A Mechanistic Study on the Oxidative Degradation of Dibenzazepine Derivatives by Manganese(III) Complexes in Acidic Sulfate Media

The oxidative degradation of tricyclic antidepressants (TCA) was studied in the presence of a large excess of the oxidizing agent manganese(III) and its reduced form manganese(II) sulfate in acidic media. The products were detected and identified using UV–vis, ESI‐MS, IR, and EPR methods. The mechanism of the reaction was studied for the following two classes of TCA: 10,11‐dihydro‐5H‐dibenz[b, f]azepines and dibenz[b, f]azepines. The oxidative degradation between dibenz[b, f]azepines and the manganese(III) ions resulted in the formation of substituted acridine with the same substituent as in the origin dibenz[b, f]azepine derivative. The pseudo–first‐order rate constants (k_obs) were determined for the degradation process. The dependences of the observed rate constants on the [Mn^III] with a zero intercept were linear. The reaction between 10,11‐dihydro‐5H‐dibenz[b, f]azepines, and the manganese(III) sulfate ion resulted in oxidative dehydrogenation, which proceeded via the formation of the following two intermediates: a free organic radical and a dimer. Further oxidation of the second intermediate led to a positively charged radical dimer as the single final product. Linear dependences of the pseudo–first‐order rate constants (k_obs) on the [Mn^III] with a zero intercept were established for the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines. The observed rate constants were dependent on the [H⁺] and independent of the [TCA] within the excess concentration range of the manganese(III) complexes used in the isolation method. The radical product of the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines was not stable in the aqueous solution and was subsequently transformed to a nonradical dimer in the next slower step. The observed rate constants were independent of the [Mn^III], independent of the [H⁺] and increased slightly with increasing TCA concentrations when TCA was used in excess. The mechanistic consequences of all of these results are discussed.     

Structure and electrochemical behaviour of 4,7-diazaheptyl-trimethoxy-silane and vinyl-trialkoxy-silane adsorbed at silver surface

Novel self-assembled monolayers were obtained on silver using 4,7-diazaheptyl-trimethoxy-silane (SiN) and vinyl-trialkoxy-silane (SiVA, where the alkyl group is 3,6,9,12,15,18,21,24,27,30,33,36,39,42,45,48,51,54,57,60-eicozaoxa- hexaheptaconan). It was shown that thus modified metal surface was protected against electrooxidation. A densely packed monolayer remained stable and did not desorb from the Ag electrode on the potential cycling. The structure of SiN and SiVA as well as their complexes with Li⁺ cations were calculated and visualised by the AM1d and PM5 semi-empirical methods.     

Variety of LaSrMnO structures induced by growth conditions and laser irradiation

Crystallographic phase transitions in perovskite-like LaSrMnO metallic oxides are studied. The transitions are induced when internal stresses generated during film synthesis (at temperatures between 450 and 730°C) vary (decrease or increase) upon subsequent irradiation by a KrF laser emitting in the UV range. As the synthesis temperature T _s grows, the rhombohedral-to-orthorhombic phase transition occurs at 650–670°C. The resistivity is shown to be either temperature-independent, ρ(T)=const, at T<T _crit, or varies and reaches a maximum, ρ(T)=ρ_max, at the Curie temperature T _c. Optical transmission spectra taken at photon energies ℏω=0.5–2.5 eV exhibit both a high (0.8–0.9) and low (0.1–0.3) transmission coefficient t, depending on the synthesis temperature. As follows from X-ray diffraction data, the laser irradiation causes a phase transition only in LaSrMnO films grown at T _s<650°C. Phases of different size scales appear: the long-range-order orthorhombic matrix and mesoscopic-range-order rhombohedral clusters are observed in the films grown at T _s=450–550°C and the rhombohedral matrix with orthorhombic clusters, in the films grown at T _s=550–650°C.     

A marker method for the solution of the damped Burgers' equation

A new method for the solution of the damped Burgers' equation is described. The marker method relies on the definition of a convective field associated with the underlying partial differential equation; the information about the approximate solution is associated with the response of an ensemble of markers to this convective field. Some key aspects of the method, such as the selection of the shape function and the initial loading, are discussed in some details. The marker method is applicable to a general class of nonlinear dispersive partial differential equations. © 2005 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2006     

Pullback attractors for non-autonomous 2D-Navier–Stokes equations in some unbounded domains

In this Note we first introduce the concept of pullback asymptotic compactness. Next, we establish a result ensuring the existence of a pullback attractor for a non-autonomous dynamical system under the general assumptions of pullback asymptotic compactness and the existence of a pullback absorbing family of sets. Finally, we prove the existence of a pullback attractor for a non-autonomous 2D Navier–Stokes model in an unbounded domain, a case in which the theory of uniform attractors does not work since the non-autonomous term is quite general. To cite this article: T. Caraballo et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Codimension-one minimal projections onto Haar subspaces

Let H_n be an n-dimensional Haar subspace of and let H_n−1 be a Haar subspace of H_n of dimension n−1. In this note we show (Theorem 6) that if the norm of a minimal projection from H_n onto H_n−1 is greater than 1, then this projection is an interpolating projection. This is a surprising result in comparison with Cheney and Morris (J. Reine Angew. Math. 270 (1974) 61 (see also (Lecture Notes in Mathematics, Vol. 1449, Springer, Berlin, Heilderberg, New York, 1990, Corollary III.2.12, p. 104) which shows that there is no interpolating minimal projection from C[a,b] onto the space of polynomials of degree n, (n2). Moreover, this minimal projection is unique (Theorem 9). In particular, Theorem 6 holds for polynomial spaces, generalizing a result of Prophet [(J. Approx. Theory 85 (1996) 27), Theorem 2.1].     

Acyclovir terminated thiophosphate dendrimers

An efficient synthesis of antiviral dendritic prodrug candidates, water-soluble, polyanionic conjugates of 1st and 2nd generation thiophosphate dendrimers with acyclovir, is described.     

The number of linear extensions of bipartite graphs

The number of linear extensions among the orientations of a bipartite graph is maximum just if the orientation itself is bipartite, the natural one.