ministry of education and science of the republic of kazakhstan...

1

MINISTRY OF EDUCATION AND SCIENCE OF THE REPUBLIC OF KAZAKHSTAN

ACADEMICIAN Ye.A. BUKETOV KARAGANDA STATE UNIVERSITY

THEORETICAL

AND EXPERIMENTAL

CHEMISTRY

Abstracts of the VIth

International scientific conference,

dedicated to EXPO-2017

1517 June

Karaganda

2017

2

UDC 542

LBC 24.1

44

Scientific committee

Ye.K.Kubeyev (Chairman), Kh.B.Omarov (Vice-Chairman),

Z.M.Muldahmetov (Kazakhstan, Karaganda), Z.A.Mansurov (Kazakhstan,

Almaty), S.M.Adekenov (Kazakhstan, Karaganda), S.O.Baysanov

(Kazakhstan, Karaganda), N.I.Kopylov (Russia), A.A.Bakibayev (Russia),

Jorg Kreuter (Germany), M.Zh.Burkeyev (Kazakhstan, Karaganda),

R.Sh.Yerkasov (Kazakhstan, Astana), A.K.Tashenov (Kazakhstan, Astana),

S.E.Kudaybergenov (Kazakhstan, Almaty), David Havlicek

(Czech Republic), Mitko Stoev (Bulgaria),

Xintai Su (China), Ma Feng Yun (China)

Organizing committee

Ye.M.Tazhbayev (Chairman), A.S.Masalimov, M.I.Baikenov,

L.K.Salkeyeva, N.Merhatuly, N.Kh.Ibraev

Secretaries: S.B.Abeuova, Ye.V.Minayeva, I.A.Pustolaikina, A.S.Uali

44 Theoretical and experimental chemistry: Abstracts of the VIth

International scientific conf. (June 15-17, 2017). Karaganda: Publ.

House of KSU, 2017. 138 p.

ISBN 978-9965-07-990-0

Abstracts of the VIth International scientific conference Theoretical and

Experimental Chemistry are published in the Book. This conference is traditional and

is held every 23 years since 2000 based on the chemistry faculty of the Academician

Ye.A. Buketov Karaganda State University.

The main topics of the conference are inorganic chemistry, organic chemistry,

novel materials, chemistry and technology of polymers, analytical chemistry, physical

chemistry, nanochemistry and nanotechnology, electrochemistry, computational

chemistry and molecular modeling, chemical engineering and ecological safety. In 2017

Theoretical and Experimental Chemistry conference is dedicated to the International

specialized exhibition EXPO-2017,which will be held in the period from 10 June till 10

September 2017 in the capital of Kazakhstan Astana.

UDC 542

LBC 24.1

ISBN 978-9965-07-990-0 Karaganda State University, 2017

3

SECTION 1 CONTEMPORARY ISSUES OF THEORETICAL

AND EXPERIMENTAL CHEMISTRY

THERMODYNAMIC FUNCTIONS OF THE FORMATION OF Nd (III)

COMPLEXES WITH 2-HYDROXYBENZOYL-HYDRAZIDE IN

AQUEOUS-ETHANOL MEDIUM

Amerkhanova Sh.K.1, Abdiken F.S.

1, Nurkenov O.A

.2, Belgibaeva D.S.

3

1 Academician Ye.A. Buketov Karaganda State University,

Karaganda, Kazakhstan 2Institute of Organic Synthesis and Coal Chemistry of the Republic of

Kazakhstan, Karaganda, Kazakhstan 3L.N. Gumilev Eurasian National University, Astana, Kazakhstan

[email protected],[email protected]

The modern development of coordination chemistry is characterized by

the intensive use of complex metal compounds with organic reagents to

separate, concentrate and quantify various elements. The results of a study of

the complexation of 2-hydroxybenzoylhydrazide with neodymium (III) ions in

an aqueous-ethanol medium at different temperatures (298-318 K) are

presented in this paper.A pH-metric study of the 2-hydroxybenzoylhydrazide-

neodymium (III) ions system in an aqueous-organic medium: water-ethanol

(ratio 10:90, 30:70, 50:50, 70:30, 90:10) has been carried out. From the data on

the change in Gibbs energy, enthalpy, entropy, it follows that for the 90:10,

10:90 ratios, complexation with an organic ligand is difficult due to the high

solvating ability of water with respect to metal ions, as well as the solvation of

the ligand by ethanol molecules. However, at aqueous-ethanol ratios of 50:50

and 70:30, the bonding of metal ions to the ligand is strengthened. It was found

that the decrease in the complexing ability is observed in the series of aqueous-

ethanol ratios of 10:90, 30:70, 50:50, 70:30, 90:10. The ligand forms donor-

acceptor complexes with neodymium (III) ions, and water molecules form

complexes with ionic bonds [1]. Thus, as a result of the studies, the

thermodynamic characteristics of the formation of nitrogen-containing ligand

complexes with Nd (III) ions were calculated. It is shown that the replacement

of water by an organic solvent is accompanied by an increase in the covalence

ratio of the metal-oxygen bond, which is reflected in the complexing capacity

of the ligand.

References:

1. IGNATYEVA, K.A. and DEVYATOE, F.V. 2007. Solvation and

complexation in the dysprosium (III) system L-histidine-water-acetonitrile (0-

72 vol.%). Bulletin of the Kazan Technological University, 2, pp.22 - 25.

4

STEREOCONTROLLED SYNTHESIS OF EUDESMANOLIDES

ON THE BASIS OF HANPHILLINE

Abeuova S.B., Omarova A.T., Muslimova D.M., Shakhmanova B.A.,

Amanzholova A.S., Merkhatuly N.

Academician Ye.A. Buketov Karaganda State University,

Karaganda, Kazakhstan

[email protected]

Reactions of stereospecific electrophilic carbocyclization of (+)-

hanphilline (1) were investigated and different trans-eudesman sesquiterpene -

lactones were synthesized. E,E Germacranolide (+)-hanphilline was isolated

by us from Achillea nobilis L.

HO

O

O

O

O

O

HO

O

O

H H

(1)

(2),71 % (3),19 %

H H HH

Amberlite IR 120 40-50 C

OO

HO

(4) 40 %

OO

HO

(5) 50 %

HO

acidic acetone

OO

HO

(6), 30%

OO

(7), 40%

O

Br2 / DMSO

rt

CrO3 Py

O

OO

(9), 35%

O

OO

(8), 30%

rt

rt

The structures of synthesized eudesmanolides (2-9) have been

investigated using IR-, 1H NMR, mass-spectroscopy and X-Ray analysis.

5

SYNTHESIS OF -SANTONIN NEW DERIVATIVES

Abeuova S.B., Omarova A.T., Muslimova D.M., Shakhmanova B.A.,

Amanzholova A.S., Merkhatuly N.



[email protected]

Currently, natural sesquiterpene -lactones of eudesmanolide structure are

competitive objects due to their availability and wide spectrum of biological

activity [1-3]. New derivatives (2-6) of eudesmanolide -santonin (1) were

synthesized by us with the aim of finding new biologically active compounds.

O

OO(1)

OH

OCO2Me(3), 96%

MeONa / MeOH

OH

OCO2Et(2), 94 %

EtONa / EtOH

rt rt

ON

HO

O(4)

(5), 52 % (6), 25%

N

OO

O

HN

OO

O

HH

TsCl / THF boiling

NH2OH HCL Py, boiling

The structures of synthesized derivatives (2-6) have been investigated

using IR-, 1H NMR, mass-spectroscopy and X-Ray analysis.

References:

1. RYBALKO, K.S. 1978. Natural sesquiterpene lactones. M.: Meditsyna

2. MERHATULY, N., ADEKENOV, S.M. 2002. Chemistry and biological

activity of sesquiterpene -lactones. Karaganda: KarGU

3. MERKHATULY, N., VOJTISEK, P., ABEUOVA, S.B., BAKYTZHAN, G.,

AND SULEIMBEKOVA Z.S. 2013. Synthesis and biological activity of

nitrogen-containing derivatives of -santonin. Bulletin of University of

Karaganda. Chemistry series, 4 (72), pp.37 40.

6

INTERMOLECULAR INTERACTIONS IN AZOCOMPOUNDS:

A FIRST-PRINCIPLES DENSITY FUNCTIONAL APPROACH

Abulyaissova L.K., Boribayeva A.M., Aitan M.



[email protected]

The well-known classes of azocompounds such as Schiff-bases and

azobenzenes are used as mesogenic substances. Mesogenic (liquid crystalline)

properties are associated with the processes of molecular aggregation.

In this work, we report a theoretical study on molecular structure of the

entitled thermotropic liquid crystals using the density functional theory (DFT)

approach. We have simulated and studied the molecules with electron-donating,

electron-withdrawing substituents in the para-position of aryl rings and

reference unsubstituted azocompounds. Possible options for the relative

position of a pair of molecules for stacking, plane and terminal interactions

were considered. We aim to analyze the relative stabilities of several different

dimeric associates, and to report theoretical results regarding an intermolecular

interaction energy, HOMO-LUMO energies and their energy gaps, etc.

Interaction energy of molecules in the dimers of various configurations

and other physico-chemical properties are calculated at the affordable

B3LYP/3-21G, B3LYP/6-31G (with polarization and diffuse functions) levels

of theory.

The structure of azocompound molecules in the isolated state is optimized

by quantum chemical calculations with the 6-31G(d,p), 6-31++G(d,p) basis

sets. The geometry of dimers have been calculated at the B3LYP/3-21G level.

The results show that for short-range order the energy and thermodynamic

stabilities of the dimers depend on the intermolecular distance, relative

orientation, structure and physical characteristics (dipole moment,

polarizability, etc.).

