Total synthesis of (+/-) maculalactone A, maculalactone B and maculalactone C and the determination of the absolute configuration of natural (+) maculalactone A by asymmetric synthesis

Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (-) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature. (C) 2004 Elsevier Ltd. All rights reserved.

Calculation of converged rovibrational energies and partition function for methane using vibrational-rotational configuration interaction

The rovibration partition function of CH4 was calculated in the temperature range of 100-1000 K using well-converged energy levels that were calculated by vibrational-rotational configuration interaction using the Watson Hamiltonian for total angular momenta J=0-50 and the MULTIMODE computer program. The configuration state functions are products of ground-state occupied and virtual modals obtained using the vibrational self-consistent field method. The Gilbert and Jordan potential energy surface was used for the calculations. The resulting partition function was used to test the harmonic oscillator approximation and the separable-rotation approximation. The harmonic oscillator, rigid-rotator approximation is in error by a factor of 2.3 at 300 K, but we also propose a separable-rotation approximation that is accurate within 2% from 100 to 1000 K. (C) 2004 American Institute of Physics.

The ERA-Interim reanalysis: configuration and performance of the data assimilation system

ERA-Interim is the latest global atmospheric reanalysis produced by the European Centre for Medium-Range Weather Forecasts (ECMWF). The ERA-Interim project was conducted in part to prepare for a new atmospheric reanalysis to replace ERA-40, which will extend back to the early part of the twentieth century. This article describes the forecast model, data assimilation method, and input datasets used to produce ERA-Interim, and discusses the performance of the system. Special emphasis is placed on various difficulties encountered in the production of ERA-40, including the representation of the hydrological cycle, the quality of the stratospheric circulation, and the consistency in time of the reanalysed fields. We provide evidence for substantial improvements in each of these aspects. We also identify areas where further work is needed and describe opportunities and objectives for future reanalysis projects at ECMWF

Extension of explicit formulas in Poissonian white noise analysis using harmonic analysis on configuration spaces

Harmonic analysis on configuration spaces is used in order to extend explicit expressions for the images of creation, annihilation, and second quantization operators in L2-spaces with respect to Poisson point processes to a set of functions larger than the space obtained by directly using chaos expansion. This permits, in particular, to derive an explicit expression for the generator of the second quantization of a sub-Markovian contraction semigroup on a set of functions which forms a core of the generator.

A note on an integration by parts formula for the generators of uniform translations on configuration space

An integration by parts formula is derived for the first order differential operator corresponding to the action of translations on the space of locally finite simple configurations of infinitely many points on Rd. As reference measures, tempered grand canonical Gibbs measures are considered corresponding to a non-constant non-smooth intensity (one-body potential) and translation invariant potentials fulfilling the usual conditions. It is proven that such Gibbs measures fulfill the intuitive integration by parts formula if and only if the action of the translation is not broken for this particular measure. The latter is automatically fulfilled in the high temperature and low intensity regime.

RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297

Importance of resolution and model configuration when downscaling extreme precipitation

Dynamical downscaling is frequently used to investigate the dynamical variables of extra-tropical cyclones, for example, precipitation, using very high-resolution models nested within coarser resolution models to understand the processes that lead to intense precipitation. It is also used in climate change studies, using long timeseries to investigate trends in precipitation, or to look at the small-scale dynamical processes for specific case studies. This study investigates some of the problems associated with dynamical downscaling and looks at the optimum configuration to obtain the distribution and intensity of a precipitation field to match observations. This study uses the Met Office Unified Model run in limited area mode with grid spacings of 12, 4 and 1.5 km, driven by boundary conditions provided by the ECMWF Operational Analysis to produce high-resolution simulations for the Summer of 2007 UK flooding events. The numerical weather prediction model is initiated at varying times before the peak precipitation is observed to test the importance of the initialisation and boundary conditions, and how long the simulation can be run for. The results are compared to raingauge data as verification and show that the model intensities are most similar to observations when the model is initialised 12 hours before the peak precipitation is observed. It was also shown that using non-gridded datasets makes verification more difficult, with the density of observations also affecting the intensities observed. It is concluded that the simulations are able to produce realistic precipitation intensities when driven by the coarser resolution data.

