The 4TH ANNUAL STUDENT SCIENTIFIC CONFERENCE IN ENGLISH

The Ministry of Education and Science of the Russian Federation

Far Eastern Federal University

School of Natural Sciences

The 4TH ANNUAL STUDENT SCIENTIFIC

CONFERENCE IN ENGLISH

Vladivostok

03 – 15 May 2017

CONFERENCE PROCEEDINGS

Scientific electronic publication

Vladivostok


2017 © ФГАОУ ВО «ДВФУ», 2017

ISBN 978-5-7444-4038-1

THE 4th ANNUAL STUDENT SCIENTIFIC CONFERENCE IN ENGLISH

Vladivostok, 03–15 May 2017

2

UDC 082

LBC 94.3

T44

Editorial board:

S.G. Krasitskaya (chief editor),

V.B. Kolycheva, E.V. Kravchenko, O.K. Titova, G.L. Ardeeva,

I.F. Veremeeva, Yu.O. Kamornaya, M.I. Balanov

The 4th Annual Student Scientific Conference in English,

Vladivostok, 3–15 May 2017 [Electronic resource] : conference

proceedings / chief editor S.G. Krasitskaya. – Electr. dat. –

Vladivostok: Far Eastern Federal University, 2017. Uniform

Resource Locator: https://www.dvfu.ru/schools/school_of_natural_

sciences/sciences/the-conference/. – Title screen. ISBN 978-5-7444-4038-1

The collected volume contains proceedings of the contest of scientific

reports in English and the results of scientific studies made by students,

master's degree students and postgraduate students of the School of

Natural Sciences, FEFU 03 – 15 May 2017.

UDC 082

LBC 94.3

Text electronic edition

Minimum System Requirements:

Минимальные системные требования:

Web browser Internet Explorer 6.0 or higher,

Opera version 7.0 or higher,

Google Chrome version 3.0 or higher)

A computer with Internet access

Posted on the website of 06.20.2017

Volume 3.1 MB


690950, Vladivostok, Sukhanova st., 8

Теl. /Fax: (423) 226-54-43, 265-22-35 (*2383)

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

© FEFU, 2017

T44

https://www.dvfu.ru/schools/school_of_natural_sciences/sciences/the-conference/

https://www.dvfu.ru/schools/school_of_natural_sciences/sciences/the-conference/



3

CONTENTS

Section I BIOLOGY, ECOLOGY AND GEOSCIENCES ............................................................. 5

Zharikova E. Ardeeva G.L. ADULT NEUROGENESIS IN NON-MAMMALIAN

VERTEBRATES .................................................................................................................................. 5 Ilyaskina D.V., Shved N.A., Grinchenko A.V.,Ardeeva G.L. BACTERIA AGGLUTONATION

BY LECTIN FROM HEMOLIMPH OF MODIOLUS KURILENSIS (MOLLUSCA: BIVALVIA) 7 Knyazkina M.I., Grinchenko A.V., Ardeeva G.L. PROTEIN FROFILE OF CELL-FREE

HEMOLIMPH OF MODIOLUS KURILENSIS (MOLLUSCA: BIVALVIA) FROM IMPACTED

AND NON-IMPACTED WATER AREAS OF THE SEA OF JAPAN .............................................. 9 Lebedev I.I., Ardeeva G.L. NATURAL DISASTERS AS A FACTOR OF COASTAL ZONE

CHANGE IN PRIMORYE ................................................................................................................. 11

Lupakov S., Ardeeva G.L. ABOUT SELECTION OF CLIMATIC SCENARIOS UNDER

MAXIMUM FLOW MODELING ..................................................................................................... 13 Maschenko V.N. Ardeeva G.L. INFLUENCE OF CONSTANT MAGNETS ON THE

ORBITAL MOMENT ........................................................................................................................ 16

Section II MATHEMATICS AND INFORMATION TECHNOLOGY ..................................... 19

Varlataya S.K., Fayzenger A.A., Kamornaya Yu.O. IDENTIFYING THE VULNERABILITIES

OF INFORMATION SYSTEMS AS THE MAIN STAGE OF RISK ASSESSMENT .................... 19 Digor A.G., Lukina E.M. DEVELOPMENT OF TRAINING SIMULATOR FOR ACCENT

REDUCTION IN NON-NATIVE LANGUAGE SPEECH ............................................................... 20

Dobrzhinskaia T. BLOCKCHAIN TECHNOLOGY SECURITY ISSUES AND

CHALLENGES .................................................................................................................................. 21

Zalepukhin A., Grinyak V., Kamornaya Yu.O. DEVELOPMENT OF A METHODOLOGY

FOR ASSESSING THE MARITIME TRAFIC RISKS ..................................................................... 24

Ivanenko Yu., Grinyak V., Kamornaya Yu.O. ESTIMATION OF DIGITAL RADAR SYSTEM

RESOLUTION ................................................................................................................................... 25

Kalashnikov P.V., Gorodetskaya E.Ya. OPTIMAL FUNDING OF PENSION SCHEMES AS

A TASK OF DYNAMIC CONTROL ................................................................................................ 27 Krasitskaya A.I., Stepanova A.A., Gorodetskaya Ye.Ya. COMPLETE CLASSES OF

DIVISIBLE S-ACTS .......................................................................................................................... 28

Lemza A.O., Kovtanyuk L.V., Norkina P.S. CREEP AND PLASTIC FLOW INITIATION

AND DEVELOPMENT IN A MATERIAL PLACED BETWEEN COAXIAL CYLINDERS ...... 29 Perevolotsky V.S. Veremeeva I.F. IT SERVICE MANAGEMENT: OPTIONS FOR

INTERACTION IT AND CORE BUSINESS ................................................................................... 30

Rassolov E.A. Veremeeva I.F. ALGEBRAIC ATTACK ............................................................ 31 Romashko D., Nurminski E.A. HIDDEN MARKOV MODEL IN GENOMIC DATA

ANALYSIS ........................................................................................................................................ 33

Smekhun Y. A. Veremeeva I.F. TEXT ANALISIS IN MODELING OF KNOWLEDGE

DOMAIN ............................................................................................................................................ 35 Tarasenko О., Dudko O., Veremeeva I.F. CONDUCTING COMPUTATIONAL

EXPERIMENTS WHEN SOLVING OF FLAT SELF-SIMILAR PROBLEMS OF NONLINEAR

ELASTICITY THEORY .................................................................................................................... 36

Tretiak E., Vereshchagina E. Veremeeva I.F. RESEARCH OF COMPUTER GAME

TECHNOLOGIES FOR TEACHING OF INTERNATIONAL STUDENTS................................... 38

Section III CHEMISTRY AND CHEMICAL TECHNOLOGY ................................................. 40

Bragina J.A., Kolycheva V.B. TO GRIND OR TO BURN: A REVIEW OF USED TYRES

UTILIZATION METHODS............................................................................................................... 40 Vinichenko I., Titova O.K. CATALYTIC PROPERTIES OF IMMOBILIZED IONIC

LIQUIDS DURING THE ISOMERIZATION OF HYDROCARBONS .......................................... 42



4

Grinenko E.F., Arefieva O.D., Titova O.K. THE ENVIRONMENTAL STATE OF THE

OL’KHOVYY CREEK IN THE INDUSTRIAL AREA OF THE ABANDONED "NAGORNAYA"

MINE (GUERRILLA COAL BASIN, PRIMORSKY KRAI) ........................................................... 45 Zharinov D., Titova O.K. RECYCLING OF POLYETHYLENE TEREPHTHALATE ............ 46 Malakhova I., Privar Y., Bratskaya S. , Kolycheva V.B. HIGHLY POROUS SORBENTS OF

IONS OF TRANSITION METALS BASED ON POLYETHYLENEIMINE .................................. 49

Pugacheva N., Anufriev A., Kolycheva V.B. SELECTION OF SOLVENT FOR THE

PROCESS OF OBTAINING IZOPRENE FROM C5 PYROLYSIS FRACTION BY EXTRACTIVE

DISTILLATION ................................................................................................................................. 50 Zvereva А., Vasilyeva M., Rudnev V., Kilin K., Sergeev A., Nepomnyaschiy A., Voznesenskiy

S., Ustinov A., Kolycheva V.B COMPOSITION, STRUCTURE AND PHOTOCATALYTIC

PROPERTIES OF Fe-CONTAINING COATINGS ON TITENIUM ............................................... 52

Pak M. A., Zhidkov M. E., Kolycheva V.B. FASCAPLYSIN DERIVATIVES AS μ-OPIOID

RECEPTOR AGONISTS: MOLECULAR MODELING STUDY ................................................... 54 Khrebtov A.A., Lim L.A, Fedorenko E.V., Cherevatiuk G.V., Kolycheva V.B.

INVESTIGATION OF POSSIBILITY OF USING POLYMERIC FILMS DOPED WITH BORON

DIFLUORIDE DIBENZOYLMETHANATE ON GLASS SUBSTRATE AS A LUMINESCENT

SOLAR CONCENTRATOR .............................................................................................................. 57

Perviakova A., Titova O.K. EXTRACTION OF RARE EARTH ELEMENTS FROM COAL

BY SUPERCRITICAL CARBON DIOXIDE EXTRACTION ......................................................... 59 Pisartseva A., Soldatkina O., Akimova T.I., Titova O.K. INVESTIGATION OF

INTERACTION ALICYCLIC DIKETON 2-(2-OXOCYCLOHEXYLMETHYL)

CYCLOHEXANONE WITH HYDROGEN PEROXIDE IN THE SUBACID MEDIUM ............... 61 Rudenko A.A. , Lim L. A., Yarygin D.V., Titova O.K. RESEARCH OF OIL CAPACITY OF

POLYMER SORBENT FROM SECONDARY POLYETHYLENE ................................................ 63 Rymina A. A., Kapustina A.A., Kravchenko E.V. MECHANOCHEMICAL SYNTHESIS OF

POLYTINPHENYLSYLOXANES.................................................................................................... 65 Samus’ M., Krasitskaya S.G., Kolycheva V.B. INVESTIGATION OF PHYSICAL

CHEMICAL CHARACTERISTICS AND SORPTION PROPERTIES OF

POLYALUMINOPHENYLSILOXANE BASED FUNCTIONAL MATERIALS........................... 66 Smirnova M.G, Sokolova L.I., Shapkin N.P., Kolycheva V.B. APPLICATION OF SORBENTS

BASED ON NATURAL ALUMINOSILICATES FOR CONCENTRATING OF

CEPHALOSPORIN ANTIBIOTICS IN THE CONDITIONS OF THE DYNAMIC SORPTION .. 68 Khmelevskaia E.A., Pelageev D.N., Kravchenko E.V. SYNTHESIS OF 1,4-

NAPHTOQUINONE-CARBOHYDRATE CONJUGATES OF NON-GLYCOSIDE NATURE .... 69

Cherevatiuk G.V, Lim L.A., Khrebtov A.A., Kravchenko E.V. INTERACTION OF

POLYSTYRENE AND DICHLOROETHANE IN FRIEDEL-CRAFTS REACTION .................... 71

Chernova A.V., Reutov V.A., Kravchenko E.V. GAS – LIQUID CROMATOGRAPHY ........ 72 Shirokovskaya D.A., Reutov V.A., Kravchenko E.V. MODERN TECHNOLOGIES OF

POLYPROPYLENE'S PRODUCTION ............................................................................................. 73 Yarygin D.V., Rudenko A.A., Lim L.A., Kravchenko E.V. THE STUDY OF THE

PROPERTIES OF POLYETHYLENE FIBER SORBENT ............................................................... 75



5

THE CONTEST OF SCIENTIFIC REPORTS

Section I

BIOLOGY, ECOLOGY AND GEOSCIENCES

_________________________________________________________________________

Zharikova E. Ardeeva G.L.

ADULT NEUROGENESIS IN NON-MAMMALIAN VERTEBRATES

1Far Eastern Federal University, School of Natural Sciences 2Far Eastern Federal University, Oriental Institute-School of Regional and International Studies

[email protected]

Investigation of the mechanisms of postembryonic and reparative neurogenesis in the

brain of vertebrates is an interesting theoretical and fundamental problem. It has been presently

established that the study of regenerative-competent organisms gives clear advantages in the

study of the biology of neural stem cells (NSCs), their interaction with the cellular

microenvironment and metabolic features (1). The problems of neurogenesis in adult animals

first described by Joseph Altman 50 years ago (2), are now an independent trend in

neuroscience. Recent studies indicate that in mammals and humans neurogenesis processes in

the brains of adult animals are present in the hippocampus and in the olfactory bulb (3).

Neurogenesis can stimulate and suppress various factors such as physical activity, changes in

habitat conditions or stress (4). These factors have a multidirectional effect on the intensity of

neurogenesis and determine the ultimate success of this process.

Another area of research on neurogenesis in adult animals is related to the study of the

activity of neurogenic processes in animals of different phylogenetic groups (5). Such

investigations make it possible to establish more completely, and often not only in the

laboratory, the features of the flow of this process in various groups of vertebrates. They allow to

assess the processes of persistent neurogenesis in vivo and provide extensive information for

comparative analysis. Studies on conventional model objects are of great importance for

clarifying the details of many physiological processes. For example, studies of regenerative

processes in the mammalian CNS are being actively compared with research on regenerative-

competent organisms. In particular, representatives of phylogenetically ancient groups, with an

increased proliferative potential of the brain, are successful models for such studies.

Totipotent stem cells are of great importance for the function of many organs, since they

are donors in the physiological renewal of cells in case of their loss as a result of trauma or

disease. The absence of such stem cells is considered to be the reason for the limited

regeneration of adult mammals in the central nervous system. However, recently in their brains,

in the subendymal zone of the lateral ventricle, where the interneurons of the olfactory bulb,

migrating through the rostral migratory flow, and the subgranular zone of the dentate gyrus of

the hippocampus producing granular neurons, cells with stem cell functions have been detected

(6). To understand the influence of physiological factors and the basic molecular mechanisms

governing the fate of neural stem cells, numerous studies are currently underway (3).

Today the brain of rodents (mice and rats) is used as a generally accepted model system

that simulates conditions in the human brain. Nevertheless, neurogenesis in the mature brain is

found not only in mammals, but also in other vertebrates, including birds, reptiles, amphibians

and fish (7). When studying the species of these non-mammal vertebrates, interesting data were

obtained, through which comparative models for the study of adult neurogenesis were compiled.

In particular, this is due to the study of the effect of the cellular microenvironment, the factors



6

necessary to maintain the NSC, the factors regulating the rate of formation of adult-born neurons

in the proliferative regions of the brain (8)

After studying the molecular and cellular characteristics of long-lived neuronal

progenitor cells identified for each class, it was proved that adult precursor cells of non-

mammalian vertebrate neurons are equivalent in their properties to mammalian stem cells. These

observations raise the fundamental question of why neurogenesis is present in some species of

animals and is absent in others. The discussion on this issue unites consideration of internal and

external mechanisms that enhance or inhibit the plasticity of the brain, as well as the way in

which it varies during life in different species of animals.

References:

1. Manger P. R. Presence and absence of adult hippocampal neurogensis in mammals and

effect of the environment // Adult Neurogenesis: Evolution, Regulation and Function.

Dresden, Germany, May 6-8, 2015. Abstr. 3.

2. Altman J, Das GD. Autoradiographic and histological evidence of postnatal hippocampal

neurogenesis in rats // J Comp Neurol. 1965. Vol. 124. P. 319– 335.

3. Berninger B, Hack MA, Gotz M. Neural stem cells: on where they hide, in which

disguise, and how we may lure them out // Handb Exp Pharmacol. 2006. Vol. 174 P. 319–

360.

4. Hutton C., Dery N., Rosa E., Lemon J., Rollo C. D., Fahnestock M., deCatanzaro D.,

Wojtowicz J. M., Becker S. Mitigating the effects of stress on the hippocampus with diet

and exercise // Adult Neurogenesis: Evolution, Regulation and Function. Dresden,

Germany, May 6-8, 2015. Abstr. 23

5. Parolisi R., Cozzi B., Bonfanti L. Adulr neurogenesis in aquatic mammals devoid of

olfaction // Adult Neurogenesis: Evolution, Regulation and Function. Dresden, Germany,

May 6-8, 2015. Abstr. 15

6. Jagasia R, Song H, Gage FH, Lie DC. New regulators in adult neurogenesis and their

potential role for repair // Trends Mol Med. 2006. Vol.129. P. 400–405.

7. Garcia-Verdugo JM, Ferron S, Flames N, Collado L, Desfilis E, et al. The proliferative

ventricular zone in adult vertebrates: a comparative study using reptiles, birds, and

mammals // Brain Res Bull. 2002. Vol. 57. P. 765–775.

8. Lindsey BW, Tropepe V. A comparative framework for understanding the biological

principles of adult neurogenesis // Prog Neurobiol. 2006. Vol. 80. P. 281–307.



7

Ilyaskina D.V.1, Shved N.A.2,3, Grinchenko A.V.1,2,Ardeeva G.L.

BACTERIA AGGLUTONATION BY LECTIN FROM HEMOLIMPH OF

MODIOLUS KURILENSIS (MOLLUSCA: BIVALVIA)

1Far Eastern Federal University, School of Natural Sciences,

Department of Cell Biology and Genetics 2Far Eastern Federal University, School of Biomedicine,

Laboratory of biomedical cell technologies 3National Research Center of Marine Biology, Laboratory of pharmacology

4Far Eastern Federal University, Oriental Institute-School of Regional and International Studies

[email protected]

Lectins are glycoproteins consisting of several subunits that main function is recognition

of the molecules. Soluble extracellular lectins are one of the main protective factors of humoral

immunity of invertebrates, capable of performing a number of functions, with main being

opsonization, agglutination and cytotoxicity [1]. One of the most important characteristics of

protective substances is their ability to target different groups of pathogens. Bacteria are the most

representative group of these pathogens and are usually divided into two groups depending on

the structure of the cell wall: Gram "+" and Gram "-".

The test lectin was isolated from cell-free hemolymph (plasma) of Modiolus kurilensis

bivalve mollusks by plasma coarse fractionation by ammonium sulfate salting out and then

purifying the fraction containing the target lectin by affinity chromatography using a lectin-

specific ligand. Prior to the evaluation of lectin binding to bacteria the conjugate of the lectin

with FITC (FITC-celite F1628, Sigma) was prepared according to the procedure described by

the manufacturer using protein: FITC molar ratio of 1:5, followed by purification of the

conjugate from unbound dye by gel-filtration Chromatography.

Bacteria of the species Bacillus subtilis (Gram "+") and Vibrio alginolyticus (Gram "-")

were isolated from marine organisms and were cultivated on a solid nutrient medium Yashimiza-

Kimura [2]. After that the colonies were flushed with phosphate buffer saline (PBS: 10 mM

NaH2PO4-Na2HPO4, 150 mM NaCl, pH 7.4), adjusting the concentrations of the suspensions to

2×108 cells / ml. Large bacterial conglomerates were destroyed.

Further, the lectin-FITC conjugate was added to the suspensions at a final concentration

of 5 μg / ml. The mixture was incubated at room temperature for 30 minutes and was washed

three times by PBS from potentially unaffected lectin. Results were visualized using

magnification of 100x on a multi-photon system of deep optical imaging based on the Olympus

FV1000 microscope, obtaining a series of images along the Z-axis to create the Z-projection.

The results showed that lectin agglutinates both types of bacteria (Fig. 1), confirming the

involvement of the test protein in the immune defense in M. kurilensis. For some other Bivalvia

lectins, agglutinating activity is also shown for both Gram "+" and Gram "-" bacteria [3, 4],

which indicates the presence of binding patterns in both cases. Thus, it can be concluded that the

studied lectin is specific to carbohydrate determinants, and this does not depend on the structure

of the cell wall of bacteria stained by Gram.

The work was supported by the Russian Science Foundation, project №15-15-20026.

mailto:[email protected]



8

Figure 1 - Agglutination of bacteria with lectin from the hemolymph of Modiolus kurilensis

Bacillus subtilis without adding lectin-FITC conjugate (A) and agglutination after addin

conjugate (B); Vibrio alginolyticus without adding lectin-FITC conjugate (C) and agglutination

after addin conjugate (D); Scale segment is 5 μm

References:

1. Olafsen, J. A. Role of Lectins in Invertebrate Humoral Defense / J. A. Olafsen // Amer.

Fish. Soc. Sp. Publ. – 1988. – Vol. 18. – P. 189-205

2. Youshimizu, M. Study of intestinal microflora of salmonids / M. Youshimizu, T. Kimura

// Fish Pathol. – 1976. – Vol. 10. – P. 243-259.

3. He, X. A novel sialic acid binding lectin with anti-bacterial activity from the Hong Kong

oyster (Crassostrea hongkongensis) / X. He, Y. Zhang, F. Yu, Z. Yu // Fish & Shellfish

Immunology. – 2011. – Vol. 31. – P. 1247-1250.



9

4. Wang, L. A multi-CRD C-type lectin with broad recognition spectrum and cellular

adhesion from Argopecten irradians / L. Wang, L. Wang, J. Yang, H. Zhang, M. Huang,

P. Kong, Z. Zhou, L. Song // Developmental and Comparative Immunology. – 2012. –

Vol. 36. – P. 591–601.

Knyazkina M.I. 1, Grinchenko A.V. 2, Ardeeva G.L.3

PROTEIN FROFILE OF CELL-FREE HEMOLIMPH OF MODIOLUS KURILENSIS

(MOLLUSCA: BIVALVIA) FROM IMPACTED AND NON-IMPACTED WATER

AREAS OF THE SEA OF JAPAN

1Far Eastern Federal University, School of Natural Sciences 2Department of Cell Biology and Genetics


[email protected]

The structure of a living organism imposes communication between the blood cells,

tissues and organs, as well as the necessity to defend the whole organism. The circulatory system

acts as a communication channel between all the fragments of a living organism and is one of the

key systems for protecting the body and maintaining homeostasis.

The subjects of the study were mature specimens of Modiolus kurilensis. The animals

were collected by a diving method: 48 from the Vostok Bay and 30 from the Amur Bay, the

Sportivnaya gavan' (impact area with a high anthropogenic pressure). Hemolymph was taken

with a syringe from the posterior adductor muscle hemal sinus, plasma (cell-free hemolimph)

was separated by centrifugation. The protein composition of plasma was studied by protein SDS-

PAGE in 9% polyacrylamide gel stained by Coomassie Brilliant Blue G-250. Analysis of the

content of images was made in the program "RflpScan", statistical processing of the results was

made in the "Statistica 6.0" software package.

20 fractions of proteins with a mass of 12 kDa to 252 kDa were detected. Evaluation of

detection frequency revealed that not all of the detected fractions may be present in each sample.

