, Dagestan Republic,

Physical Faculty of Southern Federal University, Zorge str., 5, Rostov-on

Te

N

S

R

Te

N

S

R

a

b Scheme 3

Te spectra of compounds 2, 3 (atom labeling see on Fig. 2) demonstrate next signals (DMSO-d6,

), 7.08 (1H, dd, H-C5), 7.35 (1H, ), 7.97 (1H, dd, H-C7); 13C - 17.07

), 123.60 (C4), 126.56 (C6), ), 168.64 (C2); 15N - 173.73; 125Te -

2), 7.09 (1H, dd, H-C5), 7.24, ), 7.35 (1H, dd, H-C6), 7.80 (1H, dd, H-C4),

37.31 (C11), 123.53 (C5), 123.66 (C4), ), 133.87 (C8), 159.66 (C9), 166.50 109.14 (N3); 125Te - 1001.73.

Te

N

S

NH2

O

1

2

34

78

9

10

1112

133 ure 2

H NMR spectrum of 3 is y of proton signals of aminogroup that may be

caused by participation of one proton in the formation of

and 3 don’t demonstrate any atom and alkyl hydrogens; it may mean

e sulfur atom (path b, Scheme 3). So, we have shown that unsubstituted 2-

mercaptobenzotellurazole exists as thione form 1b but alkylation proceeds to the sulfur atom.

All measurements were performed on the equipment of SFU “Molecular Spectroscopy”.

Coord. Chem. Rev., 253, 1056-1098

Coord. Chem. Rev., 253, 1947-1965

A.D. Garnovskii, G.S.Borodkin, A.S. Antsyshkina, Sadekov, A.I. Uraev, A.A.

asil'chenko, I.G. Borodkina, V.S. Rus. J. Coord. Chem., 25,

tellurazoles –

Borodkin1, A.-M. M. Ali3, Chepurnoi1,

Burlov1,

Southern Federal University, Stachki pr. 194/2,

, Dagestan Republic, Russia

Dagestan Republic, Russia

on-Don, 344090, Russia

Introduction Zinc complexes of azomethine ligands are the matter of

interest as active layers for OLED devices owing to their

thermal stability with high temperature of vitrifaction, light

sublimation during formation of amorphous films,

variability of structures, comparative simplicity of their

synthesis, good photo- (PL) and electroluminescent (EL)

properties and electron-transfer characteristics.

Chelate complexes containing quinoline fragment are the

matter of the great interest. Tang and Van

tris(8-hydroxyqunolinato)aluminum, playing double role

both as light emitter and electro-transfer material,

construction of the first OLED device working at low

temperature.

In continuation of the efforts on the search of the

advanced PL and EL materials, usable

OLED devices, we have obtained novel aminomethylene

derivative of 1-phenyl-3-methyl

methyleneamino)-1-H-pyrazole-5-one with 3

aminoquinoline (I) and synthesized zinc and cadmium

complexes (II, III) on its base.

Results and Discussion Compound I as it shown by IR (νNH) and NMR spectra

data (double =CH- and –NH- signals) exists in ketimine

form (Fig. 1) both in solid and solution.

Zinc and cadmium complexes were obtained by coupling

the ligand with metal acetates in methanol. Disappearing the

NH stretching band in IR spectra and NH signal (as is

singlet character of CH signal) in 1H NMR spectra of

Heteronuclear and 2D NMR Investigation of PyrazoleLigand and its Zn and Cd Complexes

Inna G. BorodkinaАrtem V. DmitrievDmitrii A. GarnovskiiIgor S. VasilchenkoЕvgenii I. Mal’tsevGennadii S. Borodkin

1Institute of Physical and Organic Chemistry

Stachki pr. 194/2, 344090 Rostov

E-mail: [email protected] of Physics of Southern Federal University, Stachki ave. 194, R3A. N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Leninskii ave. 31/4,

Moscow 119991, Russia4Southern Scientific Centre of Russian Academy of Sciences, Chekhova ave. 41, R

Russia 5National Research Centre ‘‘Kurchatov Institute’’, Academician Kurchatov sq. 1, Moscow, Russia6A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of

Vavilova str. 28, M7Southern Federal University, Sadovaya str. 105/42, Rostov8Physical Faculty of Southern Federal University, Zorge str., 5, Rostov


nc complexes of azomethine ligands are the matter of

devices owing to their

thermal stability with high temperature of vitrifaction, light

sublimation during formation of amorphous films,

ative simplicity of their

(PL) and electroluminescent (EL)

transfer characteristics.

Chelate complexes containing quinoline fragment are the

Van Slyke [1] used

roxyqunolinato)aluminum, playing double role

transfer material, in

device working at low

In continuation of the efforts on the search of the

advanced PL and EL materials, usable for construction of

devices, we have obtained novel aminomethylene

methyl-4-(quinolyl-3-

one with 3-

and synthesized zinc and cadmium

as it shown by IR (νNH) and NMR spectra

signals) exists in ketimine

Zinc and cadmium complexes were obtained by coupling

the ligand with metal acetates in methanol. Disappearing the

tretching band in IR spectra and NH signal (as is

H NMR spectra of

complexes point to the deprotonation of the ligand molecule

under complexation

12

34

5

6

7

8

9 9

10 10

11

12 13

14

15 16

1718

19

202122

NN

CH3

OH

N

H

N

I

H

Figure 1

Signal of H(6) proton in

34.5 Hz) and signal of 113Cd (δ =

is comparatively seldom in registration of

spectra of cadmium metallochelates.

So, we have obtained novel zinc and cadmium

metallochelates of pyrazole-quinoline containing ligand

potential working elements for OLEDs.

Acknowledgements All measurements were performed on the equipment of


References [1] Tang C.W., Van Slyke S.A.

(1987).

Heteronuclear and 2D NMR Investigation of PyrazoleLigand and its Zn and Cd Complexes

Borodkina1, Anatolii S. Burlov1, Valerii G. VlasenkoDmitriev3, Vasilii V. Chesnokov1, Ali I. Uraev1, Garnovskii1,4, Yan V. Zubavichus5,6, Alexander A.

Vasilchenko1, Pavel B. Chepurnoi1, Dmitrii A. LypenkoMal’tsev3, Тatiana V. Lifintseva7, Yuriy F. Mal’tsev

Borodkin1

of Physical and Organic Chemistry, Southern Federal University,

Stachki pr. 194/2, 344090 Rostov-on-Don, Russia

[email protected]

Institute of Physics of Southern Federal University, Stachki ave. 194, Rostov

N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Leninskii ave. 31/4,

oscow 119991, Russia

entific Centre of Russian Academy of Sciences, Chekhova ave. 41, R

National Research Centre ‘‘Kurchatov Institute’’, Academician Kurchatov sq. 1, Moscow, Russia

N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of

Vavilova str. 28, Moscow 119991, Russia

Southern Federal University, Sadovaya str. 105/42, Rostov-on-Don 344006, Russian Federation

Physical Faculty of Southern Federal University, Zorge str., 5, Rostov-on


complexes point to the deprotonation of the ligand molecule

12

34

5

6

7

8

9 9

10 10

11

12 13

14

15 16

1718

19

202122

NN

CH3

OM/2

N

H

N

II: M = Zn, III: M = Cd

Figure 2

(6) proton in III is doublet (J3H(6)-Cd =

(δ = -580.71 ppm) is triplet that

is comparatively seldom in registration of 113Cd NMR

spectra of cadmium metallochelates.

So, we have obtained novel zinc and cadmium

quinoline containing ligand –

OLEDs.

All measurements were performed on the equipment of

SFU “Molecular Spectroscopy”.

Tang C.W., Van Slyke S.A. – Appl. Phys. Lett., 51, 913

Heteronuclear and 2D NMR Investigation of Pyrazole-Quinoline

Vlasenko2,

A. Trigub5, Lypenko3,

Mal’tsev8,

Southern Federal University,

ostov-on-Don, Russia

N. Frumkin Institute of Physical Chemistry and Electrochemistry of RAS, Leninskii ave. 31/4,

entific Centre of Russian Academy of Sciences, Chekhova ave. 41, Rostov-on-Don,

National Research Centre ‘‘Kurchatov Institute’’, Academician Kurchatov sq. 1, Moscow, Russia

N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,

Don 344006, Russian Federation

on-Don, 344090 Russia


Introduction The polymorphic transitions are the phase transitions

causing regrouping of molecules in crystals.

serious problems with the offer of mechanisms which could

explain, that actually occurs with molecules in time and in

space.

The purpose of the present work is researching of the

phase transitions in paradichlorobenzene

relaxometry methods with use of Laplace

inversion [1]. The choice of the paradichlorobenzene

sample is caused by that this substance was studied

wide range of experimental methods including NQR.

However, the mechanisms of phase transitions in

not been clarified in detail to the present time.

Results and discussion The experiments were performed on the

NQR spectrometer with TNMR software.

pulse sequences were used to measure the

Kinetics Exp TNMR script was used at studying processes

in time. The program RILT described in work

Marino [2] was used for inversion of Laplace

transformation. The polycrystalline samples were obtained

from the melt. The crystalline phase of the sample was

identified using known temperature dependen35Cl NQR frequencies for different paradichlorobenzene

phases.

Figure 1. 35

Cl NQR frequency change in the

from the β-phase to the α - phase of the p

at T =298 K, f0 = 34.26 MHz

Distributions of relaxation times T1, T1

β-phases of paradichlorobenzene are measured. The

The application of the NQR relaxometry fotransitions in the molecular crystals

Philipp Dolinenkov

1Immanuel Kant Baltic Federal University, A. Nevsky St. 14, 236041 Kaliningrad, Russia1E-mail: [email protected] State Academy, Molodi2E-mail: [email protected]

– 11, 2014 – 44 –

The polymorphic transitions are the phase transitions

causing regrouping of molecules in crystals. Thus there are

of mechanisms which could

explain, that actually occurs with molecules in time and in

The purpose of the present work is researching of the

paradichlorobenzene by NQR

Laplace transformation

paradichlorobenzene as a

substance was studied by a

of experimental methods including NQR.

However, the mechanisms of phase transitions in p-C6H4Cl2

esent time.

were performed on the Tecmag Apollo

TNMR software. The well-known

o measure the relaxation times.

was used at studying processes

described in work Iari-Gabriel

Marino [2] was used for inversion of Laplace

The polycrystalline samples were obtained

The crystalline phase of the sample was

identified using known temperature dependences of

NQR frequencies for different paradichlorobenzene

the phase transition

p-C6H4Cl2 with time

= 34.26 MHz

1ρ and T2* for α- and

are measured. The non-

thermal factors stimulating

investigated.

The effect of mechanical pretreatment of the sample

(grinding), causing mechanical stresses and changes in the

spectral and relaxation parameters of the sample and the

subsequent recovery is studied.

Multimodal character of distribution of spin

relaxation in the rotating frame

a mixture of amorphous and crystalline material.

Figure 2. Distributions of relaxation times T

β-phases of the paradichlorobenzene

Conclusion It is established, that after hardening of

the melt only β-phase is formed

spontaneously turns into a stable

material preliminary impregnated with th

spontaneous phase transition does not occur and

kept steadily.

Acknowledgement This work is partly supported by RFBR, research project

No. 14-03-00038a. Authors thanks for the support.

References [1] N. Sinyavsky, P. Dolinenkov, G.

Magn. Reson., 45 (5), 471–[2] Iari-Gabriel Marino, Regularized Inverse Laplace

http://www.mathworks.com/matlabcentral/fileexchange/6523-rilt/content/rilt.m

The application of the NQR relaxometry for the study of phase transitions in the molecular crystals

Dolinenkov1, Irina Korneva1,2, Nikolay Sinyavsky1,2

Immanuel Kant Baltic Federal University, A. Nevsky St. 14, 236041 Kaliningrad, Russia

[email protected]

Baltic State Academy, Molodiozhnaya St. 6, 236029, Kaliningrad, Russia

[email protected], [email protected]

phase transitions are

The effect of mechanical pretreatment of the sample

(grinding), causing mechanical stresses and changes in the

pectral and relaxation parameters of the sample and the

Multimodal character of distribution of spin-lattice

T1ρ is caused, apparently, by

a mixture of amorphous and crystalline material.

Distributions of relaxation times T1ρ in α- and

paradichlorobenzene

It is established, that after hardening of p-C6H4Cl2 from

phase is formed which in time

spontaneously turns into a stable α-phase. In the porous

material preliminary impregnated with the molten sample,

spontaneous phase transition does not occur and β-phase is

ly supported by RFBR, research project

00038a. Authors thanks for the support.

N. Sinyavsky, P. Dolinenkov, G. Kupriyanova. – Appl.

–482 (2014). Regularized Inverse Laplace. –

http://www.mathworks.com/matlabcentral/fileexchange

r the study of phase

Immanuel Kant Baltic Federal University, A. Nevsky St. 14, 236041 Kaliningrad, Russia

ozhnaya St. 6, 236029, Kaliningrad, Russia

Introduction MRI at low field (as EFNMR) and very low (less than the

Earth field) more and more become widespread subject of

research. In this aspect it is useful to consider effect of

concomitant fields for a concrete gradient system. It is

known the appearance of gradient of certain component of

potential field produces inevitably gradients of other,

orthogonal, components [1]. Magnetostatic fi

hence this effect is inherent to procedure of getting NMR

image [1]. This effect is negligible for practical MRT,

nevertheless it can be important in low field experiments:

The less a magnetostatic field strength is and the more a

gradient and the sample volume are, the more concomitant

gradients effects exhibit [2, 3].

The optimization of NMR-imager gradient magnetic system

An analysis of the contribution of concomitant gradient

magnetic fields to quality of magnetic resonance imaging is

made. Their revealing in the concrete gradient system,

namely in the system of two coaxial coils is considered

example. A design of such systems supposes the best

linearity of the magnetic field dependence on a coordinate

along the axe. in explored volume. But taking into account

the concomitant gradient effect requires to modify the

design parameters. The direct calculation of magnetic field

spatial distribution generating by a such system was

performed. The conditions of the smallest distortion are

determined.

Calculation methods The calculations of the magnetic field components out the

axe of a gradient system have carried out with known

integral formulas based on Bio – Savart

An optimization of the coil interspacing are made acc

to the criterion of standard deviation minimum for

dependence of the field total module from a straight line.

The numeric computations have performed with the

environment MathCad 14.

A reduction of concomitant magnetic fields effect through the optimization of the gradient magnetic system

Viatcheslav Frolov

Faculty of Physics, Saint Petersburg State University



MRI at low field (as EFNMR) and very low (less than the

and more become widespread subject of

aspect it is useful to consider effect of

concomitant fields for a concrete gradient system. It is

known the appearance of gradient of certain component of

potential field produces inevitably gradients of other,

orthogonal, components [1]. Magnetostatic field is potential,

hence this effect is inherent to procedure of getting NMR-

. This effect is negligible for practical MRT,

nevertheless it can be important in low field experiments:

The less a magnetostatic field strength is and the more a

t and the sample volume are, the more concomitant

imager

An analysis of the contribution of concomitant gradient

magnetic fields to quality of magnetic resonance imaging is

made. Their revealing in the concrete gradient system,

namely in the system of two coaxial coils is considered as an

. A design of such systems supposes the best

linearity of the magnetic field dependence on a coordinate

. But taking into account

the concomitant gradient effect requires to modify the

design parameters. The direct calculation of magnetic field

spatial distribution generating by a such system was

performed. The conditions of the smallest distortion are

The calculations of the magnetic field components out the

axe of a gradient system have carried out with known

Savart – Laplace low [4].

An optimization of the coil interspacing are made according

to the criterion of standard deviation minimum for z-

the field total module from a straight line.

The numeric computations have performed with the

Results Results of the concomitant gradient analysis

presented. The optimum parameters depend both on relation

of the maximum field generated by gradient system in

sample volume to the main static field, and on dimensions

and position of the sample.

Conclusion It is shown a magnetic field concomitant with a

longitudinal gradient enhances the nonlinearity of

coordinate dependence of the field. This misrepresents MRI

because of scale variations within investigated object. To

minimize the harmful effect, it is necessary to change

parameters of the system generating

gradients. For example, in system from two coils the

distance between the coils should be incremented in

comparison with Maxwell position to 1.35 coil radius. In so

doing in the worst extreme case when the main homogenous

magnetic field is negligible, the standart deviation from

linearity within object in the size about of half

coils will make no more than 4 %.

References [1] Norris D. G., Hutchison, J. (1990).

magnetic field gradients and their effects on imaging at low magnetic field strengths. imaging, 8 (1), 33-7.

[2] M. A. Bernstein, K. F. King, X.MRI Pulse Sequences. Elsevier 2004. 1017 p.

[3] O. G. Ilina. Concomitant gradients terms in lowMRI. Inernational Symposium and Summer Scool in Saint Petersburg “Nuclear Magnetic Resonance in Codensed Matter. 10th Sciences”. July 8—12 2013. Publicher, Saint Petersburg, 2013. 128 p.

[4] B. L. Alievsky, V. L. Orlov. The calculation of theaxially symmetric coils magnetic field parameters (in Russian) - Energoatomizdat, Moscow.

A reduction of concomitant magnetic fields effect through the timization of the gradient magnetic system

Frolov, Oksana Ilina

Faculty of Physics, Saint Petersburg State University



concomitant gradient analysis will be

sented. The optimum parameters depend both on relation

of the maximum field generated by gradient system in

sample volume to the main static field, and on dimensions

t is shown a magnetic field concomitant with a

enhances the nonlinearity of

ordinate dependence of the field. This misrepresents MRI

because of scale variations within investigated object. To

minimize the harmful effect, it is necessary to change

generating magnetic field

, in system from two coils the

distance between the coils should be incremented in

comparison with Maxwell position to 1.35 coil radius. In so

doing in the worst extreme case when the main homogenous

negligible, the standart deviation from

linearity within object in the size about of half-radius of

coils will make no more than 4 %.

G., Hutchison, J. (1990). Concomitant magnetic field gradients and their effects on imaging at

agnetic field strengths. Magnetic resonance

F. King, X. J. Zhou. Handbook of MRI Pulse Sequences. Elsevier – Academic Press,

G. Ilina. Concomitant gradients terms in low-field posium and Summer Scool in

Saint Petersburg “Nuclear Magnetic Resonance in meeting: NMR in Life

12 2013. Abstracts. “SOLO” Publicher, Saint Petersburg, 2013. 128 p.

L. Orlov. The calculation of the axially symmetric coils magnetic field parameters (in

Energoatomizdat, Moscow. 1983.

A reduction of concomitant magnetic fields effect through the


Introduction Dynamic polarization of nuclear using Overhauser effect

(DNP) is new and promising direction in the application of

magnetic resonance imaging (MRI). Res

application (DNP) in low magnetic fields

popularity the past 15 years. Application of this technique in

MRI remains is a scientific problem and it is

scope of individual experiments.

Theoretical assumption Using the method of dynamic nuclear polarization, based

on the Overhauser effect can be increased intensity of the

NMR signal. However, the frequency of the polarizing pulse

for most MRI scanners (more than 1 T) is equal to a few

hundred gigahertz, which destroys many organic substances

and dangerous for living organisms. The use of weak fields

on the order tens of mT allows you to use the polarizing

pulse order of hundreds of MHz, which is more secure.

Figure 1. OMRI protocol (from [1])

Experimental review Now most of the experiments conducted

Tesla. Experiments DNP in MRI (OMRT) are able to pass

under normal temperature conditions without strong cooling

investigated object of study. Observed

noise ratio, as well as the ability to use both the spin echo

(SE) and gradient echo (GRE) for space

Opportunity to enhance the contrast of MRI images using dynamic nuclear polarization in low magnetic fields

Dmitry M. Furman

St.Peterburg State University, 1 Uly


– 11, 2014 – 46 –

using Overhauser effect

new and promising direction in the application of

magnetic resonance imaging (MRI). Researchs in the

magnetic fields gained widespread

pplication of this technique in

is a scientific problem and it is not beyond the

ing the method of dynamic nuclear polarization, based

on the Overhauser effect can be increased intensity of the

NMR signal. However, the frequency of the polarizing pulse

for most MRI scanners (more than 1 T) is equal to a few

troys many organic substances

and dangerous for living organisms. The use of weak fields

on the order tens of mT allows you to use the polarizing

pulse order of hundreds of MHz, which is more secure.

Figure 1. OMRI protocol (from [1])

conducted in fields of 1

P in MRI (OMRT) are able to pass

under normal temperature conditions without strong cooling

improved signal /

lity to use both the spin echo

ce encoding. In the

experiment, nitroxyl radicals as contrast agent (TEMPO

(C9H18NO)), due to their good stability over time. Method

contrast is that the places where the application of thi

radical DNP MR image is more intense signal (from the

hydrogen nuclei). DNP method is applicable to the nuclei 13C, 15N, 31P and 1H.

Figure 2. Images of phantom composed of an array of 8

internal diameter glass tubes filled with aqueous solutions

of TEMPOL nitroxide free radical

Scientific prediction The DNP by Overhauser effect is able to occur in the low

magnetic fields. DNP can be applied in the case of these

fields. OMRT can be used to improve the quality of the MRI

image, and to more accurately tissue staining. The use of

low magnetic field will produce an in vivo MRI.

