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2004 year, number 2

1.
Natural Halogenated Polyethers, Pyrones, Coumarins and Flavones

VALERY M. DEMBITSKY1 and GENRICH A. TOLSTIKOV2
1Department of Pharmaceutical Chemistry and Natural Products,
School of Pharmacy, The Hebrew University of Jerusalem,
P.O. Box 12065, Jerusalem 91120 (Israel), E-mail: dvalery@cc.huji.ac.il
2Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 9, Novosibirsk 630090 (Russia), E-mail: gtolstik@nioch.nsc.ru
Pages: 129-138

Abstract >>
Halogenated polyethers, pyrones, coumarins and flavones compose four comparatively small but interesting groups of natural compounds. Some of these compounds are antibiotics, toxins or biologically active substances. They have been found in microorganisms, e. g. cyanobacteria, fungi, plants, algae and in invertebrates. Structures of about 100 compounds have been considered, and data on their biological activity presented.



2.
Mechanocomposites as New Materials for Solid-Phase Cosmetics

TATIANA F. GRIGORYEVA, IRINA A. VORSINA, ANTONINA P. BARINOVA and NIKOLAY Z. LYAKHOV
Institute of Solid State Chemistry and Mechanochemistry,
Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 630128 (Russia), E-mail: grig@solid.nsk.su
Pages: 139-146

Abstract >>
The initial stages of mechanical activation of the layered silicates with higher alcohols and hydroxyacids are investigated by means of IR spectroscopy and X-ray phase analysis. The formation of new materials is established; they are dispersed layered mechanocomposites formed due to neutralization of the active centres of basic character on the silicate surface by the protons of carboxylic groups of hydroxyacids or hydroxyl groups of higher alcohols. Hydroxyl groups of acid do not participate in the reaction with silicates. They are likely to form hydrogen bonds both with hydroxyl groups of silicates and with water molecules



3.
Influence of Lignin-Like Additives on the Solubility f Mechanically Activated Phosphates

SESEGMA G. DORZHIEVA1 and JIBZEMA G. BAZAROVA2
1Buryatia State University, Ul. Smolina 24a, Ulan Ude 670000 (Russia)
2Baikal Institute of Nature Management, Siberian Branch of the Russian Academy of Sciences,
Ul. Sakhyanovoy 8, Ulan Ude 670047 (Russia), E-mail: jbaz@binm.baikal.net
Pages: 147-153

Abstract >>
The influence of mechanical activation conditions on the solubility of phosphate compounds of phosphorites from the Burenkhan deposit of Mongolia in 2 % solution of citric acid and in water medium was studied. It is established that the efficiency of planetary mill EI-2&x150 is considerably higher than that of vibration mill DRM-75T. As the time of activation is increased to 100 min, the assimilable phosphorus content of natural phosphates is heightened. For the vibration mill DRM-75T it is optimal to use as the milling body a steel cylindrical core with a mass of 1000 g. A mechanical activation of phosphorites was carried out with adsorbing additives in the form of lignosulphonates, zeolites and brown coals. The content of assimilable and water-soluble phosphates was determined depending on the composition and nature of additives. As the activation is continued when the amount of assimilable phosphorus is increased, the amount of water-soluble phosphorus is diminished. When lignin-containing additives are used, products with a high degree of phosphorus transition to 2 % solution of citric acid are formed with respect to activated phosphorites under equal treatment conditions. In this way, the possibility of obtaining organophosphorus fertilizers of prolonged action with various assimilability of phosphorus is estimated



4.
Features of Mechanical Alloying in Fe-B System

EUGENE P. ELSUKOV, ALEXANDER L. UL'YANOV and GENNADIY A. DOROFEEV
Physical and Technical Institute, Ural Branch of the Russian Academy of Sciences,
Ul. Kirova 132, Izhevsk 426001 (Russia), E-mail: Yelsukov@fnms.fti.udm.ru
Pages: 155-164

Abstract >>
The sequence and kinetics of solid-phase reactions that take place during mechanical alloying of the mixtures of Fe and B powders with the atomic ratios Fe(68)B(32) and Fe(85)B(15) were investigated by means of Mössbauer spectroscopy and X-ray diffraction. It was established that the initial stage of mechanical alloying includes the formation of nanostructural state in a-Fe particles and the formation of the Fe-B amorphous phase with the atomic fraction of boron up to 20 %. For other conditions being kept constant, a substantial difference in the kinetics of the initial stage in Fe-B and Fe-C systems was discovered. On the basis of indirect experimental data, it is assumed that the kinetics of the stage under consideration is determined by the size of B and C atoms.



