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701.
A quasichemical method that combines ab initio treatment of explicit solvent with dielectric continuum models has been used to study the origin of a strong effect of methanol on the extent of iron(III) [tetrakis(pentafluorophenyl)]porphyrin chloride dissociation in acetonitrile-methanol solutions. It is shown that the dissociation is energetically more favorable in methanol than in acetonitrile primarily because of the strong specific interactions between the chloride anion and the solvent methanol molecules in its first solvation shell. These interactions are weaker in acetonitrile. The final estimate for the difference in the dissociation free energies in methanol and acetonitrile is -23 kJ/mol, in a good agreement with the experimental value of -21 kJ/mol. Energy decomposition analysis of chloride-solvent interactions suggests that stronger chloride-methanol binding is a result of the contribution of charge delocalization effects to the chloride-methanol interactions. 相似文献
702.
Total syntheses of six brominated marine sponge bis(indole) alkaloids of the hamacanthin, spongotine, and topsentin classes are described. Retrosynthetic analysis shows that their structures all include the 1-(6'-bromoindol-3'-yl)-1,2-diaminoethane unit 13a. This key moiety has been prepared from brominated indolic N-hydroxylamine 5b via synthetic intermediate 8b. 相似文献
703.
Vallée MR Majkut P Wilkening I Weise C Müller G Hackenberger CP 《Organic letters》2011,13(20):5440-5443
Site-specific functionalization of proteins by bioorthogonal modification offers a convenient pathway to create, modify, and study biologically active biopolymers. In this paper the Staudinger reaction of aryl-phosphonites for the chemoselective functionalization of azido-peptides and proteins was probed. Different water-soluble phosphonites with oligoethylene substituents were synthesized and reacted with unprotected azido-containing peptides in aqueous systems at room temperature in high conversions. Finally, the Staudinger-phosphonite reaction was successfully applied to the site-specific modification of the protein calmodulin. 相似文献
704.
Dr. Franck Pereira Dr. Alida Chan Dr. Karine Vallé Dr. Pascal Palmas Dr. Janick Bigarré Dr. Philippe Belleville Prof. Clément Sanchez 《化学:亚洲杂志》2011,6(5):1217-1224
Organic–inorganic hybrid membranes of poly(vinylidene fluoride)–cohexafluoropropylene (PVdF–HFP) and mesostructured silica containing sulfonic acid groups were synthesized by using the sol‐gel process. These hybrid membranes were prepared by in situ co‐condensation of tetraethoxysilane and an organically modified silane (ormosil) by a self‐assembly route using organic surfactants as templates for tuning the architecture of the hybrid organosilica component. In this paper, we describe the elaboration and characterization of hybrid membranes all the way from the precursor solution to the evaluation of the fuel cell performances. These hybrid materials were extensively characterized by using NMR and IR spectroscopy, electron microscopy, or impedance spectroscopy so as to determinate their physicochemical and electrochemical properties. Even though the ion‐exchange capacity (IEC) was quite weak, the first fuel cell tests performed with these hybrid membranes show promising results relative to optimized Nafion 112 thanks to great water management of the silica inside the hydrophobic polymer. 相似文献
705.
We develop a theory based on relative entropy to show the uniqueness and L 2 stability (up to a translation) of extremal entropic Rankine?CHugoniot discontinuities for systems of conservation laws (typically 1-shocks, n-shocks, 1-contact discontinuities and n-contact discontinuities of large amplitude) among bounded entropic weak solutions having an additional trace property. The existence of a convex entropy is needed. No BV estimate is needed on the weak solutions considered. The theory holds without smallness conditions. The assumptions are quite general. For instance, strict hyperbolicity is not needed globally. For fluid mechanics, the theory handles solutions with vacuums. 相似文献
706.
Bernard Ducomet ?��rka Ne?asov�� Alexis Vasseur 《Journal of Mathematical Fluid Mechanics》2011,13(2):191-211
We consider the Cauchy problem for the equations of spherically symmetric motions in
\mathbb R3{\mathbb {R}^3}, of a selfgravitating barotropic gas, with possibly non monotone pressure law, in two different situations: in the first
one we suppose that the viscosities μ(ρ), and λ(ρ) are density-dependent and satisfy the Bresch–Desjardins condition, in the second one we consider constant densities. In
the two cases, we prove that the problem admits a global weak solution, provided that the polytropic index γ satisfy γ > 1. 相似文献
707.
Lux F Mignot A Mowat P Louis C Dufort S Bernhard C Denat F Boschetti F Brunet C Antoine R Dugourd P Laurent S Vander Elst L Muller R Sancey L Josserand V Coll JL Stupar V Barbier E Rémy C Broisat A Ghezzi C Le Duc G Roux S Perriat P Tillement O 《Angewandte Chemie (International ed. in English)》2011,50(51):12299-12303
708.
de Carné-Carnavalet B Archambeau A Meyer C Cossy J Folléas B Brayer JL Demoute JP 《Organic letters》2011,13(5):956-959
The substrate scope of the copper-free Sonogashira coupling has been successfully extended to cyclopropyl iodides, allowing an efficient access to a wide variety of functionalized alkynyl cyclopropanes. 相似文献
709.
Mihaela Popovici Johan Swerts Kazuyuki Tomida Dunja Radisic Min‐Soo Kim Ben Kaczer Olivier Richard Hugo Bender Annelies Delabie Alain Moussa Christa Vrancken Karl Opsomer Alexis Franquet Malgorzata A. Pawlak Marc Schaekers Laith Altimime Sven Van Elshocht Jorge A. Kittl 《固体物理学:研究快报》2011,5(1):19-21
Crystalline rutile TiO2 films were grown by atomic layer deposition on oxidized Ru electrodes using a titanium methoxide as the metal precursor and O3 as the oxidant. A protective layer of ~0.3 nm TiO2 grown with H2O as the oxidant was first deposited in order to avoid etching of the Ru bottom electrode by the O3 used for the growth of the TiO2 (bulk) layer. Electrical evaluation of the capacitor stacks with TiO2 as dielectric, RuO2/Ru and Pt as the bottom and top electrodes respectively, resulted in superior characteristics of the rutile phase as compared to the anatase. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
710.
Stability is a particular problem for biopharmaceutical products because the efficacy of peptides and proteins as therapeutic or diagnostic agents can be affected during preparation, shipping, and storage. A particular formulation may have no immediately apparent effect on physical or chemical stability, and the time required for these studies at ambient temperature can be very lengthy because chemical reactions proceed relatively slowly at low temperatures. Undoubtedly, accelerated and stress testing of stability can provide useful information for future product development. The many methods used to study kinetics in aqueous solution may be experimental or computational. Experimental approaches may be isothermal or non-isothermal. Non-linear and linear regression methods can be used to analyze data from these experimental approaches, and the Monte Carlo method could be useful to obtain information about uncertainties in experimental data.The purpose of this review is to describe and to discuss options for the accelerated study of peptide and protein drugs. These options are not necessarily the same as those used for regulatory testing to set expiration dates. We also review statistical techniques to estimate kinetic parameters (rate constant, activation energy, and pre-exponential factor). Further, we establish the advantages and the limitations of both thermal approaches. We analyze and discuss all aspects using the most recent examples of peptide and protein stability. 相似文献