References [1] A. Milton Franklin Benial 1, Kazuhiro Ichikawa,

Ramachandran Murugesan, KenUtsumi - Dynamic nuclear polarization properties of nitroxyl radicals used in Overhausersimultaneous molecular imaging Resonance 182 (2006) 273–

[2] David J. LurieT, Gareth R. Davies, Margaret A. Foster, James M.S. Hutch ison - Fieldof free radicals with detection at 450 mT Resonance Imaging 23 (2005) 175

Opportunity to enhance the contrast of MRI images using dynamic nuclear polarization in low magnetic fields

Furman, Viatcheslav V. Frolov

St.Peterburg State University, 1 Ulyanovskaya st., Petrodvorets, 198504, St.Peterburg, Russia


experiment, nitroxyl radicals as contrast agent (TEMPO

(C9H18NO)), due to their good stability over time. Method

contrast is that the places where the application of this

MR image is more intense signal (from the

method is applicable to the nuclei

Images of phantom composed of an array of 8-mm

internal diameter glass tubes filled with aqueous solutions

TEMPOL nitroxide free radical (from [2])

The DNP by Overhauser effect is able to occur in the low

magnetic fields. DNP can be applied in the case of these

fields. OMRT can be used to improve the quality of the MRI

accurately tissue staining. The use of

low magnetic field will produce an in vivo MRI.

A. Milton Franklin Benial 1, Kazuhiro Ichikawa, Ramachandran Murugesan, Ken-ichi Yamada, Hideo

Dynamic nuclear polarization properties of dicals used in Overhauser-enhanced MRI for

simultaneous molecular imaging - Journal of Magnetic

–282 David J. LurieT, Gareth R. Davies, Margaret A. Foster,

Field-cycled PEDRI imaging ection at 450 mT - Magnetic

(2005) 175–181

Opportunity to enhance the contrast of MRI images using dynamic

anovskaya st., Petrodvorets, 198504, St.Peterburg, Russia

Introduction 3-pyridinecarboxamide (nicotinamide, B3 vitamin, PP

provitamin) as well as nicotinic acid is an antipellagric

agent. In the living tissues both of compounds participate in

synthesis of NAD and NADP coenzymes. Furthermore,

nicotinamide has a number of additional functions. It

influences protein and RNA formation, synth

other bioactive molecules, etc.

On the other hand, 3-pyridinecarboxamide is a promising

compound which could be used as basis for synthesis of

metal complexes with greater biological activity than in case

of non-bound ligand. Nicotinamide is k

coordination bond with d-metal ions donating them a lone

electron pair of nitrogen heteroatom. The solvation state of

donor centre greatly affects the complexation

thermodynamics. Therefore, the solvation of this molecular

fragment should be studied in details.

Experimental The HMBC 15N-1H spectra of nicotinamide solutions

(0.2975-0.3025 mol/kg) in aqueous ethanol were recorded

on Avance III Bruker 500 NMR spectrometer with operating

frequencies of 50.701 MHz at the 298.2 K temperature. A 5

mm 1H/31P/D-BBz-GRD Triple Resonance Broad Band

Probe (TBI) was employed. Nitromethane was used as

external standard.

An experimental error of chemical shift measuring did

not exceed 0.1 ppm. The accuracy of temperature

maintaining using temperature unit BVT-

Figure 1. Dependence of 15

N nicotinamide heteroatom

chemical shift on aqueous ethanol solvent composition.

Chemical shift values are given with respect to CH

The nicotinamide of extra pure grade was used without

additional purification. The deaerated bidistilled water was

Nicotinamide solvation in aqueous ethanol:

G. A. Gamov1,

1Research Institute of Thermodynamics and Kinetics of Chemical Process

University of Chemistry and Technology

E-mail: [email protected] of Solution Chemistry


pyridinecarboxamide (nicotinamide, B3 vitamin, PP

as well as nicotinic acid is an antipellagric

agent. In the living tissues both of compounds participate in

synthesis of NAD and NADP coenzymes. Furthermore,

nicotinamide has a number of additional functions. It

influences protein and RNA formation, synthesis of some

pyridinecarboxamide is a promising

compound which could be used as basis for synthesis of

metal complexes with greater biological activity than in case

bound ligand. Nicotinamide is known to form the

metal ions donating them a lone

. The solvation state of

donor centre greatly affects the complexation

thermodynamics. Therefore, the solvation of this molecular

H spectra of nicotinamide solutions

0.3025 mol/kg) in aqueous ethanol were recorded

on Avance III Bruker 500 NMR spectrometer with operating

at the 298.2 K temperature. A 5

GRD Triple Resonance Broad Band

Probe (TBI) was employed. Nitromethane was used as

An experimental error of chemical shift measuring did

not exceed 0.1 ppm. The accuracy of temperature

-3000 was ±0.1 K.

N nicotinamide heteroatom

chemical shift on aqueous ethanol solvent composition.

Chemical shift values are given with respect to CH315

NO2

The nicotinamide of extra pure grade was used without

fication. The deaerated bidistilled water was

used for every solution preparation. The ethanol was

purified via distillation at atmospheric pressure. Water

content in the alcohol was controlled by densitometry (3.98

mass. %) and was taken into account when

solvents were made. The results of HMBC

nicotinamide solutions are given in Fig. 1

Discussion of the resultsThe chemical shift of heterocyclic nitrogen increases

smoothly depending on the aqueous ethanol solvent

composition (Fig. 1). It probably means the nearly uniform

replacing of H-bonded complexes of heteronitrogen with

water by that with ethanol in the overall interval of binary

solvent composition.

Nevertheless, we should note the more significant

changes in the nitrogen shielding at some ethanol

concentrations. When going from mixed solvent with X

= 0.16 m.f. to that with XEtOH = 0.25 m.f., the variation of 15Nheter chemical shift is 0.8 ppm, but when going from

solvent with XEtOH = 0.25 m.f. to that with X

i.e. organic component content increases by 0.05 m.f., the

chemical shift gains 1 ppm. In the interval of binary solvent

composition of XEtOH = 0.16

heteroatom nitrogen H-complexes with water by that with

ethanol seems to pass in the greater degree than it occurs at

other concentrations of organic solvent.

It was shown in our previous works

and 13C NMR spectroscopy that the maximal changes in the

solvation of heterocyclic fragment occur at X

data is in accordance with the presented results of

spectroscopic study. However, chemical shifts of nitrogen

atom give no possibility to calculate the equilibrium

constant of its resolvation process. The thermodynamics of

nicotinamide heteronitrogen transfer from water to aqueous

ethanol was determined from 13C NMR experiment [2].

Acknowledgements Study was carried out with financial support of Council

on grants of the President of Russian Federation under grant

№14.Z56.14.5963-MK.

References [1] G. A. Gamov, S. V. Dushina, V. V. Aleksandriiskii, V.

A. Sharnin, O. I. Koifman. 510-517 (2003).

[2] V. A. Sharnin, V. V. Aleksandriysky, S. V. Dushina, G. A. Gamov. – Magn. Reson. Chem.

Nicotinamide solvation in aqueous ethanol: 15N NMR study

, S. V. Dushina1, V. V. Aleksandriiskii1,2, V. A.

Research Institute of Thermodynamics and Kinetics of Chemical Process

University of Chemistry and Technology, Ivanovo, Russia

[email protected]

Institute of Solution Chemistry, Russian Academy of Sciences, Ivanovo,


used for every solution preparation. The ethanol was

purified via distillation at atmospheric pressure. Water

content in the alcohol was controlled by densitometry (3.98

mass. %) and was taken into account when the binary

The results of HMBC 15N-1H study of

are given in Fig. 1

Discussion of the results The chemical shift of heterocyclic nitrogen increases

smoothly depending on the aqueous ethanol solvent

g. 1). It probably means the nearly uniform

bonded complexes of heteronitrogen with

water by that with ethanol in the overall interval of binary

Nevertheless, we should note the more significant

hielding at some ethanol

concentrations. When going from mixed solvent with XEtOH

= 0.25 m.f., the variation of

chemical shift is 0.8 ppm, but when going from

0.25 m.f. to that with XEtOH = 0.3 m.f.,

i.e. organic component content increases by 0.05 m.f., the

chemical shift gains 1 ppm. In the interval of binary solvent

= 0.16 – 0.3, the replacing of

complexes with water by that with

in the greater degree than it occurs at

other concentrations of organic solvent.

n our previous works [1, 2] by means of 1H

C NMR spectroscopy that the maximal changes in the

solvation of heterocyclic fragment occur at XEtOH < 0.3. This

is in accordance with the presented results of 15N NMR

However, chemical shifts of nitrogen

atom give no possibility to calculate the equilibrium

constant of its resolvation process. The thermodynamics of

gen transfer from water to aqueous

C NMR experiment [2].

with financial support of Council

ussian Federation under grant

. Gamov, S. V. Dushina, V. V. Aleksandriiskii, V. A. Sharnin, O. I. Koifman. – Russ. Chem. Bull., 61,

V. A. Sharnin, V. V. Aleksandriysky, S. V. Dushina, G. Magn. Reson. Chem., 51, 193-198 (2013).

N NMR study

A. Sharnin1

Research Institute of Thermodynamics and Kinetics of Chemical Processes, Ivanovo State

, Russia


Introduction The identification of chemical compoun

NMR includes detecting NMR relaxation parameters

selected material [1]. Earth’s Magnetic Field NMR

(EFNMR) has some perspectives for application like

analytical method in mobile systems. However, the Signal to

Noise Ratio (SNR) of the NMR signal in Earth’s magnetic

field is very small in comparison of high field NMR

Outside interference has very high level compare to

EFNMR signals. We analyzed of EFNMR signals and

applied the wavelet processing technique for EFNMR signal

de-noising.

Statistical analysis of signalsspectrometer

In main methods of the gain of SNR it is usually accepted

that noise is Gaussian (“white”). Thus the first important

question is following: what is statistics of the noise signal?

May it is possible to accept (use) the Gaussian distribution

for the noise? We studied statistical properties of the noise

in EFNMR spectrometer. For this purpose we compared

the statistical properties of the noise signal and model

noise signal. Usually we also suppose

signal is a “white” Gaussian noise. Then

experimental noise in our spectrometer and model noise

signal.

In our measurements, SNR was measured by relation of

the maximum amplitude to noise dispersion. SNR after

quadrature detector is close to Rayleigh-Rice distribution

means that the noise signal distribution is normal. Thus we

can conclude that the noise in our experiments is “white”.

Minor distortions from the fit could be found, however in

first approximation, it is clear that the noise distribution is

“normal”.

The application of wavelet analysis to EFNMR de-noising

Two ways of the signal representation are usually

applied: time domain and frequency domain. In fact the

wavelet transform gives a possibility for the tw

dimensional representation of the signal amplitude in both

time and frequency dimensions. For simplicity in our

analysis we use only figures where the amplitude is shown

as function of one parameter only (frequency or time).

used two approaches for the signal de

approach is based on the wavelet filtering of a signal in the

Signal Denoising in Earth’s

Ilknur Gunduz1

Georgy Mozzhukhin

1Gebze Institute of Technology2Physics-Technical Faculty3Physics department, Kazan Power State Engeering Ubiversity, Kazan, Russia


– 11, 2014 – 48 –

he identification of chemical compounds by a low field

NMR relaxation parameters for the

[1]. Earth’s Magnetic Field NMR

(EFNMR) has some perspectives for application like

However, the Signal to

in Earth’s magnetic

in comparison of high field NMR [2].

Outside interference has very high level compare to

EFNMR signals. We analyzed of EFNMR signals and

applied the wavelet processing technique for EFNMR signal

s in EFNMR

In main methods of the gain of SNR it is usually accepted

). Thus the first important

question is following: what is statistics of the noise signal?

ible to accept (use) the Gaussian distribution

We studied statistical properties of the noise

in EFNMR spectrometer. For this purpose we compared

the statistical properties of the noise signal and model

suppose that noise model

Then we compared the

experimental noise in our spectrometer and model noise

In our measurements, SNR was measured by relation of

the maximum amplitude to noise dispersion. SNR after

Rice distribution. It

means that the noise signal distribution is normal. Thus we

can conclude that the noise in our experiments is “white”.

Minor distortions from the fit could be found, however in

lear that the noise distribution is

The application of wavelet analysis to

Two ways of the signal representation are usually

applied: time domain and frequency domain. In fact the

wavelet transform gives a possibility for the two-

dimensional representation of the signal amplitude in both

time and frequency dimensions. For simplicity in our

analysis we use only figures where the amplitude is shown

as function of one parameter only (frequency or time). We

e signal de-noising: a) first

approach is based on the wavelet filtering of a signal in the

frequency domain; b) second one is based on de

signal by Donoho-Johnstone method [3] with the next

restoration of the signal in the time domain

filtering of a signal in the frequency domain Matlab Wavelet

ToolBox has been used. Different levels of decomposition

and various modifications of wavelet filtering were applied

to obtain the best SNR. The results of the application of

wavelet transform reveal that de

and Doubeshi wavelets work well for our EFNMR spectra.

It should be however noted here that a genuine signal has

rather high SNR of about 10. Therefore wavelet filtering in

the frequency domain was enough to obt

results. The application in time domain based on

Johnstone method shows effective denoising too. However,

comparison of Symlet wavelet with Dobeshi wavelet reveals

that the last one gives slightly better results.

Conclusion We applied the wavelet methods for time domain and

frequency domain. Use of both Symlet and Doubeshi

wavelet produces the similar results in

domain, while Doubeshi wavelet decomposition to level 4

and 8 gives better results in

demonstrated that various variants of wavelet transform

could be used for successful denoising of the EFNMR

signal. Also we applied wavelet transform

signal processing for recognition of a priory known signals

(i.e. for identification/detection of substances) as well as for

denoising of the spectra of mixtures or fine structure of

spectra of EFNMR signals.

Acknowledgements This work is supported by the Scientific and Research

Council of Turkey (TUBITAK) (grant #212T131).

References [1] Mauler, E.Danieli, F.Casanova, B.Blumich,

“Identification of liquids encountered in carrluggage by mobile NMR. In: Explosives Detection using Magnetic and Nuclear Resonance Techniques. NATO Science for Peace and Security Series B: Physics and Biophysics. FraissarOlga (Eds.) Springer, 295 p., P.193

[2] Aleš Mohoric, Janez Stepišnik,magnetic field, Progress in Nuclear Magnetic

Resonance Spectroscopy 54[3] Donoho D.L., Johnstone I.M. Neo

problems, thresholding, and adaptation // 1996, № 1. pp. 39-62

Signal Denoising in Earth’s Field Magnetic Resonance1, Ivan Mershiev, Erdem Balcı1, Galina Kupriyanova

Mozzhukhin1,3, Bulat Rameev1

Gebze Institute of Technology, P.K.141,Gebze-Kocaeli, 41400 Turkey

Technical Faculty, Baltic Federal State University, Kaliningrad, 236014, Russia

Physics department, Kazan Power State Engeering Ubiversity, Kazan, Russia

[email protected]

frequency domain; b) second one is based on de-noising of a

Johnstone method [3] with the next

restoration of the signal in the time domain. For wavelet

filtering of a signal in the frequency domain Matlab Wavelet

ToolBox has been used. Different levels of decomposition

and various modifications of wavelet filtering were applied

to obtain the best SNR. The results of the application of

orm reveal that de-noising using both Symlet

and Doubeshi wavelets work well for our EFNMR spectra.

It should be however noted here that a genuine signal has

rather high SNR of about 10. Therefore wavelet filtering in

the frequency domain was enough to obtain rather good

results. The application in time domain based on Donoho-

Johnstone method shows effective denoising too. However,

omparison of Symlet wavelet with Dobeshi wavelet reveals

that the last one gives slightly better results.

ed the wavelet methods for time domain and

Use of both Symlet and Doubeshi

wavelet produces the similar results in the frequency

, while Doubeshi wavelet decomposition to level 4

the time domain. Thus we

demonstrated that various variants of wavelet transform

could be used for successful denoising of the EFNMR

wavelet transform approach in

signal processing for recognition of a priory known signals

on of substances) as well as for

denoising of the spectra of mixtures or fine structure of

This work is supported by the Scientific and Research


anieli, F.Casanova, B.Blumich, “Identification of liquids encountered in carr-on-luggage by mobile NMR. In: Explosives Detection using Magnetic and Nuclear Resonance Techniques. NATO Science for Peace and Security Series B: Physics and Biophysics. Fraissard, Jacques; Lapina, Olga (Eds.) Springer, 295 p., P.193-203, (2009). Aleš Mohoric, Janez Stepišnik, NMR in the Earth’s

Progress in Nuclear Magnetic

54 (2009) 166–182. Donoho D.L., Johnstone I.M. Neo-classical minimax problems, thresholding, and adaptation // Bernoulli,

Field Magnetic Resonance

Kupriyanova2,

Baltic Federal State University, Kaliningrad, 236014, Russia

Physics department, Kazan Power State Engeering Ubiversity, Kazan, Russia

Introduction The human brain has between 50-100 billion nerve cells

or neurons that constantly interact with each other

the human brain is one of the great scientific challenges of

the 21st century. This review is about a

complete map of the neural connections in a brain

History of connectomics A field of neuroscience that analyzes neuronal

connections is called the connectomics

actually started before the word existed.

nearly complete cellular connection map of the nematode

Caenorhabditis elegans was represented in 1986

term “connectome” was first defined in 2005 by O.

as “a comprehensive structural description of the network of

elements and connections forming the human brain”

Independently and in parallel, in 2005 in his

Hagmann coined the term “connectomics”, defined as the

study of the brain's set of structural connections

the five-year Human Connectome Project (HCP)

launched. The purpose of this project is to characterize brain

connectivity and function and their variability in healthy

adults.

Connectome construction Methods

Several methods are used in obtaining connectivity

information: electroencephalography (EEG),

magnetoencephalography (MEG), positron emission

tomography (PET), single-photon emission computed

tomography (SPECT), electron microscopy techniques (EM)

The structure connectome: a review

Oksana Ilina, Viatcheslav

Faculty of Physics, Saint Petersburg State Univercity



100 billion nerve cells

or neurons that constantly interact with each other. Mapping

he human brain is one of the great scientific challenges of

This review is about a connectome, the

complete map of the neural connections in a brain.

field of neuroscience that analyzes neuronal

onnectomics. Connectomics

actually started before the word existed. For example a

nearly complete cellular connection map of the nematode

Caenorhabditis elegans was represented in 1986 [1]. The

term “connectome” was first defined in 2005 by O. Sporns

as “a comprehensive structural description of the network of

elements and connections forming the human brain” [2].

Independently and in parallel, in 2005 in his Ph.D. thesis P.

Hagmann coined the term “connectomics”, defined as the

n's set of structural connections [3]. In 2009

Human Connectome Project (HCP) was

to characterize brain

connectivity and function and their variability in healthy

Several methods are used in obtaining connectivity

information: electroencephalography (EEG),

magnetoencephalography (MEG), positron emission

photon emission computed

tomography (SPECT), electron microscopy techniques (EM)

and other modalities. But the main methods for mapping the

connectome are the functional magnetic resonance imaging

(fMRI) and the diffusion MRI

obtain functional and structural connectomes, respectively.

The analysis of structural and fu

between different regions of the brain provides

comprehensive insight into its underlying organization.

Structural connectome construction It was observed that white matter exhibits reliable

anisotropic properties and that it is po

tract trajectories using diffusion MRI (Diffusion Tensor

Imaging). But DTI was unable to resolve multiple fiber

bundle orientation inside an imaging voxel. The methods

that allow to solve this problem are

Imaging (DSI) and High Angular Resolution Diffusion

Imaging (HARDI) techniques. Challenges and perspectives

of these methods and the structural connectome construction

were reviewed.

References [1] J. G. White, E. Southgate, J. N. Thomson and S.

Brenner. The Structure of the Nervous System of the Nematode Caenorhabditis elegansSoc.Lond. B, 12 November 1986 vol. 340 (1986).

[2] O. Sporns, G. Tononi, R. Kötter.connectome: a structural description of the human brain. – PLoS Comput. Biol

[3] P. Hagmann. From Diffusion MRI toConnectomics: PhD Thesis. Polytechnique Fédérale de Lausanne

The structure connectome: a review

Viatcheslav V. Frolov

Faculty of Physics, Saint Petersburg State Univercity



her modalities. But the main methods for mapping the

functional magnetic resonance imaging

diffusion MRI. These methods allow to

obtain functional and structural connectomes, respectively.

The analysis of structural and functional connectivity

between different regions of the brain provides a

into its underlying organization.

Structural connectome construction It was observed that white matter exhibits reliable

anisotropic properties and that it is possible to infer fiber

rajectories using diffusion MRI (Diffusion Tensor

But DTI was unable to resolve multiple fiber

bundle orientation inside an imaging voxel. The methods

that allow to solve this problem are Diffusion Spectrum

and High Angular Resolution Diffusion

Challenges and perspectives

tructural connectome construction

J. G. White, E. Southgate, J. N. Thomson and S. f the Nervous System of the

Nematode Caenorhabditis elegans. – Philos. Trans. R.

12 November 1986 vol. 314 no. 1165 1-

Tononi, R. Kötter. The human connectome: a structural description of the human

. Biol., 1, 245–251 (2005). From Diffusion MRI to Brain

Connectomics: PhD Thesis. – Lausanne: Ecole Polytechnique Fédérale de Lausanne (2005).


Introduction Quantitative 1H NMR spectroscopy is the primary

method of quantitative measurements [1]. Through a

combination of unique opportunities (short measurement

time, accuracy and precision, no need for standards and

calibration, nondestructive and conclusiveness, no need to

extract the analyte from a mixture, determination of the

complete molecular structure) qNMR as the differential

isotope method has no analogues for the analysis of

pharmaceuticals and their metabolome, various natural

objects and complex mixtures.

Typical problems solved by qNMR in pharmaceutical chemistry

• Identification of the structure of drug substances

• Quantitative determination of the active substance

• Identification and quantitative determination of

residual solvents and impurities;

• Determination of stability and structure changes of

medicines during the storage;

• Getting of a “fingerprint” of multicomponent systems

(extracts, infusions, etc.);

• Determination of composition of multicomponent

drugs;

• Determination of isomeric composition, relationship of

diastereoisomers and enantiomers (using chiral solvents

complexing agents).

