Galvano-dipolar effect

The phenomenology of the photogalvanic effect permits prediction of a number of physical phenomena, the most interesting of which is the galvano-dipolar effect. This effect consists in the appearance of an electric dipole moment in a sample through which an electric current is passed. A possible microscopic mechanism of this phenomenon, which can be realized in centrosymmetric media as well, is considered.     

Longitudinal DC electric discharge in a supersonic air flow

A longitudinal dc electric discharge in a submerged high-pressure supersonic air jet is described. Photographs of the discharge are provided. The experimental voltage across the discharge gap and the discharge current are given for two resistances of the resistor that limits the discharge current over a certain range of the discharge channel length along the air flow. The current-voltage discharge characteristic is provided at a constant discharge length. The main discharge characteristics are obtained from a comparison of the experimental and theoretical results calculated on the basis of the simplest model.     

Synthesis of Phosphocapped Derivatives of β-Cyclodextrin

Russian Journal of General Chemistry -     

Spectral and luminescence manifestations of intermolecular interactions of dyes in polymer matrices (review)

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 3, pp. 418–432, March, 1991.     

The kinetics of living free-radical polymerization of styrene in the presence of alkoxyamine: Interpretation within the framework of secondary inhibition hypothesis

The kinetics of the free-radical polymerization of styrene at 120°C in the presence of alkoxyamine as a living polymerization agent has been studied. The alkoxyamine forms in situ with a 100-fold variation in the initial concentration of 2,2,6,6-tetramethyl-1-piperidinyloxy. The rate of the process at the stationary stage decreases with an increase in the initial concentration of 2,2,6,6-tetramethyl-1-piperidinyloxy. The computer simulation of the kinetic features of the process under study demonstrates that this tendency is related to the possible secondary inhibition of the process by alkoxyamine and/or hydroxylamine arising in the system in the course of polymerization.     

An efficient approach towards the convergent synthesis of "fully-carbohydrate" mannodendrimers

Glycosylation of sugar trityl ethers with sugar 1,2-O-(1-cyano)ethylidene derivatives (the trityl-cyanoethylidene condensation) has been applied to the synthesis of highly branched (dendritic) mannooligosaccharides incorporating a Manalpha1-->3(Manalpha1-->6)Man structural motif. The convergent synthetic strategy used to assemble these oligosaccharides was based on the use of glycosyl acceptors and/or a glycosyl donor already bearing this structural motif. The former were represented by mono- and ditrityl ethers of ManalphaOMe, Manalpha1-->3ManalphaOMe, and Manalpha1-->3(Manalpha1-->6)ManalphaX, where X=OMe or SEt. The pivotal glycosyl donor was the peracetylated 1,2-O-(1-cyano)ethylidene-3,6-di-O-(alpha-D-mannopyranosyl)-beta-D-mannopyranose (1), prepared by orthogonal Helferich glycosylation of the known 1,2-O-(1-cyano)ethylidene-beta-D-mannopyranose with tetra-O-acetyl-alpha-D-mannopyranosyl bromide followed by O-acetylation. Glycosylation of acetates of methyl 6-O-trityl-alpha-D-mannopyranoside and methyl 3,6-di-O-trityl-alpha-D-mannopyranoside with one equivalent of the donor 1 gave rise to the isomeric tetrasaccharide derivatives, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6ManalphaOMe and Manalpha1-->3(Manalpha1-->6)Manalpha1-->3ManalphaOMe, respectively. The latter derivative was further mannosylated at the remaining 6-O-trityl acceptor site to give the protected pentasaccharide Manalpha1-->3(Manalpha1-->6)Manalpha1-->3(Manalpha1-->6)ManalphaOMe. The isomeric pentasaccharide, Manalpha1-->3(Manalpha1-->6)Manalpha1-->6(Manalpha1-->3)ManalphaOMe, was prepared by reaction of 1 with the 6-O-trityl derivative of (Manalpha1-->3)ManalphaOMe. In a similar fashion, 6'- and 6"-O-trityl derivatives of the branched trisaccharide Manalpha1-->3(Manalpha1-->6)ManalphaOMe served as precursors for two isomeric mannohexaosides. The 3,6-di-O-trityl ether of ManalphaOMe and the 6',6"-di-O-trityl ether of Manalpha1-->3(Manalpha1-->6)ManalphaX (X=OMe or SEt) were efficiently bis-glycosylated with the donor 1 to give the corresponding protected mannoheptaoside and mannononaoside. The yields of these glycosylations with the donor 1 ranged from 50 to 66 %. Final deprotection of all the oligosaccharides was straightforward and afforded the target products in high yields. Both the acylated and deprotected products were characterized, and the intersaccharide connectivities were elucidated by extensive one- and two-dimensional NMR spectroscopy. The described blockwise convergent approach allows assembly of a variety of 3,6-branched mannooligosaccharides.