Theoretical studies of mechanisms of cycloaddition reaction between difluoromethylene carbene and acetone

Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P_2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P₃ via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

聚丙烯熔体的零切变粘度与粘均分子量的关系

<正> 零切变粘度η_0是聚丙烯熔体流变性能的一个基本物理量,零切变粘度-分子量关系不仅具有理论上的兴趣,而且也有较大的实用意义。在文献中零切变粘度通常都是用毛细管粘度计数据外推求得的,但是由于聚丙烯熔体有较强的非牛顿性,即使在毛细管粘度计测量下限测得的粘度仍表现出明显的切变速率依赖性。因此,难于用外推的方法     

Density functional study of HO(H2O)n (n = 1–3) clusters

The hydrogen bonding complexes HO(H₂O)_n (n = 1–3) were completely investigated in the present study using DFT and MP2 methods at varied basis set levels from 6‐31++G(d,p) to 6‐311++G(2d,2p). For n = 1 two, for n = 2 two, and for n = 3 five reasonable geometries are considered. The optimized geometric parameters and interaction energies for various complexes at different levels are estimated. The infrared spectrum frequencies and IR intensities of the most stable structures are reported. Finally, thermochemistry studies are also carried out. The results indicate that the formation and the number of hydrogen bonding have played an important role in the structures and relative stabilities of different complexes. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Enhanced Acid/Base Catalysis in High Temperature Liquid Water

High temperature liquid water (HTLW), as an environmentally benign medium, has drawn increasing attention for organic chemical reactions and biomass conversion1-3. HTLW has a strong tendency to ionize and can act as an acid and/or base catalyst. In addition, HTLW can dissolve organic compounds to some extent allowing for a homogenous reaction within an aqueous phase. Extensive researches4-10 have been pursued on acid/base-catalysis reactions in HTLW without addition of acid or base. Howe…     

某些分子光谱分析法测定核酸的进展

对近年来利用分光光度法、荧光法和共振光散射法定量测定核酸的现状进行了评述，表中列出了重要的反应体系及分析特征，引用文献77篇。     

Cell detection based on protein array using modified glass slides

A protein array for cell detection was fabricated by spotting different antibodies on modified glass slides. Glass slides were modified to allow antibodies to be immobilized on it and to selectively bind antigens. Antibodies were specially selected with the cells to be detected as targets, which permitted target cells in samples to bind specifically to the array with little nonspecific binding. Results can be obtained by directly putting the samples onto the array for 1 h or a little longer to let the cells specifically interact with the antibodies. After washing the unbound samples away, images were observed with a microscope and captured with a CCD camera. The assessment of antibody-cell binding was evaluated by capturing red blood cells (RBCs) in human blood with blood group antibodies (anti-A and anti-B). Blood group antibodies were spotted on the modified glass slide and kept at 4<.deg> degrees C overnight for immobilization. Human blood samples diluted to different concentrations were used to examine the sensitivity and specificity of the method.     

Y-shaped two-photon absorbing molecules with an imidazole-thiazole core

Two new classes of two-photon absorbing Y-shaped molecules have been developed to possess an imidazole-thiazole core and a stilbene-type conjugation pathway with either nitro or sulfonyl as terminal electron-accepting group.     

Effect of La_2O_3/γAl_2O_3 Catalyst on the Activation of CH_4 and CO_2 to C_02 Hydrocarbons under Non-equilibrium Plasma

The oxidative coupling of methane (OCM) to C2 hydrocarbons using carbon dioxide as oxidant is an attractive process from environmental point of view. Only a few research papers reported for it1-3. In general, the yield of C2 hydrocarbons was about 6%. This indicated that the method of catalytic activation was unfavorable to the reaction. It is necessary for us to find a new method in order to activate reaction and improve C2 hydrocarbon yield. Non-equilibrium plasma is a cold plasma in…     

聚苯乙烯稀溶液的小角激光弹性和准弹性光散射

随着激光技术的发展,近年来出现了与散射光频加宽相应的光子相干光谱即准弹性光散射。于是,利用光散射(也称弹性光散射)法不仅能获得高聚物的各种物性参数如分子量(?),第二维利系数A_2和均方旋转半径(),而且还能得到大分子在溶液中的动态参数,即扩散系数D_0。由D_0求得流体力学半径R_H。本文只涉及小角度准弹性光散射(1°<θ<7°)对稀溶液范围的平动扩散系数的测定。与文献比较,表明方法是成功的。