Objects of study In this work, possibilities of the method are applied to the

analysis of substances and medicines developed in Russia

thymodepressin(A), sedatin(B) and imunofan(C).

A

HOOC CH2C

H2C C

HN C COOH

H

CH2

H

NH2

O

NH

**

*

* *

H2N CH

CH2

CH2

CH2

NH

C

HN N

Analysis of the identity and quality of peptidequantitative

V. A. Ivlev, G. A

Peoples’ Friendship University of Russia, Moscow, Mikluho


– 11, 2014 – 50 –

H NMR spectroscopy is the primary

e measurements [1]. Through a

combination of unique opportunities (short measurement

time, accuracy and precision, no need for standards and

calibration, nondestructive and conclusiveness, no need to

extract the analyte from a mixture, determination of the

complete molecular structure) qNMR as the differential

isotope method has no analogues for the analysis of

pharmaceuticals and their metabolome, various natural

Typical problems solved by qNMR in

tification of the structure of drug substances;

Quantitative determination of the active substance;

Identification and quantitative determination of

Determination of stability and structure changes of

of multicomponent systems

Determination of composition of multicomponent

Determination of isomeric composition, relationship of

diastereoisomers and enantiomers (using chiral solvents and

In this work, possibilities of the method are applied to the

analysis of substances and medicines developed in Russia -

thymodepressin(A), sedatin(B) and imunofan(C).

Monographs dedicated to the analysis of transbu

films were developed for medicines A u B (substance

concentration - 0.037 g/ml and 0.7 mg/ml, respectively) and

for the medicine (B) – in the form of injection solution (50

mg /ml).

Quantitative determination was held by comparing

integral intensities of inputted reference compound and

signals marked with symbols “*” in the formulas. A typical

spectrum of peptide drugs is shown on an example of

thymodepressin as transbuccal film in Figure 1.

Figure 1

The active compound content in the weighed portion

calculated by the following equation:�� /�� ∗ ��/�where X - the active compound, IS

mass, M-molar mass, I - the integral intensity of signals, N

the number of protons.

References [1] B. King, Accredit. Qual. Assur.

436.

C NH

CH

NH2

O

B

CH2

C

O

HN

CHCH3

C

O NH

CH

H2C

O

HN

CH2

C

OHO

OH

*

*

*

*

* *

*

*

*

H2N CH CHN

HC C

HN CH

CH2

CH2

CH2

NH

C

HN NH2

O

CH2

COOH

O

CH2

CH2

CH2

CH2

NH2

Analysis of the identity and quality of peptide-based drugs by 1H NMR spectroscopy (qNMR)

A. Kalabin, V. G. Vasil’ev

Peoples’ Friendship University of Russia, Moscow, Mikluho-Maklay st., 10/2

[email protected]

Monographs dedicated to the analysis of transbuccal

films were developed for medicines A u B (substance

0.037 g/ml and 0.7 mg/ml, respectively) and

in the form of injection solution (50

Quantitative determination was held by comparing

of inputted reference compound and

signals marked with symbols “*” in the formulas. A typical

spectrum of peptide drugs is shown on an example of

thymodepressin as transbuccal film in Figure 1.

Figure 1

The active compound content in the weighed portion

calculated by the following equation: ��/��/�� ∗ �� the active compound, IS - internal standard, m -

the integral intensity of signals, N -

Accredit. Qual. Assur. 5 (2000) 266-271, 429-

CHN

HC C

HN C

HN

HC

O

CHH3C CH3

O

CH2

O

CH2

COOH

OH

CH2

CH2

CHN NH2

**

* *

C

**

based drugs by

Maklay st., 10/2

Introduction Medical ordinary clinics need cheap complexes,

determine the decease stage and control of particular kidney scarcity (KS). It can be done dependences of nuclear (proton) magnetic resonance structure-dynamical parameters from parameters of blood and plasma changes, which accompany sharp and chronic kidney scarcity. To realize such approach corresponding device must be elaborated and NMR relations must be revealed.

NMR-relaxometer for decease Was elaborated portable relaxometer NMR,

fig.1 and defeated by RF patents №67719, №2319138, №73486. Power supply is autonomous –or grid. Control and data processing – bymagnetic system from NdFeB alloys. Magnetic field inhomogeneity is less, than 4·10-4B0. Inhomogeneity of B2% in 75% of its coil volume.

Figure 1

Cоefficient of sensitivity is К = ν02⋅D3

-4150, where ν0 = 10-12 МHz – frequencymagnetic resonance, D = 10-30 mm –probehead coil. Power < 15 VA. Weight < 15

Dependence of NMR-parameters from blood phys-chemical properties

Last decades NMR-tomography is widely used fordeceases diagnosis. In Zavoisky Kazan PhycicalInstitute was elaborated and produced NMRsuccessfully exploited in several medical centers. Using NMR-relaxation parameters of blood, plasma or urea of pacients, diagnosis, control of their treatment can be done using NMR data, which on the example of cancer diagnosis demonstrated its powerfullness. However practically were not established correlations for KS. Interesting also to study by NMR the influence of hemodialysis on blood structure.

NMR-complexscarcity decease

R. S. Каshaev,

Chair of Instruments and Automated Drive, Каzan State Power Engineering Universit


Каzan State Medical Academy


clinics need cheap complexes, able to control of its cure, in

kidney scarcity (KS). It can be done using magnetic resonance (NMR)

physical-chemical and plasma changes, which always

kidney scarcity. To realize vice must be elaborated and

decease diagnosis Was elaborated portable relaxometer NMR, presented at

№67719, №2319138, – from accumulator by Notebook. Used

magnetic system from NdFeB alloys. Magnetic field . Inhomogeneity of B1 <

[МHz2сm3] = 2700 frequency of proton

– diameter of the < 15 kg.

ers from blood

tomography is widely used for deceases diagnosis. In Zavoisky Kazan Phycical-Technical Institute was elaborated and produced NMR-tomograph, successfully exploited in several medical centers. Using

relaxation parameters of blood, plasma or urea of pacients, diagnosis, control of their treatment can be done using NMR data, which on the example of cancer diagnosis demonstrated its powerfullness. However practically were

for KS. Interesting also to study by NMR the influence of hemodialysis on blood structure.

Up to contemporary times discussed the influence of hemodialysis on rheological properties of blood [1]. Majority of the works are devoted to study of influence of hemodialysis on aggregation of eritrocites and trombocites and the prognosis of KS terminations stages are made on clinic laboratory statistics and histomorphology data. NMRtomography was used for qualitativefrom kidney tomograms and spinprotons density, intensity of NMRtomograph ВМТ 1100 (Bruker) [2].

According to Asaba H. [3] at pathological stages of KS appear sufficient amount of peptides with molecular mass 300-5000 dalton – so called molecular mass (MММ), which are the products of the peptide leasing and which work as secondary endotoxines. Appeared also the communications aboutspectrophotometric method of determination of intoxication index and catabolic pool of MMM in plasma from absorbance at the wave length confirmed, that pool of MMM in blood is stable and is determined by organism state [4].

We revealed the relations between stage of KS and NMRparameters. Relaxation times measurementusing Carr-Parcell-Meiboom-Gill method in blood plasma. Spin-echo envelope had two components with different relaxation times, but in the blood could be extracted up to three components with error ± 4%.

Measurements resultsWas revealed linear relation

concentration M, normalized to peptide concentrationblood. For creatinin К exponential relation between its concentration. Correlations are describedМ � 54К � 4.71

Sensitivity S of relation М(ТConstant C in equation (2) correspond to the shortest relaxation time C = 577 ms, terminal stage of the kidney decease, at which

Obtained results can be explained“middle weight substances” (MWS)times due to increasing restriction of molecular motionsBeeing the products of peptide leasing, they, probably act as secondary endotoxines.

References [1] Ganeev Т.S. Dissertation thesis. Кazan state institute of

усоверш. врачей. 1993. [2] Теvzadze М.Ch. Dissertation thesis. Institute

cardiology. АМS USSR. Моscow. 1990[3] Asaba H. Accumulation and excreation of middle

molecules // Clinic. Nephrol.

123. [4] Тitova О.N. Dissertation thesis. SPb. 1996.

complex for diagnosis and control of cure of kidney scarcity decease

, A. S. Kopilov


[email protected]

Каzan State Medical Academy


Up to contemporary times discussed the influence of hemodialysis on rheological properties of blood [1].

of the works are devoted to study of influence of emodialysis on aggregation of eritrocites and trombocites

and the prognosis of KS terminations stages are made on clinic laboratory statistics and histomorphology data. NMR-tomography was used for qualitative-quantitive analysis

pin-lattice relaxation times Т1, protons density, intensity of NMR-signals on NMR-tomograph ВМТ 1100 (Bruker) [2].

According to Asaba H. [3] at pathological stages of KS appear sufficient amount of peptides with molecular mass

so called substances of the middle molecular mass (MММ), which are the products of the peptide leasing and which work as secondary endotoxines. Appeared also the communications about spectrophotometric method of determination of intoxication

of MMM in plasma from absorbance at the wave length λ = 238-258 nm. Was confirmed, that pool of MMM in blood is stable and is determined by organism state [4].

We revealed the relations between stage of KS and NMR-parameters. Relaxation times measurements were done

Gill method in blood plasma. echo envelope had two components with different

relaxation times, but in the blood could be extracted up to 4%.

Measurements results between Т2А and мочевина

normalized to peptide concentration in exponential relation between Т2А and

Correlations are described: 54 – 0.033�� (1) ��/�� (2) Т2А) equals S = 33 (unit/sec)

in equation (2) correspond to the shortest , probably corresponding to

terminal stage of the kidney decease, at which К = 4.7. explained by the increase of the

MWS), having short relaxation times due to increasing restriction of molecular motions.

leasing, they, probably act as

. Dissertation thesis. Кazan state institute of

Теvzadze М.Ch. Dissertation thesis. Institute of cardiology. АМS USSR. Моscow. 1990 Asaba H. Accumulation and excreation of middle

Nephrol. 1983. V.19. #3. P.116-

Тitova О.N. Dissertation thesis. SPb. 1996.

cure of kidney

Chair of Instruments and Automated Drive, Каzan State Power Engineering University


Introduction Biological processes are controlled by molecular

dynamics on the surface, because the structure of water

surrounding cell, determines the membrane ability to

provide substrate and energy exchange with environment.

NMR-method gives opportunity for study

problems. It is the most powerful analytic method for

quantitative investigations of phases in microbial oil/water

dispersions in-vivo [1-2].

Apparatus and nethods

Measurements of the NMR-parameters: spin

relaxation times T2i and proton populations

performed using Carr-Purcell-Mayboom

sequence on the elaborated relaxometer NMR, defeated by

RF patents №67719, №2319138 [3], №73486.

is autonomous – from accumulator or grid. Control and data

– by Notebook. Cоefficient of sensitivity is

[МHz2сm3] = 2700 -4150, where ν0

frequency of proton magnetic resonance,

diameter of the coil. Power < 15 VA. Weight

Samples of microbial bacteria Pseudomonas Put

Rhodococcus Robropertinctus were sited

polymer carrier in retort with nourishing solution

suspension. Cultivation of oil bacteria

communities was processed by professor of Kazan State

University Naumova R.P. As a source of substrate

used sulphurous Devon Romashkinskaya

Tatarstan), which have density ρ = 880 kg/m

blach mineral oil (BMO) fraction with S = 3%

= 5,6. Concentration of microorganisms in suspension was

measured by light absorption (λ = 580 nm

Experimental results Measurements of relaxation time dependences from

bacteria concentration on fig. 1 showed that spin

envelopes has two components for nourishing bulk water

media with the relaxation times T2A and

using NMR-parameters: T = 6 s, τ = 400

5-10; and two components for near microbial cells water

protons with the relaxation times T2B and

using parameters: T = 2 s, τ = 200 µs, N =

impulse sequence gives opportunity to measure mainly

amplitudes, regarding to T2B and T2B/ relaxation times.

attributed to protons of water molecules that form solvate

envelope as a result of interaction of water OH

NMR – study of the water molecules on the microbial cell surface at microbial growth process

R. S. Каshaev,


E-mail: kashaev2007@yandex

– 11, 2014 – 52 –

controlled by molecular

surface, because the structure of water,

determines the membrane ability to

and energy exchange with environment.

study of mentioned

is the most powerful analytic method for

investigations of phases in microbial oil/water

parameters: spin-spin

and proton populations Pbw were

Mayboom-Gill pulse

on the elaborated relaxometer NMR, defeated by

, №73486. Power supply

from accumulator or grid. Control and data

efficient of sensitivity is К = ν02⋅D3

0 = 10-12 МHz –

frequency of proton magnetic resonance, D = 10-30 mm –

. Power < 15 VA. Weight < 15 kg.

Pseudomonas Putida and

sited on saturated by oil

with nourishing solution and cells

suspension. Cultivation of oil bacteria of bacteria

communities was processed by professor of Kazan State

As a source of substrate were

Romashkinskaya oil (Republic of

= 880 kg/m3 with heavy

= 3% and CH3/CH2

Concentration of microorganisms in suspension was

nm).

of relaxation time dependences from

showed that spin-echo

for nourishing bulk water

and T2A/, measured

400 µs, N = 4000, n =

for near microbial cells water

and T2B/, measured

= 1000, n = 50. Last

mpulse sequence gives opportunity to measure mainly

relaxation times. T2B is

olecules that form solvate

water OH-groups with

NH3+ and COOH-- groups

membranes. peripheral proteins

Figure 1. Upper Dependence of proton populations

different relaxation times from N

suspension. • - T2A = 1,7÷ο - T2B = 500 ms, Θ

The explanation of results can be based on the ability of

water molecules to form macromolecular structures or

conglomerates of water [4-5] in cell's solvate covers.

order to estimate correlation times of water protons in

solvate covers we use the results of NMR relaxation theory

of the proton relaxation in solutions in the

diamagnetic ions [2]. The relaxation

cover will be determined by the contributions from intra,

inter molecular interactions and from non aver

interactions (T2or)-1

in solvate water �� !" � �1 � #$%��&'(%)!"Contributions are averaged by proton exchange.

From (1) can be determined

known:

#$% � 0,296�� Calculations show, that when

to 300ms the percentage of structured water protons rise

from 0,345 to 0,909.

References [1] Renou J.P.; Bonnet M.; Bielicki G.; Rochdi A.;

Gatellier P. 1994. Biopolymer.,

[2] Fukuzaki M. 1995. J. Phys.

[3] Idiatullin Z.Sh.; Kashaev R.S.; Temnikov A.N. 2006. Device for sample thermostation inPatent of RF on invention #

[4] Davis C.M.; Jr.Litovitz T.A. 2563.

[5] Aizenberg D.; Kaupman V.Vody, L.GMI.

study of the water molecules on the microbial cell surface at microbial growth process

, A. S. Kopilov


[email protected]

of amino acids of cell

Dependence of proton populations Pi of

Nk concentration in bacteria

÷2 s, ∇ - T2A/ = 1÷1,2 s,

Θ - T2B/ = 120 ms

can be based on the ability of

water molecules to form macromolecular structures or

] in cell's solvate covers. In

order to estimate correlation times of water protons in

results of NMR relaxation theory

of the proton relaxation in solutions in the presence of

he relaxation rate (T2or)-1 in solvate

cover will be determined by the contributions from intra,

inter molecular interactions and from non averaged proton

water cover:

&'(%) . ��&'(/%!" � . #$%��$%!" (1)

ontributions are averaged by proton exchange.

Por if all relaxation times are

� 0,078 (2)

, that when T2bw decrease from 700 ms

to 300ms the percentage of structured water protons rise

Renou J.P.; Bonnet M.; Bielicki G.; Rochdi A.; Biopolymer., 34. 1615.

Phys. Chem., 99.431. shaev R.S.; Temnikov A.N. 2006.

Device for sample thermostation in relaxometer NMR. Patent of RF on invention # 2319138; Davis C.M.; Jr.Litovitz T.A. 1965. J. Chem. Phys. 42.

Aizenberg D.; Kaupman V.1975. Structura i Svoistva

study of the water molecules on the microbial cell surface

Chair of Instruments and Automated Drive, Каzan State Power Engineering University

Introduction Understanding the properties of water in biological

systems is a problem of fundamental interest in chemistry

and biology. Studies of protein hydration dynamics in

solution have been an active field of research for years [1].

In this context, computer simulations, capable to provide a

detailed molecular-level description of solution structure,

should be very fruitful for further investigation of this issue

In the present study the water dynamics in the hydration

layer around the B1 domain of immunoglobulin

protein L [2] (Fig. 1) at normal conditions

by classical Molecular dynamics simulations.

Figure 1. Structure of the B1 domain of

binding protein L (PDB code 2PTL

Molecular Dynamics simulationsMDynaMix package [3] was used in the present study. A

solution of 1 protein molecule (963 atoms) among 7404 H

molecules was simulated. Molecular dynamics simulations

were carried out in an isothermal-isobaric (

in a cubic periodic cell at 1 atm and 25°C. Water was

simulated with the rigid SPC/E model [4]. To describe water

interactions with protein molecule the force field

by Cornell et al. [5] was employed. The temperature was

kept constant by using Nosé-Hoover thermostat and pressure

was regulated by Hoover barostat. The equations of motion

were solved using the Verlet algorithm with a time step of

Water dynamics in the aqueous solution of the B1 domain of immunoglobulinsimulation study

Ekaterina A. Krylova

Faculty of Physics, Saint

Ulianovskaya 1, 198504, Saint



Understanding the properties of water in biological

systems is a problem of fundamental interest in chemistry

ology. Studies of protein hydration dynamics in

solution have been an active field of research for years [1].

simulations, capable to provide a

level description of solution structure,

er investigation of this issue.

e water dynamics in the hydration

layer around the B1 domain of immunoglobulin-binding

normal conditions has been treated

by classical Molecular dynamics simulations.

Structure of the B1 domain of immunoglobulin-

PDB code 2PTL)

Molecular Dynamics simulations package [3] was used in the present study. A

solution of 1 protein molecule (963 atoms) among 7404 H2O

d. Molecular dynamics simulations

isobaric (NPT) ensemble

in a cubic periodic cell at 1 atm and 25°C. Water was

simulated with the rigid SPC/E model [4]. To describe water

interactions with protein molecule the force field proposed

by Cornell et al. [5] was employed. The temperature was

Hoover thermostat and pressure

was regulated by Hoover barostat. The equations of motion

were solved using the Verlet algorithm with a time step of

2.0 fs. The Coulomb interactions were calculated using the

Ewald summation method. The SHAKE procedure was

employed to constrain all the bond lengths. The system was

equilibrated during a 30 ps run. Further, a 50 ps simulation

was performed.

Results A detailed view on the water dynamics around the protein

can be given through the reorientational correlation

functions: �1 � ⟨#3�1�where P is the first rank Legendre polynomial, and

unit vector pointed along the α axis in the molecular fr

of each water molecule. The correlation time,

obtained by fitting the correlation functions using the

following expression: �1 � �In our analysis we have used three different axes: the H

vector, RHH, the molecular dipol

plane of the molecule, RP.

In the present study the motions of water molecules in

protein hydration layer have been evaluated and compared

with the bulk water data.

Acknowledgements This work was supported by the grant of the R

Foundation for Basic Research (13

authors also acknowledge Saint

for a research grant 11.0.63.2010.

References [1] B. Bagchi. – Chem. Rev., 105[2] J. W. O’Neill, D. E. Kim, D. Baker, K. Y. J.

Acta Cryst. D, 57, 480-487 (2001).[3] A. P. Lyubartsev, A. Laaksonen.

128, 565-589 (2000). [4] H. J. C. Berendsen, J. R. Grigera, T.P. Straatsma.

Phys. Chem., 91, 6269-6271 (1987).[5] W. D. Cornell, P. Cieplak, C. I. Bayly, et al.

Chem. Soc., 117, 5179-5197 (1995).

Water dynamics in the aqueous solution of the B1 domain of noglobulin-binding protein L. A molecular dynamics

simulation study

Krylova, Andrei V. Egorov

hysics, Saint Petersburg State University

Ulianovskaya 1, 198504, Saint Petersburg, Russia



ulomb interactions were calculated using the

Ewald summation method. The SHAKE procedure was

employed to constrain all the bond lengths. The system was

equilibrated during a 30 ps run. Further, a 50 ps simulation

he water dynamics around the protein

can be given through the reorientational correlation

3 �4� ∙ �1�0�6⟩, is the first rank Legendre polynomial, and eα is the

unit vector pointed along the α axis in the molecular frame

of each water molecule. The correlation time, τα, can be

obtained by fitting the correlation functions using the

�!(/89.

In our analysis we have used three different axes: the H-H

, the molecular dipole, RD, and the normal to the

In the present study the motions of water molecules in

protein hydration layer have been evaluated and compared

This work was supported by the grant of the Russian

Foundation for Basic Research (13-03-01073-a). The

authors also acknowledge Saint Petersburg State University

for a research grant 11.0.63.2010.

105, 3197-3219 (2005). J. W. O’Neill, D. E. Kim, D. Baker, K. Y. J. Zhang. –

487 (2001). A. P. Lyubartsev, A. Laaksonen. - Comp. Phys. Comm.,

H. J. C. Berendsen, J. R. Grigera, T.P. Straatsma. – J.

6271 (1987). W. D. Cornell, P. Cieplak, C. I. Bayly, et al. – J. Am.

5197 (1995).

