Unique stereochemistry of 3-borabicyclo[3.3.1]nonane derivatives

The conformational equilibrium in solution was examined by NMR spectroscopy for a series of 7-phenyl-3-borabicyclo[3.3.1]nonane derivatives containing various substituents at the boron atom. The structures of these derivatives were studied in the crystalline state (X-ray diffraction analysis) and by quantum-chemical calculations (B3Pw91/6-31G*). The B...Ph transannular interactions corresponding to charge transfer from the system of the phenyl group to the vacant p-orbital of the B atom were demonstrated to be responsible for unique stability of the chair-chair conformation of these derivatives.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1884–1896, September, 2004.     

NMR Studies of Mixed-Ligand Lanthanide Complexes in Solution: Pseudorotation and Ring Inversion of 18-Crown-6 Molecule in Cerium Subgroup Chelates

¹H and ¹³C NMR measurements are reported for the CDCl₃ and CD₂Cl₂ solutions of [La(NO₃)₃(18-crown-6)] (I), [Pr(NO₃)₃(18-crown-6)] (II) and [Ce(NO₃)₃(18-crown-6)] (III) complexes. Temperature dependencies of the ¹H NMR spectra of II have been analyzed using the dynamic NMR methods for multi-site exchange. Two types of conformational dynamic processes in II were identified (the first one with activation enthalpy ΔH ^‡=26 ± 4 kJ/mol is conditioned by interconversion of complex enantiomeric form and pseudorotation of macrocycle molecule upon the C ₂ symmetry axis, the second one with ΔH ^‡=46 ± 5 kJ/mol is conditioned by macrocycle molecule inversion). Studies of the values of the lanthanide-induced shifts revealed that the structure of complexes in solution is similar to that reported for the complex I in the crystal state.This revised version was published online in July 2005 with a corrected issue number.     

Application of HPLC to measure vanadium in environmental,biological and clinical matrices

Vanadate and vanadium compounds exist in many environmental, biological and clinical matrices, and despite the need only limited progress has been made on the analysis of vanadium compounds. The vanadium coordination chemistry of different oxidation states is known, and the result of the characterization and speciation analysis depends on the subsequent chemistry and the methods of analysis. Many studies have used a range of methods for the characterization and determination of metal ions in a variety of materials. One successful technique is high performance liquid chromatography (HPLC) that has been used mainly for measuring total vanadium level and metal speciation. Some cases have been reported where complexes of different oxidation states of vanadium have been separated by HPLC. Specifically reversed phase (RP) HPLC has frequently been used for the measurement of vanadium. Other HPLC methods such as normal phase, anion-exchange, cation-exchange, size exclusion and other RP-HPLC modes such as, ion-pair and micellar have been used to separate selected vanadium compounds. We will present a review that summarizes and critically analyzes the reported methods for analysis of vanadium salts and vanadium compounds in different sample matrices. We will compare various HPLC methods and modes including sample preparation, chelating reagents, mobile phase and detection methods. The comparison will allow us to identify the best analytical HPLC method and mode for measuring vanadium levels and what information such methods provide with regard to speciation and quantitation of the vanadium compounds.     

Effect of Neck Formation on the Measurement of Dynamic Interfacial Tension in a Drop Volume Tensiometer

Dynamic interfacial tension values obtained by drop volume tensiometry will be affected under certain experimental conditions by the formation of a neck between the drop and the capillary tip. This phenomenon must be accounted for to obtain accurate values of interfacial tension. In this work, neck formation for a water–mineral oil system is studied under conditions where hydrodynamic effects can be neglected. A model originally developed for the determination of the surface tension of a suspended drop is modified for application to dynamic interfacial tensions of surfactant-containing liquids. The model relates apparent values of interfacial tension calculated from drops possessing necks to actual values. Experiments with Span 80 (sorbitan monooleate) and sodium dodecyl sulfate (SDS) surfactants in a mineral oil–water system are used to test the validity of the developed model. For the small tip diameter used, good agreement is obtained for Span 80 up to the critical micelle concentration, and for low concentrations of SDS, when the surfactant adsorption is diffusion-limited. In both cases, the neck diameter of the growing drop can be considered constant over the range of dynamic interfacial tensions tested.     

考虑跟随企业搭便车行为的创新企业定价策略研究

文章通过构建博弈模型探讨了存在跟随企业搭便车行为时创新企业的定价策略及定价模式(稳定定价或动态定价),并分析了忠实消费者规模及需求溢出效应等特征对创新企业定价决策与利润的影响.结果表明,无论创新企业采用稳定定价或动态定价模式,跟随企业搭便车行为均会降低创新企业利润,需求溢出效应的增强总能使创新企业和跟随企业均获得更高的...     

