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.     

Naphthalimide‐phthalimide derivative based photoinitiating systems for polymerization reactions under blue lights

Naphthalimide‐phthalimide derivatives (NDPDs) have been synthesized and combined with an iodonium salt, N‐vinylcarbazole, amine or 2,4,6‐tris(trichloromethyl)‐1,3,5‐triazine to produce reactive species (i.e., radicals and cations). These generated reactive species are capable of initiating the cationic polymerization of epoxides and/or the radical polymerization of acrylates upon exposure to very soft polychromatic visible lights or blue lights. Compared with the well‐known camphorquinone based systems used as references, the novel NDPD based combinations employed here demonstrate clearly higher efficiencies for the cationic polymerization of epoxides under air as well as the radical polymerization of acrylates. Remarkably, one of the NDPDs (i.e., NDPD2) based systems is characterized by an outstanding reactivity. The structure/reactivity/efficiency relationships of the investigated NDPDs were studied by fluorescence, cyclic voltammetry, laser flash photolysis, electron spin resonance spin trapping, and steady state photolysis techniques. The key parameters for their reactivity are provided. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 665–674     

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.     

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.     

Ion-carrier controlled precipitation of calcium phosphate in giant ABA triblock copolymer vesicles

An ionophore assisted metal-ion transport across block copolymer membranes has been used to control the local Ca2+ concentration during precipitation of calcium phosphate in giant block copolymer vesicles.