Les Sels de Bismuth (III) Comme Catalyseurs Dans la Reaction D'ouverture Des Epoxydes Par Les Amines

BiCl 3 and Bi (OTf) 3 catalyze the opening of epoxides ( 1-7 ) by amines ( 8-12 ). High regioselectivities are observed. BiCl 3 et Bi (OTf) 3 catalysent la réaction d'ouverture des époxydes ( 1-7 ) par les amines ( 8-12 ). La réaction est fortement régiosélective.     

Complexes of Tin(IV) Tetrachloride with 3-Formylpyridine Semicarbazone and Thiosemicarbazones

The reaction of tin(IV) tetrachloride with 3-formylpyridine semicarbazone and different 3-formylpyridine thiosemicarbazones produces [Sn(HL)CL 3 ][SnCl 5 ] where HL stands for the neutral ligand. The tin(IV) complexes were characterized using a variety of spectroscopic techniques. Coordination through the pyridine nitrogen occurs in all cases. Solvation studies in DMSO indicated that dissociation of the ligands and their complete replacement by solvent molecules occurs.     

Le Triflate de Bismuth(III) Comme Catalyseur Dans la Reaction de Carbonyl-Diels-Alder

In presence of bismuth(III) triflate, a carbonylated electrophile (ethyl mesoxalate or glyoxylate) and usual diene led selectively (60-100) the hetero carbonyl-Diels-Alder reaction with the ene reaction product. Bi(OTf) 3 exhibits strong catalytic activity and reacts under mild conditions. En présence de triflate de bismuth(III) le mésoxalate et le glyoxylate d'éthyle réagissent avec des diènes usuels pour donner un mélange de carbonyl-Diels-Alder et du produit de la ène réaction. Bi(OTf) 3 présente une forte activité catalytique et réagit dans des conditions douces.     

Liquid-crystalline comb copolymers with lipoamino acid side chains Synthesis and structure study

In order to obtain liquid-crystalline polymers without using classical mesogenic groups, comb copolymers consisting of a polyacrylamide main chain and lipoamino acid side chains have been synthesized. These copolymers were obtained by the polymerization of lipoamino acid macromonomers. These macromonomers were obtained from, α,ω-aliphatic amino acids by linking a polymerizable group at the amino end and an α-amino acid at the carboxyl end. The macromonomers were then transformed into comb copolymers by free-radical polymerization. These comb copolymers exhibit mesophases both in aqueous solution and in the anhydrous state. The range of stability and the structures of the mesophases were determined by X-ray diffraction. Two types of structures were found, corresponding to the lyotropic lamellar and hexagonal mesophases. The influences of the nature of the amino acid and the water concentration on the domain of stability and the geometrical parameters of the mesomorphic structures were investigated.     

Quantification of Intact and Truncated Stromal Cell-Derived Factor-1α in Circulation by Immunoaffinity Enrichment and Tandem Mass Spectrometry

Stromal cell-derived factor 1α (SDF-1α) or CXCL12 is a small pro-inflammatory chemoattractant cytokine and a substrate of dipeptidyl peptidase IV (DPP-IV). Proteolytic cleavage by DPP-IV inactivates SDF-1α and attenuates its interaction with CXCR4, its cell surface receptor. To enable investigation of suppression of such inactivation with pharmacologic inhibition of DPP-IV, we developed quantitative mass spectrometric methods that differentiate intact SDF-1α from its inactive form. Using top-down strategy in quantification, we demonstrated the unique advantage of keeping SDF-1α’s two disulfide bridges intact in the analysis. To achieve the optimal sensitivity required for quantification of intact and truncated SDF-1α at endogenous levels in blood, we coupled nano-flow tandem mass spectrometry with antibody-based affinity enrichment. The assay has a quantitative range of 20 pmol/L to 20 nmol/L in human plasma as well as in rhesus monkey plasma. With only slight modification, the same assay can be used to quantify SDF-1α in mice. Using two in vivo animal studies as examples, we demonstrated that it was critical to differentiate intact SDF-1α from its truncated form in the analysis of biomarkers for pharmacologic inhibition of DPP-IV activity. These novel methods enable translational research on suppression of SDF-1 inactivation with DPP-IV inhibition and can be applied to relevant clinical samples in the future to yield new insights on change of SDF-1α levels in disease settings and in response to therapeutic interventions.

High order integration schemes on the unit sphere

A method for refining high order numerical integration schemes is described. Particular focus is on integration schemes over the unit sphere with octahedral symmetry. The method is powerful enough that new integration schemes can be found from rough intuitive guesses. New schemes up to order 59 are presented. © 1996 by John Wiley & Sons, Inc.     

Effect of polymerization of synthetic glycolipids on their supramolecular assemblies

Sugar-derived surfactants bearing a polymerizable acryloyl moiety on one of the branches of the double-chain hydrophobic tail were prepared. The non–ionic hydrophilic head and the biantennary hydrophobic tail were built on, respectively, an aspartic acid and a tris(hydroxymethyl)aminomethane core. Ultraviolet irradiation of aqueous dispersions of these surfactants above their transition phase temperature (T_c) was achieved. The morphology of self-assemblies produced in such a way were investigated by transmission electron microscopy. TEM photographs revealed that irradiation leads to the formation of unilamellar vesicles. Neither fibers nor tubules were detected in contrast to what was observed before polymerization.     

Epitaxy of helical polyolefins

The structural rules which govern the epitaxial crystallisation of polymers - and especially polyolefins - on organic substrates are established. Illustrative examples involve isotactic and syndiotactic polypropylenes and poly( l-butene). Investigation of the film structure by electron microscopy, electron diffraction and atomic force microscopy reveals some unprecedented features, including in particular the selection of the contact plane according to the chirality of its constituent helices, and direct observation of both right and left hands of polyolefin helices.