Ring-opening polymerization of decamethylcyclopentasiloxane initiated by a superbase: Kinetics and rheology

The use of phosphazene bases in combination with water was proved to be efficient in order to obtain polysiloxane polymers from cyclic monomers. Only a few minutes are necessary to obtain polymer chains with a monomer concentration of 5% at the equilibrium. For that purpose the space which is between a rheometer's plates is the most convenient device to monitor this reaction concerning a chemical and viscoelastic point of view. Therefore, here is proposed a chemo-rheology study that leads in the same time to the chemical kinetics equations and to the variation of the viscoelastic functions during the polymerization. In this way different catalysts are used and their efficiencies are compared as a function of their “basicity tank”. Whatever the experimental conditions involved are, viscosity versus polymer concentration or conversion shows a master curve for catalysts suitable to be used under extrusive conditions. Thus, only a few experiments are needed in order to develop a model which can be used to foresee the variation of the viscosity during the reaction.     

Towards a new definition of EPOC parameters for anionic electrochemical catalysts: case of propene combustion

The electrochemical promotion of catalysis (EPOC) of propene combustion was investigated using Pt sputtered thin film on an O²⁻ conductor, 8 mol% Y₂O₃-stabilized-ZrO₂ (YSZ). In order to separate the influence of the thermal migration of the O²⁻ oxide ions from the electrolyte to the catalyst surface and the impact of an electrical polarization on the catalytic activity, several light-off experiments (cool down and heat up procedures) were successively performed under different polarizations, i.e. OCV, +2 and −2 V. These experiments have clearly shown that the presence of O²⁻ (thermally or electrochemically induced) inhibits the catalytic activity of the platinum for the propene deep oxidation. These results demonstrate the importance to define a normalized rate enhancement ratio, ρ _n , from a reference value of the catalytic rate corresponding to a Pt surface state free of O²⁻ ions.     

Catalysis, the turntable for a clean future

Upgrading the bottom of the barrel for clean fuel production, developing new engines with optimized catalytic posttreatments, implementing clean catalytic combustion technologies, improving the overall CO₂ balance via catalytic processes and, lastly, developing new water purification techniques represent major upheavals in catalysis linked to refining and environmental protection. This paper, thus, will focus on the determining contribution of catalysis to the most recent achievements in these domains. A technico-economic approach will follow, underlining their main incentives and drawbacks within the framework of future environmental constraints.     

Partial or total silylation of dextran with hexamethyldisilazane

The silylation reaction of dextran with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) in DMSO was studied as the first step of the synthesis of new amphiphilic polyester-grafted dextrans. According to the experimental conditions, i.e. dextran molar weight, medium temperature and reaction time, HMDS/OH ratio, addition of a catalyst and co-solvent, partially or totally silylated dextrans were recovered. The highest silylation yields were obtained with the lowest molecular weight dextrans. The increase in temperature medium and/or reaction time, the presence of catalyst or co-solvent favored the protection yield. Whatever the dextran used, complete silylation of the polysaccharide chain could be achieved by adequate selection of the experimental conditions. The thermal properties of resulting silylated polysaccharides were investigated by temperature modulated DSC. It was observed that T_g values of partially silylated dextran were maintained between 120 and 140 °C, independently of the dextran molecular weight. Interestingly, DMSO proved to behave as an efficient plasticizer of (partially) silylated dextrans. The partially silylated dextrans were efficiently used as multifunctional macroinitiators for the controlled ring-opening polymerization (ROP) of lactone. The ROP was then promoted from the remaining hydroxyl groups in the presence of tin or aluminium activator. After polymerization and ultimate deprotection of the silylated dextran backbone, amphiphilic polyester-grafted dextrans were readily recovered.     

Radiosity with Well Distributed Ray Sets

In this paper we present a new radiosity algorithm, based on the notion of a well distributed ray set (WDRS). A WDRS is a set of rays, connecting mutually visible points and patches, that forms an approximate representation of the radiosity operator and the radiosity distribution. We propose an algorithm that constructs an optimal WDRS for a given accuracy and mesh. The construction is based on discrete importance sampling as in previously proposed stochastic radiosity algorithms, and on quasi Monte Carlo sampling. Quasi Monte Carlo sampling leads to faster convergence rates and the fact that the sampling is deterministic makes it possible to represent the well distributed ray set very efficiently in computer memory. Like previously proposed stochastic radiosity algorithms, the new algorithm is well suited for computing the radiance distribution in very complex diffuse scenes, when it is not feasible to explicitly compute and store form factors as in classical radiosity algorithms. Experiments show that the new algorithm is often more efficient than previously proposed Monte Carlo radiosity algorithms by half an order of magnitude and more.     

