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121.
A catalytic diastereoselective sulfonium ylide epoxidation of aldehydes furnished original vinyl epoxides, having an MBH backbone. These highly functionalized building blocks were used for a formal synthesis of the antibiotic conocandin, and opened up a stereodivergent route towards beta-hydroxy-alpha-methylene lactones, core units of naturally occurring compounds. Under acidic conditions, the oxiranes were mainly transformed, with moderate to good yields, into trans beta-hydroxy-alpha-methylene lactones. On the other hand, a user-friendly palladium-catalysed CO2 insertion and cyclisation sequence gave the cis beta-hydroxy-alpha-methylene lactone counterparts along with an interesting cis-trans equilibration of the pi-allyl intermediates. 相似文献
122.
Bottier C Géan J Desbat B Renault A Marion D Vié V 《Langmuir : the ACS journal of surfaces and colloids》2008,24(19):10901-10909
Puroindolines (PINs), basic and cysteine-rich proteins of wheat endosperm, are composed of two proteins, puroindoline-a (PIN-a) and puroindoline-b (PIN-b). Using a monolayer assay at the air/liquid interface, both PIN-a and PIN-b were studied in pure components and mixed with wheat galactolipids, 1,2-di-O-acyl-3-O-(beta-d-galactopyranosyl)- sn-glycerol (MGDG) and 2-di-O-acyl-3-O-(beta-d-galactopyranosyl-1,6-beta-d-galactopyranosyl)-sn-glycerol (DGDG). Following the adsorption of PINs at the air/liquid interface thanks to surface pressure increases, we concluded that PIN-a displays a more amphipathic character than PIN-b. Compression isotherms combined with ellipsometric measurements showed that the area per molecule is smaller and the protein film is more condensed for PIN-a than for PIN-b. According to the polarization modulation-infrared reflection-absorption spectroscopy data, both proteins display a highly alpha-helical structure and the alpha-helices are oriented rather parallel to the interface. By measuring the overpressure due to PIN adsorption into MGDG and DGDG monolayers, we observed that PIN-a interacts more strongly into lipid films than PIN-b. The observation by atomic force microscopy of mixed protein/lipid films showed that the nature of the lipid plays a significant role in the organization of PINs, particularly for PIN-a. The presence of galactolipids at the interface stabilizes the alpha-helical structure of PINs, but significant changes were observed concerning the orientation of the alpha-helices. They adopt a perfect parallel orientation to the interface in the MGDG monolayer, whereas the bundle of alpha-helices orients normal to the interface in the DGDG film. 相似文献
123.
Coupling of liquid chromatography at critical conditions (LCCC) with on-line mass spectrometry (MS) detection was implemented via an electrospray ionization (ESI) interface, using a mobile phase containing the cationizing agent. Critical conditions established for poly(ethylene oxide) were used to characterize a poly(ethylene oxide)/polystyrene block copolymer (PEO-b-PS) in both MS and MS/MS modes. As co-oligomer molecules were successfully separated according to the PS block size, structural information could be reached from simplified MS spectra. The microstructure of this copolymer, synthesized by nitroxide-mediated polymerization, could further be unambiguously characterized in LCCC/ESI-MS/MS experiments since the PS block size could be reached by both the co-oligomer chromatographic behavior and its MS/MS pattern. 相似文献
124.
Copper(II) complexes of bispidines (bispidine = tetra-, penta-, or hexadentate ligand, based on the 3,7-diazabicyclo[3.3.1]nonane backbone) display several isomeric forms. Depending on the substitution pattern of the bispidine and the type of coligands used, the structure elongates along one of the three potential Jahn-Teller axes. In an effort to develop a computational tool which can predict which isomer is observed, 23 bispidine-copper(II) complexes with 19 different ligands are analyzed theoretically by ligand field molecular mechanics (LFMM). With two exceptions, the lowest-energy LFMM structure and the experimental solid-state structure agree concerning the Jahn-Teller axis. However, in most cases and especially for six-coordinate complexes, LFMM predicts a second local minimum within a few kilojoules per mole. Although detailed analysis reveals that the current force field is too "stiff", reasonable quantitative reproduction of the structural data is achieved with Cu-L bond length root mean square (rms) deviations for nine complexes of 0.05 A or less and with 20 reproduced to a rms deviation of 0.1 A or less. Across all of the complexes, the Cu-amine and Cu-pyridyl bond length rms deviations are 0.07 and 0.12 A, respectively. 相似文献
125.
