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Chemistry for Sustainable Development

2016 year, number 6

Protatranes as Effective Biostimulators for Agriculture, Biotechnology, and Microbiology

Favorsky Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk, Russia
Keywords: протатраны, 2-гидроксиэтиламины, арилхалькогенилуксусные кислоты, биостимуляторы, protatranes, 2-hydroxyethyl amines, arylchalcogenylacetic acids, biostimulators

Abstract >>
A series of water soluble, nontoxic, available in the production of salts and ion liquids that are protatranes and their analogs of the formula ArХCH2COO- .НN+R1R2CH2CH2OH, where Ar = aryl, indolyl; X = O, S, SO2, Se; R1, R2 = H, Me, CH2CH2OH, etc. were synthesized by the reaction of biogenic hydroxyethyl amines with biologically active arylchalcogenylacetic acids. Earlier, their high and diverse pharmacological activities (immunotropic, antitumor, antimetastatic, antithrombotic, adaptogenic, etc .) were detected. Additionally, protatranes in low (nano) concentrations (to 1 ∙ 10-10 mass %) turned out to be powerful biostimulators of various biological processes. This review discusses the study results of the stimulatory action of protatranes on animals, plants, fungi, bacteria, cells, enzymes. It was shown that the application of protatranes in agriculture enhanced the productivity of plant cultivation, sericulture, aviculture, animal husbandry, fish breeding, as well as the production of fertilizers from wastes (lignin). The use of protatranes in biotechnology contributes to an increase in the rate and the selectivity of processes, as well to the production yield, is important for creating new economic methods of the preparation of malt, bakery yeast, fodder and dietary protein, citric acid, bioethanol, lactic Bifidumbacterin, ginseng biomass, stem cells, etc . Stimulators were found for microbiology, and nutrient media for the growth of staphylococcal and other bacteria that allow repeatedly speeding up the analysis and diagnostics of socially significant diseases and, consequently, timely prescribing adequate treatment were elaborated.

Synthetic Fibres with Coatings from Poorly Soluble Copper and Zinc Compounds and Their Bactericidal Properties

1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
2Vektor-Vita Ltd, Koltsovo, Novosibirsk Region, Russia
3Institute of Cytology and Genetics, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: синтетические волокна, катионообменные волокна, малорастворимые соединения меди и цинка, покрытия, антимикробные свойства, synthetic fibres, cation exchange fibres, slightly soluble copper and zinc compounds, coatings, antimicrobial properties

Abstract >>
The application possibility of the earlier elaborated preparation method of bactericidal Ag-containing coatings on synthetic fibres for the synthesis of more accessible and inexpensive bactericidal coatings based on Cu and Zn was investigated. It was identified that the transition to more active metals liable to the formation of oxides significantly hampers the synthesis of the desired compounds on the metallised surface of fibres and led to the localization of the precipitate growth and a dramatic decline in its mass. Another synthesis method of slightly soluble compounds of these metals that is based on the use of ion-exchange fibres and allows increasing the mass of the synthesizable coatings and improves the uniformity of their distribution over the surface was proposed. Coatings with slightly soluble Cu and Zn compounds (copper carbonate and a mixture of copper oxide and hydroxide, oxide and a mixture of zinc hydroxide and oxide) using FIBAN K-1 cation exchange fibres (Byelorussia) were synthesized. A comparative analysis of the antimicrobial activity of these materials on two bacterial test cultures was carried out: Staphylococcus aureus and Escherichia coli . It was demonstrated that the resulting coatings exhibited various bactericidal and bacteriostatic activities depending on the type of the material and the coating, their sample weight, type of the test strain and its contact duration with the material. In all cases, materials based on ion exchange fibres demonstrate higher antimicrobial properties. Materials with Cu- and Zn-containing coatings can be promising for the application as bactericidal filters in air and water purification systems.