The effect of model configuration on modelled hillslope–riparian interactions

The transfer of hillslope water to and through the riparian zone forms a research area of importance in hydrological investigations. Numerical modelling schemes offer a way to visualise and quantify first-order controls on catchment runoff response and mixing. We use a two-dimensional Finite Element model to assess the link between model setup decisions (e.g. zero-flux boundary definitions, soil algorithm choice) and the consequential hydrological process behaviour. A detailed understanding of the consequences of model configuration is required in order to produce reliable estimates of state variables. We demonstrate that model configuration decisions can determine effectively the presence or absence of particular hillslope flow processes and, the magnitude and direction of flux at the hillslope–riparian interface. If these consequences are not fully explored for any given scheme and application, the resulting process inference may well be misleading.

Managing change in complex projects: configuration management, asset information and big data

As we enter an era of ‘big data’, asset information is becoming a deliverable of complex projects. Prior research suggests digital technologies enable rapid, flexible forms of project organizing. This research analyses practices of managing change in Airbus, CERN and Crossrail, through desk-based review, interviews, visits and a cross-case workshop. These organizations deliver complex projects, rely on digital technologies to manage large data-sets; and use configuration management, a systems engineering approach with mid-20th century origins, to establish and maintain integrity. In them, configuration management has become more, rather than less, important. Asset information is structured, with change managed through digital systems, using relatively hierarchical, asynchronous and sequential processes. The paper contributes by uncovering limits to flexibility in complex projects where integrity is important. Challenges of managing change are discussed, considering the evolving nature of configuration management; potential use of analytics on complex projects; and implications for research and practice.

A coupled cloud physics–radiation parameterization of the bulk optical properties of cirrus and its impact on the Met Office unified model global atmosphere 5.0 configuration

A new coupled cloud physics–radiation parameterization of the bulk optical properties of ice clouds is presented. The parameterization is consistent with assumptions in the cloud physics scheme regarding particle size distributions (PSDs) and mass–dimensional relationships. The parameterization is based on a weighted ice crystal habit mixture model, and its bulk optical properties are parameterized as simple functions of wavelength and ice water content (IWC). This approach directly couples IWC to the bulk optical properties, negating the need for diagnosed variables, such as the ice crystal effective dimension. The parameterization is implemented into the Met Office Unified Model Global Atmosphere 5.0 (GA5) configuration. The GA5 configuration is used to simulate the annual 20-yr shortwave (SW) and longwave (LW) fluxes at the top of the atmosphere (TOA), as well as the temperature structure of the atmosphere, under various microphysical assumptions. The coupled parameterization is directly compared against the current operational radiation parameterization, while maintaining the same cloud physics assumptions. In this experiment, the impacts of the two parameterizations on the SW and LW radiative effects at TOA are also investigated and compared against observations. The 20-yr simulations are compared against the latest observations of the atmospheric temperature and radiative fluxes at TOA. The comparisons demonstrate that the choice of PSD and the assumed ice crystal shape distribution are as important as each other. Moreover, the consistent radiation parameterization removes a long-standing tropical troposphere cold temperature bias but slightly warms the southern midlatitudes by about 0.5 K.

The Met Office Global Coupled model 2.0 (GC2) configuration

The latest coupled configuration of the Met Office Unified Model (Global Coupled configuration 2, GC2) is presented. This paper documents the model components which make up the configuration (although the scientific description of these components is detailed elsewhere) and provides a description of the coupling between the components. The performance of GC2 in terms of its systematic errors is assessed using a variety of diagnostic techniques. The configuration is intended to be used by the Met Office and collaborating institutes across a range of timescales, with the seasonal forecast system (GloSea5) and climate projection system (HadGEM) being the initial users. In this paper GC2 is compared against the model currently used operationally in those two systems. Overall GC2 is shown to be an improvement on the configurations used currently, particularly in terms of modes of variability (e.g. mid-latitude and tropical cyclone intensities, the Madden–Julian Oscillation and El Niño Southern Oscillation). A number of outstanding errors are identified with the most significant being a considerable warm bias over the Southern Ocean and a dry precipitation bias in the Indian and West African summer monsoons. Research to address these is ongoing.