More than 50% of the samples contained 17 of the 20 fractions, as in the case of each water area,

and for the all selection (Figure 1). The remaining three fractions have a mass of 252 kDa, 12

kDa and 14 kDa. Experimental studies have shown that 14 km kDa (23% for the Vostok Bay and

60% for the Sportivnaya gavan' ), 124 kDa (67% for the Vostok Bay and 80% for the

Sportivnaya gavan'). The percentage of different fractions increases in samples taken from

animals from the Sportivnaya gavan' (Figure 2). Exceptions are fractions of 26 kDa, 33 kDa, 36

kDa, 62 kDa of 145 kDa and a major fraction of 55 kDa. Fractions of 14 kDa, 78 kDa, 124 kDa

and a major 55 kDa, as well as a fraction of 12 kDa significantly stand out (p ≤ 0,05) by three

criteria among the water areas for all four experiments. Among them, often detectable (≥72%)

are: 55 kDa, 78 kDa, 124 kDa.

Thus, fractions of 55 kDa, 78 kDa and 124 kDa of hemolymph of M. kurilensis plasma

can be considered potential markers for the presence of anthropogenic pressure on the marine

areas in which this mollusc is distributed.

The work was supported by the Russian Foundation for Basic Research, project

No. 16-34-00173.




10

Figure 1. Frequency of detection of protein fractions in hemolymphic samples of Modiolus

kurilensis plasma after SDS-PAGE in 9% polyacrylamide gel stained by Coomassie Brilliant Blue

G-250

Figure 2. Mean percentage of protein fractions in the plasma samples of the hemolymph Modlius

kurilensis after SDS-PAGE in a 9% polyacrylamide gel stained by Coomassie Brilliant Blue G-

250 (confidence intervals at p ≤ 0.05)



11

Lebedev I.I.1,2, Ardeeva G.L. 3

NATURAL DISASTERS AS A FACTOR OF COASTAL ZONE CHANGE IN

PRIMORYE

1Far Eastern Federal University, School of Natural Sciences 2Pacific Geographical Institute FEB RAS, Vladivostok


[email protected]

Coastal zone is a dynamic system exposed to the influence of different factors. Natural

disasters are one of the most dangerous among them.

Natural disasters are natural phenomena accompanied by irreversible landscape and

environmental changes [9]. Catastrophic processes and events are characterized by ultimately

negative impact especially on a relief - substrate base with limit dislocation of inner connection

in geosystems. It is necessary to distinguish instantaneous, quick and slow catastrophic events to

estimate catastrophic processes [4]. The most dynamic manifestation of catastrophic events can

be the result of consequence accumulation in geosystems due to the direct-inconvertible

influence of extreme processes. They disturb a geological-geomorphology mantle from stability

[3].

Russian Far East and Primorsky krai in particular are extremely hazardous due to

catastrophic events. A great number of such processes arise in coastal zone. These events can be

divided into two groups: endogenous and exogenous processes (Fig.1).

Fig.1. Types of coastal natural disasters in Russian Far East

There are two types of coasts in Primorsky krai: ria coast and abrasion coast. The impact

of the Holocene transgression and, probably, catastrophic processes affects the type of the coast

There was an ingression flood in Primorye on the territory of 20 000 km2 [8].

Exogenetic processes have an impact on the Primorye coast. It is due to the frequent

passage of typhoons, extreme storms.

The impact of typhoons and storms is associated with a monsoon climate in Primorye.

Usually they occur from July to September. The most significant piling up of water mass to the



12

shore and a very intensive reflux back to the sea are due to such wave mode. A great deal of

sedimentary deposits are carried out in the same way, evidently in suspended state. The

formation of coarser (mainly sand) band is typical among silt deposits field [2]. Large sand

waves caused by big storms belong to the landform [1].

Storm surge impact (Typhoon Goni (2015) and Lionrock (2016)) was studied in

Spokoynaya bay (Russkiy Island). Relief forming impact of typhoons was small. Penetration of

waves was limited by modern storm rampart. Storm offset covered modern beach zone and there

were landslide-colluvial crusts at a height of 3 meters on abrasion parts of the coast.

At present time landslides occur on a small scale in the continental south of Russian Far

East due to a relatively weak activity of erosion and abrasion processes, moderate steepness of

slope and wide-spread of grass on slopes. The presence of serious landslides in coastal zone with

outward zone of movement shows landslide youth (the Povorotniy cape, interfluve rivers: the

Amgu and the Sevastyanovskaya, the Sobolevka and the Kuznetcovaya, the Baklaniy cape, the

Gilyak cape, Nemi bay, etc.). Small-scale observation of one of such landslides (coastal district

to the north from Nemi bay) found out that ground waters appear below its foundation in beach

zone and on the bottom of the sea. A frontal part of landslide is constantly breaking both by sea

and denudation [5].

Catastrophic tsunami is rare event in Primorye coastal zone. It is known only about few

events during the last 100 years (1940, 1964, 1971, 1983, 1993) [7]. After the two latest events

there were observations throughout Primorye coasts from the Tuman river mouth to the Zolotoy

cape. The main geomorphological consequences of tsunami passing were relief erosion of

underwater coastal slope, bringing detrital material in surf zone and formation of vast sandy

terraces at the foot of the bench. Tsunami effect was especially strong in the mouths of the large

rivers where tsunami eroded surface peat-deposits on low lagoon terrace [6].

The impact of natural disasters on Primorye coastal zone works out in different ways.

Tsunami makes the most severe impact on coastal zone because its erosion activity is great due

to the wave power.

References:

1. Dolotov Y.S. Dynamic relief-forming and depositional sedimentary environments in the

near-shore marine area / Y.S. Dolotov. – M.: Science, 1989. – 269 p.

2. Johnson H.D. Shallow siliclastic seas // Sedimentary environments and facies / H.D.

Johnson. - Oxford, 1978. – P. 43-56

3. Korotky A.M. Anomalous natural processes and their influence on state of geosystems of

south of Russian Far East / A.M. Korotky, V.V. Korobov, G.P. Skrylnik. – Vladivostok:

Dalnauka, 2011. – 265 p.

4. Korotky A.M. Common sustainability of subaerial geocomplexes and method its

valuation / A.M. Korotky // Sustainable development of Far Eastern regions: ecology-

geographical aspects. – Vladivostok: Dalnauka, 1999. – P.66-81

5. Korotky A.M. Landslides and landfalls of the South Far East / A.M. Korotky, V.V.

Korobov, G.P. Skryl’nik // Geomorphology. – 2009. - №2. – P. 50-59

6. Korotky A.M. The effect of tsunami on the coastal zone of Primorye / A.M. Korotky,

V.V. Kulikova // Vestnik of the FEB RAS. – 2008. - №6. – P. 34-47

7. Kurkin A.A. Comparable Estimation of Tsunami Danger for the Russian Coast of the

Japan Sea Based on Numerical Simulations / A.A. Kurkin, E.N. Pelinovsky, B.H. Choi,

J.S. Lee // Oceanology. – 2009. – T.44. - №2. – P. 179-187

8. Petrenko V.S. Spatial and temporal evolution of Primorye coast / V.S. Petrenko // Coastal

zone – future perspectives: materials of XXV international coastal conference. – M.,

2014. – T.2. – P.41-43



13

9. Vaganov, P.A. Disasterology / P.A. Vaganov. – SPb: St. - Petersburg State University,

2003. – 123 p.

Lupakov S., Ardeeva G.L.

ABOUT SELECTION OF CLIMATIC SCENARIOS UNDER MAXIMUM FLOW

MODELING


[email protected]

We can notice a growing interest to hydrological studies after historical flood in the

Amur river basin (2013). It caused serious injury to the national economy such as harvest failure,

casualties, damage to buildings, roads and infrastructure on the whole, etc. One of the

appropriate means to compute it and to avoid such hazards is the mathematical (dynamic-

stochastic) modeling [1, 2], even in sense of climatic changes.

The main idea of the presented work is to define how to assign an operation algorithm

(i.e. climatic scenarios) under modeling of maximum flow. The prime tool of our study is the

Flood Cycle Model (FCM) [3], which shows the behavior of different parts of the basin storage

in the framework of so-called «flood cycle», including the antecedent dry period before a flood,

the rain event and basin response. The input is statistical series of daily rainfall, so, by

transforming this dataset, we can assign the climatic scenario. To make climatic scenarios we

used three ways, which will be described below.

The first way was just to increase rainfall data by coefficient. This method is very simple,

but it could be used for preliminary analysis. We have made the archive of real daily rainfall,

where data are fed to the model input. So we took real measured data, just increased them by

10% and 20%, as the most reliable climate change options, and made simulation experiment

with FCM (Fig. 1), where output are maximal discharges and total runoff depth, and plotted

probability curves for it, as suitable forecasting edition.



14

Figure 1. Examples of empirical and modeled probability curves for r.Ussuri-V.Breevka

station. Dots-empirical curve, lines-modeled curves with corresponded scenario, stipple line-1%

confidence intervals

As we can see, the result is quite good: confidence intervals imbound empirical curve

almost completely, scenarios with +10% and +20% lay in the graph in a reasonable way. We

made such simulation experiments for some basins within the Ussuri river basin (right tributary

of the Amur river) and got quite similar results (table 1).

Table 1. Used river basins and its characteristics

The second way to make a scenario was to try to use one more stochastic model, which is

capable to simulate real precipitation data. It is called «stochastic weather generator». This

model takes real precipitation data (even from some meteorological station), passes them

through algorithm and in output we have statistical series of daily rainfall for necessary period of

time (for 1, 100 or 1000 years). We modeled such statistical series for five meteorological

stations of the Primorsky Territory (V.Breyevka, Vinogradovka, Yasnoe, Grodekovo,

Molchanovka) over a period of 1000 years. So, to make a scenario in this way, we could change

two statistical moments of the distribution - mean and variation coefficient. Then we changed

these initial parameters and plotted probability curves for modeled rainfall data. It turned out that

changed value of mean lays on plot rationally and, in a whole, repeats behavior of the plot from

the first way, changed value of the variation coefficient gives ambiguous results and will not be

estimated further. In fact, the second way does not differ much from the first, but it is much more

sophisticated.

The third way was to classify real hydrometeorological data. There is a hydrological

classification of river hydrographs (Fig. 2) [4].

River-Stage gauge Area,

km2

Avg.height,

m

Avg.slope,

m/100m

Forest

cover, %

Arsenievka-Vinogradovka 940 652 0,18 99%

Varfolomeyevka-

Varfolomeyevka 256 307 0,14 99%

Izvilinka-Izvilinka 1160 836 0,25 91%

Kamenka-Kamenka 138 632 0,23 100%

Krylovka-Krylovka 1070 251 0,11 82%

Muraveika-Grodekovo 761 592 0,18 99%

Pavlovka-Antonovka 2670 623 0,12 98%

Ussuri-V.Breyevka 1720 752 0,21 99%



15

Figure 2. Types of Far Eastern river hydrographs (A-D). X axis - months, Y axis -

discharge, l/s

Type A means spring flood-time, without high rainfall in summer; type B means single

high flood in spring and summer, divided by dry period; type C means very strong single

floodwaters in summer and type D means permanent flood period. Based on this classification,

we decided to classify hydrological data, to attach it for precipitation data and put this

information to «stochastic weather generator» (so, by this way we just use Monte Carlo method

and «play out» probabilities of the appearance of one of these types). So, we classified our rivers

data (stations from Table 1) and calculated occurrence probability of each type (Table 2).

Table 2. Distribution of A-D types

River

Types Su

m A B C D

Arsenievka-Vinogradovka 16 8 24 10 58

Varfolomeyevka-

Varfolomeyevka 27 5 20 9 61

Izvilinka-Izvilinka 18 8 19 12 57

Kamenka-Kamenka 33 5 17 8 63

Krylovka-Krylovka 29 5 21 11 66

Muraveika-Grodekovo 22 12 19 8 61

Pavlovka-Antonovka 18 2 18 6 44

Ussuri-V.Breyevka 16 6 26 9 57

Avg, % 38% 11% 35% 16% 100%

We see that types A and C occur more often, than others and it looks sensible. But it is

interesting that: if we sum up type A and B (as more dry), and C and D (as more wet), we'll get

49% to 51% respectively. And it is perfect for modeling: we calculated two climatic scenarios,

and it’s very comfortable to compute.

So we used three ways to assign climatic scenarios. The first way is very easy, so it could

be used only for preliminary analysis, the second way is more serious, but it has its own

limitations and difficulties, so we won’t use both in future work. The third way isn’t completed,



16

it’s still in process. But even now we can say that the third way is well enough and we’ll work in

this direction with modeling of maximum flow in the Far East of Russia.

References:

1. Vinogradov Yu.B. Mathematical modeling of runoff formation processes.. L.:

Hydrometeoizdat, 1988. 311 p.

2. Gelfan A.N. Dynamic-stochastic modeling of snowmelt runoff formation. M.: IWP RAS,

2007. 294 p.

3. Gartsman B.I. Rain floods on the rivers of Far Eastern south: design methods, prediction

and risk assessment methods. Vladivostok: Dalnauka, 2008. 244 p.

4. I.N. Gartsman, V.M. Lylo, V.G. Chernenko. Flood runoff of Far Eastern rivers. L.:

Hydrometeoizdat, 1971. 263 p.

Maschenko V.N. Ardeeva G.L.

INFLUENCE OF CONSTANT MAGNETS ON THE ORBITAL MOMENT


[email protected]

The purpose of the article is the study of the effect of magnetic fields on the atoms of

different natural elements. When placing an atom in a magnetic field, the precession (change of

movement) arises. This article will consider the placing of an atom in two external magnetic

fields of opposite poles.

Phenomena in which the moment of the body quantity movement is changing due to the

influence of the magnetic field are called magnetomechanical. Since the substance is in an

external magnetic field, its magnetic permeability is less than one, that is the magnetic induction

field in the material is less than the magnetic induction of the external field [1]. So let’s consider

one of the magnetomechanical phenomena - the precession of the magnetic moments in a

magnetic field (Fig. 1)

. Fig. 1. The precession of the magnetic field

Suppose that an electron in an atom moves in a circular orbit, the plane of which is

perpendicular to the induction vector of the magnetic field. Lorentz force action on the electron

will reduce the gravity force of the electron to the nucleus. The centripetal force will be equal to

the difference between the Coulomb force of the electron gravity to the nucleus, and the Lorentz

mailto:aк[email protected]



17

force [2]. As a result, the angular velocity of the electron motion in a circular orbit will be

changed. It will be different from that which the electron had in the absence of an external

magnetic field. If an external magnetic field is variable (generating current), the change in the

angular velocity of the electron motion occurs during growth of the magnetic field in which atom

is placed. Thus there is an induction vorticity electric field affecting the electron in the atom. The

intensity of this field is tangential to the electron orbit [3]. Orbital magnetic moment of the

electron makes an angle α with the direction of the magnetic field at an arbitrary location of the

electron orbit with respect to the magnetic induction vector. In this case, the orbit precesses

around the direction of the induction vector. This means that the orbital vector perpendicular to

the orbital plane, keeping the angle of inclination α to the pitch direction unchanged is rotated

around the induction of an angular velocity different from the initial one. Such rotation of the

vector around the direction of the magnetic induction at a constant angle α is called the Larmor

precession. The influence of the magnetic field on the electron orbit is reflected in the Larmor

theorem: the only result of the influence of magnetic field on the electron orbit in the atom is the

precession of the orbit and the vector with an angular velocity around the axis passing through

the nucleus of the atom and parallel to the vector of the magnetic field [4]. Precession orbit

motion leads to the additional orbital current and the corresponding induced orbital magnetic

moment. The changed orbital vector is directed opposite to the vector of the magnetic induction.

Thus, the electron atom orbits under an external magnetic field perform a precessional motion,

which is equivalent to a circular current loop.

Estimated effect of the external magnetic fields on soil.

When applying the substance in a magnetic field with induction on the electron moving

in the direction of the orbital vector, torque acts on the part of the magnetic field :

∙ (1)

where –is the orbital vector

= g (2)

where g – is gyromagnetic ratio,

(3)

Such orbital vector under the influence of the magnetic moment will move in a circle

relative to the magnitude of the magnetic induction, thus to produce precession. If the substance

with the equal gyromagnetic ratio is put in a static magnetic field magnetic flux density 2.6 T

(with respect to two back-directed magnets), then the magnetic moments will precess around the

magnetic induction vector at an angular velocity:

ω = g ⋅ B= = (4)

Precession of the orbital moment in the atom manifests the appearance of additional orbital

current directed opposite to the current I:

(5)

At this point, additional current generates additional movement [5]. In this case the orbital

magnetic moment arises due to the anti direction of the magnetic induction:

S = S A (6)

where S – projected area of the electron orbit on the plane.

Experimental section. The study was conducted under standard conditions. The object of the

experience was the wet loam, soil category - 2. With a certain distance, the magnetic field had

effect on the loam. The total number of experimental tests for each distance is 40, except for the

fifth position.



18

The fifth position is a position of the optimal magnet arrangement as loam becomes the most

fragile.

Dm= (22х5х9) (7)

If the magnet will have a length, a width and a height of 22, 5 and 9 mm, respectively, then

the distance between the magnets Dm should form approximately the seventh part of the magnet

length.

Thus, these studies have shown the effectiveness of the correct magnet arrangement in the

panel. And in general the theory of the precession of the magnetic moments in a magnetic field

was proved in an experimental way. Such arrangement is appropriate and effective in the field of

cleaning.

Using magnetic elements we can achieve such effect as a reduction of soil stickness, thereby

there is no necessity to fettle farming equipment.

References:

1. Borovik Е.S, Еrеmеnkо V.V., Milner А.S. Lectures on magnetism. 3rd,ed. Revised. ext

2005 year. 512p.

2. Glebov А.N., Budanov A.R. Magnetochemistry: Magnetic properties and structure of

materials in 1997.

3. Pletnev S.V. The magnetic field, properties, applications Edition: С-P.: Gumanistika,

2004.

4. Poplavko Y.M. Dielectrics Physics 1980 years. 400p.

5. Savelyev I.V. Course of general physics. — М.: Science, 1998.

https://ru.wikipedia.org/wiki/Савельев,_Игорь_Владимирович

https://ru.wikipedia.org/wiki/Наука_(издательство)



19


Section II

MATHEMATICS AND INFORMATION TECHNOLOGY

___________________________________________________________________________

Varlataya S.K.1, Fayzenger A.A.2, Kamornaya Yu.O. 3

IDENTIFYING THE VULNERABILITIES OF INFORMATION SYSTEMS AS

THE MAIN STAGE OF RISK ASSESSMENT

1Far Eastern Federal University, School of Natural Sciences 2Bank of Russia, Far Eastern Main Department

3 Far Eastern Federal University, Oriental Institute School of Regional and International Studies

[email protected]

Identifying the vulnerabilities of the information system is one of the main steps in the

risk assessment process in the information system. The purpose of this step is to compile a list of

vulnerabilities that can be applied in information security incidents, analyze vulnerability

sources, conduct a security test and verify compliance with security requirements.

Vulnerabilities associated with working conditions of information system can be

determined through methods of information collection. The study of various sources of

vulnerabilities will be useful in the test preparation and receipt of these vulnerabilities that can

be applied to a particular IS.

Vulnerability is any characteristic or property of IS, the use of which an attacker can lead

to the realization of a threat. A threat is a probabilistic event or process that can affect the

operation of information systems to the detriment of the violation of the confidentiality of

restricted access information.

While carrying out the attack, the attacker exploits the vulnerabilities of the information

system. In other words, if there is no vulnerability, then there is no threat of attack, using it.

Therefore, one of the most important mechanisms for protecting limited access information of

organization is a process of searching, assessing and eliminating IS vulnerabilities. Vulnerability

assessment is formed on the basis of a set of information about source of origin, characteristics

and number of known technical defects in the protecting information system.

The classification of vulnerabilities by main sources of occurrence is as follow:

1. Vulnerabilities of microprograms, firmware, and hardware drivers. Manufacturers of

firmware or drivers often don’t contain in its software the necessary means of protection and

anyone changes it at their discretion, or makes mistakes during the creation of software, which

are detected after a long period of time and don’t eliminate the patch. As a result, an attacker can

collect various information about IS or gain access to an administrator.

2. Vulnerability of special software. Many application programs have errors that they

didn’t correct for a long time and were used for obtaining a high level of rights in the

information system. In addition, their use doesn’t require in-depth knowledge of programming.

3. Vulnerabilities in the network layer of the OSI model. Although vulnerabilities at the

network level are widely known, they are not theoretically removable, or they are not given the

attention to software developers. For their implementation, adequate knowledge is required in

the field of building information networks. An attacker can collect information about an user

account or access it.




20

4. Vulnerabilities in the transport layer of the OSI model. Like previous vulnerabilities,

vulnerabilities at the transport level are not theoretically removable. In-depth knowledge and

specialized software are needed for their development. As a consequence, the violator

significantly reduced the performance of the information system.

5. Vulnerabilities in the application layer of the OSI model. Implementation of the

vulnerabilities requires a solid level of training and the availability of special software. Once

implemented, an attacker can break work of the information system or gain access to a user

account.

Institutes, software developers in the information security field form databases, which

include known vulnerabilities, to speed up their elimination and also protection against these

vulnerabilities. As a result of work on the compilation of such databases, a list of standard names

for the vulnerabilities Common Vulnerabilities and Exposures has appeared.

Competent and detailed study of the vulnerabilities of information systems will help draw

up a correct risk assessment report that helps the management of the organization in making

decisions on the issues of information security policy, budget and management of the

organization. The risk assessment report should be presented in a systematic way so that

management understands the risks and can allocate resources to reduce or avoid potential losses.

References:

1. The basic model of threats to the security of personal data when processing them

in information systems of personal data (extract). FSTEC of Russia, 2008.

2. Algorithm of risk analysis for optimal construction of business processes and

management of the organization's information system. / Varlataya S.K., Fayzenger A.A.,

Timofeeva A.I.// Collection of scientific papers on the results of the 2nd International Scientific

and Practical Conference, Samara. - 2015. – P.132-135.

3. Identifying the vulnerabilities of information systems as a way to reduce threats.

/Varlataya S.K., Fayzenger A.A., Timofeeva A.I. // Collection of scientific papers on the results

of the 4th International Scientific and Practical Conference, St. Petersburg. - 2017г. – P.120-122.

Digor A.G.1, Lukina E.M.2

DEVELOPMENT OF TRAINING SIMULATOR FOR ACCENT REDUCTION IN

NON-NATIVE LANGUAGE SPEECH


[email protected]

Today most areas of human activity, including foreign language teaching, have become

automated. However, pronunciation training most often occurs with the help of a teacher. The

difficulty for automation lies in speech evaluation by means of computer [1]. Moreover, the

features of the phonetic structure both of native and acquired languages should be taken into

account in pronunciation improvement process. As part of the pronunciation evaluation problem,

the issue of identifying such features and developing exercises, considering them, arises.

Many existing training simulators offer to listen to and copy the pronunciation without

feedback [2]. In other words, the trainee does not receive information about the quality of the

work done. Simulators that have a function of assessing the quality of pronunciation do not

always provide effective recommendations for errors correction and often do not have an option

to adapt the course of the exercises for a particular student.

The current work is devoted to the development of an instrumental shell for creating a

training simulator for accent reduction in the speech in a non-native language.

