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2011 year, number 5

1.
2-Hydroxyethylammonium Salts of Organylsulphanyl(sylphonyl)acetic Acids as Novel Pharmacologically Active Compounds

A. N. MIRSKOVA, R. G. MIRSKOV, S. N. ADAMOVICH and M. G. VORONKOV
Favorsky Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Favorskogo 1, Irkutsk 664033 (Russia)
E-mail: mirskova@irioch.irk.ru
Keywords: organylsulphanyl(sulphonyl)acetic acids, 2-hydroxyethylammonium salts, synthesis, pharmacological activity
Pages: 429-439

Abstract >>
Preparative methods of the synthesis of organylsulphanyl(sulphonyl)acetic acids and their 2-hydroxyethylammonium salts developed by the authors are presented in this review. The latter salts represent a new class of pharmacologically active substances possessing antiaggregant, membrane-stabilizing, antioxidant, cytostatic, cardiotropic and hypocholesterolemic activity. Compounds with combined immunotropic and antitumour activity promising for the development of up-to-date remedies for treating immunodeficient, autoimmune, oncological and other diseases were found.



2.
Denaturation of Cellulosolytic Enzymes
in the Presence of Water

A. L. BYCHKOV, V. A. BUKHTOYAROV andO. I. LOMOVSKY
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 6300128 (Russia),
bychkov.a.l@gmail.com
Keywords: enzymes, thermal denaturation, stability, mechanoenzymatic processes
Pages: 441445

Abstract >>
Denaturation of cellulosolytic enzymes produced by microorganisms Trichoderma viride in the presence of water was studied. Effective kinetic constants characterizing denaturation process were determined. It was shown that the enzymes in solution possess a narrow zone of stability, are stable at a temperature below 55 ° and rapidly gets denaturated when heated above 65 . In the dry state, the enzymes possess higher stability and get noticeably denaturated only at temperatures above 80 . The effective rate constant of denaturation is exponentially dependent on the concentration of water in the enzymatic preparation.

UDC 544.421+577.151



3.
Mechanochemical Interaction of Silicon Dioxide
with Organic Acids

I. A. VORSINA,T. F. GRIGORIEVA,A. P. BARINOVA andN. Z. LYAKHOV
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 6300128 (Russia),
grig@solid.nsc.ru
Keywords: mechanochemical activation, mechanochemical interaction, organic acids, silicon dioxide
Pages: 447455

Abstract >>
The interaction of amorphous silicon oxide (aerosil) with organic acids during mechanical activation in high-energy ball mill was studied by means of IR spectroscopy. It was demonstrated that monomer molecules of mono-, polyhydric and aromatic acids get bound with aerosil through the molecules of adsorbed water: aerosil–adsorbed wateracid. Water molecules form rather strong hydrogen bonds with the basic surface centres in aerosil and with hydroxyls of carboxylic groups in monomer molecules of acids. Both basic and acidic surface centres of the carrier take part in the mechanochemical interaction with aerosil.

UDC 541.18.053+543.42



4.
Advanced Method for Catalytic Dechlorination
of Polychlorinated Biphenyls

ABDUL GHAFFAR1, MASAAKI TABATA2, FARHANA MAZHER3 and AZHAR MASHIATULLAH1
1 IAD, Pakistan Institute of Nuclear Science & Technology,
P.O. Nilore Islamabad (Pakistan)
ghaffargreat@yahoo.com
2 Faculty of Science and Engineering,
Saga University (Japan),
3 Lahore Women Collage University,
Lahore (Pakistan)
Keywords: activated carbon, catalysis, water/organic solvent mixture, temperature
Pages: 457461

Abstract >>
Activated carbon was for the first time used as catalytic substrate in dechlorination process and a significant dechlorination (79 %) of most persistent 2,4,5–trichlorobiphenyl was achieved at 110 ºC in water/isopropanol solvent by applying reducing media. It was observed that carbon particles played a catalytic role to enhance the dechlorination process through substitution reactions and by suppressing further chlorination in reaction mixture. Dechlorination at the ortho position of biphenyl was clearly preceded through substitution reaction by hydroxyl and thiol ions. Moreover, in the absence of activated carbon, dechlorination was decreased and substituted products did not observed.

