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2003 year, number 4

1.
Halogenated Phenol Compounds in Lichens and Fungi

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: 557-565

Abstract >>
The structures of hundred halogenated metabolites of phenolic nature generated by lichens and fungi are considered. The groups of depsides, depsidones, fungoid metabolites are marked out. The problems related to biological activity are discussed.



2.
Natural Halogenated Mononuclear Phenol Compounds and Their Derivatives

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: 567-575

Abstract >>
Mononuclear halogenated simple phenol compounds and their derivatives formed from mono- and polyhydroxybenzenes are represented in nature by metabolites of insects, fungi, plants and microorganisms living on land and in water. The structures of a hundred compounds of phenol, quinones and cyclitol types, their metabolism and data on their biological activity are considered in the review.



3.
Methane Emission from Bottom Sediments

NIKOLAY M. BAZHIN
Institute of Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences,
Ul. Institutskaya 3, Novosibirsk 630090 (Russia) E-mail: bazhin@ns.kinetics.nsc.ru
Pages: 577-580

Abstract >>
The problem concerning the extraction of the characteristics of methane formation and transport processes from the experimental data is discussed.



4.
Phase and Elemental Composition and Distribution of Urinary Calculi in Patients from Novosibirsk and Omsk Regions

OLGA A. GOLOVANOVA1, POLINA A. PYATANOVA1, NADEZHDA A. PALCHIK2, VALENTINA N. STOLPOVSKAYA2, TAMARA N. GRIGORYEVA2, ALEXANDER I. NIZOVSKIY3 and SERGEI S. SHKURATOV4
1Omsk State University, Pr. Mira 55a, Omsk 644077 (Russia) E-mail: PAKach@orgchem.univer.omsk.ru
2Trofimuk United Institute of Geology, Geophysics and Mineralogy,
Siberian Branch of the Russian academy of Sciences, Pr. Akademika Koptyuga 3,
Novosibirsk 630090 (Russia) E-mail: nadezhda@uiggm.nsc.ru
3Boreskov Institute of Catalysis, Omsk Division,
Siberian Branch of the Russian Academy of Sciences, Ul. Neftezavodskaya 54, Omsk 644040 (Russia)
4Region Clinic, Ul. Nemirovicha-Danchenko 130, Novosibirsk 630015 (Russia)
Pages: 581-587

Abstract >>
Investigation of endemic features of urolithiasis taking into account local factors, both natural and technology-related ones, allows one to obtain additional information about one of the reasons of this disease. Mineral composition and distribution of urinary calculi in patients from Novosibirsk and Omsk Regions are investigated. A common feature of urolithiasis in the regions under comparison is noticeable predominance of oxalate urinary calculi. However, at the conservation of the general trend of distribution with respect to the prevailing component, patients from Novosibirsk Region exhibit an increase in phosphate and decrease in urate urolithiasis. Noticeable differences in paragenesis of minerals comprising multicomponent urinary calculi and in the composition of single-component concretions are observed. In the Novosibirsk samples, single-mineral concretions are more frequently composed of whwellite, while in the Omsk samples it is anhydrous uric acid. Comparative analysis of the mineral composition and distribution of urinary calculi in other regions according to literature data was carried out.



5.
Effect of Fe3+ and Y3+ Cations on the Crystallization of Tetragonal Zirconia under Mechanical Activation of Amorphous Zirconium Hydroxide

PETER N. KUZNETSOV1, LYUDMILA I. KUZNETSOVA1, ANATOLIY M. ZHYZHAEV1, GENNADIY L. PASHKOV1and VLADIMIR V. BOLDYREV2,3
1Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences,
Ul. K. Marxa 42, Krasnoyarsk 660049 (Russia)
2Institute of Solid State Chemistry and Mechanochemistry,
Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
3Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia) E-mail: kuzpn@krsk.info
Pages: 611-619

