Electrical switching and thermal studies on Ge22Te78-xIx chalcohalide glasses: The effect of iodine on network-topology

Investigations on the electrical switching behavior and thermal studies using Alternating Differential Scanning Calorimetry have been undertaken on bulk, melt-quenched Ge22Te78-,Is (3 <= x <= 10) chalcohalide glasses. All the glasses studied have been found to exhibit memory-type electrical switching. The threshold voltages of Ge22Te78-I-x(x) glasses have been found to increase with the addition of iodine and the composition dependence of threshold voltages of Ge22Te78-xIx glasses exhibits a cusp at 5 at.% of iodine. Also, the variation with composition of the glass transition temperature (Tg) of Ge22Te78-I-x(x) glasses, exhibits a broad hump around this composition. Based on the present results, the composition x = 5 has been identified as the inverse rigidity percolation threshold at which Ge22Te78-I-x(x) glassy system exhibits a change from a stressed rigid amorphous solid to a flexible polymeric glass. Further, a sharp minimum is seen in the composition dependence of non-reversing enthalpy (Delta H-nr) of Ge22Te78-I-x(x) glasses at x = 5, which is suggestive of a thermally reversing window at this composition. (C) 2007 Elsevier Ltd. All rights reserved.

Studies in sesquiterpenes-XIX. Action of perbenzoic acid on longifolene

Oxidation of longifolene, a mono-olefinic sesquiterpene, with a chloroform solution of perbenzoic acid proceeded to almost two mole consumption of the peracid to furnish a number of products, important ones being an α-ketol, a norketone (longicamphenilone) and the corresponding C14-alcohols. Under certain conditions it has been possible to arrest the reaction at one mole consumption and to isolate longifolene-α-epoxide, which is the major product; some amounts of epimeric longifolaldehydes and longicamphenilone were also formed. Further action of perbenzoic acid on longifolene oxide and longifolaldehydes has been investigated and the results used to interpret the mechanism of abnormal peracid oxidation of longifolene.

X-ray studies on crystalline complexes involving amino acids and peptides. XV. Crystal structures of L-lysine D-glutamate and L-lysine D-aspartate monohydrate and the effect of chirality on molecular aggregation

L-Lysine D-glutamate crystallizes in the monoclinic space group P2(1) with a = 4.902, b = 30.719, c = 9.679 A, beta = 90 degrees and Z = 4. The crystals of L-lysine D-aspartate monohydrate belong to the orthorhombic space group P2(1)2(1)2(1) with a = 5.458, b = 7.152, c = 36.022 A and Z = 4. The structures were solved by the direct methods and refined to R values of 0.125 and 0.040 respectively for 1412 and 1503 observed reflections. The glutamate complex is highly pseudosymmetric. The lysine molecules in it assume a conformation with the side chain staggered between the alpha-amino and the alpha-carboxylate groups. The interactions of the side chain amino groups of lysine in the two complexes are such that they form infinite sequences containing alternating amino and carboxylate groups. The molecular aggregation in the glutamate complex is very similar to that observed in L-arginine D-aspartate and L-arginine D-glutamate trihydrate, with the formation of double layers consisting of both types of molecules. In contrast to the situation in the other three LD complexes, the unlike molecules in L-lysine D-aspartate monohydrate aggregate into alternating layers as in the case of most LL complexes. The arrangement of molecules in the lysine layer is nearly the same as in L-lysine L-aspartate, with head-to-tail sequences as the central feature. The arrangement of aspartate ions in the layers containing them is, however, somewhat unusual. Thus the comparison between the LL and the LD complexes analyzed so far indicates that the reversal of chirality of one of the components in a complex leads to profound changes in molecular aggregation, but these changes could be of more than one type.

X-ray studies on crystalline complexes involving amino acids and peptides XIX. Effects of change in chirality in the complexes of succinic acid with dl- and l-arginine

Crystals of dl-arginine hemisuccinate dihydrate (I)(monoclinic; P21/c; a = 5.292, b = 16.296, c = 15.203 Å; α= 92.89°; Z = 4) and l-arginine hemisuccinate hemisuccinic acid monohydrate (II) (triclinic; P1; a = 5.099; b = 10.222, c = 14.626 Å; α= 77.31, β= 89.46, γ= 78.42°; Z = 2) were grown under identical conditions from aqueous solutions of the components in molar proportions. The structures were solved by direct methods and refined to R = 0.068 for 2585 observed reflections in the case of (I) and R = 0.036 for 2154 observed reflections in the case of (11). Two of the three crystallographically independent arginine molecules in the complexes have conformations different from those observed so far in the crystal structures containing arginine. The succinic acid molecules and the succinate ions in the structures are centrosymmetric and planar. The crystal structure of (II) is highly pseudosymmetric. Arginine-succinate interactions in both the complexes involve specific guanidyl-carboxylate interactions. The basic elements of aggregation in both the structures are ribbons made up of alternating arginine dimers and succinate ions. However, the ribbons pack in different ways in the two structures. (II) presents an interesting case in which two ionisation states of the same molecule coexist in a crystal. The two complexes provide a good example of the effect of change in chirality on stoichiometry, conformation, aggregation, and ionisation state in the solid state.