A ring-closing metathesis route to 7-membered aza-heteroannulated sugars

Azepane rings have been constructed diastereoselectively upon a carbohydrate derivative utilising reductive amination and RCM. The stereochemistry of the ring junctions was confirmed by X-ray crystallography and NMR. Diastereoselective dihydroxylation has also been employed to afford a tetrahydroxylated azepane carbohydrate derivative with potential biological activity.     

The effect of metal oxides on the oxidation of polybutadiene

Carboxy-terminated polybutadiene (CTPB) was oxidised as a coating on various metal oxides by heating in air on a thermobalance. The oxidation was found to be free from diffusion control and was catalysed by certain of the oxides. The catalysis was shown to be independent of semiconductor type and to be associated with those oxides for which the width of the forbidden zone between the valence and conduction bands (U) is less than 1.9 eV. In general, low values of U result in high catalytic activity. It is proposed that catalysis occurs by a redox mechanism, viz. RO₂H + p → RO₂^. + H⁺, RO₂H + e → RO^. + OH^?.     

The thermal degradation and oxidation of polybutadiene

Detailed studies have been made of the successive stages in the thermal degradation in air and nitrogen of carboxy-terminated polybutadiene (CTPB). During oxidation at high temperatures, a protective surface film is first formed; this film ruptures at temperatures where pyrolysis leads to the formation of volatile products in the bulk of the polymer. Thermogravimetric curves for the degradation of CTPB in nitrogen are complex in shape; it appears that the free-radical crosslinking and cyclisation reactions cause an increase in the thermal stability of the polymer during degradation.     

Phosphoryl and Thiophosphoryl Transfer Reactions: Stereochemical Imperatives for Metaphosphate and Thiometaphosphate

Abstract

The stereochemical courses of phosphoryl transfer reactions in aprotic solvents and thiophosphoryl transfer reactions in protic solvent have been determined. The extensive racemisation observed in both instances is discussed in terms of metaphosphate and thiometaphosphate intermediates of significant life-times.     

Photostabilisation of wood using aromatic vinyl esters

Thin wood veneers were esterified to different weight gains with vinyl benzoate, vinyl cinnamate or vinyl-4-T-butylbenzoate to graft aromatic groups to wood's molecular components. We hypothesised that such modification would increase the resistance of wood to photodegradation. There was a linear relationship between the level of esterification of wood with vinyl benzoate and the photostability of the modified veneers exposed to natural weathering. Vinyl benzoate protected lignin and cellulose in wood from photodegradation at high weight gains (>30%) whereas modification of wood with vinyl-4-T-butylbenzoate provided no such protection and vinyl cinnamate increased the photodegradation of wood. We provide an explanation for why these effects occurred and discuss the implications of our findings for the development of weather-resistant wood materials.     

As-rich reconstruction stability observed by high temperature scanning tunnelling microscopy

Atomic resolution scanning tunnelling microscopy (STM) has been used to study in-situ the As-terminated reconstructions formed on GaAs(0 0 1) surfaces in the presence of an As₄ flux. The reconstructions c(4×4), (2×4) and (3×1) are long established for GaAs(0 0 1) between 400 and 600 °C for varying Ga and As flux, however the stoichiometry of incommensurate transient reconstructions is still uncertain. By performing high temperature STM on an initial (2×4) surface between 250 and 450 °C in the absence of an As flux, small domains with varying reconstruction are observed in a similar manner to the InAs/GaAs(0 0 1) wetting layer. The local storage of excess Ga in Ga-rich domains could provide insight into sub ML homo- and hetero-epitaxial growth.     

CBE growth of GaAs/GaAlAs HBTs using the new DEAlH-NMe3 precursor and all-gaseous dopants

This paper describes the first reported use of diethylaluminium hydride-trimethylamine adduct (DEAlH-NMe₃) for the growth of GaAs/GaAlAs power heterojunction bipolar transistors (HBTs) by chemical beam epitaxy (CBE). This precursor possesses a significantly higher vapour pressure than the more conventionally used triethylaluminium (TEA), and leads to much less stringent requirements for bubbler and gas-line heating, and also much-improved GaAs/GaAlAs heterojunction definition when no carrier gas is employed. The use of all-gaseous n- and p-type dopants offers significant technological advantages in CBE, and the current paper also provides the first report of the use of hydrogen sulphide for n-type doping of CBE-grown GaAlAs HBT emitter regions. In conclusion, DC and RF data obtained from the heterojunction bipolar transistors fabricated to date are described. A DC gain of 40 has already been measured and encouraging early data obtained from RF-probed devices are also presented.     

Molecular dynamics simulation of (100)InGaAs/GaAs strained-layer relaxation processes

Molecular dynamics simulations on In_1−xGa_xAs/GaAs(100) systems are performed showing the dynamics of threading dislocations in the overlayers and the formation of misfit dislocations at the heterojunction interface. The developed code, using a modified Tersoff potential, simulates the threading dislocation dynamics in the InGaAs overlayer, and also the formation of interface misfit dislocations. Values for critical thicknesses are predicted and the atomic structure of the dislocation cores are determined.