The first total synthesis of (R)-convolutamydine A

The first total synthesis of (R)-convolutamydine A has been achieved by the organocatalytic addition of acetone to 4,6-dibromoisatin. The absolute configuration was determined by single crystal X-ray diffraction. DFT studies were used to model the transition states for the aldol reaction and equilibrium geometries of the post-aldol reaction intermediates. The DFT study revealed that the aldol bond forming reaction was considerably endothermic.     

Microperforated insertion units: An alternative strategy to design microperforated panels

Microperforated panels (MPPs) coupled to a rigid wall have been proposed recently as an alternative to porous absorbers in situations having concerns with bacterial contamination and small particles discharge, like food, pharmaceutical and microelectronic industries. There exists also an increasing interest for MPP absorbers in the transportation industry and civil engineering. In general, an optimally designed MPP with good broadband absorption requires many submillimetric holes distributed over a panel of also submillimetric thickness. Such thin plates or foils become so fragile that they need to be protected from mechanical damage. In this paper, an alternative strategy is investigated which allows the design of MPPs with panels of millimetric thickness while maintaining their acoustic performance. These absorbers, named microperforated insertion units (MIUs), avoid the structural problems of the classical MPPs. An assessment of the sound absorption properties of these structures is presented. Comparisons between calculations and measurements are also made under two experimental conditions: plane waves at normal incidence (impedance tube) and free field (anechoic room).     

Bayesian Object Identification: Variants

We present a Bayesian theory of object identification. Here, identifying an object means selecting a particular observation from a group of observations (variants), this observation (the regular variant) being characterized by a distributional model. In this sense, object identification means assigning a given model to one of several observations. Often, it is the statistical model of the regular variant, only, that is known. We study an estimator which relies essentially on this model and not on the characteristics of the “irregular” variants. In particular, we investigate under what conditions this variant selector is optimal. It turns out that there is a close relationship with exchangeability and Markovian reversibility. We finally apply our theory to the case of irregular variants generated from the regular variant by a Gaussian linear model.     

Neutron Scattering on Magnetic Materials Under Extreme Conditions

Many materials exhibit various magnetic phenomena as a function of magnetic field, temperature and/or pressure. Usually, bulk magnetic measurements provide first information on the magnetic state of the material by measuring their response on the applied magnetic field. However, it is necessary to investigate materials also on a microscopic scale. This is often done by means of neutron scattering. In this contribution we discuss basic ideas of this method and we report on few experimental results obtained with a split-pair coil 14.5 T superconducting magnet which can be combined with dilution stick offering temperatures as low as 30 mK and/or with a small clamped-type pressure cell which offers pressure up to 1.0 GPa.     

Temperature dependent structure of spider silk by X-ray diffraction

We have investigated the structure of spider dragline silk by X-ray diffraction over a broad temperature range from room temperature up to thermal denaturation conditions. The dominating signal from the β-sheet crystallites is analyzed. Pronounced changes of scattering intensity starting at temperatures around 150 °C are observed. These changes are discussed in view of the respective lattice constants, crystal size, size distribution, crystallite number density and amino acid composition. PACS 87.68.+z; 87.15.-v; 87.64.Bx     

Physical Analysis of a Possibility to Reach the 1.30-μm Emission from the GaAs-Based VCSELs with the InGaAs/GaAs Quantum-Well Active Regions and the Intentionally Detuned Optical Cavities

Physical aspects of an operation of the GaAs-based InGaAs/GaAs quantum-well (QW) VCSELs with the intentionally detuned optical cavities have been considered in the present paper using the comprehensive three-dimensional self-consistent optical–electrical–thermal-gain simulation. In GaAs-based structures, very good DBR resonator mirrors and a very efficient methods to confine radially both the current spreading and the electromagnetic field with the aid of oxide apertures may be applied. It has been found using the above simulation that even currently available immature technology enables manufacturing the above devices emitting radiation of wavelengths over 1.20 μm. In particular, while the room-temperature 1.30-μm lasing emission is still beyond possibilities of the InGaAs/GaAs QW VCSELs, these structures may offer analogous 1.25-μm emission, especially for the high-power and/or high-temperature operation.     

On the concentration and determination of plutonium in natural waters by adsorption on MnO2 filters

A new method of analysis of the efficiency of four filters of MnO₂ in series which takes into account the reactions induced in plutonium by the sorbent is described. The system of differential equations describing the behaviour of plutonium in water as it passes through the filters is solved and the parameters of the filters are determined for a best fitting of the solutions corresponding to the experimental uncertainties. The method is checked by numerical simulation and then applied to water solutions with a known plutonium concentration and to some experimental results given by other authors. In all occassions the results are consistent with the possibility of determining the contents of plutonium in sea and continental waters with uncertainties of the order of 10%.     

Preconcentration of trace antimony in tap and sea water on activated alumina. Determination by graphite furnace atomic absorption spectrometry

Summary A method is described for antimony preconcentration based on retention on a column of activated alumina. Recovery is 80% when no pH-control and 4 mol/l HCl as eluent are used. The preconcentration factor is 400. The method was applied to the determination of antimony in spiked tap and sea water. The analytical performance of the method is discussed.     

Improvement of the properties of polyarylate reinforced with liquid crystalline polymers

Blends of polyarylate of bisphenol A, PAr, with two commercial main chain liquid crystalline polymers, Vectra A950 and Vectra B950, are studied. From dynamic viscoelastic measurements it is deduced that both systems (PAr/Vectra A950 and PAr/Vectra B950) are immiscible and scanning electron microscopy (SEM) micrographs show the presence of spherical domains of the liquid crystalline polymer when PAr constitutes the matrix. Extrusion capillary measurements reveal that, under conditions of temperature and shear rate similar to those of processing, the viscosity is reduced to approximately 10% of its value when the content of liquid crystalline polymer is only 20%. This great improvement of the rheological properties is observed in both PAr/Vectra A950 and PAr/Vectra B950 blends. The effect of draw ratio on Young's modulus for different compositions is also analyzed, pointing out the reinforcing action of both liquid crystalline polymers on polyarylate: for instance, 20% of Vectra B950 in the blend gives rise to a 700% increase of the modulus of fibres prepared at a draw ratio of 50. SEM of the extrudates reveals that the spherical domains are elongated at the entrance of the capillary giving rise to a microfibrillar morphology which is related to the excellent rheological and mechanical properties of the blends.     

General base catalysis in the decomposition of N-Cl-Valine in aqueous solution

This article analyzes the kinetics of the decomposition of N-Cl-Valine in aqueous solution, which is formed rapidly by chlorination of Valine with sodium hypochlorite. A general-base catalyzed process not yet described is reported. The experimental evidence shows two competitive decomposition paths: an unimolecular concerted fragmentation process (k = (1.8 ± 0.1) · 10^?4 s^?1 at 298 K) and the other one is an E2 elimination process whose importance increases with pH and depends on the nature and the concentration of the bases present in the medium. © 1994 John Wiley & Sons, Inc.