In situ UV-visible assessment of extent of reduction during oxidation reactions on oxide catalysts

The extent of reduction of active centers during oxidative alkane dehydrogenation on VOx/Al2O3 was measured from pre-edge UV-visible spectral features and found to increase with increasing VOx domain size and propane/O2 ratio.     

Direct sulfonation of methane to methanesulfonic acid with SO2 using Ca salts as promoters

Direct liquid-phase sulfonation of methane to methanesulfonic acid (MSA) with SO2 has been achieved in triflic acid using K2S2O8 as the oxidant and a small amount of a Ca salt as the promoter. The effects of reaction conditions on the conversion of SO2 to MSA were examined. Included were the influence of solvent acidity, reaction duration, reaction temperature, amount of K2S2O8, and composition and amount of promoters.     

SERRS dyes. Part 3. Synthesis of reactive benzotriazole azo dyes for surface enhanced resonance Raman scattering

A series of eleven specially designed benzotriazole monoazo dyes for use in surface enhanced resonance Raman scattering studies are reported. Unlike previous benzotriazole dyes produced for SERRS, these dyes have been synthesised to be trifunctional in nature. The presence of the benzotriazole moiety provides surface complexing properties, the azo linkage provides the colour and hence extra sensitivity and the nucleophilic amine group enables further functionalisation.     

Wetting behaviour,moisture up-take and electrokinetic properties of lignocellulosic fibres

The wetting and moisture up-take behaviour, as well as the electrokinetic properties of various lignocellulosic fibres were characterised. Knowledge of surface and water uptake properties of this kind of materials will help to tailor their potential use in different end user applications. The surface tension of the fibres was determined from wetting measurements using the capillary rise technique. The wetting data were used to determine the surface tension of the fibres. Our results show that the surface tension of the lignocellulosic fibres is a linear function of their cellulose content. Zeta-potential measurements were exploited to characterise the surface chemistry of the fibres. Measuring the zeta-potential as function of time enables the rapid assessment of the water up-take, i.e. the swelling behaviour of the fibres. The results obtained by the zeta potential measurements correlate, with the exception of flax, in a linear manner with the results obtained from conventional moisture uptake measurements. Even though all lignocellulosic fibres are very hydrophilic due to the presence of polar oxygen containing groups they have different grades of hydrophilicity, which is also reflected in the different water uptake capabilities measured. The wetting, moisture uptake and electrokinetic properties of the lignocellulosic fibres are determined by the availability of the surface functional groups present, which is usually consequence of the processes used to separate, and extract the fibres from the plant (retting), as well as any further processing used to improve the fibre quality.     

Computational and experimental investigation of the Diels-Alder cycloadditions of 4-chloro-2(H)-pyran-2-one

4-Chloro-2(H)-pyran-2-one undergoes thermal Diels-Alder cycloaddition with electron-deficient dienophiles to afford, without any significant selectivity, 6-endo- and 5-endo-substituted bicyclic lactone cycloadducts. In contrast to 3- and 5-bromo-2(H)-pyran-2-one, 4-chloro-2(H)-pyran-2-one does not undergo thermal cycloadditions with electron-rich dienophiles. The regio- and stereochemical preferences of the cycloadditions of 4-chloro-2(H)-pyran-2-one and other related 2(H)-pyran-2-ones are investigated computationally. Calculations were carried out on the transition states leading to the four possible regio- and stereoisomeric cycloadducts using density functional theory (B3LYP/6-31G). These studies allow prediction of the regio- and stereoselectivity in these reactions which are in line with experimental observations.     

Photo-Induced Halogen-Atom Transfer: Generation of Halide Radicals for Selective Hydrohalogenation Reactions

The first photo-mediated process enabling the generation of halide radicals by Halogen-Atom Transfer (XAT) is described. Contrary to radical transformations involving XAT reactivity, which exploit stable carbon radicals, this unique approach uses 1,2-dihaloethanes for the generation of unstable carbon radicals by XAT. These transient radicals then undergo β-scission with release of ethylene and formation of more stable halide radicals which have been used in selective hydrohalogenations of a large number of unsaturated hydrocarbons, including Michael acceptors, unactivated alkenes and alkynes. This hydrohalogenation is tolerant of a broad range of functionalities and is believed to proceed through a radical-chain manifold that propagates by the use of silane derivatives.