7

THE BEHAVIOR OF MESOGEN SYSTEM AT VARIATION OF

GRAPHENE RIBBON SIZES AND VARIOUS IMPACTS

Agelmenev M.E., Bratukhin S.M., Polikarpov V.V.



[email protected]

Graphene has a great interest due to its electrical and thermoelectric

properties. As noted in [1], the ratio between length and width of the graphene

is strongly affected by these properties. The effect of the flow of nematic liquid

crystals that we found (NLC) [2] on the graphene surface at the temperature

changehad found its experimental confirmation in [3]. Therefore, it is necessary

to consider the understanding of the influence of thegraphenesize and its type

on the properties located on the surface of such electronic products as the NLC,

when creating optoelectronic devices based on these compounds.

In this regard, the aim of this study was to research the influence of the

size and type of graphene, the effects of temperature and electric field on the

dynamics of nematic liquid crystals based on the arylpropargyl ethers of

phenols. As a sample the nematic liquid crystal - phenylpropargyl ether of p-

chlorphenol (PEC), located on the graphene in a planar orientation was used.

For the modeling of the behavior of these compounds we used the method

of molecular dynamics based on the program GROMACS version 3.3.1

approaching liquid state. The performed experiments on computer modeling of

the behavior of the polar PEC, located on the surface of grapheme ribbon,

allowed identifying a number of laws. The little effect of the graphene ribbon

type on the behavior of the NLC was shown. It was established that the

ordering of nematic liquid crystals increase non-linear with increasing of the

electric field. The determining role of graphene and the electric field on self-

organization of the NLC in the enlightenment region was shown. It was found

that in the area of enlightenment the ordering of the NLC starts to grow when

the value of the ratio of width to length is 3: 1. This allows stating that at least

two processes are taking place under the influence of temperature and electric

field: First - "flow" of the molecules in the direction of X, the second - the

rotation of the molecule in the direction of this axis. The second process may be

due to the reorientation relative to the electric field of the molecules.

References: 1. DIVARI, P.C. and KLIROS, G.S. 2010. Physica E., 42, p.2431.

2. AGELMENEV, M.E., MULDAKHMETOV, Z.M., BRATUKHIN, S.M., and

POLIKARPOV, V.V. 2011. Mol. Cryst. Liq. Cryst., 545, p.36.

3. JEONG-SEON YU, SUNG JO KIM, AND JONG-HYUN KIM. 2010. In: 23

International Liquid Crystals Conference, 9/16 July 2010, Krakow: 23 International

Liquid Crystals Conference, p.223

8

EFFECT OF GOLD NANOPARTICLES ON COUMARIN DYE

AND QUANTUM DOT MIXTURE IN POLYMER MATRIX

Aldongarov A.1, Irgibaev I,

2, Mantel A.

3 and Mukataev I.

2

1L.N. Gumilyov Eurasian National University, Department of Technical

Physics, Astana, Kazakhstan 2L.N. Gumilyov Eurasian National University, Laboratory of Physical and

Quantum Chemistry, Astana, Kazakhstan 3Luminescent Materials Research Center Ltd., Astana, Kazakhstan

[email protected]

Thin films of PMMA samples containing coumarin dye C-440,

semiconducting quantum dots (QDs) CdSxSe1-x/ZnS and 3 nm gold

nanoparticles (GNPs) were prepared. Measurements of luminescence spectra of

the samples show that for this three component system presence of GNPs may

increase emission intensity of QDs while for two component system of QDs

and GNPs no such increase is observed. It is suggested that fluorescence

resonance energy transfer (FRET) takes place in the three and two component

system since increase of QDs emission happens at the expense of decrease of

C-440 emission intensity. We have used DFT level of approximation to

consider a model of three component system. This model has included single

C-440 molecule, two Au5 and Zn6Se6 clusters. Theoretical results show that

addition of GNPs may provide increase of absorption rate of C-440 in two

component system (C-440+GNPs) and in three component system (C-

440+QDs+GNPs). While for QDs GNPs provide decrease of absorption

probability. It is shown that absorption properties of QDs and C-440 do not

depend on their relative positions.

9

CONSTRUCTION OF A DIAGRAM OF THE STATE OF THE TRIPLE

SYSTEM OF NAPHTHALENE-DIPHENYL-DIBENZYL WITH

SUPERCOOLING

Aleksandrov V.D., Pokyntelytsia O.A., Pokyntelytsia A.Ye.

Donbas National Academy of Civil Engineering and Architecture,

Donetsk

[email protected]

Non-equilibrium phase diagrams of the naphthalene-diphenyl,

naphthalene-bibenzyl and diphenyl-bibenzyl systems were plotted under the

same experimental conditions. Thereby we need to merge them into a single

tripple system.

As we can see from expanded phase diagram of naphthalene-diphenyl-

bibenzyl (N-Dp-Db) system, there is a trend to reduce liquidus temperature as

each binary alloy approaches the corresponding eutectic compositions E1, E2,

E3. Point E represents the ternary eutectic in the center of the concentration

triangle. According to the literature [1] the composition of the ternary eutectic

is 27 mol% of N (21.9 wt% of N) + 33.8 mol% of Dp (33 wt% of Dp) + 39.2

mol% of Db (41.5 wt% of Db). The temperature of the triple eutectic point E is

equal to TE=290.4 K. In order to check the parameters of the triple eutectic, we

use the corresponding parameters of the binary eutectic in mass percent 40%

N+60% Dp (E1312 ); 51% Dp+49% Db (E2303 ); 68% Db+32%N

(E3304 ).

The estimated composition of ternary eutectic and its temperature have

been found using the conditions of phase equilibrium on the phase boundary

between liquid and liquid-solid state, which is expressed by the equality to zero

of the change in Gibbs energy. In the approximation of ideal solutions, this

condition is represented by the following system of equations: HN(1-

T/TN)+RTlnxN=0, HDp(1-T/TDp)+RTlnxDp=0, HDb(1-

T/TDb)+RTlnxDb=0, xN+xDp+xDb=1.

Solving the system of equations numerically, we have found the

composition of the ternary eutectic and its equilibrium temperature: E = 293

, N = 26.9 mol%, Dp = 32.8 mol%, Db = 40.3 mol%. Expressing the

coordinates of ternary eutectic alloy in mass fractions, we get: N =21.8 %,

Dp =31.9 %, Db = 46.3%.

It is seen that the parameters of the ternary eutectic are in good agreement

with the literature.

References:

1. STANLEY M. WALAS. 1985. Phase Equilibria in Chemical Engineering.

Butterworth-Heinemann

https://ru.scribd.com/author/256634184/Stanley-M-Walas

10

COLD STORAGE MATERIALS ON THE BASIS OF Na2S2O35H2O

Na2SO410H2O, Na2S2O35H2O Na2SO37H2O AND Na2SO410H2O

Na2SO37H2O CRYSTALLINE HYDRATES MIXES

Aleksandrov V.D., Sobol O.V., Sobolev A.Yu., Syrovatsky V.A.

Donbas National Academy of Civil Engineering and Architecture,

Donetsk

[email protected]

Recently much attention is paid to cold accumulation. It is due to the fact

that it was widely used for temperature stabilization of some radio elements and

the optoelectronic package, in the refrigerating equipment for storage and

transportation of medical supplies, foodstuff, etc. Cold accumulation is carried

out, as a rule, by means of individual substances or their mixes, which absorb

or emit energy due to the latent heat of phase change "liquid-solid" without

mass transfer at temperatures below 0C. However in the absence of important

physical and chemical characteristics (character of melting and crystallization,

reversibility and stability of melting and crystallization temperatures at repeated

phase changes, etc.) for many water-salt systems excludes a possibility of use

them as cold accumulators without carrying out special researches. Practical

use of cold storage materials demands development of the reliable constructive

decisions directed to the maximum use of merits of the specified materials.

In this work we offered selection methodology of crystalline hydrates

mixes compositions on the basis of creation and the analysis of equilibrium and

nonequilibrium phase diagrams for ensuring crystallization with small

supercoolings depending on concentration of components and the thermal

history of a fluid phase.

By the methods of thermal analysis there were studied supercoolings in

mixes of sodium thiosulphate pentahydrate (Na2S2O3 5H2O), decahydrate of

sodium sulfate (Na2SO4 10H2O) and sodium sulfite heptahydrate (Na2SO3

7H2O) crystalline hydrates to ascertain best compositions fulfil requirements

imposed to cold storage materials.

11

EXTRACTION OF La(III) IONS FROM AQUEOUS SOLUTIONS

USING MODIFIED ACTIVATED CHARCOAL

Amerhanova Sh.K.1, Uali A.S.

1, Imankulova A.E.

1, Kuatbek A.M.

1,

Tatibayeva M.S.2


Karaganda, Kazakhstan 2National Center of Science and Technology Evaluation JSC, Almaty,

Kazakhstan

[email protected], [email protected]

Salts of rare earth metals are widely used in various fields of technology,

so the development of new and improvement of known methods of extracting

these elements from various sources is a relevant. In this work, the activated

charcoal (BAU), model solutions containing La(III) ions of various

concentrations had been chosen as objects of investigation. It is known that the

adsorption of inorganic cations is strongly influenced by the acid-base

properties of BAU, in particular, the presence of carboxyl or other groups with

low pK values on their surface, therefore, BAU was modified by

ethylenediaminetetraacetic acid (EDTA) [1].

Experiments on the study of sorption in static conditions had been carried

out by the mathematical planning method under the influence of various

conditions (pH of aqueous solutions, temperature, and initial concentration of

REE). Interpretation of experimental data had been carried out on the basis of

models of Langmuir, Freundlich, BET and Fowler-Guggenheim.

