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951.
[reaction: see text] C(2)-symmetric tridentate bis(oxazoline) and bis(thiazoline) ligands with a diphenylamine backbone have been investigated in the catalytic asymmetric Henry reaction of alpha-keto esters with different Lewis acids. Their Cu(OTf)(2) complexes furnished S enantiomers, while Et(2)Zn complexes afforded R enantiomers, both of them with higher enantioselectivities (up to 85% ee). Reversal of enantioselectivity in asymmetric Henry reactions was achieved with the same chiral ligand by changing the Lewis acid center from Cu(II) to Zn(II). The results show that the NH group in C(2)-symmetric tridentate chiral ligands plays a very important role in controlling both the yields and enantiofacial selectivity of the Henry products. 相似文献
952.
固定pH滴定法测定弱酸弱碱性药物 总被引:8,自引:0,他引:8
报道一种水溶液吕测定弱酸弱碱性药物的新型滴定分析方法-固定pH滴定法,其理论基础是弱酸弱碱在水溶液中各种存在形式的分布系数在pH值固定时为常数,对甲硝唑,盐酸美西律等离散常数在10^-8至10^-11范围内的7种弱酸弱碱性药物进行测定。结果与药典法吻合,回收率在99.4%~100.6%,方法简便,快速,准确,制剂中的赋形剂及色物不影响测定。 相似文献
953.
Andrzej Czerwiński Iwona Kiersztyn Michał Grdeń 《Journal of Solid State Electrochemistry》2003,7(6):321-326
The effect of temperature on hydrogen and deuterium electrosorption into a palladium LVE (limited-volume electrode) has been
investigated. A decrease in hydrogen capacity (H/Pd ratio) with increasing temperature has been observed. Temperature strongly
influences the plots of measured H(D)/Pd values vs. potential scan rate. In addition, hydrogen absorption was found to be
dependent on the composition of the surrounding electrolyte solution. These results have confirmed the hypothesis that two
different mechanisms of hydrogen desorption from the palladium electrode take place, namely electrochemical oxidation and
non-electrochemical recombination. Further, the ratio between the rate constants for these two processes has been found to
change with temperature.
Electronic Publication 相似文献
954.
We report completely optimized ONIOM DFT/AM1 molecular orbital calculations on several collagen-like triple helices based upon the repeating triad, ProProGly. The requirement of Gly as every third amino acid in collagen can be attributed to its enantiomorphic nature, as it behaves as a Damino acid in collagen. We, therefore, explored related collagen-like triple helices with one of the central Gly's mutated to either L or DAla; l-Ala appreciably destabilizes, while d-Ala slightly stabilizes the triple helical structure. Mutation of the same Gly to DSer, which is simply DAla with an OH in place of one of the methyl H's, induces a much greater stabilization due to an additional H-bond formed between this OH and a C=O on an adjacent peptide strand. Energies are presented for the triple helices and their component strands (both optimized and distorted to their triple helical geometries) relative to the component amino acids. The variation of relative energies with the chosen reference is delineated. 相似文献
955.
Employing hot tungsten filament to thermal dissociate molecular hydrogen,we generated gas phase atomic hydrogen under ultra-high vacuum(UHV)conditions and investigated its interaction with Pt(111) surface.Thermal desorption spectroscopy(TDS)results demonstrate that adsorption of molecular hy- drogen on Pt(111)forms surface Had species whereas adsorption of atomic hydrogen forms not only surface Had species but also bulk Had species.Bulk Had species is more thermal-unstable than surface Had species on Pt(111),suggesting that bulk Had species is more energetic.This kind of weakly- adsorbed bulk Had species might be the active hydrogen species in the Pt-catalyzed hydrogenation reactions. 相似文献
956.
Baopei Xu C. Peter Lillya James C. W. Chien 《Journal of polymer science. Part A, Polymer chemistry》1992,30(9):1899-1909
A spiro(benzoxasilole) catalyst, 3,3,3′,3′-tetrakis(trifluoromethyl)-1,1′-(3H,3H′)-spirobis(1,2-benzoxasilole) was used to polymerize 3,3-R,R′-oxetanes: BEMO (R, R′ = ethoxymethyl), AMMO (R = azidomethyl, R′ = methyl), NMMO (R = nitratomethyl, R′ = methyl), BAMO (R, R′ = azidomethyl), and BCMO (R, R′ = chloromethyl) with descending rates in this order. 31P-NMR of polymerization mixtures quenched using Bu3P are consistent with an oxonium ion propagating species. Water is not a cocatalyst because it increases the induction period which is not eliminated by the proton trap 2,6-di-t-bu-tylpyridine. The propagating chains were terminated by transfer with the ether oxygen of the polymer either intermolecularly or intramolecularly. The index of propagation to chain transfer, Kkikp/ktr, varies over more than three orders of magnitude for BEMO > AMMO > NMMO > BAMO. However, kp/ktr for the four monomers differ by less than a factor of five indicating the same factors are affecting propagation and chain transfer. Addition of benzyl alcohol and propandiol produced poly(BEMO) having one and two hydroxyl termini, respectively. These telechelic polymers can be used to synthesize linear triblock or multiblock copolymers of oxetane derivatives. © 1992 John Wiley & Sons, Inc. 相似文献
957.
A silica polymorph, silica-sodalite was synthesized from a nonaqueous system NaOH-SiO2-C2H4(OH)2 and its chemical compositionwas determined to be Si12 O24,2C2H4(OH)2 by the X-fluorescence,thermogravimetric and organic elemental analyses. The single crystal X-ray diffraction structure determination of the silica-sodaliteshowed that the silica-sodalite is cubic, spacing group I23 and unitcell parameter a= 8.8354A. The IF and solid state high resolution Siand 13 C NMR spectra of the silica-sodalite were measured and discussed . 相似文献
958.
959.
考察氧化物担体对Fe-MnO催化剂反应性能影响的结果表明,担体的类型对Fe-MnO催化剂CO加氢反应性能影响很大,其低碳烯烃选择性相差悬殊,Al_2O_3、SiO_2和MgO担载的Fe-MnO催化剂都不利于低碳烯烃的生成,而TiO_2担载的Fe-MnO催化剂则具有较高的烯烃选择性和催化活性。从担体-金属相互作用本质的差异,研究了担体对金属活性组分化学状态的影响及催化活性相与F-T合成烯烃的关系,发现担体-金属间的电子效应有利于催化剂活性和选择性的提高,其它物理化学效应引起的相互作用则不利于改善催化剂性能;还表明Fe_(?)C是催化活性相,Fe~(2+)物种的存在不利于提高烯烃的选择性。 相似文献
960.
The optical characteristics of absorption and circular dichroism (CD) spectroscopy of an alpha-subunit of C-phycocyanin (C-PC) were investigated by using time dependent density functional theory (TDDFT) combined with the polarizable continuum model (PCM). When the protonation of alpha-84 phycocyanobilin (PCB) and its interaction with the protein moiety in C-PC have been taken into account, satisfactory assignment of the absorption and CD spectra of alpha-84 PCB can be achieved. The TDDFT-PCM calculations conclude that in the visible absorption region the main peak arises from the pi electron excitation of the pyrrole rings and the shoulder peak comes from the charge transfer from Asp87 (a nearby amino acid residue) to PCBH(+). 相似文献