Photocatalytic chemical
synthesis by coupling abiotic photosensitizers
to purified enzymes provides an effective way to overcome the low
conversion efficiencies of natural photosynthesis while exploiting
the high catalytic rates and selectivity of enzymes as renewable,
earth-abundant electrocatalysts. However, the selective synthesis
of multiple products requires more versatile approaches and should
avoid the time-consuming and costly processes of enzyme purification.
Here we demonstrate a cell-based strategy supporting light-driven
H2 evolution or the hydrogenation of CC and CO
bonds in a nonphotosynthetic microorganism. Methylviologen shuttles
photoenergized electrons from water-soluble photosensitizers to enzymes
that catalyze H2 evolution and the reduction of fumarate,
pyruvate, and CO2 in Shewanella oneidensis. The predominant reaction is selected by the experimental conditions,
and the results allow rational development of cell-based strategies
to harness nature’s intrinsic catalytic diversity for selective
light-driven synthesis of a wide range of products.
Collective and single-particle spin-flip excitations of a two-dimensional electron gas in a semimagnetic Cd(1-x)Mn(x)Te quantum well are observed by resonant Raman scattering. Application of a magnetic field splits the spin subbands and a spin polarization is induced in the electron gas. Above 1 T the collective modes, which disperse with the in-plane wave vector, dominate the spectra. The local spin-density approximation provides a good description of our results and enables us to confirm that the energy of the low wave vector collective mode is given by the bare Zeeman energy.
The rise in antibiotic resistance is a major threat for human health. Basidiomycete fungi represent an untapped source of underexploited antimicrobials, with pleuromutilin—a diterpene produced by Clitopilus passeckerianus—being the only antibiotic from these fungi leading to commercial derivatives. Here we report genetic characterisation of the steps involved in pleuromutilin biosynthesis, through rational heterologous expression in Aspergillus oryzae coupled with isolation and detailed structural elucidation of the pathway intermediates by spectroscopic methods and comparison with synthetic standards. A. oryzae was further established as a platform for bio-conversion of chemically modified analogues of pleuromutilin intermediates, and was employed to generate a semi-synthetic pleuromutilin derivative with enhanced antibiotic activity. These studies pave the way for future characterisation of biosynthetic pathways of other basidiomycete natural products in ascomycete heterologous hosts, and open up new possibilities of further chemical modification for the growing class of potent pleuromutilin antibiotics.
We report a remarkable enhancement of the magnetic moments of excitons as a result of their motion. This surprising result, which we have observed in magneto-optical studies of three distinct zinc-blende semiconductors, GaAs, CdTe, and ZnSe, becomes significant as the kinetic energy of the exciton becomes comparable with its Rydberg energy and is attributed to motionally induced changes in the internal structure of the exciton. The enhancement of the magnetic moment as a function of the exciton translational wave vector can be represented by a universal equation.
The Water Framework Directive (WFD) identifies diffuse pollution as a long-term threat to water quality. Farming contributes significantly to this pollution. There is a clear need for mitigation measures and assessment of their efficacy. Accordingly, Demonstration Test Catchments (DTCs) have been established in England to test the effectiveness of changes in agricultural practice on river water quality and ecology. However, the presence of groundwater in these hydrological systems implies a wide range of travel times for pollutants from source to receptor. Unless flow routes are better characterised, it will be difficult to gauge the success of control measures in the short-term.Using 3D modelling and supplementary hydrochemical information, this study considers the hydrogeology of several sub-catchments in the Avon DTC, southern England. Data suggest that groundwater ages >25 years exist in parts of the catchments; clearly observations like these must be used to judge the likely effectiveness of targeted control measures. The revealed hydrogeological complexity of the Avon catchment is unlikely to be unique, so the techniques described here should be applicable to other lowland river systems with moderate-to-high baseflow indices (>0.5). To support the WFD, groundwater conceptual models should inform the design of effective measures for diffuse pollution mitigation..
Very large changes in the Zeeman splittings and in the diamagnetism of excitons as they acquire kinetic energy in wide quantum wells of CdTe are reported. The changes are found to be functions of the translational wave vector K z of the exciton in the growth direction of the well, irrespective of the width of the well, and are also found to be strong functions of the direction of the magnetic field. The behavior is accounted for by a model in which mixing occurs between the hydrogenic states which describe the exciton in the center of mass or adiabatic approximation. The mixing is ascribed to terms which arise in the Luttinger Hamiltonian when it is extended to describe excitons. Excellent quantitative agreement with experiment, including the results of changing the strain in the wells, is obtained by using Luttinger parameters close to those previously reported. The model is applicable to wide quantum wells made from any zinc-blende semiconductor and confirms that the huge motion induced changes in magnetic properties, observed here for CdTe and previously also for ZnSe and GaAs, should be universal for such materials.
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