UDC 547



5.
Effect of Organic and Inorganic Impurities
on the Nucleation of Calcium Oxalate Monohydrate

O. A. GOLOVANOVA1, YU. O. PUNIN2, A. S. VYSOTSKIY1 and V. R. KHANNANOV1
1 Omsk State University,
Pr. Mira 55A, Omsk 644077 (Russia)
golovanoa2000@mail.ru
2 St. Petersburg State University,
Universitetskaya Naberezhnaya 7/9,Saint Petersburg 199034 (Russia)
Keywords: calcium oxalate monohydrate, induction period, amino acids, inhibition, crystallization
Pages: 463470

Abstract >>
On the basis of the experimental data, a set of problems connected with the features of the crystallization of wavellite in the presence of additives is considered. It is established with the help of X-ray phase analysis that the precipitates formed under the conditions studied are presented by calcium oxalate monohydrate. The presence of magnesium ions, hydrophosphate, phosphate and sulphate ions in solution has an inhibiting action on the crystallization of calcium oxalate monohydrate. The hindering effect of the additive increases proportionally to an increase in the concentration of the additive. It was proved experimentally that amino acids have diverse effects on nucleation: some of them (glutamic acid, glycine, lysine etc.) inhibit the process, whereas the others (proline, alanine, valine etc.) act as catalysts; a number of amino acids (serine, phenylalanine) exhibit an insignificant effect on nucleation.

UDC 577.118.543.422



6.
Composition and Purification of Wastewater
from the Alkaline Hydrolysis of Rice Shuck

L. A. ZEMNUKHOVA1,2, O. D. AREFYEVA2 and A. A. KOVSHUN2
1 Institute of Chemistry, Far East Branch of the Russian Academy of Sciences Far East Federal University,
Pr. 100-letiya Vladivostoka 159, Vladivostok 690022 (Russia)
2 Far East Federal University,
Ul. Sukhanova 8, Vladivostok 690950 (Russia),
arod@marbio.dvgu.ru
Keywords: rice shuck, alkaline hydrolysis, purification methods, silicon dioxide
Pages: 471476

Abstract >>
Alkaline hydrolyzates obtained from rice shuck processing were investigated. Results of the purification of alkaline hydrolyzates by means of coagulation, neutralization with the release of silicic acid, and sorption are presented. It is demonstrated that the purification methods used do not provide the requirements for preliminarily purified and fresh water for use in manufacturing unbleached cellulose with respect to the main hydrochemical parameters (coloration, mineralization, pH). It is established that alkaline hydrolyzates can be utilized with the formation of amorphous silicon dioxide which has a broad range of applications.

UDC 542.06:628.386:633.258



7.
Evaluation of the Technological and Geochemical Conditions of Sludge Pits of the West Siberian Oil and Gas Complex
for Reclamation Process Optimization

L. A. IGNATYEV1 and L. F. ZHEGALINA2
1 Institute of Soil Science and Agricultural Chemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Sovetskaya 18, Novosibirsk 630099 (Russia),
ignatev37@ngs.ru
2 Monitoring JSC, Khanty Mansi Autonomous Area,
Ul. Studencheskaya 2, Khanty Mansyisk 628012 (Russia),
lije@mail.ru
Keywords: drilling waste, high molecular weight hydrocarbons content, ionic and ultimate composition, biotesting, toxicity
Pages: 477481

Abstract >>
Data on the concentrations of hydrocarbons in the water phase and bottom settlings of sludge pits for the sludge pit technology of oil and gas well drilling are presented. Ionic and ultimate composition of the aqueous phase and bottom settlings were determined, as well as the concentration of radioactive elements. It was established that the high toxicity of sump hole content is mainly associated with the presence of high molecular fractions of hydrocarbons and the ions of sodium, potassium and chlorine. A substantial part of the sludge pit content is weakly toxic or non-toxic, it is confirmed by biotesting analysis. It is proposed to use the differentiated approach to the utilization of these wastes, in order to decrease material and energy expenses and increase the labour productivity.

UDC 504.064.47+504.054:622.816



8.
Low-Temperature Method of Synthesis of Nanopowder for the Production of Dense Ceramics Composed of ZrO2 - 8 mol. % Y2O3

G. R. KARAGEDOVandE. G. AVVAKUMOV
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences,
Ul. Kutateladze 18, Novosibirsk 630128 (Russia),
garik@solid.nsc.ru
Keywords: zirconium dioxide, synthesis, sintering
Pages: 483488

Abstract >>
Possibility of the low-temperature synthesis of zirconium dioxide nanopowder stabilized with yttrium (8 mol. %) from a mixture of hydrated zirconium oxynitride and yttrium carbonate mechanically activated in a continuous-type mill. It was shown that the powder formed even at 600 ° is easily moulded by dry pressing after disaggregation; its density after sintering is close to the theoretical value.