Nitrogen-Containing Resin Bases from Heavy Oils of the Usinsk Deposit

Institute of Petroleum Chemistry, Siberian Branch, Russian Academy of Sciences, Tomsk, Russia
Keywords: тяжелая нефть, смолы, азотсодержащие основания, содержание, состав, heavy oil, resins, nitrogen containing bases, content, composition

Abstract >>
The distribution and the composition of nitrogen-containing bases in heavy oil of the Usinsk deposit and its resinous components were studied. It was determined that resins of the Usinsk oil accumulated more than half of basic nitrogen contained in it. Nitrogen containing bases of oil and its resinous components are presented by high and low molecular compounds. Bases with various molecular masses were isolated using precipitation methods with hydrogen chloride and sulphuric acid extraction. The resulting concentrates were studied by structural group analysis and gas chromatography-mass spectrometry methods. It was demonstrated that middle molecules of nitrogen bases of oil and resins were composed of polycyclic nuclei including aromatic and saturated cycles with various alkyl framing. Naphthenic rings make the main contribution to the cyclicity of their middle molecules. Middle molecules of resins bases are notable by a more pronounced naphthenic nature and developed alkyl substitution. Quinoline, benzo-, and dibenzoquinoline alkyl derivatives are present in the composition of low molecular weight nitrogen bases of oil and resins, in the composition of high molecular mass - benzo- and dibenzoquinoline and azapyrene alkyl derivatives. The compounds identified are mainly presented by alkylbenzoquinolines, the qualitative composition of which practically does not depend on the nature and the molecular mass of the sample under study.

Extraction of Non-Ferrous Metals and Iron (III) from Sulphate Solutions with Versatic 10 Monocarboxylic Acid Hydrazides

Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
Keywords: сернокислые растворы, цветные металлы, экстракция, гидразиды монокарбоновых кислот, протонодонорные добавки, sulphuric acid solutions, non-ferrous metals, extraction, monocarboxylic acid hydrazides, proton-donor additives

Abstract >>
Extraction of nickel, cobalt, zinc and iron (III) with Versatic 10 acid hydrazides in a mixture with proton donor additives (HR) - 2-ethylhexanol, Cyanex 272, Versatic 10, was investigated. It was demonstrated that all mixtures of Versatic 10 acid hydrazides with HR could be used for effective purification of cobalt solutions from nickel. By the efficiency impact on the separation selectivity Ni and Co they form the following row: Versatic 10 > Cyanex 272 > 2-ethylhexanol. Mixtures of Versatic 10 acid hydrazides that are characterized by the maximum separation factors of nickel and cobalt: βNi/Co = 890-2240 are of the greatest interest. Additionally, extraction systems based on Versatic 10 acid hydrazides can be used for isolating nickel from iron-containing solutions, as well as when purifying zinc sulphate solutions from nickel. In a mixture of Versatic 10 acid hydrazides and 2-ethylhexanol, the following extraction order is observed: Ni > Fe(III) > Co > Zn. The following separation factors of metals were obtained at pH 1.5: βNi/Co ≈ 400, βNi/Fe = 50, βNi/Zn = 630, βCo/Zn ≈ 1.6, i. e. nickel can be extracted from solutions containing these impurities. Extracting zinc and cobalt from iron-containing solutions is impossible, as and cobalt from zinc solutions due to extremely low separation factors of this pair of metals. The data on hydrazides based on tert -monocarboxylic acids obtained for the first time can be optimized, since extraction characteristics will depend heavily on various factors including the concentration of components in the organic phase, their ratio, the type of proton donors (alkylphenols, monocarboxylic acids, etc .), composition of the water phase etc . The work results are of practical interest for the hydrometallurgy of nickel, cobalt and zinc.

