New redox system: Trichloromethylarene —pyridine base

A redox reaction of trichloromethylarenes with pyridines results in respective N-(-chloroarylmethyl)substituted pyridiniurn chlorides which give, on hydrolysis, aromatic aidehydes and 4-chloropyridines or 1, 4-bipyridiniurn salts.N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow, Russia. Published in Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1373–1375, October, 1995. Original article submitted September 5, 1995.     

1H and13C NMR spectra of 1,5-disubstituted 1,3,4-oxadiazoles

The¹H and¹³C NMR spectra of 2, 5-disubstituted 1,3,4-oxadiazoles with aliphatic, aromatic, and hetero-aromatic substituents have been described and interpreted. The electronic effect of the 1,3,4-oxadiazole group as a benzene ring substituent was evaluated using¹³C NMR spectroscopy.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 834–842, June, 1994. Original article submitted April 8, 1994.     

Synthesis of 2,5-disubstituted 1,3,4-oxadiazoles from trichloromethylarenes and acylhydrazines

A preparative synthesis of 2,5-disubstituted 1,3,4-oxadiazoles by the reaction of trichloromethylarenes with hydrazides of carboxylic acids of the aliphatic, aromatic and heteroaromatic series in methanol or ethanol in the presence of pyridine was developed.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, 117913. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 686–692, May, 1994. Original article submitted April 8, 1994.     

Comparison of the accuracy of approximate methods TrESP and TrCAMM for evaluation of pigment coupling in light-harvesting complexes

Due to the large size of light-harvesting complexes, approximate methods are commonly used for calculating the coupling energies between their constituents. Two approximate methods are studied in this work: TrESP and the recently suggested TrCAMM method, based on the expansion of the one-particle density matrix. The quality of approximation of the electrostatic potential in the framework of these two approaches has been compared for two biological pigments as an example—chlorophyll a and bacteriochlorophyll a. It has been shown that both approaches provide high accuracy of approximation of the matrix elements of the electrostatic potential operator. In addition, it has been demonstrated that symmetrization of the one-particle density matrix in the framework of the TrCAMM method significantly improves the calculation accuracy and makes the computational procedure unambiguous.     

Collective modes of quantum dot ensembles in microcavities

Emission spectra of quantum dot arrays in zero-dimensional microcavities are studied theoretically. It is shown that their form is determined by the competition between collective superradiant mode formation and inhomogeneous broadening. A random sources method is used to calculate the photoluminescence spectra from an nonresonant pumped microcavity, and a standard diagram technique is used to provide a microscopic justification for the random sources method. The emission spectra of a microcavity are analyzed taking into account the spread of exciton energy due to inhomogeneous distribution of quantum dots and tunneling between them. It is demonstrated that the luminescence spectra of strongly tunnel-coupled quantum dots are sensitive to the dot positions, and the collective mode can (under certain conditions) be stabilized by random tunneling links.     

Dynamics of codeposition of metals inside porous electrode operating in direct-flow mode

Using an extended dynamic model of liquid flow-through porous electrode (PE), the effect of kinetics of deposition of individual components and conditions of potentiostatic electrolysis on the dynamics and final parameters (the cathodic deposit weight, the ratio between the amounts of components, and the spatial distribution of components) of codeposition of two metals M₁ and M₂ is studied. An equipotential PE operating in the direct-flow mode in the absence of anodic dissolution of electronegative component M₂ is considered. The effects of concentration, exchange currents, a difference between the equilibrium potentials M₁ and M₂, a prescribed voltage on PE, and solution flow velocity and direction are analyzed. It is shown that, for this version of codeposition of metals, the rates of M₁ and M₂ deposition averaged over the PE width are constant in time. However, this does not mean that their local deposition rates are constant. The general tendency is that the metal deposition rate on the rear part of PE decreases with the time, whereas the deposition rate on the frontal zone of PE, which is closer to the anode, increases. As a result, the final profiles for M₁ and M₂, which are calculated for equal deposition times taking into account and ignoring the redistribution of current during the deposition, differ essentially.     

Performance Analysis of a Stabilization System for Bodies of Neutral Buoyancy Anchored by an Elastic Cable

Nonlinear dynamic problems for a floating body anchored by an inhomogeneous cable are solved using a discrete elastic-thread model. The body, which is imponderable in water, stabilizes when suspended at the center of buoyancy via a hinged joint. The studies carried out for a particular example reveal that the approach we use to stabilize the body against angular oscillations does not always minimize the perturbations introduced by the tugboat under rough-water conditions. Also, we obtain conditions under which the body moves steadily and demultiplex resonances are absent.     

Checking of applicability of conditions for reaching the limiting-current mode to flow-by porous electrodes

For the flow-by porous electrodes, which differ in thickness, specific surface area, solution flow rate, and a ratio between the phase conductivities, the conditions providing the limiting-current mode over the entire electrode surface at nearly 100% current efficiency are determined using the method of successive refinement of total current and profile of its distribution along the solution flow. The used values of electrode thickness L are compared with available estimates for the limiting thickness of porous electrode L _lim derived for the ideal limiting-current mode and calculated using real values of the width of the limiting-current plateau of overall polarization curve, solution conductivity, and the diffusion limiting current in the zone of solution input into the electrode. It is found that these values are close to each other in all cases. The largest error of estimation of L _lim does not exceed 10% indicating that it can be used for preliminary estimation of the conditions for reaching the limiting-current mode for the flow porous electrodes of this type.     

Three-component synthesis of spiro compounds with a carbamate functionality

1,3-Dipolar cycloaddition of methyl 4-[2-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)acetyl]phenylcarbamate to non-stabilized azomethine ylides generated by decarboxylation of α-amino acid (sarcosine and proline) adducts with ketones (isatin and ninhydrin) occurred regioselectively with formation of the corresponding spiro compounds having a carbamate moiety.