Synthesis of novel 2-perfluoroacylcyclohexane-1,3-diones

A one-pot synthesis of 2-perfluoroalkanoylcyclohexane-1,3-diones via C-acylation of cyclohexane-1,3-diones with N-perfluoroacylimidazole as an acylating agent is reported. A reaction was examined with isolated N-trifluoroacetylimidazole and with N-perfluoroacylimidazoles generated in situ from perfluorocarboxylic acid anhydrides or perfluorocarboxylic acids.     

Hamiltonian N2‐locally connected claw‐free graphs

A graph G is N₂‐locally connected if for every vertex ν in G, the edges not incident with ν but having at least one end adjacent to ν in G induce a connected graph. In 1990, Ryjá?ek conjectured that every 3‐connected N₂‐locally connected claw‐free graph is Hamiltonian. This conjecture is proved in this note. © 2004 Wiley Periodicals, Inc. J Graph Theory 48: 142–146, 2005     

Liquid–gas critical phenomena under confinement: small-angle neutron scattering studies of CO2 in aerogel

Small angle neutron scattering (SANS) is a well-established technique for investigating the behavior of confined binary liquid solutions, as it can probe the correlation length and susceptibility in pores on length scales 1 – 100 nm. We applied SANS to explore the influence of confinement on critical behavior of an individual fluid carbon dioxide (CO₂) in a highly porous aerogel. The results demonstrate that quenched disorder induced by aerogel significantly depresses density fluctuations. Despite the negligible volume occupied by aerogel (< 4%), the macroscopic phase separation of confined CO₂ into coexisting liquid and gaseous phases is suppressed and below the critical temperature of the bulk fluid frozen methastable microdomains are formed. Experimental data show that critical adsorption is as important as the effect of confinement in defining the behavior of confined fluids.     

Li3N、Mg3N2、Ca3N2催化作用的比较和分析

 Li₃N、Mg₃N₂和Ca₃N₂是高温高压下以hBN为原料合成cBN的催化剂。在实验中发现它们对常压高温下生成hBN的反应也表现出催化作用。对比了三种氮化物催化效果的差异，发现三种氮化物都只有在熔融状态下才能表现出催化效果，以及三种氮化物对生成hBN反应的催化效果与它们在高温高压下合成cBN反应的催化效果次序相似。提出了对合成hBN有催化作用的化合物也将对合成cBN表现出催化作用的观点。     

A theoretical study of the ion pair SN2 reaction between lithium isocyanates with methyl fluoride with inversion and retention mechanism

This paper is devoted to a detailed theoretical study of an ion pair S_N2 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.     

A Promising MoO_x-based Catalyst for n-Heptane Isomerization

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…     

纳米氧化钛-乙二醇溶胶溶液的研究

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．     

The preparation of 2-iodoamides from glucals and their further transformations into oxazolines

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.     

3,7-二硝基亚氨基-2,4-二氮杂双环[3,3,0]辛烷的放热分解反应动力学

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 .