小角X射线散射表征AOT/水层状溶致液晶的有序性

用小角X射线散射研究了AOT/水层状溶致液晶的有序性. 通过对散射曲线的解析, 讨论了表面活性剂浓度、温度和助表面活性剂等三个方面对溶致液晶层状相结构有序性的影响. 在一定的范围内, 提高温度, 改变表面活性剂浓度和加入少量助表面活性剂可使碳氢链排列由稀疏转变为密实, 层状相也相应地由“柔性双层”过渡到更加有序化的“平面双层”. 基于形状因子和体系内分子间作用力, 提出了层状相形成与有序化的机理, 同时采用分子模拟的方法展现了不同浓度下的液晶结构.     

Synthesis of a novel rigid molecule family for the investigation of electron and energy transfer

Three new rigid bridging ligands for metal complexation (7=bmb, 8=bqb and 11=btb) were prepared from a rigid triptycene spacer connected to two bipyridine ligands using a Horner–Emmons type reaction. The triptycene spacer is substituted by methoxy groups in the case of bmb and in the case of bqb by a benzoquinone substituent. The corresponding metal complexes (ruthenium and/or osmium) were synthesised and the different luminescence behaviour was tested. They show great potential for the investigation of intramolecular electron and energy transfer reactions. The dinuclear metal complex Ru---bqb---Os is an interesting system in which the bridging ligand bqb acts as a redox switch, able to tune the conductivity for energy or electrons across the bridge.     

聚合物体系散射函数的热力学基础

利用链段浓度和链头浓度的概念，根据热力学涨落理论，给出了聚合物二元共混体系ｄｅＧｅｎｎｅｓ散射函数的一个普遍的热力学证明，指出了这个函数和Ｆｌｏｒｙ－Ｈｕｇｇｉｎｓ共混自由能公式一样，也依赖于忽略构象涨落的假设．     

Molecular determinants in the bioactivation of the dopaminergic neurotoxin N-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP)

Summary Nineteen analogs of the dopaminergic neurotoxin N-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) have been used as probes to study the structural parameters that influence MAO-catalyzed oxidation. In this study, the efficiency of enzyme-catalyzed substrate oxidation was found to be unrelated to parameters such as the ionization potential, dipole moment, net atomic charge at C5 and the dihedral angle between the phenyl ring and the tetrahydropyridine moiety. Conformational analysis revealed that substitution at the C2 position of MPTP yields atropisomers. It is suggested that one of these atropisomers would be either inactive or substantially less active than the other. Therefore, the relative oxidative efficiency and toxicity of these compounds reported earlier may have been significantly underestimated. Based on the conformational analysis and other data, a rudimentary model of the MAO substrate site has been developed which partially explains the substrate specificities of MAO A and MAO B.Each substrate binding site can be divided into two regions, (a) an amine-binding pocket (for the tetrahydropyridine moiety), and (b) a bulky substituent region (for the phenyl group and its substituents). The length of the substrate binding site (measured along the long axis of MPTP) is approximately 8.5 Å, and the width of the amine-binding pocket is approximately 2.5 Å (from C3 to C5). The bulky substituent region contains a central area for binding the phenyl group of MPTP. This central area is flanked by two hydrophobic pockets, P2 and P3. In MAO A, the pocket P2-A is oriented 45–135° relative to the plane of the tetrahydropyridine moiety, with a radius of 3.1 Å from C2 of the phenyl ring. The radius of a similar but smaller pocket, P2-B, in MAO B, is approximately 2.7 Å. In MAO B, the pocket P3-B (radius 2.36 Å from C3) is larger than a similar pocket P3-A (radius 1.70 Å from C3) in MAO A. The foregoing characterization suggests that differences in the size and topography of both of the substituent pockets play an important role in determining the substrate specificities of these two isozymes.     

Laser-pulse photocurrent transient measurements at oxygen evolving n-PtS2

Laser-pulse transient measurements have been performed at single crystalline n-PtS₂ electrodes with the aim of understanding light-induced hydroxide, oxide and oxygen formation. Different detected time constants permit the identification of distinct reaction products. They form surface states which function both as centers for recombination and charge accumulation in the interface. The rate constants determined are influenced by the RC-constant of the measuring circuit and can be interpreted only qualitatively. In the presence of recombination processes time constants faster than R_LC_SC are found. Evidence is given that the reaction step leading to oxygen evolution is dependent on the building-up of an electric field in the Helmholtz layer. This result may be of importance for the development of materials for the photoelectrolysis of water.     