5.
Chemical Composition of the Surface Layer of Atmospheric Aerosol of the Baikal Region Studied by Means of Secondary Ion Mass Spectrometry

VYACHESLAV P. IVANOV1, SERGEY N. TRUKHAN1,2, DMITRIY I. KOCHUBEY1, OLGA G. NETSVETAEVA3, LYUDMILA V. GOLOBOKOVA3 and TAMARA V. KHOJER3
1Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), E-mail: vpivanov@catalysis.nsk.su
2Novosibirsk State Architectural University, Ul. Leningradskaya 113, Novosibirsk 630090 (Russia)
3Limnological Institute, Siberian Branch
of the Russian Academy of Sciences, Ul. Ulan-Batorskaya 3, Irkutsk 664033 (Russia)
Pages: 165-173

Abstract >>
Elemental and phase composition of the surface layers of two kinds of atmospheric aerosol sampled in Irkutsk, Listvyanka settlement and at the mountainous station Mondy was investigated by means of secondary ion mass spectrometry. The first kind includes the aerosol collected by pumping air through the filters, the second one includes aerosol particles captured while snow was falling, and afterwards collected on filters when pumping the melted snow. It was established that the action of water causes washing out Na, Ca and Ti from the surface layers and the formation of hydroaluminosilicates. Such an effect of water allows assuming that large range of scattering of the element concentrations in the surface layers of airborne aerosol particles is due to the action of atmospheric humidity, which depends on the residence time of aerosol in the atmosphere.



6.
Reaction Capacity of Mechanically Activated Tinstone

EKATERINA A. KIRILLOVA1, TALGAT S. YUSUPOV1 and MIKHAIL P. LEBEDEV2
1Trophimuk United Institute of Geology, Geophysics and Mineralogy,
Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia)
2Yakutsk Scientific Centre, Siberian Branch of the Russian Academy
of Sciences Ul. Petrovskogo 2, Yakutsk 677891 (Russia)
Pages: 175-179

Abstract >>
An effect of mechanical activation on reaction capacity of tinstone under its dispersion with the minerals with different hardness and in the presence of reducing agents was investigated. Dependence of degree of SnO2 dilution in HCl on the hardness of the added under grinding mineral and on redox capacity of used reagents was fixed. It was determined that an activation barrier decreases with increasing reaction capacity.



7.
Bromine and Iodine in Natural Waters of the South of West Siberia

GALINA A. KONARBAEVA
Institute of Soil Science and Agricultural Chemistry,
Siberian Branch of the Russian Academy of Sciences, Ul. Sovetskaya 18,
Novosibirsk 630099 (Russia), E-mail: soil@issa.nsc. ru
Pages: 181-192

Abstract >>
The bromine and iodine content and distribution in the soils and natural waters of the south of West Siberia are studied. Questions associated with the pattern of accumulation and migration of halogens in the soil profile, and with the conditions in natural waters contributing to, or hindering the accumulation of halogens in them, are discussed.



8.
Solid-Phase Transformations of Monoclinic Zirconium Oxide under Mechanical Treatment in the Devices of Different Types

PETER N. KUZNETSOV1, LILIA I. KUZNETSOVA1, ALEXEY M. ZHIZHAEV1, GENNADIY L. PASHKOV1 and VLADIMIR V. BOLDYREV2
1Institute of Chemistry and Chemical Technology,
Siberian Branch of the Russian Academy of Sciences,
Ul. K. Marxa 42, Krasnoyarsk 660049 (Russia), E-mail: kuzpn@icct.ru
2Institute of Solid State Chemistry and Mechanochemistry,
Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 630128 (Russia), E-mail: boldyrev@nsu.ru
Pages: 193-199