Review of Cliniques de thérapie comportementale.

Reviews the book, Cliniques de thérapie comportementale/Clinical behavioral therapy edited by O. Fontaine, J. Cottraux, and R. Ladouceur (1985). This book is a work which seeks to fill a vacuum while proposing to illustrate in a concrete manner how the behaviorist acts in his daily practice. It comprises 25 chapters which frequently illustrate this pragmatic prospect within the framework for pathologies used in behavioral private clinics, from infantile autism to dementia in old age, while passing by depression, alcoholism, chronic pain, etc. This book is the result of the collaboration of about thirty specialists of reputation: Beligian, Canadian, French and Swiss. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Swiss journey through the clinical and genetic characteristics of diabetes in young patients

The aim of this study is to understand better the genetic causes of type II diabetes and the phenotypic consequences of the genetic changes. We first investigated the relative prevalence of the different forms of diabetes in young adults and their clinical features. 51 non-obese patients were identified in whom diabetes had been diagnosed before age 40; cases of typical insulin-dependent type I diabetes were excluded. A search for mutations of the glucokinase and HNF-1 alpha genes and for mitochondrial DNA was made, anti-islet and anti-GAD antibodies were determined and HLA class II genotyping was performed. Patients were subdivided on clinical grounds into a MODY (maturity onset diabetes of the young) group (n = 19) and a non-MODY group (n = 32). MODY is a form of diabetes which has an autosomal dominant inheritance for which 3 genes have already been implicated (MODY1, HNF-4 gene; MODY2, glucokinase gene, and MODY3, HNF-1 alpha gene). In the MODY group we identified 3 patients with MODY2, 1 with MODY3, 1 with the 3243 mitochondrial mutation and a further patient with autoimmune diabetes. In the non-MODY group we found 5 patients with autoimmune diabetes and 1 with MODY2. No clinical parameter was helpful in classifying patients in one of these subclasses of diabetes; however, glucagon stimulated C-peptide was useful in discriminating between MODY2 patients and the others. Young and lean non-insulin-dependent diabetic patients thus constitute a very heterogeneous group, though presenting similar clinical features. In the second study we analyzed hepatic glucose metabolism in patients with a mutation of the glucokinase gene expressed in both liver and islet beta cells. We found that endogenous glucose production is inadequately inhibited by hyperglycemia, a fact which contributes to the pathogenesis of hyperglycemia in these patients.     

Systemic and intracerebroventricular injections of vasotocin inhibit appetitive and consummatory components of male sexual behavior in Japanese quail.

The authors investigated the behavioral actions of vasotocin (VT) in castrated testosterone-treated male Japanese quail. The appetitive and consummatory components of sexual behavior as well as the occurrence frequency of crows were inhibited, in a dose-dependent manner, by injections of VT. The authors observed opposite effects after injection of the V1 receptor antagonist, dPTyr(Me)AVP. Lower doses of VT were more active after central than after systemic injection, and effects of systemic injections of VT were blocked by a central injection of dPTyr(Me)AVP. The behavioral inhibition was associated with a modified diuresis after systemic but not central injection. These results provide direct evidence that VT affects male sexual behavior in quail by a direct action on the brain independent of its peripheral action on diuresis. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Identifying the criterion spontaneously minimized during the take-off phase of a sub-maximal long jump through optimal synthesis

Optimal synthesis of human movement or the prediction of the kinematics of a new movement require not only that the multi-body system be modeled but also that a performance criterion is specified. For sub-maximal movements the selection of a suitable performance criterion, able to generate realistic dynamic behavior is difficult. A two-dimensional simulation model of the take-off phase of a sub-maximal long jump was developed to study the effect of criterion choice on the realism of simulated movements. A parametric optimization technique was employed to obtain solutions to the constrained equations of motion. Seven different criteria were evaluated, by comparing simulated movements with an actual performance, to identify the criterion which most closely approximated that spontaneously minimized by the athlete. Synthesis of the take-off phase of a sub-maximal long jump was found to be sensitive to the chosen criterion, with a criterion based on minimizing joint intersegmental forces found to perform well.