For the most flexible set up, the simulator system should consist of the following parts:

../../Tulio%20Guerrero/Downloads/[email protected]



21

Knowledge Base Editor

Accent Identification module

Module for Exercise Setting

Theoretical module

Module of Exercises

The Knowledge Base Editor is necessary for setting the rules of the foreign language

pronunciation. It should include the capability to replenish the speech corpus, which contains

records of both standard and accented speech. The tool for trainees’ errors annotation will allow

the simulator to recognize the type and the degree of accent more accurately. The core of this

method is language model training with HTK for phoneme recognition [3].

The grammar that contains all possible sentence errors is generated in the Accent

Identification module before recognition. After building the model, grammar and receiving the

trainee’s audio file, which must be recognized, it is possible to identify mistakes made by the

trainee and to extract information for the recommendation formation. Feedback includes not only

identification of mistakes and deviations but also recommendations for their correction. For

better understanding, these recommendations should contain examples from the trainee’s speech.

The Module for Exercise Setting will allow the teacher, supervising the training process,

to set the exercises that will be effective for the particular trainee.

The Theoretical module contains information about the distinctive feature of the native

and acquired languages (articulatory and phonetic features), the training course of IPA.

The Module of Exercises contains exercises for the trainee. At the stage of training

separate sounds and simple sound combinations the trainee is offered an audio realization of the

target sound, a text commentary and animation of the articulation of this sound as well as an

audio, text and animation for the “similar” sound (or sounds) of the native language.

Thus, the system, being developed, allows for teaching pronunciation more effectively,

helping to reduce the level of accent phenomena presence in non-native language speech.

References:

1. Zheltov, P.V., Semenov V.I., Trofimova A.I., Shurbin A.K. Algorithms for

identification of phonemes and word formation in speech recognition systems based on wavelet

transform // Bulletin of the Chuvash University. – 2014. – №2. – P. 98-102.

2. Pribytkova, A.A. Steps of forming pronunciation skills for students based on

multimedia programs // Bulletin of Tambov University. Series: The humanities. – 2013. – №4. –

P. 259-263.

3. Ai, R. Automatic Pronunciation Error Detection and Feedback Generation for CALL

Applications // Lecture Notes in Computer Science. – 2015. – vol. 9192. – pp. 175-186.

Dobrzhinskaia T.

BLOCKCHAIN TECHNOLOGY SECURITY ISSUES AND CHALLENGES

1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies

[email protected]

Distributed ledger technology – commonly referred to as Blockchain – has emerged as

candidate for financial institutions to reform their businesses. Blockchain, mostly known as the

backbone technology behind Bitcoin, is one of the hottest and most intriguing technologies

currently in the market. Since 2013 Google searches for “blockchain” have risen 1900%. Similar

to the rising of the internet, blockchain has the potential to truly disrupt multiple industries and

make processes more democratic, secure, transparent, and efficient. Entrepreneurs, startup




22

companies, investors, global organizations and governments have all identified blockchain as a

revolutionary technology [3].

A blockchain can be defined as a digital, chronologically updated, distributed and

cryptographically sealed record, of all data transfer activity. It may be thought of as a cloud-

based ledger that is shared among a network of users (the “participants”), recording all data

being transferred between them. This record displays all the information related to the data,

while at the same time allowing the identity of the involved participants to remain confidential.

The record can be viewed by all participants, but updates can only be made after being agreed

upon by a majority of participants. Furthermore, once the data is entered into the record it can no

longer be deleted.

Fig.1. Distributed Ledger (Blockchain) Ecosystem

Instead of depending on a central entity such as a single financial institution to track the

validity of ownership of funds, a distributed ledger maintains all transactions and holdings and is

updated by a number of counterparties.

The distributed ledger allows counterparties to use smart contracts1 and enhanced

transaction privacy. Updates to the Blockchain or “distributed ledger” leave an audit trail and

allow auditing to verify how an agreement was executed. Blockchain protocols are believed to

provide a transaction and application environment, by using a mix of consensus and transaction

protocols to determine valid transactions, as well as reach agreement on the current state of items

such as a contract or account balance.

The European Union Agency for Network and Information Security (ENISA) has

published a new report on blockchain tech, which seeks to highlight the security challenges that

large businesses might experience in the face of broader blockchain adoption [2]. Key

management, data privacy and oversight of smart contracts were some of the major items

identified in the report.

ENISA identified some issues that we believe could be improved or where the

technology needs to evolve (Table 1):

https://www.enisa.europa.eu/news/enisa-news/enisa-report-on-blockchain-technology-and-security



23

Table 1. Distributed Ledger (Blockchain) Security Issues That Require Further

Improvement and Recommendations upon Their Improvement.

OPEN CHALLENGES RECOMMENDATIONS

Information security standards:

- to keep data confidential

- what and how data needs to be deleted

from the ledger

- The Industry in cooperation with the regulators to

define what to be kept confidential in order to remain

compliant with regulatory requirements, such as

General Data Protection Regulation, as well as sector

or local regulations

- The Industry in cooperation with the regulators to

identify or develop standard methods for removing

data from a ledger

Monitoring illegal activity - The Industry to explore how current anti-fraud and

anti-money laundering technologies need to be adapted

or new ones created to work with the distributed

ledger.

Interoperability between different

distributed ledger protocols

- The Industry should explore the possibility to

standardize requirements and harmonization of

interoperability of different distributed ledger

protocols

- XML standards could potentially be good candidate

for data operability

Quantum computing - The Standardization bodies in cooperation with the

Industry to research the use of post-quantum

algorithms for asymmetric cryptography

Privacy preserving smart contracts - The Industry to research availability of contracts

preserving privacy, e.g. smart preserving contracts21

Governance controls - Financial regulators in cooperation with the

industry to explore mechanisms to add assurance and

governance controls (standard legal and compliance

items)

Wallet Management - Industry to explore the possibility for creating

standards for wallet software to store multiple keys

from different distributed ledgers

The following issues should be considered: In the public blockchains, the system that

allows anyone to read or write transactions, this decentralixation and relative freedom of access

causes some unexpected consequences: transactions stimulate black market trading, consensus

protocol is energy consuming, and most users operate in the countries with cheap electricity

which makes the network decentralized, possible to collide, and vulnerable to changes in policy

on electricity subsidies. Private blockchains can ultimately give greater control to businesses.

Primarily used in financial contexts, private blockchains give their operators control over who

can read the ledger of verified transactions, who can submit transactions, and who can verify

them. The applications for private blockchains include a variety of markets in which multiple

parties wish to participate simultaneously but do not fully trust one another. For example, private

blockchain systems supporting land and physical asset registries, commodities trading,

and private equity distribution are all being tested. As these systems develop and evolve, they,

too, may encounter unexpected consequences, some of which will have repercussions for the

security of the system and the assets it manages or stores. As in software and product

http://www.forbes.com/sites/laurashin/2017/02/07/the-first-government-to-secure-land-titles-on-the-bitcoin-blockchain-expands-project

http://treasurytoday.com/2016/01/blockchain-sets-sights-on-commodities-trade-ttti

http://www.zdnet.com/article/ibm-northern-trust-partner-on-financial-security-blockchain-tech/)



24

development, considering security at an early stage alleviates the difficulty of making

fundamental changes to a product to address a security flaw later on.

Blockchain, the distributed ledger technology underlying bitcoin, may prove to be far more

valuable than the currency it supports. But it’s only as valuable as it is secure. As we begin to put

distributed ledger technology into practice, it’s important to make sure that the initial conditions

we’re setting up aren’t setting us up for security issues later on [1].

References:

1. Berke, Allison. How Safe Are Blockchains? It Depends. – Harward Business Review,

March 7, 2017. / https://hbr.org/2017/03/how-safe-are-blockchains-it-depends

2. ENISA (European Union Agency For Network And Information Security). Distributed

Ledger Technology & Cybersecurity: Improving information security in the financial sector. –

ENISA, December 2016. / https://www.enisa.europa.eu/publications/blockchain-security

3. Sorin, M. Israel: A Hotspot for Blockchain Innovation. / Michael (Misha) Sorin, Stas

Senyuk, Deborah Ben-Yosef Gelernter, Yakov Flaumenhaft, Jeremy Cooper, Hagai Zachor. –

Deloitte, February, 2016. / https://www2.deloitte.com/content/dam/Deloitte/nl/Documents/

innovatie/deloitte-nl-innovatie-blockchain-israel-a-hotspot-for-blockchain-innovation.pdf

Zalepukhin A., Grinyak V., Kamornaya Yu.O.

DEVELOPMENT OF A METHODOLOGY FOR ASSESSING THE MARITIME

TRAFIC RISKS


[email protected]

Today securing the traffic of ships still remains an actual problem, despite the long history

of the issue. Although a great number of technical means is available for navigators, collisions of

ships are rather frequent and, unfortunately, tragic accidents.

When organizing navigation in marine areas, it is necessary to solve the task of developing

a traffic scheme that ensures the greatest safety in a particular water area. At the same time, it is

necessary to take into account the specific geography of the area, the rules of navigation and the

features of real water traffic [1].

The solution of this problem is connected with the assessment of the risk level for the

existing traffic pattern [2]. One possible approach to this assessment is to analyze the frequency of

occurrence of possible dangerous ship – ship encounters. By dangerous encounters is mainly

meant a dangerous closing of ships. To assess the points of the shortest approach and the distances

of such closing, real data on the water area traffic collected from open Internet sources are used.

https://hbr.org/2017/03/how-safe-are-blockchains-it-depends

https://www.enisa.europa.eu/publications/blockchain-security

https://www2.deloitte.com/content/dam/Deloitte/nl/Documents/%20innovatie/deloitte-nl-innovatie-blockchain-israel-a-hotspot-for-blockchain-innovation.pdf

https://www2.deloitte.com/content/dam/Deloitte/nl/Documents/%20innovatie/deloitte-nl-innovatie-blockchain-israel-a-hotspot-for-blockchain-innovation.pdf




25

Fig. 1. Points of the shortest closing of ships

The points of the shortest approaching of ships (Fig. 1), where meeting vessels are

especially close to an intolerably short distance (less than two corps) between two ships are

highlighted in bright black. The remaining points do not represent a particular danger, since the

distance between meeting ships there reaches less than five corps (gray dots), and less than 1000

meters (white dots).

These data are obtained by calculating the minimum distance between vessels at a certain

time. With the help of the obtained data, it is possible to formulate and solve the problem of

planning the scheme of motion in the water area, ensuring maximum safety of navigation. This

technique is extremely relevant for operators monitoring the traffic of sea-going vessels in this

water area. Based on this technique, the operator decides how often he needs to correct the ship's

traffic in order to avoid collisions. In this case, we see that there is the maximum number of

critical encounters between ships in the north-west direction. To unload such traffic with a high

probability of ships close encounters, it is necessary to provide new fairways taking into account

the geographical peculiarities of given water area.

References:

1. Grinyak VM, Golovchenko BS, Malko V.N. Recognition of dangerous situations by traffic

control systems // Transport: science, technology, management. - 2011. - №8. - P. 11-14.

2. Mironenko AA Model of the software movement of the vessel in confined waters //

Mechatronics, automation, control - 2013. - №2. - P. 65-70.

Ivanenko Yu. 1, Grinyak V. 1, Kamornaya Yu.O. 2

ESTIMATION OF DIGITAL RADAR SYSTEM RESOLUTION


[email protected]

Current paper deals with evaluation of measurement error in distributed digital radar

system with limited network bandwidth. Radar system considered under this paper consists of 2

main blocks: ADC converter that digitalizes original radar signal and block of secondary data

processing. Since high sampling frequency generates big digital datasets to be transmitted from

ADC to secondary processing block(s), bandwidth has crucial impact on system accuracy. [1]

Authors emphasize their efforts on analyzing the systems where secondary processing

block is based on common widely available hardware. Typical personal computer as common

hardware is considered to be suitable for the research purposes. [2] This paper studies two-

coordinate radar based system limitation.

The Problem can be summarized as follows. By processing the radar signal ADC

generates amplitude matrix, where rows represent angular sampling values and columns

represent distance sampling values. [3] The matrix is transmitted to the secondary processing

block that is responsible for tasks like: recognizing objects, objects tracking and rendering.

The paper refers to comparison of the data transmission protocols between 2 physical (PC

based) hardware connected into a network. Following protocols are considered to be the most

suitable for inter-process communications: DDE, Mail-slots, Named-pipes, Sockets, memory-

mapped files. This particular paper deals with sockets.




26

Computational experiments have been performed for the system of 2 personal computers

connected into local network.

In order to simulate different external conditions following types of tests have been

performed: both hosts running data receiving-transmission without extra load, both hosts running

data receiving-transmission with extra CPU utilization, both hosts running data receiving-

transmission with extra memory utilization, both hosts running data receiving-transmission with

extra network utilization.

Fig.1 depicts a graph for the case when both hosts running data receiving-transmission

without extra load. And Fig.2 depicts a graph for the when both hosts running data receiving-

transmission with extra network utilization case.

The Ox axis represents time in seconds when both hosts running. The Oy axis shows

periodical change of the data transmission speed (GB per second).

Fig. 1. Data receiving transmission without extra load

Fig. 2. Data receiving transmission with extra network utilization

The paper presents results of data transmission experiments in charts. For 1 Gbit/s Ethernet,

in case when both hosts running data receiving-transmission without extra load (Fig. 1) average

transmission speed is about 70 Mbyte/s with 5-10% fluctuations rate. In case when both hosts

running data receiving-transmission with extra network utilization (Fig. 2) average transmission

speed is about 60 Mbyte/s.

The results obtained suggest that data transmission speed depends directly on network

utilization. Therefore based on data transmission speed calculations the main result of the

research is the amplitude matrix maximum size dependency and the measurement error for

typical radar system represented in charts.

References

1. Donderi D.C., Mercer C.R., Hong M.B., Skinner C.D. Simulated Navigation

Performance with Marine Electronic Chart and Information Display Systems (ECDIS) // Journal

of Navigation. – 2004. – Vol. 57. – p. 189-202.

2. Degtyarev O.V., Orlov V.S. Broadcast algorithms for detection and decentralized

resolution of unsafe approach of airborne aircraft based on the force field method // Journal of

computer and systems sciences international. – 2013. – No. 5. – p. 764-782.

3. Dorozhko V.M. Radar logging of the initial stage of acceleration of a vessel //

Measurement techniques. – 2010. – No. 6. – p. 629-636.



27

Kalashnikov P.V., Gorodetskaya E.Ya.

OPTIMAL FUNDING OF PENSION SCHEMES AS A TASK OF DYNAMIC CONTROL


[email protected]

A retirement system is an important part of modern society’s life. Actuarial mathematics

is a theoretical basis which is used for effective organization and functioning of various pension

schemes.

A defined benefit scheme has higher level of efficiency among existing methods for

financing pension funds. The volume of benefits for pensioners is defined in advance with the

help of using this scheme.

It is necessary to use optimal control for determining the needed volume of contribution

and the adjustment payment between accrued liability and the accumulated scheme funds. The

main idea in this context is to search the criterion of the quality of the control process.

The major models which are used for researching different criteria for control of the

pension funds for the minimization of the loss in the case of discrete and continuous time are

presented in articles [1],[2]. These models ignore the case of incomplete information about the

future structure for actuarial base which is used for calculation of the volume of the fund.

The present model which is developed with the quadratic loss function for the case of

discrete time is shown in the article [3]. This model is of the most interest for research.

Generalization of this model for the case of incomplete information about the future

structure of the actuarial base allows us to calculate the optimum volume of contributions to

pension scheme. This may be done by means of the dynamic programming based on Bellman’s

principle of optimality.

The “Optimal Feedback Control Law” represents a dynamic pension funding plan for the

incomplete state information case designed by using control optimization. The optimality

structure of the solution is assured by Separation Principle. This principle is limited to stochastic

LQP optimization problem with incomplete state information. Two parts of the optimal

controller can be designed independently and separately as optimal solutions of an estimation

and control problem.

References:

1. Benjamin, S. Driving the pension fund // Journal of the Institute of Actuaries. – 2009. –

№. 116. – P. 717 -735.

2. O'Brien, T. A stochastic-dynamic approach to pension funding insurance // Mathematics

and Economics. - 2010. - № 5. – P. 141 – 146.

3. Haberman, S., and Sung, J.-H. Dynamic approaches to pension funding insurance //

Mathematics and Economics. - 1994. - № 15. – P. 151 – 162.




28

Krasitskaya A.I.1, Stepanova A.A.1, Gorodetskaya Ye.Ya.2

COMPLETE CLASSES OF DIVISIBLE S-ACTS


[email protected]

In this paper an emphasis is put on the model-theoretic properties of divisible S-acts. The

questions of completeness, model completeness, and categoricity are considered for this class of

S-acts. Similar questions have been investigated for classes of regular, projective, flat, and free

S-acts in [1-2].

A consistent theory of the language is complete if or for any

sentence of the language . A consistent theory of the language is called model complete

if

for any models of .

Let be a class of the -structures. A class of the infinite structures of is denoted by

. . The class is called complete (model complete), if the theory of the infinite

structures of this class is complete (model complete). A class of -structures is called

categorical in cardinality or -categorical if all structures from of cardinality are

isomorphic. The class is called categorical if is categorical in some infinite cardinality

Let be a monoid (a semigroup with ). An element is called right cancellable if

for , implies .

Let be a set. If there is a mapping

such that

(a)

(b) for ,

then is called a left -act or a left act over (denote ). An act is said to be

divisible if for any right cancellable element .

The class of divisible -acts is denoted by S-Div

Theorem. The following conditions are equivalent for a monoid :

(1) S-Div is complete;

(2) S-Div is model complete;

(3) S-Div is categorical;

(4) .

References:

4. Mikhalev, A.V. Model-theoretic properties of regular polygons / A.V. Mikhalev, E.V.

Ovchinnikova, , E.A. Palyutin, A.A. Stepanova // Fundamental and Applied Mathematics. –

2004. – Vol.10, Issue 4. – P. 107-157.

5. Gould, V. Model-theoretic properties of free, projective and flat S-acts/ V. Gould, A.V.

Mikhalev, E.A. Palyutin, A.A. Stepanova // Fundamental and Applied Mathematics. – 2008. –

Vol.14, Issue 7. – P. 63-110.

6. Kilp, M. Monoids, Acts and Categories / M. Kilp, U. Knauer, A.V. Mikhalev. – Berlin:

Walter De Gruyter, 2000. – 546 p.




29

Lemza A.O.1, Kovtanyuk L.V.1,2, Norkina P.S.3

CREEP AND PLASTIC FLOW INITIATION AND DEVELOPMENT IN

A MATERIAL PLACED BETWEEN COAXIAL CYLINDERS

1Far Eastern Federal University, School of Natural Sciences, Vladivostok, Russia 2Institute of Automation and Control Processes, FEB RAS, Vladivostok, Russia

3Far Eastern Federal University, Oriental Institute School of Regional and International Studies [email protected]

The present article considers a boundary value problem of deforming of an

incompressible material with nonlinear elastic, viscous and plastic properties placed between

rigid coaxial cylinders. The solution of the problem is constructed in cylindrical coordinates and

in the framework of the large strains model [1]. Material viscous properties are taken into

account both on the stage of plastic flow and before its development.

The material is deformed when the internal cylindrical surface rotates around its

axis while the external one is motionless. The adhesion conditions are set on both rigid

surfaces and boundary conditions can be written as

where and are medium point displacement and velocity vectors, respectively;

is the angular velocity, is the central angle of twisting, are the

functions set by an investigator. The surface rotates with variable velocity:

The equilibrium equations can be written in the cylindrical coordinate system in the form:

In (1) and (3), are the components of the stress tensor. Stresses are determined by

reversible strains with the help of relations which are parallel to the Murnaghan formula from

the nonlinear theory of elasticity:

Taking into account (4), the integration of the second equation from (3) gives the next

relations:

Irreversible strains which can be both creep strains and plastic ones are initially

accumulated in the material because of slow process of creep. Then, at some instant the

plasticity condition is satisfied in the neighborhood of the internal cylindrical surface , and

viscoplastic flow begins to develop. Thus, there are two areas in the cylindrical layer of the




30

material, namely the area of elastic and creep strains and the area of viscoplastic

flow . These areas are separated from each other by a moving elastoplastic

boundary , which position can be determined by solving the next differential equation:

The numerical solution of (6) at , , Pa, Pa,

Pas, , is graphically presented in Fig. 1.

Fig. 1. The initiation and movement of the elastoplastic boundary

Here relations are applied to transform equations to

dimensionless form. According to the main relations of the used model, the equation

is valid in the region of viscoplastic flow. Hence, known time distribution of the

elastoplastic boundary is the key value for subsequent evaluation of stresses and strains in

the medium according to (4), (5), (7) and constitutive equations of the large elastoplastic

deformations theory [1], which is the basis of the present research.

References:

1. Burenin, A.A. Large irreversible strains and elastic aftereffect / A.A. Burenin, L.V.

Kovtanyuk. – Vladivostok : Dalnauka, 2013. – 312 p.

Perevolotsky V.S. Veremeeva I.F.

IT SERVICE MANAGEMENT: OPTIONS FOR INTERACTION IT AND

CORE BUSINESS

Department of information management system



31


[email protected]

An important trend of IT activities is the development of IT service management; in

particular, the main goal is the organization of IT services.

IT Service Management, (ITSM) is an approach to management and organization of IT

services aimed at meeting business needs. It can be built in two directions: the first direction is

insourcing that is transfer of certain types of company activities to the employee or internal

department. The second direction is outsourcing. "Outsourcing involves transferring a part of a

company to another company or a whole process of activity. It is this action that allows us to

focus on the main and basic functions of the enterprise, adapt to new technologies, increase

reliability and market reputation and significantly reduce production costs." [1].

With a view of efficient organization of the whole business, it is necessary to determine

the major and non-major activities, and to establish whether they are rationally organized.

Outsourcing is "a decision made directly by the head of the enterprise and directly related

to organizational issues, about the transfer of any business functions or parts of the business

process to an outside contractor." [1].

Most often, this decision is made not by the manager, but by the owner of the enterprise,

because the manager is inclined to act, relying on his economic interest, which can go against the

interests of the company.

The decision on the transition to outsourcing is made based on one criterion - economic

benefit.

"The criteria for determining the economic feasibility of outsourcing can be considered a

comparison of own costs for the implementation of a given function or process with the cost of

these works from the outsourcer." [2].

An analysis of the economic benefits consists in comparing the payment of services of a

third-party organization in case of transition to outsourcing and payment of employees who are

in the state of the company in the case of a standard organization of IT activities.

It is necessary to be able to calculate the values of the two main indicators. The first

indicator is the cost of the company to pay for the services of the outsourcer. The second

indicator is the means that could be saved because of the reduction of non-core activities.

If, in the case of insourcing, you can get by with internal regulatory documents, there is a

need to conclude an outsourcing contract when switching to outsourcing - "Service Level

Agreement"(SLA). The purpose of this document is to determine the list and level of services

that are provided to the client by the supplier and approval of tariffs for which these services will

be implemented.

It can be predicted that the transition to outsourcing will be a promising trend in the

development of IT service management, and consequently, IT consulting services will be in

demand when analyzing the advisability of switching to outsourcing IT services for a wide range

of organizations.

