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.     

Interrelated functionalities of hierarchically CNT/CeO2/Pt nanostructured layers: synthesis, characterization, and electroactivity

We present a free-standing catalyst layer comprising current collector/CNTs (catalyst support)/CeO(2)/Pt (catalyst) nanostructured layers, each layer constructed upon the one below it. FESEM and TEM showed that a CeO(2) layer has a fluffy morphology recalling the texture of cotton, whereas Pt nanoparticles assemble into cauliflower or broccoli-like arrangement. New insights have been gained into the effect of CeO(2) on the structural properties of the beneath CNTs layer and on the above Pt layer. First, by means of Raman analysis, it was found that interaction of CeO(2) with CNTs induced a decrease in the crystallinity of the latter. Second, by TEM and XPS analyses, it was observed that the size of Pt nanoparticles in the CNT/CeO(2)/Pt structure was inferior to that in the CNT/Pt, implying that CeO(2) influenced the dispersion quality of Pt nanoparticles. For the first time, it is observed that CeO(2) supported CNTs undergo oxidation/reduction reactions at low potentials in the ethanol electrolyte. The electrochemical analysis showed that entities produced from those redox processes are surface adsorbed/desorbed species most likely hydroxides. This unexpected electroactivity is due to the beneath CNTs that boosted the conductivity of CeO(2). Such improved conductivity of CeO(2) has fostered the electron-transfer kinetics of ethanol at Pt as demonstrated by the decreased overpotential required to oxidize ethanol and by the specific mass activity, which was greater than that of CNT/Pt.     

On steady motions of a rigid body bearing three-degree-of-freedom control momentum gyroscopes and their stability

Equations of motion are obtained for a rigid body bearing N three-degree-of-freedom control momentum gyroscopes in gimbals and the entire set of steady motions in a homogeneous external field is determined. The steady motion dependence on the magnitude of the system angular momentum is studied and a detailed analysis of the secular stability is performed.     

Separation of representations with quadratic overgroups

Any unitary irreducible representation π of a Lie group G defines a moment set Iπ, subset of the dual g^? of the Lie algebra of G. Unfortunately, Iπ does not characterize π. If G is exponential, there exists an overgroup G⁺ of G, built using real-analytic functions on g^?, and extensions π⁺ of any generic representation π to G⁺ such that Iπ⁺ characterizes π.In this paper, we prove that, for many different classes of group G, G admits a quadratic overgroup: such an overgroup is built with the only use of linear and quadratic functions.     

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.     

Missing boundary data reconstruction by the factorization method

We consider the data completion problem for the Laplace equation in a cylindrical domain. The Neumann and Dirichlet boundary conditions are given on one face of the cylinder while there is no condition on the other face. This Cauchy problem has been known since Hadamard (1953) to be ill-posed. Here it is set as an optimal control problem with a regularized cost function. We use the factorization method for elliptic boundary value problems. For each set of Cauchy data, to obtain the estimate of the missing data one has to solve a parabolic Cauchy problem in the cylinder and a linear equation. The operator appearing in these problems satisfy a Riccati equation that does not depend on the data. To cite this article: A. Ben Abda et al., C. R. Acad. Sci. Paris, Ser. I 347 (2009).     

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.