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31.
Numerous mercaptopropyl-functionalized silica spheres have been prepared by either post-synthesis grafting of MCM-41 and MCM-48 or self-assembly co-condensation of mercaptopropyltrimethoxysilane (MPTMS) or mercaptopropyltriethoxysilane (MPTES) and tetraethoxysilane (TEOS) precursors in hydroalcoholic medium in the presence of a cationic surfactant as templating agent and ammonia as catalyst. These materials of approximately the same particle size and morphology featured different functionalization levels, various degrees of structural order, and variable distribution of thiol groups in the mesopores. Their reactivity in solution has been studied using Hg(II) as model analyte. Total accessibility (on a 1:1 S:Hg stoichiometry basis) was demonstrated and quantified for well-ordered materials whereas less open and less organized structures with high degrees of functionalization were subject to less-than-complete loadings. Capacities measured at pH 2 were lower than at pH 4 because of distinct mercury-binding mechanisms. Kinetics associated to the uptake process were studied by in situ electrochemical monitoring of Hg(II) consumption from aqueous suspensions containing the various adsorbents. They indicate only little difference between materials of the MCM-41 and MCM-48 series at similar functionalization levels, fast mass transport in well-ordered mesostructures in comparison to the poorly or non-ordered ones (except at pH 2 where charge formation induced some restriction in materials characterized by long-range structural order), and even faster processes in the wormlike frameworks (characterized by shorter range structural order). Hg(II) binding to thiol-functionalized materials obtained by post-synthesis grafting was found to occur more rapidly in the early beginning of the uptake process as a result of a higher concentration of binding sites at the pore entrance in comparison to the more homogeneous distribution of these groups in the mesochannels of materials obtained by co-condensation. 相似文献
32.
Fabrice Collin Dominique Bonnefont‐Rousselot Saï Yous Catherine Marchetti Daniel Jore Monique Gardès‐Albert 《Journal of mass spectrometry : JMS》2009,44(3):318-329
The hydrogen–deuterium exchange of protonated melatonin and its in vitro oxidation end‐products have been examined by liquid chromatography coupled with ion‐trap mass spectrometry. Specific H/D scrambling of protons in the C2 and C4 positions of the indole ring during gas‐phase fragmentation process was observed for both melatonin and its oxidation products. Collision‐induced dissociation spectra showed losses of variably deuterated NH3, H2O and CH3CONH2. In addition, a similar H/D scrambling behaviour was observed for the oxidation products, obtained from the opening of the indole ring by oxidative attack. Fragmentation pathways are proposed and H/D scrambling has been employed as a fingerprint, allowing identification of N1‐acetyl‐5‐methoxykynurenin (AMK), N1‐acetyl‐N2‐formyl‐5‐methoxykynurenin (AFMK), dehydro‐AFMK and hydroxymelatonin as the oxidation products of melatonin in vitro. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
33.
Fabrice Poirion Quentin Mercier Jean-Antoine Désidéri 《Computational Optimization and Applications》2017,67(2):317-360
An algorithm for solving nearly-separable quadratic optimization problems (QPs) is presented. The approach is based on applying a semismooth Newton method to solve the implicit complementarity problem arising as the first-order stationarity conditions of such a QP. An important feature of the approach is that, as in dual decomposition methods, separability of the dual function of the QP can be exploited in the search direction computation. Global convergence of the method is promoted by enforcing decrease in component(s) of a Fischer–Burmeister formulation of the complementarity conditions, either via a merit function or through a filter mechanism. The results of numerical experiments when solving convex and nonconvex instances are provided to illustrate the efficacy of the method. 相似文献
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Mathematical justifications are given for a simulation technique of multivariate non-Gaussian random processes and fields based on Rosenblatt's transformation of Gaussian processes. Different types of convergences are given for the approaching sequence. Moreover an original numerical method is proposed in order to solve the functional equation yielding the underlying Gaussian process autocorrelation function. 相似文献
36.
Candice Botuha Fabrice Chemla Franck Ferreira Julien Louvel Alejandro Pérez-Luna 《Tetrahedron: Asymmetry》2010,21(9-10):1147-1153
The stereoselective synthesis of alkynyl 1,2-amino alcohols by the addition of 3-chloro- and 3-methoxymethoxy- allenylzincs to chiral tert-butylsulfinylimines is described. The methodology is applicable to the preparation of alkynyl 2-amino-1,3-diols (O,N,O stereotriads) using α-alkoxy tert-butylsulfinylimines as chiral starting materials. The scope and limitations of the methodology along with recent applications to the efficient asymmetric syntheses of natural and/or bioactive alkaloids and polyhydroxylated alkaloids are presented. 相似文献
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Fabrice Gamboa Alexandre Janon Thierry Klein Agnès Lagnoux 《Comptes Rendus Mathematique》2013,351(7-8):307-310
We define and study a generalization of Sobol sensitivity indices for the case of a vector output. 相似文献
40.
Véronique Dupuis Nils Blanc Luis E. Diaz-Sanchez Arnaud Hillion Alexandre Tamion Florent Tournus Gustavo M. Pastor Andrei Rogalev Fabrice Wilhelm 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2013,67(2):1-4
In this paper, the one-way absorption property in one-dimensional dielectric/metal photonic crystal structure with a dielectric defect layer is studied. The effects of incident angle and state of polarization on one-way absorption behaviour of the anti-resonant (AR) mode are investigated. The normally incident wave from left to right propagation is totally allowed to penetrate to the structure but right to left propagation totally reflected at the same wavelength. It is found that, with increasing of the incident angle, the AR mode shifts to the lower wavelengths and its intensity decreases. Simultaneously, another AR mode with reversed one-way property appears at higher wavelength. The one-way behaviour on absorption is observed at the both states of polarizations but is localized on different wavelengths. Those effects, are suggesting that the proposed structure can be used as a direction sense polarization splitter or reflector/antireflector device. 相似文献