Stereochimie de l'hydrogenation des (±) Δ3(3a)-hydrindenones-4. Comparaison avec le cas de la (+) methyl-3 Δ3(3a)-hydrindenone-4 et de ses dioxolannes

We show that the four studied 4-hydrindenones (with or without a methyl substituant at C3 or C7a) give by hydrogenation on Raney nickel or on Pd/C, in various solvants, the cis 4-hydrindanones, by a kinetically controlled process. During the hydrogenation, the double bond can migrate only in the positions conjugated to the carbonyl group.In contrast, when the carbonyle is protected as a dioxolanne, the double bond is free to migrate around the five membered ring. In spite of this mobility the optical purity of the saturated dioxolannes formed is high. In the case of the (+)3-methyl Δ^3(3a) 4-hydrindenone, the enantiomeric hydrindanones $\text{9a}$ obtained by direct hydrogenation or with isomerization of the double bond are not the same. Therefore, the optical purity of the product is low, but its value allows an estimation of the relative importance of the two reaction pathways.     

The decay from the dark npi* excited state in uracil: an integrated CASPT2/CASSCF and PCM/TD-DFT study in the gas phase and in water

By integrating the results of MS-CASPT2/CASSCF and TD-PBE0 calculations, we propose a mechanism for the decay of the excited dark state in pyrimidine, fully consistent with all the available experimental results. An effective conical intersection (CI-npi) exists between the spectroscopic pi/pi* excited state (Spi) and a dark n/pi* state (Sn), and a fraction of the population decays to the minimum of Sn (Sn-min). The conical intersection between Sn and the ground-state is not involved in the decay mechanism, because of its high energy gap with respect to Sn-min. On the other hand, especially in hydrogen bonding solvents, the energy gap between Sn-min and CI-npi is rather small. After thermalization in Sn-min, the system can thus recross CI-npi and then quickly proceed on the Spi barrierless path toward the conical intersection with the ground state.     

A preventive maintenance policy for a continuously monitored system with correlated wear indicators

A continuously monitored system is considered, that gradually and stochastically deteriorates according to a bivariate non-decreasing Lévy process. The system is considered as failed as soon as its bivariate deterioration level enters a failure zone, assumed to be an upper set. A preventive maintenance policy is proposed, which involves a delayed replacement, triggered by the reaching of some preventive zone for the system deterioration level. The preventive maintenance policy is assessed through a cost function on an infinite horizon time. The cost function is provided in full form, and tools are provided for its numerical computation. The influence of different parameters on the cost function is studied, both from a theoretical and/or numerical point of view.     

Synthesis and photochemical properties of novel pentamethylated norbornadiene containing polyimides

A novel pentamethylated norbornadiene (NBD) based dianhydride, α,α′‐bis‐(3,4,5,6,7‐pentamethylcyclopenta‐2,4‐dienyl)meta‐xylene‐1,2‐dianhydride (3), was prepared from α,α′‐bis‐(pentamethylcyclopentadienyl)meta‐xylene (1) and acetylene dicarboxylic acid. The bis‐adduct formed via Diels–Alder reaction afforded tetra‐acid (2), which was chemically cyclodehydrated to lead the targeted dianhydride (3). New polyimides containing NBD moieties in the main chain were prepared from the dianhydride monomer (3) and various aromatic diamines. The chemical structure of the polymers was confirmed by both ¹H and ¹³C NMR analysis. Their Molecular weights were also measured by SEC. All of these polyimides are soluble at room temperature in common organic solvents, such as chloroform, dichloromethane, THF, DMSO, DMF, and NMP, and show good thermal stabilities. The photochemical isomerization of the NBD into quadricyclane (QC) was investigated by UV/vis spectrophotometry from polymer films using visible sunlight as irradiation source. It was found that the kinetic rate of the conversion NBD‐QC which proceeded smoothly is a first kinetic order. The stored energies released by the transformation of QC groups into NBD ones of the irradiated polymer films were also evaluated by DSC measurement and were found to be around 90 kJ mol^?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Descent algorithm for nonsmooth stochastic multiobjective optimization

