Solvent Effects on the Kinetics of Amide Bond Cleavage in p-Chloro and p-Bromo Oxazolinones in Acetonitrile–Water Mixtures

The kinetics of amide bond cleavage in p-chloro and p-bromo oxazolinone have been studied using triethylamine as a base catalyst under pseudo-first order conditions, in the temperature range (303.15?C333.15?K). The reaction rate was measured spectrophotometrically over a range of acetonitrile?Cwater mixed solvent (30?C70?%, v/v) compositions. The reaction rate was found to be faster for p-Cl than for p-Br oxazolinone. The thermodynamic parameters of activation were calculated: ?G* increased gradually as the mole fraction of the cosolvent increased due to quasi-mirror image compensation of ?H* and ?S* (entropy?Centhalpy compensation). The isokinetic temperature indicates that the reaction is enthalpy controlled. The reactivity was analyzed in the light of various simple and multiple regression equations using the Kamlet?CTaft solvatochromic parameters.     

Antioxidant Properties of Gluten-Free Pasta Enriched with Vegetable By-Products

The only therapy for coeliac disease patients is to completely avoid foods containing gluten, a protein complex common in several small-grain cereals. However, many alternative gluten-free foods available on the market present nutritional deficiencies. Therefore, the aim of this research was to evaluate the composition and the antioxidant properties of gluten-free pasta enriched with 10% or 15% of tomato waste or linseed meal, two food industry by-products. The traits analysed were protein, lipid, ash and fibre content, heat damage, tocols, carotenoids and phenolics composition (by HPLC), antioxidant capacity, and pasta fracturability. The enriched pastas contained more fibre and lipids than the control, while the protein and ash values were similar. The addition of tomato and linseed waste improved tocols concentration but had no effect on carotenoids content. The free soluble polyphenols increase was similar for both by-products and proportional to the enrichment percentage, while the bound insoluble polyphenols were higher in linseed-enriched pastas. The samples with linseed meal showed the greatest antioxidant capacity and, at 10% addition, the highest fracturability value. In conclusion, the addition of tomato and linseed by-products significantly increases the presence of bioactive compounds (particularly polyphenols), improving the nutritional value of gluten-free pasta.     

A tandem C-H insertion—acetal cleavage sequence: stereocontrolled synthesis of substituted tetrahydrofurans

A short sequence involving Rh(II) mediated carbene insertion followed by Lewis acid promoted reductive acetal cleavage with Et₃SiH provides a stereoselective method for the construction of 2,3,5-trisubstituted tetrahydrofuran rings.     

Missing boundary data recovering for the Helmholtz problem

This Note is dedicated to the numerical treatment of the ill-posed Cauchy–Helmholtz problem. Resorting to the domain decomposition tools, these missing boundary data are rephrased through an ‘interfacial’ equation. This equation is solved via a preconditioned Richardson algorithm with dynamic relaxation. The efficiency of the proposed method is illustrated by some numerical experiments. To cite this article: R. Ben Fatma et al., C. R. Mecanique 335 (2007).     

Stability analysis of steady rotations of a rigid body bearing two-degree-of-freedom control moment gyros with dissipation in gimbal suspension axes

To study the stability of steady rotations of a control moment gyro system with internal dissipation, we use the Barbashin-Krasovskii theorem and the relation, established in [1], between the Lyapunov function and steady motions. Taking into account the special properties of the original problem, we reduce it to a lower-dimensional problem.We give a detailed presentation of an algorithm for analyzing the stability of steady motions of a gyrostat and use this algorithm to perform a complete study for two systems consisting, respectively, of one and two gyros whose gimbal axes are parallel to the principal axis of inertia of the system. Each steady motion is identified as either asymptotically stable or unstable. We find periodic motions that exist only in the presence of dynamic symmetry and which are regular precessions. For the system with two gyros, we prove the asymptotic stability of quiescent states and prove that in the angular momentum range where these states are defined the system does not have any other stable motions.     