UDC 514.182+541.053



9.
Composition and Application of Soluble Products
of Wheat Straw Catalytic Oxidative Delignification

B. N. KUZNETSOV1,2, I. G. SUDAKOVA1, N. V. GARYNTSEVA1 and N. M. IVANCHENKO1
1 Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences Siberian Federal University,
Ul. K. Marksa 42, Krasnoyarsk 660049 (Russia),
bnk@icct.ru
2 Institute of Chemistry and Chemical Technology, Siberian Branch of the Russian Academy of Sciences,
Pr. Svobodny 79, Krasnoyarsk 664041 (Russia)
Keywords: wheat straw, oxidative delignification, soluble products, composition, application, binders, enterosorbents
Pages: 489495

Abstract >>
The composition of the soluble products of wheat straw delignification in the medium acetic acid–hydrogen peroxidewatersulphuric acid catalyst was studied by means of elemental and chemical analysis, IR spectroscopy and gas chromatography-mass spectrometry. It was established that the vat residue formed in the regeneration of spent alkali liquor contains the products of polysaccharide degradation (4.7 rel. %), esters (19.9 rel. %) and sterols (37.2 rel. %). The acetic lignin precipitated from the alkali liquor contains a substantial amount of oxygen-containing functional groups. A promising character was demonstrated experimentally for the presently unclaimed bio-renewable resource such as wheat straw as a chemical raw material for obtaining sorbents and binders in the production of wood-based panels.

UDC 547.474:543.8:676.164



10.
Choice of Sorbent for Selective Recovery of Palladium
from Electrolytes of Silver Refining

A. B. LEBED,O. YU. MAKOVSKAYA,V. I. SKOROKHODOV,S. S. NABOICHENKO andG. I. MALTSEV
Uralelektromed JSC,
Ul. Lenina, 1, Verkhnyaya Pyshma 624091 (Russia),
mgi@elem.ru
Keywords: palladium, silver, iolite, electrolyte, sorption, desorption
Pages: 497502

Abstract >>
Selective sorption and desorption of the complex compounds of palladium from nitric solutions of silver on the ionites of different kinds was studied. Anionite VP-1P is recommended for the purification of electrolyte solutions from palladium in silver refining.

UDC 661.183: 669.23



11.
Effect of High-Dose Ion Implantation of Niobium
on Changing the Mechanical Properties and Structure
of Molybdenum Used at the Stage of Sintering Nuclear Fuel from Uranium Dioxide

F. V. MAKAROV1, V. V. GUZEEV1, V. P. PISHCHULIN1, A. YA. SVAROVSKY1and T. I. GUZEEVA2
1 Seversk Technological Institute of National Research Nuclear University MEPhI,
Pr. Kommunisticheskiy 65, Tomsk Region, Seversk 636036 (Russia),
mfedorv@rambler.ru
2 Tomsk Polytechnical University,
Pr. Lenina 30, Tomsk 634050 (Russia)
Keywords: molybdenum, uranium dioxide, destruction, molybdenum carbides, molybdenum nitrides, molybdenum microstructure, ion implantation, operational reliability
Pages: 503508

Abstract >>
Results of the investigation of reasons causing the destruction of molybdenum containers used for sintering the pellets of fuel uranium dioxide are reported. An effect of niobium ion implantation changing the microstructure and mechanical properties of molybdenum was investigated. It was demonstrated that niobium prevents the formation of carbide, nitride and oxide phases on the boundaries of molybdenum grains, causes the rate of metal grain growth in the course of recrystallization to decrease and stabilizes mechanical properties thus increasing the operational reliability by 30–60 %.

UDC 669.28:54



12.
BIUSan Effective Agent for Increasing the Yield
of Spring Wheat and Potatoes

M. P. POLOVINKA1, N. G. VLASENKO2, A. A. MALYUGA2, M. T. EGORYCHEVA2, N. F. SALAKHUTDINOV1 and G. A. TOLSTIKOV1
1 Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,
Pr. Lavrentyeva 9, Novosibirsk 630090 (Russia),
polovina@nioch.nsc.ru
2 Siberian Research Institute of Farming and Agriculture Chemization, Siberian Branch of the Russian Academy of Agricultural Sciences,
Novosibirsk Region, Krasnoobsk 630501 (Russia)
Keywords: fir extract, bisamine, 2,4-dichlorophenoxyacetic acid, Usnea lichens, spring wheat, potato, phytopathogens, yield capacity
Pages: 509514

Abstract >>
A new efficient broad spectrum agent comparable in efficiency with chemical fungicides was developed on the basis of the aqueous solution of the salts of fir extract with bisamine, with the addition of the salt of 2,4-dichlorophenoxyacetic acid with bisamine and the Usnea lichen extract. The agent suppresses the development of fungal diseases and increases the yield of spring wheat and potato.

