Crystal and Molecular Structure of 3，4－diphenyl－5－ethyl－5－methyl－1，3，4－diazaphospholidin－2－thione－4－oxide

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煤显微组分分子结构模型的量子化学研究

采用分子力学和半经验量子化学方法，研究了神木煤显微组分的分子结构模型，比较了镜质组和惰质组分子模型的能量构成、不同类型键的键长和键裂解能。研究结果表明，扭转能和范德华能是分子中的主要作用力，取代基对体系能量有明显影响，烷基取代基使体系能量增加，而苯基取代基使体系能量降低；脂肪C—C键长比芳香C—C键长长，说明脂肪C—C在受热过程中比芳香C—C更容易断裂分解。对各键裂解能的计算结果表明，Car—Cal键的裂解能高于Cal—Cal，Car—O醚键的裂解能高于Cal—O醚键。而惰质组结构模型中除C—O醚键外，各键的裂解能均高于镜质组，说明惰质组结构模型比镜质组有较高的热稳定性。     

纳秒强激光场中苯电离产生高价离子的研究

用25 ns脉冲Nd-YAG 532 nm的激光，在1010～1011 W•cm－2的光场强度下，利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时，除观察到C2＋、C2H2+、C3H3+、C6H6+离子外，还观察到很强的Cq＋(q=1～3)高价离子.这些离子都有很高的平动能， C2＋的最可几平动能为12.9 eV， C3＋为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验，可以认为这些高价离子来源于含苯团簇的库仑爆炸过程.     

酞菁类化合物对MH/Ni电池性能的影响

针对MH/Ni电池充电过程中氧的产生和不恰当的消除方式带来的内压升高和热量聚集使电池总体性能衰减很快的问题, 提出采用降低化学催化氧还原的比例, 提高热量产生少的电催化氧还原比例的方法加以解决.金属酞菁类化合物是一种电催化氧还原剂.添加酞菁的MH/Ni电池与对比电池进行容量衰减、内压、大电流放电等特性比较, 其性能均有显著提高.     

Enantioseparation of Amino Acid Derivatives with a Cellulose-Based Chiral Stationary Phase

Five structurally related amino acid derivatives were enantioseparated by HPLC with a commercially available chiral stationary phase, Chiralcel OD-H. The chromatographic experiments were performed in the normal phase mode. n-Hexane/polar alcohol was used as mobile phase. Excellent baseline enantioseparations could be obtained for all these solutes. The effects of the concentration of polar alcohol and the column temperature on the retentions and enantioseparations were studied in detail. From the van't Hoff plots the corresponding apparent thermodynamic parameters were derived. Mechanism aspects of chiral recognition were discussed based on the relationship between the thermodynamic parameters and the structures of the solutes. It was found that the substituent of the phenyl group on the residual group of the amino acid derivatives was close relevant to thermodynamic origin of enantioseparation. Much better enthalpy–entropy compensation effect was obtained by plotting the differential, rather than the original, thermodynamic parameters.     

Theoretical study of initiated reaction mechanism of polymerization of maleic anhydride catalyzed by OH−1 anion

A theoretical study of the polymerization reaction mechanism of maleic anhydride (MA) initiated by hydrate is presented. The reaction pathway has been studied with the density functional theory (DFT) method at the B3LYP/6‐311G** level. The geometrical parameters of transition states (TS) are optimized; intrinsic reaction coordinate (IRC) calculations have also been performed to obtain further credible features. Frequency analyses of all the stationary points are calculated at the same basis sets. The total energies of all geometries are corrected at second‐order Møller–Plesset (MP2)/6‐311G**. Calculation results reveal that the reaction mechanism is attributable to anion polymerization. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

A highly reactive mononuclear Zn(II) complex for phosphodiester cleavage

The activity of a Zn(II) complex of a tetradentate, tripodal ligand for catalyzing phosphodiester cleavage is enhanced 750-fold by introducing three hydrogen bond donors to the ligand. Inhibition studies show that the Zn-aqua complex is the kinetically active form and that it binds the transition state with a formal dissociation constant of 3 x 108 M-1. The effect of these ligand modifications on the transition-state affinity is comparable to the rate acceleration provided by the metal ion itself. Overall, this mononuclear complex is more active than the most reactive dinuclear Zn(II) complexes reported to date.     

High-performance liquid chromatography of some basic drugs on a n-octadecylphosphonic acid modified magnesia-zirconia stationary phase

The high-performance liquid chromatographic behavior of some basic drugs was studied on a n-octadecylphosphonic acid modified magnesia-zirconia (C18PZM) stationary phase. The effect of mobile phase variables such as methanol content, ionic strength, and pH on their chromatographic behavior was investigated. The retention mechanism of basic drugs on the stationary phase was elucidated. The results indicate that both hydrophobic and cation-exchange interactions contribute to solute retention under most chromatographic conditions. The inherent Br?nsted-acid sites and also the adsorbed Lewis base anionic buffer constituents on accessible ZM surface Lewis acid sites play a role in the retention of ionized solutes by cation-exchange interaction. However, especially at high mobile phase pH, the retention of basic drugs depends mainly on hydrophobic interactions between solutes and support. Separations of the basic drugs on the C18PZM phase by a predominantly reversed-phase retention mode were very promising. The mixed-mode retention feature on this phase, as a result of the adsorbed Lewis base anionic buffer constituents acting as sites for cation-exchange, could also be very useful, e.g. for enhancing the chromatographic selectivity of such analytes. The C18PZM seems to be an excellent alternative to silica-based reversed-phase stationary phase for the separation of strongly basic solutes.     

TEOS-MTES基SiO2溶胶微结构的SAXS研究

正硅酸乙酯(TEOS)为前驱体,在碱性条件下制备含有无定形SiO2颗粒的溶胶,以甲基三乙氧基硅烷(MTES)在酸性条件下获得聚甲基硅氧链,二者混合后应用同步辐射X射线进行混合溶胶的SAXS散射强度测定,计算了溶胶的平均回转半径、平均粒径、两相界面层厚度、散射体体积分数、两相间比表面积等参数,辅以光子相关光谱法(PCS)和透射电子显微镜(TEM)观测溶胶粒度,证实SiO2颗粒被MTES混合物连接成族团.实验发现所测混合溶胶样品均表现出对Porod定理的负偏离,说明溶胶中颗粒与溶剂之间存在很明显的两相间界面层.     

新显色剂噻二唑偶氮二甲氨基苯甲酸与铜(Ⅱ)显色反应的研究和应用

本文研究了噻二唑偶氮二甲氨基苯甲酸与Cu(Ⅱ)显色反应条件,确定在pH3.0～4.5范围形成蓝紫色络合物,组成比为1:1,摩尔吸光系数ε=4.55×10~4L·mol~(-1)·cm~(-1),1gβ=7.32。应用拟定的方法测定天然水中微量铜,获得满意的结果。