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排序方式: 共有1611条查询结果,搜索用时 15 毫秒
1.
Alexander Zeller 《Journal of organometallic chemistry》2006,691(21):4379-4385
The ethylene polymerization reaction of a neutral nickel catalyst was studied by DFT calculations at the Becke3LYP/6-31G(d) level of theory. As in related cases a β-agostic bond stabilizes the nickel alkyl ground states. Transition states for the insertion of the olefin show a distinct α-agostic interaction, which has not been observed for late metal polymerization catalysts before. An ethylene-alkyl complex was identified as the resting state of the reaction. The overall barrier height of the reaction amounts to 17.54 kcal/mol, which slightly increases to 17.60 kcal/mol for the polymerization of deuterated ethylene. Therefore, a small positive kinetic isotope effect (kH/kD = 1.09) can be calculated, which is caused by the α-agostic interaction in the transition state. A comparison to other late metal based polymerization systems reveals that the ethylene coordination step of highly active catalysts is significantly lower in energy compared to catalysts which are only moderately active. 相似文献
2.
Guofen Yu Yuanci Gao Shenggang Liu Wenxiang Wang Jin Wu 《International Journal of Infrared and Millimeter Waves》2002,23(8):1261-1269
Analysis of the field distributions in a single biological cell under electromagnetic wave is given. With Debye approximation, the dielectric relaxation of each part of the cell, including the extracellular and cellular media, the cell membrane and the nuclear membrane, was taken into account. Making use of some typical parameters for a cell, the voltage across nuclear and cytoplasma membranes under electromagnetic waves are calculated up to millimeter wave frequency range. The calculated result indicates that it is unlikely to generate electroporation by present available millimeter wave sources. 相似文献
3.
A scheme for vehicle density and velocity estimation in a stretch of highway based on a modified cell transmission model [C.
F. Daganzo, Transportation Research, Part B, 28B(4),269–287, 1994. Elsevier is presented. The scheme is intended for use with on-ramp metering control algorithms, providing
local knowledge of densities and velocities that is helpful to improve on-ramp metering control performance. Estimation of
density is obtained by nonlinear estimators, while velocity estimation is obtained by gradient algorithms. There is one density–velocity
estimator for free traffic flow and other for congested traffic flow. Both estimator schemes work in parallel. The final estimation
of density and velocity results from a convex combination of the predictions of the two estimators. This combination depends
on occupancy or density measurements at the boundaries of the stretch and is produced by a fuzzy inference system. Stability
and convergence of the density and velocity estimation scheme is proved by Lyapunov based techniques. Simulation results comparing
measured and estimated traffic data are presented. They confirm good performance of the estimators.
Research sponsored by grants UNAM PAPIIT IN110403 and CONACYT 47583. 相似文献
4.
Based on the investigation of a non-ionic surfactant-salt-H2O liquid-liquid extraction system, general rules concerning salt selection are concluded and the mechanism of phase separation is explained. The extraction behavior of chlorpromazine hydrochloride (CPZ) and procaine hydrochloride (PCN) in such a system is studied. Research shows that the extraction efficiency of CPZ can amount to 96% by twice extraction, which means that quantitative extraction is realized, while that of PCN is 77%. This system produces distribution coefficients (KD) of 12.3 and 2.6, respectively, for CPZ and PCN. Extraction mechanism is deduced according to ultraviolet absorbance; and molecular fluorescence spectra change of the drugs in the system studied. 相似文献
5.
聚苯基膦酸二苯砜酯对PET凝聚相阻燃作用的研究 总被引:3,自引:0,他引:3
采用热重分析、X-射线光电子能谱和红外光谱分析等手段,研究了含聚苯基膦酸二苯砜酯(PSPPP)的聚对苯二甲酸乙二酯(PET)阻燃体系的热化学,探讨了PSPPP对PET的阻燃机理.PSPPP的加入,明显改变了PET的热分解行为:PSPPP拓宽了PET的分解温度范围,降低了PET在可燃温度范围内的分解产物的量;在PET的点燃温度以下,PSPPP对PET的降解起到一定的促进作用,而在点燃温度以上,产生的降解产物有利于促进炭化.400℃以上,PET和PSPPP的结构发生了明显的变化,所产生的结构有利于PET的降解,使PET的分子量急剧减小,粘度下降,易于形成熔滴,有利于促使着火部分离开火源,增加燃烧的PET表面的物质损耗和热损耗,起到阻燃作用. 相似文献
6.
W/O型微乳液活化能和导电机理研究 总被引:15,自引:0,他引:15
电导行为是微乳液的重要性质之一。自Lagourette和Lagues发现了W/O型微乳液电导渗透(Percolation)现象后,人们开始了微乳液导电机理的研究。较流行的观点认为,界面层中表面活性剂分子的阴离子在微乳颗粒碰撞时发生跃迁而使W/O型微乳液具有导电性。 相似文献
7.
8.
A. G. Taranto J. W. de M. Carneiro F. G. de Oliveira M. T. de Araujo C. R. Correa 《Journal of Molecular Structure》2002,580(1-3):207-215
Artemisinin is a sesquiterpene lactone with an endoperoxide function that is essential for its antimalarial activity. Endoperoxides are supposed to act on heme leading to the reduction of the peroxide bond and production of radicals, which can be responsible for killing the parasite. The geometries of artemisinin, radical anions and neutral species generated by rearrangement after reduction of the peroxide bond were fully optimized with the AM1 and PM3 semi-empirical methods, in order to characterize the intermediates formed during the process. Among the radicals calculated along the pathway for reductive decomposition of artemisinin, the secondary radical centered on carbon C4 has the highest stability when compared to other radicals that can be achieved either by hydrogen migration to the original O-centered radical or by homolytic break of C–C bond. This suggests that the C4-centered radical may be the species responsible for killing the parasite, as has been indicated previously in experimental studies. 相似文献
9.
固相热分解反应最可几机制的判断 总被引:1,自引:0,他引:1
固相热分解反应最可几机制的判断高永煜,邹文樵,冯仰婕(华东理工大学化学系上海200237)关键词热分解,动力学方程,反应机制固相热分解反应机制的判断,是热分析动力学中令人感兴趣的领域。常用的方法是从含机制函数的非等温积分动力学方程出发,分别用Sest... 相似文献
10.