Sébastien Duminil Mohammed Heyouni Philippe Marion Hassane Sadok 《Numerical Algorithms》2016,71(2):383-394
The CMRH (Changing Minimal Residual method based on the Hessenberg process) method is a Krylov subspace method for solving large linear systems with non-symmetric coefficient matrices. CMRH generates a (non orthogonal) basis of the Krylov subspace through the Hessenberg process, and minimizes a quasi-residual norm. On dense matrices, the CMRH method is less expensive and requires less storage than other Krylov methods. In this work, we describe Matlab codes for the best of these implementations. Fortran codes for sequential and parallel implementations are also presented. 相似文献
126.
127.
Marion N Díez-González S Nolan SP 《Angewandte Chemie (International ed. in English)》2007,46(17):2988-3000
Organocatalyzed reactions represent an attractive alternative to metal-catalyzed processes notably because of their lower cost and benign environmental impact in comparison to organometallic catalysis. In this context, N-heterocyclic carbenes (NHCs) have been studied for their ability to promote primarily the benzoin condensation. Lately, dramatic progress in understanding their intrinsic properties and in their synthesis have made them available to organic chemists. This has resulted in a tremendous increase of their scope and in a true explosion of the number of papers reporting NHC-catalyzed reactions. Here, we highlight the ever-increasing number of reactions that can be promoted by N-heterocyclic carbenes. 相似文献
128.
Laurent Djakovitch Nadine Essayem Marion Eternot Franck Rataboul 《Molecules (Basel, Switzerland)》2021,26(22)
This review article highlights part of the research activity of the C’Durable team at IRCELYON in the field of sustainable chemistry. This review presents a landscape of the work performed on the valorization of lignocellulosic biopolymers. These studies intend to transform cellulose, hemicellulose and lignin into valuable molecules. The methodology usually consists in evaluating the behavior of the biopolymers in the absence of catalyst under various conditions (solvent, temperature), and then to assess the influence of a catalyst, most often a heterogeneous catalyst, on the reactivity. The most significant results obtained on the upgrading of cellulose and lignin, which have been mainly investigated in the team, will be presented with an opening on studies involving raw lignocellulose. 相似文献
129.
Birgit Reiter Marion Lechner Eberhard Lorbeer Reiner Aichholz 《Journal of separation science》1999,22(9):514-520
A rapid method for the isolation and quantitative determination of wax esters in vegetable oils was developed. For the first time wax esters in oils were separated from the triglyceride matrix by means of solid-phase extraction, which allows rapid sample preparation in parallel and therefore a high sample throughput. The thus obtained wax ester fractions of fennel and caraway seed oils were analyzed by high temperature gas chromatography. GC-MS analyses were carried out using electron impact ionization in order to characterize the wax ester fraction. With respect to the results of the GC-MS analyses different isomers of saturated wax esters with the same carbon number were observed. Additional monounsaturated wax esters with an unsaturated fatty acid moiety were identified. 相似文献
130.
D.J.-Y. Marion P. Berthault H. Desvaux 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2009,51(3):357-367
When a system composed of dissolved laser-polarized xenon with negative spin temperature is put inside a high field NMR magnet,
a series of spontaneous maser emissions can be observed. We report here their spectral and temporal features using a processing
model derived from the solution of the Bloch equations in the presence of radiation damping. We show, in particular, that
by combining Fourier transformation and squared modulus, a parameter allowing the characterization of the burst of transverse
magnetization can be determined. This parameter is shown to be correlated with the radiated energy. Moreover, this processing
clearly reveals features which can probably be assigned to effects resulting from distant dipolar fields. Finally, the analysis
of the experimental data reveals an unexpected behavior of the 129Xe transverse self-relaxation. 相似文献