Transformations of the Carbohydrate Portion of Secondary Plant Raw Materials Subjected to Cavitation in Alkaline Aqueous Media

Yugra State University, Khanty-Mansiysk, Russia
Keywords: гуминовые кислоты, механохимическое воздействие, полиозы, целлюлоза, щелочной гидролиз, окисление, кавитация, humic acid, mechanical action, polyoses, cellulose, alkaline hydrolysis, oxidation, cavitation

Abstract >>
The composition of polyoses isolated from the products of the mechanochemical treatment of plant raw materials was studied by physicochemical methods. It was demonstrated that mechanochemical action exerted on the components of the cell wall of plants led to hydrolytic decomposition of glycoside bonds of polyoses. A decrease of the polymerization degree of polyoses and the removal of the reaction products as water soluble substances is observed. Complete hydrolysis of polyoses at cavitation does not occur; polyose accumulation with the minimum polymerisation degree of 70-80 units is registered. The intensity of hydrolytic destruction at cavitation is conditioned by the strength of the base used in the process of mechanochemical action. Alongside with hydrolysis, oxidation of primary and secondary hydroxyls in structural units of polyose molecules takes place, resulting in the formation of carboxyl and carbonyl groups, respectively. It was suggested that at the stage of tribochemical impacts, the primary hydroxyl glucoside ring is primarily oxidized, leads to the transformation of individual sections of the cellulose chain to structure resembling irregular polymer of the glucuronic acid. Subsequent cavitation in aqueous alkaline solutions leads to decarboxylation, resulting in the transformation of the glucuronic fragment of oxidized cellulose is transformed into the D -xylose. Herewith, the entire molecule of oxidized cellulose turns into an irregular polymer consisting of the glucuronic acid and xylose. The intensity of oxidative destruction at cavitation is also conditioned by the strength of the base used in the mechanochemical action process. It was demonstrated that all polyoses obtained as a result of the mechanochemical action in aqueous ammonia solutions contain organically bound nitrogen. The use of stronger bases at cavitation contributes to its partial removal from the polymer structure. It can be assumed that nitrogen is present in polyoses as amine and amide groups.

Study of the Distribution of Macroand Microelements in Coal Preparation Wastes of the Kuznetsk Coal Basin

1West Siberian Test Centre OJSC, Novokuznetsk, Russia
2Institute of Coal Chemistry and Chemical Materials, Federal Research Centre Coal and Coal Chemistry, Siberian Branch, Russian Academy of Sciences, Kemerovo, Russia
3Novokuznetsk Institute, Novokuznetsk, Russia
Keywords: породы углеобогащения, токсичные элементы, валовые, подвижные формы элементов, отходы, coal preparation rocks, toxic elements, gross, mobile forms of elements, wastes

Abstract >>
Volumes of accumulated coal preparation wastes and trends to their increase in the coming decades represent a serious problem for a number of Russian regions. At the same time, they can find application as technogenic raw materials and secondary energy resources. With the objective of determining the possibility of their safe use in processing and disposal technologies, the distribution of toxic elements and toxic compounds in coal preparation rocks of the Kuznetsk coal basin. According to the results of the analysis of 17 samples of coal preparation wastes, major statistical characteristics for data sets including the content of toxic elements in gross and mobile forms in the samples studied. It was determined that the concentrations of the gross forms of toxic elements (cadmium, vanadium, copper, and nickel) did not exceed the maximum allowable indicators for major soil types of the Kemerovo Region. For coal preparation wastes, the maximum average total sulphur content (1397 mg/kg), manganese (943 mg/kg) and zinc (115 mg/kg) are typical. Maximum exceeding MPC of mobile forms of elements was observed for copper (84.6 %), lead (69.2 %), nickel (53.8 %) and manganese (46.2 %). The confidence intervals of the concentrations of copper and manganese that are contained in coal preparation wastes in the movable form and obey the normal distribution were determined. By the multiplicity excess of indicators for mobile forms of toxic elements contained in coal preparation wastes, the following row can be proposed: F > Pb > Zn > Cu > Ni > Mn.

Preparation of Microporous Carbon Adsorbents from the Birch Bark

1Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
2Krasnoyarsk Scientific Centre, Siberian Branch, Russian Academy of Sciences, Akademgorodok, Krasnoyarsk, Russia
3Institute of Hydrocarbons Processing, Siberian Branch, Russian Academy of Sciences, Omsk, Russia
Keywords: береста коры березы, щелочная активация, термообработка, углеродный материал, удельная поверхность, микропористость, birch bark, alkaline activation, thermal treatment, carbon material, specific surface, microporosity

Abstract >>
A preparation technique of microporous carbon materials from the initial and preliminarily modified under conditions of pyrolysis of the birch bark by the method of alkaline activation with potassium hydroxide was proposed. It was demonstrated that the preliminary thermal treatment of the birch bark in a range of 280-400 °C contributing to the formation of carbon materials with a developed specific surface S BET = 1300-2100 м2/g and micropore volume of 0.87 cm3/g exerts the greatest influence on the formation of the porous structure of the resulting samples.