Abstract >>
The effect of mechanical activation of amorphous zirconium hydroxide in centrifugal planetary mill on the formation of crystalline zirconia in the presence of Fe3+ and Y3+ cation additives is investigated. It is established that the pulsed mechanical impact stimulates dehydration and crystallization of the nanosized metastable form of tetragonal zirconia in a mechanochemical apparatus at the room temperature. The solid-phase mechanochemical synthesis proceeds with a high rate through sequential and parallel routes with the intermediate formation of stable monoclinic modification of ZrO2. Introduction of additives favours the formation of the tetragonal form; in the presence of small amount of Y3+ cations, the process is completed within 2_5 min. The formation of metastable phase in the mechanochemical apparatus can occur due to the pulsed mode of powerful mechanical impact, resulting in the creation of thermodynamically and kinetically favourable conditions, and also due to small crystallite size (12_16 nm) as a result of efficient grinding.



6.
Analysis of Element Distribution in Biogeocenoses on the Basis of Composts of the Wastes from Pulp and Paper Industry

NATALYA N. KULIKOVA, ALEXANDER N. SUTURIN, LYUDMILA F. PARADINA and SERGEY M. BOYKO
Limnological Institute, Siberian Branch of the Russian Academy of Sciences,
Ul. Ulan-Batorskaya 3, Irkutsk 664033 (Russia) E-mail: kulikova@lin.irk.ru
Pages: 595-602

Abstract >>
Analysis of the distribution of elements in biogeocenoses based on organomineral composts is performed. Introduction of composts of the wastes from plant and cardboard industry, heat-and-power engineering, cattle breeding did not cause accumulation of microelements in soils in concentrations exceeding the phytotoxicity level and maximum permissible values. Differences in microelemental composition of the experimental and reference plants were insignificant. Compost made of the wastes from industry can be used for reclamation of land disturbed by man's impact.



7.
Development of Processes for Purification of Coal Processing Gases from Sulphur and Cyan for the Application in Energy Technologies

NIKOLAY N. KUNDO and GALINA A. FADDEENKOVA
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia) E-mail: Kundo@catalysis.nsk.su
Pages: 603-609

Abstract >>
For the efficient use of gases formed in a number of thermochemical procedures of carbon processing, it is necessary to purify them from hazardous impurities, such as H2S, HCN, NH3, resinous substances. To purify the gases, it is proposed to use the liquid catalytic procedure with the soluble derivatives of cobalt phthalocyanine as a catalyst. This method allows achieving the required purification extent with low expenses. The purified gases can be used to obtain electricity and heat, and also as chemical raw material for obtaining ammonia, methanol, liquid fuel, etc. Elemental sulphur is obtained as a result of purification.



8.
Effect of Particle Size on Solubility and Neutralizing Ability of Carbonate Minerals

VICTOR N. MAKAROV, OLGA P. KORYTNAYA, ALLA S. LUGOVSKAYA, TATIANA N. VASILIEVA and DMITRIY V. MAKAROV
Tananaev Institute of Chemistry and Technology of Rare Elements
and Mineral Sources, Kola Scientific Centre of the Russian Academy of Sciences,
Ul. Fersmana 26a, Apatity 184200 (Russia) E-mail: makarovdv@chemy.kalasc.net.ru
Pages: 621-626

Abstract >>
The effect of particle size of carbonate minerals (dolomite and calcite) on the kinetics of their interaction with water and ferrous sulphate solution is investigated. It is established that the efficiency of solution neutralization is to a noticeable extent determined by the particle size of the reagent. The application of calcite as a material for the construction of artificial geochemical barriers is preferential over dolomite. In the case when reagent consumption is much higher than the stoichiometric amount, or under lengthy interaction (for example, in filtering dams of artificial geochemical barriers) the particle size of the material has no substantial effect.