Water dynamics in the aqueous solution of the B1 domain of molecular dynamics


Introduction The study of NMR relaxation in biological tissues gives

us the important information not only about the dynamics of

the molecular structure but also about

individual fragments. Such information can be extrac

from the study of spin-lattice and spin-spin relaxation time

T1, T2, and the nuclear Overhauser effect, as all of these

characteristics are determined by the spectral density

function of fluctuating magnetic, which are directly related

to the structural parameters of the molecules and correlation

times of molecular motion. If several types of interactions

give the contribution to the relaxation of the nuclei then

correlation relaxation mechanisms may occur. The most

interesting data on the movement of individual fragments

can be obtained from the relaxation data of CH

[1, 2].

Experimental details In this work, the samples of adipose tissues with different

deuterium content (300 ppm, 800

5000 ppm) were investigated by 1H, 13C and

spectra and relaxation measurements were performed on a

spectrometer VARIAN 400MHz. Correlation experiments

COSY (1H-13C) were carried out to identify signals

and 1H NMR spectra. Particular attention was paid to the

and 13C NMR relaxation of CH2 groups in terms of defining

the model of rotational motion and the

mechanisms between protons and deuterium

inversion recovery experiments and spin echo techniques

were used to measure the longitudinal relaxation and the

transverse relaxation times correspondingly

experiments were carried out to elucidate the mechanisms of

exchange between protons and deuterium with increasing

deuterium concentration in the samples.

Theoretical details Preliminary investigations showed t

spectra of all samples of adipose tissue have characteristic

peaks. It was found that the intensity of the signals

to CH2 groups is different for the sample with different

deuterium concentration. More significant

structure of the spectra of different samples

13C NMR relaxation in adipose tissue samples

Galina KupriyanovaElena Makhno

Physics-Technical Faculty


– 11, 2014 – 54 –

tudy of NMR relaxation in biological tissues gives

not only about the dynamics of

the motion of its

individual fragments. Such information can be extracted

spin relaxation time

T1, T2, and the nuclear Overhauser effect, as all of these

characteristics are determined by the spectral density

function of fluctuating magnetic, which are directly related

l parameters of the molecules and correlation

eral types of interactions

the relaxation of the nuclei then

correlation relaxation mechanisms may occur. The most

ndividual fragments

can be obtained from the relaxation data of CH2 groups

adipose tissues with different

ppm, 1000 ppm,

C and 2H NMR. The

spectra and relaxation measurements were performed on a

z. Correlation experiments

dentify signals in 13C

. Particular attention was paid to the 1H

groups in terms of defining

and the exchange

mechanisms between protons and deuterium. Standard

and spin echo techniques

were used to measure the longitudinal relaxation and the

erse relaxation times correspondingly. NOESY

o elucidate the mechanisms of

exchange between protons and deuterium with increasing

that the 1H NMR

of adipose tissue have characteristic

ntensity of the signals refered

is different for the sample with different

More significant differences in the

different samples is observed in

13C NMR spectra in the region assigned to the

To interpret the experimental results

describing the relaxation of each

triplet of CH2 groups were used.

longitudinal relaxation rates of each

the nucleus 13C scalar coupled

individual and equal

SRR λ−= 00

, 1R R±

Here R0 is the relaxation rate

R±1 is the relaxation rate of

autocorrelation contributions from the

(DD), chemical shift anisotropy

are included in R0. λ is DD(C

correlation term, µ is CSA-DD

difference in the decay rates of extreme

arises in the presence of CSA (13

(HH) cross-correlations. The various

molecular motion such as the rigid molec

model of rotational jumps in the area

angle are used [2, 3].

Results The studies have shown that

a significant difference in quantity and

groups. The model of rotational

more suitable for the interpretation of experimental

the 13C NMR relaxation CH2 group belonging to the chain

(CH2)n in the sample contained deuterium

the exchange process between deuterium and protons

involves protons, not only OH groups, but also the CH

groups belonging to the chain (CH

observed in samples in which the deuterium concentrations

are 5000 ppm, 1000 ppm.

References [1] Ernst M., Ernst R. Heteronuclear dipolar cross

correlation cross-relaxation for the investigation of side-chain motions. J. Magn. Reson.

202 [2] B. Vögeli J. Chem. Phys. 133[3] G. Lipari and A. Szabo, J. Am.

1982

C NMR relaxation in adipose tissue samples

Kupriyanova, Aleksander Bagaychuk, Svetlana Ruzshyeva

Technical Faculty, Baltic Federal State University, Kaliningrad, Russia

[email protected]

region assigned to the CH2 groups.

results the operator equations

of each component of the 13C

were used. It was found that the

of each line in the spectrum of

coupled with two protons are

10 SR R λ µ± = + ± .

relaxation rate of the central component,

of extreme components. The

autocorrelation contributions from the dipole interaction

chemical shift anisotropy of the nucleus (CSA) 13C

DD(C-H1)-DD(C-H2) cross-

DD cross-correlation term. The

of extreme spectral components 13C)-D (CH) and CSA (H)-D

The various models of internal

the rigid molecule model and

in the area bounded by a certain

adipose tissue samples have

difference in quantity and mobility of the CH2

rotational jumps in a bounded area is

the interpretation of experimental data on

group belonging to the chain

in the sample contained deuterium. It was found that

the exchange process between deuterium and protons

olves protons, not only OH groups, but also the CH2

groups belonging to the chain (CH2)n. This effect was

observed in samples in which the deuterium concentrations

Ernst M., Ernst R. Heteronuclear dipolar cross-relaxation for the investigation of

J. Magn. Reson. 1994, v. A 110, p.

133, 014501 (2010); J. Am. Chem. Soc. 104, 4546

Ruzshyeva,

Baltic Federal State University, Kaliningrad, Russia

Introduction In recent years the physical properties research with

change of the matter particle size has causes considerable

interest. Earlier it was experimentally shown that

longitudinal and transverse relaxation times of a nuclear

quadrupole resonance (NQR) depend

microparticles of a sample [1, 2]. In microcomposite

structures it was obtained that longitudinal relaxation times

T1 have unimodular distribution, but transverse

times have multimodal distribution [3]. However, for

complex samples of the molecular crystals with impurities,

for micro-powders, micro-composites, porous media due to

different intermolecular interactions, relaxation time

distribution is continuous and requires a multi

inversion as for T1 and T2 [2]. For the purpose of increa

in the measurement accuracy of relaxation times and

obtaining detailed information on the internal factors

influencing distribution of relaxation times, we carried out

the study of composite pulses action on the NQR line width,

the ratio signal/noise and relaxation parameters.

Experimental details In this work the powder samples with various sizes of

granules were investigated. Fractions were allocated with

the sizes: > 1000 microns, 500-600 microns, 300

microns and 200-250 microns. The sizes of part

their distribution were determined by an electronic

microscope with using of the special software ImageJ. NQR

signals on 13Сl were registered on NQR/NMR spectrometer

Tecmag with Apollo console. Potassium chlorate KClO3

was chosen as a sample for study by 35Cl NQR: asymmetry

parameter η = 0, a quadrupole constant e2Qq = 1,058 MHz

at T = 299 K, NQR frequency ν = 28,954 MHz at T = 77 K.

NTNMR software was used for composite pulses generation

and processing of measurements results.

Three composite pulses intended to compensate for the

effects associated with the inhomogeneous of sample

excitation and the imperfection of 900 pulse were selected

for the experiments [4]. The following sequences of

composite pulses were used: 45180135

315(0) 225(180) 90(0) for relaxation experiments.

Results Our study showed that the use of composit

to narrowing of NQR linewidths and to increase in the

signal/noise ratio. The greatest strengthening of NQR

signals was reached with using a compo

300(90) for the samples containing 200

Increasing signal/noise in the NQR measuremencomposite pulse

Galina Kupriyanova

Physics-Technical Faculty



properties research with

causes considerable

interest. Earlier it was experimentally shown that

longitudinal and transverse relaxation times of a nuclear

on the size of

In microcomposite

it was obtained that longitudinal relaxation times

transverse relaxation

[3]. However, for the

crystals with impurities,

composites, porous media due to

different intermolecular interactions, relaxation time

distribution is continuous and requires a multi-exponential

. For the purpose of increase

measurement accuracy of relaxation times and

obtaining detailed information on the internal factors

influencing distribution of relaxation times, we carried out

the study of composite pulses action on the NQR line width,

d relaxation parameters.

In this work the powder samples with various sizes of

granules were investigated. Fractions were allocated with

600 microns, 300-350

250 microns. The sizes of particles and

their distribution were determined by an electronic

microscope with using of the special software ImageJ. NQR

signals on 13Сl were registered on NQR/NMR spectrometer

with Apollo console. Potassium chlorate KClO3

Cl NQR: asymmetry

e2Qq = 1,058 MHz

at T = 299 K, NQR frequency ν = 28,954 MHz at T = 77 K.

NTNMR software was used for composite pulses generation

intended to compensate for the

effects associated with the inhomogeneous of sample

pulse were selected

The following sequences of

1350; 90(0) 300(90),

relaxation experiments.

use of composite pulses leads

NQR linewidths and to increase in the

. The greatest strengthening of NQR

signals was reached with using a composite pulse 90(0)

300(90) for the samples containing 200-250 microns

fractions. The use of composite pulses for carrying out

relaxation measurements allowed us to obtain more detailed

information on relaxation times

distribution in the samples containing s

(Fig.1). It was proved that distribution of longitudinal

relaxation times T1 and transverse relaxation times T2 has

multimodal character. Especially essential distinction in

relaxation times distribution was received for samples with

sizes of granules from 300 to 350 microns and

microns.

a)

Figure 1. T2 relaxation times distribution in the samples

containing a) 300-350 micron granules b)

granules with the use of the composite pulse

Conclusion The use of composite pulses for

in powder containing different

allowed us to achieve linewidth narrowing

the signal-noise ratio. Elimination of

with the inhomogeneous irradiati

imperfection of 900 - and 1800 pulses

pulses enabled us to extract more detailed information on

relaxation times distribution.

References [1] N.Ya. Sinyavsky, G.V. Mozzhukhin, P. Dolinenkov, in

Magnetic Resonance Detection of Explosives and Illicit Materials, NATO Science for Peace and Security Series B: Physics and Biophysics (Springer, Dordrecht, 2014), pp. 69–76.

[2] P.N. Dolinenkov, N.Ya. Sinyavsky, Immanuel Kant Baltic Federal University

10, 119–126 (2012). [3] N. Sinyavsky, P. Dolinenkov, G.S.Kupriyanova. The

T1 and T2 relaxation times distribution for the 35Cl and 14 N NQR in micromaterials // Appl. Magn. Reson

[4] G.S.Kupriyanova, V.V.MolchanovI.G.Mershiev. Compose pulses on inhomogeneous field NMR. In Magnetic Resonance Detection of Explosives and illicit Materials. Springer 2014, p.137

signal/noise in the NQR measurements uscomposite pulse

Kupriyanova, Ivan Mershiev, Filip Dolinenkov, Valeriy

Technical Faculty, Baltic Federal State University, Kaliningrad, Russia

yandex.ru


se of composite pulses for carrying out

relaxation measurements allowed us to obtain more detailed

distribution in the samples containing small granules

(Fig.1). It was proved that distribution of longitudinal

relaxation times T1 and transverse relaxation times T2 has

multimodal character. Especially essential distinction in

relaxation times distribution was received for samples with

o 350 microns and 200-250

b)

relaxation times distribution in the samples

micron granules b) 200-250 micron

use of the composite pulse 451801350

pulses for recording NQR signals

containing different sizes of microparticles

linewidth narrowing and to increase

Elimination of the effects associated

irradiation of the sample and the

pulses by applying composite

more detailed information on

N.Ya. Sinyavsky, G.V. Mozzhukhin, P. Dolinenkov, in Detection of Explosives and Illicit

Materials, NATO Science for Peace and Security Series B: Physics and Biophysics (Springer, Dordrecht, 2014),

P.N. Dolinenkov, N.Ya. Sinyavsky, Vestnic of the

Immanuel Kant Baltic Federal University, Kaliningrad

N. Sinyavsky, P. Dolinenkov, G.S.Kupriyanova. The T1 and T2 relaxation times distribution for the 35Cl and 14 N NQR in micro-composites and in porous

Reson, 2014, 45. pp. 471-482 G.S.Kupriyanova, V.V.Molchanov, E.A.Severin,

Compose pulses on inhomogeneous field NMR. In Magnetic Resonance Detection of Explosives and illicit Materials. Springer 2014, p.137-14

ts using

, Valeriy Sabirekian

Baltic Federal State University, Kaliningrad, Russia


Introduction Understanding transport in heterogeneous media is

important in various disciplines ranging from materials science, to porous catalysts, to oil recovery, to biophysics. The complexity of the microscopic structure of the object, such as heterogeneity in diffusive properties and restrictions on molecular motion, results in non-Gaussian evolution of particle displacements. In particular, the effective self

diffusion coefficient ( )D t itself becomes time

and shows a decrease from the value of the bulk selfdiffusion coefficient 0D to a constant value

time limit. In the present work, we find an analytical expression for the self-diffusion coefficient

molecules in a 2D heterogeneous medium.

Theory Inspired by the structure of the cell membrane and the

adjacent membrane cortex, we consider a particle diffusing in 2D in presence of a meshwork with permeable barriers characterized by a mean mesh sizemacroscopically long period of time t a diffusing molecule covers, as a result of the Brownian motion, a distance (diffusion displacement) in. The square of this didisplacement 2L is a sum of squares of diffusion

displacements 2il of this molecule in all meshes this

molecule has visited during time t . Hence, the average value of the square of the diffusion displacement of molecules in the medium under consideration over time interval t is as follows:

( )2 2 4L k l D R t∞= =

where 1k >> is the average number of passages from one

mesh to another during time t , ( )D R∞

self-diffusion coefficient, and 2l is the average square of

the molecule diffusion displacement for the time period

between two consecutive entries into neighboring meshes.

Previously it has been shown [1] that the dependence of the

self-diffusion coefficient on the geometry of the

heterogeneous medium can be described by the expression

( ) ((0 expst

D R D P R∞ = −

where 0D is the self-diffusion coefficient of the bulk liquid

and ( )stP R is the probability of “steric interaction” with a

barriers which generally depends on the size and shape of the mesh, permeability of the barriers, and size of diffusing particles.

Self-Diffusion in Cell Membranes in the Long Time Regime

Valentin V. Loskut

1Baker Hughes, Russian Science Center, Kutateladze 4A, Novosibirsk, 632Mari State University, Lenin Sq. 1, Yoshkar

E-mail: [email protected] Planck Institute of Biochemistry, Department of Cellular and Molecular Biophysics, Am

Klopferspitz 18, 82152 Martinsried, Germany

– 11, 2014 – 56 –

anding transport in heterogeneous media is important in various disciplines ranging from materials science, to porous catalysts, to oil recovery, to biophysics. The complexity of the microscopic structure of the object,

roperties and restrictions Gaussian evolution of

particle displacements. In particular, the effective self-

itself becomes time-dependent

e of the bulk self-to a constant value D∞ in the long

time limit. In the present work, we find an analytical diffusion coefficient D∞ of diffusing

molecules in a 2D heterogeneous medium.

Inspired by the structure of the cell membrane and the adjacent membrane cortex, we consider a particle diffusing in 2D in presence of a meshwork with permeable barriers

h size R . Over a t a diffusing molecule

covers, as a result of the Brownian motion, a distance L(diffusion displacement) in. The square of this diffusion

is a sum of squares of diffusion

of this molecule in all meshes this

. Hence, the average e of the diffusion displacement of

molecules in the medium under consideration over time

L k l D R t .

is the average number of passages from one

)D R is the long-time

is the average square of

the molecule diffusion displacement for the time period

es into neighboring meshes.

Previously it has been shown [1] that the dependence of the

diffusion coefficient on the geometry of the

heterogeneous medium can be described by the expression

))D R D P R ,

diffusion coefficient of the bulk liquid

is the probability of “steric interaction” with a

barriers which generally depends on the size and shape of the mesh, permeability of the barriers, and size of diffusing

Comparison with Computer SimulationsRecently, the effect of membrane microheterogeneity on anomalous subdiffusion in cell membranes was studied by Monte Carlo simulations of twolipid membranes coupled to a model membrane cowas found that the long time diffusion coefficient shows a pronounced reduction decrease with an increase in the filament pinning density (Figs. 1 and 2).

Figure 1. Representative snapshots of the lipid membrane

(left) and time-dependent effective diffusion coefficient

( )D t (right) at various filament pinning densities

Figure 2. Long time effective diffusion coefficient

function of the filament

In agreement with predictions of the model [1], the dependence of the long time effective diffusion coefficientD∞ on the filament pinning density follows the exponential

dependence. We will discuss the relationship between the physical and geometrical paracortex and parameters of the model.

References [1] V. V. Loskutov, V. A. Sevriugin.

29–41 (2009). [2] J. Ehrig, E. P. Petrov, P. Schwille.

89 (2011).

Diffusion in Cell Membranes in the Long Time Regime

Loskutov1,2, Eugene P. Petrov3

Baker Hughes, Russian Science Center, Kutateladze 4A, Novosibirsk, 63

Mari State University, Lenin Sq. 1, Yoshkar-Ola, Russia


Max Planck Institute of Biochemistry, Department of Cellular and Molecular Biophysics, Am

Klopferspitz 18, 82152 Martinsried, Germany

Comparison with Computer Simulations the effect of membrane microheterogeneity on

anomalous subdiffusion in cell membranes was studied by Monte Carlo simulations of two-component (DMPC/DSPC) lipid membranes coupled to a model membrane cortex [2]. It was found that the long time diffusion coefficient shows a pronounced reduction decrease with an increase in the filament pinning density (Figs. 1 and 2).

Figure 1. Representative snapshots of the lipid membrane

effective diffusion coefficient

filament pinning densities

. Long time effective diffusion coefficient D∞ as a

function of the filament pinning density

ions of the model [1], the long time effective diffusion coefficient

on the filament pinning density follows the exponential

dependence. We will discuss the relationship between the physical and geometrical parameters of the membrane–

cortex and parameters of the model.

V. V. Loskutov, V. A. Sevriugin. J. Porous Media, 12,

J. Ehrig, E. P. Petrov, P. Schwille. Biophys. J., 100, 80–

Diffusion in Cell Membranes in the Long Time Regime

Baker Hughes, Russian Science Center, Kutateladze 4A, Novosibirsk, 630128, Russia

Max Planck Institute of Biochemistry, Department of Cellular and Molecular Biophysics, Am

Introduction In the recent theoretical papers [1, 2] it wa

intramolecular and intermolecular contributions

dipole-dipole interaction in polymer melts

time dependences and generally one cannot neglect

intermolecular part as it was done before.

Theoretical predictions For polymer melts with T2 ≥ τ1 (terminal relaxation time)

the expression for intermolecular contribution into the

transverse relaxation rate is as follows: 1��&'(/% � :10 ; :16 <= >�?@A

B C4D4 . ∑ 1 � exp��4��I!"JK"

∞

8LFor polymer melts with T0<< τ1 approximation of the

transverse relaxation decay should be done with the use of

that expression:

M�4� N exp O�P 23: 36:�1 . Q�5�2 � 3R��4 � 3Rexp S� D 4��T=!U1� V

This works in the case of anomalous diffusion with

relative mean-squared displacement time dependence of this

type: W X̃��4� Z [41,

where α < 2/3.

Polyisoprene transverse relaxation studyTransverse relaxation was measured with the use of Hahn

echo pulse sequence in cis-polyisoprene-

mass dependence of T2 relaxation time is shown on the

Fig. 1.

For samples with molecular mass larger than 22000

T2. So curves of the transverse relaxation decay for samples

with M = 7100, 13200 and 22000 were studied with the use

of the expression (1). The results of calculated

NMR Studies of intermolecular interaction in

A. Lozovoy1, N.

1Kazan Federal University

E-mail: [email protected] Universität Ilmenau, 98693, Ehrenb


2] it was shown that

ntramolecular and intermolecular contributions to the

dipole interaction in polymer melts have different

time dependences and generally one cannot neglect

intermolecular part as it was done before.

(terminal relaxation time)

intermolecular contribution into the

?\A]

(1)

� ��TU�

approximation of the

transverse relaxation decay should be done with the use of

� � <=>�4�?W X̃��4� ^U� _ �

(2)

VThis works in the case of anomalous diffusion with

squared displacement time dependence of this

(3)

Polyisoprene transverse relaxation study ransverse relaxation was measured with the use of Hahn

-1,4. The molecular

relaxation time is shown on the

lecular mass larger than 22000 τ1 >>

nsverse relaxation decay for samples

7100, 13200 and 22000 were studied with the use

. The results of calculated

intermolecular contribution to the transverse relaxation rate

and measured transverse relaxation rate are gathere

table 1.

Figure 1. Dependence of T

molecular weight

Table 1. Comparison of experimental transverse relaxation

rate and the theoretical calculation

contribution

It is clear that contribution of intermolecular interactions

are not negligible while concerning nuclear magnetic

transverse relaxation.

Acknowledgements Financial support from Deutsche Forschungsgemein

schaft (DFG) through grants STA 511/13

and 907/16 is gratefully acknowledged.

References [1] N.Fatkullin, A.Gubaidullin, C. Mattea, and S. Stapf:

The Journal of Chemical Physics

224907, 2012. [2] Fatkullin, A. Gubaidullin, S. Stapf,

094903 (2010)

1000 10000

1E-3

0,01

0,1

T2, s

Mol. weight

NMR Studies of intermolecular interaction in polymer melts

, N. Fatkullin1, S. Stapf2, C. Mattea2

niversity, 420000, Kremlin str. 18, Kazan, Russia

[email protected]

Technische Universität Ilmenau, 98693, Ehrenbergstraße 29, Ilmenau, Germany

M "̀�, s-1

7100 110

13200 281

22000 384


intermolecular contribution to the transverse relaxation rate

and measured transverse relaxation rate are gathered in the

1. Dependence of T2 relaxation time on the

molecular weight

Table 1. Comparison of experimental transverse relaxation

rate and the theoretical calculation of intermolecular

It is clear that contribution of intermolecular interactions

are not negligible while concerning nuclear magnetic

Financial support from Deutsche Forschungsgemein-

schaft (DFG) through grants STA 511/13-1 and RO 907/15

and 907/16 is gratefully acknowledged.

