含有一个非平面杂环胺配体的新型反铂抗癌药物的水解机理

用B3LYP杂化泛函和等电子聚焦极化连续模型(IEF-PCM)研究了trans-[PtCl2(NH3)(Am)](Am: 非平面哌啶或哌嗪)新型反铂抗癌药物的水解反应机理. 对经由一般的SN2机理的第一步和第二步水解反应势能面上的稳定点进行了全优化和表征. 在水解中, 最显著的结构变化发生在反应过渡态和中间体的五配位三角双锥的赤道面上. 与经典顺铂(cisplatin)比较, 反式[PtCl2(NH3)(piperazine)]的第一步和第二步水解活化能均低于顺铂, 而反式[PtCl2(NH3)(piperidine)]的第一步水解活化能稍高于顺铂, 第二步水解活化能稍低于顺铂. 计算表明, 这些含有非平面杂环胺反铂的配合物减小了赤道面上的立体效应和水解势垒.     

十二烷基吗啉选择性吸附氯化钠的分子模拟

采用分子模拟方法研究氯化钠-光卤石反浮选体系中捕收剂十二烷基吗啉(DMP)选择性吸附氯化钠的机理. 用Material Studio 4.0软件和COMPASS分子力场方法建立了DMP在氯化钠和光卤石两种矿物表面的吸附模型, 并进行动力学模拟和能量优化, 确立了DMP在两种矿物表面的最佳吸附构型. 结果表明, DMP分子通过其官能团中的O、N原子与氯化钠界面水结构中的H原子之间的氢键作用吸附在氯化钠表面, 吸附作用能为-119.49 kJ·mol-1, 而光卤石界面水结构不能保持稳定排列, 致使DMP直接作用在光卤石表面, 吸附能为-37.97 kJ·mol-1, 在两种矿物共存体系中, 这种吸附能差异导致了DMP在氯化钠表面的选择性吸附.     

流动注射化学发光法测定盐酸雷尼替丁——基于在反胶束纳米微反应介质中的反应

在0.05 mol·L-1盐酸介质中,雷尼替丁(RNTD)经质子化的RNTD+与AuCl-4络阴离子反应生成离子缔合物RNTD+·AuCl-4,用正辛醇5 mL将其萃取入有机相.萃取液作为样品溶液注入流动注射分析仪中,由载流正辛烷载带至汇合点与由鲁米诺溶液与CTMAC的正辛烷-环乙烷溶液所组成的反胶束的纳米微反应剂混合液汇合并流入反应盘管中完成由从离子缔合物中释出的AuCl-4与鲁米诺在反胶束纳米微反应介质中的化学发光反应,并测得其化学发光强度,由此间接测得RNTD的含量.化学发光信号强度与RNTD浓度在0.001～10 mg·L-1之间保持线性关系,方法的检出限(3s)为0.03μg·L-1.应用此方法分析了雷尼替丁的片剂和针剂,还测定了人尿及血浆中RNTD的含量.测得结果与药典法的结果相符.     

A novel correlation for estimation of hydrate forming condition of natural gases

An inherent problem with natural gas production or transmission is the formation of gas hydrates, which can lead to safety hazards to production/ transportation systems and to substantial economic risks. Therefore, an understanding of conditions where hydrates form is necessary to overcome hydrate related issues. Over the years, several models requiring more complicated and longer computations have been proposed for the prediction of hydrate formation conditions of natural gases. For these reasons, it is essential to develop a reliable and simple-to-use method for oil and gas practitioners. The purpose of this study is to formulate a novel empirical correlation for rapid estimation of hydrate formation condition of sweet natural gases. The developed correlation holds for wide range of temperatures (265–298 K), pressures (1200 to 40000 kPa) and molecular weights (16−29). New proposed correlation shows consistently accurate results across proposed pressure, temperature and molecular weight ranges. This consistency could not be matched by any of the widely accepted existing correlations within the investigated range. For all conditions, new correlation showed average absolute deviation to be less than 0.2% and provided much better results than the widely accepted existing correlations.     

