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101.
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
102.
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
103.
104.
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
105.
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
106.
The development of the poly(3‐hydroxybutyrate) (PHB) morphology in the presence of already existent poly(vinylidene fluoride) (PVDF) spherulites was studied by two‐stage solidification with two separate crystallization temperatures. PVDF formed irregular dendrites at lower temperatures and regular, banded spherulites at elevated temperatures. The transition temperature of the spherulitic morphology from dendrites to regular, banded spherulites increased with increasing PVDF content. A remarkable amount of PHB was included in the PVDF dendrites, whereas PHB was rejected into the remaining melt from the banded spherulites. When PVDF crystallized as banded spherulites, PHB could consequently crystallize only around them, if at all. In contrast, PHB crystallized with a common growth front, starting from a defined site in the interfibrillar regions of volume‐filling PVDF dendrites. It formed by itself dendritic spherulites that included a large number of PVDF spherulites. For blends with a PHB content of more than 80 wt %, for which the PVDF dendrites were not volume‐filling, PHB first formed regular spherulites. Their growth started from outside the PVDF dendrites but could later interpenetrate them, and this made their own morphology dendritic. These PHB spherulites melted stepwise because the lamellae inside the PVDF dendrites melted at a lower temperature than those from outside. This reflected the regularity of the two fractions of the lamellae because that of those inside the dendrites of PVDF was controlled by the intraspherulitic order of PVDF, whereas that from outside was only controlled by the temperature and the melt composition. The described morphologies developed without mutual nucleating efficiency of the components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 873–882, 2003 相似文献
107.
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
108.
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
109.
Hubert Grudziński 《Reports on Mathematical Physics》2004,53(2):317-328
The eigenvalues and eigenfunctions of an elementary 3-fermion 2-body operator 3P2g∧I1A3∑1≤i≤j≤3P2g(i, j)A3 acting on a 3-particle antisymmetric finite-dimensional Hilbert space have been found. Here Pg2 denotes the projection operator onto a 2-particle antisymmetric function g2, while A3 denotes the 3-particle antisymmetrizing operator. 相似文献
110.
Ya. I. Kurys’ N. S. Netyaga V. G. Koshechko V. D. Pokhodenko 《Theoretical and Experimental Chemistry》2007,43(5):334-342
A guest-host nanocomposite based on electroconducting polyaniline doped with 12-phosphotungstic acid and V2O5 as well as its bifunctional analog containing not more than 5 mass% nanosized platinum were obtained. A study was carried
out on the structure of these nanocomposites, their redox characteristics, and electrocatalytic activity in the reduction
of oxygen. These nanocomposites were found to display catalytic properties in the electrochemical reduction of oxygen, while
the presence of even a slight amount of nanosized platinum in the bifunctional composite leads to a significant increase in
its electrocatalytic activity.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 5, pp. 307–314, September–October, 2007. 相似文献