Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

FEM study of palladium and molybdenum clusters on an alumina covered field emitter

Palladium and molybdenum polycrystalline layers (clusters) have been deposited in a stainless steel UHV system onto a layer of alumina (Al₂O₃). This layer has been prepared by high temperature oxidation of an aluminium layer. The interaction of this system with nitrogen has been investigated at room temperature by an FEM technique. Under these conditions nitrogen spillover from molybdenum to palladium has been observed.     

Infrared picosecond absorption spectroscopy of microcrystalline silicon: separation between carrier recombination in crystalline and amorphous fractions

We have studied ultra-fast carrier dynamics of photo-excited carriers in hydrogenated microcrystalline silicon prepared by a very high frequency glow-discharge technique. We report on direct observation of two types of dynamics using selective photo-excitation in picosecond pump and probe measurements. One type of the observed dynamics has been found to be independent of the sample preparation, while the other reflects the relative weights of crystalline and amorphous fractions. We propose a simple rate-equation model that describes the carrier dynamics in microcrystalline silicon in terms of the composition of those in Si microcrystallites and in the a-Si:H tissue which surrounds the microcrystallites. The model without any fitting parameters reproduces the experimental data very well when the dynamics are scaled with relative volume fractions as obtained from Raman spectra. Received: 23 November 2000 / Accepted: 17 March 2001 / Published online: 23 May 2001     

Some remarks to multivariate regression model

Some remarks to problems of point and interval estimation, testing and problems of outliers are presented in the case of multivariate regression model. This work was supported by the Council of Czech Government J14/98:153100011.     

An interior–exterior Schwarz algorithm and its convergenceUn algorithme de Schwarz intérieur–extérieur et sa convergence

In this work we study the solution of Laplace's equation in a domain with holes by an iteration consisting of splitting the problem in an exterior one, around the holes, plus an interior problem in the unholed domain. We show the existence of a decomposition of the solution when the exterior problem is represented by means of a single-layer protential. Also, for the three-dimensional case and with some adjustments for the two-dimensional case, we prove convergence of the method by writing the iteration as a Jacobi iteration for an operator equation and studying the spectrum of the iteration operator. To cite this article: R. Celorrio et al., C. R. Acad. Sci. Paris, Ser. I 334 (2002) 923–926.     

Influence of copper solute on the creep rate sensitivities of aluminium

The presence of copper atoms as continuous networks at the grain boundaries of an aluminium-copper alloy has been considered not preventing the moving of dislocations during creep (or at least partially). The dislocations can bs absorbed by these boundaries and penetrate through them. That leads to changés of shape and structure of grains and also to the sliding of grains against each other. This was deduced from the accelerating increase in the sensitivity of the steady state creep rate to the applied stress of an aluminium 2·8 wt% copper alloy examined at wide range of temperatures (50–350 °C) and applied stresses (7–170 MPa). This rapid increase in the sensitivity parameter of the steady state creep rate occurs in Al-Cu alloys at quite higher ranges of applied stresses and may be attributed mainly to the contribution of the grain boundary movements to the creep strain.     

Capillary Electrophoresis Chiral Separation for Enantiomeric Purity Determination of a Basic Drug in Pharmaceutical Formulations

Capillary electrophoresis using a running buffer composed of β-cyclodextrin as the chiral selector and ethanolamine mesylate at pH 9.6 is being used to monitor the stereochemical stability of a hydrophobic drug, containing two chiral centers, in two different formulated self-emulsifying drug delivery system (SEDDS) products. The separation takes place in less than 25 min. Strategies for enhancing the method reproducibility and detection sensitivity in the lower potency formulation are presented. The results demonstrating the specificity, assay precision, recovery, linearity and range achieved during the method validation experiments are presented in this paper.Presented at: CE in the Biotechnology and Pharmaceutical Industries: 7th Symposium on the Practical Applications for the Analysis of Proteins, Nucleotides and Small Molecules, Montreal, Canada, August 12–16, 2005.     

Indirect Methods For Determination of The Protective Effects of Coating Films on The Surface of Crystals

The extents of the protective effects of coating films on the surface of crystals were determined. Three different samples were made with different quantities of coating fluid (Sepifilm LP 010 in 10% aqueous solution). Since the atomizing rate was constant, the coating time increased in parallel with the volume of coating fluid applied. The direct measurement of film thickness and smoothness is very difficult, and therefore indirect methods were used. Dimenhydrinate was chosen as model drug; this is a heat-sensitive antihistamine with a low melting point. This temperature can be reached during the tableting process. The behaviour of samples on exposure to heat was examined by differential scanning calorimetry. The water uptakes of the samples were determined with an Enslin apparatus. Plasticity was studied with an instrumented tablet machine. These indirect methods (thermal conductivity, water uptake and plasticity measurements) revealed connections between the results of the various experiments. An overlong coating time decreased the protective effect of the coating film. This revised version was published online in August 2006 with corrections to the Cover Date.