Thermal decomposition of anomeric glycopyranosides

Thermal analysis studies coupled with chemical studies indicate that glycopyranosides undergo thermal decomposition in two overlapping stages. The initial reaction of the glycosides at temperature between 200 and 300°C is cleavage and volatilization of the glycosidic group as the corresponding alcohol, followed by intra- or inter-molecular condensation of the glycosyl portion of the molecule. At higher temperatures (310–340°C) the major reaction is fragmentation of the carbohydrate into a variety of low molecular-weight compounds. Studies with a series of anomeric methyl and phenyl glycosides indicate that, with the methyl and phenyl glycosides, the rate of the low-temperature condensation reaction was dependent on anomeric configuration of the starting glycoside.     

A translation plane of order 192 admitting SL(2,5), obtained by 12-nest replacement

The problem of determining two-dimensional translation planes admitting SL(2,5) in the translation complement has been intensively studied. Most examples arise from multiple-derivation of a Desarguesian plane. In this paper, we construct two translation planes of order 19² admitting SL(2,5), one of which is obtained by 12-nest replacement.      

Effects of nuclear dynamics in the low-kinetic-energy Auger spectra of CO and CO2

The CO and CO(2) carbon and oxygen Auger spectra have been measured by electron impact and compared with accurate theoretical calculations accounting for the effects of the dynamics of the nuclei on the energy and linewidth of the Auger bands. The calculations for CO were previously published [L. S. Cederbaum et al., J. Chem. Phys. 95, 6634 (1991)], while for CO(2) they are new and presented here for the first time. For both molecules, particular attention has been paid to the low-kinetic-energy region of the spectra, which corresponds to doubly charged ion states with the two holes mainly localized in the inner valence region. New bands have been observed. It is shown that a proper consideration of the vibrational broadening and shift of the bands due to the dynamics of the nuclei is needed to assign these features. For CO, very large energy shifts between corresponding features in the C 1s and O 1s spectra have been observed, confirming the theoretical predictions of 1991. The new computed spectra of CO(2) allow a very accurate analysis of the experiments over the whole energy range.     

Isomorphous replacement in nylon 6 by 4-aminomethylcyclohexanecarboxylic acid

It was desired to determine the effect of geometric configuration on the ability of 4-aminomethylcyclohexanecarboxylic acid (AMCC) to “isomorphously” replace ε-aminocaproic acid residues in nylon 6. However, we found that cis-AMCC isomerized to the more thermodynamically stable trans isomer during copolymerization with caprolactam (CL) and also during homopolymerization. A 20/80 cis/trans ratio of AMCC residues was found in the 50:50 copolyamides regardless of whether a high-cis (72/28) or high-trans (15/85) AMCC was used. Powder x-ray diagrams showed similar interplanar spacings for the copolyamides made from both high-cis and high-trans AMCC. The x-ray study also showed that the nylon 6 lattice can accommodate less than 30 mole-% AMCC residues before a new structure appears. DTA and TGA data of the CL:AMCC copolyamide showed that AMCC raised the melting point, T_g, T_c, and stability of nylon 6.     

Supramolecular control over donor-acceptor photoinduced charge separation

A novel donor-bridge-acceptor system has been synthesized by covalently linking a p-phenylene vinylene oligomer (OPV) and a perylene diimid (PERY) at opposite ends of a m-phenylene ethynylene oligomer (FOLD) of twelve phenyl rings, containing nonpolar (S)-3,7-dimethyl-1-octanoxy side chains. For comparison, model compounds have been prepared in which either the donor or acceptor is absent. In chloroform, the oligomeric bridge is in a random coil conformation. Upon addition of an apolar solvent (heptane) the oligomeric bridge first folds into a helical stack and subsequently intermolecular self-assembly of the stacks into columnar architectures occurs. Photoexcitation in the random coil conformation, where the interaction between the donor and acceptor chromophores is small, results only in long-range intramolecular energy transfer in which the OPV singlet-excited state is transformed into the PERY singlet-excited state. In the folded conformation of the bridge, donor and acceptor are closer and their enhanced interaction favors the formation the OPV(*)(+)-FOLD-PERY(*)(-) charge-separated state upon photoexcitation. As a result, the extent of photoinduced charge separation depends on the degree of folding of the bridge between donor and acceptor and therefore on the apolar nature of the medium. As a consequence, and contrary to conventional photoinduced charge separation processes, the formation of the OPV(*)(+)-FOLD-PERY(*)(-) charge-separated state is more favored in apolar media.