References:

1. Efimova S. Outsourcing // Peshkova T. Konik N. Rytik S. - Litres - 2017. - 5 p.

2. Sosunova LA, Karpova NP. Criteria for assessing the appropriateness of

outsourcing // Russian Entrepreneurship - No. 3-2 (180), - 2011 - p. 38-43

3. Service Level Agreement – SLA [Electronic source] – URL:

http://www.smlogic.ru/g-it-s/itsm/soglashenie-ob-urovne-uslug-sla

Rassolov E.A. Veremeeva I.F.

ALGEBRAIC ATTACK




32


[email protected]

The work is devoted to the task of cryptanalysis of stream ciphers. It is assumed that a

combined generator [5] creates the key sequence. To complicate the key sequence, a nonlinear

function is used.

The purpose of the attack is the initial state of the memory registers of the key sequence

generator. It is assumed that the encryption algorithm and algebraic cipher platform are known.

In addition, the attacker has a fragment of the real key sequence. In the final analysis, everything

reduces to solving a system of algebraic equations over a finite field.

As an algebraic model, consider a generator over a field that uses three RSLOS [3]. Their

initial states are denoted by , и .

The minimal polynomial of the RSLOS A has the form , And the feedback function

looks like . Similarly for registers B and C – , . In this

case, the key K is equal to . When working on our

combine each cycle t generate gamma element , Which depends on the function

. At the initial state of the registers

), ), ) generation of gamma and the creation of a

system of equations has the form (Table 1).

table 1

Gamma generator t 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

0 0 1 0 1 1 1 0 0 1 0 1 1 1 0 0 1 0 1 1

0 0 0 1 1 1 1 0 1 0 1 1 0 0 1 0 0 0 1 1

1 0 1 1 1 0 1 0 1 0 0 0 0 1 0 0 1 0 1 1

0 0 1 0 0 1 0 0 0 0 0 1 0 1 0 0 1 0 0 0

1

2

3

4

5

6

7

8

9

10

11

12

13

14

15

16

17

18

19

20



33

The system of equations is nonlinear and in the general case there are no effective

algorithms for solving such systems. We use two methods. The method of linearization, which

allows us to reduce the solution of a nonlinear system of algebraic equations to the solution of a

linear system with a large number of unknowns. The new unknowns are monomials of degree

two or more. An alternative method of linearization is the method based on the construction of

the Grebner basis in the polynomial ring of several variables over a field. The Grebner base

allows solving the problem of the polynomial's belonging to the ideal. The fact is that the

expressions on the left-hand side of the non-linear system of equations are polynomials in

several variables and the presence of a Grebner basis allows one to answer the question of the

uniqueness of the solution of the system.

One of the qualitative indicators of the cryptographic properties of the output function of

the generator is its algebraic immunity [5]. Further it is supposed to develop algorithms and code

of the program, which would allow to build functions with high algebraic immunity.

References:

1. Armknecht, F. Algebraic attacks on certain stream ciphers. – WEWORC. 2005. – 18 c.

2. Courtois, N. Algebraic Attacks on Stream Ciphers with Linear Feedback / N. Courtois,

W. Meier. // Proceedings of Eurocrypt 2003, Lecture Notes in Computer Sciences. 2003.

– 345 c.

3. Armknecht, F. Constracting Single and Multi-output Boolean Functions with Maximal

Algebraic Immunity / F. Armknecht, M. Krause. // Proceedings of ICALP 2006, Lecture

Notes in Computer Sciences. 2006. - 180 c.

4. A. Braeken and B. Preneel. On the algebraic immunity of symmetric Boolean functions.

In Maitra et al. [DBLP:conf/indocrypt/2005], pages 35–48. 80, 113, 194, 195

Romashko D., Nurminski E.A.

HIDDEN MARKOV MODEL IN GENOMIC DATA ANALYSIS

Far Eastern Federal University, School of Natural Sciences

[email protected]

The objective of this work is to perform a review on usage of Hidden Markov Model

(HMM) in basic analysis of bacterial genomic sequences. HMM based pattern searching models

are becoming rather popular among bioinformatic researchers, which can be seen from the

amount of articles and software tools based on this technique.

Searching for patterns is a well-known field of data analysis, but general methods cannot

be efficiently used for genome sequences. Even sequences with the same function are usually

differ from one another, two such sequences could have less than 30% identical parts [2].

Searching algorithm should detect these similarities and be able to build some relative estimation

of it.

Genomic data analysis has a rich history of specialized algorithms; the most important of

them is BLAST – heuristic algorithm for comparing biological sequence information. It is a

primary tool for matching sequence against databases, however it gives relative estimation of

matching based on internal evaluations, moreover it is primary used for matching one known

sequence at a time. It works best when we want to find a sequence or a part of it in a large

database. If we want find something known in database – a certain gene in genome queries for

example, then we have multiple gene examples each with its own sequence as input data and

HMM model may seems preferable.

Let us formally define HMM model. All possible observations are described by finite set

. Model also contains hidden states from the finite set . The




34

hidden state at the moment is denoted by . We assume that the hidden state sequence is a

time-homogeneous first-order Markov chain with transition matrix

, a vector of the initial hidden state probabilities

and observable states emission matrix .

For example, consider input genetic data with four sequences:

. In that case consist of observable amino-acids (22

or less), and is represented in our example by letters: . We assume that

hidden states are represented by letter position in observable sequence. In simple case

transition matrix is all zeroes except elements above the main diagonal, which equals to one.

That is because sequence is linear and positions replace one another in order. Usually the

structure of is more complicated because initial sequences have different length and structure

and so should be aligned. It results in “gap” states – areas with special visible states emissions.

In our example, after aligning we obtain sequences:

Hidden states in the example are: , in

our case states always starts from the beginning, so . Emissions vector

calculated by count of occurrence of each letter in position . Illustration of the example is in the

Fig. 1.

Fig. 1. The HMM example

While calculations is simple for small cases (like our example with only four learning

sequences, each seven letters long after aligning), in practice we have to deal with more than

dozen sequences each several hundred letters long, task unsuitable for manual calculations.

Preparing data is the first problem for programming implementation, all learning

sequences will be in FASTA (or some similar) format. We have to transform them into array of

hidden states (instances). An instance is a complicated data structure: it should contain the start

and the end positions and letters it stores. In addition, instance should contain boolean flag if it is

a (contains any ‘-’ letters) or not. In a case instance should contain number of

sequences that have no letters (only ‘-’) in this instance (field Fig. 2).

If initial data represented as 2-dimensional matrix, where rows are aligned sequences

then instances generated by iterating columns. If column does not have an ‘-’ element then it is

not instance and start = end = column number, stored letters for such instance consist of

occurrence number of each letter in this column. If column does have an ‘-’ element then it is

instance, start = column number and end =

. Rule for the end field assures

that all columns with ‘-’ are in the same instance if they are not separated by not column. In

our example:



35

Fig. 2. Creating hidden states

Array of instances is all what needed to calculate hidden state transition matrix and

emission matrix . Transition matrix will be square with number of rows equals to number of

instances, all matrix elements at the beginning equal to zero. For every instance we should: take

the and instances, if both are not then . If is not and is

then and , in our

example it is amount of sequences in input data. If is and is not

then and

[2]. is a sum of all numerical elements, in Fig. 2

case it will be . Emission matrix is simpler – one row for each

hidden state , .

HMM solves several problems. First, HMM allows to evaluate the most likely and

unlikely sequences. Second, for any given sequence HMM can calculate the most likely hidden

state chain (Viterbi algorithm) and so evaluate the sequence. Third, HMM is a machine-learning

algorithm, it is simple to adjust the model’s parameters and find the optimal variant for any

given data. Problems that HMM does not solve. False negative results, HMM heavy rely on

learning sequences. Complicated model construction. Markov chain hidden state dynamics – that

is commonly not true. Algorithm speed – HMM related methods often relies on enumerating all

possible paths [1].

References:

1. Byung-Jun, Y. Hidden Markov Models and their Applications in Biological

Sequence Analysis // Curr Genomics. – 2009. – P. 402–415.

2. Krogh, A. An Introduction to Hidden Markov Models for Biological Sequences //

Center for Biological Sequence Analysis Technical University of Denmark Computational

Methods in Molecular Biology. – 1998. – P. 45-63.

Smekhun Y. A. Veremeeva I.F.

TEXT ANALISIS IN MODELING OF KNOWLEDGE DOMAIN


[email protected]

There are many difficulties in interpreting natural language. These difficulties can be

classified into specific phenomena – such as scope ambiguity, anaphora, ellipsis and

presuppositions. Historically, different phenomena have been explored within different frameworks,

based upon different philosophical and methodological foundations. The nature of these




36

frameworks, and how they are formulated, has an impact on whether a given analysis is

computationally feasible. Thus the topic of computational semantics can be seen to be concerned

with the analysis of semantic phenomena within computationally feasible frameworks [2].

A high quality of texts analysis can be received, only having full analysis. But there are

difficulties in creating of semantic text analysis based on full model of data.

Ontological semantics directly supports such applications as machine translation of natural

languages, information extraction, text summarization, question answering, advice giving,

collaborative work of networks of human and software agents, etc.

Ontology is a hierarchical web of terms where each term connects with other terms. It is a

kind of formal description of knowledge domain [1].

Natural language is an object of linguistic processors. The text is a sample of speech which

can be verbal or written. Generally computational linguistic work with written texts. The text has

one-dimensional, linear structure, and also has a certain sense.

There are different levels of text fragmentation:

1. level of sentences – syntactic level

2. level of words - morphological level

3. level of phonemes – phonetic level

The syntactic and semantic analyses are solved separately: at first the syntactic sentence

structure and then the semantic structure which based on previous one. There is a dependence of

syntactic mistakes in the normal work of semantic analysis and vice-versa.

At the stage of semantic analysis of the text, a semantic analysis of the text is carried out,

where each word carries a certain meaning and from the correct interpretation at the final stage

of analysis; the understanding of the text depends on the machine [3].

In this research, the method of the semantic-syntactical analysis is studied.

This method has integrated procedure of syntactic dependency trees creation and

definition of role structures of statements. For the successful solution in semantic analysis of

texts in a natural language, there are not enough grammar of language knowledge. It is also

important to have the knowledge about terminology in specific subject domain. At the expense

of information obtained at a stage of the sentence semantic analysis the syntactic tree is corrected

that helps to correct mistakes in role structure of the statement. That is why we use the ontology,

which has such knowledge. The method allows increasing the quality of both the syntactic and

semantic analysis.

References:

1. Artemjeva I. L., Knyazeva M.A., Kupnevich O.A. Processing of knowledge about

optimization of classical optimizing transformations //International Journal on

Information Theories and Applications. 2003. - Vol. 10, K2. PP.126-131. – ISSN 1310-

0513.

2. Patel-Schneider P. F., Hayes P., and Horrocks I.. OWL Web Ontology Language

Semantics and Abstract Syntax. Technical report, W3C, Feb. 2004.

3. Raskin, V. Afterword to V. Raskin, S. Attardo and D. H. Attardo, Augmenting Linguistic

Semantic Description for NLP: Lexical Knowledge, Encyclopedic Knowledge, Event

Structure. In: Peeters, 2000. PP. 481-483.

Tarasenko О.1, Dudko O.1,2, Veremeeva I.F.

CONDUCTING COMPUTATIONAL EXPERIMENTS WHEN SOLVING OF FLAT

SELF-SIMILAR PROBLEMS OF NONLINEAR ELASTICITY THEORY


http://www.lingvo-online.ru/ru/Search/Translate/GlossaryItemExtraInfo?text=%d0%bd%d0%b0%d0%be%d0%b1%d0%be%d1%80%d0%be%d1%82&translation=vice-versa&srcLang=ru&destLang=en



37

[email protected]

The development of modern technologies over the past decades is associated with the use

of new materials and extensive use of various types of elastic elements in structures. The use of

any structural or natural material must be preceded by a thorough investigation of its

deformation properties under the action of various kinds of loads. Such studies can be carried out

experimentally or theoretically, i.e. using methods of mathematical modeling. The latter method

is related to the construction of mathematical models, the formulation of boundary value

problems of deformation, and their solution with the use of both known and specially developed

computational algorithms. At the same time, an important problem is not only the development

and analysis of the properties of mathematical models, but also the automation of these studies.

The subject matter of the paper is related to the solution of a certain class of boundary

value problems of the mechanics of a deformed rigid body, namely, plane self-similar problems

of dynamic deformation of nonlinear elastic materials. Mathematical models (formal statements)

of such problems and their solutions are presented in a series of papers [1-3].

Since self-similarity is, a special case of setting up a boundary value problem that

assumes the non-uniqueness of its solution [4], in [1-3] a two-criterion procedure was included

in numerical schemes to select a single physically grounded solution from all mathematically

possible variants.

Obtaining theoretical solutions to such problems is the basis and the first stage of

modeling the deformation properties of various solid natural and artificial materials. The next

stage is quite laborious, since it requires a series of computational experiments aimed at testing

solutions with a multitude of values of the initial parameters. The difficulty lies in the fact that

the organization of such a computational process for the problems of dynamic deformation is not

yet automated and requires a lot of time.

There is no software tool that performs not only the solution of the self-similar problem

in its specific formulation (that is, the application of a certain numerical scheme for the

corresponding system of model equations), but also the choice of a single physically grounded

formulation depending on some initial parameters. Therefore, the problem of developing a

software package for carrying out computational experiments is relevant.

Thus, the main goal of the work is the implementation of a software complex, which

includes computational schemes for solving flat self-similar problems of the dynamics of

deformation of elastic materials and allows one automatically carry out series of computational

experiments at various initial parameters.

The goal is achieved by consistently performing the following steps:

1) development of a general form of the algorithm for solving a particular boundary value

problem chosen from a given class of plane self-similar problems, which includes a two-criteria

search procedure for a single solution;

2) selection of the necessary numerical methods [5] and numerical solution of the chosen

problem for the given parameters;

3) modification of the developed algorithm, taking into account the specifics of the

formulation of each of the problems of the class considered;

4) directly implementation of the program complex.

For the software implementation of the complex, MATLAB is chosen. It is a high-level

language and an interactive environment for programming, numerical calculations and

visualization of results [6]. In addition to this environment, the products Mathcad, Wolfram

Mathematica and Maple were also considered. The variant with the development of the complex

in the high-level programming language was not considered, because computer algebra systems

offer a number of ready-made functions that implement various numerical methods. The choice

of this package of mathematical modeling was based on its following advantages among other

systems of computer algebra:




38

1. MATLAB includes tools that allow an engineer to interactively construct a graphical user

interface to create a complete application;

2. MATLAB includes MATLAB Compiler tool, with which it is possible to package the

MATLAB application into an independent application;

3. Open source code of the predefined functions.

References:

1. Burenin, A.A. On the collision of two elastic solids with plane boundaries / A.A.

Burenin, O.V. Dudko, D.A. Potianikhin // Computational Continuum Mechanics. – 2013.

– Book. 6. – № 2 – P. 157-167.

2. Dudko, O.V. A self-similar problem of nonlinear dynamic elasticity theory concerning

the interaction between a longitudinal shock wave and a rigidly clamped boundary / O.V.

Dudko, D.A. Potianikhin // Computational Continuum Mechanics. – 2008. – Book. 1. –

№ 2 – P. 27-37.

3. Potianikhin, D. A. Flat automodelling problems of dynamics of deformation / D.A.

Potianikhin. – Vladivostok: The Institute of Automation and Control Processes Far

Easter Branch of RAS, 2010. – P. 106.

4. Kulikovskii, A.G. Nonlinear Waves in Elastic Media, / A.G. Kulikovskii, E.I.

Sveshnikova. – M.: Moscow Lyceum, 1998. – P. 412.

5. Kalitkin, N.N. Numerical methods / N.N. Kalitkin. – SPb.: BHV-Petersburg, 2011. – P.

592.

6. MATLAB [Home page] – URL: http://matlab.ru/products/matlab [accessed: March 21,

2017]

Tretiak E. 1, Vereshchagina E. 1 Veremeeva I.F. 2

RESEARCH OF COMPUTER GAME TECHNOLOGIES FOR TEACHING OF

INTERNATIONAL STUDENTS


[email protected]

In Far Eastern Federal University in 2016 about 3000 foreign students from 52 countries

of the world studied. Many applicants come from the PRC, the Republic of Korea, Vietnam,

Malaysia and other countries of the Asia-Pacific region, as well as from all CIS countries.

Every year the number of foreign students studying in FEFU increases, which shows an

interest in learning Russian as a foreign language. Many students undergo a one-year preparation

for the subsequent development of professional educational programs in Russian [1].

When foreign students study subjects on their specialty, one of the main problems is

accessibility for understanding and memorizing information.

Standard teaching methods involve learning exactly the language. Experience shows that

when training in special disciplines, the problem in learning is not so much the subject itself as

for the terms. Terms, which in difference from usual words are not connected with a context, are

elements of professional lexicon.

To improve the perception and increase students' interest in the learning process, it is

proposed to use information computer technologies to memorize terms in the disciplines of the

chosen direction, in particular, technical. Thus, the issue of creating an additional electronic

means for teaching these disciplines by foreign students of the FEFU is relevant.

Currently, the most common means for learning foreign languages are Internet sites,

electronic dictionaries and textbooks, game programs, courses using Skype and others. Now




39

popularity is gained by technology of game training or Edutainment. This direction is a form of

educational process, realizing education process through entertainment, mainly in the form of

computer games.

Educational games by genre are divided into the following types:

- quest;

- arcade;

- simulator;

- computer simulator;

- an interactive course [2].

The arcades are aimed at the reproduction of simple repetitive operations, reminiscent of

board games. Simulation games help to simulate a process. Computer simulators help in teaching

phonetics, pronunciation. The interactive course is like an electronic textbook. For training in

terms the decision to use technologies of quests is made - they are able to combine all these

types of games, they allow to give an integrity and direction for the game process.

In quests, as a rule, the search for specific artifacts is realized, with the help of which the

student remembers the names of known subjects in the learned language. The solution of

puzzles, which can be tasks such as assembling equipment, creating models also allows you to

master the terminology.

Thus, the student remembers the terms, in which the visualization helps him; the skill of

solving problems in a foreign language improves. Also in the quest, the student will not be able

to go to the next location until he finishes the current one.

The aim of this work is to investigate gaming computer technologies for teaching foreign

students, in particular, gaming learning technologies, using the example of a web-based quests

game.

Further realization of a game of web quest is planned by using the designer Zunal Web

Quest Maker and its implementation in the learning process [3].

References:

1. Students from five continents have chosen Far Eastern Federal University [Electronic

source] – URL: https://www.dvfu.ru/news/fefu-news/students_from_five_continents_have_

chosen_to_study_the_far_eastern_federal_university/

2. Learning game [Electronic source] – URL: https://ru.wikipedia.org/wiki/Обучающая _игра

3. Try to create a web quest [Electronic source] – URL: https://edugalaxy.intel.ru/?show

topic=3079



40


Section III

CHEMISTRY AND CHEMICAL TECHNOLOGY

___________________________________________________________________________

Bragina J.A. 1, Kolycheva V.B. 2

TO GRIND OR TO BURN: A REVIEW OF USED TYRES UTILIZATION METHODS


[email protected]

The utilization of tyres from vehicles is an important environmental problem. Over 4 billion

waste tyres are currently stockpiled worldwide [1]. Massive piles of scrap tyres and landfilling

are unsustainable management practices which causes countless environmental and health

problems. Therefore, there is an extreme demand to organize an effective disposal of used tyres.

Nowadays there are numerous approaches targeted to recycle the tyre rubber in various

applications but very few of them are considered to have practical significance.

The purpose of the research was to review and compare how waste tyres are treated and

disposed and where the products of utilization can be applied.

There are two main groups of utilization methods applicable to waste tyres. The first group

of methods is based on a mechanical treatment of tyres. Grinding is a complex process, and as

tyres have a high mechanical strength, they need specialized equipment that is able to shred and

grind tyres to a desirable size and at a high degree of purity. The major obstacle of this method is

that the steel and textile parts are to be removed beforehand. There are different types of

grinding such as mechanical, cryogenic, wet, and high-pressure grinding. The comparison of

most applied grinding methods is showed in table 1.

Table 1 – A Comparison of Grinding Methods [1]

Grinding Method Advantages Disadvantages

Mechanical Grinding High surface area and volume

ratio

The danger of combustion due to

increased temperature, need for

cooling, surface granulation

oxidation

Cryogenic Grinding No surface oxidation, cleaner

granulates

Expensive liquid nitrogen, high

humidity of granulate

Wet Grinding

High surface area and volume

ratio, decrease of degradation of

granulates

Drying after grinding is required

Water Jet Grinding

Environmentally safe, energy

saving, decrease in noise level,

no pollutants

High pressure equipment,

experienced staff



41

Berstoff’s Method Less humidity, small grain size

with large specific area Not specified

However, mechanical grinding remains the most widely used method despite of its

disadvantages [1].

Obtained crumb rubber can be used as feed for production of other rubber materials. The

most common uses are light landfill cover, drainage and insulation. The main uses of granules

(particles of about 0.8–20 mm) include solid wheels, livestock mattresses, floor tiles, roofing

materials, vibration, articles for road marking, asphalt, sports flooring, rubber asphalt, curbs,

road barriers, and crash cushions. Powder (dispersed particles below 0.8 mm) is an ingredient

which can be mixed with virgin material. This powder is subsequently used in the construction

of roads or as a coating material by adding it to a solvent to form a rubber suspension.

Furthermore, it can be used as paint, spray or dip bath to automatically scan waterproofing

properties. The main uses include shoe soles, sports facilities, coatings for electrical cables,

automobile parts, dyes, inks, binders for porous asphalt, coatings and sealants, and flooring [2].

Another group of utilization methods comprises various thermochemical transformations of

waste rubber. There are two main ways of chemical disposal of tyres: combustion and pyrolysis.

Scrap tyres due to their high heating value (29–39 MJ/kg) which is higher than that of coal can

be used as a source of fuel in many combustion applications such as cement kilns, boilers and

smelters. Tyres can be used without any downsizing or can be processed into crumb or powder.

In comparison with coal combustion, combustion of tyre-derived fuel (TDF) is less

environmentally hazardous because of the lower emissions. The high temperature of cement

kilns enables tyres to be used more effectively than coal in this industry [3].

Co-combustion of tyres with coal is a useful way for recovering energy from waste tyres,

and reduction of air pollution. Scrap tyres in the form of shredded or ground tyres can be co-

combusted with coal in other industries such as electricity generation by increasing the thermal

efficiency of boilers and furnaces and reducing emissions [3].

Combustion of waste tyres to produce biofuel is another common way to recover the energy

in the furnaces, boilers, and burners. Thermochemical processes for liquid biofuels including

gasification, hydrothermal liquefaction and pyrolysis are commonly used to convert scrap tyres

to transportation fuels. Gasification is an applicable method to produce syngas (CH4, C2H6, H2,

CO, CO2, O2) with up to 39.6 MJ/m3 heating value.

