Ordering of structural vacancies in vanadium monoxide of substoichiometric composition

The order-disorder phase transition in vanadium monoxide of substoichiometric compositions VO_y has been studied for the first time in situ by the Faraday method with a pendulum magnetic balance of the Domenically type. A minimum is found on the temperature dependence of the magnetic susceptibility of vanadium monoxide of different compositions at a temperature of about 700 K. X-ray diffraction analysis performed before and after measuring the magnetic susceptibility confirmed the change in the structure of vanadium monoxide and the possibility of atom-vacancy processes upon cooling and heating of the samples.     

Hydrolysis of phosphorus acid esters in the sodium bis(2-ethylhexyl)sulfosuccinate—<Emphasis Type="Italic">n</Emphasis>-nonane—polyethylene glycol—water supramolecular system before and after the percolation threshold

The kinetics of alkaline hydrolysis of O-ethyl O-p-nitrophenyl chloromethylphosphonate in a sodium bis(2-ethylhexyl)sulfosuccinate—n-nonane—polyethylene glycol—water reverse micellar system was studied in a wide range of concentrations of the surfactant and water. The sign of the catalytic effect of micelles is inverted in the presence of the polymer. A sharp change in the apparent rate constant of hydrolysis of the phosphonate was found in a region of the temperature percolation threshold. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 60–67, January, 2007.     

Micellization and catalytic activity of the cetyltrimethylammonium bromide-Brij 97-water mixed micellar system

Surface tension measurements and the kinetic study of the basic hydrolysis of ethyl p-nitrophenyl chloromethyl phosphonate were used to examine the structural behavior and catalytic activity of the cethyltrimethylammonium bromide (CTAB)-polyoxyethylene (10) oleyl ether, C(18)H(35)(OCH(2)CH(2))(10)OH (Brij 97)-water mixed micellar system. Application of the regular solution model to the experimental data yields the value of the interaction parameter beta as -4.6, which indicates an attractive interaction of the surfactants in the mixed micelle and reflects synergistic solution behavior of the mixture. The mixed micellar composition is found to be enriched in the surfactant with the lower critical micelle concentration (cmc). In the kinetic study a nonmonotonic change in the pseudo-first-order rate constant of basic hydrolysis of the substrate is observed with increasing mole fraction of nonionic surfactant. The pseudophase micellar model reveals that the concentration factor mainly contributes to the catalytic effect, while the microenvironmental factor plays a negative role.     

Synthesis and some properties of the methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid

The methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid were obtained by the reaction of the corresponding 4-substituted 2-hydrazino-5-phenylthiazole with NaNO₂ in acid media. IR and UV spectroscopy were used to show that the compounds synthesized retain azide form in both the crystalline state and in solution. The reaction of azides with dicarbonyl compounds gave derivatives of 2-[5-methyl-4-acetyl-or 2-[5-methyl-4-ethoxycarbonyl-1,2,3-triazol-1-yl]-5-phenylthiazole-4-carboxylic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 710–714, May, 1993.     

Self-assembling catalytic systems based on new amphiphile containing purine fragment,exhibiting substrate specificity in hydrolysis of phosphorus acids esters

Micellar catalytic systems based on new purine-containing amphiphile for hydrolytic decomposition of organophosphorus toxicants have been prepared. The aggregation threshold of the system has been estimated by means of tensiometry, conductometry, spectrophotometry, and dynamic light scattering. The solubilizing action of the amphiphile towards the hydrophobic dye has been demonstrated. Kinetic studies of hydrolysis of phosphonates differing in the hydrophobicity have disclosed the substrate specificity of the micellar catalysts; inhibition instead of catalysis has been observed in the case of the less hydrophobic substrate.     

The influence of the structure of tetracoordinate phosphorus acid esters on the catalytic effect of the sodium dodecyl sulfate-hexanol-water ternary reverse micellar system

The catalytic effect of the sodium dodecyl sulfate-hexanol-water ternary reverse micellar system in the alkaline hydrolysis ofO-alkylO′-aryl chloromethylphosphonates as a function of the substrate structure was studied. The micellar effect is mainly determined by a change in the electronic properties of the substituents, while the hydrophobicity plays a secondary role. The kinetic data were examined in the framework of the pseudo-phase model of micellar catalysis. The rate constants of the reaction in the surface layer and the partition constants of the reactants were calculated. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1366–1370., August, 2000.     

The influence of the nature of surfactants and dispersion medium on the catalytic effect of reverse micellar systems

The catalytic effect of reverse micellar systems in alkaline hydrolysis of phosphonic acid esters is to a considerable extent determined by the structure of the substrate and surfactant and the nature of the oil phase but weakly depends on the surface potential of the aggregates. AOT-butanol-decane-water, sodium dodecyl sulfate-butanol-decane-water, and cetyltrimethylammonium bromide-butanol-decane-water microemulsions exhibit specific catalytic properties rather than catalytic properties intermediate between those of the surfactant-alkane-water and surfactant-alkanol-water three-component systems.     

The influence of detergentless microemulsion on the kinetics of hydrolysis of di(p-nitrophenyl) methylphosphonate catalyzed by amines

The influence of the detergentless water/oil microemulsion formed in then-hexane-water-2-propanol system on the kinetics of the hydrolysis of di(p-nitrophenyl) methylphosphonate under the conditions of general base catalysis by primary, secondary, and tertiary aliphatic amines was investigate. The leveling of the catalytic rate constants and basicities of the amines was found for this reaction in a microemulsion. The catalytic rate constants for the amines containing hydrophilic groups increase in microemulsions as compared to those in an aqueous medium, while the catalytic constants for the amines containing hydrophobic groups decrease. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1339–1342, July, 1998.