N.Fatkullin, A.Gubaidullin, C. Mattea, and S. Stapf: The Journal of Chemical Physics, v. 137, №22,

Fatkullin, A. Gubaidullin, S. Stapf, J. Chem. Phys. 132,

100000 1000000

Mol. weight

polymer melts

ergstraße 29, Ilmenau, Germany

"̀�&'(/%

, s-1 Relative

contribution

29 26

83 29

210 55


Introduction Since their introduction in the late 70s [1], composed

pulses proved itself as a useful tool for compensating RF

field inhomogeneity and pulse length imperfections,

especially in spin-echo NMR experiments. In the past few

years, activity in this area of research increased due to using

of composite pulses in NMR quantum information

processing [2]. In this work, we present broadband

composite pulse sequences for NQR with limited phase

shift.

Composite pulses in NQR In NQR composite pulses usually used to compensa

field inhomogeneity and frequency offset effects. To design

NQR composite pulses, different methods were used:

perturbation approach, numerical calculations and

quaternion algebra [3]. Calculation of composite pulses

effects in NQR is generally more complex than similar ones

in NMR, because of SU(3) symmetry group of spin I=1

nuclei and effects of excitation averaging in powders and

amorphous substances. Because of that, pulse lengths

corresponding to maximum signal amplitude and spin

inversion is usually referred as “pseudo-

180°” pulses. Their actual length, comparing to NMR pulse,

is 119.5° and 257° accordingly. Another downside of

averaging effects is complex behavior of signal phase after

excitation with composite pulse.

Optimization goals and constraintsComposite excitation in NQR can reduce NQR line

broadening, increase signal magnitude, and increase

effective excitation range for remote detection.

Studying the effects of composite pulses, we could not

explore many composite pulse sequences due to hardware

limitations. Our NQR spectrometer, Tecmag Apollo, is

capable to 32-step phase modulation only

11.25°). Another issue is that many composite pulse

sequences is prone to strong phase distortion. Abrupt phase

changes may result in “holes” in excitation profile at

corresponding pulse lengths. In this case, minimization of

phase distortion would be beneficial.

Our goal was to design composite pulses with discrete

phase modulation, broadband excitation, limited phase

variance, and capable to phase cycling. For

calculations, we used fictitious operator approach by Vega

and Pines [4]. Numerical calculations performed with mixed

discrete-integer optimization using genetic algorithm. All

calculations were performed for on-resonance case.

Composite pulses for

Ivan Mershiev,

Institute of Physics and Technology

E-mail: IMershiev@

– 11, 2014 – 58 –

e their introduction in the late 70s [1], composed

pulses proved itself as a useful tool for compensating RF

field inhomogeneity and pulse length imperfections,

echo NMR experiments. In the past few

ch increased due to using

of composite pulses in NMR quantum information

processing [2]. In this work, we present broadband

composite pulse sequences for NQR with limited phase

In NQR composite pulses usually used to compensate RF

field inhomogeneity and frequency offset effects. To design

NQR composite pulses, different methods were used:

perturbation approach, numerical calculations and

quaternion algebra [3]. Calculation of composite pulses

complex than similar ones

in NMR, because of SU(3) symmetry group of spin I=1

nuclei and effects of excitation averaging in powders and

amorphous substances. Because of that, pulse lengths

corresponding to maximum signal amplitude and spin

-90°” and “pseudo-

180°” pulses. Their actual length, comparing to NMR pulse,

is 119.5° and 257° accordingly. Another downside of

averaging effects is complex behavior of signal phase after

on goals and constraints Composite excitation in NQR can reduce NQR line

broadening, increase signal magnitude, and increase

effective excitation range for remote detection.

Studying the effects of composite pulses, we could not

se sequences due to hardware

limitations. Our NQR spectrometer, Tecmag Apollo, is

step phase modulation only (multiple to

. Another issue is that many composite pulse

sequences is prone to strong phase distortion. Abrupt phase

may result in “holes” in excitation profile at

corresponding pulse lengths. In this case, minimization of

Our goal was to design composite pulses with discrete set

phase modulation, broadband excitation, limited phase

variance, and capable to phase cycling. For theoretical

we used fictitious operator approach by Vega

and Pines [4]. Numerical calculations performed with mixed

integer optimization using genetic algorithm. All

resonance case.

Results Fig. 1 shows simulated nutation curves for singe

excitation pulse and proposed composite pulses. Simulation

takes into account effects of powder averaging.

Figure 1. Nutation curves of NQR signal magnitude after

excitation with single pulse and proposed composite pulses.

Composite pulse sequences are shown in table 1

Composite pulses can provide uniform excitation of the

sample in a wide range of radiofrequency field intensities or

varieties of pulse lengths. Limited an

variation allows straightforward use of these composite

pulses in NQR experiments.

Table 1. Composite pulse sequences and limits of phase

variance

Composite pulse

A 0.15ϴ(180°)-0.25ϴ(157,5°)

B 0.17ϴ(247,5°)-0.5ϴ(67,5°)-

C 0,54ϴ(90°)-0,55ϴ(213,75°)

References [1] Malcolm H Levitt, Ray Freeman,

pulse imperfections in NMR spinJournal of Magnetic Resonance

Issue 1, April 1981, Pages 65[2] Boyan T. Torosov, Nikolay V. Vitanov

composite pulses for high-fidelity quanprocessing, Physical Review A

[3] K. L. Sauer, C. A. Klug, J. B. Miller, A. N. GarrowayUsing quaternions to design composite pul1 NQR, Applied Magnetic Resonance

Issue 3-4 , pp 485-500 [4] S. Vega and A. Pines, Operator formalism for double

quantum NMR, The Journal of Chemical Physics

Volume 66, Issue 12

Composite pulses for 14N NQR with minimal phase distortion

, Galina S. Kupriyanova

Institute of Physics and Technology, Immanuel Kant Baltic federal university, Kaliningrad, Russia

@kantiana.ru

1 shows simulated nutation curves for singe

excitation pulse and proposed composite pulses. Simulation

takes into account effects of powder averaging.

. Nutation curves of NQR signal magnitude after

tion with single pulse and proposed composite pulses.

Composite pulse sequences are shown in table 1

Composite pulses can provide uniform excitation of the

sample in a wide range of radiofrequency field intensities or

varieties of pulse lengths. Limited and smooth phase

variation allows straightforward use of these composite

Composite pulse sequences and limits of phase

∆φ

ϴ(157,5°)-0.35ϴ(225°) ±7°

-0.26ϴ(180°) +0.2°, -7°

ϴ(213,75°)-0,27ϴ(236,25°) +6°, -0.4°

Malcolm H Levitt, Ray Freeman, Compensation for pulse imperfections in NMR spin-echo experiments, Journal of Magnetic Resonance (1969), Volume 43,

, Pages 65-8 Nikolay V. Vitanov Smooth

fidelity quantum information Physical Review A 83, 053420 (2011)

K. L. Sauer, C. A. Klug, J. B. Miller, A. N. Garroway, Using quaternions to design composite pulses for spin-

Applied Magnetic Resonance, Volume 25,

Operator formalism for double The Journal of Chemical Physics,

N NQR with minimal phase distortion

Immanuel Kant Baltic federal university, Kaliningrad, Russia

Introduction There is growing interest to the studies of non

configurations of nuclear quadrupole resonance (NQR)

technique. For instance, a kind of the NQR parametric

detection, using irradiation of the sample by a carrier high

(microwave) frequency, has been proposed recently [

Another example, which has been already verified

experimentally, is a broadband NMR/NQR setup with non

resonant probe [2]. In our case we have studied an effect of

additional low-frequency radiation on the parameters of

higher frequency NQR signal.

Experiments and discussionTwo-channel NQR spectrometer on the base of

Apollo console with two-frequency probe and two Tomco

amplifiers have been used. RDX (C

trinitroperhydro-1,3,5-triazine) and sodium nitrite (NaNO

have been used as the samples in our experiments. One

channel has been used for detection of spin echo signal and

the second one has been used for non resonance irradiation

of the sample. Two frequency RF probe consisted of two

mutually orthogonal coils, each tuned to the own resonance

frequency.

The non-resonance attenuation of the echo signals has

been observed in the case of irradiation at the second

frequency. A pulse at the non-resonant frequency in the

range of 80 kHz – 800 kHz has been applied between 90

and 180o echo pulses. The value of attenuation depends from

the pulse duration, frequency and amplitude of RF magnetic

field induction B1, acting at the second channel (see Fig.1).

The linewidth broadening has been observed also in the free

induction decay (FID) experiments. In this case non

resonant irradiation pulse has been applied before

during the RF pulse. Our experiments reveal that: a) the

application of powerful radiofrequency pulse destroys the

spin coherency that in turn produces the attenuation of the

echo signal; b) irradiation pulse at the second frequency

results in broadening for 30% of FID signal; c) bo

and FID effects are decreasing with the frequency.

Two mechanisms may be responsible for disappearing of

the echo signal and broadening of FID signal. The first,

obvious mechanism is Zeeman effect of the oscillating RF

field on the quadrupole system. It is known [

application of the static or low-frequency magnetic field

Non resonance signal suppression in

Georgy Mozzhukhin

1Gebze Institute of Technology, 41400 Gebze2Kazan State Power Engineering University, 420066 Kazan, Russian Federation 3Baltic Federal State University, 320014 Kaliningrad, Russian Feder4Kazan Physical-Technical Institute (KPhTI), 420029 Kazan, Russian Federation



There is growing interest to the studies of non-standard

configurations of nuclear quadrupole resonance (NQR)

tance, a kind of the NQR parametric

detection, using irradiation of the sample by a carrier high

(microwave) frequency, has been proposed recently [1].

Another example, which has been already verified

experimentally, is a broadband NMR/NQR setup with non-

]. In our case we have studied an effect of

frequency radiation on the parameters of

Experiments and discussion channel NQR spectrometer on the base of Tecmag

y probe and two Tomco

amplifiers have been used. RDX (C3H6N6O6 – 1,3,5-

triazine) and sodium nitrite (NaNO2)

used as the samples in our experiments. One

channel has been used for detection of spin echo signal and

one has been used for non resonance irradiation

of the sample. Two frequency RF probe consisted of two

mutually orthogonal coils, each tuned to the own resonance

resonance attenuation of the echo signals has

irradiation at the second

resonant frequency in the

800 kHz has been applied between 90o

echo pulses. The value of attenuation depends from

the pulse duration, frequency and amplitude of RF magnetic

, acting at the second channel (see Fig.1).

he linewidth broadening has been observed also in the free

induction decay (FID) experiments. In this case non-

resonant irradiation pulse has been applied before and

periments reveal that: a) the

application of powerful radiofrequency pulse destroys the

spin coherency that in turn produces the attenuation of the

echo signal; b) irradiation pulse at the second frequency

results in broadening for 30% of FID signal; c) both echo

and FID effects are decreasing with the frequency.

Two mechanisms may be responsible for disappearing of

the echo signal and broadening of FID signal. The first,

obvious mechanism is Zeeman effect of the oscillating RF

m. It is known [3] that

frequency magnetic field

results in the broadening of powder NQR spectra.

possible mechanism is related to the effect of the electric

field component on piezoelectric crystals, like NaNO

Figure 1. The effect of the secondary irradiation

echo signal of RDX. The measurement error i

30%. The resonance frequency

channel frequency is 260 kHz. The values of the

been estimated for the 90° RF pulse

Conclusion

It has been shown that application of the secondary low

frequency irradiation suppresses the NQR echo signal and

results in broadening of FID signal. The effect may be

practically utilized in the two frequency RF probe

explosive detection devices to discriminate between the

NQR and spurious signals.

Acknowledgements



References [1] J. Apostolos, W. Mouyos,J. Feng, W. Chase

power stimulated emission nuclear quadrupole resonance detection system utilizing Rabi transitions, SPIE Defense, Security, and Sensing 2013, Baltimora, May 2013, ML, USA, 8709

[2] S.Mandal, S. Utsuzawa, Y.broadband low-frequency MR system, and Mesoporous Materials

[3] I.A.Safin, D.Ya.Osokin: Nuclear quadrupole resonance in nitrogen compounds. Publishing House Nauka, Moscow, USSR (1977).

resonance signal suppression in pulse NQR

Mozzhukhin1,2, Galina Kupriyanova3, Bulat Rameev

Gebze Institute of Technology, 41400 Gebze-Kocaeli, Turkey



Technical Institute (KPhTI), 420029 Kazan, Russian Federation



results in the broadening of powder NQR spectra. Another

possible mechanism is related to the effect of the electric

field component on piezoelectric crystals, like NaNO2.

secondary irradiation on the spin

The measurement error is near 20-

frequency is 3358 kHz and the second

frequency is 260 kHz. The values of the B1 have

pulse in NQR measurements

It has been shown that application of the secondary low-

frequency irradiation suppresses the NQR echo signal and

results in broadening of FID signal. The effect may be

practically utilized in the two frequency RF probes of

explosive detection devices to discriminate between the



J. Apostolos, W. Mouyos,J. Feng, W. Chase, Low-power stimulated emission nuclear quadrupole resonance detection system utilizing Rabi transitions, SPIE Defense, Security, and Sensing 2013, Baltimora, May 2013, ML, USA, 8709-66, www.spie.org S.Mandal, S. Utsuzawa, Y.-Q. Song, An extremely

frequency MR system, Microporous

178 (2013) 53–55 I.A.Safin, D.Ya.Osokin: Nuclear quadrupole resonance in nitrogen compounds. Publishing House Nauka,

Rameev1,4, Bekir Aktas1


ation

Technical Institute (KPhTI), 420029 Kazan, Russian Federation


Introduction Currently, significant attention is focused on

preclinical research and the number of

experimental techniques is constantly extending. Magnetic

Resonance Imaging (MRI) is one of the most promising

in vivo techniques due to non-invasiveness and absence of

the harmful radiation. The image contrast

parameters specific to MRI such as T1 and T2 as

biological properties of tissue such as water content, blood

flow and diffusion, etc. Another option is to use

contrast agents to highlight the region of interest

Equipment and techniques The laboratory in the University of Nizhny Nov

equipped with state of the art preclinical MR spectrometer,

9.4T superconducting wide bore magnet is driven by Agilent

DDR2 console (Fig. 1). The main directions of research

Nizhny Novgorod would be the functional imaging (fMRI)

– measurement of temporal changes of blood flow in the

different parts of the brain [1]; the diffusion

(DTI) – measurement of localized diffusion

determine the fiber structure of the brain [2]; the

angiography (ASL) – mapping the distribution of

in the brain [3]. In addition, we are going to use

most advanced MR techniques the chemical exchange

saturation transfer (CEST) – enchantment of the contrast

based on the magnetization transfer of highly diluted

contrast agent weak signal to strong water

signal can be registered directly [4].

Figure 1. The experimental setup: Agilent DDR2 400WB

Preclinical in

Maria S. MuravyevaElena V. Zagaynova

1Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, Russi

E-mail: [email protected]/MRC Oxford Institute fo3Nizhny Novgorod State Medical Academy, Nizhni Novgorod, Russia

– 11, 2014 – 60 –

attention is focused on the

the number of applicable

is constantly extending. Magnetic

maging (MRI) is one of the most promising

invasiveness and absence of

image contrast could be based on

parameters specific to MRI such as T1 and T2 as well as on

biological properties of tissue such as water content, blood

flow and diffusion, etc. Another option is to use specific

to highlight the region of interest.

in the University of Nizhny Novgorod is

equipped with state of the art preclinical MR spectrometer,

is driven by Agilent

directions of research

functional imaging (fMRI)

emporal changes of blood flow in the

diffusion tensor imaging

measurement of localized diffusion anisotropy to

iber structure of the brain [2]; the

mapping the distribution of blood flow

we are going to use one of the

chemical exchange

enchantment of the contrast

based on the magnetization transfer of highly diluted

ignal to strong water signal, which

mental setup: Agilent DDR2 400WB

Preliminary results The research in the MRI lab is still on the preliminary

stage. Significant work is devoted to the installa

various scientific equipments. The main focus of research is

going to be on the development of new contrast agents for

tumor detection. As preliminary results, we are

demonstrating here the first ever in vivo MR images taken

in Nizhny Novgorod. Anatomical T2*

mouse brain are shown in Fig. 2 (experimental parameters:

FOV = 40x40mm, matrix = 128x128; slice thickness =

1mm; echo time = 2ms; repetition time = 40ms; total

experimental time = 50s).

Figure 2. T2*-weighted in vivo imag

References [1] P.A. Bandettini. – Neuroimage

[2] A. Lerner, MA Mogensen, PE Kim, MS Shiroishi, DH Hwang, M Law. – World Neurosurg

00897-8 (2013). [3] EC Wong. – NMR Biomed.,

[4] G Liu, X Song, KW Chan, MT McMahon. Biomed., 26 (7), 810-28 (2013).

in vivo MR Imaging using the mouse m

Muravyeva1, Alexandr A. Khrapichev1,2, Marina V.Zagaynova1,3

Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, Russi

[email protected]

Oxford Institute for Radiation Oncology, University of Oxford, Oxford, UK

Nizhny Novgorod State Medical Academy, Nizhni Novgorod, Russia

The research in the MRI lab is still on the preliminary

stage. Significant work is devoted to the installation of

various scientific equipments. The main focus of research is

going to be on the development of new contrast agents for

tumor detection. As preliminary results, we are

demonstrating here the first ever in vivo MR images taken

tomical T2*-weighted images of

mouse brain are shown in Fig. 2 (experimental parameters:

FOV = 40x40mm, matrix = 128x128; slice thickness =

1mm; echo time = 2ms; repetition time = 40ms; total

weighted in vivo images of the mouse brain

Neuroimage., 62 (2), 575-88 (2012). A. Lerner, MA Mogensen, PE Kim, MS Shiroishi, DH

World Neurosurg., pii: S1878-8750,

NMR Biomed., 26 (8), 887-91(2013). X Song, KW Chan, MT McMahon. – NMR

28 (2013).

the mouse model

V. Shirmanova1,3,

Lobachevsky State University of Nizhni Novgorod, Nizhni Novgorod, Russia

, University of Oxford, Oxford, UK

The cardiac MRI, commonly used

specialized centers, is rarely applied in general hospitals.

While the percentage of cardiac pathology is one of the

biggest among other diseases. That is why

problem for a cardiology and radiology. Together with other

modalities, cardiac MR has a large field for research and




a difficult diagnostic case, when other



and function. The using of ECG-gating gives a possibility to



cardiac axes – gives anatomically-correct pattern of the

cardiac structures.


The “dark-blood” sequences are based on the spine echo,



the “bight-blood” sequences are based on the gradient ec



assumption in Echocardiography, the evaluation of the

cardiac function by MRI allows an accurate





tagging technique with the inversion pre-pul

Possibilities of the MRI in a complex assessment of cardiac diseases

I. N. Petrov, V.

Saint Petersburg State University

Mariinskaya hosp. Liteyniy,



The cardiac MRI, commonly used in cardiology-

in general hospitals.

percentage of cardiac pathology is one of the

biggest among other diseases. That is why it is a significant

cardiology and radiology. Together with other

, cardiac MR has a large field for research and



the MRI is an irreplaceable modality in

a difficult diagnostic case, when others are not reliable



gives a possibility to



correct pattern of the

ipal types of sequences.

blood” sequences are based on the spine echo,



blood” sequences are based on the gradient echo



Echocardiography, the evaluation of the

rdiac function by MRI allows an accurate quantification of

volumes, the ejection fraction and




pulses.

Quantification of the blood flow

other intracardiac hemodynamic

phase-encoding technique. It is actively used to determine


disease.

In spite of the higher resolution given by CT in coronary


to the iodine contrast agents. MR

improving and probably will be able to compete with CT

angiography soon.


ischemia and infarction. MR-perfusion has the best tissue

sensitivity. Combined with the


which is particularly important,

myocardium and determines the need of the

revascularization.

Delayed contrast-enhanced MRI gives a possibility to

reveal myocarditis, sarcoidosis, hypertrophic cardio

myopathy, myocardial scar. Moreover, myocardial mapping

enables to quantify these lesions.


abovementioned MR-methods, occasionally the real clinical


determine the right diagnosis. It forces to use the com

examination of the patient, from physical examination

tech modalities and to improve the current

imaging techniques

Possibilities of the MRI in a complex assessment of cardiac


Petersburg State University, Medical faculty, 21 line V.O., 8a


[email protected]


flow volumes, velocities and

hemodynamic values are enable via the

encoding technique. It is actively used to determine


higher resolution given by CT in coronary


MR-coronary angiography is

improving and probably will be able to compete with CT-

dality in visualization of the myocardial

perfusion has the best tissue

the stress-test, it gives accurate



determines the need of the

enhanced MRI gives a possibility to

reveal myocarditis, sarcoidosis, hypertrophic cardio-

myopathy, myocardial scar. Moreover, myocardial mapping

quantify these lesions.


methods, occasionally the real clinical



examination of the patient, from physical examination to hi-

to improve the current diagnostic

Possibilities of the MRI in a complex assessment of cardiac


Introduction Magnetic field pulses acting on nuclear spin echo

in magnetically ordered material, may be regarded as an

additional method for study of the substance, [1]. Recently

this technique was developed for such cases, as, for

example, domain walls investigation in poly

crystals of magnetic oxides, [2, 3]. Except of the use of the

method in physical search, it can be utilized in experimental

equipment elaboration and other branches of engineering.