Use of Coalhumic Preparations for Localizing Uranium and Mercury in Liquid and Solid Production Drains of Rosatom State Nuclear Energy Corporation

1State Specialized Design Institute OJSC, Novosibirsk, Russia
2EIDOS Ltd, Novosibirsk, Russia
3Novosibirsk Chemical Concentrates Plant, Novosibirsk, Russia
4Tomsk Polytechnic University, Tomsk, Russia
Keywords: углегуминовые препараты, жидкие радиоактивные отходы (ЖРО), уран, ртуть, илы, твердые отходы, сорбция, локализация, coalhumic preparations, liquid radioactive wastes (LRW), uranium, mercury, slimes, solid wastes, sorption, localization

Abstract >>
The use of coalhumic preparations (CHP) obtained by mechanochemical activation of the brown coal of the Kansk-Achinsk coal basin and sodium percarbonate for sorption of mobile forms of uranium and mercury from pulp storage decantates and their localization (immobilization) in the insoluble matrix adapted to nature was considered. The study was carried out in the framework of the elaboration of the technology and liquidation of pulp storages of Rosatom Corp. containing radioactive and mercury-containing wastes accumulated at the programme performance on the output of uranium and lithium products for the needs of armament and energetics. Uranium- and mercury-containing decantates and slimes of the pulp storage of liquid radioactive wastes formed at precipitation of the neutralisation products of uranium containing nitric acid raffinates using lime milk, as well as mercury containing building wastes were used. It was determined that the decantate temperature in a range of 6-25 °C had little effect on the sorption process of uranium and mercury on CHP. IR spectra of CHP samples indicate the predominantly sorption nature of the interaction of uranium and mercury compounds with CHP. The possibility of CHP to reduce the concentration of uranium in the decantate to the normative indicators at its prolonged contact with the uranium-containing sludge of liquid radioactive wastes (LRW) of pulp storage was demonstrated. An effect of the CHP additive on the mobile phase concentration of mercury in mercury-containing wastes was studied. It was proposed to use CHP for the solution of environmental problems facing Rosatom Corp. and allied industry areas.

Technological Cascade for Purification of Zirconium Tetrafluoride from Hafnium Using Zirconium Dioxide

1Seversk Technological Institute, Seversk, Russia
2Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, Russia
Keywords: фторидная технология, сублимация, тетрафториды циркония и гафния, диоксид циркония, хемосорбция, очистка, десублимация, технологический каскад, fluoride technology, sublimation, zirconium and hafnium tetrafluorides, zirconium dioxide, chemisorption, purification, desublimation, technological cascade

Abstract >>
A chemisorptive purification method of zirconium tetrafluoride from hafnium by passing vapours of the initial mixture of zirconium tetrafluoride and hafnium tetrafluoride through a sorbent layer from zirconium dioxide was proposed and investigated. Herewith, the exchange interaction of hafnium tetrafluoride vapours with solid powdery zirconium dioxide and the formation of volatile zirconium tetrafluoride (ZTF) and nonvolatile hafnium dioxide occur. Thermodynamics of the process was considered and the possibility of the exchange interaction between zirconium dioxide and hafnium tetrafluoride (HTF) was demonstrated. The thickness of a layer of zirconium dioxide required for the preparation of both nuclear purity ZTF by the content of hafnium (0.01 mass % and less) and a hafnium concentrate with a concentration of almost 100 % in zirconium dioxide was experimentally defined. Based on the experimental data, the equilibrium coefficient of a chemisorption separation process of zirconium and hafnium tetrafluorides was calculated. The technological cascade consisting of three major knots was calculated using the equilibrium coefficient - purification knot of ZTF from HTF, preparation knot of a hafnium concentrate and fluorination knot. This cascade is waste-free and allows utilizing zirconium production wastes. The chemisorption purification method of ZTF from HTF and technological cascade scheme are protected by patents of the Russian Federation.