Thermal stability of atmospheric plasma sprayed (Ni, Cu, Co)–YSZ and Ni–Cu–Co–YSZ anodes cermets for SOFC application

This paper reports the results of the thermal stability study of M–YSZ (M=Ni, Cu, Co, Cu–Co, Ni–Cu–Co) SOFC anode cermets materials at different heat treatment temperatures. The cermets were elaborated by atmospheric plasma spraying (APS) with optimized conditions and then submitted to heat treatments at 800 and 1000 °C, respectively. Scanning electron microscopy and X-ray diffraction were used to characterize, respectively, the morphology and structure of obtained films, before and after thermal annealing. A correlation was made between the differential scanning calorimetry analysis results and those obtained by X-ray diffraction. Focusing, in this study, on YSZ matrix thermal stability, the obtained results were as follows: the monometallic cermets with the lowest amount of metal and the trimetallic one exhibited a good stability at 800 °C, whereas at 1000 °C, all considered cermets were unstable with a eutectoid decomposition of YSZ matrix.     

Tetranuclear cobalt trimethylacetate Co4(μ3-OH)2(μ-OOCBut)6(C4H6N2O)4 containing coordinated 3-methyl-5-pyrazolone

We found that the reaction of the compound obtained by alloying hydrous cobalt(II) acetate and pivalic acid with 3-methyl-5-pyrazolone in refluxing hexane produces the tetranuclear complex Co₄(μ₃-OH)₂(μ-OOCBu^t)₆·(C₄H₆N₂O)₄·2HOOCBu^t (complex 3). The complex has been structurally characterized using single-crystal X-ray diffraction     

Influence of solvent structure on the aquation of <Emphasis Type="BoldItalic">trans</Emphasis>-[Ru(3-MePy)<Subscript>4</Subscript>Cl<Subscript>2</Subscript>] complex in mixed aqueous solvents

The kinetics of the solvolytic aquation of trans-[Ru (3-Me Py)₄Cl₂] was studied spectrophotometrically in water – isopropanol in the range (30–90% v/v), and water acetonitrile in the range (10–70% v/v), and in the temperature range 50–65 °C. Plots of log k versus the reciprocal of the relative permittivity and Grunwald–Winstien gave non-linear plots. This non-linearity is derived from a large differential effect of solvent structure between the initial and transition states. The plot of log k versus water concentration was also non linear; evidence for the presence of a S _N ¹ mechanism. However, extrema in the variation of enthalpy ΔH* and entropy ΔS* of activation correlate well with the extrema in physical properties of the mixtures which are related to changes in solvent structure. Linear plots of ΔH* versus ΔS* were obtained and the iso- kinetic temperature indicates that the reaction is entropy controlled.     

The asymptotic properties of the motions of satellites in a central field due to internal dissipation

A satellite in the form of a system of bodies that does not have the property of a gyrostat in the general case is considered. An algorithm for determining all the equilibrium configurations of the system that correspond to steady motions in a central gravitational field and an algorithm for analysing their stability are given. A method based on Routh's first theorem is used to investigate the asymptotic stability of the steady motions in the unconstrained problem. Three effects caused by internal dissipation are established in a model example: stabilization of the satellites in a neighbourhood of rotations about a normal to the orbital plane, which is codirectional with the axis of the largest moment of inertia, evolution of elliptic orbits into circular orbits, and capture of the satellites in resonant oscillatory modes of motion.     

The properties of the steady motions of a body carrying a system of two-degree-of-freedom powered gyroscopes

The steady motions of a rigid body carrying several two-degree-of-freedom powered gyroscopes in a uniform external field are investigated. It is shown that when the installation scheme of the gyroscopes in the carrying body is collinear, the problem of determining the steady motions of the system and analysing their secular stability reduces for the most part to the previously solved, similar problem for a system with one gyroscope. It is established that when there is dissipation in the axes of the gyroscope frames, the system tends asymptotically to a state of rest if the absolute value of the total angular momentum of the system lies in the segment of possible absolute values of the angular momentum of the gyroscope rotors. The results of an analysis of the steady motions of a system carrying two gyroscopes with a non-collinear installation scheme are presented.