Pyrolysis of waste tyres is a favourable way of recycling that converts tyres into bio-oil. The

product yields and composition depend on material particle size, temperature, heating rate, and

the condensation temperature of the volatile fraction. Tyre pyrolysis has been the subject of

many studies; a major reason is it is environmentally friendly and its lower emission except for a

few equipment leakage and minor fugitive sources. The reactor is an important part of the

pyrolysis process. A wide range of reactors including fixed-bed (batch), fluidized-bed, rotary

kiln, screw kiln, and vacuum have been used by researchers for scrap tyre pyrolysis among

which fixed-bed (batch) reactors is extensively applied in waste tyre pyrolysis. Using a

thermogravimetric analysis (TG), it is observed that the tyre thermal degradation temperature

commences at around 350 °C. Thus, the pyrolysis temperature range should consider the

degradation temperature, and it is normally defined in the range of 450–700 °C. However, the

investigation of rotary kilns fluidised bed and moving bed reactors are more favourable because

they are continuous processes even though there are some commercial batch reactors for tyre

pyrolysis [4].

Summing it up, the most applicable method of converting tyre to biofuel is pyrolysis. Much

research has been carried out to investigate the effects of the various parameters on the oil, gas,

and solid yields via pyrolysis. Having reviewed waste tyre pyrolysis, the oil yield is

predominantly dependent on temperature, heating rate, and reactor type [4].



42

The pyrolytic oil can be used as a component of fuel oils due to the high amount of aromatic

hydrocarbons. Properties of pyrolytic oil appear to be quite similar to diesel and it can be used as

an alternative fuel at either full load or blended with diesel [5].

All things considered it is worth noting that the method of utilization of waste tyres depends

on a desired product and sector of its further application. The two main groups of methods have

been reviewed and ways of products uses examined. Thus, all the discussed methods have a

great importance for treatment of used tyres as they allow using petrochemical resources more

effectively.

References:

1. Rowhani, A. Scrap Tyre Management Pathways and Their Use as a Fuel—A Review / A.

Rowhani, T. Rainey – M.: Mir, 1983. – 552 p.

2. Torretta, V. Treatment and disposal of tyres: Two EU approaches. A review / V. Torretta,

E. Rada, M. Ragazzi, E. Trulli, I. Istrate – M.: Mir, 1983. – 552 p

3. Giere, R. Chemical composition of fuels and emissions from a coal plus tire combustion

experiment in a power station / R. Giere, K. Smith. – Fuel, 2006. – Vol. 85. – P. 2278–

2285.

4. Hita, I. Opportunities and barriers for producing high quality fuels from the pyrolysis of

scrap tires / I. Hita, M. Arabiourrutia, M. Olazar // Renew. Sustain. Energy Rev. – 2016.

Book 56. – P. 745–759.

5. Williams, P. Aromatic chemicals from the catalytic pyrolysis of scrap tyres / P. Williams,

A. Brindle // J. Anal. Appl. Pyrolysis – 2003. Vol. 67 – P. 143–164.

Vinichenko I., Titova O.K.

CATALYTIC PROPERTIES OF IMMOBILIZED IONIC LIQUIDS DURING THE

ISOMERIZATION OF HYDROCARBONS


Catalysts used now do not correspond to the model of sustainable development. The use of

bifunctional catalysts is becoming less profitable due to higher energy costs and production

costs. Therefore, it is very important to find a replacement for such catalytic systems from the

economic and environmental point of view. An ionic liquid may become such a replacement.

The use of an ionic liquid as an isomerization catalyst makes it possible to carry out the

process at low temperatures, which greatly affects the reduction of energy consumption. Ionic

liquids are selective, easily regenerated, and they allow to obtain a high yield of the product.

Immobilization of the ionic liquid allows the consumption of the liquid to be reduced by itself,

and the advantage of immobilization is a simpler separation, recovery and regeneration of the

catalyst, minor contamination of the product, and a synergistic action exerted by the carrier. Low

volatility and the possibility of repeated use of ionic liquids in such processes minimize the risk

of environmental pollution.

The aim of the work is to evaluate the influence of the immobilized ionic liquid on the

isomerization of hydrocarbons on the basis of an analysis of the scientific and technical

literature. The tasks of the work were:

1. To determine the influence of the carrier for the immobilization of ionic liquid for

catalysis.

2. To determine the effect of impurities and additives on the catalytic activity of the

complex based on ionic liquid.



43

Ionic liquids are a special class of salts that have low melting points. Ionic liquids used as

catalysts in the hydrocarbon isomerization process are most often composed of an organic cation

and an inorganic anion. The main components of ionic liquids are presented in figure 1 [3].

Fig. 1. Basic cationic and anionic components of ionic liquids

In the presence of acid-type catalysts, isomerization proceeds along the carbocation

mechanism. This stage can occur both as a result of the detachment of hydride-ion by a strong

Lewis acid and under the influence of extremely reactive protons H +, which can be formed as a

result of partial hydrolysis of the ionic liquid [1,2,5].

Immobilization is necessary in order to increase the activity of the catalytic complex and

facilitate its use. The most commonly used carriers for the immobilization are zeolite catalyst,

silica gel and gamma-alumina. There are three main ways of immobilization: adsorption,

covalent immobilization through the anion, covalent immobilization through the cation [3]. The

method of immobilization through the anion consists in the chemical reaction of functionalized

anions of the ionic liquid containing active groups (such as AlCl4-), with the formation of a

covalent bond between the carrier and anions of the ionic liquid. The method of immobilization

through a cation are based on the interaction of the surface groups of the carrier and the

functional fragment of the cation of ionic liquid. Two options are possible here: either the

cationic component of the ionic liquid is introduced during the preparation of the carrier itself, or

it is grafted onto the prepared carrier, and then a metal halide. The simplest method is the

adsorption deposition of the ionic liquid. In this case, the carrier is impregnated with an ionic

liquid and then, if necessary, the metal complex is introduced as an active component or its

precursor, followed by conversion into the metal complex. Thus, the properties of the catalyst

obtained on the basis of the immobilized ionic liquid are determined not only by the nature of the

support, the content of the ionic liquid and the active metal, but also by the method of "grafting"

the carrier of ionic liquid to the pore walls. In the ideal case of a chemically grafted ionic liquid,

an ultrathin layer or even a monolayer of the Langmuir-Blodgett type is formed on the carrier

surface. In this case, the molecular dimensions of the ionic liquid and the pore diameter of the

carrier are selected so that the internal space of the porous substrate does not get blocked [3]. Let

us compare different types of carriers for immobilization in the process of isomerization of n-

hexane using an ionic liquid of composition: Et3NHCl: AlCl3. It was found that the highest

activity in the cyclohexane isomerization reaction was achieved with the participation of a

catalyst based on the zeolite catalyst KN-30. This fact manifested itself both in the speed of the

reaction and in achieving maximum conversion. While catalysts based on γ-Al2O3 and large-

pore silica gel showed more modest and comparable results that can be seen from figure 2 [7].



44

Fig. 2. Dependence of cyclohexane conversion on temperature

A - τ = 60 minutes; B – τ = 180 minutes; C – τ = 300 minutes

As impurities and additives affect the process of isomerization when using an immobilized

ionic liquid, there may be substances: copper salts, nitrogen and sulfur containing components,

benzene. The influence of benzene impurity has been studied. This impurity negatively affects

the catalytic complex, completely deactivating it during the isomerization of hydrocarbons.

Inhibitory effect is also caused by impurities of nitrogen and sulfur compounds. However, the

introduction of copper salt such as CuCl2 into the composition of ionic liquids leads to an

increase in the activity of the catalytic complex. For example, during the isomerization of n-

hexane, it was found that when the addition of 0.08 mol / mol of copper (CuCl2) in the ionic

liquid (C2H5)3NH-Al2Cl7, the yield of hexane isomers reaches a maximum and it is 27.54% of

mass. It was found that an increase in the content of the activating additive of more than 0.08

mol / mol leads to an insignificant decrease in the isomerization depth of 4-5% by weight. It was

found that with the content of the modifier in the amount of 0.12 mol / mol in the ionic liquid of

the composition [BMIm] [Al2Cl7] -CuCl2, the best results are achieved, similar to the reaction

using [(C2H5) 3NH-Al2Cl7] -CuCl2 catalyst with a copper chloride concentration of the order

of 0.02-0.04 mol / mol. [6].

Research of ionic liquids is a promising direction, since they allow to reduce energy costs.

Analysis of the literature testifies to the wide possibilities that are discovered when using ionic

liquids in petrochemical processes. It is very likely that new fundamental data can be obtained in

the near future, and new technological processes can be developed using these unusual solvents

and catalysts.

References:

1. Ksenofontov V.A., Vasina T.V., Zubarev Y.E., Kustov L.M. // React. Kinet. Catal. Lett.

2003. V. 80. № 2. P. 329.

2. Ksenofontov V.A. Katalitichiskie svoystva ionnykh zhidkostey v izomerizatsii

uglevodorodov [Catalytic properties of ionic liquids in the isomerization of hydrocarbons].

dissertation of the candidate of chemical sciences, 2003

3. Onishchenko M.I. [Synthesis and properties of pd-containing catalysts based on ionic

liquids immobilized on mesoporic molecular sites] dissertation for the degree of candidate

of chemical sciences, 2015

4. Zhang J., Huang C., Chen B. [Isobutane/2-butene alkylation catalyzed by chloroaluminate

ionic liquids in the presence of aromatic additives]. Journal of Catalysis, 2007, v. 38, pp.

261-268.

5. Zhang R., Meng X.H., Liu Z.C. [Isomerization n- pentane catalyzed by acidic

chloroaluminate ionic liquids]. Ind. Eng. Chem. Res., 2008, v. 47 (21), pp. 8205-8210



45

6. Herbst K., Houzvicka J., Jespersen T.B., Zavilla J. Process for paraffin hydrocarbon

isomerisation and composite catalyst therefore, comprising ionic liquid and metal salt

additive / EP 1346768 A2; applicant and patent holder Haldor Topsoe A/S 2800 Kgs.

Lyndgby (DK). _ № 03005229.4; claiming. 10.03.2003; publ. 24.09.2003

7. Malikov I.V., Zavalinskaya I.S., Yasyan Y.P. Investigation of hydrocarbon conversion c5-

c6 in isomerization reaction at the catalyst based on immobilized ionic liquid Journal

fundamental studies № 2, 2015

Grinenko E.F. 1, Arefieva O.D. 1, Titova O.K. 2

THE ENVIRONMENTAL STATE OF THE OL’KHOVYY CREEK IN THE

INDUSTRIAL AREA OF THE ABANDONED "NAGORNAYA" MINE (GUERRILLA

COAL BASIN, PRIMORSKY KRAI)


[email protected]

Partizansk coal deposits of the southern Far East are actively exploited by underground

mining from 1918 to 1998. Natural landscapes were transformed into anthropogenic landscapes

[1]. "Nagornaya" mine was operated from 1950-s. Mining and dewatering at the mine was

suspended in 1998 by its submergence. In 2006 the work on construction of objects of

dewatering complex in the area of streets Partizanskaya and Zashtolnaya on the left side of

Ol’khovyy Creek to prevent flooding of the urban area by the mine waters was completed. The

integrated design of wastewater treatment facilities consisted of dewatering complex of ponds

accumulating ponds-regulators, filter arrays with loading of carbonaceous claystone with zeolite

loading [2, 3]. Since 2014, the sewage treatment facilities have not been operated and industrial

waters without treatment enter Ol’khovyy Creek.

The objective of this study was to investigate the chemical composition of waters of

Ol’khovyy Creek, located in the industrial area of the abandoned "Nagornaya" mine, Partizansk

coal basin.

The objects of study were samples of water taken from the creek in the area of the

abandoned complex of treatment facilities of the liquidated mine "Nagornaya", mine Partizansk

coal basin (1), from Ol’khovyy Creek downstream (2), and the Postyshevka River (3) at the

confluence of Ol’khovyy Creek. Samples were taken in November 2016. In the samples there

were determined the main hydrochemical parameters and metals content (aluminum, cadmium,

cobalt, chromium (VI), lead, copper, potassium, lithium, sodium, nickel, strontium, manganese,

zinc).

The results showed that in the area of discharge of underground mine waters (point 1) of

Ol’khovyy Creek are highly mineralized, with average hardness, high color and turbidity. The

salinity and alkalinity reduced 1.5 times downstream (point 2), while pH, hardness, calcium,

magnesium, chloride ions, sulfate ions remain practically unchanged. Water stream in

Ol’khovyy Creek in points 1 and 2 do not differ in color, turbidity and permanganate oxidability.

Besides, the values of these indicators exceed the established norms. The obtained results of

chemical composition of waters of Ol’khovyy Creek indicate that the Creek is dominated by

mine waters. The chemical composition of the waters of the Postyshevka River meets the quality

standards for the main hydrochemical indicators.

In water samples, the metal content was determined by atomic emission spectroscopy.

Concentrations of strontium, manganese, copper and zinc exceed the MPC for fishery water

bodies, aluminum, lithium, for water bodies of fishery and domestic purposes. The chromium

content does not exceed standards. Cobalt, cadmium, lead and Nickel are not identified.



46

Thus, studies show that the Ol’khovyy Creek and Postyshevka River are under the

influence of the abandoned "Nagornaya" mine. A decrease of the main hydrochemical

parameters and concentrations of lithium, strontium is downstream of the Creek.

References

1. Fisenko, A. I. Planning for the prioritization of funding for environmental works at

liquidation of coal mines / I. A. Fisenko // Bulletin of Khmelnitsky national University. – 2009. -

No. 3. – Pp. 218-221.

2. Extract from the report on the implementation of works on realization of the working

project "Environmental monitoring in the liquidated mines and cuts in Primorsky Krai and the

Sakhalin oblast" for the first and second quarter of 2005. – Vladivostok, 2005. – 28 S. –

Unpublished material.

3. Development of recommendations on technology of cleaning of mine waters. –

Vladivostok, 2002. – 250 S. – Unpublished material.

Zharinov D. 1, Titova O.K. 2

RECYCLING OF POLYETHYLENE TEREPHTHALATE


[email protected]

Polyethylene terephthalate (PET) is one of the most common polymers in the world. PET

is a saturated polyester of ethylene glycol and terephthalic acid.

The widespread use of chemically obtained PET is becoming bigger every year in various

fields of human activities. The PET bottle was patented in 1973 by Nathaniel Wyeth and began

to be used popularly for the production of disposable soft drink bottles in the 1980s [1].

According to experts in 2013, the total number of produced bottles exceeded 500 billion units

[2]. In 2015, the total production of PET in the world amounted to about 70 million tons.

Strength, lightness, heat resistance, chemical inertness of the material, high barrier properties led

PET to one of the leaders in the field of packaging of goods, in particular, food products [1].

Despite their complete inertia and safety, the use of such quantity of bottles creates

problems with the littering of the environment. In addition, a struggle to minimize CO2

emissions into the atmosphere is very urgent, especially in the West. The use of recycled PET

contributes to this minimization of emission by reducing energy consumption. In the production

of bottles from recycled PET, approximately 60% less energy is consumed than with the new

PET. In addition, the price of recycled PET in some countries reaches 70-80 % of the cost of

primary polymer. Thus, the combination of technological, environmental and economic factors

objectively contributes to the growth of collection and recycling of post-consumer PET

containers [2].

There are several main recycling directions of post-consumer PET. Mechanical, chemical

or thermal transformations are used in recycling. About 70-75% of PET is mechanically

recycled, 20 – thermally and only 5% - chemically [2].

Burning

According to this method, plastic is destroyed by combustion releasing energy, which is

used for other needs. This method is actively used, for example, in the US, and the generated

energy is applied for industrial needs. It is safely enough, because when plastics are burned,

dioxins are not released, and their toxicity in combustion is equal to the toxicity of burning

wood. Nevertheless, this has no practical sense, since the calorific value of PET is 22,700 kJ / kg

(as in low-quality coal) with the cost of 1 ton of PET waste reaching 25,000 rubles [2].

Chemical recycling



47

Chemical recycling involves the transformation of polymer chain. It is carried out either

by solvolysis or by pyrolysis. Solvolysis is the degradation by solvents including water, and

pyrolysis involves the degradation by heat in the absence of oxygen or air, or vacuum. As a

result of chemical recycling monomers, petroleum liquids and gases are released. Purified and

dried monomers are used for manufacture of polymers.

Solvolysis process is divided into: hydrolysis, aminolysis, ammonolysis, methanolysis

and glycolysis.

Hydrolysis

It involves the hydrolysis of post-consumed PET to terephthalic acid and ethylene glycol.

Thus, the terephthalic acid is obtained and it can be re-used. The main disadvantage of this

method is the use of high temperature (200–250 °C) and pressure (1,4–2 MPa) which are

necessary for complete depolymerization. Commercially, hydrolysis is not widely used to

produce food-grade recycled PET because of the high cost associated with purification of the

recycled terephthalic acid. PET hydrolysis can be carried out as alkaline hydrolysis, acid

hydrolysis and neutral hydrolysis [1].

Aminolysis

The aminolysis of PET yields diamides of terephthalic acid, which is known as bis (2-

hydroxy ethylene) terephthalamide. This method is not used on a commercial scale in PET

recycling. However, it is sometimes used when it is necessary to improve certain properties of

PET in the manufacture of fibers. The reaction was usually carried out using primary amine

aqueous solutions, most frequently methylamine, ethylamine and ethanolamine in the

temperature range of 20–100 °C [1].

Ammonolysis

Terephthalamide is produced by the action of ammonia on PET in an ethylene glycol

environment. The process was carried out under a pressure of about 2 MPa in a temperature

range of 120–180 °C for 1–7 h. The product has a purity of not less than 99%, and the yield is

above 90% [1]. This method is not also widely used in PET recycling.

Methanolysis

Methanolysis actually involves the degradation of PET by methanol at high temperatures

and high pressures with the main products being dimethyl terephthalate, which is one of raw

material for the PET production, and ethylene glycol. Temperatures between 180 °C and 280 °C

and pressures from 2 to 4 MPa are required for methanolysis. The main advantage of this method

is that an installation of methanolysis can be located in the polymer production line. In this way,

waste arising in the production cycle is used, and the monomers recovered can be re-used in the

manufacture of a proper polymer. The main disadvantage of this method is high price of product

separation [1].

Glycolysis The glycolysis reaction is the molecular degradation of PET polymer by glycols, in the

presence of trans-esterification catalysts, where ester linkages are broken and replaced with

hydroxyl terminals. There are four distinct methods for the glycolysis of postconsumer PET

materials: solvent-assisted glycolysis, supercritical glycolysis, microwave-assisted glycolysis,

catalyzed glycolysis [1].

Glycolysis is a promising method for recycling PET. Currently, a lot of researches are

being done in this area. Today many reagents have been proposed for glycolysis, but researching

in this area is continuing. For example, recently it has been proposed to use castor oil [4] and

neopentyl glycol [5] for depolymerization. Glycolysis allows obtaining composite materials [6],

insulation foam, coatings.

Pyrolysis

This technology assumes that during the high-temperature splitting of polyethylene

terephthalate in the absence of air, a number of substances widely used in industry are obtained.

Also, during the PET destruction by pyrolysis, a large amount of heat is released. This energy



48

can be used by the enterprise of various technological processes. The undoubted advantage is

that for the recovery of bottles by the pyrolysis method they do not need to be sorted [3]. The

disadvantage of pyrolysis is the release of harmful substances. The removal of them requires

additional costs.

Mechanic-chemical method

This is the most common and, as a rule, the most economical method of processing

crushed and purified PET waste. PETs are consistently melted, homogenized, cleaned of

impurities and filtered in an extruder with vacuum degassing. After the extruder, the melt is

filtered from mechanical impurities and is granulated. After granulation, the product can be

supplied for additional polycondensation in the solid phase. If this is required for further use, it is

possible to increase the viscosity of PET and, at the same time, effectively clean it of

contaminants. Thanks to this method, it is possible to achieve a rather high purity of PET. For

example, using technology Super-Clean-Recycling, a pure polymer is obtained, and it is

impossible to determine impurities in it by any modern method. [2].

Application of recycled PET

The areas of application of recycled PET waste are mainly determined by the degree of

contamination and the molecular weight of the material. Most of the recycled PET is used for the

production of films, fibers, foams, coatings or new bottles. An important area for the use of post-

consume PET is the production of textiles.

Conclusion

The most commonly used method for recycling is mechanic-chemical method, but

according to the condition of wastes, all the described processes may make PET recycling

possible. The main principle when choosing a specific technology is to maximize the use of the

potential capabilities of a particular post-consume PET, for the production of which valuable

organic raw materials and energy are spent, with the full safety of the use of final recycled

products.

References:

1. Al-Sabagh, A.M. Greener routes for recycling of polyethylene terephthalate /

F.Z.Yehia, Gh.Eshaq, A.M. Rabie, A.E. ElMetwally // Egyptian Journal of Petroleum

– 2016. – Vol. 25, N 1. – P 53.

2. Kernitsky, V.I. Recycling of polyethylene terephthalate wastes / V.I Kernitsky, N.A.

Zhir // Polymeric materials – 2014. – Vol. 201, N 8. – P 11.

3. Bazunova, M.V.. Methods of utilizing waste polymers / M.V. Bazunova, Yu. A.

Prochuhan // Bulletin of Bashkir University – 2008. – Vol. 13, N 4. – P 875.

4. Benes, H. Recycling of waste poly(ethylene terephthalate) with castor oil using

microwave heating / H. Benes, J. Slaba, Z. Valterova, D. Rais // Polymer Degradation

and Stability – 2013. – Vol. 98, N 11. – P 2232.

5. Kathelevar, M. Chemical recycling of PET using neopentyl glycol: Reaction kinetics

and preparation of polyurethane coatings / M. Kathelevar, N. Dhopatkar, B.

Pacharane, A. Sabnis, P. Raut, V. Bhave // Progress in Organic Coating – 2013. – Vol.

76, N 1. – P 147.

6. Roy, P.K. Tertiary recycling of poly(ethylene terephthalate) wastes for production of

polyurethane–polyisocyanurate foams / P.K. Roy, R. Muthur, D. Kumar, C. Rajagopal

// Journal of Environmental Chemical Engineering – 2013. – Vol. 1, N 4. – P 1062.



49

Malakhova I. 1, Privar Y. 2, Bratskaya S. 2 , Kolycheva V.B. 3

HIGHLY POROUS SORBENTS OF IONS OF TRANSITION METALS BASED ON

POLYETHYLENEIMINE

1Far Eastern Federal University, School of Natural Sciences

2Institute of chemistry, Far-Eastern Branch of the Russian Academy of Sciences 3Far Eastern Federal University, Oriental Institute School of Regional and International Studies

[email protected]

Polyethyleneimine (PEI) is known as effective synthetic sorbent of transition and noble

metal ions [1-4]. Due to the presence of primary, secondary and tertiary amino groups in the

structure, PEI is soluble in a wide pH range. For using PEI as a sorbent, the polymer should be

crosslinked using epichlorohydrin [5] or other crosslinking agents. The main disadvantage of

granular sorption materials is low kinetic characteristics. The most perspective solution of this

problem is obtaining of highly porous materials by the cryogel method. In which the process of

crosslinking is carried out at negative temperatures, and the emerging ice crystals play role of

pore-forming templates.

