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151.
Alberto Escarpa María Cristina González Antonio Javier Blasco Maria del Carmen Rogerio Miriam Hervás 《Electroanalysis》2007,19(9):952-957
The accuracy of a novel electroanalytical route to determine total isoflavones using a secondary standard from Drug Master File (SW/1211/03) as metrological reference with well‐known traceability and its applicability using representative soy samples is demonstrated. Calibration protocols were used i) for choosing a suitable isoflavone standard to determine the total isoflavone content, ii) to evaluate matrix effects and, iii) to evaluate the overall reliability and performance of the method in analytical operations, extraction and analysis. The inherent electroactivity of both, aglycones and glycoside structures and the similar analytical sensitivity exhibited by the prominent soy isoflavones was relevant to determine the total amount with reliability in terms of accuracy (E<10%) and precision (RSDs<7%) in soy samples. In consequence, the introduction of the term isoflavonoid index as the total amount of isoflavones obtained when they are amperometrically monitorized at +1.0 V as a particular case of the electrochemical index concept is proposed. 相似文献
152.
Corzana F Motawia MS Du Penhoat CH Perez S Tschampel SM Woods RJ Engelsen SB 《Journal of computational chemistry》2004,25(4):573-586
The hydration behavior of two model disaccharides, methyl-alpha-D-maltoside (1) and methyl-alpha-D-isomaltoside (2), has been investigated by a comparative 10 ns molecular dynamics study. The detailed hydration of the two disaccharides was described using three force fields especially developed for modeling of carbohydrates in explicit solvent. To validate the theoretical results the two compounds were synthesized and subjected to 500 MHz NMR spectroscopy, including pulsed field gradient diffusion measurements (1: 4.0. 10(-6) cm(2). s(-1); 2: 4.2. 10(-6) cm(2). s(-1)). In short, the older CHARMM-based force field exhibited a more structured carbohydrate-water interaction leading to better agreement with the diffusional properties of the two compounds, whereas especially the alpha-(1-->6) linkage and the primary hydroxyl groups were inaccurately modeled. In contrast, the new generation of the CHARMM-based force field (CSFF) and the most recent version of the AMBER-based force field (GLYCAM-2000a) exhibited less structured carbohydrate-water interactions with the result that the diffusional properties of the two disaccharides were underestimated, whereas the simulations of the alpha-(1-->6) linkage and the primary hydroxyl groups were significantly improved and in excellent agreement with homo- and heteronuclear coupling constants. The difference between the two classes of force field (more structured and less structured carbohydrate-water interaction) was underlined by calculation of the isotropic hydration as calculated by radial pair distributions. At one extreme, the radial O em leader O pair distribution function yielded a peak density of 2.3 times the bulk density in the first hydration shell when using the older CHARMM force field, whereas the maximum density observed in the GLYCAM force field was calculated to be 1.0, at the other extreme. 相似文献
153.
Emilia Vassileva Hervé Baeten Michel Hoenig 《Analytical and bioanalytical chemistry》2001,369(6):491-495
The application of a fast program combined with the advantages of the iridium permanent modifier is proposed for trace element analysis of plant samples by electrothermal atomic absorption spectrometry (ETAAS). For two volatile elements (Cd, Pb) and two mid-refractory elements (Cr, Ni) it was demonstrated that coating of the platform or of the tube atomization area with Ir is an efficient means of improving the accuracy and precision of results. A detailed study of interference from individual main matrix components and from composite plant matrices has confirmed the usefulness of the whole approach. The validity of the method has been confirmed by analysis of eight reference plant materials. 相似文献
154.
Marie‐Thérèse Grosse Michel Lamotte Marc Birot Hervé Deleuze 《Journal of polymer science. Part A, Polymer chemistry》2008,46(1):21-32
Microcellular polysiloxane monoliths were prepared from the continuous phase of a concentrated inverse emulsion. The formulation of the material was adapted to obtain monoliths having structural properties similar to those of common poly(styrene‐co‐divinylbenzene) polyHIPEs. The network was generated by hydrosilylation reaction between a vinylsiloxane crosslinking agent and an oligomeric hydrogenosiloxane. The solids obtained were characterized by mercury porosimetry, nitrogen sorption, and SEM. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 21–32, 2008 相似文献
155.
