Open‐chain unsaturated selanyl sulfides: stereochemical structure and stereochemical behavior of their 77Se–1H spin–spin coupling constants

Stereochemical structure of nine Z‐2‐(vinylsulfanyl)ethenylselanyl organyl sulfides has been investigated by means of experimental measurements and second‐order polarization propagator approach calculations of their ¹H–¹H, ¹³C–¹H, and ⁷⁷Se–¹H spin–spin coupling constants together with a theoretical conformational analysis performed at the MP2/6‐311G** level. All nine compounds were shown to adopt the preferable skewed s‐cis conformation of their terminal vinylsulfanyl group, whereas the favorable rotational conformations with respect to the internal rotations around the C–S and C–Se bonds of the internal ethenyl group are both skewed s‐trans. Stereochemical trends of ⁷⁷Se–¹H spin–spin coupling constants originating in the geometry of their coupling pathways and the selenium lone pair effect were rationalized in terms of the natural J‐coupling analysis within the framework of the natural bond orbital approach. Copyright © 2012 John Wiley & Sons, Ltd.     

α-Acetylene Hydrosilanes as Hydrosilylating Agents for Terminal Arylacetylenes

The hydrosilylation of a number of acetylenes RCCH (R, R' = Ph, CH₂OPh, CH₂SPh) with -ethynylhydrosilanes Me₂SiHCHCR' in the presence of H₂PtCl₆ was investigated. The addition did not occur regioselectively, but was stereospecific and afforded a mixture of - and trans--adducts. The replacement of phenyl substituent by phenoxymethyl both in the molecule of ethynylsilane and the acetylene substrate resulted in growing proportion of the -adduct in the reaction mixture up to 10-60%.     

Honeycomb pattern formation by laser-beam filamentation in atomic sodium vapor

We have observed transverse pattern formation leading to highly regular structures in both the near and far fields when a near-resonant laser beam propagates without feedback through an atomic sodium vapor. One example is a regular far-field honeycomb pattern, which results from the transformation of the laser beam within the vapor into a stable three-lobed structure with a uniform phase distribution and highly correlated power fluctuations. The predictions of a theoretical model of the filamentation process are in good agreement with these observations.     

Solid-Phase Luminescence Determination of Ciprofloxacin and Norfloxacin in Biological Fluids

A simple, rapid, and sensitive luminescence test method for the determination of ciprofloxacin (CIP) and norfloxacin (NOR) has been described. The method is based on the intramolecular energy transfer from organic acid to terbium (Tb³⁺) ion. Luminescence of terbium (III) complex with CIP (NOR), sorbed on the zeolite has been studied. Under optimized conditions the detection limit is 1 g/mL in urine and human plasma.     

Heegner points,cycles and Maass forms

We derive for Hecke-Maass cusp forms on the full modular group a relation between the sum of the form at Heegner points (and integrals over Heegner cycles) and the product of two Fourier coefficients of a corresponding form of half-integral weight. Specializing to certain cycles we obtain the nonnegativity of theL-function of such a form at the center of the critical strip. These results generalize similar formulae known for holomorphic forms. Partially supported by NSF grant # DMS-9096262. Partially supported by NSF grant # DMS-9102082.     

Conformational isomerism of 1,2-diformyl-, diacetyl-, and di(trifluoroacetyl) hydrazines and their methyl analogs

Conclusion The PMR method was used to determine the conformations of the 1,2-diformyl-, diacetyl-, and di(trifluoroacetyl)hydrazines and their 1-methyl and 1,2-dimethyl analogs. The effect of the structure and the medium, on the population of the conformers was discussed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1428–1430, June, 1982.     

Dependence of the composition of the products of thermal fragmentation of thiacyanine dyes on the length of their polymethine chain

The pathways of thermal fragmentation of thiacyanine dyes with different lengths of the external polymethine chain were investigated. The results of thermolysis of the thiacyanines are compared with the results of quantum-chemical calculations of their molecules.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 188–192, February, 1982.