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81.
反胶束笼对纳米氯化银反应性能的微环境限定   总被引:4,自引:0,他引:4  
研究了反映束中直径为10 ̄17nm的AgCl微料与亚甲基蓝之间的作用,比较了阴离子型和非离子型表面活性剂组成的反胶束微环境的影响,讨论了亚甲基蓝在粒子上的吸附,二聚体形成的钠米AgCl粒子对亚甲基蓝荧光猝灭机制。  相似文献   
82.
The reaction mechanism of the l-proline-catalyzed α-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C–O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C–O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of l-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C–O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C–O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for l-proline-catalyzed α-aminoxylation of aldehyde reaction. The addition of H2O to substituted imine proline, intermolecular proton-transfer steps, and the l-proline elimination process were also studied in this paper.  相似文献   
83.
A macro-azoinitiator containing polyarylate segment and azo group was prepared by the solution polycondensation of azobiscyanopentanoyl chloride and hydroxy-terminated polyarylates having viscosity-average molecular weights of 6200, 8100, and 12 400. These macro-azoinitiators were used in the radical polymerization of styrene to synthesize polyarylate-polystyrene block copolymers. Thermal properties measured by the differential scanning calorimetry indicated the phase separated morphology of the block copolymers except at low molecular weight of the block constituents. © 1993 John Wiley & Sons, Inc.  相似文献   
84.
85.
Amide-water mixtures are studied by all-atom molecular dynamics (MD) simulations and the relative temperature-dependent NMR experiment. The weak C-H...O contacts are found in the amide-water systems theoretically and experimentally. The statistical results of the average numbers of hydrogen bonds indicate that the methyl groups in amide molecules represent different capabilities in forming the weak C-H...O contacts. The statistics also imply that the C-H...O contacts are more obvious in the amide-rich region than those in the water-rich region. The temperature-dependent NMR spectra are also adopted to investigate the weak C-H...O contacts in the amide-water systems. The relative chemical shifts of the methyl groups are in good agreement with the MD simulations.  相似文献   
86.
选择性氧化含氰基的对硝基苯硫醚   总被引:2,自引:0,他引:2  
选择性氧化含氰基的对硝基苯硫醚岳国仁,王建华,张正(南京大学化学系南京210008)关键词含氰基硫醚,选择性氧化,四水合过硼酸钠据报道[1]对硝基苯磺酰基乙腈的合成,反应时间长,可采用四水合过硼酸钠(NaBO3·4H2O)作为氧化剂,受到重视[2,3...  相似文献   
87.
稀土体系三种元素同时分离的工艺最近已有发表,但非稀土方面的工作尚未见报导.对Cu、Co、Ni三种元素,通常是将Cu、Co作为一个组份与Ni分离.本工作对组成为Cu:Co:Ni=1:1:1的水相合成料液设计了两种工艺,进行了串级实验,实现了该三种元素的同时分离, 串级实验以HEH(EHP)作萃取剂,煤油为稀释剂,其它试剂均用分析纯.  相似文献   
88.
基团的电子效应与单取代苯对位1H、13C的化学位移*韩长日冯娇杨钟照平(海南师范学院化学系海口571158)关键词1H的化学位移13C的化学位移基团电负性共轭效应引言在1H、13C核磁共振谱中,化学位移值的大小主要取决于屏蔽作用的大小,而屏蔽作用的大...  相似文献   
89.
Loniceroside C,an antiinflammatory saponin from Lonicera japonica   总被引:6,自引:0,他引:6  
A new triterpenoid saponin, loniceroside C was isolated from the aerial parts of Lonicera japonica. Its structure was established to be 3-O-beta-D-glucopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl (1-->2)-[beta-D-xylopyranosyl(1-->6)]-beta-D-glucopyranosyl ester by spectroscopic techniques and chemical transformations. Loniceroside C showed in vivo antiinflammatory activity against mouse ear edema provoked by croton oil.  相似文献   
90.
The secondary reduction in the direct and oxazaborolidine‐catalyzed asymmetric borane reduction of ketones was investigated by the use of GC/MS tracing titration and control experiments. The results indicate that the secondary reduction affects the enantioselectivity only in noncoordinated solvents at low temperature and not under the usual catalytic reduction conditions because the intermediate alkoxyborane is unstable and quickly converts to borane and dialkoxyborane. The function of an alcohol additive in the asymmetric borane reduction of ketones is to consume excess borane in the reduction system thus inhibiting noncatalytic reduction, which leads to increased enantioselectivity in the catalytic reduction.  相似文献   
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