9.
Aging of Oxyhydroxide Sorbents Saturated with the Cations of Nonferrous Metals

SOPHIA I. PECHENYUK, VASILIY V. SEMUSHIN and TATIANA G. KASHULINA
Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Sources,
Kola Scientific Centre of the Russian Academy of Sciences, Ul. Fersmana 26a, Murmanskaya obl.,
Apatity 184209 (Russia) E-mail: pechenyuk@chemy.kolasc.net.ru
Pages: 627-633

Abstract >>
The aging of freshly precipitated and immediately saturated with a sorbate (Cu(II), Ni(II), Cr(III), Pb(II) and Cd(II) cations) oxyhydroxides of Fe(III), Cr(III), Al(III), Zr(III) and Ti(IV) in 0.25 M solution of NaCl at room temperature is studied. It is established that the aging is accompanied by spontaneous acidification of the oxyhydroxide suspension and by partial desorption of the sorbate, which is to the highest extent exhibited with aluminium oxyhydroxide with Cd sorbed, and by the lowest extent with



10.
Investigation of the Mechanism of Decomposition of Artificial Scheelite in Nitric Acid

ESHMURAT A. PIRMATOV
Uzbek Plant of High-Melting and Heat-Proof Metals, Ul. V. Khaydarova 1, Tashkent Region, Chirchik 702119 (Uzbekistan)
Pages: 635-638

Abstract >>
The mechanism of decomposition of artificial scheelite in nitric acid is investigated by recording the curves of anodic charging. This method involves fixation of temporal changes in the potential of platinum electrode in reaction medium. It is established that the reaction between artificial scheelite and nitric acid is not a solid-phase process but a usual exchange reaction in aqueous medium with the dissolution of scheelite and formation of precipitate which is tungsten trioxide monohydrate.



11.
Study of Mechanism and Improvement of the Process of Oxidative Cleavage of Lignins into the Aromatic Aldehydes

VALERI E. TARABANKO and DMITRIY V. PETUKHOV
Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences, Ul. K. Marxa 42, Krasnoyarsk 660049 (Russia) E-mail: veta@icct.ru
Pages: 655-667

Abstract >>
Known hypotheses concerning the mechanism of formation of aromatic aldehydes (vanillin and syringaldehyde) in the processes of oxidative cleavage of lignins are discussed. A new mechanism of lignin oxidation is described, which starts from the formation of phenoxyl radical and is completed by the formation of vanillin through the retro-aldol cleavage of substituted coniferyl aldehyde. Oxidation of the model compounds is studied and experimental confirmations of the proposed mechanism are obtained. Coniferyl alcohol, the postulated intermediate of eugenol oxidation, was detected by GC-MS. Comparison of the kinetics and oxidation products of vanillidenacetone and lignosulphonates, eugenol and isoeugenol, guaiacyl ethanol and quaiacyl propanol confirms the proposed mechanism. On its basis, possibilities are found to elevate the selectivity of lignin oxidation by oxygen into aromatic aldehydes by accelerating the process due to tightening conditions.



12.
Testing of Solvent Extraction Process for Recovery and Affining of Fission Palladium from Model Nitrate-Nitrite Solutions

VLADIMIR V. TATARCHUK1, IRINA A. DRUZHININA1, TAMARA M. KORDA1, VALERIY K. VARENTSOV2, EDOUARD V. RENARD3 and VLADISLAV G. TORGOV1
1Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 3, Novosibirsk 630090 (Russia) E-mail: tat@che.nsk.su
2Novosibirsk State Technological University, Pr. K. Marxa 20, Novosibirsk 630092 (Russia)
3Bochvar All-Russian Research Institute of Inorganic Materials, Ul. Rogova 5, Moscow 123060 (Russia)
Pages: 679-688

Abstract >>
In relation to the problem of recovery of fission palladium from highly active liquid wastes from spent nuclear fuel reprocessing, the efficiency of a flow sheet based on solvent extraction and electrochemical processes for palladium purification from a number of accompanying elements (Ag, Te, Se, Sb) was tested using model (in the absence of radiation) nitrate-nitrite solutions. The flow sheet is composed of two extraction cycles which involve solvent extraction of palladium with petroleum sulphides, washing of the extracts with acid solutions, and palladium stripping with aqueous ammonia. In the first cycle imitating recovery from HLW, ~99 % Pd and ~25 % Ag is recovered and separation from other accompanying elements is achieved. High efficiency of palladium separation from silver (105) is achieved during the second cycle due to solvent extraction affining from hydrochloric solution. For passing from the ammonia strip liquor of palladium and silver, which is the final product of the first cycle, to the starting hydrochloric solution for the second cycle, electrochemical operations are applied, involving co-deposition of these metals on the cathode followed by their anodic dissolution in HCl solution. The efficiency of these operations was also not less than 99 %. At the final stage, purified palladium is recovered from the strip liquor of the second cycle as a difficultly soluble trans-dichlorodiammine ("palladozammine", PZA). End-to-end palladium fraction extracted with the help of this flow sheet is 97_98 %. No Te, Se or Sb admixtures were detected in the resulting PZA; Ag content is close to the level observed in the reference experiment (mass concentration 10_5 %).



