Hydrophobic Effect Driven Esterification of Sucrose in Aqueous Medium 1

Sucrose is an attractive molecule for chemistry because it is pure, abundant, inexpensive, and produced from renewable sources. Amoung its derivatives, sucrose esters are valuable targets for the chemical valorization of sugar, either as polymerizable derivatives, surfactants, or non-caloric fat substitutes.² But although such potential commercially attractive sucrose derived molecules can be targeted, methods consistent with low-cost sucrouse diversification have still to be found. The issue of the solvent being critical, we have been interested in evaluating water as a possible solvent for some transformations of sucrose, and we report herein some preliminary results on the esterification of this sugar in basic aqueous medium.

     

Aluminium Mediated Glycosaminoglycan/Amyloid-β Association Mechanism

In Alzheimer’s disease, it has been proposed that glycosaminoglycans facilitate amyloid fibril formation and/or stabilize the plaque aggregates. Chondroitin sulfates are sulfated glycosaminoglycans represented an ideal distribution of charge for amyloid-β (Aβ) interactions. Recent studies have suggested a possible link between the neurotoxicity of aluminum and the pathogenesis of Alzheimer’s disease. In this paper, the interaction of Aβ with chondroitin sulfates immobilized on a chromatographic column and the role of aluminum had been studied using a biochromatographic approach (molecular chromatography). A novel biochromatographic column was developed in our laboratory for studying this interaction. This study demonstrated that the aluminum interacted with Aβ and played a role in the Aβ/chondroitin sulfates association. For a Al³⁺ concentration (x) in the medium less than 30 μmM, the Aβ/chondroitin sulfates binding decreased with x due to a decrease of the charge–charge interactions between Aβ and its chondroitin sulfates binding site. Above 30 μmM of Al³⁺ in the medium, the affinity of Aβ to chondroitin sulfates increased slightly with x because the net number of ions (n) (Al³⁺ or Cl⁻) released or bound upon complex formation is low. As well, it was clearly demonstrated, that above 30 μmM the n value depend on the Al³⁺ concentration in the bulk solvent. This dependence was due to a gradual and conformational change of the Aβ which around 80 μmM adopted a less flexible structure; its binding site was thus less accessible to Aβ and Aβ/chondroitin sulfates association decreased slightly.

     

Electronic and Steric Ligand Effects in the Radical Polymerization of Vinyl Acetate Mediated by β‐Ketoiminate Complexes of Cobalt(II)

Complexes Co[OC(Ph)CHC(Me)NAr]₂ [Ar=Ph, 1 ; o,o′‐C₆H₃Me₂ (Xyl), 2 ; p‐C₆H₄CF₃, 3 ] are tested in the polymerization of vinyl acetate (VAc) initiated by V‐70 (0.8 equiv) at 30 °C. Polymerization occurs without any notable induction time yielding PVAc with relatively low polydispersity, but with higher than expected M_n values, which indicates inefficient trapping processes. The apparent polymerization rate constant varies in the order 2 > 1 > 3 . Controlled polymer growth is also observed when the polymerization is conducted in the presence of a much higher V‐70/ 1 ratio, demonstrating that this system can also function as a transfer agent in a degenerative transfer process. Competition between chain growth and catalyzed chain transfer (CCT) is also observed, the latter prevailing at higher temperatures. Comparison of these results with previous reports on bis(β‐diketonato) complexes allows a separate assessment of ligand electronic and steric effects in the ability to control polymerization.     

Preparation of Enantiomerically Pure 1,3-Butanediol from Threonine

Enantiomerically pure R or S 1,3-butanediols were prepared in four steps from L or D threonine by nitrous deamination in the presence of bromide ion followed by esterification and reduction.     

Inverse thermal analysis of the drying zone of the evaporator of an axially grooved heat pipe

An inverse approach is performed to characterize the thermal behaviour of an axially grooved heat pipe, in steady state, for various operating conditions. For this purpose, an experimental set up, as well as a network conduction model, are developed to simulate the heat transfer in the wall at the evaporator section. The minimization of an objective function, taking into account the discrepancy between measured temperatures and computed ones, allows then the estimation of a heat transfer coefficient as well as the drying out front positions for all the axial grooves. Hence, at the burnout point, the significant temperature increase in the evaporator extremity is considered to be a direct consequence of the restriction of the evaporative zone. Therefore, the distribution of liquid phase in the capillary structure of the heat pipe can be obtained through the analysis of the measured temperature gradient in the evaporator section where the dry out front was expected to occur. Furthermore, the dry out front expansion can be observed when the input heat load is increased or when the adiabatic temperature is decreased. Introducing an adverse tilt angle also shows the effect of the puddle.     

Horocycles récurrents sur des surfaces de volume infini

Nous construisons des exemples de surfaces à courbure négative de volume infini, sur lesquelles tous les horocycles sont récurrents. Ces exemples reposent sur le résultat suivant: si le rayon d’injectivité le long d’une géodésique n’est pas minoré, alors l’horocycle associé est récurrent.