Synthesis of N-octyland N-Phenyl-substituted (Co)polymers of a Series of Polyalkylguanidines and Their Antimicrobial Activity Towards Conditionally Pathogenic Microorganisms

1Baikal Institute of Nature Management, Siberian Branch, Russian Academy of Sciences, Ulan Ude, Russia
2Buryat State University, Ulan Ude, Russia
3East Siberia State University of Technology and Management, Ulan Ude, Russia
Keywords: поликонденсация, полигуанидины, дезинфекционные свойства, антибактериальные свойства, polycondensation, polyguanidines, disinfecting properties antibacterial properties

Abstract >>
Polyhexamethylene guanidine hydrochloride N-alkyl- and N-phenyl-substituted derivatives were synthesized and their antimicrobial activity towards to conditionally pathogenic microorganisms was investigated. The structure and molecular mass characteristics of the polymers and copolymers obtained were investigated by physicochemical methods. The determination of the antimicrobial activity of (co)polymers was carried out on gram-positive and gram-negative bacteria ( B. cereus and E. coli , respectively). As a polymer test sample, Polyhexamethylene guanidine hydrochloride (PHMG hydrochloride) that is widely used as the reactant in many modern disinfectants was selected. The assessment of antibacterial properties was carried out based on the serial dilution method in an agar. It was determined that E. coli possessed the highest sensitivity towards N-octyl-substituted products with a high degree of substitution. The effectiveness of alkylated polyguanidines is conditioned by macromolecule sorption on the bacterial cell wall as a result of hydrophobic interactions due to octyl substituents that act as hydrophobic structural elements in these compounds. (Co)polymers with a low substitution degree possess the maximum antimicrobial activity out of N-phenyl-substituted samples. With an increase in the substituent content in a polymer chain, their activity towards the bacteria under study is linearly decreased to a level comparable with the test sample. Unlike N-octyl-substituted copolymers, B. cereus bacteria possess a greater sensibility to N-phenyl-substituted samples. Thus, N-octyl- and N-phenyl-substituted (co)polymers exceed polyhexamethyl guanidine hydrochloride on the reduction percentage in 2-4 times. The resulting (co)polymers are promising materials for the elaboration of high performance disinfectants based on them.

Solid-Phase Synthesis of Superfine Chromium (III) Molybdate Based on the Cr2(SO4)3-Na2CO3-MoO3 System

Berbekov Kabardino-Balkarian State University, Nalchik, Russia
Keywords: твердофазный синтез, система, молибдат хрома (III), solid state synthesis, system, chromium (III) molybdate

Abstract >>
The synthesis of demanded chromium (III) molybdate by the solid phase method based on the Cr2(SO4)3-Na2CO3-MoO3 system, in which the initial mixture of reagents at the thermal treatment may transform into triple mutual exchange (Na, Cr//CO3, SO4) and displacement (Na(Cr)CO3(SO4)-MoO3) systems was proposed. The thermodynamic parameters of the indicated reactions were studied and it was demonstrated that processes associated with the synthesis of Cr2(MoO4)3 were characterized by the significant negative Gibbs energy D GT , and this is fundamentally for achieving the desired goal. A special role in this is played by the interaction of Cr2(SO4)3 with Na2CO3, resulting in the formation of a thermodynamically quite unstable phase - the transition state Cr2(СO3)3 that is a donor of highly defective Cr2O3. The latter intensively reacts with thermally activated MoO3 by forming chromium (III) molybdate. Alongside with thermodynamic data, the results of kinetic studies of the reagent reaction in the Cr2(SO4)3-Na2CO3-MoO3 system depending on temperature (500 and 600 °С) are given. Reaction rate constants and activation energies were calculated according to them, and complete correlation with regularities of a change in isobaric potentials of appropriate processes was demonstrated. The synthesis of Cr2(MoO4)3 was carried out by the thermal treatment of a stoichiometric mixture of the reagents with the specified mass at 600 °C (precision of ±10 °C) during 1.5-2.0 h followed by leaching and isolating the Cr2(MoO4) preparation. It was identified by XPA, chemical and sedimentation analysis methods.