UDC 547.99+632.934.1



13.
Sulfation of Microcrystalline Cellulose
Using Ultrasonic Activation in N,N-Dimethylformamide

M. A. TORLOPOV
Institute of Chemistry, Komi Science Centre, Ural Branch of the Russian Academy of Sciences,
Ul. Pervomayskaya 48, Syktyvkar 167982 (Russia),
torlopov-ma@chemi.komisc.ru
Keywords: microcrystalline cellulose, cellulose sulphates, ultrasonic treatment
Pages: 515519

Abstract >>
A method is proposed for the sulfation of microcrystalline cellulose in the system N,N-dimethylformamide/chlorosulphonic acid with preliminary treatment of cellulose with ultrasound in an organic solvent. It is demonstrated that the treatment with ultrasound results in an increase in the reactivity of cellulose in the sulfation reaction as well as in occurring the sulfation in homogeneous medium. The action of ultrasound on microcrystalline cellulose is accompanied by a decrease in the polymerization level of the cellulose material and does not affect its crystallinity index. Water-soluble cellulose sulphates with the substitution level up to 1.5 were obtained using the method proposed.

UDC 541.64



14.
Investigation of the Surface
of Mechanically Activated Manganese Oxides

A. V. FETISOV1, G. A. KOZHINA2, V. B. FETISOV3 and E. A. Pastukhov1
1 Institute of Metallurgy, Ural Branch of the Russian Academy of Sciences,
Ul. Amundsena 101, Yekaterinburg 620016 (Russia),
fetisovav@mail.ru
2 Ural State Economics University,
Ul. 8 Marta 62, Yekaterinburg 620218 (Russia),
3 Ural State Agricultural Academy,
Ul. Karla Libknekhta 42, Yekaterinburg 620075 (Russia)
Keywords: mechanical activation, manganese oxides, surface, X-ray photoelectron spectroscopy
Pages: 521530

Abstract >>
The surface of oxides Mn3O4, Mn2O3 and MnO2 subjected to mechanical activation with the help of high-intensity grinding was studied by means of X-ray photoelectron spectroscopy. It was discovered that the surface layers of all the three oxides were transformed during mechanical activation into Mn2O3 possessing increased chemical stability against environmental action. The results are due to the thermal effect and the catalytic action of extrinsic iron in the surface layer of MnmOn particles.

UDC 546.713'712–31'71331'71431:544.3.032.2:543.428.4



15.
Novel Ecological and Energy Saving Method
of Single-Stage Synthesis of Isoprene

K. E. BURKINand R. A. AKHMEDYANOVA
Kazan State Technological University,
Ul. K. Marksa 68, Kazan 420015 (Russia)
izopren_russkij@mail.ru
Keywords: isoprene, trimethylcarbinol, 1,3,5-trioxane, cation-exchange resin, isobutylene, formaldehyde, energy saving
Pages: 531535

Abstract >>
The possibility of single-stage synthesis of isoprene from 1,3,5-trioxane and trimethylcarbinol in the presence of heterogeneous catalyst – strongly acidic macroporous cation-exchange resin was established. The composition of the reaction mixture was determined by means of gas-liquid chromatography. Along with isoprene, unreacted trimethylcarbinol was detected, as well as by-products: unsaturated isoamylenic alcohols and 4,4-dimethyldioxane-1,3 precursors of isoprene; the formation of an additional amount of isoprene during the decomposition of these compounds is possible. Optimal process conditions were chosen, providing the degree of trioxane conversion up to 99 %, selectivity of the process with respect to isoprene 65 %, and the yield of isoprene per transformed trioxane 64 %. In comparison with the existing two-stage methods of isoprene synthesis from the aqueous solution of formaldehyde and isobutylene, the proposed method allows one to decrease energy consumption and diminish the amount of waste water due to the “soft” technological conditions of the process.

UDC 54.05:542:547.315.2:504.064.043:620.9



16.
Recovery of Platinum Complexes from Chloride Solutions Using Oxidized Carbon Sorbents

V. S. GOLOVIZINandL. M. LEVCHENKO
Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences,
Pr. Akademika Lavrentyeva 3, Novosibirsk 630090 (Russia),
Wlad2007INX@ yandex.ru
Keywords: recovery of platinum group metals, surface functional groups, sorption, solutions of H2PtCl6 and 2PtCl4, oxidized carbon sorbents
Pages: 537540

Abstract >>
Sorption of platinum chloro complexes from solutions with the help of oxidized carbon sorbents was studied. An effect of the oxygenated surface functional groups of oxidized carbon sorbents on their sorption capacity was studied using IR spectroscopy, pH-metry, titrimetry. Sorption isotherms for H2PtCl6 and 2PtCl4 were obtained. It was established that the capacity of the sorbent with respect to H2PtCl6 increased by a factor of 2.4.

UDC 544.723: 546.26: 546.92