In this case, the process of sorption of La(III) ions in BAU modified by

EDTA is adequately described by the Fowler-Guggenheim equation [2]. This

equation characterizes the intermolecular interaction of adsorbate-adsorbate in

a monolayer. The optimum parameters for extraction of La(III) ions from

aqueous solutions on the modified BAU sorbent had been established. Also the

thermodynamic characteristics of sorption processes had been calculated.

References: 1. MARWANI, H.M., ALBISHRI, H.M., JALAL, T.A. AND SOLIMAN, E.M. 2013. Study of isotherm and kinetic models of lanthanum adsorption on activated

carbon loaded with recently synthesized Schiffs base. Arabian Journal of Chemistry, 10

(1), pp.10321040.

2. MUHAMMAD, I.D., MUHAMMAD L.M., SADIA A., MAKSHOOF, A. AND IJAZ, U.M. 2013. Thermodynamics of Biosorption for Removal of Co(II) Ions by

an Efficient and Ecofriendly Biosorbent (Saccharum bengalense): Kinetics and Isotherm

Modeling. Hindawi Publishing Corporation. Journal of Chemistry, 1 (2), p.11.

12

THE OBTAINING OF COPPER, SILVER AND PALLADIUM

NANOPARTICLES FROM AQUEOUS SUPRAMOLECULAR GELS

BY VARIOUS WAYS

Amerkhanova Sh.K., Uali A.S., Bailen A.S.



[email protected]

Interest in nanostructures is primarily associated with the possibility of

obtaining materials with new physical-chemical properties that are different

from macrocrystalline ones. The most attractive feature of nanosystems is the

ability to regulate the physical response of the material depending on the

particle size. Thus, it is obvious that controlling the size, and in many cases

even the shapes of particles at the nanoscale, can lead to a change in the

properties of well-known materials and open them to applications in new areas.

In this work, the obtaining of Cu, Ag, Pd nanoparticles from an aqueous

supramolecular gel consisting, presumably, of complexes from metal ions and

quercetin was carried out in 3 ways: 1) chemical reduction with sodium

borohydride (NaBH4); 2) action by electric alternating current (EAC), 50 Hz, 1

h; 3) the combined effect of NaBH4 and EAC (50 Hz, 1 h).

It has been established that as a result of the interaction of metal ions with

quercetin in the aqueous solution a supramolecular gel is formed, while the

kinematic viscosity of the solution sharply increases. Further, metal

nanoparticles are formed in the result of action to gel by the above-described 3

methods. The formation of metal nanoparticles was determined by laser

diffraction on a Nano-S90 laser particle size determinant.

Complexation of quercetin with metal ions was studied at temperatures of

298-313 K (step is 5 K). The stability constants were determined by pH-metric

titration according to Berrum at the pH-meter Metrohm pH 827. The

background electrolyte was sodium nitrate (I=0.1, 0.25, 0.5, 0.75, 1). It is

shown that the size of nanoparticles also depends on the stability of the

complexes formed during the interaction of the components of the initial

system.

References:

1. TAN, Y.N., LEE, J.Y., AND WANG, D.I. 2010. J. Am. Chem. Soc., 132 (16),

pp.56775686.

2. AMERKHANOVA, Sh.K. 2005. Electrochemical and physical-chemical properties of

the chalcogenides of the subgroup of copper and metals of the first transition series:

Author's abstract. Dis.... Dr. Chem. Sciences: Karaganda, p. 50.

13

VOLTAMPERMETRICAL BEHAVIOR REGULARITIES OF

GLYCINE ON ORGAN-MODIFIED ELECTRODE

Auyelbekova A.Zh.

National Research Tomsk Polytechnic University,

Tomsk, Russia

The amino-acid analysis is well studied and at the same time developing

section of modern analytical chemistry. Recently, amino acid is in stable

demand. They are used in medicines, drinks and the food industry as the

amplifier of taste, the additive increasing nutritional value of bread; livestock

production and poultry farming, and also are used for increase in fodder value

of protein feeds and mineral fertilizers. One of widely applied representatives

of amino acid is glycine (aminoacetic acid, aminoethane acid), it is a part of the

majority of vegetable and animal protein. Now there is a number of methods of

quantitative definition of glycine in vegetable raw materials, in medicines and

biological liquids.

Voltampermetric is widespread among electrochemical methods of a

research of organic compounds. Achievements in this area are connected with

emergence of chemically modified electrodes. This method differs in high

sensitivity, good reproducibility, accuracy and an expressiveness of definitions.

Research objective was studying of electrochemical behavior of glycine

on the organ-modified electrode and development of the technique algorithm of

its definition in mineral fertilizers.

Researches on the choice of background electrolyte were conducted. PH

6,86 borax buffer was chosen as working background solution. The kinetics of

glycine restoration on the organ-modified electrode was studied and shown that

the maximum value of an analytical signal is observed at the potential of

accumulation-1.4 B and speed of development of 30 mV / sec.

Determinations of glycine on buffer solutions with a voltampermetric

method on graphite, modified with 4 azophenylbenzyldiazonium tosylate, an

electrode include concentration of electroactive connection on the electrode

surfaces and receiving an analytical signal at the potential change. We have

received an analytical signal of glycine on the pH 6.86 buffer solution

background for the first time. The influence of modifier maintenance was

studied (time of the contact and concentration of 4 azophenylbenzyldiazonium

tosylate) on a surface of the graphite electrode. The maximum analytical signal

of glycine was shown during 180 seconds contact time and concentration of the

modifier = 30 mg/l.

Thus, an opportunity was shown for the first time and conditions of

quantitative voltampermetric definition of glycine on the reaction basis of its

electrocatalytic oxidation on surface of the graphite electrode which was

previously modified with 4 azophenylbenzyldiazonium tosylate.

14

DETERMINATION OF NEW ANTITHROMBOTIC DRUG IN BLOOD

PLASMA BY HPLC

Bakibaev A.A.1, Leonov K.A.

2, Vishenkova D.A.

2

1National Research Tomsk State University, Tomsk, Russia

2National Research Tomsk Polytechnic University, Tomsk, Russia

[email protected]

Thrombosis along with hypertension and ischemia of heart tissue and

brain are the main reasons for development of such deadly states as: acute

coronary syndrome, myocardial infarction, stroke.

Platelet aggregation inhibitors (antiplatelet agents) with a different

mechanism of action using for thrombosis prevention. Development of new

antithrombotic agents and study of its properties is actual task. Specialists of

the Iphar company (Tomsk, Russia) have synthesized an innovative

antiplatelet agent representing the 2-[2-[5-(hydroxymethyl)-3-methyl-1.3-

oxazolidin-2-ylidene]-2-cyanoethylidene] indoline-3-on (code name - GRS).

One of the main aspects of innovative drugs investigation is the study of

its pharmacokinetic properties, which allows to determine the features of an

absorption, distribution, transformation in an organism and drug recovery.

The purpose of this work was determination of new antithrombotic drug

in rats plasma by HPLC during the study of pharmacokinetics.

For the quantitative determination of GRS in rat plasma a bioanalytical

technique has been developed and validated on a chromatograph Milichrom-

A02 (CJSC "EcoNova", Novosibirsk, Russia) with spectrophotometric

detection. The studied substance in suspension form was intragastrically

introduce into an animals. In accordance with a temporal points animals were

decapitated and was made excretion of blood plasma. The concentration of

GRS was determined in the samples in accordance with the bioanalytical

technique. On the basis of the obtained data a pharmacokinetic profile was

constructed and pharmacokinetic parameters were calculated.

15

QUANTUM-CHEMICAL MODELING OF INTERMOLECULAR

HYDROGEN BONDING BETWEEN NEUTRAL MOLECULES

Chagandai I.M., Sadykova A.., Nikolskiy S.N.



[email protected]

Semiempirical quantum mechanical PM7 method is successful for

molecular energies reproducing, molecular structures replicating, and chemical

reactions interpreting. Twenty neutral complexes were optimized by PM7

method with the help of Molecular Orbital PACkage MOPAC. Results of the

PM7 calculations and experimental data are presented on the table.

Complex D A r(

D-A

),

Charge

transfer

Heats of association,

kcal/ mol

PM7 Exp.

H2O - H2O H2O H2O 2.79 -0.009 -7,01 -4.4 - -5.4

(H2O)3 H2O H2O 2.63 -0.006 -6,07

(H2O)4 H2O H2O 2.56 -0.009 -4,58

(H2O)5 H2O H2O 2.56 -0.009 -7,67

(H2O)6 H2O H2O 2.55 -0.009 -7,51

H2O - CH3OH H2O CH3OH 2.77 -0.022 -5,00 -3.2 - 7.3

H2O - HCOOH H2O HCOOH 2.74 -0.011 -9,67

H2O - CH3COOH H2O CH3COOH 2.74 -0.010 -8,41

H2O - C6H5COOH H2O C6H5COOH 2.74 -0.009 -10,2

H2O - CH2O H2O CH2O 2.74 -0.024 -3,78

H2O - NH3 H2O NH3 2.74 -0.004 -6,41 -4.4

It was found that for water dimer the length of hydrogen bond is 1.825

and the energy of hydrogen bond is 7.01 kcal mol-1

. Structures of water trimer,

tetramer and pentamer were calculated to evaluate the relationship between

hydrogen bond strength and charge transfer. The structure of water pentamer

was taken similar to the ice structure in calculations. It was assumed that the

pentamer symmetrical configuration helps more efficient charge transfer

between molecules in the complex. It was established that hydrogen bond

energies and geometric characteristics of hydrogen bond are close in value for

water-methanol complex and methanol dimer. It was noted that methanol dimer

has the weakest hydrogen bond, then followed the water methanol complex and

the methanol water complex. These results, as well as results for water dimer,

indicate that water molecule compared to methanol is the best donor as well as

acceptor.

