A quantum chemical study on structure of 1,2-bis(diphenylphosphinoyl)ethane and phenol cocrystal

The cocrystal of 1,2-bis(diphenylphosphinoyl)ethane (DPPEO) with phenol (1:1) were studied theoretically with AM1, PM3, MNDO and MINDO/3 semi-empirical methods to elucidate its structure. The bond lengths and angles from theoretical studies of molecule DPPEO/phenol (1:1) were found to be as expected. Theoretical results, concerning with intermolecular van der Waals forces in cocrystal, were compared with the previously obtained experimental data and AM1 results were found to be the best fit for bond lengths and angles of DPPEO/phenol.     

用PM3量化参数预测多氯代二苯并呋喃的logKow

从现有的PCDFs分子的正辛醇 /水分配系数 (logKow)实验数据出发 ,建立定量结构 性质关系方程(QSPR) .采用G98W程序包中的PM3方法对 13 5个多氯代二苯并呋喃 (PCDFs)分子和二苯并呋喃进行了优化计算 ,作业命令为 #pPM3optfreqscf(conver =9) ,以计算所得的分子轨道能量、碳原子电荷作为PCDFs分子结构描述符 ,运用多元线性回归技术建立了PCDFs的logKow与分子结构描述符的四元方程 ,最优相关系数为 0 .95 0 7,标准偏差为 0 .173 7,经检验该模型的稳健性好 ,并对未有实验数据的 85个PCDFs的logKow进行预测     

Temperature coefficient of NH chemical shifts of thioamides and amides in relation to structure

NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl₃ and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation.     

Robust Speed Control of a Low Damped Electromechanical System Based on CRONE Control: Application to a Four Mass Experimental Test Bench

Robust speed control of a low damped electromechanical system with backlash is studied, controlled load angular speed being not measured. The proposed control strategy combines a Luenberger observer (load angular speed and load torque disturbance estimations) and a robust CRONE controller. The observer provides estimation of the load angular speed and of the disturbance torque applied on the load. Through the computation of only three independent parameters (as many as a PID controller), the CRONE controller permits to ensure the robust speed control of the load in spite of plant parametric variations and speed observation errors. The proposed control strategy is applied to a four mass experimental test bench.     

Preparation and characterization of acrylic‐based black particles of poly(methyl methacrylate‐co‐ethylene glycol dimethacrylate) by dispersion polymerization for electrophoretic displays

Ultrafine black particles, ranging in diameter from 1 to 3 μm, were prepared by dispersion polymerization in a methanol/water mixture with vinyl monomers, nonpolymerizable Sudan black B dyes, and fluorescein isothiocyanate labeled charge control additives. Both the ratio of the methanol to the water dispersion medium and the polymeric stabilizer concentration had significant effects on the particle size. The important role of the stabilizer concentration lay in the particle formation step, during which it determined the particle stability and final particle size. These could affect the extent of the aggregation of nuclei by changing the adsorption rate of the stabilizer and the viscosity of the dispersion medium, resulting in smaller particles. The fluorescent‐labeled charge control additives strongly affected the electrophoretic mobility. A small concentration of fluorescent‐labeled charge control additives increased the electrophoretic mobility. However, a further addition reduced the electrophoretic mobility of the polymer particles. The concentration dependence of the fluorescent‐labeled charge control additives on the deposition behavior in the polymer particles was successfully imaged and thereafter quantified by image analysis. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5608–5616, 2004     

强流束晕-混沌的外部磁场开关控制

研究了强流离子束在周期聚焦磁场通道中束晕-混沌的外部磁场开关参数控制方法. 将该方法应用在多粒子模型中，实现了对5种不同初始分布质子束的束晕-混沌的有效控制，得到了消除束晕及其再生现象的理想结果.在强流加速器系统中，由于外部磁场是可测和可调 的物理量，因此该控制方法有利于实验研究，可为强流质子加速器中周期聚焦磁场的设计和实验提供参考. 关键词： 强流离子束 周期聚焦磁场通道 束晕_混沌 混沌控制 开 关控制     

基于径向基函数神经网络的Lorenz混沌系统滑模控制

针对受参数不确定和外扰影响的混沌Lorenz系统，提出一种基于径向基函数（RBF）神经网 络的滑模控制方法.基于被控系统在不稳定平衡点处状态误差的可控规范形，设计滑模切换 面并将其作为神经网络的唯一输入.单入单出形式的RBF控制器隐层只需7个径向基函数，网 络的权值则依滑模趋近条件在线确定.仿真表明该控制器对系统参数突变和外部干扰具有鲁棒性，同时抑制了抖振. 关键词： 混沌控制 滑模 径向基函数神经网络 Lorenz系统     

Study on the covalence of Cu and chemical bonding in an inorganic fullerene-like molecule, [CuCl]20[Cp*FeP5]12 [Cu-(CH3CN)+2Cl-]5, by a density functional approach

The electronic structure and chemical bonding in a recently synthesized inorganic fullerene-like molecule, [CuCl]₂₀[Cp*FeP₅]₁₂[Cu-(CH₃CN) ⁺ ₂Cl⁻]₅ has been studied by a density functional approach. Geometrical optimization of the three basic structural units of the molecule is performed with Amsterdam Density Functional Program. The results are in agreement with the experiment. Localized MO’s obtained by Boys-Foster method give a clear picture of the chemical bonding in this molecule. The reason why CuCl can react with Cp*FeP₅ in solvent CH₃CN to form the fullerene-like molecule is explained in terms of the soft-hard Lewis acid base theory and a new concept of covalence.     

Study on the covalence of Cu and chemical bonding in an inorganic fullerene-like molecule, [CuCl]_(20)[Cp~*FeP_5]_(12)[Cu-(CH_3CN)_2~+Cl~-]_5, by a density functional approach

The titled inorganic fullerene-like molecule (hereafter abbreviated as IFM) was recently synthe-sized by Bai et al.[1], which attracts a lot of interests from inorganic and organometallic chemists, and questions are raised for this smart molecule: (ⅰ) Why CuCl can react with Cp*FeP5 in solvent CH3CN to form IFM? (ⅱ) What is the nature of chemical bond-ing? (ⅲ) What is the covalence of Cu in this mole-cule? In this paper we intend to answer these questions in terms of the soft-hard …