An algorithm for solving nearly-separable quadratic optimization problems (QPs) is presented. The approach is based on applying a semismooth Newton method to solve the implicit complementarity problem arising as the first-order stationarity conditions of such a QP. An important feature of the approach is that, as in dual decomposition methods, separability of the dual function of the QP can be exploited in the search direction computation. Global convergence of the method is promoted by enforcing decrease in component(s) of a Fischer–Burmeister formulation of the complementarity conditions, either via a merit function or through a filter mechanism. The results of numerical experiments when solving convex and nonconvex instances are provided to illustrate the efficacy of the method.     

Belief functions contextual discounting and canonical decompositions

In this article, the contextual discounting of a belief function, a classical discounting generalization, is extended and its particular link with the canonical disjunctive decomposition is highlighted. A general family of correction mechanisms allowing one to weaken the information provided by a source is then introduced, as well as the dual of this family allowing one to strengthen a belief function.     

Controlled growth of Ti4O7 crystals by chemical transport reactions

Ti₄O₇ is a striking example of the difficulties involved in the simultaneous control of crystal growth and composition. In this respect, the usual back-transport step must be avoided because it results to the formation of mixed phases. However, an appropriate H₂ heat treatment can reduce these mixed crystals into single phase single crystals. This result is ascertained by accurate and sensitive physical methods. Finally suitable pulling transport experiments lead to the growth of centimeter long crystals.     

Bestimmung des Stickstoffs im Harn mit unterbromigsaurem Natron

Ohne Zusammenfassung     

Syntheses and characterizations of bis(trialkoxysilyl)oligoimides. II. Syntheses and characterizations of fluorinated crosslinkable oligoimides with low refractive indices

Novel crosslinkable fluorinated oligoimides were prepared in two steps. The first involved the synthesis of oligoimides terminated with nadic or allylic double bonds, and the second step was materialized either by a radical addition of mercaptotrialkoxysilane derivatives onto nadic double bonds or a hydrosilylation reaction of hydrogenotrialkoxysilane derivative onto allylic double bonds. Three kinds of crosslinking of the trialkoxysilane end groups were studied. The first kind entailed a thermal self‐crosslinking of trialkoxysilane groups. The second process of crosslinking incorporated a bicomponent system—the crosslinked agent was 1,1,1‐tris(4‐hydroxyphenyl)ethane (TRIOH). The trialkoxysilane groups reacted with the hydroxyl–phenol groups of TRIOH to give thermally stable phenoxysilane bonds as well as a crosslinking network. The last method was also a bicomponent system; the oxalic acid was added into an oligoimide solution where by thermal treatment water was created. The water molecules hydrolyzed the trialkoxysilane groups into silanol groups that polycondensed into a crosslinked network following a sol–gel process. The mechanism of the different crosslinking reactions was investigated by Fourier transform infrared spectroscopy and solid‐state ²⁹Si NMR. The self‐crosslinked material prepared from precursor α,ω‐trimethoxysilyl fluorinated oligomer (M_n = 5500 g · mol^?1) exhibited a 10 wt % loss temperature under air higher than 420 °C and a low birefringence (Δn = 0.008) at 1.300 μm. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2602–2619, 2001     

Time-harmonic acoustic propagation in the presence of a shear flow

This work deals with the numerical simulation, by means of a finite element method, of the time-harmonic propagation of acoustic waves in a moving fluid, using the Galbrun equation instead of the classical linearized Euler equations. This work extends a previous study in the case of a uniform flow to the case of a shear flow. The additional difficulty comes from the interaction between the propagation of acoustic waves and the convection of vortices by the fluid. We have developed a numerical method based on the regularization of the equation which takes these two phenomena into account. Since it leads to a partially full matrix, we use an iterative algorithm to solve the linear system.