16

VOLTAMMETRIC SENSOR FOR TOTAL CHOLESTEROL

DETERMINATION IN BLOOD SERUM

Derina K.V.1, Taishibekova Ye.K.

2

1 National Research Tomsk Polytechnic University, Tomsk, Russia



[email protected]

Cholesterol is an essential compound in a human body. Nevertheless,

cholesterol blood level is strongly connected with a risk of cardiovascular

diseases (CVDs) in clinical practice. The suddenness of mortality is the key

moment in CVDs diagnosis and therapy. According to the World Health

organization statistics 21% of CVDs patients are dying at pre-state period [1].

Therefore, point-of-care testing plays a vital role in the successful treatment of

CVDs. Electrochemistry is one of the best solutions for such systems due to its

simplicity and low-costs [2].

We report on a novel electrochemical sensor for total cholesterol

determination. It is based on modified working electrode. 2,6-diacetyl-2,4,6,8-

tetraazobicyclo[3.3.0]octane-3,7-dion-diphosphonic acid was chose as a

modifier. The modifier is structurally similar to flavin adenine dinucleotide.

The three-electrode cell was used for the performing of experiments.

Silver chloride electrodes were used as a reference and auxiliary electrodes.

Such approach provides an opportunity to the increasing of potential

stabilization and the decreasing of signal-to-noise ratio. Standard phosphate

buffer (pH 6.9) was used as a supporting electrolyte.

The cholesterol oxidation peak was obtained at +0.9 V by means of cyclic

voltammetry. Besides, the Taffel plot was drawn. The charge transfer

coefficient was 0,5. Mass diffusivity by Kotrell was 6 10-6 sm2/s. The

electrochemical process was quasi-reversible. The differential pulse

voltammetry usage helped to decrease the potential of oxidation peak to 0,6 V.

Callibration curve was linear from 0,5 mmol/L to 10,5 mmol/L.

Therefore, obtained sensor is very promising for clinical practice.

References:

1. ROTH, G.A., FIHN, S.D., MOKDAD, A.H., AEKPLAKORN, W.,

HASEGAWA, T., LIM, S.S. 2011. High total serum cholesterol, medication

coverage and therapeutic control. Bull. of the WHO, 89 (2), pp.92101.

2. BANIKA, F.-G. 2012. Chemical and biological sensors: Fundamentals and

applications, New York: Wiley

17

DETERMINATION OF GOLD BY THE METHOD OF AN INVERSION

VOLTAMPEROMETRY WITH THE USE OF GRAPHITIZED

ELECTRODE MODIFIED BY ANTIMONY

Dudkina A. A., Kolpakova N. A.

National Research Tomsk Polytechnic University, Tomsk, Russia

[email protected]

The purpose of this work was to study the possibility of defining gold on

GE modified by antimony. The voltamperometric TA-4 analyzer (LLC Tom

analit, Tomsk), with a three-electrode cell was used in work. As a working

electrode served graphitized electrode (GE) impregnated by paraffin and

polyethylene of low pressure; an electrode of comparison and an auxiliary

electrode saturated by chloride silver (ch.s.e.). Electrodeposition of

precipitation of the antimony and gold had been carried out from solution 1 M

of HCl at electroconcentration potential minus 0,4B.

During precipitation of gold and antimony electrooxidation three peaks

can be observed on a volt-ampere curve. The peak at potential 0,0 B

corresponds to the process of electrooxidation of antimony from GE surface;

the peak at potential plus 0,4 B is caused during the process of selective

electrooxidation of antimony from a surface of gold centers; the peak at

potential plus 0,8 B corresponds to the process of electrooxidation of gold from

GE surface. At electrodeposition of antimony current of electrooxidation of a

deposit of antimony increases on GE with the rising of antimony ions

concentration (III) in solution. When the content of gold increases at electrode

surfaces current of electrooxidation of antimony decreases, but there is an

additional anode peak current of that is caused by the process of

electrooxidation of antimony from a surface of the gold centers. The total

amount of settled on GE concentration of antimony remains constant. Current

of intermediate peak is proportional both to the maintenances of ions of

antimony (III) in solution, and of ions of gold (III). When the current

disappears electrooxidation of antimony and the current of electrooxidation of

intermediate peak also ceases to increase. As a result of the research it has been

established that definition of antimony can be carried out both on gold

electrooxidation peak, and on peak of selective electrooxidation of bismuth

from alloy with gold. The greatest sensitivity of definition is reached on

determining gold by the EB method on peaks of electrooxidation of gold from a

surface of GE modified by antimony.

References:

1. BUDNIKOV, G. K., EVTYUGIN, G. A., et all. 2010. Modified electrodes

for voltamperometry in chemistry, biology and medicine. M.: BINOMIAL

2. STOZHKO, N. YU. 2005. Analytical chemistry journal, 60 (6), pp.610-615.

3. Nemodruk, A. A. 1978. Analytical chemistry of antimony. Moscow

18

INVESTIGATION OF PROTECTION ACTIVITY OF COMPOSITION

SPGK AS INDUSTRIAL INHIBITORS IN ACIDIC AND NEUTRAL

MEDIUM

Fedotova M.A., Plotnikova M.D.

Perm State University, Perm, Russia

[email protected]

Nowadays the main problem of oilfield is corrosion of equipment. The

use of corrosion inhibitors is one of the most effective ways of protection

metals from corrosion in various aggressive environments.

In the work the industrial compositions of SPGK as corrosion inhibitors

were investigated. In the capacity of working solutions we used: NaCl 3%;

environment NACE, composition, g/l: NaCl 5; CH3COOH 0,25, used in the

National Association of Corrosion Engineers, USA; HCl 10%. According to

the results of gravimetric tests in 3% NaCl solution the protective effect of

inhibitors of the series of SPGK is the lowest compared to the other

investigated corrosion medium. A greater protective effect was observed in the

following environments: NACE 71.5% for SPGK-I1 and 79.4 for SPGK-I2;

and in 10% solution of HCl 82.6% and 87.1% for SPGK-I1 and SPGK-I2,

respectively.

The value of the protective effect, as close as possible to the requirements

for industrial application is observed in Cl 10% and NACE. It explains the

choice of conditions for electrochemical investigations.

According to the polarization tests the reviewed compositions are

inhibitors of mixed type in 10% HCl solution, since their presence causes a

decrease in speed in both cathodic and anodic processes. The protective effects

of the compositions, calculated on the basis of electrochemical testing,

constitute 52.6% for SPGK-I1 and 45.6% for SPGK-I2, the rate of corrosion

slows down 2.1 and 1.8 times, respectively. In NACE the compositions

investigated are cathodic inhibitors, as their presence causes a decrease in speed

mainly of cathodic process. The protective effects of the compositions are

69.8% for SPGK-I1 and 48.3% for SPGK-I2, the corrosion rate slows down 3.3

and 1.9 times.

The difference between the results of the protective effects, defined by

two methods, is proved with the fact that the values obtained by gravimetric

method, are time-averaged (24 hours), and the values obtained by

electrochemical measurements show a protective effect at the moment of

testing.

Thus, further investigation of the composition of SPGK as corrosion

inhibitors is useful in acidic and NACE medium.

19

STOCHASTIC-DETERMINATED DESIGN OF EXPERIMENT FOR

LIBS SPECTROMETERS CALIBRATION

Fomin V.N., Omarov Kh.B., Aldabergenova S.K.



[email protected]

Atomic emission spectral analysis, in most variants of its implementation,

is characterized by comparatively low accuracy and reproducibility of the

results. This is mainly due to the instability of the radiating plasma and the

significant influence of the chemical nature of the matrix. From this follows the

direct need for statistical processing of spectral data, incl. rather "sophisticated

[Kremers, Radziemsky, 2009].For hardware quality management of the

recorded spectrum, many instruments have several configurable parameters.

Theoretically, it is not possible to predict the optimum set of values of these

parameters. For the adjustment of spectral devices it is recommended to use the

design of experiment [Kalinkin, 2002].The most intensely negative effect of

random processes is manifested in the case of laser inducted breakdown

spectroscopy. LIBS devices, as a rule, have several parameters for excitation

and registration of the spectrum, which have to be selected manually. A

technique that simultaneously optimizes the spectrometer's settings and

statistically describes the quantitative characteristics of the analysis is very

much in demand in industrial and laboratory spectral analysis. Stochastic-

determinated design of experiment makes it possible to achieve these goals in a

relatively small number of experiments (SDDE) with calibration samples of

known composition [Fomin, 2016]. There is a problem of assigning spectral

lines in samples of complex composition to one or another element. We have

experimentally proved that the composition of the calibration samples can be

one of the factors in the SDDE method. With this approach, it is simultaneously

possible to select the optimal laser and spectrometer settings, as well as

analytical lines of elements that are free from the influence of the matrix and

other components of the sample. References:

1.KREMERS, D., and RADZIEMSKI, L. 2009. Laser-spark emission spectroscopy. M.:

Technosphere

2.KALINKIN, I.P. 2002. A new reference book for a chemist and a technologist.T.4.

Analytical chemistry.SPb: ANO NGO "Peace and Family". Part 1. 954p.

3.FOMIN, V.N. AND OTHERS. 2016. Calibration of the spectrometer "LNPP Matrix

Continuum" for the analysis of a mixture of oxalates. In: Science yesterday, today,

tomorrow: Sat. Art. By mater.XXXIX Intern.Scientific-practical.Conf., Novosibirsk,

P.98-105

20

PATTERNS OF ELECTROCHEMICAL REDUCTION OF

GLUTATHIONE ON A CARBON-CONTAINING ELECTRODE

MODIFIED WITH GOLD

Gashevskaya A.S., Dorozhko E.V.


