N-labelling studies of the reaction of 2,6-di-t-butyl-4-methyl-4-nitrocyclohexa-2,5-dienone with nitrogen dioxide; A revised mechanism

Reaction of the ¹⁵N-4-nitrodienone (1) with excess nitrogen dioxide in benzene for 16 h gives the 4,5,6-trinitro ketone (2), labelled (¹⁵NO₂) at C6 but not at C4, and recovered 4-nitrodienone (1) in which extensive loss of ¹⁵NO₂ has occurred. The mechanistic implications of these and related results are discussed.     

Multiple nitrene insertions into metal-sulfur bonds of dithiocarbamate complexes: synthesis of sulfido-amido and zwitterionic tetraamido complexes

The iodine(III) reagent, PhI[double bond, length as m-dash]NTs, acts as a source of the nitrene fragment NTs, which undergoes facile insertion into the metal-sulfur bonds of a range of dithiocarbamate complexes. Addition of two equivalents of PhI=NTs to [M(S(2)CNR2)2] affords sulfido-amido complexes [M{SC(NR2)SNTs}2](M=Ni, Cu), which insert two further nitrene fragments to afford zwitterionic tetraamido complexes [M{TsNSC(NR2)SNTs}2](M=Co, Ni, Cu). Crystallographic studies have been carried out on both types of complex allowing possible resonance hydrids of the new ligand types to be assessed.     

High-performance liquid chromatographic analysis of free long chain fatty acids produced during lipolysis by anaerobic digestor sludge

The development of sample extraction techniques in conjunction with application of a modified version of an established HPLC technique allowed the rapid estimation of concentrations of long chain fatty acids (LCFA) produced by the lipolytic activity of bacteria in anaerobic digestor sludges or experiments using the sludges as inocula. It was established that free long chain fatty acids will preferentially partition into certain phases in the sludge or experimental cultures. These data, and application of the developed techniques for monitoring of LCFA, may lead to the avoidance of toxicity and failure of full-scale anaerobic digestors treating high lipid content waste in the future.     

An optimal two-step quadratic spline collocation method for the Dirichlet biharmonic problem

Numerical Algorithms - A two-step quadratic spline collocation method is formulated for the solution of the Dirichlet biharmonic problem on the unit square rewritten as a coupled system of two...     

Glass capillary gas chromatography of amino acid enantiomers

Glass capillaries coated with Chirasil-Val, a chirally functionalised polysiloxane, are capable in principle of resolving all protein amino-acid enantiomers in a single run and within a short analysis time, thus allowing for example the quantitative amino acid determination by enantiomer labelling. The elution characteristics of the individual amino acids however are also dependent upon the chemical nature of the capillary wall surface, and a surface pretreatment is found to be necessary if all protein amino acids are to be analysed. Of the various methods of pretreatment tested, etching of borosilicate glass with gaseous HCl followed by deposition of colloidal silicic acid is considered to be the most suitable.