A theoretical study of topomerization of imine systems: Inversion,rotation or mixed mechanisms?

The different mechanisms, rotation, inversion, or intermediate mechanism, by which occur the topomerization of imine systems R₂ CN X have been studied by applying ab initio, B3LYP, and MP2 methods. The effect of a wide variety of substituents R and X on the isomerization pathway have been examined by computing fully optimized structures of the ground and transition states (136 isomers belonging to different imine families were studied and more than 300 transition structures were determined at various levels of theory). Energy barriers have been also obtained and it was found that the groups R and X have a strong influence on the type of mechanism involved and the activation energies. Thus, and depending on the type of substituents, transition state structures related to the following kinds of processes were found: pure inversion, intermediate mechanisms, rotation, and enhanced rotation (hyper‐rotation). In turn, the corresponding activation energies range between very low (<10 kcal/mol) and extremely high (> 70 kcal/mol) values. A simple index that allows us to quantify the percentage of inversion or rotation mechanism is proposed. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

通过确定初始电离位点预测吲哚类生物碱质谱的特征裂解规律

确定初始电离位点是EI源质谱解析中一个至关重要的环节. 本文提出了一种确定初始电离位点的新方法. 该法通过计算和分析分子离子自旋密度, 进而比较从中性分子到分子离子的电荷变化和键长变化, 从而确定初始电离位点. 对简单吲哚类生物碱质谱的特征裂解机理进行了预测, 结果与标准物质的质谱吻合. 在此基础上, 与传统的根据基团电离能确定电离位点的方法进行了比较. 结果表明, 该法优于电离能方法. 此法不仅可用于预测以α-裂解为主导的吲哚生物碱和其它含氮化合物的质谱裂解规律, 还为揭示其它小分子化合物以及气相多肽离子的裂解机理奠定了基础.     

矩阵多项式秩的和的恒等式及其应用

证明了矩阵A的两个多项式秩的和等于它们最大公因式与最小公倍式秩的和,这个结果不仅可以概括近期文献的相关工作,而且可以对应用矩阵多项式求逆矩阵的方法作进一步的研究,同时也可使关于矩阵秩恒等式的最新讨论获得一种简单统一的处理方法.     

平面C-B样条的奇拐点分析

平面C-B样条曲线是三次均匀B样条的推广.通过移动C-B样条曲线段的一个控制点而固定其余三个控制点的方法,讨论了在曲线上形成零曲率点的移动控制点的轨迹,得到了C-B样条曲线段的尖点判别曲线、拐点判别区域,同时也给出了在曲线段上生成重结点的移动控制点的轨迹区域.     

两个极限的注记

利用数值积分方法给出了波利亚的名著中两个极问题的证明,并给出了两个结论更强的结果.     

Two sample applications of a classical isoperimetric problem of the calculus of variations to fluid mechanical problems in fluidization and spouting

This paper is devoted to outlining precisely the basic mathematics of a classical isoperimetric problem of the calculus of variations and showing how significant fluid mechanical problems in fluidization and spouting can be addressed using this approach.     

Intensive variables in the framework of the non-extensive thermostatistics

By assuming an appropriate energy composition law between two systems governed by the same non-extensive entropy, we revisit the definitions of temperature and pressure, arising from the zeroth principle of thermodynamics, in a manner consistent with the thermostatistics structure of the theory. We show that the definitions of these quantities are sensitive to the composition law of entropy and internal energy governing the system. In this way, we can clarify some questions raised about the possible introduction of intensive variables in the context of non-extensive statistical mechanics.     

测定金属电阻温度系数的方法研究

从金属电阻率与温度的线性关系出发,设计了测定金属电阻温度系数的实验方案。利用基本的电磁学仪器和热学仪器组合进行实验,以漆包铜线作为待测金属丝测定出铜的电阻温度系数,分析了导致系统误差产生的主要原因,并就待测金属丝的选取原则、温度控制的方法进行了讨论。