[email protected]

Biologically active sulfur-containing compounds, such as glutathione,

containing thiol (SH-) groups play an important role in physiological and

biochemical processes in the human and animal organisms [1]. Glutathione

(GSH) acts as an antioxidant, prevents the peroxidation of lipids and

phospholipids in cells, tissues of humans and animals. Its antioxidant effect is

also in the ability to interact with organic free radicals, including oxygen

radicals. The most active functional group of the molecule is thiol (sulfhydryl)

SH-group, due to which GSH takes an active part in many oxidation-reduction

processes in the human body and animals [2].

Therefore, studies on predicting the oxidation-reduction behavior of GSH

in model systems are relevant to date. The electrochemical properties of GSH

on a carbon-containing electrode modified with gold were investigated. A gold

film was applied to a carbon-containing electrode voltammetrically (W = 5

mV/s, in the potential range from -0.1V to +0.05V) from a standard solution of

HAuCI4 of 100 mg/l. Prior to the cathodic properties of GSH, oxygen was

removed by applying 0.1M sodium sulfite solution. It was noted that when

GSH is introduced into the cell (concentration 6.6*10-6

M), the oxygen

reduction current increases at a potential of -0.6V, which increases from the

time of the experiment.

It is known that GSH is an antioxidant that binds to oxygen radicals.

Thus, when GSH is introduced into a cell, it binds to oxygen radicals according

to the mechanism:

2RSH + O2- O2 + RSSR + 2H

+

This leads to the formation of O2, which is restored at E = -0.6 V on a

carbon-containing electrode modified with gold.

This technique of depositing a gold film, as well as thiolating the gold

surface of the electrode, is further applicable to the creation of a biosensor.

References:

1. KALAIYARASAN, G., NARENDRA KUMAR A. V., SIVAKUMAR, C., JOSEPH,

J. 2015. Electrochem. Commun., 56, pp. 29-33.

2. HARFIELD, C., BATCHELOR-MCAULEY, C., COMPTON, R.G. 2012. Analyst.,

137, pp. 22852296.

21

PHOSPHINITE POCN PINCER LIGANDS: SYNTHESIS AND

COORDINATION CHEMISTRY

Gudun K. A., Segizbayev M., Khalimon A.Y.

Nazarbayev University, Department of Chemistry, School of Science and

Technology, Astana, Kazakhstan

[email protected]; [email protected]

Transition metal pincer complexes are complexes with rigid tridentate

ligands, in which three donor atoms are located in meridional fashion. Over the

past few decades, pincer complexes have attracted significant interest from a

large number of research groups.Such compounds have been extensively

studied in C-H, C-C, C-N, C-O andrecently N-H and O-H activation reactions

[1]. The pioneering research by Shaw et al. on 1,3-bis(phosphino)phenyl(PCP)

pincers hasinspired many others and during the past two decades transition

metal pincers have evolved into powerfulcatalysts for dehydrogenation of

alkanes, Heck type reactions, and many other processes. The rigid natureand

easily tunable steric and electronic properties of pincer ligands provide a unique

balance of stability vs.reactivity for pincer complexes, often enhancing the

selectivity of the catalytic reactions [2]. Whereas chemistry of transition metal

pincer complexes of symmetrical EXE type ligands with neutral 2e donor side-

arms E (e.g. NR2, PR2 etc.) and either neutral or anionic 2e donors in the

bridgehead position X (e.g. C, N, N, etc.) is now at the advanced stage of

development [1-2], significant opportunities continue to exist in this area of

organometallic chemistry. Among a variety of pincer ligands known in the

literature, the chemistry of unsymmetrical pincer complexes with different side-

arm donors, such as PXN, PXS, etc. (X = C, N, N), is studied to a lesser

extent and restricted to either neutral ligands or anionic ligands, having an

anionic donor at the bridgehead position. Such ligands usually act as "spectator"

ligands, allowing for unique balance of stability vs. reactivity for pincer

complexes. Although pincer complexes having anionic groups in the side-arm

positions are known, the examples of application of such systems in catalysis

are scares [3]. Here we report a series of novelimino-and aminophosphinite

pincerligands (POCN) derived from 3-hydroxybenzaldehyde by stepwise

installation of imino/amino and phosphinite functionalities. Coordination

chemistry of these ligands with late transition metals, such as Fe, Ir and Ni, was

studied.

References:

1. MORALES-MORALES, D., JENSEN, C.M. The Chemistry of Pincer

Compounds. 2011. Amsterdam: Elsevier

2. CHOI, J., MacArthur, A.H R., BROOKHART, M., GOLDMAN, A.S. Chem.

Rev. 2011. 111, p.1761.

3. SPASYUK, D.M.; ZARGARIAN, D. Inorg. Chem. 2010. 49, p.6203.

22

REGULARITIES OF MODIFICATION OF SOLID CARBON-

CONTAINING ELECTRODES WITH TOSILATE SALTS OF

ARYLDIAZONIUM

Gusar A.O, Dorozhko E.V, Slepchenko G.B


[email protected]

The search for new electrode materials and electrode surface modifiers in

the voltammetry method extends the possibilities of this method in determining

both inorganic and organic substances with a higher sensitivity. Among the

wide range of organic modifiers used for the surface modification of solid

electrodes, promising organic agents are tosylate salts of aryldiazonium, which

during the electrolysis ensure the covalent bonding of the functional groups of

aryl (Ar) to the electrode surface [1]. To date, only work on the electrochemical

modification of carbon-containing electrodes by tosylate salts of aryldiazonium

has been known, however, the question of their application for the chemical

modification of solid carbon-containing electrodes has not been considered [2].

The novelty of this work is due to the fact that the development of new

organically-modified solid carbon-containing electrodes modified with tosylate

salts of aryldiazonium with phenyl groups by a chemical method will make it

possible to determine a wide range of elements with higher sensitivity and

selectivity.

In the work, carbon-containing, glass-graphite and carbon-steel electrodes

were used as working electrodes. They were kept in solution of tosylate salts of

aryldiazonium with phenyl groups ([COOHC6H4N2]OJ3, [CNC6H4N2]OJ3,

[C16H33C6H4N2]OJ3). Silver chloride electrodes were used as auxiliary and

reference electrodes. To evaluate the reversibility of electrode processes on

carbon-containing electrodes before and after chemical modification by tosylate

salts of aryldiazonium with phenyl substituents, an equimolar mixture of

Fe(CN)63-/4-

0,25 M hexacyanoferrate salts in the background of 0,5 M KCl was

used. Carrying out the data of the study, it was observed that the oxidation and

reduction currents of Fe(CN)63-/4-

are maximal for the [COOHC6H4N2]OJ3

modifier of the carbon electrode at the time of holding the indicator electrode in

the solution of the above aryldiazonium salt for 2 seconds. And at a

concentration of the modifier of 30 mg/l.

References:

1. MCCREERY, RICHARD. 2008. Advanced carbon electrode materials for molecular

electrochemistry. Chem. Rev., 108 (7), pp.26462687. 2. BANIKAS, FG. 2014. Chemical and biological sensors: fundamentals and

applications. Moscow: Technosphere

23

DEHYDRATION/POLYCONDENSATION OF LACTIC ACID UNDER

MICROWAVE IRRADIATION

Gusar A.O, Guba G.Ya.


[email protected]

At present, microwave irradiation (MWI) is widely used in the synthesis of

biopolymers [1-2]. MW application helps to significantly reduce reaction time

and, from the other hand, to increase the yield and product molecular weight.

Besides, this kind of synthesis is useful in eco-friendly methods development

for the synthesis of biologically active compounds. Reactions under MWI

conditions are susceptible to energy distribution in the reaction chamber and a

different speed occurs in monomode and multimode microwave reactors.

Lactic acid oligomer is an important intermediate in the synthesis polylactic

acid. Also, it is used for drug delivery in clinical practice. The main

disadvantage of the synthesis lactic acid oligomer is a long reaction time. Lactic

acid (LA) synthesis was carried out under thermal dehydration conditions more

than 6 hours.

In this paper we demonstate the influence of microwave power in the

process of dehydration/polycondensation of LA in multimode reactor.

LA was charged 20 g in 100 ml flask, placed n a reactor and sparged with

nitrogen at a pressure of 200 mm Hg, under radiation power of 80, 130, 280,

360 and 500 watts.

The synthesized samples were investigated by IR and 1H NMR

spectroscopic methods. Molecular weight was determined by viscometric

method.

The temperature of LA samples under MWI power at 280, 360, 500 W were

the same and equal 215C.

According to the data 1H NMR and IR suggested that the 80 W mostly

removed physically bound water molecules. At 130-280 W, water removal and

LA polycondensation were carried simultaneous and the conversion of LA

changed from 64 to 67 %. LA polycondensation proceeds most effectively at

360 watts. Vacuum MWI application results the increasing of product

molecular weight.

Thus, keeping the LA oligomer under vacuum for 1 hour at 360 W helps to

increase the product molecular weight in 10 times.

From the obtained data it ensuethat the process of LA polycondensation at

the same temperature (215C) is determined by power radiation of MWI: under

radiation power of 360 W the process of dehydratation/polycondensation was

carried out faster, than at 280 W, i.e. there is a so-called "microwave effect".

24

STUDY OF STRUCTURE AND PHYSICOCHEMICAL PROPERTIES

OF ACIDIC SODIUM SELENITES BY COMPUTATIONAL

CHEMISTRY

Kasymova M.C., Soltanbek E., Abulyaissova L.K.



[email protected]

Study of the physical and chemical properties of substances and

determining the relationship between the structure and properties are of

theoretical and practical interest.

According to the modern requirements quantum chemistry methods

systemize chemical phenomena and objects and also allows predicting a

geometric structure, energy and other properties of polymolecules. All of these

are realized in the GAUSSIAN program. Above mentioned properties for the

sodium selenites were investigated.

