Synthesis and characterisation of Fe₆ and Fe₁₂ clusters using bicine

Reaction of bicine {BicH3, N,N-bis(2-hydroxyethyl)glycine} with an Fe(III) oxo-centered pivalate triangle in MeCN in the presence of Et<sub>2</sub>NH yields [Et<sub>2</sub>NH<sub>2</sub>]<sub>2</sub>[Fe<sub>6</sub>O<sub>2</sub>(OH)<sub>2</sub>(Bic)<sub>2</sub>(O<sub>2</sub>CCMe<sub>3</sub>)<sub>8</sub>], which possesses an S = 5 ground state. Changing the base to NaOMe produces [Fe<sub>12</sub>O<sub>4</sub>(Bic)<sub>4</sub>(HBic)<sub>4</sub>(O<sub>2</sub>CCMe<sub>3</sub>)<sub>8</sub>], which contains two Fe6 units bridged by the carboxylate arms from the bicine ligands. The complex displays strong antiferromagnetic coupling leading to an S = 0 ground state

Kinetic study of adsorption and photo-decolorization of Reactive Red 198 on TiO2 surface

Recycling and reuse of wastewater after purification will reduce the environmental pollution as well as fulfill the increasing demand of water. Adsorption-based water treatment process is very popular for dye-house wastewater treatment. The present study deals with treatment of wastewater contaminated by reactive dye. TiO2 is used as adsorbent and the spent adsorbent has been regenerated by Advanced Oxidation Process (AOP), without using any other chemicals. TiO2 adsorbs dye molecules and then those dye molecules have been oxidized via a photocatalytic reaction in presence of UV irradiation. Kinetics of dye adsorption and photocatalytic oxidation reaction has been developed in this study. Photocatalyst adsorbent (TiO2) has been reused several times after regeneration. The activity of catalyst decreases after each cycle; due to poisoning cause by intermediate by-products. Kinetic of this catalyst deactivation has been incorporated with L–H model to develop the photocatalytic reaction kinetic model

Chlorination and oxidation of heparin and hyaluronan by hypochlorous acid and hypochlorite anions: effect of sulfate groups on reaction pathways and kinetics.

Hypochlorous acid (HOCl), produced in inflammatory conditions by the enzyme myeloperoxidase, and its anion hypochlorite (OCl(-)) exist in vivo at almost equal concentrations. Their reactions with hyaluronan and heparin (as a model for sulfated glycosaminoglycans in the extracellular matrix) have been studied as a function of pH. The major product in these reactions is the chloramide derivative of the glycosaminoglycans. Spectral, chloramide yield, and kinetic measurements show sharply contrasting behavior of heparin and hyaluronan and the data allow the calculation of second-order rate constants for the reactions of both HOCl and OCl(-) for all reaction pathways leading to the formation of chloramides and also oxidation products. By comparison with hyaluronan, it can be demonstrated that both N-sulfate and O-sulfate groups in heparin influence the proportions of these pathways in this glycosaminoglycan. Evidence is also given for further oxidation pathways involving a reaction of HOCl with the chloramide product of hyaluronan but not with heparin. The significance of these results for the mechanisms of inflammation, particularly for fragmentation of extracellular matrix glycosaminoglycans, is discussed

A Proton Magnetic Resonance Study of the Association of Lysozyme with Monosaccharide Inhibitors

It has been shown that the acetamido methyl protons of N-acetyl-d-glucosamine undergo a chemical shift to higher fields in their proton magnetic resonance spectrum when the inhibitor is bound to lysozyme. The observed chemical shift in the presence of the enzyme is different for the agr- and ß-anomeric forms of 2-acetamido-2-deoxy-d-glucopyranose indicating either a difference in the affinity of the anomeric forms for lysozyme or different magnetic environments for the methyl protons in their enzyme-bound state. That the agr- and ß-anomeric forms of GlcAc bind to lysozyme in a competitive fashion was indicated by observing the proton magnetic resonance spectra in the presence of 2-acetamido-d3-2-deoxy-agr-d-glucopyranose. The methyl glycosides, methyl-agr-GlcAc and methyl-ß-GlcAc, were also shown to bind competitively with both anomers of GlcAc. Quantitative analysis of the chemical shift data observed for the association of GlcAc with lysozyme was complicated by the mutarotation of GlcAc between its agr- and ß-anomeric forms. However, in the case of the methyl glucosides, where the conformation of each anomer is frozen, it was possible to analyze the chemical shift data in a straightforward manner, and the dissociation constant as well as the chemical shift of the acetamido methyl protons of the enzyme-inhibitor complex was determined for both anomers. The results indicate that the two anomers of methyl-GlcAc bind to lysozyme with slightly different affinities but that the acetamido methyl groups of both anomers experience identical magnetic environments in the enzyme-inhibitor complex

Teenage Conduct Problems: A Lifetime of Disadvantage in the Labour Market?

Using data from two British birth cohorts born in 1958 and 1970 we investigate the impact of teenage conduct problems on subsequent employment prospects through to age 42. We find teenagers with conduct problems went on to spend fewer months both in paid employment, and in employment, education and training (EET) between age 17 and 42 than comparable teenagers who did not experience conduct problems. Employment and EET disadvantages were greatest among those with severe behavioural problems. The ‘gap’ in time spent in employment or EET by conduct problem status was similar for men and women across cohorts, with only a small part of the gap being attenuated by differences in social background, individual characteristics and educational attainment in public examination at age 16. We discuss the implications of our findings