The possible application belongs to functional electronics

[4], when a medium operates as a signal processing unit. It

is well known that the NMR in ferrites can be

this way in so called echo-processors,

regarded as an output signal of a system,

promising, such devices posses, however, a problem of

spurious signals, forming as responses of sample to

excitation by the radio frequency (RF) pulses from different

sequences (crossed echoes).

Here we discuss the suppression of the spurious

from interacting two-pulse trains by long m

pulse, overlapping in time the second RF sequence and the

interval, where the multiple responses appear.

Experimental method As an operating medium in this work a lithium

ferrite (Li0.425Fe2.425Zn0.15O4) was used, where the nuclear

spin echoes of 57Fe were excited by two series of RF pulses

(S1 and S2, including A, B and C, D pulses correspondingly).

An additional pulsed magnetic field with amplitude h

applied to the sample during the time of

formation interval τ. This scheme is illustrated

where the time diagrams of the pulse sequences with the

necessary notations are shown. As it is seen from the figure,

the combinations of RF pulses from S1 and S

two-pulse and stimulated mechanisms) a number of

responses, masking the desired signal (echo from two pulses

in every series).

Results Fig. 1 demonstrates the effect of pulsed magnetic field

onto the set of sample responses: the entire

cross echoes was completely suppressed when h

enough, while the signals excited by AB

persisted. The nature of the phenomenon is connected with

the fact that the NMR was observed from the domain walls,

Pulse magnetic field control of NMR signal in a ferrite domain walls

Pavel S. Popov1

1Saint Petersburg State Poly2Ioffe Institute, 194021 St


– 11, 2014 – 62 –

Magnetic field pulses acting on nuclear spin echo, excited

in magnetically ordered material, may be regarded as an

additional method for study of the substance, [1]. Recently

this technique was developed for such cases, as, for

investigation in poly- and single

crystals of magnetic oxides, [2, 3]. Except of the use of the

method in physical search, it can be utilized in experimental

and other branches of engineering.

The possible application belongs to functional electronics

[4], when a medium operates as a signal processing unit. It

is well known that the NMR in ferrites can be exploited by

processors, when the echo

regarded as an output signal of a system, [5]. Being

promising, such devices posses, however, a problem of

signals, forming as responses of sample to the

excitation by the radio frequency (RF) pulses from different

Here we discuss the suppression of the spurious echoes

by long magnetic field

in time the second RF sequence and the

responses appear.

ing medium in this work a lithium-zinc

was used, where the nuclear

Fe were excited by two series of RF pulses

pulses correspondingly).

with amplitude hM was

applied to the sample during the time of S2 action and echo

formation interval τ. This scheme is illustrated by Fig. 1,

where the time diagrams of the pulse sequences with the

necessary notations are shown. As it is seen from the figure,

and S2 produced (by

and stimulated mechanisms) a number of

echo from two pulses

Fig. 1 demonstrates the effect of pulsed magnetic field

onto the set of sample responses: the entire ensemble of

ompletely suppressed when hM was high

enough, while the signals excited by AB- or CD-pulses

persisted. The nature of the phenomenon is connected with

the fact that the NMR was observed from the domain walls,

which could be displaced by the external magneti

the latter has a form of pulse, shown in Fig. 1, and

overlapping the interval, where the response of the spin

system onto the action of S2 series is excited and registered,

the spins, involved to the formation of the echo signals from

S1 and S2 belong to the spatially separated areas. It means

that the different pulse trains no longer interact, and cross

echoes cannot arise.

Figure 1. Suppression of spurious signals by the magnetic

field pulse: (a) – RF pulse sequences with the

system responses, (b) – pulse of magnetic field, (c)

echoes, persisted after the magnetic field

The relationship of the suppression value with hconfirmed the model: the intensities of crossed echoes decreased with the increasing obeying the different dependencies for twostimulated responses.

Acknowledgements The work was supported by the

Academy of Sciences, Program P

References [1] L.A. Rassvetalov, A.B. Levitski.

Phys., 23, 3354–3359 (1981)[2] G.I. Mamniashvili, T.O. Gegechkori

C.A. Gavasheli. – Low Temperature Physics

472 (2012) [3] I.V. Pleshakov, N.S. Klekhta, Yu.I. Kuzmin.

Technical Physics Letters, 39[4] L.A. Rassvetalov. Functional electronics

Novgorod University Publ., Novgorod, 1999.[5] M.M. Nesterov, I.V. Pleshakov,

lytical Instrumentation (in Russian),

Pulse magnetic field control of NMR signal in a ferrite walls

1, Ivan V. Pleshakov1,2

Petersburg State Polytechnic University, 195251, St. Petersburg, Russia

194021 St. Petersburg, Russia


which could be displaced by the external magnetic field. If

the latter has a form of pulse, shown in Fig. 1, and

overlapping the interval, where the response of the spin

series is excited and registered,

the spins, involved to the formation of the echo signals from

belong to the spatially separated areas. It means

that the different pulse trains no longer interact, and cross

Suppression of spurious signals by the magnetic

RF pulse sequences with the full set of spin

pulse of magnetic field, (c) – desired

magnetic field switching on

The relationship of the suppression value with hM confirmed the model: the intensities of crossed echoes decreased with the increasing magnetic pulse amplitude, obeying the different dependencies for two-pulse and

supported by the Presidium of Russian

Academy of Sciences, Program P-03.

L.A. Rassvetalov, A.B. Levitski. – Sov. Solid State

3359 (1981) Gegechkori, A.M. Akhalkatsi,

Low Temperature Physics, 38, 466–

I.V. Pleshakov, N.S. Klekhta, Yu.I. Kuzmin. – 39, 644–646, (2013)

L.A. Rassvetalov. Functional electronics (in Russian). – rod University Publ., Novgorod, 1999.

Pleshakov, Ya.A. Fofanov. – Ana-

(in Russian), 16, 3–21 (2006).

Pulse magnetic field control of NMR signal in a ferrite

Petersburg, Russia

Introduction Recently extensively studied influence

reactions exchange on different physiological and pathological processes in biological objethe blood. However, so far not studied featureexchange in human breast milk and oral fluid, which is important for the development of non-invasive diagnostic methods, including the monitoring of environmental safety in the population.

Materials and methods Determination of deuterium concentration in water, bloo

plasma, human breast milk (HBM) and oral fluid (OFperformed using nuclear magnetic resonance spectrom(NMR) JEOL JNM-ECA 400MHz at the Center for collective use "Diagnostics of the structure nanomaterials" in Kuban State University (Krasnodar)Spectra were recorded at the corresponding resonance frequency of deuterium nuclei, 61.4 MHz. The recording parameters were acquisition time, 6.7 s; relaxation delay 20 s; x-pulse, 5.6 µs; and 0.15 hz resolution). The recording temperature was 25 s at a stabilization accuracy of 0.2 s. Themeasurements were performed using ampoules 5 mmdiameter, inside of which sealed capillaries were rigfixed. The latter contained mixtures nondeuterated dimethylsulfoxide (DMSO), cconcentration scale under determination. This yielded a 2D NMR signal in the region of 3.4 ppm (with respect to (СD3)4Si), while the 2D NMR signal of HDO lay in the field of 4.7 m.d. (with respect to (СD3)4Si). The obtained spewere processed by determining the ratio of the integral intensities of the 2D NMR signal of HDO in the investigated sample with respect to the 2D NMR signal of DMSOintensity of which was in turn determined under theconditions relative to standards (samples ofprecisely determined deuterium contents ofppm). The measurements for each samplerepeatedly to reduce the experimental error. The error of determination for the deuterium content in blood plasma was ±1 ppm [1]. Indicators D / H exchange were studiedbiological substrates in two groups of women in cwere examined in the Municipal Budget Institution of Health "Maternity" (Krasnodar). In group 1 (n = 14) were included women receiving an ordinary diet, group 2 (n = 8) were included women receiving, besides the usual dietdeuterium depleted water (60 ppm) in a volume of 1,liters per day for 25-30 days before the test . Statistical processing was performed using the R Development Core Team, (2008), the difference was considered significant at p <0.05. For evaluation of correlations used Pearson's coefficient (r).

Determination of deuterium concentration in the biological fluids using NMR spectroscopy

Kirill Sharapov1

Ilya M. Bykov2,

1Physics and engineering department, Kuban state university,

149, Stavropolskaya st., Krasnodar, Russia, 350040 2Kuban state medical university,



Recently extensively studied influence the isotopic D / H physiological and

pathological processes in biological objects, especially in features of deuterium

exchange in human breast milk and oral fluid, which is invasive diagnostic

methods, including the monitoring of environmental safety

Determination of deuterium concentration in water, blood plasma, human breast milk (HBM) and oral fluid (OF) were performed using nuclear magnetic resonance spectrometer

at the Center for re and properties of

State University (Krasnodar).. corresponding resonance

nuclei, 61.4 MHz. The recording 6.7 s; relaxation delay 20 solution). The recording

ature was 25 s at a stabilization accuracy of 0.2 s. The measurements were performed using ampoules 5 mm in

ich sealed capillaries were rigidly of deuterated and

nondeuterated dimethylsulfoxide (DMSO), calibrated in the tion. This yielded a 2D

3.4 ppm (with respect to D NMR signal of HDO lay in the field

The obtained spectra ing the ratio of the integral

signal of HDO in the investigated D NMR signal of DMSO-D1, the

determined under the same conditions relative to standards (samples of water with precisely determined deuterium contents of 3.7, 51, 150 ppm). The measurements for each sample were performed

error. The error of tent in blood plasma

Indicators D / H exchange were studied in biological substrates in two groups of women in childbirth,

Budget Institution of roup 1 (n = 14) were

included women receiving an ordinary diet, group 2 (n = 8) , besides the usual diet,

(60 ppm) in a volume of 1,5-2 30 days before the test . Statistical

the R Development Core nsidered significant at p

. For evaluation of correlations used Pearson's

Deuterium content in biological fluidsThe studies found that under man phy

conditions there is a gradient of the deuterium content (>> plasma >> HBM) and the last fluids differ significantly, as represented in the table below:

Table 1. Useful terms

Index Plasma

D, ppm 144,3±0,6 159,8

It is known that the indicators of deuterium in natural conditions in water, proteins, lipids, carbohydrates are differ significantly, due to different speeds of isotope (D / H) exchange reactions in various chemical bonds ibiomolecules:-OH, -SH, -NH2 (=in order to clarify the causes of the above described isotopic D / H gradient was carried out a correlation analysis of the relationship between deuterium content in biological fluids and biochemical composition of

As a result, it was found that there was a direct correlation relationship between the content of water in the biological fluids and deuterium parameters: r = 0,85 (p <0,05), whereas between the content of organic components in biological fluids and deuterium relationship: for proteins r = -0,45, carbohydrates r = lipids r = -0,96 (p <0,05), it should be considered in designing algorithms noninvasive assessment of heavy nonradioactive isotope in body, including deuterium, since the biochemical composition of biological fluids can be quite variable depending on the person's lifestyle (diet, physical activity and other factors) [2]. who consume deuterium depleted significant deuterium decrease at 19,7% (p <0,05).same time deuterium indicators also decreasedHBM, but the presence of isotopic D / H gradient (plasma ≥ HBM) survived. Thus, on the basis offound that in human biological fluids H gradient: OF >> plasma > HBdue primarily by features of the biochemical composition of the plasma, OF and HBM. The highest negative correlation (r = -0,96) noted between deuterium concentration and lipid content in the appropriate biological fluids.

Supported by the grant of the President of the Russian Federation for state support of young Russian scientists MK-1568.2014.4

References [1] Baryshev M.G., Basov A.A., Dzhimak S.S. et al.

Bulletin of the Russian Academy of Sciences: Physics

76 (12), 1349–1352 (2012).[2] O’Brien D.M., Wooler M.J.

Mass Spectrometry, 21, 2422

Determination of deuterium concentration in the biological fluids using NMR spectroscopy

1, Stepan S. Dzhimak1, Mihail G. Barishev1, , Karina I. Melkonyan2, Denis I. Shashkov1,

Physics and engineering department, Kuban state university,

149, Stavropolskaya st., Krasnodar, Russia, 350040

Kuban state medical university, 4, Sedina st., Krasnodar, Russia, 350063

[email protected]


Deuterium content in biological fluids The studies found that under man physiological

conditions there is a gradient of the deuterium content (OF ) and the last indicators in biological

fluids differ significantly, as represented in the table below:

OF HBM

159,8±0,4 141,6±0,4

It is known that the indicators of deuterium in natural conditions in water, proteins, lipids, carbohydrates are differ significantly, due to different speeds of isotope (D / H) exchange reactions in various chemical bonds in

(=N-H) и –R2C-H. Therefore, in order to clarify the causes of the above described isotopic D / H gradient was carried out a correlation analysis of the relationship between deuterium content in biological fluids and biochemical composition of plasma, OF and HBM.

As a result, it was found that there was a direct correlation relationship between the content of water in the biological fluids and deuterium parameters: r = 0,85 (p <0,05), whereas between the content of organic components

cal fluids and deuterium content there is inverse 0,45, carbohydrates r = -0,61,

0,96 (p <0,05), it should be considered in designing algorithms noninvasive assessment of heavy non-

cluding deuterium, since the biochemical composition of biological fluids can be quite variable depending on the person's lifestyle (diet, physical

In blood plasma of women depleted water, there was a

decrease at 19,7% (p <0,05). At the deuterium indicators also decreased in OF and

, but the presence of isotopic D / H gradient (OF >> Thus, on the basis of our studies

found that in human biological fluids there is an isotopic D / HBM, the presence of which is

features of the biochemical composition of he highest negative correlation

0,96) noted between deuterium concentration and lipid content in the appropriate biological fluids.

upported by the grant of the President of the Russian of young Russian scientists

Baryshev M.G., Basov A.A., Dzhimak S.S. et al. – Bulletin of the Russian Academy of Sciences: Physics,

1352 (2012). O’Brien D.M., Wooler M.J. – Rapid communication in

2422-2430 (2007).

Determination of deuterium concentration in the biological fluids

, Aleksandr A. Basov2, , Denis V. Kashaev1

Russia, 350063


Introduction Stable complexes of azacrownethers and cryptands with

metal ions are known more than two decades. Of special

interest are the lanthanide derivatives The application of

lanthanides in many fields is closely related to their

unusually high co-ordination number and large charge

density. Many uses require complexation of the lanthanide

with suitable organic ligands, which then allow, for

example, introduction of other functions into systems like

chemical nucleases. Of special interest is their superb

hydrolytic cleavage of biocidic phosphate esters, DNA and

RNA. There are not many structural investigations with such

systems (see e.g. [1, 2]).

Results and discussion We have studied the complexation of MX

and Pr; X = Cl, NO3 and SO3CF3) with 1,10

crown-6 with R = H at N (I), R = n

[221]cryptand (III) and [222]cryptand (IV

NMR spectra revealed for the complexes different types of

coordination sphere for the lanthanide ions. The nature of

solvent is important factor for controlling the ligature type.

In classical innersphere complexes, metal atom binds to all

co-ordination sites of the ligands (first of all N

Complexation leads to dramatic effect on c

the ligand, which studied by detailed analysis of multiplet

structure of high resolution 1H NMR spectra and supported

for the most important cases by X-Ray studies.

provides important information on the structure of first co

ordination shell of the lanthanide complexes in solutions.

Complexation with monocyclic ligands

deshielding effect of 139La nuclei by 30 ppm, while co

ordination with bicyclic IV (D3h-symmetry complex)

enlarges shielding by 100-130 ppm.

complexes of host-guest type are rigid on the NMR time

scale. Their structure analysis was performed using the

whole magnitude of NMR spectral information, first of all

the spin-spin coupling network for the diamagnetic La(III)

Structure and stability of

Alla K. Shestakova

1State Research Institute of Chemistry and Technology of Organoelement Compounds, sh.

Entuiastov 38, 111123 Moscow, Russia

E-mail: [email protected] of Chemistry, Moscow State University, Leninskie Gory 1/3, 119992 Mosco


– 11, 2014 – 64 –

Stable complexes of azacrownethers and cryptands with

metal ions are known more than two decades. Of special

interest are the lanthanide derivatives The application of

closely related to their

ordination number and large charge

density. Many uses require complexation of the lanthanide

with suitable organic ligands, which then allow, for

example, introduction of other functions into systems like

nucleases. Of special interest is their superb

hydrolytic cleavage of biocidic phosphate esters, DNA and

RNA. There are not many structural investigations with such

We have studied the complexation of MX3 (M = La, Eu

) with 1,10-diaza-18-

), R = n-C10H23 (II),

IV). The 1H and 13C

NMR spectra revealed for the complexes different types of

lanthanide ions. The nature of

solvent is important factor for controlling the ligature type.

In classical innersphere complexes, metal atom binds to all

ordination sites of the ligands (first of all N-atoms).

Complexation leads to dramatic effect on conformation of

the ligand, which studied by detailed analysis of multiplet

H NMR spectra and supported

Ray studies. 139La NMR

provides important information on the structure of first co-

tion shell of the lanthanide complexes in solutions.

Complexation with monocyclic ligands I and II leads to

La nuclei by 30 ppm, while co-

symmetry complex)

The innersphere

guest type are rigid on the NMR time

scale. Their structure analysis was performed using the

whole magnitude of NMR spectral information, first of all

spin coupling network for the diamagnetic La(III)

complexes. Comparison of the chemical shifts for the

diamagnetic La(III) and paramagnetic Eu(III) and Pr(III)

complexes provides a contact and pseudocontact shielding

terms for both 1H and 13C nuclei, which also allows the

geometry interpretation.

Monocyclic ligands I and II

symmetry and cis-conformation

(chloroform, acetonitrile, methanol), which supported also

by Xray data of complex between lanthanum nitrate and

macrocycle I [1]. The complexes with [221]cryptand are

highly stable even in water solutions. We show, that

complexes with the [222]cryptand of the type EuX

Cl, NO3 and SO3CF3; L = IV) exist in the two forms: with

D3h and C2v-symmetry. In contrast to monocyclic ligands,

lanthanide cryptates are formed slowl

(see e.g. [2]). We present here results of the kinetics studies

of their formation for europium chloride and triflate in

methanol solution. Xray diffraction data revealed the

structure of innersphere almost C

with [221]cryptand and hydrated lanthanum triflate. A series

of ECP quantum chemical calculations (Lanl2dz approach)

supports the structure of complexes under study.

Experimental vicinal spin-spin coupling constants between

protons of neighboring CH2-

lanthanum salts with macrocyclic ligands

solutions (CDCl3, CD3OD and CD

agreement with the ab’inito calculated ones (PFT DFT with

Ub3lyp and 6G/311(d) basis set, see e.g. [3]). The

conformation of the biggest loop

close to that of 1,10-diaza-18-crown

complexes.

References [1] A.K. Shestakova, V.A. Chertkov,

Letters, 41, 6753-6756 (2000[2] A.K. Shestakova, V.A. Chertkov, H.

Lysenko, Org. Letters, 3, 325[3] W. Deng, J.R. Cheeseman, M.J. Frisch,

Theory and Comput., 2 1028

and stability of lanthanide cryptates in solutions

Shestakova1, Vyacheslav A. Chertkov2

State Research Institute of Chemistry and Technology of Organoelement Compounds, sh.

Entuiastov 38, 111123 Moscow, Russia


Department of Chemistry, Moscow State University, Leninskie Gory 1/3, 119992 Mosco


on of the chemical shifts for the

diamagnetic La(III) and paramagnetic Eu(III) and Pr(III)

complexes provides a contact and pseudocontact shielding

C nuclei, which also allows the

form complexes with C2v –

conformation in weak solvating solvents

(chloroform, acetonitrile, methanol), which supported also

by Xray data of complex between lanthanum nitrate and

. The complexes with [221]cryptand are

ly stable even in water solutions. We show, that

complexes with the [222]cryptand of the type EuX3L (X =

) exist in the two forms: with

symmetry. In contrast to monocyclic ligands,

lanthanide cryptates are formed slowly on NMR time scale

(see e.g. [2]). We present here results of the kinetics studies

of their formation for europium chloride and triflate in

methanol solution. Xray diffraction data revealed the

structure of innersphere almost C2v–symmetrical complex

[221]cryptand and hydrated lanthanum triflate. A series

of ECP quantum chemical calculations (Lanl2dz approach)

supports the structure of complexes under study.

spin coupling constants between

-groups for complexes of

lanthanum salts with macrocyclic ligands I and III in

OD and CD3CN) are in good

calculated ones (PFT DFT with

Ub3lyp and 6G/311(d) basis set, see e.g. [3]). The

conformation of the biggest loop of the [221]cryptand is

crown-6 in their lanthanum

A.K. Shestakova, V.A. Chertkov, H.-J. Schneider, Tetr.

2000). A.K. Shestakova, V.A. Chertkov, H.-J. Schneider, K.A.

325-327 (2001). W. Deng, J.R. Cheeseman, M.J. Frisch, J. Chem.

1028-37 (2006).

ryptates in solutions

State Research Institute of Chemistry and Technology of Organoelement Compounds, sh.

Department of Chemistry, Moscow State University, Leninskie Gory 1/3, 119992 Moscow Russia

Introduction Heat shock protein Hsp70 is known to stimulate anti

tumor immune response and thus could be applied for

immunotherapy in neuro-oncology [1]. Previously, it was

reported that targeted delivery of Hsp70 to the glioblastoma

could be achieved by implication of magnetic nanoparticles

(MNPs) [2]. Further analyses of magnetic conjugates

distribution in vivo by MR imaging and magnetometry is

highly important for optimizing therapy.

