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71.
72.
This paper is devoted to a detailed theoretical study of an ion pair SN2 reaction LiNCO+CH3F in the gas phase and in solution at the level of MP2(full)/6-31+G**//HF/6-31+G**. Two possible reaction mechanisms, inversion and retention, are discussed. There are eight possible reaction pathways. The inversion mechanism is more favorable no matter in the gas phase or in solution based on analyses of the transition structures. Methyl isocyanate should form preferentially in the gas phase and more stable methyl cyanate is the main product in solution. The retardation of the reaction in solvents was attributed to the difference in solvation in the separated reactants and in the transition state. 相似文献
73.
A Promising MoO_x-based Catalyst for n-Heptane Isomerization 总被引:1,自引:0,他引:1
Song Hai CHAI Xin Ping WANG* Ying Jun WANG Tian Xi CAI State Key Laboratory of Fine Chemicals Dalian University of Technology Dalian 《中国化学快报》2003,14(7)
The increasing demand for higher-octane gasoline and the regulations limiting the amount of aromatics in the fuel motivate the interest in catalytic isomerization of n-alkanes. In the last ten years, transition metal oxides or oxycarbides based on molybdenum or tungstate have attracted much attention due to their high activity and isomerization selectivity compared to the conventional bifunctional supported platinum catalyst and high resistance to sulphur and nitrogen catalyst poisons1-5. Ma… 相似文献
74.
The turbulent flow in a compound meandering channel with a rectangular cross section is one of the most complicated turbulent flows, because the flow behaviour is influenced by several kinds of forces, including centrifugal forces, pressure‐driven forces and shear stresses generated by momentum transfer between the main channel and the flood plain. Numerical analysis has been performed for the fully developed turbulent flow in a compound meandering open‐channel flow using an algebraic Reynolds stress model. The boundary‐fitted coordinate system is introduced as a method for coordinate transformation in order to set the boundary conditions along the complicated shape of the meandering open channel. The turbulence model consists of transport equations for turbulent energy and dissipation, in conjunction with an algebraic stress model based on the Reynolds stress transport equations. With reference to the pressure–strain term, we have made use of a modified pressure–strain term. The boundary condition of the fluctuating vertical velocity is set to zero not only for the free surface, but also for computational grid points next to the free surface, because experimental results have shown that the fluctuating vertical velocity approaches zero near the free surface. In order to examine the validity of the present numerical method and the turbulent model, the calculated results are compared with experimental data measured by laser Doppler anemometer. In addition, the compound meandering open channel is clarified somewhat based on the calculated results. As a result of the analysis, the present algebraic Reynolds stress model is shown to be able to reasonably predict the turbulent flow in a compound meandering open channel. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
75.
76.
陈海珍 《宁波大学学报(理工版)》2004,17(4):444-448
选用了钛酸丁酯、硬脂酸和乙二醇作为表面活性剂,采用表面化学修饰和表面物理修饰2种方法修饰纳米氧化钛,然后分散在乙二醇溶剂中形成溶胶溶液.并通过红外光谱仪、紫外分光计、原子力显微镜,分析了表面化学修饰后的纳米氧化钛表面化学结构的变化,观测了纳米氧化钛溶胶在乙二醇溶剂中稳定性.试验结果表明表面活性剂与纳米氧化钛的表面的不饱和键之间形成了新的化学结构,粒子表面可能接枝上有机长链,提高了纳米粒子在溶剂中的相容性.表面化学修饰后的纳米氧化钛与乙二醇溶剂形成了较稳定的溶胶体系,而且纳米溶胶粒径较小.表面活性剂添加量与纳米粒子添加量控制在(1~1.2):1时,可以获得纳米溶胶粒径较小,同时溶胶稳定性较好的纳米氧化钛-乙二醇溶胶体系. 相似文献
77.
Michael De Castro 《Tetrahedron letters》2004,45(34):6501-6504
2-Deoxy-2-iodo-glycosylamides have been prepared from a variety of protected d-glucals by their reaction with N-iodosuccinimide and amides. Benzyl protected 2-iodoamides, when treated with sodium hydride and 15-crown-5, gave stable C1 N-linked 2-glycooxazolines as the major products. Silyl protected 2-iodoamides afforded the C1 O-linked 2-glycooxazolines; presumably by the rearrangement of unstable N-acylaziridine intermediates. 相似文献
78.
The Raman shifts of nanocrystalline GaSb excited by an Ar^ ion laser at wavelengths 514.5, 496.5, 488.0, 476.5,and 457.9nm are studied by an SPEX-1403 laser Raman spectrometer respectively, and they are explained by phonon confinement, tensile stress, resonant Raman scattering and quantum size effects. The Stokes and anti-Stokes Raman spectra of GaSb nanocrystals strongly support the Raman feature of GaSb nanocrystals. The calculated optical spectra compare well with experimental data on Raman scattering GaSb nanocrystals. 相似文献
79.
在程序升温条件下 ,用DSC研究了标题化合物的放热分解反应动力学 .用线性最小二乘法、迭代法以及二分法与最小二乘法相结合的方法 ,以积分方程、微分方程和放热速率方程拟合DSC数据 .在逻辑选择建立了微分和积分机理函数的最可几一般表达式后 ,用放热速率方程得到相应的表观活化能 (Ea)、指前因子 (A)和反应级数 (n)的值 .结果表明 :该反应的微分形式的经验动力学模式函数、Ea 和A值分别为 (1-α) 0 .44、2 30 .4kJ/mol和 10 18.16s-1.借助加热速率和所得动力学参数值 ,提出了标题化合物放热分解反应的动力学方程 .该化合物的热爆炸临界温度为 30 2 .6℃ .上述动力学参数对分析、评价标题化合物的稳定性和热变化规律十分有用 . 相似文献
80.
细菌内毒素(LPS)是革兰氏阳性阴性菌细胞外膜层的主要成分,由其引起的革兰氏阴性杆菌脓度症和休克是导致战创伤病人死亡的主要原因之一。而从类脂A(LipidA)的结构出发,以非肽类物质拮抗内毒素受体CD-14为治疗手段的研究在国外刚刚起步。2-乙酰氨基-3,4,6-三乙酰葡萄糖是合成LipidA结构类似物的重要中间体[1,2]。它的合成一般是通过氨基葡萄糖五乙酸酯的选择性水解[3-6]脱去一个乙酰基得到。氨基葡萄糖五乙酸酯是通过氨基葡萄糖的乙酰化反应得到的,由于氨基葡萄糖不稳定,一般是用氨基葡萄糖的盐酸盐作为起始原料。由于… 相似文献