Electrochemical oxidation of 9-methylxanthine

The electrochemical oxidation of 9-methylxanthine proceeds via four voltammetric oxidation peaks at the pyrolytic graphite electrode. The first voltammetric oxidation peak (peak I_a) is a 1e reaction giving a radical which dimerizes to 8,8′-bi-9-methyl-9H-purine-2,6-(1H, 3H)-dione. Peak II_a is a further 2e electrooxidation of the peak I_a dimer to another yellow dimer 8,8′-bi-9-methyl-9H-purine-2,6-(1H)-dione-3,5-(3H)-diiminylidene. This dimer is not very stable and it hydrolyzes to 1-methyl allantoin. Peak III_a is an adsorption pre-peak to peak IV_a which corresponds, overall, to a direct 4e?4H⁺ electrooxidation of 9-methylxanthine to an unstable diimine of 9-methyluric acid. Hydrolysis of this diimine leads to a variety of ultimate products.     

Synthesis of periphery-functionalized dendritic molecules using polylithiated dendrimers as starting material

A general method for the functionalization of Si-Cl terminated carbosilane dendritic molecules via organolithium or organomagnesium reagents is described. Quantitative exchange of the bromine atoms of 4-bromophenyl-functionalized dendrimers affords polylithiated species that are valuable starting materials for further functionalization, e.g., into pyridyl alcohols. The latter were successfully applied as catalyst precursors in a ruthenium-mediated ring-closure metathesis reaction.     

Chemo-bio catalysis using carbon supports: application in H2-driven cofactor recycling

Heterogeneous biocatalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction. This approach relies on enzymes powered by H₂-driven NADH recycling. Commercially available carbon-supported metal (metal/C) catalysts are investigated here for direct H₂-driven NAD⁺ reduction. Selected metal/C catalysts are then used for H₂ oxidation with electrons transferred via the conductive carbon support material to an adsorbed enzyme for NAD⁺ reduction. These chemo-bio catalysts show improved activity and selectivity for generating bioactive NADH under ambient reaction conditions compared to metal/C catalysts. The metal/C catalysts and carbon support materials (all activated carbon or carbon black) are characterised to probe which properties potentially influence catalyst activity. The optimised chemo-bio catalysts are then used to supply NADH to an alcohol dehydrogenase for enantioselective (>99% ee) ketone reductions, leading to high cofactor turnover numbers and Pd and NAD⁺ reductase activities of 441 h⁻¹ and 2347 h⁻¹, respectively. This method demonstrates a new way of combining chemo- and biocatalysis on carbon supports, highlighted here for selective hydrogenation reactions.

Heterogeneous chemo-bio catalytic hydrogenation is an attractive strategy for clean, enantioselective C X reduction.     

Three‐dimensional wave impact on a rigid structure using smoothed particle hydrodynamics

Navier–Stokes computations of a wave–structure interaction are performed with the aim of assessing the potential of smoothed particle hydrodynamics to accurately estimate impact loading time history. A three‐dimensional dam‐break flow with a rectangular column located downstream is considered. The net force and impulse exerted on the column is monitored throughout the simulation with the results correlating well with existing experimental data. Initial and boundary conditions and numerical parameters are varied and their effect on the column load investigated. The column load is found to be most sensitive to the choice of boundary treatment. Copyright © 2011 John Wiley & Sons, Ltd.     

Dust modelling using a combined CFD and discrete element formulation

The production and dispersal of airborne dust is an important issue in both environmental and industrial contexts. Dust pollution is a major environmental concern, and long exposure in occupational settings has been linked with numerous respiratory health issues. Industrial dust pollution can also present a significant explosion hazard, even in facilities with dust extraction systems. Computational models for dust generation and dispersal have, however, generally been formulated for specific geophysical applications and restricted to static, two‐dimensional, approaches. Here, we present a method for simulating dust production from a dynamic granular bed by using a three‐dimensional coupled discrete element method and Navier–Stokes computational model. Dust production is based on an energy formulation in which micro‐scale dust particles are assumed to overcome cohesion to macro‐scale grains. This model is used over the entire range of energies present within the system, from macro‐scale collisions to aerodynamic entrainment and bombardment of micro‐scale particles. The dust concentration is modelled as a scalar density field, which is advected and diffused through turbulence in the gas flow field. The model is tested against empirical predictions for two test cases, a slug of granular material dropped from a set height and air flow over a granular stockpile. Both give good agreement to the empirical relations, showing that the model can accurately predict the production and subsequent dispersal of dust from a dynamic granular bed. Copyright © 2012 John Wiley & Sons, Ltd.     

Oscillatory melting temperature of the vortex smectic phase in layered superconductors

We report on transport measurements of YBa 2Cu 3O (7-delta) single crystals with different oxygen contents in the geometry B, J ||ab (J perpendicularB). Our data show that the vortices become confined between the Cu-O planes below a well-defined temperature at which the effective size 2xi of the vortex core is approximately equal to the period of the Cu-O layers. This confinement strongly increases the vortex liquid freezing temperature. A new melting line is found separating a vortex liquid and a smectic phase, which shows an oscillatory field dependence reflecting differences between commensurate and incommensurate smectic states.