Denis J.‐Y. Marion Gaspard Huber Dr. Patrick Berthault Dr. Hervé Desvaux Prof. 《Chemphyschem》2008,9(10):1395-1401
We report a new phenomenon observed when the magnetization of dissolved hyperpolarized 129Xe is intense and opposite to the Boltzmann magnetization. Without radio‐frequency (rf) excitation, the system spontaneously emits a series of rf bursts characterized by very narrow bandwidths (0.03 Hz at 138 MHz). This chaotic NMR‐maser illustrates the increase in the complexity of spin dynamics at high magnetization levels by unveiling an inhomogeneous spatial organization of the xenon magnetization and an apparent dependence of the xenon transverse relaxation time on its polarization and/or on time. 相似文献
156.
Kohut-Svelko N Reynaud S Dedryvère R Martinez H Gonbeau D François J 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1575-1583
A simple way to obtain a conducting nanocomposite is described, and the conducting particles are characterized. Core-shell particles [polystyrene-polyaniline (PANI)] have been obtained by the dispersion process from three types of polystyrene latexes: a no-cross-linked core stabilized by a nonylphenolethoxylate (NP40) and two cross-linked cores stabilized by NP40 and a mixture NP40/Surfamid (a surfactant bearing an amide group). The surface of these particles has been extensively characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy, and scanning electron microscopy. A maximum coverage of 94% was obtained for the high PANI content as revealed by XPS analysis. A better coverage was obtained for the cross-linked polystyrene latex stabilized by the Surfamid. The amide group of this surfactant allows the H-bonding formation with the PANI backbone and, thus, improves the conductivity. It was shown that a uniform coverage of the core particles was not required to ensure a good conductivity. 相似文献
157.
Micha?l?Canipelle Sébastien?Tilloy Anne?Ponchel Hervé?Bricout Eric?MonflierEmail author 《Journal of inclusion phenomena and macrocyclic chemistry》2005,51(1-2):79-85
Interactions between the meta-substituted monosulfonated triphenylphosphine and chemically modified β-cyclodextrins were investigated in aqueous solution by NMR and UV–vis spectroscopy. Titration and continuous variation plots obtained from 31P NMR data indicate that the monosulfonated triphenylphosphine forms 1:1 inclusion complexes with the 2-hydroxypropylated β-cyclodextrin, the methylated β-cyclodextrin and the (2-hydroxy-3-trimethylammoniopropyl)-β-cyclodextrin chloride. These inclusion complexes are more stable that those formed with native β-cyclodextrin, confirming that poisoning of the chemically modified β-cyclodextrins by the hydrosoluble phosphine occurs when modified cyclodextrins are used as mass transfer promoters in aqueous-phase organometallic catalysis.This revised version was published online in July 2005 with a corrected issue number. 相似文献
158.
Sueur B Leclercq L Sauthier M Castanet Y Mortreux A Bricout H Tilloy S Monflier E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6228-6236
A new class of cationic alpha-cyclodextrins bearing 2-hydroxy-3-trimethylammoniopropyl groups has been synthesised. We investigated their efficiency as mass-transfer promoters in a biphasic hydroformylation reaction catalysed by a rhodium trisulfonated triphenylphosphine system. These cationic alpha-cyclodextrins greatly increased the reaction rate, the chemoselectivity, and, surprisingly, the linear-to-branched aldehyde ratio. We attributed this unexpected enhancement of the linear-to-branched aldehyde ratio to the in situ formation of new catalytic supramolecular species obtained by ion-exchange between the catalyst ligand and the cationic alpha-cyclodextrins. 相似文献
159.
The study of the dissolution of laser-polarized xenon in degassed deuterated benzene is reported. We show that the time evolution of the xenon signal implies that a transient convective process takes place. It is characterized by velocity-encoding magnetic resonance measurements and MRI experiments. 相似文献
160.