Photocatalytic production of hydrogen in systems based on Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Zn<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>S/Ni<Superscript>0</Superscript> nanostructures

A relation was established between the composition of Cd _x Zn_1–x S nanoparticles and their ability to accumulate excess negative charge during irradiation. The rate of expenditure of the accumulated charge depends on the composition of the nanoparticles and is determined by their electric capacitance. A correlation was found between the photocatalytic activity of the Cd _x Zn_1–x S nanoparticles in the release of hydrogen from solutions of Na₂SO₃, their composition, and their capacity for photoinduced accumulation of excess charge. It was shown that Ni⁰ nanoparticles photodeposited on the surface of Cd _x Zn_1–x S are effective cocatalysts for the release of hydrogen. It was found that Zn^II additions in photocatalytic systems based on Cd _x Zn_1–x S/Ni⁰ nanostructures have a promoting action on the release of hydrogen from water–ethanol mixtures. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 1, pp. 8–16, January-February, 2009.     

Kinetics of nonstationary condensation of methane on a perovskite catalyst

The interaction of methane with the oxidized surface of the KNaSrCoO_3−x is first order in methane with respect to formation of higher hydrocarbons and zero order with respect to formation of CO₂. At the initial stage the rate of formation of the reaction products is independent of the amount of oxygen from the catalyst consumed (up to 5–7 monolayers of oxygen), after which the rate of the reaction falls linearly. The overall amount of oxygen consumed in the reaction reaches 30 monolayers. L. V. Pisarzhevskii Institute of Physical Chemistry, National Academy of Sciences of Ukraine, 31 Prospekt Nauki, Kiev 03039, Ukraine. Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 36, No. 3, pp. 182–187, May–June, 2000.     

Comparative Effectiveness of Oxygen and Nitrous Oxide in the Partial Oxidation of Methane on V2O5/SiO2

It is shown that at relatively low temperatures the rate of oxidation of methane by nitrous oxide over the catalyst V₂O₅/SiO₂ exceeds the rate of oxidation of methane by oxygen, whereas at higher temperatures the opposite relation is observed between the comparative rates of the reactions. This effect is explained on the basis of a heterogeneous chain mechanism for the oxidation of methane.     

Growth and spectroscopic characterization of CdSe nanoparticles synthesized from CdCl2 and Na2SeSO3 in aqueous gelatine solutions

CdSe nanoparticles were synthesized in comparatively mild conditions from Na₂SeSO₃ and CdCl₂ in aqueous gelatine solutions. Kinetics of the formation and growth of CdSe nanocrystals as well as the effect of various parameters of reacting mixture on the size of CdSe nanocrystals are investigated. Optical properties of thin gelatine films, containing CdSe nanoparticles of different size, are characterized using absorption and Raman spectroscopy.     

Studies of the heat capacity and thermal expansion of the Na0.95K0.05NbO3 solid solution

The heat capacity and thermal expansion of ceramic samples of the Na_0.95K_0.05NbO₃ solid solution have been investigated over a wide temperature range of 100–750 K. The observed anomalies in the heat capacity and thermal expansion at T ₄ = 297 K, T ₃ = 535 K, T ₂ = 665 K, and T ₁ ≈ 710 K correspond to the sequences of phase transitions N → Q → G → S → T1. It has been shown that, as a result of the phase transitions, the unit cell volume at T ₄ and T ₂ decreases, and at T ₃ and T ₁, increases with increasing temperature. The directions of the shift of the phase transition temperatures induced by hydrostatic pressure have been determined. It has been established that all structural transformations are accompanied by relatively small variations in the entropy. Different mechanisms of the structural distortions have been discussed.     

Effect of the Composition of Mn-, Co- and Ni-Containing Perovskites on their Catalytic Properties in the Oxidative Coupling of Methane

The catalytic properties of complex oxide catalysts with ABO₃ perovskite structure (A = Sr, Ba, La; B = Mn, Co, Ni) in the oxidative coupling of methane were studied with separate introduction of methane and oxygen onto the catalyst. The greatest catalytic activity was found for the nickel-containing oxides but these catalysts have much lower operational stability than Mn- and Co-containing catalysts. Modification of the oxide systems studied by partial replacement of the strontium or transition metal ions by alkali metal ions considerably improves their activity and selectivity.__________Translated from Teoreticheskaya i Eksperimental’naya Khimiya, Vol. 41, No. 2, pp. 110–114, March– April, 2005.     