Materials and Methods Superparamagnetic nanoparticles w

carbodiimide modified Hsp70 (Hsp70-SPIONs) as

earlier [2]. The biodistribution of conjugates was analyzed

in the model of intracranial glioma C6 in rats. On the 20

day following tumor implantation conjugates were

intravenously administered. After 24 hours animals were

sacrificed and tissue samples were obtained for

magnetometry. The methods of longitudinal nonlinear

response to a weak ac magnetic field and registration of

electron magnetic resonance were used for detail study of

the Hsp70-SPIONs in tissues [3]. The tumor selectivity of

MNPs was analyzed in the MRI scanner at 11

Results Synthesized SPION-Hsp70 conjugates had the properties

of the negative MR T2-contrast agents. Intravenous

administration of the conjugates resulted

the particles in the glioma that was detected by MR scans

(Fig. 1).

Figure 1. MR imaging of the Hsp70-SPIONs

in the glioma C6 (shown by red arrows)

Magnetic biosensing of experimental glioblastoma targerting with superparamagnetic nanocarriers tagged to heat shock protein Hsp70

Maxim A. ShevtsovYaroslav Y. Marchenko

1Institute of Cytology of the Russian Academy of Sciences (RAS), Russia, St.

E-mail: [email protected] Institute of Highly Pure Biopreparations, Russia, St.3Petersburg Nuclear Physics Institute, NRC Kurchatov Institute, Russ


Heat shock protein Hsp70 is known to stimulate anti-

tumor immune response and thus could be applied for

oncology [1]. Previously, it was

reported that targeted delivery of Hsp70 to the glioblastoma

be achieved by implication of magnetic nanoparticles

(MNPs) [2]. Further analyses of magnetic conjugates

by MR imaging and magnetometry is

were coupled to

SPIONs) as reported

The biodistribution of conjugates was analyzed

in the model of intracranial glioma C6 in rats. On the 20th

day following tumor implantation conjugates were

inistered. After 24 hours animals were

sacrificed and tissue samples were obtained for

magnetometry. The methods of longitudinal nonlinear

response to a weak ac magnetic field and registration of

electron magnetic resonance were used for detail study of

SPIONs in tissues [3]. The tumor selectivity of

MNPs was analyzed in the MRI scanner at 11 T.

Hsp70 conjugates had the properties

contrast agents. Intravenous

in accumulation of

the particles in the glioma that was detected by MR scans

SPIONs accumulation

in the glioma C6 (shown by red arrows)

Further magnetometry of tissue samples confirmed the

preferential accumulation of the Hsp70

with distribution in other tissues as follows: glioma > liver >

lungs > heart > muscle > brain > skin. The magnitude of

signal was calibrated and represented in relative units as

measure of magnetic material in samples. T

of magnetic conjugates was found in glial tumor in

comparison to surrounding normal brain tissues thus proving

the tumor retention of the nanoparticles (

Figure 2. ReM2 (a) and ImM2 (b) versus magnetic field H

for brain and glioma tissues. Solid and open symbols are

used for curves recorded at direct and reverse H

respectively. The parameters of ReM2(H) that are used in

data analysis are displayed in panel (a)

Conclusions 1. The applied magnetic biosensing is sensitive method

for measuring the magnetic conjugates in tissues.

2. Hsp70-SPION conjugates could be accumulated in

glioblastoma in high dosage.

Acknowledgements Authors thank A. V. Dobrodumov, A.

I. N. Voevodina for support of the study.

References [1] M.A. Shevtsov, et al. – In

10.1002/ijc.28858 [2] M.A. Shevtsov, L.Y. Yakovleva, B.P. Nikolaev, et al.

Neuro-Oncology, 16, 38–49 (2014)[3] V.A. Ryzhov et al. – Appl.

(2014).

Magnetic biosensing of experimental glioblastoma targerting with superparamagnetic nanocarriers tagged to heat shock protein

Shevtsov1, Boris P. Nikolaev2, Ludmila Y. YakovlevaMarchenko2, Vyacheslav A. Ryzhov3

itute of Cytology of the Russian Academy of Sciences (RAS), Russia, St.

[email protected]

Research Institute of Highly Pure Biopreparations, Russia, St. Petersburg

Petersburg Nuclear Physics Institute, NRC Kurchatov Institute, Russia, Gatchina


Further magnetometry of tissue samples confirmed the

ation of the Hsp70-SPIONs in tumor

with distribution in other tissues as follows: glioma > liver >

lungs > heart > muscle > brain > skin. The magnitude of

signal was calibrated and represented in relative units as

measure of magnetic material in samples. The high content

of magnetic conjugates was found in glial tumor in

comparison to surrounding normal brain tissues thus proving

the tumor retention of the nanoparticles (Fig. 2).

. ReM2 (a) and ImM2 (b) versus magnetic field H

tissues. Solid and open symbols are

used for curves recorded at direct and reverse H-scans,

respectively. The parameters of ReM2(H) that are used in

data analysis are displayed in panel (a)

The applied magnetic biosensing is sensitive method

or measuring the magnetic conjugates in tissues.

SPION conjugates could be accumulated in

Dobrodumov, A. M. Ischenko,

for support of the study.

Int. J. Cancer, 2014, DOI:

M.A. Shevtsov, L.Y. Yakovleva, B.P. Nikolaev, et al. – 49 (2014).

Magn. Reson., 45, 339–352

Magnetic biosensing of experimental glioblastoma targerting with superparamagnetic nanocarriers tagged to heat shock protein

Yakovleva2,

itute of Cytology of the Russian Academy of Sciences (RAS), Russia, St. Petersburg

Petersburg

Gatchina


Introduction Dendrimers are a relatively new class of polymer systems

with unique properties, which have applications in various areas of polymer chemistry, biology and medicine.work the method of nuclear magnetic resonance for studying the rotational mobility of atomsincluded in the internal part (the kernel) dendrimers and beyond the kernel (spacer or limit the group) for carbosilane dendrimers of the 5th generation, containing end groups butyl hydroxyphenyl ether of hydroxybenzoicto the matrix via ethyleneglycol of the spacer.

The chemical and structural formulas of the dendrimer are shown in Fig. 1.

3 6 3 3 6 3 Si(-CH2-CH2-CH2)4[Si-(CH2-CH2-CH2 | CH3 1

CH2

H2C

CH2

OCH2

H2C

O

H2C

CH2

OCH2

H2C

O

H2C

CH2

SiOSi

CH3

CH3

CH3

CH3

O C

O

2 2

22

3a 10

13 14

15

8

12

12

12 12

12

Figure 1. Structural and chemical formula

dendrimers of the 5th generation (Peg

The main task of the work was a detailed comparison of the temperature dependences of rates NMR relaxation of hydrogen nuclei (1/Tgroups of dendrimers of the 5th generation (Peg

The experimental part The studied systems were solutions of dendrimers in the

deuterated chloroform (CDCl3) with concentration of dendrimers and of about 3% wt. The measurements of 1HNMR spectra were carried out with the spectrometer AVANCE 400 and AVANCE 600 (Bruker, relaxation measurements - spectrometer AVANCE 400).

The choice of the temperature range of research (225320 K) was determined by the boiling and freezing points of deuterochloroform.

Results and discussion The work was directed to build

dependences of the relaxation rates in the temperature range T = 228 – 318 K and to determine the main parameters, such as the activation energy and the correlation time.

Figure 2 shows the temperature dependence of the relaxation rate for carbosilane dendrimers and its approximation.

Spin-lattice relaxation of hydrogen nuclei icarbosilane dendrimers mesogenic groups attached

E. V. Shishmakova

Department of physics, St. Petersburg State University,

Ulyanovskaya street 1, Petrodvorets


– 11, 2014 – 66 –

Dendrimers are a relatively new class of polymer systems with unique properties, which have applications in various areas of polymer chemistry, biology and medicine. In this

netic resonance is applied rotational mobility of atoms, which

included in the internal part (the kernel) dendrimers and spacer or limit the group) for carbosilane

generation, containing end groups hydroxybenzoic acid, attached

of the spacer. hemical and structural formulas of the dendrimer

2)2]124 [R]128

O C

O

O CH2

H2C

CH2

CH3

5

7

9

11

Structural and chemical formulas of carbosilane

generation (Peg-But)128

The main task of the work was a detailed comparison of rates of the spin-lattice

hydrogen nuclei (1/T1H) for different generation (Peg-But).

The studied systems were solutions of dendrimers in the deuterated chloroform (CDCl3) with concentration of dendrimers and of about 3% wt. The measurements of 1H-NMR spectra were carried out with the spectrometer

CE 600 (Bruker, relaxation spectrometer AVANCE 400).

The choice of the temperature range of research (225 K ÷ 320 K) was determined by the boiling and freezing points of

ild the temperature in the temperature range

the main parameters, such as the activation energy and the correlation time.

Figure 2 shows the temperature dependence of the for carbosilane dendrimers of fifth generation

3,1 3,2 3,3 3,4 3,5

1,4

1,6

1,8

2,0

2,2

2,4

1/T

1, [

1/se

k]

1000/T, [1/K]

Figure 2. Temperature dependence of the relaxation rate

carbosilane dendrimers of the

It was obtained that not all lines have a bellas in Fig. 2. Most of the lines were presented in a more complex form, which was impossible to handle the exponential curve.

For the theoretical description of the expected temperature dependences the standard fun

( )(0 0

1H 0 0

( ) ( )1, 4

1 ( ) 1 2 ( )cor cor

cor cor

AT

τ τω

ωτ ωτ

= +

+ +

T TT

T T

where, Ea is the activation energy, ωfrequency, τcor is the correlation time.processing relaxation rates for 1 and 3 lines of dendrimers.

Table 1. The results of processing

dependences of the relaxation rates

investigated dendrimers

№ Peak Ea, kJ/mol

(±5%) τ0, ps

(±20%)1 18,4 0,133 19,1 -

Conclusion As it follows from the temperature dependences, only the

lines relating to the core of dendrimers (“demonstrate a simple bell-shaped form, the corresponding dependence (1) with one correlation time. The majority of the remaining lines show more complicated temperature dependence, which can be described as a combinatwo or more dependence of the type is explained by the superposition of several types of reorientation, when there is a large number offreedom involving these groups.

lattice relaxation of hydrogen nuclei in dilute solutions carbosilane dendrimers of the 5th generation with integral mesogenic groups attached by ethyleneglycol spacers

Shishmakova

Department of physics, St. Petersburg State University,

Ulyanovskaya street 1, Petrodvorets, St.Petersburg, 198504, Russia


3,5 3,6 3,7 3,8 3,9

1000/T, [1/K]

Rel_L1

Temperature dependence of the relaxation rate of

5 generation (Peg-But)128

that not all lines have a bell-shaped form as in Fig. 2. Most of the lines were presented in a more complex form, which was impossible to handle the

For the theoretical description of the expected temperature dependences the standard function was taken:

) ( )2 2

0 0

( ) ( ), 4

1 ( ) 1 2 ( )cor cor

cor cor

τ τ

ωτ ωτ

= +

+ +

T T

T T

, (1)

is the activation energy, ω0 is the resonance correlation time. Table 1 presents data

for 1 and 3 lines of dendrimers.

esults of processing of the experimental

rates for 1 and 3 lines of the

, ps (±20%)

А0, 1010 (±20%)

τcor, ns (±20%)

0,13 0,40 0,43 - 0,56 0,38

As it follows from the temperature dependences, only the of dendrimers (“internal” line) shaped form, the corresponding

one correlation time. The majority of the remaining lines show more complicated temperature dependence, which can be described as a combination of

the type (1). Apparently, this type is explained by the superposition of several types of

a large number of the degrees of freedom involving these groups.

n dilute solutions generation with integral

spacers

Introduction The intermetallic compound Ti3Al having the hexagonal

DO19-type structure shows excellent mechanical properties

and oxidation resistance. The alloy is also a candidate for

light hydrogen-storage material. Since hydrogen absorption

may lead to strong changes in properties of an

intermetallic [1], it is important to have a clear microscopic

picture of the hydrogen effects in the Ti

aim of the investigation is to obtain experimental

information on H-sites, hydrogen mobility and hydrogen

induced changes in the electronic structure. In this work we

report the results of a nuclear magnetic resonance (NMR)

study of the Ti3AlHx system over wide range of

concentrations (0 ≤ x ≤ 4.3).

Results and discussion The intermetallic compound Ti3Al was charged with H

gas at a pressure of about 1 bar using a Sieverts

vacuum system and the hydrogen content was determined

from the pressure change in the calibrated volume of the

system. According to x-ray diffraction analysis, two samples

with hydrogen content of x = 0.31 and

solutions, but other samples with H content of

have different crystal structures. Lattice parameters and the

crystal structures are presented in table 1.

Table 1. Lattice parameters of studied samples Ti

Sample α (hexagonal) β (b.c.c)

aa, Å c, Å

Ti3Al 5.8 4.66

Ti3AlH0.31 5.8 4.65

Ti3AlH0.51 5.8 4.65

Ti3AlH1 5.76 4.9 3.28

Ti3AlH2 - - 3.29

Ti3AlH4.32 - - 3.27

The measured spin-lattice relaxation rate 27Al is the sum of several contributions. In metal

system, the main contributions to T1-1

interaction between nuclear spins and conduction electrons

(T1e-1) and the dipole-dipole interaction of nuclear spins

modulated by hydrogen motion (T1d-1). At low temperatures,

the T1d-1 contribution is negligible, and the

is determined directly from T1-1. The electronic contribution

is proportional to temperature, T1e-1 = A +

A and Ce obtained from the linear approximation are listed

Hydrogen in Ti

A. V. Soloninin, A.

Institute of Metal Physics, Ural Division of the Ru

S. Kovalevskoi 18, Ekaterinburg 620

E-mail: alex.soloninin


Al having the hexagonal

type structure shows excellent mechanical properties

ance. The alloy is also a candidate for

storage material. Since hydrogen absorption

may lead to strong changes in properties of an

[1], it is important to have a clear microscopic

picture of the hydrogen effects in the Ti3Al-H system. The

aim of the investigation is to obtain experimental

sites, hydrogen mobility and hydrogen-

induced changes in the electronic structure. In this work we

report the results of a nuclear magnetic resonance (NMR)

system over wide range of

Al was charged with H2

gas at a pressure of about 1 bar using a Sieverts-type

vacuum system and the hydrogen content was determined

ure change in the calibrated volume of the

ray diffraction analysis, two samples

0.31 and x = 0.51 are solid

solutions, but other samples with H content of x = 1; 2; 4.32

. Lattice parameters and the

Lattice parameters of studied samples Ti3AlHx

β (b.c.c) a, Å

γ (f.c.c.) a, Å

- -

- -

- -

3.28 -

3.29 -

3.27 4.35

lattice relaxation rate T1-1 of 1H and

Al is the sum of several contributions. In metal-hydrogen

are the hyperfine

interaction between nuclear spins and conduction electrons

dipole interaction of nuclear spins

). At low temperatures,

contribution is negligible, and the T1e-1 contribution

. The electronic contribution

+ CeT. The values of

e linear approximation are listed

in table 2. Ce is proportional to the square of full density of

electron states at the Fermi level,

of Ce for 27Al and 1H nuclei in Ti

N(EF) in the compounds with increasi

Large value of A for 1H can be explained by the significant

impurity concentrations.

Table 2. Values of A and Ce obtained from the low

temperature data on T1-1

of nuclei

23 MHz

Sample A, s-1 27Al 1H

Ti3Al 0.01 -

Ti3AlH0.31 ~0 0.229

Ti3AlH0.51 ~0 0.475

Ti3AlH1 ~0 1.45

Ti3AlH2 ~0 0.253

Ti3AlH4.32 ~0 0.368

Figure 1 shows the temperature dependence of the spin

lattice relaxation rate of 1H in Ti

Significant T1-1 deviations from the linear behavior were

detected only above 300 K at 23.8 MHz for samples with

x ≥ 1. These deviations can be attributed to H mobility. The

hydrogen mobility in Ti3AlHx with

the occupation of the tetrahedral interstitial sites by H

atoms.

0 50 100 150 200 2500

5

10

15

20

25 23.8MHz

Ti3AlH

0.31

Ti3AlH

0.51

Ti3AlH

1

Ti3AlH

2

Ti3AlH

4.32

T1

-1, s-1

T, K

Figure 1. Temperature dependences of the spi

relaxation rate of protons in Ti

References [1] P. S. Rudman, J. J. Reilly, R. H. Wiswall.

Common Met., 58, 231-240 (1978).

Hydrogen in Ti3Al: a nuclear magnetic resonance study

, A. V. Skripov

Institute of Metal Physics, Ural Division of the Russian Academy of Sciences

S. Kovalevskoi 18, Ekaterinburg 620990, Russia

[email protected]


is proportional to the square of full density of

electron states at the Fermi level, N2(EF), and a comparison

H nuclei in Ti3AlHx shows an increase in

) in the compounds with increasing hydrogen content.

H can be explained by the significant

obtained from the low-

of nuclei 1H at 90MHz and

27AL at

Ce, s-1K-1

H 27Al 1H

- 0.0084 -

0.229 0.009 0.005

0.475 0.0108 0.007

1.45 0.0118 0.004

0.253 0.0468 0.009

0.368 0.0548 0.008

Figure 1 shows the temperature dependence of the spin-

H in Ti3AlHx at 23.8 MHz.

deviations from the linear behavior were

detected only above 300 K at 23.8 MHz for samples with

1. These deviations can be attributed to H mobility. The

with x≥1 is likely to be due to

the occupation of the tetrahedral interstitial sites by H

250 300 350 400 450

T, K

Temperature dependences of the spin-lattice

relaxation rate of protons in Ti3AlHx at 23.8 MHz

P. S. Rudman, J. J. Reilly, R. H. Wiswall. – J. Less-

240 (1978).

etic resonance study

Academy of Sciences


Introduction In this report we discuss results from our study of

H2O-H2O2-D2O system with different concentration D

and H2O2. It is known that H2O, H2O2 and D

play an important role in a variety of different biochemical

reactions and biophysical processes of live cells.

compared the results of studies of the spin

time, chemical shift (2D) of H2O-H2O2-D

systems.

Experiment Measurements were carried out on a NMR spectrometer

JEOL JNM-ECA 400. It was used the distilled water with

resistance 300 kOm/sm and D2O (enriched to 99.8% in

deuterium). The water samples for the deuterium

measurements were prepared with different concentrations

of D2O (C), lay in the range of 7 – 97 %.

samples for the deuterium measurements were prepared with

different concentrations of D2O, lay in the range of

100%. The point 0% means that the sample cont

H2O2 (37% of peroxide and native concentration of

deuterium) and the point 100% is equal the net D

(enriched to 99.8% in deuterium). The spin

times (T1) were measured at 61.4 MHz. The pulse sequence

used was 180° - τ - 90°. The temperature in the probe was

controlled with the accuracy of ±0.5 K. The uncertainties of

the derived T1 values was estimated to be

Results and discussion The concentration dependence of the

relaxation time in H2O-D2O and H2O-

present in figure 1. T1 is determined at 293 K. Results

indicates, that the spin-lattice relaxation time

has the polynomial form. Curve approximations are shown

on the figure 1. The upper curve corresponds to the

H2O2-D2O system, the lower curve - H2O

figure 1 shows that the curves differ from each other.

Extremes of polynomial functions are located in different

places in the concentration range. Function

D2O) has a maximum and a minimum (H

We used the expression obtained in [1]

time, to determine the parameters that change when you add

the peroxide in the H2O-D2O system.

these parameters are the activation energy (related to the

correlation time) and the so-called parameter

Specified parameter describes the structure of a nonuniform

NMR research into

Nikolay S. Vasilyev

1Physics and engineering department, Kuban state university,

149, Stavropolskaya st., Krasnodar, Russia, 3500402South Scientific Centre of Russian Academy

41, Chehova st., Rostov


– 11, 2014 – 68 –

In this report we discuss results from our study of the

O system with different concentration D2O

and D2O molecules

play an important role in a variety of different biochemical

reactions and biophysical processes of live cells. We

spin-lattice relaxation

D2O and H2O-D2O

easurements were carried out on a NMR spectrometer

400. It was used the distilled water with

O (enriched to 99.8% in

deuterium). The water samples for the deuterium

e prepared with different concentrations

97 %. The peroxide

samples for the deuterium measurements were prepared with

, lay in the range of 0 –

100%. The point 0% means that the sample contains only

(37% of peroxide and native concentration of

deuterium) and the point 100% is equal the net D2O

The spin-lattice relaxation

were measured at 61.4 MHz. The pulse sequence

he temperature in the probe was

The uncertainties of

values was estimated to be 2 %.

of the 2D spin-lattice

-H2O2-D2O liquids

is determined at 293 K. Results

lattice relaxation time dependence

form. Curve approximations are shown

The upper curve corresponds to the H2O-

O-D2O system. The

shows that the curves differ from each other.

Extremes of polynomial functions are located in different

places in the concentration range. Function (H2O-H2O2-

has a maximum and a minimum (H2O-D2O system).

] for the relaxation

time, to determine the parameters that change when you add

We conclude that

these parameters are the activation energy (related to the

called parameter of asymmetric.

Specified parameter describes the structure of a nonuniform

electric field (deviation from axial symmetry)

lattice relaxation time has a polynomial quadratic

dependence on the parameter of

energy varies linearly with increasing concentration of

deuterium in the H2O-D2O system.

