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.

Detecting the number of signals using antenna array: a single threshold solution

A new approach is presented to identify the number of incoming signals in antenna array processing. The new method exploits the inherent properties existing in the noise eigenvalues of the covariance matrix of the array output. A single threshold has been established concerning information about the signal and noise strength, data length, and array size. When the subspace-based algorithms are adopted the computation cost of the signal number detector can almost be neglected. The performance of the threshold is robust against low SNR and short data length.

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.

Interferometric technique for measuring terahertz antenna phase patterns

A quasi-optical interferometric technique capable of measuring antenna phase patterns without the need for a heterodyne receiver is presented. It is particularly suited to the characterization of terahertz antennas feeding power detectors or mixers employing quasi-optical local oscillator injection. Examples of recorded antenna phase patterns at frequencies of 1.4 and 2.5 THz using homodyne detectors are presented. To our knowledge, these are the highest frequency antenna phase patterns ever recovered. Knowledge of both the amplitude and phase patterns in the far field enable a Gauss-Hermite or Gauss-Laguerre beam-mode analysis to be carried out for the antenna, of importance in performance optimization calculations, such as antenna gain and beam efficiency parameters at the design and prototype stage of antenna development. A full description of the beam would also be required if the antenna is to be used to feed a quasi-optical system in the near-field to far-field transition region. This situation could often arise when the device is fitted directly at the back of telescopes in flying observatories. A further benefit of the proposed technique is simplicity for characterizing systems in situ, an advantage of considerable importance as in many situations, the components may not be removable for further characterization once assembled. The proposed methodology is generic and should be useful across the wider sensing community, e.g., in single detector acoustic imaging or in adaptive imaging array applications. Furthermore, it is applicable across other frequencies of the EM spectrum, provided adequate spatial and temporal phase stability of the source can be maintained throughout the measurement process. Phase information retrieval is also of importance to emergent research areas, such as band-gap structure characterization, meta-materials research, electromagnetic cloaking, slow light, super-lens design as well as near-field and virtual imaging applications.

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