Synthesis and characterization of functional fluorinated telomers

The synthesis and characterizations of fluorinated telomers based on vinylidene fluoride (VDF) by iodine transfer polymerization (ITP) are presented. These telomers were prepared in the presence of ω‐iodoperfluorinated functional chain transfer agents, C₆F₁₃I or C₄F₉I. ITPs were initiated by thermal decomposition of bis(4‐tert‐butylcyclohexyl) peroxydicarbonate (BBCHPDC), in solution (in the presence of acetonitrile). The obtained telomers were characterized by different analyses such as elemental analyses, nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy, size exclusion chromatography, X‐ray diffraction (XRD), and finally by thermal analyses such as differential scanning calorimetry (DSC) and thermogravimetric analyses. These technical analyses enabled one to assess their chemical structures, various thermal properties, and their crystalline forms. The assignments of the characteristic signals obtained by ¹⁹F NMR spectroscopy enabled one to calculate the average degrees of polymerization (DPn) and percentages of ? CH₂CF₂I end group functionalities that depend on the initiator and the fractionation process after reaction. A good control of polymerization was shown by the absence of reversed ? CH₂CF₂? CF₂CH₂? (VDF–VDF dyads) and narrow polydispersity indices (<1.2). The XRD and DSC evidenced the influence of the chain length of the telomers on the crystallinity rate (>70%) and indicated two crystalline forms, α and β, that depended on DPn values. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Superconductivity Near the Normal State Under the Action of Electric Currents and Induced Magnetic Fields in {\mathbb{R}^2}

We consider the linearization of the time-dependent Ginzburg-Landau system near the normal state. We assume that an electric current is applied through the sample, which captures the whole plane, inducing thereby, a magnetic field. We show that independently of the current, the normal state is always stable. Using Fourier analysis the detailed behaviour of solutions is obtained as well. Relying on semi-group theory we then obtain the spectral properties of the steady-state elliptic operator.     

Routine Analysis of Catecholamines and Metabolites in Urine by a Liquid Chromatographic Column Switching System

Abstract

A reversed-phase liquid chromatographic technique including a column switching system has been adapted for the routine measurement of catecholamines and their metabolites (14 compounds) in urine. From 1 ml of urine all the compounds and the internal standards were obtained according to combined extraction procedures involving organic solvent, anionic and weakly cationic resins. Finally four extracts (catecholamines, methoxamines, acidic and neutral derivatives) had to be chromatographed throughout a wholly automated apparatus. For each run, the column switching system determined the analytical columns to be used to obtain the separation of the compounds from interferences due to other co-extracted endogenous substances, while the analysis times remained between 20 and 40 min. Such a system allowed the rapid clean-up of columns (in direct- and back-flush mode) carried out between two consecutive injections. By coupling on-line fluorimetric and electro-chemical detections the specificity of the technique could be checked, since the ratio of the responses of both detectors was an index of the purity of the peaks. Finally the advanced automation of the equipment allowed weekly the evaluation of catecholamines and the whole range of their known metabolites in 36 urine samples.     

Octapeptide-Specific and Sensitive Assay for Angiotensin II in Plasma

Abstract

Angiotensin-(1–8)octapeptide (angiotensin II) is the active principle of the reninangiotensin system. Crossreaction of angiotensin II-antisera with inactive precursors and metabolic fragments prevented the specific quantitation of this hormone in biological fluids. Peptide-extraction on bonded-phase silica followed by peptide-separation using isocratic reverse-phase high performance liquid chromatography and subsequent radioimmunoassay rendered possible the octapeptide-specific measurement of angiotensin II in 2 ml plasma with a detection limit of 0.4fmol/ml. The coefficient of variation for intra-assay precision was 0.06 and for inter-assay precision 0.13. ¹²⁵Iangiotensin II was recovered from plasma by solid-phase extraction to 99±2% (mean ± S.D.). The overall recovery of 5, 10 and 20 fmol unlabeled angiotensin II added to plasma was 80±10%. Plasma concentrations in supine normal humans averaged 4.1 ± 1.6 fmol/ml and were suppressed below the detection limit by angiotensin I converting enzyme inhibition.     

Introduction of a Carboxymethylamino(or oxy Or thio) Group in the 3 Position of 2-Aryl(or Arylmethyl)isoindol-1-ones from α Hydroxylactams

The preparation of 3-carboxymethylamino (or oxy or thio)-2-aryl (or arylmethyl)-isoindol-1-ones are described from hydroxylactams according to three different pathways.     

UV‐curable bismaleimides containing poly(dimethylsiloxane): Use as hydrophobic agent

The synthesis and characterization of poly(dimethylsiloxanes) bearing maleimides end‐groups (PDMSM) were carried out through imidization of maleic anhydride with three poly(dimethylsiloxanes) diamines of different molecular weights. Self‐photopolymerization of PDMSM was studied by Real‐Time Fourier Transform infrared spectroscopy (RT‐FTIR) and was possible even without photoinitiator (Darocur 1173). The reaction was found to proceed within seconds upon exposure to ultraviolet (UV) radiation to generate highly crosslinked polymer networks. The results indicated that these polymerizations were less sensitive to oxygen inhibition than the radical processes carried out on conventional UV‐curable acrylate resins. The thermal and mechanical properties of these resulting materials were studied starting from PDMS precursors with different molecular weights. These materials exhibit a low glass transition temperature (相似文献   

Proteome analysis of Aspergillus fumigatus identifies glycosylphosphatidylinositol-anchored proteins associated to the cell wall biosynthesis.

Previous studies in Aspergillus fumigatus (Mouyna I., Fontaine T., Vai M., Monod M., Fonzi W. A., Diaquin M., Popolo L., Hartland R. P., Latgé J.-P, J. Biol. Chem. 2000, 275, 14882-14889) have shown that a glucanosyltransferase playing an important role in fungal cell wall biosynthesis is glycosylphosphatidylinositol (GPI) anchored to the membrane. To identify other GPI-anchored proteins putatively involved in cell wall biogenesis, a proteomic analysis has been undertaken in A. fumigatus and the protein data were matched with the yeast genomic data. GPI-anchored proteins of A. fumigatus were released from membrane preparation by an endogenous GPI-phospholipase C, purified by liquid chromatography and separated by two-dimensional electrophoresis. They were characterized by their peptide mass fingerprint through matrix-assisted laser desorption/ionization-time of flight-(MALDI-TOF)-mass spectrometry and by internal amino acid sequencing. Nine GPI-anchored proteins were identified in A. fumigatus. Five of them were homologs of putatively GPI-anchored yeast proteins (Csa1p, Crh1p, Crh2p, Ecm33p, Gas1p) of unknown function but shown by gene disruption analysis to play a role in cell wall morphogenesis. In addition, a comparative study performed with chitin synthase and glucanosyl transferase mutants of A. fumigatus showed that a modification of the growth phenotype seen in these mutants was associated to an alteration of the pattern of GPI-anchored proteins. These results suggest that GPI-anchored proteins identified in this study are involved in A. fumigatus cell wall organization.