Abstract >>
The effect of mechanical activation of well crystallized zirconium oxide of monoclinic modification in a centrifugal planetary activator mill and in vibratory mill on the characteristics of fine crystalline structure and phase transformation depending on the treatment environment and mechanical loading is investigated. It is established that the mechanical action in the centrifugal planetary mill stimulates dispersion processes, accumulation of microdeformations, and phase transition of the oxide into the tetragonal form. The rate of processes depends on the environment of treatment: for mechanical activation of the dry powder, the phase transition occurs within 15 min, the rate of the process decreases in the presence of water as additive. Treatment in vibratory mill causes mainly crushing of the particles and accumulation of microdeformations. After 2 h, the size of crystallites decreases to 38 nm and remains unchanged during further treatment; gradual accumulation of microdeformations and amorphization of structure occur. After 15 h, the fraction of the crystalline phase was 15 %; no formation of other crystalline phases was observed. The formation of a metastable tetragonal form of ZrO2 in the activator apparatus can be due to the pulsed character of powerful mechanical action, which causes intense crushing of the crystallites (20 nm) and can create local conditions favourable thermodynamically and kinetically for the phase transition in separate regions of the solid.



9.
Optimization of the Solution-Free Process for the Preparation of Superconducting Materials from SmBa2Cu3Oy: Thermodynamic Aspects

NATA I. MATSKEVICH
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 3, Novosibirsk 630090 (Russia), E-mail: nata@casper.che.nsk.su
Pages: 201-205

Abstract >>
Thermochemistry of the decomposition reactions of Sm1 + xBa2 - xCu3Oy solid solutions (x = 0-0.8) has been studied by solution calorimetry (2M HCl, 23.15 K). Dependences of the formation enthalpies of these compounds on the samarium content have been obtained. Analysis of the experimental data shows that the Sm1 + xBa2 - xCu3Oy phases can decompose into mixtures of variable composition in both inert and oxygen atmospheres. In an inert atmosphere, decomposition reactions can form mixtures of solid solutions with high samarium contents and barium cuprate. Under oxygen, decomposition can lead either to mixtures of phases with higher and lower samarium contents or to mixtures with high samarium contents and barium cuprate. Decomposition reactions of solid solutions are assumed to increase the critical current. For samples prepared under oxygen, the critical current is admitted to be stronger than for samples synthesized under an inert atmosphere. The results of thermochemical studies will permit optimization of the solution-free process for sample preparation from SmBa2Cu3Oy, which is currently the most promising and widely used technology.



10.
Mechanochemical Synthesis of Diborane(6) by Reactions of Alkaline Tetrahydroborates with Iron (III) Chloride

KLAVDIY G. MYAKISHEV and VLADIMIR V. VOLKOV
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy
of Sciences, Pr. Akademika Lavrentyeva 3, Novosibirsk 630090 (Russia)
Pages: 207-210

Abstract >>
Reactions of FeCl3 with MBH4 (M = Li, Na, K) which take place during mechanical activation (MA) of mixtures of crystalline substances in a vibratory vacuum mill have been studied. The reactions form diborane(6) or B2H6; the product yields depend on the nature of MBH4, on the molar ratio of reagents, and on the mechanical activation time. Under optimal conditions, the yield of B2H6 is 81.5, 79.5, and 73.5% when LiBH4, NaBH4, and KBH4, respectively, are used. When mixtures of FeCl3 with MBH4 are heated without MA, reactions occur with liberation of H2, while B2H6 is not formed.



11.
Ecologically Sound Adsorption Chiller Based on Composite CaCl2 in Silica Gel: Laboratory Prototype

GIOVANNI RESTUCCIA1, ANGELO FRENI1, SALVATORE VASTA1, MIKHAIL M. TOKAREV2 and YURI I. ARISTOV2
1CNR - Istituto di Tecnologie Avanzate per l'Energia "Nicola Giordano", S. Lucia sopra Contesse,
98126 Messina (Italy), E-mail: giovanni.restuccia@itae.cnr.it
2Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia), E-mail: aristov@catalysis.nsk.su
Pages: 211-216

Abstract >>
The results of tests of the laboratory prototype of adsorption chiller based on ecologically sound working pair "water - SWS-1L adsorbent" are presented. The adsorbent relates to the family of selective water sorbents and is a mesoporous silica gel KSK modified with calcium chloride. The device produces cold water at a temperature of 5-10 oC, which can be used in air conditioning systems, to store food, etc. High coefficient of performance reaching 0.6 for low temperature of water desorption (90-95 oC) was obtained during the test of the device. This allows the investigated adsorbent to become a real alternative for traditional materials (silica gel, zeolites) for use in ecologically pure adsorption systems involving low-potential heat (T100 oC)



