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81.
The reaction mechanism of the thermolysis of azetidine to form ethylene and methylen-imine has been studied by ab initio SCF MO method at STO--3G and 3-21G levels. Two possible step-wise pathways are explored. One is the breaking of C--C bond as the first step, while the other is thebreaking of C--N bond. All the stationary points on the potential energy surface (PES) are fully optimiz-ed. MP2 / 3-21G single point calculations on all stationary points and MCSCF / STO-3G computationsfor some stationary points are also carried out. The calculations indicate that azetidine decomposesvia biradicaloid intermediates and the cleavage of C--N bond is preferable to that of C--C bond. 相似文献
82.
Gao J Fu J Lin C Lin J Han Y Yu X Pan C 《Langmuir : the ACS journal of surfaces and colloids》2004,20(22):9775-9779
Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and the complex effect of crown ether with Ag(+) and Ag. The size of silver nanoparticles could be tailored by controlling the initial concentrations of the polymer and Ag(+), and the molecular weight of the polymer. The emission of silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticles stabilized by the polymer was significantly increased due to the complex effect between the crown ether embedded in the polymer and the silver nanoparticles. 相似文献
83.
The cold and heat denaturations of bovine P-lactoglobulin A ((β-lg A) has been studied in solutions of guanidine hydrochloride
(GuHCI) by differential scanning calorimetry (DSC). The experimental results are presented and discussed. It is shown that
the number of protons bound by the monomeric molecules of β-lg A was unchanged before and after its heat denaturation below
pH 3, and that the activation energy of the heat denaturation was depressed owing to the presence of GuHCI. In the solutions
with 2.50 and 3.06 mol/L of GuHCI, both the cold and heat denaturations of P-lg A were observed. In comparison with the heat
denaturation, the activation energy of cold denaturation was far lower and the number of GuHCl molecules bound by the unfolded
polypeptide chains after culd denaturation increased a lot. The absolute value of the enthalpy of cold denaturation was larger
than that of heat denaturation. It was found by the analysis that the contribution to the total denaturational enthalpy of
conformational change itself of the monomeric molecules of β-lg A was the lowest among the globulins, according to the average
of the number of heavy atoms.
Project supported by the National Natural Science Foundation of China, and by the fund for excellent items under Director
of the Institute of Chemistry. 相似文献
84.
三苄基氯化锡最初用格氏法制得。Keiti等曾报道由锡和苄基氯直接制备,这时溶剂对反应的影响很大:用水作溶剂时得到三苄基锡;用甲苯作溶剂时得到二苄基二氯化锡;用正丁醇作溶剂时三苄基氯化锡的产率只有61%。在反应体系中加入KI、KBr或H_3PO_4等催化剂,三苄基氯化锡的产率也只有60%。本文用DMF作溶剂,AlCl_3-I_2作催化剂,并首次在反应体系中加入镁、锌、铝和钠等使副产物氯化亚锡还原成活性很高的金属锡,后者再与等基氯反应,可使三苄基氯化锡的产率提高到91.3%。文中还报导三种尚 相似文献
85.
Zhiming Liu Jiming Hao Lixin Fu Tianle Zhu Junhua Li Xiangyu Cui 《Reaction Kinetics and Catalysis Letters》2003,80(1):45-52
SnO2/Al2O3 catalyst prepared by sol-gel method showed higher activity than those prepared by impregnation method, and their activity
was significantly improved by pre-treatment in the reaction gas. The increased activity is closely related to the agglomeration
of SnO2 species and the re-exposure of Al2O3, which was previously covered by dispersed SnO2 species.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
86.
87.
利用MO-AM1方法研究了2-硝基丙烯热解的反应途径。结果表明, 2-硝基丙烯可能首先热解产生一个四元环状中间体。该中间体依照分步过程继续分解时, 存在两种可能的途径, 其中先断N—O键的反应过程比先断C—C键的过程从能量上更为有利。反应过程中电荷无明显转移, 具有双自由基反应特点。 相似文献
88.
对于烷基乙酰胺的初始热解反应机理, 通常认为与酯类的热解反应相类似。Maccoll和Nagra通过对该热解反应的动力学研究, 认为两者存在不同。差异之一, 烷基乙酰胺存在两种可能的热解途径【参见本文(129页)前述反应方程(1),(2)】。而在酯类热解反应中(2)的活化能过高, 且四元环过渡态极不稳定。差异之二, 极性溶剂(比如乙酸)对酰胺热解反应的催化作用不明显, 而对酯类等气相热解反应的催化作用是十分显著的。为此, 我们用MINDO/3分子轨道法对乙基乙酰胺的初始热解反应进行了较全面的研究。用能量梯度法对此反应的反应物、中间体和生成物的平衡几何构型进行了全优化。(如图1所示)用极小能量途径法分别寻找反应(1)和反应(2)的初始过渡态, 继而用Powell法全优化过渡态的几何构型, 计算所得的过渡态TS1、TS2和TS3分别见图2a, 图3a和图4a。为了确证这些过渡态, 进行了振动分析研究, 结果表明这些过渡态的力常数矩阵的诸本征值中均只有一个负值, 且虚振动模式展示了走向各自的反应物和生成物的趋势, (如图2b,图3b和图4b所示)。它们的总能量及反应(1)和反应(2)的活化能列于表1. 对整个热解反应(1)作了内禀反应坐标(IRC)理论分析, 反应历程见图5所示. 与IRC相应的总能偶极矩以及部分关键的键长和原子净电荷变化一并列于表2.本文研究结果表明, 在乙基乙酰胺的初始反应中主反应即反应(1)与酯类反应相类似, ... 相似文献
89.
The layered perovskites Sr2TiO4 and Sr2SnO4 are more active and selective for the oxidative coupling of methane at 1073 K than the corresponding perovskites SrTiO3 and SrSnO3. The role of the surface oxygen species for this reaction is discussed. 相似文献
90.
Wei Luo Xiang Kai Fu Li Hua Ma 《中国化学快报》2007,18(7):883-886
The high quality TiO2, MoO3-doped WO3 electrochromic film was prepared by the sol–gel method for the first time. The sol, which has hydrogen peroxide (H2O2) and oxalic acid (H2C2O4), was very stable at room temperature and quite suitable for the deposition of films. The WO3 electrochromic film prepared from this doped sol had excellent performance, such as short response time, no cracks, good adhesion to the substrate, high coloring efficiency and longevity of service. 相似文献