The purpose of this research was to select crosslinking agents and crosslinking conditions to

produce highly porous sorption materials based on PEI.

The sorption materials were obtained by crosslinking branched PEI with various

crosslinking agents: glutaraldehyde, diglycidyl ethers of 1,4-butanediol and polyethylene glycol

(PEG). In experiments, the crosslinking parameters (pH, temperature, ratio of polymer and

crosslinker) were varied, and there were investigated their effect on such properties as swelling,

porosity, static exchange capacitance with respect to protons and ions of transition (Cu (II), Ni

(II) , Co (II)) metals, kinetic characteristics of sorbents.

Comparative data on the properties of materials cross-linked at room temperature and under

conditions of formation of cryogel are presented in the table.

Table

Conditions of obtaining of sorbents based on PEI and their main characteristics

Cipher рН

Ratio of

CA /

monomer

(mol /

mol)

Crosslinking

agent*

Т of

crosslin

king, °С

Degree of

swelling,%

Exchange (sorption) capacity,

mmol / g

Cu 2+ Н+

P35PG 8.83 1:1 DE-PEG +23 288 0.60 2.24

P39PG 8.83 1:1 DE-PEG -20 605 1.50 н/о

P43But 10.18 1:1 DE-1,4BD +23 312 0.68 2.21

P44But 10.18 1:1 DE-1,4BD -20 336 1.60 4.60

P58GA 4.6 1:1 GA +23 266 0.7 3.5

P45GA 4.6 1:1 GA -20 623 1.16 8.10

P55But 8.83 1:2 DE-1,4BD +23 408 3.60 7.06

P59But 8.83 1:2 DE-1,4BD -20 708 1.12 4.75

*DE-PEG - diglycidyl ether of polyethylene glycol; DE-1,4BD - diglycidyl ether of 1,4-butanediol; GA –

glutaraldehyde

It can be seen from the table that the swelling of materials obtained by the cryogel method is

noticeably higher than that obtained at the same pH values and reagent ratio at room

temperature. Investigation of cross-linked PEI by scanning electron microscopy confirms the

formation of a developed porous structure at a temperature of -20 ° C with a pore size up to

several tens of microns (Fig. 1).



50

0 200 1200 14000

5

10

15

20

25

30

35

Concen

tra

tio

n C

u(I

I),

mg/l

Time, min

P39PG

P35PG

B

Figure 1 - The surface of the cross-linked PEI and sorption kinetics

A – The surface of cross-linked PEI

B - The kinetics of sorption of Cu (II) ions by porous (P39PG) and nonporous (P35PG) PEI from a 0.1 M solution

NH4NO3, рН 5.3, Т=23°С

It can be seen from Fig. 1B that a highly porous PEI has much higher kinetic characteristics

than a nonporous material obtained by crosslinking with the same crosslinking agent. Despite the

rather high sorption capacity of the PEI cross-linked with glutaraldehyde, the resulting material

is brittle and is not suitable for practical use. Thus, the most effective highly porous sorbents can

be obtained by cross-linking the PEI with diglycidyl ethers of polyethylene glycol and 1,4-

butanediol in an alkaline medium at a molar ratio of the reactant / monomer unit of PEI of 1: 1.

References:

1. Characterization of PEI-modified biomass and biosorption of Cu(II), Pb(II) and

Ni,(II) / Deng, SB; Ting, YP // Water research. – 2006. – Vol. 39, – Issue 10, – P. 2167-2177

2. Application of a new water-soluble polyethylenimine polymer sorbent for

simultaneous separation and preconcentration of trace amounts of copper and manganese and

their determination by atomic absorption spectrophotometry /Sabermahani, F; Taher, Ma //

Analytica Chimica Acta. – 2006 – Vol. 565, – Issue 2, - P. 152-156

3. Utilization of PEI-modified Corynebacterium glutamicum biomass for the

recovery of Pd(II) in hydrochloric solution. / Won, S. W., Park, J., Mao, J., & Yun, Y. S. //

Bioresource Technology. – 2011. – Vol. 102, – Issue 4, – P. 3888-3893.

4. Platinum recovery from ICP wastewater by a combined method of biosorption

and incineration. / Won, S. W., Mao, J., Kwak, I. S., Sathishkumar, M., & Yun, Y. S. //

Bioresource Technology. – 2010. – Vol. 101, – Issue 4, – P. 1135-1140.

5. Metal ion binding by pyridylethyl-containing polymers: experimental and

theoretical study / Bratskaya, S., Voit, A., Privar, Y., Ziatdinov, A., Ustinov, A., Marinin, D.,

Huettermann, J. // Dalton Trans. – 2016 – Issue 37, – Р. 41–127.

Pugacheva N.1, Anufriev A.1, Kolycheva V.B.2

SELECTION OF SOLVENT FOR THE PROCESS OF OBTAINING IZOPRENE FROM

C5 PYROLYSIS FRACTION BY EXTRACTIVE DISTILLATION


[email protected]

One of the most important monomer of nowadays chemical technology is isoprene.

Usually isoprene is obtained by chemical synthesis but there are many losses and further

purification is also needed. Obtaining isoprene from C5 pyrolysis fraction allows to receive

javascript:;

http://apps.webofknowledge.com/full_record.do?product=WOS&search_mode=GeneralSearch&qid=6&SID=S1M2II8I84HOOL4KCm4&page=4&doc=34&cacheurlFromRightClick=no



javascript:;



51

commodity 99.96% pure isoprene. The scheme was modeled and technological parameters were

optimized earlier [1]. The final version of this scheme is presented on picture (Fig. 1).

Fig. 1. The scheme of obtaining isoprene from C5 pyrolysis fraction

K-1, K-2, K-5–distillation column; K-3, K-4 – extractive distillation column;

С-1, С-2, С-3 – mixers

The main problem of obtaining isoprene from C5 mixture is close boiling points of

fraction’s components and formation of the azeotrope mixture upon attempt to separate it by

traditional distillation. Columns К-3 and К-4 intended for extractive rectification allow to divide

the azeotrope mixture and obtain two target streams. The main energy load of the scheme is K-3

and K-4 columns, since it requires a large amount of energy to be supplied for the azeotrope

separation. Properly selected solvent helps to reduce energy consumption in the columns of

extractive distillation and the whole process, also affects the efficiency of the whole process.

According to the literature data, it is possible to use as solvent: N, N-dimethylformamide

[1], N-methyl-2-pyrrolidone [2], acetonitrile [2], dimethylsulfoxide [3] and aniline [2]. A variant

of the technological scheme with five separation columns was considered, the parameters are

indicated in Table 1. The changes occurred only at the stage of extractive columns K-3 and K-4,

for which the solvents varied.

Table 1

Distillation columns parameters

Distillation column Number of stages The height of

feeding columns, % of

columns high from the

bottom

Reflux ratio

K-1 18 50 % 35

K-2 65 35 % 25

K-3 114 10 % 22

K-4 35 30 % 15

K-5 10 50 % 5

The modeling system with acetonitrile and dimethylsulfoxide with current specification was

not converge.The results of modeling process with N, N-dimethylformamide, N-methyl-2-

pyrrolidone and aniline are presented in Table 2.

Table 2

The results of modeling system of obtaining isoprene with different solvents

Criterion N, N-

dimethylformamide

N-methyl-2-

pyrrolidone

Aniline

Isoprene purity, % 99.66 99.66 99.47

Isoprene loss, kg/h 5.12 81.90 1245.55



52

Total heat flow, MW 62.421 62.92 71.32

If N, N-dimethylformamide is used in the scheme, an isoprene loss is 5 kg / h and a total

heat flow is 62.4 MW when the purity of isoprene is 99.66%. When compared with other

solvents, it is seen that with approximately the same purity of the product, isoprene losses are

very different in the schemes. Thus, when aniline is used, the loss of isoprene is 1.2 tph.

After analyzing all the data, it was found that the most suitable solvent for obtaining

isoprene from the C5 pyrolysis fraction by the extractive distillation is N, N-dimethylformamide.

References:

6. Anufriev A.V. Production Of Isoprene From Fraction C 5 Pyrolysis / A.V. Anufriev,

V.A. Reutov, V.P. Krivosheev , A.M. Zabolotnaya, L.A. Lim // Shestoj tehnologicheskij uklad:

mehanizmy i perspektivy razvitija[The sixth technological structure: the mechanisms and

prospects of development] Vol.1 . - Khanty-Mansiysk, 2015. P - 93-95.

7. Patent 3497566 USA, Cl. C 07 C7/08, B01d 3/40. Process for the production of

isoprene from C5-fractions substantially free of paraffins and olefins by extractive distillation of

cyclopentadiene with aniline / Hans-Walther Brandt ; Bayer Ag,Erdoelchemie Gmbh. –

24.02.1970 – 3 p.

8. Enomoto,M/ Extractive distillation solvents for the separation of isoprene / M.

Enomoto // Bulletin of The Japan Petroleum Institute. – 1971. – Vol. 13, N 2. – P. 169-176.

Zvereva А.1,2, Vasilyeva1,2 M., Rudnev1,2 V., Kilin2 K., Sergeev1,3 A., Nepomnyaschiy3 A.,

Voznesenskiy1,3 S., Ustinov1,2 A., Kolycheva V.B4

COMPOSITION, STRUCTURE AND PHOTOCATALYTIC PROPERTIES OF

Fe-CONTAINING COATINGS ON TITENIUM

1Far Eastern Federal University 2Institute of Chemistry, Far-Eastern Branch, Russian Academy of Sciences

3Institute of Automation and Control Processes, Far-Eastern Branch, Russian Academy of Sciences, 4Far Eastern Federal University, Oriental Institute - School of Regional and International Studies

Vladivostok, Russia [email protected]

One of the most important ecological problems of our time is the treatment of

wastewaters containing highly toxic and stable organic pollutants, particularly phenolic

compounds. For this reason the development of effective and reliable methods of water

treatment has great value. Using of heterogeneous photocatalysis allows one to oxidize organic

substances with high mineralization at relatively low temperature. Currently, titanium dioxide is

the most studied and effective photocatalyst for decomposition of wide range of organic and

inorganic toxic substances [1].

Last decade attention has focused on the Advanced Oxidation Processes (AOP) based on

the generation of highly reactive hydroxyl radicals. Among them, photo-Fenton process is a

highly effective method for phenol oxidation [2]. However, there is one main drawback: this

process requires additional work for final separation of soluble iron species from treated water

[3]. To solve this problem photoactive materials are planted on substrates.

Plasma electrolytic oxidation (PEO) is one of the methods for technological generation of

such oxide coatings on metals. PEO is electrochemical oxidation of metal or alloy surface under

electric spark and arc discharges [4].

The objective of this work was to study composition and structure of PEO-coatings on

titanium, formed in silicate or phosphate electrolytes, and to research their photocatalytic activity

in phenol degradation.



53

Fe-containing coatings were prepared by PEO of titanium in silicate or phosphate

electrolytes without and with an addition of K3[Fe(CN)6]. The structure, elemental and phase

compositions of the formed coatings and their surface morphology were characterized by

scanning electron microscopy (SEM) equipped with energy dispersive X-ray (EDX)

spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD).

Analysis of the coatings surface shows that iron species concentrate in hollows and

cavities – in defective areas of surface, which were formed by breakdown effects.

Photocatalytic activity of the coatings was determined by photodegradation of phenol in

aqueous solution containing hydrogen peroxide under UV-irradiation (fig. 1 – 2). Phenol

degradation does not occur without coatings or on oxide layers formed in electrolytes without

addition of K3[Fe(CN)6]. The phenol degradation degree increases with K3[Fe(CN)6]

concentration in working electrolyte. Coatings formed in silicate electrolyte are significantly

more effective than coatings formed in phosphate electrolyte.

0

20

40

60

0.6 1.6 2.6 3.6

С (K3[Fe(CN)6]), g/L

α, %

Fig. 1.Phenol degradation degree dependence on concentration K3[Fe(CN)6] in phosphate

electrolyte.

0

20

40

60

80

0.5 1 4 8

С (K3[Fe(CN)6]), g/L

α, %

Fig. 2.Phenol degradation degree dependence on concentration K3[Fe(CN)6] in silicate

electrolyte.

It is believed that formed composite oxide layers on titanium are perspective as heterogenic

Fenton-like catalysts which can find an application in water purification.

References:



54

1. Chen, X. Titanium Dioxide Nanomaterials: Synthesis, Properties, Modifications, and

Applications / X. Chen, S. S. Mao // Chem. Rev. – 2007. – Vol. 107, N 7. – P. 2891–

2959.

2. Idrissi, M. Degradation of crystal violet by heterogeneous Fenton-like reaction using

Fe/Clay catalyst with H2O2 / M.Idrissi, Y.Miyah, Y.Benjelloun, M.Chaouch // J. Mater.

Environ. Sci. – 2016. – 7 (1). – P. 50 – 58.

3. Condal, M.A. Efficient removal of phenol from water using Fe2O3 semiconductor

catalyst under UV laser irradiation / M.A. Gondal, M.N. Sayeed, Z.H. Yamani, A.R. Al-

Arfaj // J. of Environ. Science and Health Part A. – 2009. – N. 44. – P. 515 – 521.

4. F. Patcas, W. Krysmann //Appl. Catal.,A. – 2007. – Vol. 316. – P. 240.

Pak M. A., Zhidkov M. E.1, Kolycheva V.B.2

FASCAPLYSIN DERIVATIVES AS μ-OPIOID RECEPTOR AGONISTS:

MOLECULAR MODELING STUDY

1Far Eastern Federal University, School of Natural Sciences, Vladivostok, Russia 2Far Eastern Federal University, Oriental Institute School of Regional and International Studies

[email protected]

Fascaplysin (Figure 1) is a sponge-derived red pigment that exhibits a wide range of

biological activity among which are antibacterial, antifungal, antiviral and anticancer properties

[1]. Recently it was reported that fascaplysin serves as selective μ–opioid receptor (MOR)

agonist with a signaling profile that resembles endorphins [2]. It makes fascaplysin a perspective

compound for development of novel analgesics with reduced side effects.

Figure 1. Molecular structure of fascapysin 1

In this research molecular docking analysis of an array of fascaplysin derivatives was

executed against activated MOR (PDB-ID: 5C1M [3]) to find out the most promising compounds

for further synthesis and investigation. Previously we utilized docking simulations to the study

of interaction of fascaplysin derivatives with the active sites of acetylcholinesterase [4] and

cyclin-dependent kinase 4 (CDK4) [5].

Fascaplysin docking simulations resulted in several conformations differing in localization

in the active site of MOR. To reveal what conformations define MOR agonist activity docking

procedure was performed against homology model of activated -opioid receptor (DOR). It is

known that fascaplysin is inactive against DOR [2]. Superposition of results of docking with

DOR and MOR allowed to exclude matching conformations and identify interactions that are

crucial for MOR selective agonist activity (Figure 2).




55

Figure 2. Superposition of fascaplysin conformations in MOR (light grey) and DOR (black)

active sites

Nevertheless, fascaplysin ability to arrest the cell cycle via CDK4 inhibition makes it

impossible to use the alkaloid in pain treatment. This problem can be solved by substitution of

indole-NH that is crucial for CDK4 inhibition activity with N-methyl.

The docking simulations were executed with Autodock4 software according to user manual

[6]. Homology model of activated DOR was built based on the crystal structure of activated

MOR [3] using SWISS-MODEL server [7]. We studied the interaction of 160 fascaplysin and N-

methyl-fascaplysin derivatives with various substituents in position 9 (Table 1) with the binding

site of activated MOR model.

Table 1. Fascaplysin derivatives

R1=

NO2, Halogen, OH, N, Ph;

CH2OH, COOH, COOEt, C(O)Me, C(O)Et,

C(O)NH2;

OC(O)CH2(Me)Et, OC(O)CH2i-Pr,

OC(O)CH2CH(NH2)COOH,

OC(O)(CH2)2CH(NH2)COOH;

NH(CH2)nCOOH; n=1-3;

R2=H, Me.

R1=

Bu, (CH2)nt-Bu, CH(Me)CH2(Me),

CH(Me)i-Pr,

(CH2)2CH(NH2)COOH

(CH2)nMe; n=1-3;

Naphthyl, BzNHBz;

R2=H, Me.

R1=H, Me;

X=N;

R2, R3=NO2, Halogen, Me, OH, N+ -

substituent position 1-4.

R1=H, Me;

R2= Me, Et, Ph;

R3,R4=

NO2, Halogen, Me, Et, OH;

OMe, OEt, NHMe, NHEt, CH2NHMe,

C(O)Me;, NHC(O)Me - substituent position 1-4.



56

R1=H, Me;

R2,R3=NO2,

Halogen,

Me, OH -

substituent

position 1-4.

Most fascaplysin derivatives interact with amino acids of the binding site that are critical for

MOR agonist activity. Replacement of indole-NH with N-methyl shifts the ligand from the

pocket of active conformations. However, insertion of substituent in position 9 of N-methyl-

fascaplysin makes them bind to receptor according to native fascaplysin (Figure 3).

Figure 3. Orientation of fascaplysin (black), N-methyl-fascaplysin (light-grey) and

N-methyl-fascaplysin derivative with substituent in position 9 (grey) in the active site

The energies of binding of most derivatives surpassed the same parameter for fascaplysin in

absolute value what makes the studied compounds perspective for further research. The most

energetically favorable derivative is compound 2 (Figure 4) with energy value minus 15,92

kkal/mol. We have chosen compound 2 for subsequent synthesis and exploration taking into

account the score of binding energy and ligand orientation in the active site.

Figure 4. Molecular structure of compound 2

This work represents the molecular modeling study of fascaplysin derivatives as new

promising selective MOR agonists. To conclude, we defined structural fragments that enhance

the binding affinity of fascaplysin derivatives to MOR what makes them perspective for

development of analgesics with reduced liability for dependence and tolerance. One fascaplysin

derivative was chosen for synthesis and further comprehensive research.

References:



57

1. B. Bharate, S., Manda, S., Mupparapu, N., Battini, N., & A. Vishwakarma, R. (2012).

Chemistry and Biology of Fascaplysin, a Potent Marine-Derived CDK-4 Inhibitor. MRMC,

12(7), 650-664. http://dx.doi.org/10.2174/138955712800626719

2. Johnson, T., Milan-Lobo, L., Che, T., Ferwerda, M., Lambu, E., & McIntosh, N. et al.

(2016). Identification of the First Marine-Derived Opioid Receptor “Balanced” Agonist with a

Signaling Profile That Resembles the Endorphins. ACS Chemical Neuroscience, 8(3), 473-485.

http://dx.doi.org/10.1021/acschemneuro.6b00167

3. Huang, W., Manglik, A., Venkatakrishnan, A., Laeremans, T., Feinberg, E., & Sanborn,

A. et al. (2015). Structural insights into µ-opioid receptor activation. Nature, 524(7565), 315-

321. http://dx.doi.org/10.1038/nature14886

4. Пак, М. А. Изучение взаимодействия производных фаскаплизина с активным

сайтом ацетилхолинэстеразы методом молекулярного моделирования / М. А. Пак, М. Е.

Жидков // Региональная научно-практическая конференция студентов, аспирантов и

молодых учёных по естественным наукам, Владивосток 15-30 апреля 2016 г.: тез. докл. –

Владивосток, 2016. – С. 467-469.

5. Pak, M. A. Molecular docking study of fascaplysin derivatives interaction with CDK4 /

M. A. Pak, M. E. Zhidkov, V.B. Kolycheva // 3rd Fefu SNS Students, Master’s Degree Students

and Postgraduate Students Scientific-Practical Conference in English, Vladivostok 25 April – 08

May 2016: тез. докл. – Владивосток, 2016. – С. 78-81.

6. Morris, G., Huey, R., Lindstrom, W., Sanner, M., Belew, R., Goodsell, D., & Olson, A.

(2009). AutoDock4 and AutoDockTools4: Automated docking with selective receptor flexibility.

J. Comput. Chem., 30(16), 2785-2791. http://dx.doi.org/10.1002/jcc.21256

7. Biasini, M., Bienert, S., Waterhouse, A., Arnold, K., Studer, G., & Schmidt, T. et al.

(2014). SWISS-MODEL: modelling protein tertiary and quaternary structure using evolutionary

information. Nucleic Acids Research, 42(W1), W252-W258.

http://dx.doi.org/10.1093/nar/gku340

Khrebtov A.A.1, Lim L.A.1, Fedorenko E.V.2, Cherevatiuk G.V.1, Kolycheva V.B.3

INVESTIGATION OF POSSIBILITY OF USING POLYMERIC FILMS DOPED WITH

BORON DIFLUORIDE DIBENZOYLMETHANATE ON GLASS SUBSTRATE AS A

LUMINESCENT SOLAR CONCENTRATOR

1Far Eastern Federal University, School of Natural Sciences 2Institute of Chemistry of the Far-Eastern Branch of the Russian Academy of Sciences

3Far Eastern Federal University, Oriental Institute - School of Regional and International Studies

[email protected]

Recently, the problem of using renewable energy sources (for example, solar energy) is

acute due to the exhaustion of fossil fuels and contamination of environment. A luminescent

solar concentrator (LSC) is one of possible solutions of this problem, so it is necessary to

intensify work in this direction.

Traditional LSC is optically transparent plate doped with a luminophore. Luminescent

material selectively absorbs part of the solar spectrum and re-emits it in the long-wave range.

Re-emitted light is concentrated at the edges due to the total internal reflection. Photovoltaic

(PV) cells are mounted the edges and transform light into electricity. The design, which consists

of LSC and PV, can be integrated into transparent constructions of buildings (windows, stained-

glass windows). However, there are a number of technological problems in the making of

polymeric LSC for integration into the window. They can be solved by spreading a polymeric

http://dx.doi.org/10.2174/138955712800626719

http://dx.doi.org/10.1021/acschemneuro.6b00167

http://dx.doi.org/10.1038/nature14886

http://dx.doi.org/10.1002/jcc.21256

http://dx.doi.org/10.1093/nar/gku340



58

luminescent composition in the form of a thin film onto transparent substrate. As a result two-

layer structure operates as one LSC.

Previously, we investigated spectral properties of polymeric luminescent compositions based

on polystyrene (PS) with different concentrations of boron difluoride dibenzoylmethanate

(BF2DBM) [1], [2]. These compositions can be used as a material for the creation of LSC. The

purpose of this paper is to investigate the possibility of using substrate based on silicate glass

coated with a polymer composition with BF2DBM as LSC.

Samples in form of glass plates (50×50×4 mm, 50×50×8 mm, 70×70×4 mm and

70×70×8 mm) coated with films based on PS with dopant of BF2DBM (0.2 wt. %) were obtained

by dipping in solution and evaporation into the atmosphere. Dichloromethane (tboil = 40.1 °C)

and toluene (tboil = 110.6 °C) were used as solvents.