12.
Extraction of Fission Ruthenium in the Form of Heterometallic Complexes from Nitrate-Nitrite Solutions

VLADISLAV G. TORGOV1, RIMMA S. SHULMAN1, TAISIA V. US, TAMARA M. KORDA1, VASILIY A. BABAIN2, IGOR V. SMIRNOV2 and ANDREY YU. SHADRIN2
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy
of Sciences, Pr. Akademika Lavrentyeva 3, Novosibirsk 630090 (Russia), E-mail: torgov@che.nsk.su
2Khlopin Radium Institute, 2-y Murinskiy pr. 28, St. Petersburg 194021 (Russia), E-mail: igor-smirnov@atom.nw.ru
Pages: 217-224

Abstract >>
The effects of nonferrous metals on extraction of the ruthenium form [RuNO(NO2)4OH]2- (An2-), prevailing in weak acid solutions, by mixed-radical phosphine oxide (L) are investigated from the viewpoint of extraction of fission ruthenium. The synergic effect has been found to be high (n103) because [RuNO(NO2)4OHMLm] heterometallic complexes are formed (M = Zn2+, Cu2+, Co2+, Ni2+; m = 1-3). Extraction constants have been determined for the complexes, and conditions of their formation and extraction from nitrate solutions have been optimized. An approach to ruthenium extraction by nitration the starting solution to convert various forms of ruthenium into the An2- form and by extracting Ru in the form of Ru/M complexes has been verified experimentally. The suggested method for extracting ruthenium was tested on real high-level waste.



13.
Toxic Admixture Content of Industrial Polychlorophenolic Preparations

ANTONINA F. TROYANSKAYA, DIANA P. MOSEEVA and NADEZHDA A. RUBTSOVA
Institute of Ecology of North, Ural Branch of the Russian Academy of Sciences,
Naberezhnaya Severnoy Dviny 23, Arkhangel'sk 163060 (Russia), E-mail: troya@atnet.ru
Pages: 225-231

Abstract >>
The problem of contamination of chlorophenolic biocides with polychlorinated dibenzo-n-dioxines and dibenzofurans formed as admixtures in the process of preparation synthesis is considered. Results of assay of chloroorganic admixtures in the sodium pentachlorophenolate synthesized in this country are presented. A high toxicity of the preparation determined by the content of less chlorinated congenerics of polychlorinated dibenzo-n-dioxines is demonstrated.



14.
Indirect Oxidation of Maleic Acid by Fenton's Reagent with Electrochemical Generation of Hydrogen Peroxide upon Oxygen Reduction

NATALIA V. CHAENKO, VASILIY L. KORNIENKO and NINA I. PAVLENKO
Institute of Chemistry and Chemical Technology,
Siberian Branch of the Russian Academy of Sciences, Ul. K. Marxa 42, Krasnoyarsk 660049 (Russia), E-mail: kvl@icct.ru
Pages: 233-237

Abstract >>
Indirect oxidation of maleic acid by Fenton's reagent with electrochemical generation of hydrogen peroxide from oxygen in a carbon hydrophobized electrode in 1M Na2SO4 solution is studied. It is established that the process goes on destructively through a number of intermediates with mineralization to CO2 and H2O. Succinic, malic, oxalic acids and anhydrides of ketoacids were detected among the intermediates. The rate of mineralization depends on the current density and on the concentration of Fe2+ ions.



15.
Study of the Behaviour of Gallium during Reagent Carbonization of Aluminate and Zincate Solutions

LILIA A. PASECHNIK and SERGEY P. YATSENKO
Institute of Solid State Chemistry and Mechanochemistry,
Ural Branch of the Russian Academy of Sciences, Ul. Pervomayskaya 91,
Yekaterinburg 620219 (Russia), E-mail: sabirzyanov@ihim.uran.ru
Pages: 239-241

Abstract >>
The behaviour of gallium, aluminium, and zinc in the course of reagent carbonization of alkaline solutions is described. It is shown that gallium and zinc may be separated, and separation conditions have been studied. Gallium may be concentrated by co-precipitation with the basic aluminium carbonate to give rich aluminium-free gallate solutions.