Three-dimensional models of molecules of the compounds with formulas

of NaHSeO3, NaH3Se2O6, Na4H6(SeO3)5 are built by GAUSSIAN 2009 and

ChemBio3D Ultra programs. Their geometric and physicochemical parameters

are individually identified. Also comparative analysis of the properties is

carried out.

Selenium atoms in NaHSeO3, NaH3Se2O6, Na4H6(SeO3)5 sodium selenites

has tetrahedral and flat structure.

The full energy of these molecules, the kinetic energy of electrons, the

dipole moment and Malliken charges are determined.

Furthermore, nuclear repulsion energy, electron-nucleus attraction energy,

high occupied molecular orbital and low unoccupied molecular orbital energies

and energy difference are calculated.

References:

1. RUSTEMBEKOV, K.T. 2009. Synthesis, properties of inorganic

compounds on a basis of chalcogenes and their behavior in hydrochemical

processes. Abstract Diss. Dr. Chemical. Sciences, Karaganda, 32 p.

2. WELLS, A. 1987. Structural inorganic chemistry. V.2. Moscow: Mir,

pp.438-459.

25

QUANTUM CHEMICAL CALCULATIONS OF TELLURATES

WITH D-ELEMENTS

Kasymova M.S., Tansykbai A.S., Abulyaissova L.K.



[email protected]

One of the most main problems of modern chemistry is to establish the

relationships between the composition, structure and properties of the

substances[1]. Investigation of the dynamics of chemical bond formation in the

tellurium compounds and the material feature all-up optimization are actual [2].

According to thisquantum chemical calculation ofsome undefined physico-

chemical properties of tellurates with d elements is carried out.

Three dimensional spatial structures of telluratemolecules were built with

ChemBioOffice and GaussViewprograms. Quantum chemical calculation of

ZnTeO4,Zn2Te2O8,Zn3Te4O15molecules was calculated by restricted Hartree-

Fock (RHF) method with the3-21G basis. The full energy, kinetic energy of

electrons, the dipole moment and atom charges by Mulliken etc.are calculated.

Because of the different electronegativity of atoms a dipole momentum

appears and these molecules are strong polar.

Additionally, the nuclear repulsion and nuclear-electron attraction

energies are determined.

The valence angle, bond length, internal rotation angles between some

atoms of zinc tellurate are relevant to the standard value, but some aredeviated.

The charges on the atoms of zinc tellurates are compared. Spreadingthe

electron density between similar atoms are not the same because one defends

on the closest atomic environment.

References:

1. IBISHEV, K.S., KARGINA, N.A., MELESHKO, P.M., ZHALPAKOV,

D.O., UGAI, N.V. 2013. Electrochemical synthesis of nanosized tellurium

powders from electrolytes. M.: TSU, t. 18, r. 5, pp.1.

2. ASCHEULOV, A.A., MANIK, O.N., BILINSKIY-SLOTYLO, V.R. 1979.

Molecular model and chemical bond of tellurium. Electronics Materials, 7,

pp.24-102.

26

STUDY OF MAGNESIUM SELENATE USING COMPUTATIONAL

CHEMISTRY METHODS

Kasymova M.S., Zakirova K.E., Abulyaissova L.K.



[email protected]

In recent years, study of the selenium physicochemical property and

structure is rapidly developed. It should be noted that the selenates of the

alkaline-earth elements are still not enough investigated.

In addition, the methods of quantum chemistry are among the most

important tools for the theoretical study of physical and chemical properties. In

connection with this, the physicochemical properties of some compounds of

alkaline-earth selenates were carried out by quantum-chemical methods [1].

In order to obtain electronic and geometric structures of magnesium

selenates, using ChemBio3D Ultra program to create three-dimensional models

of molecules MgSeO4, MgSe2O7 . In quantum-chemical calculations of the

structure of the investigated compounds the 3-21G basis and ab initio Hartree-

Fock method were used.

MgSeO4molecule is a chemical compound in which the selenium atom

has a structure of six valence and hexagonal structure. The molecule MgSe2O7

is a part of polymer, and here selenium atom has the same valence and

structure. The several variants of molecule structure were constructed. Among

them, the most stable structure was chose. At the same time, the molecular

kinetic energy of electrons, nuclear repulsion and the nuclei-electron attraction

energies as a result of quantum-chemical calculations are determined [2].

In the course of the study, there was a dissimilar distribution of the

electron density in molecules. In addition, the different value of atomic charges

of compounds means that they have electrical properties. In other words, these

molecules have electric dipole moments, being the polar ones.

References:

1. BGNALL, K. 1971. Chemistry of selenium, tellurium and polonium. Moscow: Atomic

2. WELLS, A. 1987. Structural inorganic chemistry. V.2. Moscow: Mir

27

STUDY OF MOLYBDENUM (VI) INTERACTION WITH RUTIN

USING SPECTROPHOTOMETRIC METHOD

Khalitova A.I., Sarsenbekova A.Zh., Kurmanova A.F., Kaikenov D.A.,

Kopzhassarova A.B., Zhakisheva B.M.



[email protected]

As is known, molybdenum is widely used in various branches of modern

technology and industry. It is used for alloying steels as a component of heat-

and corrosion-resistant alloys.Molybdenum wire (tape) serves for the

production of high-temperature furnaces, inputs of electric current in bulbs.

Molybdenum compounds - sulphide, oxides, molybdates - are catalysts of

chemical reactions, pigments of dyes, glaze components. Molybdenum is a part

of microfertilizers, and also used in high-temperature vacuum resistance

furnaces as heating elements and thermal insulation.

In addition, molybdenum is one of the basic microelements in human

and animal nutrition. It is contained in many living tissues and is necessary to

maintain the activity of certain enzymes involved in the catabolism of purines

and sulfur-containing amino acids.

The relevance of developing methods for the determination of

molybdenum takes into account its role in engineering, biology and

metallurgy.In this connection, it is of great practical interest to develop new

spectrophotometric methods for the determination of molybdenum, which is an

important task of modern analytical chemistry.It is known that biologically

active compounds - flavonoids - are used to determine a number of elements.It

has been established that flavonoids have the ability to bind transition metal

ions to chelate complexes. In the literature, there is practically no information

on the complex formation of molybdenum with these compounds.

In the present work, the interaction of molybdenum (VI) with one of the

representatives of the flavonoid class - rutin - in the water-ethanol medium was

studied by the spectrophotometric method.It was found that Mo (VI) reacts

with the rutin in water-ethanol solutions to form an orange complex compound.

It is characterized by a band of maximum absorption in the spectrum at 490 nm.

Dependences of the optical density of solutions of complexes on various factors

were studied: time, solvent content, pH of the medium, concentration of rutin.

A method for determination of molybdenum has been developed.

28

ADVANTAGES OF THE HPLC METHOD FOR THE

DETERMINATION OF STABILIZING ADDITIVES IN POLYOLEFINS

Khovanskaya O.E.1,2

, Novikova E.S.2

1 National Research Tomsk Polytechnic University, Tomsk, Russia

2 LLC "NIOST", Tomsk, Russia

[email protected]

Investigation of stabilizing system of polymeric materials is often a

difficult task, due to a multicomponent composition of such materials, in

addition, there is always an influence of the polymer matrix.

An important step in the investigation is sample preparation, it often takes

more time than the analysis itself. For example, in the case of gas

chromatography it is extraction; in the case of reversed-phase high-performance

liquid chromatography it is grinding and extraction and in the case of infrared

spectroscopy it is plate pressing.

The analysis by infrared spectroscopy is rapid, but it takes time for

pressing a plate of a certain thickness and there is no reliable identification of

stabilizers having identical functional groups. The method of gas

chromatography requires preliminary extraction and has limitations on the

analysis of thermolabile compounds.

The most relevant would appear to be the method of high-performance

liquid chromatography with detection in the UV region. The HPLC method is

applicable to a much wider range of substances than gas chromatography is,

because it allows to perfom separation, detection and concentration

measurement of high molecular weight substances, unstable and nonvolatile

compounds, since the analysis is usually carried out at room temperature. The

purpose of this paper was to develop a simple and effective method for

quantitative determination of the most common stabilizers in polyolefins by

HPLC. The method consists of pre-grinding the sample, extraction with ethyl

acetate, which contains an internal standard, filtration and chromatography.

A method has been developed that allows to identify and quantitatively

determine Irganox-1010, Irganox-1330, Irganox-3114, Irgafos-168 oxidized,

Irganox-1076 and Irgafos-168 simultaneously in polyolefins by HPLC on a

column ZORBAX Eclipse XDB-C18 (size 150 4.5 mm , 5.0 m) using a

three-component mobile phase as an eluent.

29

OBTAINING AND INVESTIGATION OF SILVER NANOPARTICLES

AND THEIR BIOCONJUGATES WITH THE BOVINE SERUM

ALBUMIN FOR THE ELECTROCHEMICAL IMMUNEASSAY

Khristunova Ye.P., Dorozhko E.V., Korotkova E.I., Kratochvil B.

National Research Tomsk Polytechnic University, Tomsk, Russia [email protected]

Recently, the efforts of researchers are directed at the development of

electrochemical immunosensors, where the noble metal nanoparticles (NPs)in

the bioconjugate are used as markers in the detection of antigens-antibodies in

human blood. The conjugates of such noble metals as gold and silver (Ag) are

the most widely used ones, as they are stable and compatible with

biomolecules. Specific attention in the work was paid to the selection of

conditions for stabilizing both the Ag NPs and their bioconjugates with the

Bovine serum albumin (BSA) which was used to provide for additional Ag NPs

stabilization and to block excess Ag NPs that may potentially take part in non-

specific bindings with non-target proteins.

