Kinetic isotope effects for oxidation reaction of olefins by p-quinones in water-acetonitrile solutions of cationic and chloride anionic palladium complexes

Kinetic isotope effects for oxidation reactions of ethylene and cyclohexene in solutions of cationic palladium(ii) complexes in MeCN-H₂O(D₂O) systems, were measured. It was established that the ratio of the initial reaction rates ${{R_0^{H_2 O} } \mathord{\left/ {\vphantom {{R_0^{H_2 O} } {R_0^{D_2 O} }}} \right. \kern-0em} {R_0^{D_2 O} }} $ is equal to 1 for both reactions with the use of cationic complexes of the type Pd(MeCN) _x (H₂O)_4?x ²⁺, which differs from oxidation reactions catalyzed by chloride palladium complexes in the same solutions, where the ratio ${{R_0^{H_2 O} } \mathord{\left/ {\vphantom {{R_0^{H_2 O} } {R_0^{D_2 O} }}} \right. \kern-0em} {R_0^{D_2 O} }} $ = 5.0±0.16 and 4.73±0.14 at H⁺ molar fraction of 0.48 and 0.16, respectively (H⁺ molar fraction was calculated based on the sum of [H⁺] and [D⁺]).     

A step toward better understanding of behavior of organic materials at simultaneous high pressures and high temperatures

Using an external heating system, specifically designed for the lever-type diamond anvil cell, we investigated for the first time the phase relationships in the C₂H₂O₄ system at temperatures exceeding 850°C and pressures up to 6.5?GPa. In situ Raman spectroscopy was applied for the characterization of structural features of observed high-temperature phases, which transformed to the black carbon-rich material upon quenching and decompression. Results of this work give insights on the pressure-induced polymerization process of organic compounds at high temperatures.     

Functionalization of NH-unsubstituted androstano[17,16-d]pyrazoles. Synthesis of 2-arylamino-2-thioxoacetylandrostano[17,16-d]pyrazoles

Russian Chemical Bulletin - An approach to the synthesis of earlier unknown androstano[17,16-d]pyrazoles containing a monothiooxamide fragment at the nitrogen atom of the pyrazole ring has been...     

Temperature-Hysteresis Effects in CO Oxidation on Cement Catalysts with Various CuO Content

The temperature dependence of the degree of CO oxidation with atmospheric oxygen on coppercement catalysts was studied.     

A Solid‐State Protein Junction Serves as a Bias‐Induced Current Switch

A sample‐type protein monolayer, that can be a stepping stone to practical devices, can behave as an electrically driven switch. This feat is achieved using a redox protein, cytochrome C (CytC), with its heme shielded from direct contact with the solid‐state electrodes. Ab initio DFT calculations, carried out on the CytC–Au structure, show that the coupling of the heme, the origin of the protein frontier orbitals, to the electrodes is sufficiently weak to prevent Fermi level pinning. Thus, external bias can bring these orbitals in and out of resonance with the electrode. Using a cytochrome C mutant for direct S?Au bonding, approximately 80 % of the Au–CytC–Au junctions show at greater than 0.5 V bias a clear conductance peak, consistent with resonant tunneling. The on–off change persists up to room temperature, demonstrating reversible, bias‐controlled switching of a protein ensemble, which, with its built‐in redundancy, provides a realistic path to protein‐based bioelectronics.     

Kinetics and Energetics of Intramolecular Electron Transfer in Single-Point Labeled TUPS-Cytochrome c Derivatives

Electron transfer within and between proteins is a fundamental biological phenomenon, in which efficiency depends on several physical parameters. We have engineered a number of horse heart cytochrome c single-point mutants with cysteine substitutions at various positions of the protein surface. To these cysteines, as well as to several native lysine side chains, the photoinduced redox label 8-thiouredopyrene-1,3,6-trisulfonate (TUPS) was covalently attached. The long-lived, low potential triplet excited state of TUPS, generated with high quantum efficiency, serves as an electron donor to the oxidized heme c. The rates of the forward (from the label to the heme) and the reverse (from the reduced heme back to the oxidized label) electron transfer reactions were obtained from multichannel and single wavelength flash photolysis absorption kinetic experiments. The electronic coupling term and the reorganization energy for electron transfer in this system were estimated from temperature-dependent experiments and compared with calculated parameters using the crystal and the solution NMR structure of the protein. These results together with the observation of multiexponential kinetics strongly support earlier conclusions that the flexible arm connecting TUPS to the protein allows several shortcut routes for the electron involving through space jumps between the label and the protein surface.     

Numerical investigation of convective heat transfer in liquid hydrocarbons stored in underground reservoirs

In planning for the underground storing of liquid hydrocarbons and calculating the technological parameters of underground reservoirs formed by leeching from a rock salt massif, it is necessary to understand the hydrodynamic and heat transfer processes produced by natural convection. The paper is devoted to numerical study of the initial stage of convective heat transfer in a vertical cylindrical cavity completely filled with a liquid hydrocarbon. It is assumed that at the initial time the temperature of the liquid, which is at rest, is homogeneous, Convective flow develops in part due to the initial temperature difference between the liquid and the massif and partly due to the geothermal temperature gradient in the latter. The problem is regarded as coupled, the convective process in the liquid being determined simultaneously with the solution of the heat-conduction problem in the surrounding rock. The Grashof numbers characterizing the intensity of the real process are very large: G lO¹²–lO¹⁵. A numerical solution was obtained for moderate Grashof numbers G lO⁷–lO¹¹. The asymptotic dependences for the integral characteristics of the unsteady process obtained in a series of calculations were extrapolated to the real values of the Grashof number.Translated from Izvestiya Akademii Nauk SSSR, Mekhanika Zhidkosti i Gaza, No. 2, pp. 143–148, March–April, 1981.     

Effect of ω-substituents in the hydrazones of conjugated pregnane 20-ketosteroids on their ability to cyclize to pyrazolines

The reactions of 3β-acetoxy-5-pregnan-20-one with thiooxamic acid hydrazides were studied. Depending on the nature of substituents in the thiohydrazide, the reactions give the corresponding hydrazones or pyrazolines resulting from hydrazone cyclization. Dedicated to Academician O. M. Nefedov on the occasion of his 75th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2038–2039, November, 2006.