Also it was found [1] that the deuteron relaxation times

can be explained by considering only two contributions to

T1. One of them was associated with the bre

hydrogen bonds and another with the rotational relaxation of

single water molecules. It is possible that the both

contributions define polynomial

of the 2D spin-lattice relaxation time.

measurements of the deuterium in neat

that the motion of water is anisotropic

Consequently, an increase in deuterium concentration in

the H2O-H2O2-D2O system increases the intensity of

competition of the exchanging processes between the water

and the peroxide molecules. In addition, we obtain the time

averaged data on relaxation processes.

increase in relaxation time and the availability of near

maximum concentration (33%).

Figure 1: The 2D spin-lattice relaxation time in

and H2O-H2O2-D2O systems with different

D2O concentration

References [1] J. C. Hindman and all. –

Physics, 54, 621-634 (1971).[2] P.M. Borodin and etc.

Magnetic resonance and its applications“St. Petersburg” Publ., St. Petersburg

[3] T. C. Farrar, J. A. Ropp. Liquids, 103-127 (2002).

y = -0,0299x

y = 0,005x2 - 1,369x + 522,9R² = 0,999

300

350

400

450

500

550

0 20 40

T1,

ms

H2O-H2O2-D2O

esearch into H2O-H2O2-D2O system

Vasilyev2, Denis V. Kashaev1

engineering department, Kuban state university,

149, Stavropolskaya st., Krasnodar, Russia, 350040

ientific Centre of Russian Academy of Sciences,

41, Chehova st., Rostov-on-Don, Russia

[email protected]

electric field (deviation from axial symmetry) [2]. The spin-

elaxation time has a polynomial quadratic

of asymmetric. The activation

energy varies linearly with increasing concentration of

system.

Also it was found [1] that the deuteron relaxation times

can be explained by considering only two contributions to

. One of them was associated with the breaking of

hydrogen bonds and another with the rotational relaxation of

single water molecules. It is possible that the both

polynomial concentration dependence

lattice relaxation time. Experimental NMR

deuterium in neat D2O water indicated

that the motion of water is anisotropic [3].

Consequently, an increase in deuterium concentration in

system increases the intensity of

processes between the water

molecules. In addition, we obtain the time-

averaged data on relaxation processes. This leads to an

increase in relaxation time and the availability of near

lattice relaxation time in H2O-D2O

systems with different

O concentration

– The Journal of Chemical

634 (1971). etc. Quantum Radiophysics.

Magnetic resonance and its applications (in Russian). -St. Petersburg, 2009.

T. C. Farrar, J. A. Ropp. – Journal of Molecular

0,0299x2 + 1,9613x + 499,24R² = 0,9509

1,369x + 522,9

60 80 100

C, %D2O H2O-D2O

Introduction More than 400 billion cigarettes per year are produced in

Russia. To reduce the harm to health of the smoker, as a

rule, is used smoke filters. In this report the method for

checking the quality of filtration by using a

is proposed.

Experiment Cigarettes “Yava classic” (10 mg tar per cigarette

according to data on pack), “Next Rose

“Pall Mall” (1 mg/cig) were studied. Cigarette was

after conditioning in desiccators with relative humidity of

60% for one week. Smoking was carried through the

or elongated mouthpiece (Fig.1). Cigarette quenched up 5

mm before filter. Then filters were carefully separated from

the unburned tobacco and immediately placed in glass vials

of 10 mm in diameter with a tight lid.

was carried out by using of simple pump with a puff volume

of 35 -50 cm 3, do not more than one puff

Figure 1. One or two more filter sticks

inserted to mouthpiece with elongated nozzle to determine

the breakthrough of smoke particle through the cigarette

filter (F0)

NMR relaxometer “Hromatek-Proton

resonance frequency 20 MHz, duration 90

“dead time” 10 µs, was used for measurements.

pulses sequence like CPMG, but at step by step increasing

intervals τi between 180°-pulses [1], was used to measuring

full FID curve (FID plus echo’s amplitudes):

90°-FIDτ0-(180°-τ1-echo-τ1-)N1-∆τ1-(180°-

where τi+1 = (τI + ∆τi), I = 1, 2, 3, ….

Full FID's, recorded by this method

described by the sum of three groups of exponents.

Gaussian exponent relates to the protons of cellulose acetate,

of that is made a cigarette filter, has the largest amplitude

(Aacetate) and time T2g = 15÷19 µs. Second wide spectrum of

exponents has T2 = 0,1 ÷ 3 ms and refers to the protons of

smog water that was condensed on the

Testing of cigarette filters by low

Vladimir Y. Volkov

1Moscow State University for Equipment Engineering & Informatics, Moscow 107996, Russia2Central Research Institute of Tuberc3DNA Synthesis LLC,



More than 400 billion cigarettes per year are produced in

Russia. To reduce the harm to health of the smoker, as a

used smoke filters. In this report the method for

using a low-field NMR

(10 mg tar per cigarette

Next Rose” (3 mg/cig) and

cig) were studied. Cigarette was smoked

desiccators with relative humidity of

% for one week. Smoking was carried through the usual

igarette quenched up 5-7

were carefully separated from

the unburned tobacco and immediately placed in glass vials

10 mm in diameter with a tight lid. Cigarette smoking

simple pump with a puff volume

do not more than one puff per minute.

One or two more filter sticks (F1, F2) were

ed nozzle to determine

through of smoke particle through the cigarette

Proton-20M” with

0o-pulse 2.2 µs, and

10 µs, was used for measurements. One multi-

but at step by step increasing

pulses [1], was used to measuring

full FID curve (FID plus echo’s amplitudes):

-τ2-echo-τ2)N2-..., (1)

ed by this method (Fig. 2), are well

three groups of exponents. The first

protons of cellulose acetate,

is made a cigarette filter, has the largest amplitude

Second wide spectrum of

and refers to the protons of

on the filter. Third, the

slowest exponent has time T2 more than 20ms, and ref

the protons of crude tar that was

Figure 2. Full FID’s (FID plus echo’s amplitudes)

pure and smoked filters of Yava cigarettes

Relationship Awater/Aacetat

(Awater+Atar)/Aacetate respectively

condensed water, amount of tar and the total amount of

smog delayed by filter. So, the measurement data is

automatically normalized to the proton density of pure dry

filter and can be converted to the weight of the filter.

Figure 3. Components of tobacco smog were absorbed

by cigarette filters

Presented on Fig. 3 experimental data show that the

tested cigarette filters captures only a part the harmful

components of tobacco smog. Half or more pollutants may

penetrate through the cigarette filter depending on the depth

and frequency of puffs. Thus, the proposed method can be

used to assess the quality of cigarette filters.

References [1] Volkov V.Y., Restore FID using modified CP

sequence. Int. Conf.: Nuclear Magnetic Resonance in Condensed Matter // NMRCM 2013, July 8Petersburg, Russia, Book of Abstract,

Testing of cigarette filters by low-field NMR method

Volkov1, Ekaterina V. Sosunova2,3

Moscow State University for Equipment Engineering & Informatics, Moscow 107996, Russia

Central Research Institute of Tuberculosis, Russian Academy of Medical

DNA Synthesis LLC, Moscow 127238, Russia

[email protected]


more than 20ms, and refers to

the protons of crude tar that was captured on the filter.

(FID plus echo’s amplitudes) for

pure and smoked filters of Yava cigarettes

acetate, Atar/Aacetate, and

respectively refers to the amount of

water, amount of tar and the total amount of

smog delayed by filter. So, the measurement data is

automatically normalized to the proton density of pure dry

nd can be converted to the weight of the filter.

Figure 3. Components of tobacco smog were absorbed

by cigarette filters

Presented on Fig. 3 experimental data show that the

tested cigarette filters captures only a part the harmful

Half or more pollutants may

penetrate through the cigarette filter depending on the depth

Thus, the proposed method can be

used to assess the quality of cigarette filters.

Restore FID using modified CPMG pulse sequence. Int. Conf.: Nuclear Magnetic Resonance in

// NMRCM 2013, July 8-12, Saint Petersburg, Russia, Book of Abstract, 2013, р.119.

field NMR method

Moscow State University for Equipment Engineering & Informatics, Moscow 107996, Russia

Medical Sciences, Moscow


Author Index

Abakarov, Gasan M., 42 Acar, Hakkı, 39 Ahokas, Janne, 32 Aktas, Bekir, 59 Aleksandriiskii, Victor V., 35, 47 Ali, A.-M. M., 42 Andronenko, Sergey I., 36 Anisimov, Nikolay V., 37, 38 Archipov, Ruslan V., 39 Avilova, Irina A., 17 Bagaychuk, Aleksander, 54 Balcı, Erdem, 39, 48 Barishev, Mihail G., 63 Barras, J., 28 Basov, Aleksandr A., 63 Bertmer, Marko, 12 Bogachev, Yu. V., 40 Borisenko, Nikolay I., 41 Borisenko, Sergey N., 41 Borodkin, Gennadii S., 41, 42, 43 Borodkina, Inna G., 42, 43 Bunkov, Yury, 9, 10 Burlov, Anatolii S., 42, 43 Burmistrov, Vladimir A., 35 Bykov, Ilya M., 63 Canet, D., 14 Chepurnoi, Pavel B., 42, 43 Cherdakov, O. A., 40 Cheremisin, V. M., 21, 26, 29, 61 Chernyshev, Yury S., 39 Chertkov, Vyacheslav A., 11, 64 Cheshkov, Dmitriy A., 11 Chesnokov, Vasilii V., 43 Davydov, Vadim, 24 Dmitriev, Аrtem V., 43 Dolinenkov, Filip, 44, 55 Donets, Alexey V., 30 Drozdov, A. A., 21 Dushina, S. V., 47 Dvinskikh, Sergey V., 22, 25 Dzhimak, Stepan S., 63 Egorov, Andrei V., 53 Fatkullin, N., 57 Fokin, V. A., 40 Fraissard, J., 14 Frolov, Viatcheslav V., 45, 46, 49 Furman, Dmitry M., 46 Galimov, D., 31 Gamov, G. A., 47 Ganina, Tatiana A., 11 Garnovskii, Dmitrii A., 43 Gazizulin, Rasul, 9 Gerts, Egor, 23 Gul-E-Noor, Farhana, 12 Gulyaev, M., 37, 38 Gunduz, Ilknur, 48 Haase, Jürgen, 12 Ievlev, Alexander V., 39

Ilina, Oksana, 45, 49 Ivlev, V. A., 50 Järvinen, Jarno, 32 Kalabin, G. A., 50 Kamyishanskaya, I. G., 21, 26, 29, 61 Karseev, Anton, 24 Kashaev, Denis V., 63, 68 Kharkov, Boris, 25 Khmelenko, Vladimir, 32 Khrapichev, Alexandr A., 60 Kiselev, I. A., 31 Komolkin, Andrei V., 23 Kopilov, A. S., 51, 52 Korneva, Irina, 44 Krylova, Ekaterina A., 53 Kupriyanov, Pavel A., 39 Kupriyanova, Galina S., 28, 48, 54, 55, 58, 59 Kurbakov, A. I., 31 Kuvshinova, Sofija A., 35 Lähderanta, E., 31 Lashkul, A. V., 31 Leclerc, S., 14 Lee, David, 32 Lekar, Anna V., 41 Lifintseva, Тatiana V., 43 Lisunov, K. G., 31 Litov, Konstantin M., 35 Loskutov, Valentin V., 56 Lozovoy, Artur R., 39, 57 Lypenko, Dmitrii A., 43 Makhno, Elena, 54 Makurova T. V., 26 Mal’tsev, Yuriy F., 42, 43 Mal’tsev, Еvgenii I., 43 Mao, Shun, 32 Marchenko, Yaroslav Y., 65 Martyanov, Oleg N., 27 Mattea, C., 57 Matveev, V. V., 31 Melkonyan, Karina I., 63 Mershiev, Ivan, 48, 55, 58 Michel, Dieter, 12 Minkin, Vladimir I., 42 Misra, Sushil K., 36 Mokeev, M. V., 31 Molkanov, P. L., 31 Morozov, Evgeny V., 27 Mozzhukhin, Georgy V., 28, 39, 48, 59 Muravyeva, Maria S., 60 Nechausov, Sergey S., 11 Nikolaev, Boris P., 65 Orekhov, Vladislav Yu., 13 Pavlova, O., 37 Petrov, Eugene P., 56 Petrov, I. N., 29, 61 Petryk, M., 14 Pirogov, Yury A., 15, 37 Pleshakov, Ivan V., 62


Polyakov, Peter I., 16 Popov, Pavel S., 62 Rabdano, Sevastyan O., 30 Ramazanova, P. A., 42 Rameev, Bulat Z., 28, 39, 48, 59 Rimareva, Lubov’ V., 17 Ruzshyeva, Svetlana, 54 Ryzhov, Vyacheslav A., 31, 65 Sabirekian, Valeriy, 55 Samoylenko, A., 37, 38 Shalamova, E., 38 Sharapov, Kirill, 63 Sharnin, V. A., 47 Shashkov, Denis I., 63 Sheberstov, Kirill F., 11 Sheludiakov, Sergey, 32 Shestakova, Alla K., 11, 64 Shevtsov, Maxim A., 65 Shirmanova, Marina V., 60 Shishmakova, E. V., 66 Sinyavsky, Nikolay, 44 Skripov, A. V., 67 Skrynnikov, Nikolai R., 18 Soloninin, A. V., 67 Sosunova, Ekaterina V., 69 Srabionyan, Sofya L., 41 Stapf, S., 57

Sugonyako, D. Yu., 40 Sushkova, Svetlana N., 41 Tagirov, M., 10 Trigub, Alexander A., 43 Uraev, Ali I., 43 Vainio, Otto, 32 Vasil’ev, V. G., 50 Vasilchenko, Igor S., 42, 43 Vasiliev, Sergey, 32 Vasilyev, Nikolay S., 68 Vetrova, Elena V., 41 Vlasenko, Valerii G., 43 Volkov, Vitaly I., 17 Volkov, Vladimir Y., 69 Volkova, K., 38 Volkova, Ludmila D., 17 Xue, Yi, 18 Yakovleva, Ludmila Y., 65 Yuwen, Tairan, 18 Zagaynova, Elena V., 60 Zaichenko, Svetlana B., 42 Zhu, Fangqiang, 18 Zinkevich, D. A., 26 Zubavichus, Yan V., 43 Zvezdov, Denis, 32 Каshaev, R. S., 51, 52


List of Participants Alexandriysky Viktor V.

Ivanovo State University of Chemical Technology Ivanovo, Russia [email protected]

Andronenko Sergey

Kazan Federal University Kazan Russian Federation [email protected]

Anisimov Nikolay Viktorovich Faculty of Fundamental Medicine, Lomonosov Moscow State University, Moscow, Russia [email protected] Balci Erdem

Gebze Institute of Technology Gebze-Kocaeli, Turkey [email protected]

Borisenko Nikolay Ivanovich

Southern Federal University Rostov-on-Don, Russia [email protected]

Borodkin Gennadii

Institute of Physical and Organic Chemistry Southern Federal University Rostov-on-Don, Russia [email protected]

Borodkina Inna

Institute of Physical and Organic Chemistry Southern Federal University Rostov-on-Don, Russia [email protected]

Bunkov Yury Institut Neel, CNRS Grenoble France [email protected]

Cherdakov Oleg

Department of Physics Saint Petersburg Electrotechnical University “LETI” Saint Petersburg, Russia [email protected]

Cheremisin Vladimir Maksimovich

Faculty of Medicine Saint Petersburg State University Saint Petersburg, Russia [email protected]

Chernyshev Yuri Sergeevich Faculty of Physics Saint Petersburg State University Saint Petersburg, Russia [email protected]

Chertkov Vyacheslav

Department of Chemistry Moscow State University Moscow Russia [email protected]

Chizhik Vladimir Ivanovich

Faculty of Physics Saint Petersburg State University Saint Petersburg, Russia [email protected]

Dolinenkov Philip

IKBFU Kaliningrad, Russia [email protected] Donets Alexey V.

Faculty of Physics Saint Petersburg State University Saint Petersburg, Russia [email protected] Drozdov Aleksandr Andreevich


Dvinskikh Sergey V.

Royal Institute of Technology Stockholm, Sweden [email protected] Egorov Andrei


Fedyukina Galina, Nikolaevna

FBUN State Research Centre for Applied Microbiology and Biotechnology Obolensk, Russia [email protected]

Fraissard Jacques Paul

university P. and M. Curie, ESPCI Paris France [email protected]

Frolov Viatcheslav Faculty of Physics Saint Petersburg State University Saint Petersburg, Russia [email protected]

Furman Dmitry


Gamov George Aleksandrovich

Ivanovo State University of Chemistry and Technology Ivanovo, Russia [email protected]

Gerts Egor


Gunduz Aykac Ilknur

Gebze Institue of Technology Kocaeli, Turkey [email protected] Ilina Oksana


Ivlev Vasiliy

Peoples’ Friendship University of Russia Moscow, Russia [email protected]

Jena Vinod

ICFAI University Raipur BHILAI INDIA [email protected]

Jurga Stefan

Adam Mickiewicz University Poznan Poznań Poland [email protected]

Kamyshanskaya Irina Grigor’evna Faculty of Medicine Saint Petersburg State University Saint Petersburg, Russia [email protected]

Karseev Anton Yuryevich

Saint Petersburg State Polytechnical University Saint Petersburg, Russia [email protected]

Kashaev Rustem Sultan-Hamit

Kazan State Power Engineering University Kazan, Russia [email protected]

Kharkov Boris

Department of Chemistry, Royal Institute of Technology - KTH Stockholm, Sweden, Faculty of Physics Saint Petersburg State University Saint Petersburg, Russia [email protected]

Komolkin Andrei V.


Krylova Ekaterina

Faculty of Physics Saint Petersburg State University Saint Petersburg, Russia [email protected] Kupriyanov Paul


Kupriyanova Galina

I. Kant Balric Federal University Kaliningrad, Russia [email protected]

Lavrov Sergey


Litov Konstantin

Ivanovo State University of Chemistry and Technology Ivanovo, Russia [email protected]

Loskutov Valentin Valentinovich

Mary State University Yoshkar-Ola, Russia [email protected]


Lozovoi Artur Rudolfovich

Kazan Federal University Kazan, Russia [email protected]

Makurova Tat’yana


Malkova Anastasia

Faculty of Physics Saint Petersburg State University Saint Peterburg, Russia [email protected]

Matveev Vladimir V.


Mershiev Ivan

Immanuel Kant Baltic Federal University Kaliningrad, Russia [email protected]

Michel Dieter Institute of Experimental Physics II University of Leipzig Leipzig, Germany [email protected]

Morozov Evgeny Vladimirovich

Kirensky Institute of Physics SB RAS Krasnoyarsk Russia [email protected]

Mozzhukhin George

Gebze Institute of Technology Gebze-Kocaeli, Turkey State Power Engineering University Kazan, Russia [email protected]

Muravyeva Maria Nizhni Novgorod State University Nizhni Novgorod, Russia [email protected]

Nagarajarao Suryaprakash

Indian Institute of Science Bangalore, India [email protected] Nikolaev Boris Petrovich

Reseach Institute of Highly Pure Biopreparations Saint Petersburg, Russia [email protected]

Orekhov Vladislav

University of Gothenburg Gothenburg, Sweden [email protected]

Pavlova Maria


Petrov Ivan Nikolaevich


Pirogov Yury A.

Lomonosov Moscow State University Moscow, Russia [email protected]

Pleshakov Ivan Viktorovich

Ioffe Institute Saint Petersburg, Russia [email protected]

Podkorytov Ivan, S.

Biomolecular NMR Laboratory, St. Petersburg State University St. Petersburg, Russia [email protected]

Polyakov Peter Ivanovich

Institute for Physics of Mining Processes of NASU Donetsk, Ukraine [email protected]

Rabdano Sevastyan O.


Ruzheva Svetlana Alexandrovna

Baltic Federal University Immanuel Kant Kaliningrad, Russia [email protected]

Ryzhov Vyacheslav A. PNPI, NRC & Kurchatov Institute Gatchina, Leningrad province, Russia [email protected]

Sagdeev Renad

Novosibirsk Russia [email protected]

Sharapov Кirill, Sergeevich

Kuban State University Krasnodar, Russia [email protected]

Sharova Marina

Mari State University Yoshkar-Ola, Russia [email protected]

Sheludiakov Sergey

Department of Physics and Astronomy, University of Turku Turku, Finland [email protected]

Shelyapina Marina


Shevtsov Maxim Alexeyevich

Institute of Cytology RAS Saint Petersburg, Russia [email protected]

Shishmakova Elena Faculty of Physics Saint Petersburg State University Saint Petersburg, Russia [email protected]

Skrynnikov Nikolai R.

Department of Chemistry, Purdue University Purdue, USA, Laboratory of Biomolecular NMR St. Petersburg State University Saint Petersburg, Russia [email protected]

Smolensky Ilya

Saint Petersburg State University Saint Petersburg, Russia [email protected]

Soloninin Alexey Viktorovich

Institute of Metal Physics Ekaterinburg, Russia [email protected]

Struts Andrey

St. Petersburg State Pediatric Medical University Saint Petersburg, Russia [email protected]

Sukharzhevskii Stanislav


Tutukin Konstantin Victorovich


Vadim Davydov

Saint Petersburg state polytechnical university Saint Petersburg, Russia [email protected] Vasilchenko Igor Stanislavovich

Institute of Physical and Organic Chemistry Rostov-on-Don, Russia [email protected]

Vasilyev Nikolay, Sergeevich

Southern Scientific Center of Russian Academy of Sciences Krasnodar, Russia [email protected]

Volkov Vitaly Ivanovitch

Institute of Problems of Chemical Physics RAS Chernogolovka, Russia [email protected]

Volkov Vladimir Y.

Moscow State University for Equipment Engineering&Informatics Serpukhov, Russia [email protected]

Zinkevich Denis Alexandrovich








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