In the initial research stage, spherically shaped Ag NPs were synthesized

and purified by dialysis [1].After the dialysis has been completed, Ag NPs

absorption spectra were recorded on the Cary 2000 spectrophotometer (Agilent,

Germany) with the maximum at 395-400nmwhich is in accordance with the

average Ag NPs size of 152 nm and the TEM analysis data.The charge of Ag

NPs was measured on Zetasizer Nano ZS (Malvern, Southborough, ). The

zeta potential of Ag NP was -42 mV.In order to empirically identify the

minimum BSA concentration for stabilizing Ag NPs, flocculation test was

used.Firstly, BSA introduction shifts the maximum of the UV/VIS Ag NPs

absorption spectra into a longer-wave range (400405 nm) as compared to the

absorption maximum without the BSA. Secondly, the BSA concentration of 2

g/ml is not enough to stabilize Ag NPs with BSA in the presence of the

destabilizing agent (NaCl) even without centrifuging. The BSA concentrations

of 16 g/ml and 32 g/ml are enough to stabilize the Ag NPs colloid even after

centrifuging.The obtained Ag NPs stabilized by BSA (16 g/ml) were

researched by TEM, and the average was 252 nm, the NPs size is increased

and the protein is acting as a stabilizer (a semi-transparent "coat").

Thus, BSA can be recommended as a stabilizer in the subsequent

preparation of bioconjugates.

References:

1. SOLOMON, S.D., BAHADORY, M., JEYARAJASINGAM, A.V.,

RUTKOWSKY, S.A., CHARLES BORITZ. 2007. Journal of Chemical

Education, 84 (2), pp.322325.

30

FRONTIERS BETWEEN CHEMISTRY AND MATERIALS SCIENCE:

STATUS AND NEW PERSPECTIVES

Klyucharev V.V.

Institute of problems of chemical physics of RAS, Chernogolovka, Russia

[email protected]

As is known, Avogadro's hypothesis of chemical confinement was

pronounced in 1811. However, the topological and geometric interpretation of

its metamorphosis in actual practice has proved difficult in many cases, when

the non-arithmetical character of such transformation is involved. As an

abstractive illustration, one can consider two pairs of equal animals placed in a

cage. Assume, after Lebesgue [1], that a jolly trio ate up a co-habitant. In such

case, 2 + 2 = 4 by mass, but 2 + 2 = 3 or 2 + 2 21.5084 by confinement.

Hence, chemistry is arithmetical science in any event, but materials science

may be non-arithmetical. Thus, there appears a need to study not only the

reactions of chemical substances but also the reactions of chemical

confinement. The aim of the conference presentation is to reveal some new

ways for the introduction of the idea in chemical thinking due to the topological

of geometrical comprehension of the problems using the discovery of self-

propagating nucleation with scale doubling as a fractal reaction [2,3]. In

particular, we could talk the rounding rules of the process by its thermo-

chemical paradoxes. One can think that this decision should be helpful in

design and augmenting of new culture in chemical and social engineering based

on the precise distinction between chemistry and materials science, between the

topology and geometry for the reproduction of ones self and the reproduction

of ones similar, as well as in protection against substitutions of materials

science for materials skills, or mechanics physics and chemistry of materials,

both in high and in secondary education.

This presentation is dedicated to the 130th anniversary of Mendeleevs

Investigation of aqueous solutions by specific weight (S-Pb: Tipografiya

V. Demakova. 1887), as the becoming of chemical materials science.

References:

1. LEBESGUE, H. 1932. LEnseign. Math., 31, pp.173-206.

2. KLYUCHAREV, V.V. 2010. Glass Phys. Chem., 36, pp.463-469.

3 KLYUCHAREV, V.V., KLYUCHAREVA, S.V. 2015. J. Therm. Anal.

Calorim., 119, 1633-1651.

31

FORMATION OF SKILLS OF INFORMATION CRITICAL ANALYSIS

OF FIRST-YEAR STUDENTS

Kokibasova G.T., Serikova K.K., Kaztaeyva S.Kh., Beisova A.Zh.



[email protected]

Critical thinking development technology aimed at obtaining new

knowledge, also on the basis of knowledge already available through its critical

analysis [1]. Simultaneously with the appearance of unlimited access absolutely

to all information, is increasing the risk of links, the study of unreliable sources

with not quite trustworthy information.Considering all the above arguments,

first-year students need to develop the ability to critical analysis of information.

For this you can use new forms of independent work, contributing to the

development of critical thinking [2].We carried out a pedagogical experiment

on the subject "Chemistry of elements" classes, in which took part first-year

students. Students use a credit system, which is aimed at increasing the level of

self-education, and to individualization student learning pace.

Before the start of the experiment we have chosen the form of

independent work that promote the development of critical thinking skills, that

as a result would have led to mastering the skills of presenting the results of

their analysis in a variety of forms: a collective presentation, a Venn diagram

and schemes [3].

At the last lesson we carried out self-reflection in order to identify the

perception of students of new forms of work. As the results of the survey, most

students liked the new ways of work, and they would like to use them in future.

Despite the variety of approaches to the study of the problem and

opinions of different scientists, there is a common opinion that critical thinking

which is developed enough is an integral part of an effective teaching, good

training material possession and use of the information obtained in ordinary

life.

References:

1. KOKIBASOVA, G.T. 2016. New technologies while teaching Chemistry.

Karaganda: KarGU

2. KOKIBASOVA, G.T., SERIKOVA, K.K., AND ABISHEVA M.M. 2016.

Formation of students critical thinking in the process of teaching Chemistry.

Bulletin of KarGU, 2 (82), pp.89 94.

3. ZAIR-BECK, S.I,, MUSHTAVINSKAYA, I.V. 2011. Development of the

critical thinking at the lesson. M.: Prosveshchenie

32

QUANTUM-CHEMICAL MODELING OF PROTOLYTIC PROCESSES

IN COMPLEXES OF OXYMETHYL RADICAL WITH WATER

Kurmanova A.F., Kutzhanova K.Z., Pustolaikina I.A., Khalitova A.I.



[email protected]

Oxymethyl CH2OH is the smallest organic OH-radical by size, that

makes it unique. Due to this oxymethyl radical is an original particle for quantum-chemical modeling of protolytic processes in paramagnetic acid-base

systems.

Quantum-chemical modeling of hydrogen-bonded complexes formed

between oxymethyl radical and water have been carried out by using non-

empirical approximation in connection with the UHF 3-21G basis set with the

help of Gaussian03 program package [1]. We have found 2 stable types of

complexes:

1) hydrogen-bonded linear complex (HBLC); 2) hydrogen-bonded cyclic complex (HBCC).

It was found through the analysis of HBLC and HBCC calculated

geometric and energetic characteristics that linear complex was

thermodynamically more stable than cyclic complex by 4.58 kcal/mol. The

length of the hydrogen bridge R(O... N) was computed as 2.7 in both types of

complexes. The shape of HBLC and HBCC frontier molecular orbitals was

showed localization of unpaired electron on the oxymethyl radical. It is worth

noting that the dipole moment of HBLC is larger compared with those of

HBCC. These associated with higher polarity and lower symmetry of HBLC

structure.

Profiles of the proton transfer reaction potential energy surface for linear-

type complex were investigated. Calculations were performed with changes of

hydrogen bridge length R(O...O) from 2.7 to 3.4 ; with fixing of valence

angle (HOO) and with changes of the OH-bond length by 0.1 step. It was

established that minimum of the total energy of oxymethyl radical-water

system corresponds with the formation of molecular hydrogen-bonded

complex. The profile of the potential energy surface with two wells was

obtained for R(O...O) = 3.4 . The transition state of the system at R(O-H) =

2.1 and the final state of the system, corresponding with the formation of

hydrogen bonding ionic complex (HBIC), were identified on the profile

References:

1. FRISCH, M. J., TRUCKS, G. W., SCHLEGEL H. B., et al. 2003. Gaussian 03. -

Gaussian Inc., Wallingford CT.

33

INVESTIGATION OF THE CORRELATION BETWEEN VALUES

OF AND DEPROTONATION ENERGY FOR A MODEL NUMBER

OF AMINO ACIDS

Kutzhanova .Zh., Kurmanova .F., Pustolaikina I.., Aldangurova .U.,

Makybas .G., Bakytbekova .Zh.



[email protected]

An investigation of the acid-base properties of amino acids is

considerable interest, since the values of and the patterns of change in the

protolytic properties of these compounds are extremely important for predicting

reactivity and evaluating the pharmaceutical potential.

It was shown earlier [1] that nonempirical ab initio UHF calculations

taking into account the influence of the medium on the basis of the continuum

solvation model IEFPCM (solvent-water) give the most satisfactory results for

this purpose.

It was carried out a quantum-chemical estimation of the deprotonization

energy for the series of 15 amino acids by the nonempirical method UHF ab

initio with considering solvation within the framework of the CPCM polarized

continuum model with solvent water using the Gaussian-2009 program. The

values of were taken from the reference book [2].

The obtained graph of the dependence of the reference value of the

value on the deprotonation energy deprotonation for the studied 15 amino

acid series showed the presence of a direct proportional relationship between

these quantities. The value of the Pearson correlation coefficient index R = 0.94

indicates a close relationship between these two quantities. A linear

approximation equation y = 0.0351x + 1.8691 was found, which characterizes

the relationship between the input deprotonation. And output

parameters of the model sample.

References:

1. KUTZHANOVA, . Zh., KURMANOVA, .F. et al. 2016. Science: Scientific and Production Journal, 1, pp.269-271.

2. LURYE, U.U. 1984. Handbook of Analytical Chemistry

34

THEORETICAL STUDY OF PROTON EXCHANGE IN

AMINOACETIC ACID DIMERS

Kutzhanova .Zh., Kurmanova .F., Pustolaikina I.., Aldangurova .U.,

Makybas .G., Bakytbekova .Zh.