极化中子衍射及在电子自旋密度研究中的应用

极化中子衍射方法常用于研究含未配对电子化合物中电子自旋密度的分布．分子中电子自旋密度分布从一个独特的角度反映化合物的磁性质．本文介绍极化中子衍射方法的背景知识和基本原理．包括中子源、中子和X射线衍射、极化中子衍射,以及一些常用的实验数据处理方法．选用几个实例总结了用极化中子衍射方法得到的电子自旋密度分布在无机和有机化学中的应用．通过单分子磁体[Fe8O2（OH）12（tacn）6]^8＋和氰基桥联化合物K2[Mn（H2O）2]3[Mo（CN）7]2·6H2O,说明如何用该方法研究金属原子间的磁相互作用;并通过Ru（acac）3这个只含一个未配对电子的化合物来说明如何获得化合物中金属和配体上小的自旋密度;最后介绍了该方法在nitronylnitroxide自由基研究中的应用．     

RECURSIVE SYSTEM IDENTIFICATION

Most of existing methods in system identification with possible exception of those for linear systems are off-line in nature, and hence are nonrecursive. This paper demonstrates the recent progress in recursive system identification. The recursive identification algorithms are presented not only for linear systems （multivariate ARMAX systems） but also for nonlinear systems such as the Hammerstein and Wiener systems, and the nonlinear ARX systems. The estimates generated by the algorithms are online updated and converge a.s. to the true values as time tends to infinity.     

PERTURBED PERIODIC SOLUTIONFOR BOUSSINESQ EQUATION

We consider the solution of the good Boussinesq equation Utt -Uxx ＋ Uxxxx = （U2）xx, -∞ 〈 x 〈 ∞, t ≥ 0, with periodic initial value U（x, 0） = ε（μ ＋ φ（x））, Ut（x, 0） = εψ（x）, -∞ 〈 x 〈 ∞, where μ = 0, φ（x） and ψ（x） are 2π-periodic functions with 0-average value in [0, 2π], and ε is small. A two parameter Bcklund transformation is found and provide infinite conservation laws for the good Boussinesq equation. The periodic solution is then shown to be uniformly bounded for all small ε, and the H1-norm is uniformly bounded and thus guarantees the global existence. In the case when the initial data is in the simplest form φ（x） = μ＋a sin kx, ψ（x） = b cos kx, an approximation to the solution containing two terms is constructed via the method of multiple scales. By using the energy method, we show that for any given number T 〉 0, the difference between the true solution u（x, t; ε） and the N-th partial sum of the asymptotic series is bounded by εN＋1 multiplied by a constant depending on T and N, for all -∞ 〈 x 〈 ∞, 0 ≤ ｜ε｜t ≤ T and 0 ≤ ｜ε｜≤ε0.     

调和点列的性质与一类竞赛题的证明

设A、B、C、D是共线的四点,若满足条件面AC/CB=AD/DB,则称A、C、B、D为调和点列,亦称线段AB被C、D调和分割,或线段CD被A、B调和分割,若从共点直线外一点P引射线PA,PC,PB,PD,则称PA,PC,PB,PD为调和线束,为了证明一类竞赛题,我们先介绍调和点列的几条结论：     

四元数的复数形式及其在6R机器人反解中的应用

把四元数应用于平面旋转的特殊情况,并把旋转角度的正弦、余弦改写为复指数形式,导出平面四元数的两个复数形式的基.利用这两个基可以把表示三维变换的四元数和对偶四元数改造为复数形式,得到复数形式四元数的4个基和复数形式对偶四元数的8个基,以及它们之间乘法运算的运算法则.通过把它们应用到空间$6R$机器人的位移反解问题,证明了Dixon结式展开后的次数为16次,而不是形式上的24次,并且得到单变量的16次方程.