准饱和土体中圆形衬砌对弹性波的散射

采用Vardoulakis和Beskos提出的准饱和土体的波动控制方程,根据Helmholtz矢量分解定理,得到了准饱和土中P1波(快压缩波)、P2波(慢压缩波)和S波(剪切波)的波数的势函数表达式.将准饱和土体和圆形衬砌视为各向同性的均质体,运用波函数展开法将入射波、散射波和折射波的势函数展开成Fourier-Bessel函数的级数形式,根据准饱和土体与衬砌边界处应力和位移连续及衬砌内完全自由的边界条件,得到了平面P1波入射下,准饱和土体内深埋圆形衬砌的散射系数和折射系数的理论解,通过数值计算分析了饱和度对准饱和土体和衬砌的DSCF(动应力集中因子)及准饱和土体的PPCF(孔压集中因子)的影响规律,结果表明:准饱和土体的DSCF随着饱和度的增大而减小,衬砌的DSCF基本不受饱和度的影响,而准饱和土体的PPCF则随着饱和度的增大而增大.     

吸收湿气对微电子塑料封装影响的研究进展

微电子塑料封装中常用的聚合物材料因易于吸收周围环境中的湿气而对器件本身的可靠性带 来很大影响, 本文回顾了封装材料中湿气扩散、湿应力及蒸汽压力的产生这3个互相联系过 程的研究情况, 从理论分析、特征参数描述及其实验测定、有限元模拟分析的角度来分别予 以介绍.从已有的理论分析与实验结果中可以看出, 塑封材料吸收湿气会给器件的可靠性带 来诸多影响, 湿气的吸收、扩散、蒸发等过程, 实验测量, 以及由湿气带来的其它相关问题正 成为微电子封装可靠性研究领域中的新热点, 受到越来越多的关注与重视.     

超音速气流中受热壁板的稳定性分析

采用Galerkin方法建立二维壁板的非线性气动弹性运动方程,用一阶活塞理论模拟壁板 受到的气动力. 基于李雅普诺夫间接法分析了平壁板的稳定性,得到了壁板失稳的边界 曲线;采用牛顿迭代法分析了壁板的屈曲变形,进而分析了后屈曲状态下壁板的稳定性; 在时域中分析了后屈曲状态下壁板的颤振边界. 分析结果表明,为了保证计算精度, 在二维壁板的静态失稳及过屈曲变形分析中,至少要取二阶谐波模态;在平壁板的超音速颤 振(动态失稳)边界分析中至少应取四阶模态. 还对壁板的温升,壁板长厚比、壁板密 度和气流马赫数作了无量纲变参分析,研究了这些参数的变化对壁板稳定性的影响规律. 研 究中发现,当气流速压较低时壁板一般会稳定在低阶谐波模态的屈曲变形位置,但是如果系 统出现多个渐近稳定的不动点,即使作用在壁板上的气流速压很低,壁板也有可能在较低速 压下发生二次失稳型颤振.     

KEADA: Identifying Key Classes in Software Systems Using Dynamic Analysis and Entropy-Based Metrics

Software maintenance is indispensable in the software development process. Developers need to spend a lot of time and energy to understand the software when maintaining the software, which increases the difficulty of software maintenance. It is a feasible method to understand the software through the key classes of the software. Identifying the key classes of the software can help developers understand the software more quickly. Existing techniques on key class identification mainly use static analysis techniques to extract software structure information. Such structure information may contain redundant relationships that may not exist when the software runs and ignores the actual interaction times between classes. In this paper, we propose an approach based on dynamic analysis and entropy-based metrics to identify key classes in the Java GUI software system, called KEADA (identifying KEy clAsses based on Dynamic Analysis and entropy-based metrics). First, KEADA extracts software structure information by recording the calling relationship between classes during the software running process; such structure information takes into account the actual interaction of classes. Second, KEADA represents the structure information as a weighted directed network and further calculates the importance of each node using an entropy-based metric OSE (One-order Structural Entropy). Third, KEADA ranks classes in descending order according to their OSE values and selects a small number of classes as the key class candidates. In order to verify the effectiveness of our approach, we conducted experiments on three Java GUI software systems and compared them with seven state-of-the-art approaches. We used the Friedman test to evaluate all approaches, and the results demonstrate that our approach performs best in all software systems.     

风力机叶尖加小翼动力放大特性实验研究

本文在风力机的叶尖上通过添加V型平板小翼实验,提高了风力机的输出功率.在风洞实验研究中,进行了不同长度和宽度,不同前张角和后张角小翼的探索.实验表明小翼对风力机在一定尖速比λ范围内可以提高功率系数cp值.