Fig. 1. Samples of the same size, which are obtained with dichloromethane (left) and toluene

(right), under different illumination

1 - normal conditions

2 - short-wave irradiation (365 nm)

Films, which were obtained from solution with a low-boiling solvent, are characterized by a

heterogeneous structure and the presence of a large number of bubbles (Fig. 1). There is a low

adhesion between the glass substrate and the film in these samples. So these samples are not

suitable for the creation of LSC. A higher boiling solvent allows to obtain more homogeneous

and smooth structure with better adhesion.



59

Fig. 2. Samples of different thickness, which are irradiated by short-wave radiation (365 nm)

Thus, two-layer structures, which consist of silicate glass substrate coated with thin film

based on PS and BF2DBM, can be used as LSC due to the ability to concentrate radiation. It is

necessary to use high-boiling solvents during evaporation into the atmosphere to obtain

homogeneous films with satisfactory adhesion to the glass substrate.

References:

1. Luminescent polymeric compositions with boron difluoride dibenzoylmethane: properties

and applications. / A.A Khrebtov and others // Program and Abstract Book of 12th International

Saint-Petersburg Conference of Young Scientists, Saint-Petersburg, 14-17 November 2016. –

Saint-Petersburg: Icing, 2016. - P. 132.

2. Исследование спектральных свойств композиций на основе полистирола и

дибензоилметаната дифторида бора. / А.А. Хребтов и др. // Сборник тезисов молодёжного

научного форума "Open Science 2016", Гатчина, 16-18 ноября 2016 г. - Гатчина:

типография ФГБУ "ПИЯФ" НИЦ "Курчатовский институт", 2016. - С. 70.

Perviakova A., Titova O.K.

EXTRACTION OF RARE EARTH ELEMENTS FROM COAL BY SUPERCRITICAL

CARBON DIOXIDE EXTRACTION

1Far Eastern Federal University, School of Natural Sciences, Vladivostok, Russia 2Far Eastern Federal University, Oriental Institute - School of Regional and International Studies

[email protected]

Generally, coal is used as a source of energy, but due to its complex composition, there

are many other ways of its application. The value components may be extracted from coal, in

this case, rare earth elements [1,2]. On the early stage of coalification, metals, including rare, are

contained in the organic part in humic acids. At later stages of coalification, humic acids

disappear and in the mature coal prevail the mineral form of common mass rare metal location

such as monazite, illite, xenotime, plagioclase, allanite, cerite, thalenite [3].

There are various methods of extraction: to extract components from different solid and

porous structures. Literature analysis shows that we can apply the technologic process of




60

supercritical fluid extraction. It is based on the unique ability of solvents to extract components in

a supercritical state effectively [4].

We have tasted 18 coal samples from 9 different deposits for ash content, humidity (Table

1) and presence of rare-earth elements in solution (Table 2).

Table 1

Results of test for coal ash content and humidity

№ Deposit Ash content of

analytical coal, %

Humidity,

%

Ash content of dry

coal, %

1 Siniy utes 2,56 8,27 2,80

2 Voznovka 46,3 3,61 48,1

3 Nezhino 25,3 6,03 26,9

4 Lipovtcy 19,5 5,84 20,7

5 Rakovka 2,34 7,33 2,53

6 Pavlovka 10,6 13,07 12,2

7 Тadushy 9,62 5,14 10,1

8 Vanchino 46,8 2,93 48,2

9 Novoshahtinsk 5,90 34,1 8,94

Table 2

Presence of rare-earth elements

Element Presence in samples of various deposits

*

Maximum concentration

in solution, mg/L in coal,

mg/ton

Y 6>>8> other>4>1 0,2-20 5-500

Nd 8>6>>2>7>9≈5≈3>4>1 0,1-10 2,5-250

Се 8>6>>2>7>9>5>3>>4>1 0,2-10 5-250

La 8>6>>2>9>5≈7>3>>4>1 0,2-10 5-250

Sm 8>6>> other>4≈1 0,03-3 0,75-75

Pr 8>6>> other >4≈1 0,02-2 0,5-50

Sc 3>>7>2>9≈6>8>5>1>4 0,01-1 0,25-25

Gd 8>6> other >4>1 0,02-1 0,5-25

Yb 6>8> other >4>1 0,005-0,5 0,125-12,5

Eu 8>6>>2>7>9>3>5>4>1 0,001-0,1 0,025-2,5

Continuation of Table 2

Lu 6>> other 0,001-0,1 0,025-2,5

Er 6>8>> other >1>4 0,005-0,1 0,125-2,5

Ho 8≈6>> other >4>1 0,005-0,1 0,125-2,5

Dy 8≈6>> other >4>1 0,02-0,1 0,5-2,5

Tb 8>6>> other >4≈1 0,002-0,05 0,05-1,25



61

Note: * – deposits: 1 – Siniy utes; 2 – Voznovka; 3 – Nezhino;4 – Lipovtcy; 5 – Rakovka;

6 – Pavlovka; 7 – Tadushy; 8 – Vanchino;9 – Novoshahtinsk.

According to the primary characteristic of raw materials, tested coal during combustion

gives ash as a concentrate of mineral components (from 2,5 to 48 wt %). Each sample contains

rare-earth elements. This gives grounds to assume the possibility of extraction of these valuable

metals.

We did extraction by carbon dioxide with co-solvent and without it in plug-flow reactor

under conditions Т = 70 ºС, Р = 400 bar. The yield of the product (without co-solvent) was 0.6

wt%, it was liquid and it had yellow color. As co-solvent, we used ethanol and then extraction

gives the yellow extract with white precipitate, which was filtered, and filtrate was dried on a

rotary evaporator, after that we added brown oily substance. The end products were sent to the

chromatographic analysis.

We are planning to continue research: making extraction with other co-solvents, analyzing

the products, and comparing the results, and making a general conclusion about the practicability

of the process.

References: 8. New perspectives of non-fuel use of the chemical potential of brown and sub-

standard coals / S. D. Fyzylov, Zh. B. Satpaeva, О. А. Nurkenov, G. Zh. Caripova and other. //

Technical science. – 2016. – № 4. – P. 101-106.

9. Shvets, V. N. Ways to use effectively the economic and industrial potential of the

South Yakut region in the 21st century / V. N. Shvets, G. Yu. Boyarko // Collected scientific

papers on the materials of the Republican Scientific and Practical Conference. T. 2 / Yautsk:

YSU, 2000. - P. 16-22.

10. Arbuzov, S. I. Geochemistry of rare elements in the coals of Central Siberia: a

thesis for the degree of Doctor of Geological and Mineral Sciences / S. I. Arbuzov. - Tomsk,

2005. – 435 p.

11. Soldup, Sh. N. Investigation of coal extraction with various solvents (on the

example of Tuva deposits) / Sh. N. Soldup, G. R. Mongush, V. I. Kotelnikov, B. K. Kara-Sal //

Bulletin of Tuva Institute of Integrated Development of Natural Resources of the SB RAS,

Kyzyl. - 2006. - №. 4. - P. 56-58.

Pisartseva A. 1, Soldatkina O. 1, Akimova T.I. 1, Titova O.K. 2

INVESTIGATION OF INTERACTION ALICYCLIC DIKETON 2- (2-

OXOCYCLOHEXYLMETHYL) CYCLOHEXANONE WITH HYDROGEN PEROXIDE

IN THE SUBACID MEDIUM


[email protected]

It is known that alicyclic 1,5-diketones in the reaction with hydrogen peroxide in the

presence of strong acids give 1,2,4-trioxolanes of type II. [1]. Previously, we examined the

effect of the concentration of hydrochloric acid on the formation of the products of the reaction

of alicyclic diketone 2- (2-oxocyclohexylmethyl) cyclohexanone with hydrogen peroxide in a

medium of diethyl ether. This diketone can exist in two forms: racemic Ia and.meso-form Ic. It

was shown that when a 33, 25, 20, 15% hydrochloric acid catalyst is used, the reaction of the

racemic form of diketone Ia proceeds with a complete change in the configuration of the




62

asymmetric centers in the initial diketone with the formation of a symmetrical form of ozonide

IVb, but when 10% hydrochloric acid is used, an asymmetric ozonide IVa is formed.

Then, we studied the interaction of the racemic form of this diketone Ia with hydrogen

peroxide in the presence of 5% hydrochloric acid. The compound obtained in this reaction

differs from the expected type IVa-b ozonide both in melting temperature (124-126 ° C) and

according to IR spectra. The IR spectrum contains the absorption band of the hydroxyl group at ν

3261 cm-1, carbonyl group at ν 1710 cm-1 and the peroxide fragment –O–O– at ν 926 cm-1. This

means that the obtained compound has a structure different from the ozonide. According to the 1H NMR data, there is a singlet in the at 7.57, which indicates the presence of one hydroperoxide

proton. The NMR13C spectra with the DEPT135 experiment show 13 signals in the resulting

compound. The spectrum contains a signal of the carbon atom connected with two oxygen atoms

at 104.4, the signal of the carbon atom bounded to the carbonyl group at of 213.65, the signals of

two tertiary carbon atoms at 49.2, 38.06. Thus, based on the spectral data, we assume that the

structure of the new compound corresponds to II.

Further studies using orthophosphoric, tartaric and acetic acids as catalysts led to the

same product (II).

Scheme 1. The scheme of the process of formation of reaction products

We can assume following reaction scheme from the obtained information. The diketone

Ia,c joins hydrogen peroxide to one of the carbonyl groups under the acid influence. As a result

of 2- (2-hydroxy-2-hydroperoxycyclohexylmethyl) cyclohexanone II is formed. Such data are

obtained with 5% hydrochloric, orthophosphoric, tartaric and acetic acids. As mentioned above,

compound IVa-b is formed under the action of strong acids, which can be represented as a

further joining of hydrogen peroxide fragment to the second carbonyl group. An intermediate III

is formed as a result. Then there is a cyclization to ozonide IV. The diketone Ia can be subjected

to enolization to form Ib in the presence of acids (Scheme 1). This leads to a change in the

configuration of the initial diketone and makes it possible to obtain both symmetric and

asymmetric ozonide forms based on the racemic form of the initial diketone.

The compound IIc (2- (2-hydroxy-2-hydroperoxycyclohexylmethyl) is formed by the

action of weak and dilute acids on the basis of the unsymmetrical racemic form of 2- (2-

oxocyclohexylmethyl) cyclohexanone Ia. This compound is intermediate in 1,2,4- trioxolanes

IV formation.

References:

1. Pat. 2578609 C1 RU, MPK C07D323/06 Method of obtaining 1,2,4-trioxolanes /

Akimova Т. I., Soldatkina О. А. ; assignee Federal State Autonomous Educational

Institution of Higher Professional Education " Far Eastern Federal University ". -

2014144246/04 ; failed 31.10.2014 ; published 27.03.2016. – 21 p.

http://www.fips.ru/Archive4/PAT/2016FULL/2016.03.27/DOC/RUNWC1/000/000/002/578/609/document.pdf



63

Rudenko A.A. 1, Lim L. A. 1, Yarygin D.V. 1, Titova O.K. 2

RESEARCH OF OIL CAPACITY OF POLYMER SORBENT FROM SECONDARY

POLYETHYLENE


[email protected]

Spills of oil products represent a serious problem that poses a threat to the ecosystem. Now

synthetic sorbents [1], and especially sorbing sheet products from fibrous or polymeric materials

are becoming more popular.

When evaluating the oil sorption of sorbents, researchers use different methods and

procedures for measuring a given value. It raises problems when comparing sorbents among

themselves [2, 3]. Since April 1, 2017, two standards have come into force. They describe the

procedure for measuring and evaluating the oil capacity of various types of sorbents [4, 5].

The purpose of this work was to study the oil capacity of a two-component filled sorbent

product such as a filter cushion. In terms of GOST 33627-2015, the type of sorbent (limiting),

IIIa is an "absorbent material enclosed in a fabric or mesh shell, permeable to petroleum

products and having sufficiently small apertures to keep the sorbing material well" [4]. To fill

the sorbent product, industrial wastes of PE, provided by LLC Stavrolen (Budennovsk), were

used, in the form of a powder with a basic size of 10 to 500 μm. Sheath of non-woven

polypropylene type "spunbond" was 5x5 cm. The mass of the powder in the product was 1, 2, 4

g.

The oil capacity for diesel fuel (DT-3-K5) and industrial oil I-40A for the filter pillows were

determined. Accelerated, prolonged and dynamic tests were done according to the method

described in ISO 33627-2015 [4]. The results are shown in Figures 1 and 2.

Diesel fuel

Industrial oil

Fig. 1. Results of measurements in accelerated tests

Oil capacity of sorbent products decreases with the increasing degree of filling in all cases.

The duration of the test practically does not affect the dependence of the oil capacity on the

degree of filling for diesel fuel. For engine oil, the deviation from linearity is more significant

and the slope of the straight line depends more on the type of test. Consequently, the use of high

degrees of filling for a given type of sorbing products is inexpedient, while products of this type

are characterized by rapid absorption of oil.




64

Diesel fuel

Industrial oil

Fig. 2. Results of measurements in long-term tests

The tests described above "make it possible to obtain idealized laboratory results that can be

used to compare adsorbents by their adsorption capacity to petroleum products" [4]. Under the

actual conditions of use, the adsorbent will not contact the oil product layer, which will allow it

to saturate quickly and completely. The dynamic tests proposed in [4] theoretically make it

possible to evaluate the behavior of the adsorbent in the water-oil product system, but the

estimate is qualitative rather than quantitative. Despite the excellent test results for the

adsorption of petroleum products (the adsorbent is on the water surface, completely absorbs the

spilled oil), this test is not indicative, because the test procedure provides for the use of a fixed

volume of oil product - 3 cm3. In our case, even a filter cushion with a minimum filling absorbs

this volume completely.

Thus, in this paper sorption products of the "filter cushion" type from PE waste of LLC

"Stavrolen" were obtained, their oil capacity under dynamic and static conditions was

determined in accordance with GOST 33627-2015 [4], the dependence of the oil capacity on the

degree of filling of the sorbent product was established.

References:

1. Sirotkina, EE Materials for adsorption water purification from oil and oil products

/ EE Sirotkina, LL Novoselova // Chemistry for Sustainable Development. - 2005. - Т.13, Вып.

3. - P. 359-377.

2. Standardization of Oil Sorbent Performance Testing / A. Bazargan, J. Tan, G.

McKay // Journal of Testing and Evaluation. – 2015. – Vol.43, N.6 – p. 18-36.

3. The problem of regulatory regulation of the choice of the method for determining

the oil sorption capacity / DV Yarygin, AA Rudenko, VP Dorozhkin, Yu. V. Gulaya, AA

Dvornicin, GV Cherevatyuk, L. A Lim // // The young scientist «Actual problems of chemical

and resource-saving technologies». - 2017. - 2.1. - P. 50-53.

4. GOST 33627-2015 Activated carbon. Standard method for determining sorption

characteristics of adsorbents. - Enter. 04/01/2017. - Moscow: Standartinform, 2016. - 15 p.

5. GOST 33622-2015 Activated carbon. Standard method for determining sorption

characteristics of absorbents. - Enter. 04/01/2017. - Moscow: Standartinform, 2016. - 12 p.



65

Rymina A. A1., Kapustina A.A.1, Kravchenko E.V.2

MECHANOCHEMICAL SYNTHESIS OF POLYTINPHENYLSYLOXANES

1Far Eastern Federal University, School of Natural Sciences, Vladivostok, Russia 2 Far Eastern Federal University, Oriental Institute - School of Regional and International Studies

[email protected]

In this paper, we study interaction of a polyphenylsiloxane with tin oxides (II) and (IV)

[1] and bisacetylacetonate tin dichloride in the conditions of mechanochemical activation. The

synthesis was conducted in a planetary monomill of "Pulverisette 6" with a frequency of 600

revolutions per minute and time of activation 3 minutes. The ratio of mass of a nozzle to a lot of

the useful loading in all syntheses was made by 1,8.

The obtained connections were studied by methods of X-ray phase analysis, IR-

spectroscopy, elemental analysis.

The synthesis of polyphenylsiloxane and hydrated tin (II) oxide (synthesis 1) was carried

out at the initial Si / Sn ratio of 2: 3.

Reaction scheme:

x(C6H5SiO1.5)n + nSnO*2.7H2O → [(C6H5SiO1.5)xSnO]n + 2.7H2O

After activation the reaction mixture turned a white-gray powder. After separation of the

mixture in a Soxhlet device the soluble fraction turned a pale yellow glassy substance, the

insoluble one turned a gray powdery substance. The soluble fraction is a high molecular

compound of the composition: [(C6H5SiO1.5) 14.9SnO*2.6CHCl3]n (it is found/is calculated, %:

With 46.8/46.5; Si 17.6/17.6; Sn 5.0/5.0).

The interaction of polyphenylsiloxane and tin (IV) oxide (synthesis 2) was carried out at

the initial Si / Sn ratio of 1: 1.

Reaction scheme:

x(C6H5SiO1.5)n + nSnO2 → [(C6H5SiO1.5)xSnO2]n

The reaction mixture obtained after activation turned a gray powder. After separation a

soluble fraction with a mass fraction of 27.9% was obtained in the Soxhlet device. The insoluble

fraction is the unreacted tin (IV) oxide.

The high molecular fraction is a polytinphenysiloxane having the following composition:

[(C6H5SiO1.5) 25.5SnO2 * 1.8CHCl3]n (found / calculated,%: Si 19.3 / 19.5; Sn 3.2 / 3.2).

According to the data of X-ray phase analysis soluble fractions of synthesis 1 and 2

represent high-molecular amorphous compound. Interplanar and interchain distances in

comparison with an initial polyphenylsiloxane (d1=12.4863 Ǻ, d2=4.5456 Ǻ) decrease in

products of synthesis 1 to d1=11.7591 Ǻ, d2=4.4204 Ǻ; in products of synthesis 2 to

d1=12.15298 Ǻ, d2=4.51029 Ǻ that can demonstrate a complication of polytinphenylsiloxane

structure.

On the basis of elemental analysis, IR-spectroscopy and X-ray phase analysis it is

possible to draw a conclusion that the received soluble fractions represent polytinphenylsiloxane

with Si/Sn ratio different from a set.

The synthesis of polyphenylsiloxane and bisacetylacetonate of tin dichloride (

synthesis 3) was carried out at the initial Si / Sn ratio of 1: 1.

The resulting reaction mixture was a brown powder. Three fractions were obtained by

fractional precipitation.

Fraction 1, studied on X-ray phase analysis, IR spectroscopy and elemental analysis, is a

mixture consisting of tin oxide, polyphenylsiloxane, silicon oxide.




66

Fraction 2 is a high molecular compound with the following elemental bond:

Si O SnO

Cl

AcAc

AcAc

O Si

Cl

Fraction 3, according to X-ray diffraction analysis, is a crystalline material with a melting

point of 203-204 ° C. According to elemental analysis and IR spectroscopy, the following

structural formula can be assumed:

Si OO SnSn

AcAc

AcAc AcAc

AcAc

ClCl

Cl

Ph

As a result of the work done, the possibility of synthesizing polytinphenylsiloxanes by

mechanochemical activation was demonstrated. It has been found that the best penetration of tin

in the composition of polyphenylsiloxane occur when bisacetylacetonate of tin dichloride is

used. A crystalline compound was obtained by mechanochemical activation.

References:

1. Kapustina, A.A. Mechanochemical synthesis of poly (germanium and tin

organosiloxanes) / A.A. Kapustina, N.P. Shapkin // Russian Journal of General Chemistry -

Volume 75.- № 4.- 2005. - P. 571-574.

Samus’ M.1, Krasitskaya S.G.1, Kolycheva V.B.2

INVESTIGATION OF PHYSICAL CHEMICAL CHARACTERISTICS AND

SORPTION PROPERTIES OF POLYALUMINOPHENYLSILOXANE BASED

FUNCTIONAL MATERIALS


[email protected]

Synthetic sorbents have several advantages over natural sorbents due to the fact that it is

possible to control their structure and properties by setting certain conditions at synthesis of

sorbents.

Scientists carrying out researches in this area pay special attention to synthetic oxides with

the composition and structure forecasted in advance. The properties of the final material are

defined and clearly regulated at the process of synthesis.

This is achieved through the use of various matrices enabling to obtain materials with the

predetermined set of characteristics and active properties [1-3].

The purpose of our study was to obtain synthetic sorbents by applying a new and earlier

unknown method of treatment with an alkaline solution in which the part of a matrix is assigned

to elementorganic polymer. The siloxane is matrix providing the control of sorbent porous

structure at the moment of its synthesis.

Synthetic sorbents were produced by partly splitting of siloxane bond of poly-aluminum-

phenyl-siloxane (AlPS) (Si/Al = 3) with sodium hydroxide solution of preset concentration. In

this case, alumino-phenylsiloxane is used as a matrix and provides the control of sorbent porous

structure during its synthesis. We have investigated the dependence of obtained sorbents

properties from the concentration of NaOH in the solution.




67

During the syntheses №1-3 poly-aluminum-phenyl-siloxane was treated with NaOH solute

ion (the molar ratio Si/Na = 1/3, 1/4, 1/6, 1/9) respectively in the heterogeneous system of

toluene-water at 90◦С for 30 hours with constant stirring. The formation of insoluble white

precipitate on the boundary of phases was observed. The separated precipitate was an amorphous

substance, insoluble in organic solvents and water.

FTIR spectra of obtained products are similar to each other and are different from FTIR

spectrum of alumino-phenylsiloxane. They contain all absorption bands, characteristic of the

metallo-phenylsiloxane, but there is a noticeable splitting of absorption area, corresponding to

the vibration of the siloxane bond: there is a bright peak of linear fragment 1131 cm-1 and a

spread widening at the 1020-1080cm-1, indicating the emergence of diverse cyclical structures

which are absent in the FTIR spectrum of initial poly-aluminum-phenyl-siloxane.

The study of XRD (X-ray diffraction analysis) patterns of obtained products shows that all

end-products (1-3) are amorphous, and there are no crystalline inclusions. The comparison of

spectrum of XRD patterns of AlPS and spectra of products (1-3) shows a perceptible increase of

the interplanar and interchain distances in the structures of samples: in all XRD spectra patterns

of products (1-3) there is a noticeable offset gallo responsible for interchain distance towards

larger values (d1), which increases with the increase of the alkali concentration.

The sorption activity of obtained products was studied by the procedure provided by the

Federal standard 4453-74 [4]. The pre-dried previously to constant mass quantity of substance of

specimen were placed in a conical flask with a capacity of 100 cm3, added 25 cm3 solution of

methylene blue and shaken for 20 min. After shaking the suspension was filtrated through the

filter of "Blue Ribbon", the filtrate was diluted with distilled water at 10 times.

Optical density was measured by spectrophotometer UNICO-1201 (United Products and

Instruments, Inc., United States), using a filter with the wavelength (λ) 400 nm in cells with a

thickness of absorbing light layer 10 mm (Fig 1).

Fig 1. Sorption activity of samples

The determination of sorption activity of obtained products for methylene blue showed that

their sorption activity increases with the increase of alkali concentration.