13.
Investigation of the Composition of Lipids of Siberian Pine Seeds

ANDREY G. KHANTURGAEV1, VALENTINA G. SHIRETOROVA1, LARISA D. RADNAEVA2,3, GALINA I. KHANTURGAEVA2,3, ELENA S. AVERINA2 and NIKOLAY V. BODOEV2,3
1East-Siberian State Technological University, Ul. Klyuchevskaya 42a, Ulan-Ude 670013 (Russia)
2Baikal Institute of Natural Management, Siberian Branch of the Russian Academy of Sciences,
Ul. Sakhyanovoy 6, Ulan-Ude 670047 (Russia) E-mail: techmin@binm.baikal.net
3Buryatia State University, Ul. Smolina 24a, Ulan-Ude 670000 (Russia)
Pages: 589-593

Abstract >>
Intensification of lipid extraction from the seeds of Siberian pine with ethanol by using the electromagnetic field of super high frequency in extraction process is investigated. Physicochemical characteristics of the resulting cedar oil are determined, such as refractive index, numbers: acidic, peroxide, iodine, saponification, colour, and mass fraction of non-lipid admixtures. Fractional and fatty acid composition of the oil is investigated.



14.
Composition and Morphology of Magnetic Microspheres in Power-Plant Fly Ash of Coal from the Ekibastuz and Kuznetsk Basins

OLGA M. SHARONOVA1, NATALIA N. ANSHITS1, ALEXANDER I. ORUZHEINIKOV2, GALINA V. AKIMOCHKINA3, ALEKSEY N. SALANOV2, ALEXANDER I. NIZOVSKII2, OLGA N. SEMENOVA2 and ALEXANDER G. ANSHITS1
1Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences,
Ul. K. Marxa 42, Krasnoyarsk 660049 (Russia) E-mail: shar@icct.ru
2Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences,
Prospekt Lavrentyeva 5, Novosibirsk 630090 (Russia)
3Krasnoyarsk State Technical University, Ul. Kirenskogo 26, Krasnoyarsk 660074 (Russia)
Pages: 639-648

Abstract >>
Using a multi-stage scheme including different sequences of the stages of magnetic separation, hydrodynamic and granulometric classification, magnetic microspheres of fixed composition containing the magnetic constituent at the level of 95_99 % were separated from the fly ash of coal from the Ekibastuz and Kuznetsk basins. The yield, texture characteristics, macrocomponent and mineral phase composition were determined and globules of three morphological types were described for close-cut fractions of magnetic microspheres. A general dependence of the properties of close-cut fractions of microspheres on ferric oxide content was revealed. It was demonstrated that for the mass concentration of total Fe2O3 >60 %, mainly massive microspheres with various crystal microstructure are formed. With a decrease in iron content, the formation of porous microspheres becomes predominant. It is established that the governing factor in the formation of microspheres of morphological type is the viscosity of ferriferous silicate melt.



15.
Coumarin Compounds from Roots of Peucedanum (Peucedanum morisonii Bess.)

ELVIRA E. SHULTS, TATYANA N. PETROVA, MAKHMUT M. SHAKIROV, ELENA I. CHERNYAK, LEONID M. POKROVSKIY, SERGEY A. NEKHOROSHEV and GENRICH A. TOLSTIKOV 2Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 9, Novosibirsk 630090 (Russia) E-mail: schultz@nioch.nsc.ru
Pages: 649-654

Abstract >>
The composition of Coumarin compounds from roots of Peucedanum morisonii is investigated, 13 individual components are isolated and characterized.