THE SOLID STATE REACTIONS AND TRANSITIONS IN HIGH POLYMERIC SYSTEMS Ⅲ. THE BULK CRYSTALLIZATION OF LANTHANIDECATALYTICALLY POLYMERIZED POLYDIENES

For the mechanism of isothermal bulk crystallization of high polymers, beside the nucleation and growth steps, the unimpingement of growing crystal aggregates should be taken into account for the modification of the Avrami equation. Starting from Poisson distribution function of growing crystal aggregates, the probability of the unimpinging ones should be P(0)+P(1), then the Q-modified Avrami equation thus derived can be expressed aswhere V0 represents the volume fraction of crystal aggregates at crystallization time t at a given temperature, while the exponent n on t relates to the mode of nucleation and growth, and K_q is the corresponding shape factor. This Q-modified one is verified satisfactory by the isothermal bulk crystallization of lanthanidecatalytically polymerized polybutadiene (Ln-PB), polyisoprene (Ln-PIR) and their copolymers (LnPB/IR). Furthermore, the proposed mechanism is well identified by the change of morphological state during the course of crystallization of the corresponding east film of Ln-PB TR (92/8) at-60°(Fig. 1).Upon examination of the influence of the number of entanglement on crystallization rate, it reveals the existence of two stages of entanglementation, the primary and the secondary ones (Fig. 19)The equation for dependence of molecular weight and entanglement on bulk crystallization rate has been derived as Eq. 13 or 18 for Ln-PB, and verified by the experimental rate data of well fractionated Ln-PB samples crystallized at -9.1 to -15℃(Fig.20).     

Ion-Pair Solvent Extraction of EDTA Anions with Tetraalkylammonium Ions in Various Organic Solvents

Summary.  The ion-pair solvent extraction behavior of ethylenediaminetetraacetate (EDTA) anion by various tetraalkylammonium ions was investigated at 25.0 ± 0.1°C. The extraction of EDTA exceeded 90% from the basic aqueous solution into the organic solvents such as n-hexane and benzene derivatives containing tri-n-octylmethylammonium chloride, but EDTA was hardly extracted from acidic solution. Among the chemical species of EDTA in aqueous solution, edta ⁴⁻ is the most extractable one. On the other hand, the extraction of EDTA was less than 1% into chloroform and 1,2-dichloroethane even from the basic aqueous solution. The effect of the structure of alkylammonium ion was also examined. Tetra-n-hexylammonium and tetra-n-octylammonium ions could not extract EDTA even from the basic aqueous solution, while the use of tri-n-octylmethylammonium and di-n-lauryldimethylammonium ions enhances the extraction of EDTA. These results suggest that the steric hindrance in the ion-pair of alkylammonium and EDTA anion in the organic phase affects the extractability of EDTA containing ion-pair. The solution structure of ion-pair in the organic phase was calculated by MMFF force field and the steric effect in the ion-pair was also suggested. From the extraction constants obtained, the possibility of the extraction separation of EDTA has been shown. Present address: Chemistry Department, Heilongjiang University, Harbin, China     

Automated site-directed drug design: An assessment of the transferability of atomic residual charges (CNDO) for molecular fragments

Summary In this paper a database of atomic residual charges has been constructed for all the molecular fragments defined previously in a combinatorial search of the Cambridge Structural Database. The charges generated for the atoms in each fragment are compared with charges calculated for whole molecules containing those fragments. The fragment atomic charges lie within 1 S.D. of the mean for 68%, and within 2 S.D. for 91%, of the atoms whose charges were computed for whole molecules. The actual charges on any atom are strongly influenced by the adjacent connected atoms. There is a large spread of atomic residual charge within the fragments database.     

乙基乙酰胺热解反应机理的MO研究

对于烷基乙酰胺的初始热解反应机理, 通常认为与酯类的热解反应相类似。Maccoll和Nagra通过对该热解反应的动力学研究, 认为两者存在不同。差异之一, 烷基乙酰胺存在两种可能的热解途径【参见本文(129页)前述反应方程(1),(2)】。而在酯类热解反应中(2)的活化能过高, 且四元环过渡态极不稳定。差异之二, 极性溶剂(比如乙酸)对酰胺热解反应的催化作用不明显, 而对酯类等气相热解反应的催化作用是十分显著的。为此, 我们用MINDO/3分子轨道法对乙基乙酰胺的初始热解反应进行了较全面的研究。用能量梯度法对此反应的反应物、中间体和生成物的平衡几何构型进行了全优化。(如图1所示)用极小能量途径法分别寻找反应(1)和反应(2)的初始过渡态, 继而用Powell法全优化过渡态的几何构型, 计算所得的过渡态TS1、TS2和TS3分别见图2a, 图3a和图4a。为了确证这些过渡态, 进行了振动分析研究, 结果表明这些过渡态的力常数矩阵的诸本征值中均只有一个负值, 且虚振动模式展示了走向各自的反应物和生成物的趋势, (如图2b,图3b和图4b所示)。它们的总能量及反应(1)和反应(2)的活化能列于表1. 对整个热解反应(1)作了内禀反应坐标(IRC)理论分析, 反应历程见图5所示. 与IRC相应的总能偶极矩以及部分关键的键长和原子净电荷变化一并列于表2.本文研究结果表明, 在乙基乙酰胺的初始反应中主反应即反应(1)与酯类反应相类似, ...     

分子水平上低碳烷烃催化选择氧化的初步研究

烃类选择氧化在石油化工中极其重要.近二十多年来,随着石油化工原料逐步从烯烃、芳烃等不饱和烃向资源丰富和价格相对低廉的烷烃的转化,研究烷烃的氧化活化和定向转化来取代相应的烯烃和芳烃工艺具有非常重要的学术意义和工业价值.因而,烷烃的选择活化和氧化得到了世界范围内的