[email protected]

The molecule of aminoacetic acid has in its structure two protolytic

reaction centers: a carboxyl group with acidic properties and an amino group

with basic properties. Due to this aminoacetic acid can forms dimers caused by

hydrogen bond [1]. The structure of some dimers is favorable for the process of

intracomplex proton exchange. It was interesting to determine the most ideally

structure for proton exchange in amino acetic acid dimers by quantum-chemical

methods.

Geometries and energy parameters for three main types (1-3) of dimers

were obtained at the 3-21G UHF ab initio level:

where Q -2-NH2; R -2-COOH.

Simulation of the intermolecular proton exchange process in these dimers

was carried out with the help of Quadratic Synchronous Transit approach

(QST2) and Intrinsic Reaction Coordinate procedure (IRC). The activation

energy of the forward (Eact) and reverse (Eact) protolytic processes was

estimated for dimers 1-3. It was found that the activation energy was: for dimer

1 Eact=26 kJ/mol and Eact=34 kJ/mol; for dimer 2 Eact=244 kJ/mol and

Eact=236 kJ/mol; for dimer 3 Eact=47 kJ/mol and Eact=36 kJ/mol. It is clear

from the obtained data that the most favorable for proton exchange structures

are dimers 1 and 3 in which carboxyl and amino groups are involved in

hydrogen bonding. References:

1. Kutzhanova K.Zh., Pustolaikina I.A., et al. (2016) Bulletin of the University of

Karaganda-Chemistry, 4(84), 33-37.

35

SIMULTANEOUS DETERMINATION OF TARTRAZINE (E 102) AND

BRILLIANT BLUE FCF (E 133) AT MODIFIED ELECTRODES

Lipskikh O.I., Korotkova E.I.

Institute of Natural Resources,


Color is one of the main characteristics by which consumers evaluate the

quality of products. A large number of natural and synthetic dyes are used for

tinting different foodstuff: candies, marmalade, jellies, ice cream, soft drinks

and many others. Due to the fact that synthetic dyes are more resistant to light,

temperature, pH, they are used more often than natural ones. However, they

have a negative effect on the human health may cause allergic reactions,

kidney and liver diseases, lead to hyperactivity and overexcitation of children

[1]. Therefore the content of synthetic dyes is strictly regulated and varies from

50 (in soft drinks) to 500 (in decorative coatings) mg/kg of food [2]. Often in

order to achieve a certain color a mixture of several dyes is used. For example,

to give a green color, two synthetic dyes are often used Tartrazine (E 102)

and Brilliant Blue FCF (E133).

The aim of this work is simultaneous voltammetric determination of

Tartrazine and Brilliant Blue FCF in soft drinks. Experimental studies were

carried out in three-electrode cell. Indicator carbon-containing electrode was

modified with carbon ink (Graphite powder, polystyrene, dichloroethane).

Silver chloride electrodes were used as auxiliary and reference electrode. The

background electrolyte was Britton-Robinson buffer with pH 2.0 for Tartrazine

and pH 7.0 for Brilliant Blue analytical determination.

The linear concentration range of each dye in the presence of another was

observed in the range from 0.02 to 0.91 mg/L for Tartrazine and from 0.02 to

1.2 mg/L for Brilliant Blue FCF.

Three kinds of soft drinks containing both dyes were analyzed. In all three

samples, the content of synthetic dyes does not exceed the allowable level

according to SanPiN 2.3.2 1293-03.

References:

1. CHUNG, K.T. 2016. Azo dyes and human health: A review. J. Environ. Sci.

and Health. Part C, 34 (4), pp.233-261.

2. Sanitary Rules: Hygienic Requirements for the Use of Food Additives 2003

(2.3.2.1293-03). Moscow: Minzdrav RF.

36

USE OF CARBON SORBENTS FOR WASTE WATER PURIFICATION

Mamrayeva K.M., Kaztaeva S.H., Kokibasova G.T., Dyusekeeva A.T.,

Kezdikbaeva A.T.



[email protected]

One of the problems arising during mining is coal production waste. Of

particular value are the coals of the Shubarkol field, where besides the

extraction of high-quality coal fuel, it is possible to create a large fuel and

energy complex.

In the laboratory of coal chemistry of the Institute of Organic Synthesis

and Coal Chemistry of the Republic of Kazakhstan, research is currently

underway on the processing of off-balance coals of the Kazakhstan deposit.

Purpose of the work: purification of natural waters from heavy metals and

reduction of the total hardness of water. As the investigated object, the water of

the irrigation canal, waste water from rice pouches and extracts from the soil of

Kyzylorda were taken. For the purification of wastewater, a sorbent developed

at LLP "Institute of Organic Synthesis and Coal Chemistry of the Republic of

Kazakhstan" was used. Sorbent is obtained from oxidized off-balance coals of

the Shubarkol field. The process was carried out at room temperature for 20

minutes with slow stirring. The sediment was in a suspended state, and the

resulting flakes did not degrade. The effluents are purified by simultaneous

treatment with an aqueous solution of humic acids and coagulants. Humic acid

is supplied in an amount necessary to bind the heavy metal ions present in the

water and varies within 1-3 kg / t. Excess leads to a decrease in the efficiency

of chemical treatment. The proposed technology allows to carry out the process

of water purification in a continuous mode at high removal efficiency of heavy

metals and reduction of the total hardness of water to 2.8 meq / l, pH

37

THE IONIZATION POTENTIALS OF ACID-BASE MOLECULES

IN FAST PROTOLYTIC REACTIONS

Masalimov A.S.



[email protected]

Investigations of the fast protolytic reactions kinetic by dynamic EPR

spectroscopy show that general mechanism of proton transfer process, for

example, bet-ween H-acid (XH) and organic bases (Y) in toluene medium,

may be presented with the next scheme:

If XH is the semiquinone spin probe 3,6-di-tert.butyl-2-oxyphenoxyl (I)

then stab-le radical I gives us molecular complex with hydrogen bond B with

molecules of organic solvents, wich have the ionization potential values

approximately equal or higher then adiabatic IPa of I: spirits, ethers, water,

hexametapol etc.

Bases -IPa, eV H-acids -IPa, eV

Li 5,3917 HOH 10,4474

Na 5,1321 3 9,3274

K 4,3407 2 8,0162

NH3 8,5200 HCOOH 9,9688

CH3NH2 7,7480 CH3COOH 9,3647

(CH)2NH 7,1749 dioxane 6,9966

(CH)3N 6,1851 HCl 11,8596

(C2H5)3N 5,7297 HNO3 11,1130

tebaine 5,8430 H2SO4 10,4240

hexametapol 7,2756 I 7,7132

Alkaline metals, alcaloides and several amines with more small IPa values

then I, form ionic complex with hydrogen bond C in acid-base protolytic

reaction (1) between oxyradical (XH) and Y molecules. Table contents IPa

values obtained by ab-initio UHF 3-21G method. This data demonstrate that the

elementary electron transfer from bases molecule to acids molecule summary

determine proton transfer process in the fast protolytic reaction.

38

THE EPR INVESTIGATION OF PHENYL-SUSTITUTED CARBON

ACIDS FAST PROTON EXCHANGE REACTIONS

Masalimov A.S., Rahimzhanova A.S., Kobelkova M.N., Rimgaly M.Z., Tur

A.A.



[email protected]

The EPR investigations of several substituted carbon acids proton

exchange fast reactions (1) with semiquinone spin probe 3,6-di-tert.butyl-2-

oxyphenoxyl (I) gives the next presented on table kinetic data.

Acid kex (293K),

l/l.

Ea, kJ/mol pKa

formic (4,5 0,2).10

7 7,1 0,3 3,75

acetic (5,1 0,7).10

7 13,4 0,4 4,75

benzoic (1,7 0,1)108

5,8 0,2

4,17

phenylacetic (6,4 0,2)107 11,7 0,7 4,28

2-quinolinic (1,4 0,4)107 9.0 0,8 4,95

abietic (2,2 0,1).10

8 7,7 0,3 -

cinnamic (2,5 0,1)108 5,8 0,4 4,44

phenol (1,0 0,5).10

6 13,1 0,9 -

The rates constant for phenol was obtained in medium of melted pure

compound. The semiquinone radical I is paramagnetic H-acid, but doesnt

exchange proton with alco-hols and water molecules. Presented table shows

that benzoic acid has more protolytic activity i.e. the value of intermolecular

proton exchange rate constant kex then formic and acetic acids, but separation of

phenyl group from carboxylic group make protoly-tic activity of phenylacetic

acid similar formic and acetic acids activity. Summary electronic

conjugationon of benzene, ethylene and carboxylic group in cinnamic acid

gives us the rate constant increasing. If the influence of big substituent in

abietic acid has the difficult explanation, quinolynic group of 2-quinolynic acid

tend to formation of zwitter-ion.

39

THE POSSIBILITY OF VOLTAMMETRIC DETERMINATION OF

MELDONIUM ON CARBON-CONTAINING ELECTRODES

Mezentseva O.L., Slepchenko G.B., Cybikova S.


To date, there are several ways to determine the medicinal substances in

biological objects (chromatographic, titrimetric, optical methods). But their

limited use is primarily due to the low sensitivity of the method, the time and

reagents, and these methods are not sufficiently selective and involve many

operations. The problem of creating an express and sensitive method for the

determination of medicinal substances in various objects is still relevant.

Especially when it tells about identifying drugs on the list of banned for use in

the athletes. Since January 01, 2016 WADA inclusion of a meldonium in the

list of doping drugs, sharply exacerbated the problem of highly sensitive and

rapid detection of this substance in biological objects. A promising

electrochemical method for determining drug substances are voltammetric

methods of analysis, due to their high sensitivity and low cost of equipment.

ministry of education and science of the republic of kazakhstan...

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