the 4th annual student scientific conference in english
TRANSCRIPT
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
Far Eastern Federal University
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
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© FEFU, 2017
T44
THE 4th ANNUAL STUDENT SCIENTIFIC CONFERENCE IN ENGLISH
Vladivostok, 03–15 May 2017
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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
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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
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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
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
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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.
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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
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.
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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.
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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
3Far Eastern Federal University, Oriental Institute-School of Regional and International Studies
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.
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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)
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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
3Far Eastern Federal University, Oriental Institute-School of Regional and International Studies
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
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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
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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
1Far Eastern Federal University, School of Natural Sciences 2Far Eastern Federal University, Oriental Institute-School of Regional and International Studies
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.
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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%
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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,
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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
1Far Eastern Federal University, School of Natural Sciences 2Far Eastern Federal University, Oriental Institute-School of Regional and International Studies
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
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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.
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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.
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THE CONTEST OF SCIENTIFIC REPORTS
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
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.
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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
1Far Eastern Federal University, School of Natural Sciences 2Far Eastern Federal University, Oriental Institute-School of Regional and International Studies
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:
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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
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
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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):
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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
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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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.
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Kalashnikov P.V., Gorodetskaya E.Ya.
OPTIMAL FUNDING OF PENSION SCHEMES AS A TASK OF DYNAMIC CONTROL
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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Krasitskaya A.I.1, Stepanova A.A.1, Gorodetskaya Ye.Ya.2
COMPLETE CLASSES OF DIVISIBLE S-ACTS
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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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
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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
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1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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
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1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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
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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 immu- nity 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
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
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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:
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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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:
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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
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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
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THE CONTEST OF SCIENTIFIC REPORTS
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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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
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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].
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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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].
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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
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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)
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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
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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
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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.
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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
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).
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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
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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
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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.
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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:
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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
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).
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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.
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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:
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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
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
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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.
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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
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
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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
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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
1Far Eastern Federal University, School of Natural Sciences, Vladivostok, Russia 2Far Eastern Federal University, Oriental Institute - School of Regional and International Studies
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
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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.
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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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.
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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
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.
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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
1Far Eastern Federal University, School of Natural Sciences 2 Far Eastern Federal University, Oriental Institute School of Regional and International Studies
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.
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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.
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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
1Far Eastern Federal University, School of Natural Sciences, Vladivostok, Russia 2Far Eastern Federal University, Oriental Institute - School of Regional and International Studies
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
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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
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
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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.
THE 4th ANNUAL STUDENT SCIENTIFIC CONFERENCE IN ENGLISH
Vladivostok, 03–15 May 2017
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
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
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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
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.
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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
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
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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.
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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
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.