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61.
62.
Philippe Faury Michel Camplo Anne-Sophie Charvet Nicolas Mourier Philippe Barthelemy Jean-Christophe Graciet Jean-Louis Kraus 《Journal of heterocyclic chemistry》1994,31(6):1465-1471
Synthetic approaches for new 2,5-disubstituted-1,3-thiazolidines are described. Steric and electronic effects of the N-substituent of the thiazolidine ring represent the major parameter in the rearrangement process. The nmr studies demonstrate that N-unsubstituted 2,5-disubstituted-1,3-thiazolidines exist as epimeric mixture, while the corresponding N-acetylated analogues exist as a conformer mixture. 相似文献
63.
64.
Perrin JC Lyonnard S Guillermo A Levitz P 《The journal of physical chemistry. B》2006,110(11):5439-5444
The dynamic behavior of water within two types of ionomer membranes, Nafion and sulfonated polyimide, has been investigated by field-cycling nuclear magnetic relaxation. This technique, applied to materials prepared at different hydration levels, allows the proton motion on a time scale of microseconds to be probed. The NMR longitudinal relaxation rate R(1) measured over three decades of Larmor angular frequencies omega is particularly sensitive to the host-water interactions and thus well-suited to study fluid dynamics in restricted geometries. In the polyimide membranes, we have observed a strong dispersion of R(1)(omega) following closely a 1/square root omega law in a low-frequency range (correlation times from 0.1 to 10 micros). This is indicative of a strong interaction of water with "interfacial" hydrophilic groups of the polymeric matrix (wetting situation). Variations of the relaxation rates with water uptake reveal a two-step hydration process: solvation and formation of disconnected aqueous clusters near polar groups, followed by the formation of a continuous hydrogen bond network. On the contrary, in the Nafion we observed weak variations of R(1)(omega) at low frequencies. This is typical of a nonwetting behavior. At early hydration stages, R(1)(omega) evolves logarithmically, suggesting a confined bidimensional diffusion of protons in the microsecond time range. Such an evolution is lost at higher swelling where a plateau related to three-dimensional diffusion is observed. 相似文献
65.
We report on a cellular pattern which spontaneously forms at the surface of a thin layer of a cohesive granular material submitted to in-plane stretching. We present a simple model in which the mechanism responsible of the instability is the "strain softening" exhibited by humid granular materials above a typical strain. Our analysis indicates that such a type of instability should be observed in any system presenting a negative stress sensitivity to strain perturbations. 相似文献
66.
Ken Kamrin Chris H. Rycroft Jean-Christophe Nave 《Journal of the mechanics and physics of solids》2012,60(11):1952-1969
The reference map, defined as the inverse motion function, is utilized in an Eulerian-frame representation of continuum solid mechanics, leading to a simple, explicit finite-difference method for solids undergoing finite deformations. We investigate the accuracy and applicability of the technique for a range of finite-strain elasticity laws under various geometries and loadings. Capacity to model dynamic, static, and quasi-static conditions is shown. Specifications of the approach are demonstrated for handling irregularly shaped and/or moving boundaries, as well as shock solutions. The technique is also integrated within a fluid–solid framework using a level-set to discern phases and using a standard explicit fluid solver for the fluid phases. We employ a sharp-interface method to institute the interfacial conditions, and the resulting scheme is shown to efficiently capture fluid–solid interaction solutions in several examples. 相似文献
67.
Optically active α-aminoesters are obtained by metalation of the corresponding Schiff bases by chiral lithium amide followed by protonation by an achiral or a chiral acid. 70 % e.e. can be obtained. 相似文献
68.
Jean-Christophe Monbaliu Bernard Tinant Jacqueline Marchand-Brynaert 《Journal of Molecular Structure》2008,879(1-3):113-118
Reaction of N-(dienyl)-4-(R)-phenyloxazolidin-2-thione (1) with 1-diethoxyphosphoryl-1-buten-3-one (2a), methyl 3-(diethoxyphosphoryl)acrylate (2b) and 3-(diethoxyphosphoryl)acrylonitrile (2c) furnished the [4 + 2] cycloadducts 3a, 3b and 3c, respectively, as single stereoisomers, confirming the efficiency of the oxazolidin-2-thione chiral auxiliary in the facial discrimination of Diels–Alder reactions. The absolute configuration of the 3,4,5-trisubstituted cyclohexene derivatives (3a–c) was established by X-ray diffraction analysis. NMR studies confirmed the relative stereochemistries and showed two possible conformers in solution. 相似文献
69.
Bouteiller Y Gillet JC Grégoire G Schermann JP 《The journal of physical chemistry. A》2008,112(46):11656-11660
A set of transferable local scaling factors is established for assignment of infrared spectra of molecular systems of biological interest experimentally recorded under gas-phase conditions. Each scaling factor is specific for an experimentally observable vibrational mode chosen among those bringing significant structural information. Those factors are provided for harmonic calculations at the DFT B3LYP and DFT B3PW91 levels respectively with 7 and 2 different basis sets. The used training set of neutral molecules comprises nucleobases, aminoacids, peptides, sugars, and neurotransmitters. The proposed specific scaling factors usable for unambiguous conformer assignments lead to typical prediction errors ca. 10 cm(-1) for free and moderately hydrogen-bonded group frequencies with red-shifts up to 200 cm(-1). 相似文献
70.
Highly ordered arrays of single living bacteria were obtained by selective adsorption of bacteria onto chemical patterns with micrometric resolution. The chemically engineered template surfaces were prepared with the combination of microcontact printing process and a simple incubation technique. This methodology can be used for fundamental studies of bacterium's inner mechanisms and sub-cellular organization as well as for interfacing living bacteria with artificial microsystems. 相似文献