Photocatalytic Oxidation of Hydrosulfide Ions by Molecular Oxygen Over Cadmium Sulfide Nanoparticles

Photocatalytic activity of CdS nanoparticles in hydrosulfide-ions air oxidation was revealed and thoroughly investigated. HS⁻ photooxidation in the presence of CdS nanoparticles results predominantly in the formation of SO₃ ²⁻ and SO₄ ²⁻ ions. Photocatalytic activity of ultrasmall CdS crystallites in HS^– photooxidation is much more prononced as compared to bulk CdS crystals due to high surface area of nanoparticles, their negligible light scattering, improved separation of photogenerated charge carriers etc. It was shown that hydrosulfide ions can be oxidized in two ways. The first is HS⁻ oxidation by the CdS valence band holes. This process rate depends on the rate of comparatively slow reaction between molecular oxygen and CdS conduction band electrons. The second reaction route is the chain-radical HS⁻ oxidation induced by photoexcited CdS nanoparticles and propagating in the bulk of a solution. In conditions favourable to chain-radical oxidation of HS⁻(i.e. at low light intensities and CdS concentration and high oxygen and Na₂S concentrations) quantum yields of the photoreaction reach 2.5.     

Synergistic antitumor effect of cisplatin and the platinum(iv) nitroxyl complex BC118 and the development of resistance to their combined action

The efficacy of the combination treatment of P388 leukemia with cisplatin (cPt) and the platinum(IV) nitroxyl complex BC118 [e-ammine-d-(4-amino-2,2,6,6-tetramethylpiperidine-1-oxyl)-a,f-bis(acetato)-b,c-dichloroplatinum(iv)] applied in low doses was found to be synergistically increased. Thus, the use of 1/10 of their LD₅₀ cured 100% of animals. The monotherapy with these drugs used in the same doses and at the same schedules showed moderate efficacy, and no animals survived. A synergistic increase in the toxicity was not observed. The rate of the development of resistance decreases in the series cPt+BC118, cPt, and BC118. Strains resistant to cPt+BC118 and BC118 are highly sensitive to doxorubicin, etoposide, and cyclophosphane.     

Influence of the misfit of the crystal chemical parameters of Na and Li cations on the dielectric properties of NaNbO<Subscript>3</Subscript>-LiNbO<Subscript>3</Subscript> solid solutions

It is established that the Curie-Weiss temperature of Na_{1 − x} Li _x NbO₃ solid solutions determined by extrapolation of linear portions of the temperature dependence of the reciprocal of the permittivity ɛ⁻¹ from the cubic phase sharply increases with x, although the temperature of the ɛ(T) maximum decreases. It is shown in terms of a simple theoretical model that the experimentally observed change in the dielectric properties of Na_{1 − x} Li _x NbO₃ is well explained under the assumption of formation of a dipole system due to the displacement of Li cations from the center of the cubooctahedral cavity because of the significant steric misfit between the Na and Li cations.     

Synthesis, structure, and biological activity of mixed-ligand platinum(II) complexes with aminonitroxides

Mixed-ligand platinum complexescis-Pt^II(R⁶NH₂)(NH₃)X₂ andcis-Pt^II(R⁵NH₂)(NH₃)X₂ (R⁶ is 2,2,6,6-tetramethyl-4-piperidyl-1-oxyl and R⁵ is 2,2,5,5-tetramethyl-3-pyrrolidinyl-1-oxyl) were synthesized by either the reaction of aminonitroxides RNH₂ with Na[Pt^II(NH₃)Cl₂I] generatedin situ (for X₂=ClI) or by replacement of the iodo-chloro ligands incis-Pt¹¹(RNH₂)(NH₃)ClI by dichloro and oxalato ligands. The complexes obtained were characterized by elemental analysis and by IR, UV, and ESR spectra. Forcis-Pt¹¹(R⁵NH₂)(NH₃)Cl₂, crystal and molecular structures were determined by X-ray diffraction analysis. Cisplatin accelerates autooxidation of methyl linoleate and the platinum nitroxide complexes synthesized exhibit antioxidant properties. The rate of isolated DNA binding with the new complexes is almost as high as that for cisplatin.cis-Pt¹¹(R⁶NH₂)(NH₃)Cl₂ exhibits the highest antitumor activity. The high antitumor activity of platinum nitroxide complexes shows that the possible “radical component” is not a crucial factor in the cytotoxic action of cisplatin. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1624–1630, September, 2000.