Optimization of the Hydrolysis Process of Microcrystalline Cellulose with Concentrated Sulphuric Acid

1Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences, Krasnoyarsk, Russia
2Siberian State Technological University, Krasnoyarsk, Russia
3Siberian Federal University, Krasnoyarsk, Russia
Keywords: микрокристаллическая целлюлоза, гидролиз, концентрированная серная кислота, глюкоза, выход, оптимизация, ингибиторы ферментации, microcrystalline cellulose, hydrolysis, concentrated sulphuric acid, glucose, yield, optimization, fermentation inhibitors

Abstract >>
The effect of conditions (temperature, liquid module, and duration) of monocrystalline cellulose (MCC) hydrolysis with 80 % H2SO4 on the conversion degree of cellulose and on the yield of glucose was studied. The major advantage of the use of concentrated sulphuric acid in cellulose hydrolysis, in comparison with its diluted solutions, consists in achieving high yields of monosugars at low temperature and at atmospheric pressure at reduced power imputs. The optimum operating parameters of the process of MCC hydrolysis, at which the maximum yield of glucose and the minimum content of admixtures that inhibit the enzymatic synthesis of bioethanol are reached, were determined by experimental and calculation methods. Statgraphics Centurion XVI software package, DOE block (Design of Experiment) was used for mathematical data processing. Analysis detected a significant impact of three major factors on the conversion degree of cellulose: Х1, Х2 and Х3 - hydrolysis temperature, duration and liquid module, respectively, and on the yield of glucose - factors X1, Х2 and Х3 . The individual composition and content of monosugars in the hydrolysates obtained was studied by the chromatographic method using a Varian-450 GC gas chromatograph. The determination of the quantitative content of furfural, 5-hydroxymethylfurfyral (5-HMF) and in samples of glucose hydrolysates was carried out by the HPLC method using a Milichrom A-02 microcolumn liquid chromatograph. The yield of glucose in the hydrolysate obtained under conditions close to optimum is 98.7 mass %, and the content enzymatic processes inhibitors (furfural, 5-HMF, and levulinic acid) is significantly lower than the permissible values.

Hydrofining of Petroleum Fractions on the Ni-MoV/Al2O3 Catalysts

Samara State Technical University, Samara, Russia
Keywords: катализатор, гидроочистка, добавки ванадия, catalyst, hydrofining, vanadium additives

Abstract >>
The effect of the introduction of V2O5 in the Ni-Мo/Al2O3 catalysts on their activity in hydrofining reactions of petroleum raw materials was studied. The activity in hydrodesulphurization and hydrogenation of polycyclic aromatic hydrocarbons (PAHs) of straight-run diesel fraction and light coker gas oil was determined. A high degree of hydrodesulphurisation and high degree of hydrogenation of PAHs in the presence of the Ni-MoV/ɣ-Al2O3 catalysts were detected. It was determined that when using various molybdenum compounds the catalyst synthesized using H3[VMo12O40] . H2O possessed the highest activity in hydrodesulphurisation and hydrogenation of PAHs.

Interaction of Homoveratrylamine with Maleic and Fumaric Acids

1Samarkand State University, Samarkand, Uzbekistan
2Yunusov Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, Uzbekistan
Keywords: гомовератриламин, яблочная и фумаровая кислоты, получение амидов, гетероциклизация, homoveratrylamine, maleic and fumaric acids, preparation of amides, heterocyclization

Abstract >>
The interaction of homoveratrylamine with maleic and fumaric acids was studied. It was demonstrated that it proceeded with the formation of three products: target amides, 1-(3,4-dimethoxyphenylethyl)-1 H -pyrroline-2,5-dione imide and oxoazetidin-2-carboxamide.