Deformation of styrene—divinylbenzene copolymers and hypercrosslinked polystyrenes during solvent adsorption and desorption

An automated procedure was developed for monitoring fast changes in the size of spherical samples of polymers during their contact with a solvent or drying. The kinetics of bulk deformation in these processes was studied for a series of cross-linked polymers, viz., gel-type and porous styrene—divinylbenzene copolymers and poly(divinylbenzenes), and hypercrosslinked polystyrenes. Gel, macroporous, and hypercrosslinked polystyrenes are substantially different in the rate, mechanism, and degree of swelling, which is associated with the principal differences in their physical structures. An unusual effect of a sharp decrease followed by a temporary increase in the volume of porous polystyrene and poly(divinylbenzene) materials were observed during desorption (evaporation) of organic solvents. Water desorption is accompanied by an excessive bulk compression of porous granules giving rise to negative deformations, which gradually relax to the state equilibrium for the dry polymer. The results of dynamic desorption porometry (for water desorption) are indicative of a bimodal size distribution of micropores in hypercrosslinked polystyrene. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 467–476, March, 2007.     

Effect of dynamic loading on the structure of amorphous alloy Fe66Ni12Si20B2

Transmission- and depth-selective-conversion-electron Mössbauer spectroscopy (DCEMS) were applied to study variation of structural state in the bulk and in the surface layer (500, 1000, 1500 Å thick) of amorphous alloy under certain optimum conditions of the dynamic loading. The alloy structure remains amorphous. However, a certain variation of the short range order. An amorphous oxide Fe₂O₃ is formed on the amorphous alloy surface.     

Formation of spanning water networks on protein surfaces via 2D percolation transition

The formation of spanning hydrogen-bonded water networks on protein surfaces by a percolation transition is closely connected with the onset of their biological activity. To analyze the structure of the hydration water at this important threshold, we performed the first computer simulation study of the percolation transition of water in a model protein powder and on the surface of a single protein molecule. The formation of an infinite water network in the protein powder occurs as a 2D percolation transition at a critical hydration level, which is close to the values observed experimentally. The formation of a spanning 2D water network on a single rigid protein molecule can be described by adapting the cluster analysis of conventional percolation studies to the characterization of the connectivity of the hydration water on the surface of finite objects. Strong fluctuations of the surface water network are observed close to the percolation threshold. Our simulations also furnish a microscopic picture for understanding the specific values of the experimentally observed hydration levels, where different steps of increasing mobility in the hydrated powder are observed.     

Physicomechanical properties of grafted polymers obtained by radiation-induced polymerization by radical and ionic mechanisms

The radiation-induced grafting of acrylonitrile, 4-vinylpyridine, and styrene was carried out by both radical and ionic mechanisms. Grafted polymers with equal percentages of graft were obtained by the radical and ionic propagation of the grafted chains. The molecular weight of homopolymers has been determined. The thermomechanical properties of the graft polymers were investigated. The yield temperatures for the graft polymers obtained by ionic propagation of the grafted chains is higher than that of graft polymers obtained by a radical mechanism. This is attributed to the higher molecular weight of the grafted chains obtained by the radiation-induced grafting by the ionic mechanism. The radiation-induced grafting of polyacrylonitrile increases significantly the thermal stability of polyethylene. The differential thermal analysis shows no marked differences in properties of the polymers.     

Glass transition in the lower homologues of polyethyleneoxide

Experimental measurements of T_g for two series of lower homologues of polyethyleneoxide. differing in their end-groups, are discussed in terms of existing theories. Simple free-volume considerations predicting linear dependence of T_g on (molecular weight)^?1 are inadequate in systems with end-groups capable of specific interactions (hydrogen bonding). Thermodynamic arguments show that the true T_g of infinitely long PEO chain is 220 ± 5°K. Suitable modification of parameters of the Gibbs-DiMarzio equations to account for the dependence of the free volume fraction on the concentration of end-groups results in good fit of the experimental data for hydroxyl-terminated samples and correctly predicts T_g(∞). Analysis of the data for chlorine-substituted oligomers suggests the existence of specific intermolecular interactions in the latter, involving chlorine atoms.     

Methylation analysis in glycoprotein chemistry. General procedure for quantification of the products of solvolysis of permethylated glycopeptides and glycoproteins

A technique for the gas chromatographic analysis of the products of solvolysis of permethylated glycopeptides and glycoproteins has been developed. It involves methanolysis of a permethylated compound, quantitative transformation of methyl ethers of methyl glycosides into the corresponding O-trimethylsilyl(TMS)-O-methylalditols [2-deoxy-2-(N-methyl)acetamido-O-TMS-O-methylalditols in the case of hexosamine derivatives] and gas chromatographic quantification using a single column packed with 0.4% OV-225 on surface-modified Chromosorb.     

Synthesis of lepidine and its derivatives from aromatic amines and quaternary salts of Mannich bases

A quaternary salt of 4-(diethylamino)butan-2-one, methyldiethyl-3-ketobutylammonium methyl sulfate, is used as an alkylating agent to synthesize lepidine and 1-phenyllepidine salts. The method gives good yields, under mild conditions, of lepidine and 1-phenyllepidine perchlorate. An intermediate product is isolated, and a reaction mechanism suggested.