This work was supported by a grant from The Ministry of Education and Science of the

RUSSIAN FEDERATION, Project № 4.8063.2017/8.9

References

1. E.K. Papynov, A.S. Portnyagin, A.I. Cherednichenko, I.A. Tkachenko, E.B. Modin, V.Y.

Maiorov, A.N. Dran’kov, T.A. Sokol’nitskaya, K.A. Kydralieva, S.Z. Zhorobekova, V.A.

Avramenko, Uranium sorption on reduced porous iron oxides, Doklady Physical

Chemistry, Issue 1, 1 May 2016 67-71

2. A.N. Dran’kov, E.K. Papynov, A.S. Portnyagin, AV Perfil'ev, V.A. Avramenko,

Synthesis of hydrophobic oil sorbent based on silane-siloxane microemulsion, Proc.

dokaldov XX Mendeleev Congress on General and Applied Chemistry, Volume 4 2016

59.



68

3. Yicheng Zhang, Kake Zhu, Xinggui Zhou and Weikang Yuan, Synthesis of

hierarchically porous ZSM-5 zeolites by steam-assisted crystallization of dry gels

silanized with short-chain organosilanes, New journal chemistry 38 (2014) 5808-5816.

4. GOST 4453-74. Coal lightening active charcoal powder, to 1999.24.

Smirnova M.G1, Sokolova L.I. 1, Shapkin N.P. 1, Kolycheva V.B. 2

APPLICATION OF SORBENTS BASED ON NATURAL ALUMINOSILICATES FOR

CONCENTRATING OF CEPHALOSPORIN ANTIBIOTICS IN THE CONDITIONS OF

THE DYNAMIC SORPTION


[email protected]

Antibiotics of cephalosporin series represent an important group of drugs that are widely

used in clinical practice, because they have a significant bactericidal effect, a wide therapeutic

range and low toxicity [1]. Analytical determination of antibiotics is difficult due to its low

content in the object under study or joint use with other drugs. The use of sorbents based on

natural aluminosilicates for concentrating of cephalosporin antibiotics from biological objects

makes possible to increase its content in the analyzed extracts, to release them from the matrix

components and, consequently, to reduce the detection limit of medicinal products in the object

[2].

The purpose of this work is to research the possibility of using sorbents based on natural

aluminosilicates for the sorption of cephalosporin-type antibiotics in a dynamic regime from

biological fluids and dilute solutions. Vermiculite of the Koksharovskoye deposit (Primorsky

krai), kaolinite of the Sukholozhsky deposit (Sverdlovsk region) and montmorillonite clay mined

on the Russkoye island (Primorsky krai) were selected as the research objects.

The sorption of a standard solution of cefazolin with an antibiotic content of 0.05 mg/ml

was studied under dynamic conditions from dilute solutions at sorbate-sorbent ratio of 5:1 and a

column diameter of 10 mm. The results of the study are presented in the table below.

Table

The degree of absorption and the degree of elution of cefazolin from natural aluminosilicates

under dynamic conditions at atmospheric pressure

Ma

ss of

sorbent,

mg

Heig

ht of

sorbent

in the

column,

mm

Sorbent

Time

for the

complete

eluating of

an

antibiotic,

min

Flo

w rate,

ml/min.

Attenuati

on range (Rs),

%

Extent of

eluating (Re),

%

100

0

19 Kaolinite

burned 53

0.1

5

31.18±32

.28 >99.00

18 Unburned

kaolinite 40

0.2

0

20.02±18

.07 >99.00

21

Montmorillon

ite clay modified

with chitosan

29 0.2

8

41.58±17

.95

84.64±30

.83

17

Burned

montmorillonite

clay

30 0.3

8

55.70±7.

10

77.86±17

.34



69

52

Vermiculite

modified by

polyethylene

48 0.2

3

77.52±7.

79

90.73±37

.97

200 9 Vermiculite

modified by acid 100

0.0

4

88.55±9.

25

26.45±6.

91

It is shown that the maximum degree of absorption antibiotic is achieved using a sorbent

based on vermiculite modified acid, but significant elution (more than 50%) is not observed. The

most effective for concentration of cefazolin is a sorbent based on vermiculite modified with

polyethylene, the use of this sorbent leads to a high degree of absorption (more than 77%) and a

degree of elution (more than 90%).

Research of cefazolin sorption from biological fluids under conditions of dynamic

sorption was made. The lack of efficiency of antibiotic extraction from blood plasma with the

use of sorbents based on natural aluminosilicates was shown.

Sorption characteristics of burned kaolinite under dynamic conditions using the example

of ceftriaxone sodium using standard solutions with an antibiotic content of 0.1 mg/ml, 0.05

mg/ml, 0.02 mg/ml, 0.01 mg/ml were studied. The degree of absorption of ceftriaxone for the

above-mentioned drug contents was calculated, it was 19%, 17%, 16%, 10%, respectively. It is

shown that the most reproducible results (Δ±8%) for the degree of absorption are observed when

a standard solution with a content of ceftriaxone of 0.05 mg/ml is used. The degree of elution of

the drug was calculated, it was more than 99% with multiple elution of the antibiotic. A sorption

of a standard solution with a content of ceftriaxone of 0.05 mg/ml was carried out. The

maximum degree of absorption was 54%. The value of the total exchange dynamic capacity was

calculated, it was 0.39 mmol-e/g. The elution degree of ceftriaxone reaches more than 99% with

repeated elution of the preparation.

Thus, vermiculite modified with polyethylene can be used for concentrating

cephalosporin antibiotics from dilute solutions under conditions of dynamic sorption.

References:

1. Kukes, V.G. Clinical pharmacology: textbook for high schools: ed. 3rd revision and

additional. / V.G. Kukes. - Moscow: GEOTAR-Media, 2006. – 944 p.

2. Chuchalina, I.V. Concentrating of cephalosporin antibiotics on natural sorbents / I.V.

Chuchalina, L.I Sokolova, L.A. Zemnukhova // Electronic scientific journal

"INVESTIGATED IN RUSSIA" [Electronic resource]. - 2006. - P. 1842-1851.

Khmelevskaia E.A.1, Pelageev D.N.2, Kravchenko E.V.3

SYNTHESIS OF 1,4-NAPHTOQUINONE-CARBOHYDRATE CONJUGATES OF

NON-GLYCOSIDE NATURE

1Far Eastern Federal University, School of Natural Sciences 2G.B. Elyakova Pacific Institute of Bioorganic Chemistry, Far Eastern Branch of the Russian Academy of

Sciences 3Far Eastern Federal University, Oriental Institute - School of Regional and International Studies

[email protected]

Lately, the idea of conjugating molecules of antitumor drugs with carbohydrate

molecules to increase their selectivity with respect to tumor cells has attracted more attention.

This idea is based on the so-called Warburg effect [1]. This effect describes and explains the

ability of tumor cells and tissues to consume more glucose than normal non-tumorous cells.

Monosaccharide conjugates of antitumor drugs are the most suitable derivatives for the

development of drugs whose target process is the Warburg effect since they have high water

solubility and stability in human serum [2].

Previously, it was shown that naphthoquinone derivatives had a wide spectrum of

biological activity. So, for example, doxorubicin, mitomycin, mitoxantrone and other




70

compounds containing quinone fragments in their structure are used to treat some types of tumor

diseases [3].

To obtain the target compounds a substitution reaction of halogen atoms in halogenated

naphthoquinone 1 derivatives per sulfur atom was performed by 1,2,3,4-tetraacetyl-6-

thioglucose 2. As a result of this reaction with good yields (70-90%), products 3 were obtained

in which one or more halogen atoms were replaced by a glucose residue (Figure 1, 2).

Figure 1 - Preparation of acetylated conjugates 3

Figure 2 - Diagram of preparation of disubstituted conjugate 4g

Conjugates 3 obtained in the first stage were disacylated by sodium methoxide in

methanol (Figure 3).

Figure 3 - Disacitylation of conjugates 3

In this paper, a number of new types of quinone-carbohydrate conjugates have been

synthesized in which the fragments of naphthoquinone and carbohydrate are linked by a non-

glycosidic linkage through the sulfur atom at position 6 of glucose (Figure 3).

References:

1. On the origin of cancer cells /Warburg O// Science. -1956. -№123. - P. 309-314.

2. Glucose conjugation for the specific targeting and treatment of cancer /Calvaresi EC and

Hergenrother PJ// Chemical Science. -2013. -№4(6). - P. 2319-2333.



71

3. Anti-cancer activities of 1,4-naphthoquinones: a QSAR study//Anticancer Agents in

Medicinal Chemistry. -2006. -№6(5). - P. 489-499.

Cherevatiuk G.V.1, Lim L.A.1, Khrebtov A.A.1, Kravchenko E.V.2

INTERACTION OF POLYSTYRENE AND DICHLOROETHANE IN

FRIEDEL-CRAFTS REACTION

1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute - School of Regional and International Studies

[email protected]

Hypercrosslinked gels are obtained by forming a large number of crosslinks between

macromolecules swollen in a good solvent. This type of gel has a specific porous structure and a

significant internal stress in the dry state. Hypercrosslinked polymeric networks which have a

high degree of crosslinking can swell in any solutions and, therefore, absorb almost any

substances. This is the reason why they are widely used in refining water, separating mixtures of

the simplest mineral electrolytes, in the analyzing organic compounds and as a matrix for

nanocomposites. The density of polymer networks crosslinking depends on the chemical

structure of the initial polymer chains and on the synthesis conditions which open wide range of

possibilities to further investigation and application of products [1, 2].

Earlier [3] hypercrosslinked polystyrenes were obtained by the radical copolymerization of

monomers styrene and divinylbenzene while there is an obvious way for obtaining crosslinked

bridges by using the Friedel-Crafts reaction during interaction with dichloro-derivative. The

interaction of polystyrene (PS) with applying dichloroethane as a solvent and a crosslinking

agent at the same time under the effect of the Lewis acid (m (AlCl3) = 0.1 g) was carried out at

room temperature. After changing the color of the solution and increasing its viscosity the

reaction mass was washed several times with water to remove aluminum chloride, the organic

layer was kept above sodium sulfate and the solvent was slightly evaporated. Then the resulting

product was precipitated by using n-Hexane. The conditions of the reaction are shown in the

table. The weight-average molecular mass of the initial PS was 199,000 and the relative intensity

of the absorption band at 3025 cm-1 in the IR-spectrum was 2.25. The products of the reaction

were soluble in dichloroethane in all the experiments except the 3d one.

Synthesis conditions and product characteristics Number of

experiment Weight PS, g Reaction time,

min

Polymer yield, g Weight-

average

molecular

mass

Intensity of

the

absorption

band at 3025 см-1

1 1 20 1.2424 16000 2.98

2 2 20 1.2396 21100 2.97

3 4 14 4.6500 386100 -

4 2 60 0.8078 78365 2.29

5 1 60 0.6548 29200 2.27

The reaction of PS interaction with dichloroethane in the presence of aluminum chloride can

lead to the formation of three products: chlorinated derivative of linear PS, crosslinked

macromolecules of PS and low molecular weight residues from the destruction of linear

polystyrene. A decrease of molecular mass may indicate destructive processes in experiments 1,

2, 4 and 5. A smaller decrease in the molecular mass and a lower intensity of the absorption band

http://www.multitran.ru/c/m.exe?t=3257944_1_2&s1=%D4%F0%E8%E4%E5%EB%FF-%CA%F0%E0%F4%F2%F1%E0




72

at 3025 cm-1 may indicate partial destruction and substitution with the formation of chlorinated

derivative in experiments 4 and 5.

Summarizing the series of our experimental results we can assume that the increase of PS

concentration in solution leads to crosslinking; the increase of reaction time can probably lead to

the production of substituted products but it is accompanied by destructive processes.

References:

1. Davankov, V.A. Structure and properties of properties of hypercrosslinked polysterene –

the first representative of new class of polymer networks / V.A. Davankov,

M.P.Tsyurupa // Reactive Polym. – 1990. – N 13. – P. 27-43.

2. Сверхшитый полистирол – первый нанопористый полимерный материал / М.П.

Цюрупа, З.К. Блинникова, Н.А. Проскурина, А.В. Пастухов, Л.А. Павлова, В.А.

Даванков // Российские нанотехнологии. – 2009. – № 9-10. – С. 109-117.

3. Цюрупа, М.П. Сверхсшитый полистирол – новый тип полимерных сеток : дис …

д-ра хим. наук / М.П. Цюрупа. – М, 1985. – 427 с.

Chernova A.V., Reutov V.A., Kravchenko E.V. 2

GAS – LIQUID CROMATOGRAPHY

1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University Oriental Institute - School of Regional and International Studies

[email protected]

In this paper, we describe a gas–liquid-chromatography which permits separation and

identification on the same chromatogram of a wide range of substances. This procedure uses

hydrogen flame method, which detects organic compounds whether free or conjugated with no

requirement for specific reactive groups. We use gas-liquid chromatography for separation based

on the variance in free energy of transfer for solutes. Gas-liquid chromatography separates

solutes based on their different interactions between mobile and stationary phases. Solute’s

retention is controlled by its interaction with the stationary phase.

The results can be applied to aid the selection of suitable stationary phases for separation

of gases or alkane isomères using gas-liquid chromatography. Structural analysis can provide

additional insight into the mechanism of separation. Moreover, the retention indices can serve as

a rigorous validation for the force field used in this study.

The method is applicable to: fatty acids above butyric acid; di - et tri-carboxylic acids;

hydroxy acids and keto acids; polyhydroxy and alicyclic compounds such as glycerol, inositol,

quinic acid, shikimic acid ascorbic acid and sugar alcohols; aromatic hydroxy and acidic

compounds, both benzenoid and indolic; sesquiterpenes; steroids; glycine conjugates;

mercapturic acids.

The nature of derivatives was confirmed by combining gas chromatography with mass

spectrometry. Combined gas chromatography–mass spectrometry gives a diagnostic tool of great

power in the evaluation of metabolic patterns, and various uses are discussed. Carrier gas: the

main purpose of this gas in GC is to move the solutes along the column, mobile phase is often

referred to as carrier gas (must be inert). Common carrier gas: He, Ar, H2, N2. Carrier Gas or

mobile phase does not affect solute retention but does affect: desired efficiency for the gas-liquid

chromatography system, stability of column and solutes and response of the detector.

References:

1. Daniel C. 24. Gas Chromatography / C. Daniel, L. Robert — Freeman and Company,

1999 —P. 675–712.




73

2. Higson, S. Analytical Chemistry / S. Higson, Warring, P – OXFORD University Press,

2004. – 52 p.

3. Kevin A. Vacuum Ultraviolet Detector for Gas Chromatography". Analytical Chemistry

/ A. Kevin, D. Xing // American Analytical Chemistry. – 2010. – P. 23-35.

4. Eugene F. Modern Practice of Gas Chromatography/ F. Eugene F., I. Phillips // John

Wiley & Sons. – 2004. – Book 4. –P. 44-46.

5. Dauenhauer P. Quantitative carbon detector (QCD) for calibration-free, high-resolution

characterization of complex mixtures / P. Dauenhauer, P. Warring. – Lab Chip. – 2015.

– Book 2. –P. 440-447.

Shirokovskaya D.A.1, Reutov V.A.1, Kravchenko E.V.2

MODERN TECHNOLOGIES OF POLYPROPYLENE'S PRODUCTION

1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University Oriental Institute - School of Regional and International Studies

[email protected]

Polypropylene is a crystal product of propylene's polymerization which creates an image of

the modern world. Volume of its production ranked second after polyethylene [1].

Polypropylene's application is limited only by low frost resistance and combustibility.

Despite the popularity of this material the most tutorials have outdated technology of

suspension polymerization which is not used today. The main goal of this research is searching

for modern polymerization technologies and catalytic systems.

The literature analysis shows that it is possible to divide technological processes into 3

different ways: suspension polymerization (for example, Montedision, the licensor –

Montecatini), liquid-phase (for example, Spheripol, the licensor – Lyondell Basell) and gas-

phase (such as Unipol, the licensor – Dow Chemical).

The basic characteristics of modern technologies of polymerization are presented in table 1.

Table 1

Main modern technologies of polypropylene's polymerization [2]

Process

(licensor)

Type of

polymerization t, °С P, MPа Process description

Montedision

(Montecatini) Suspension 50-80 0.7-2.8

Polymer precipitates to form a

slurry, largely replaced by bulk and

gas phase processes.

Spheripol

(Lyondell Basell) Liquid-phase 70-90 1.4-2.8

Polymer precipitates in propylene

to form a suspension.

Unipol

(Dow Chemical) Gas-phase 60-80 1.4-4.2

Granular polymer formed in gas

phase fluidized bed, horizontal

stripped bed or vertical stripped

bed.

Sheripol technology is the most common type for production of polypropylene in the world

– over one third of the output is produced by this technology [2]. The advantages of this process




74

are high efficiency, stereospecificity and high quality of output. It leads to savings of up to 40 %

of investment compared to inefficient suspension process [3].

The gas-phase processes are the most advanced now. They were invented in 1970s. Unipol

process (Dow Chemical) is the most popular among all gas-phase processes. It allows to reduce

costs by 35 % compared to other technologies due to the significant time reduction and design

features [3].

Start of polypropylene's production is associated with the discovery of special Ziegler-Natta

catalytic system in 1953. It was complex compound of titanium (III) chloride and

diethylaluminum chloride originally.

Almost at the same time, the US Phillips Petroleum company patented catalysts based on

metal oxides, namely, chrome oxides. Now they are used only in this case when it is necessary to

obtain polypropylene with special properties.

Modern catalyst systems are metallocene and postmetallocene. Metallocene catalysts were

invented in the 1990s. They were to exceed the efficiency of Ziegler-Natta catalysts by 10 times

[4]. But nowadays the interest to these catalysts is decreasing because they are not efficient, they

are difficult to use and have extremely high price [5].

In view of metallocene catalyst’s disadvantages scientists develop new catalytic systems that

combine high stereospecificity of metallocene catalysts, high performance and low cost of

Ziegler-Natta catalytic system. Postmetallocene catalysts are still under research and don’t have

high performance [6].

To sum up, the technology of polypropylene's production has had great changes from the

opening of Montecatini factory to nowadays. Mankind has moved from a low eco-friendly

suspension polymerization in the medium of hydrocarbon solvents to new high-speed processes

in liquid and gas sector. Spheripol technology by Lyondell Basell company accounts for about

one third of global polypropylene production.

The development of technology led to improvement catalytic systems as well. However, the

most popular are titanium-magnesium catalysts – one of Ziegler-Natta catalysts generations. The

increased interest to metallocene catalysts is weakening every year due to unprofitability of their

application. Now scientists are increasingly moving away from the developments in this area and

pay attention to the conjugate of transition metals.

References:

1. Tripathi, D. Practical Guide to Polypropylene / D. Tripathi. – Rapra Technology Limited,

2002. – 106 p.

2. Malpass, D. B. Introduction to Industrial Polypropylene: Properties, Catalysts, Processes

/ D. B. Malpass, E. I. Elliot. – Scrivener Publishing LLC, 2012. – 346 p.

3. Propylene [Electronic resource] / Encyclopedia of technology. – Access mode :

http://enciklopediya-tehniki.ru/tehnologiya-dobychi-gaza-i-nefti/polipropilen.html, free.

– Title of screen.

4. Ponomareva, V. T. Polymers for metallocene catalysts / V. T. Ponomarev, N. N.

Likhacheva // Plastics.– 2001. – № 4. – P. 8-11.

5. Guseva, L. Metallocene polymers: the limit of development? / L. Guseva // Plastics. –

2015. – № 5. – P. 12-15.

6. Brylyakov K. P. Post-metallocene polymerization catalysts of olefins / Brylyakov K. P. //

Advances in chemistry.– 2007. – № 76. – P. 279-303.



75

Yarygin D.V.1, Rudenko A.A.1, Lim L.A.1, Kravchenko E.V.2

THE STUDY OF THE PROPERTIES OF POLYETHYLENE FIBER SORBENT

1Far Eastern Federal University, School of Natural Sciences 2Far Eastern Federal University, Oriental Institute - School of Regional and International Studies

[email protected]

The use of sorbents is one of the main methods of oil spill elimination. Recently, more and

more attention has been paid to polymeric sorbents. They have a high oil capacity, as well as a

number of advantages over natural ones: such sorbents retain buoyancy during long-term stay in

water, they are hydrophobic, oleophilic. For fibrous polymeric sorbents there is the possibility of

multiple regeneration. The object of our research is a sorbent obtained from polyethylene (PE)

films.

Fibrous oil sorbents were obtained from HDPE films with a thickness of 5.18, 10.80 and

18.50 μm (samples 1, 2 and 3).

Further, the oil capacity of the samples was measured in a pure petroleum product (PP), as

well as the test on a joint water sorption and PP was conducted. Winter diesel fuel (DF) and

engine oil ROSNEFT Optimum SQ / CD SAE 15W-40 (EO) were used as PP. The oil capacity

was measured by soaking 1.00 g of the sorbent in the pure PP / water with a layer of PP and by

measuring the mass of the sorbent hanged on a wire for 20 min with an interval of 1 min. The oil

capacity was calculated as the difference between the current and initial masses of the sorbent to

a mass unit. Similarly, for some samples the water adsorption was measured.

As expected, the sorption capacity decreases with a thickness increasing, but there is no

single-valued dependence of the oil capacity on the surface area. So for EO the oil capacity

referred to the surface area was close between the samples (73.3, 70.1 and 83.5 g / m2 for

samples 1, 2 and 3) but for DF such a result was not obtained.

Despite the hydrophobicity of PE, the amount of water remaining on the sorbent in tests

without PP is comparable to the amount of DT in the tests with a pure PP and in some cases the

amount of water exceeds it. Due to the hydrophobicity of PE, PP covers the surface of the

sorbent while water is in the form of droplets. As a result, PP can flow between the cells formed

by the fibers and eventually leave the volume of the sorbent. Water droplets can't move freely

around the volume of the sorbent, so the loss of liquid over 20 minutes of dripping is much less.

When comparing results of measurement in pure PP and in water with PP, it was possible to see

that the value of the sorption capacity increased. The mass of the retained liquid in the joint

sorption tests for samples 1 and 2 with DF exceeds the sum of the masses of PP and water in

separate tests (Figure 1), in the diagram "Sample 1 - EO" of the line PP + Water (joint sorption)

coincide with the line (1) + (2). Based upon the level of liquids in the beaker before and after the

sorbent test it is possible to point out that minimum 80% of the sorbed liquid in joint sorption is

PP. These facts indicate that in the joint sorption test the amount of collected PP increases

especially for low-viscosity DF. We suppose that this occurs because water droplets impede the

free movement of hydrophobic PP through the sorbent volume and prevent dripping from it. This

fact increases cell stability and allows the sorbent to retain a larger amount of PP. Also, during

the joint sorption test it was noticed that at the moment when the sample was being raised from

the beaker all the EO was accumulated on the sorbent, but the water-oil emulsion started to drain

back immediately because at that time the sorption capacity was much higher than the

equilibrium capacity. Thus, having the right amount of sorbent it is possible to collect efficiently

the PP or the emulsion of PP in water from the water surface.



76

Fig. 1. PP and water retention profiles in various tests