猪胰岛素的活力位置的电子结构分析

本文采用负因子计数方法对猪胰岛素分子作了完整分子的量子化学计算,其中对矩阵元的计算采用EHMO方法。我们将前线轨道的概念推广为靠近Fermi能级的能量区域中的分子轨道,将局域于少数氨基酸残基上的前线轨道简称为活性轨道。计算结果表明,猪胰岛素70％的活力敏感位置上局域有活性轨道。对全部结果的分析说明猪胰岛素的活性轨道和生物活力之间存在某些内在联系,但不是一一对应关系;猪胰岛素的三级构象的变化可以引起电子结构的变化;相同种类的氨基酸残基在分子的不同位置上可以有不同的活性轨道能级和轨道分布。     

A study of metals supported on active carbon with a temperature programmed reduction (TPR) technique

The influence of active carbon as support on the reducibility of supported metals (Ni, Cu, Cd, Zn) has been studied by means of a temperature programmed reduction (TPR) technique. The TPR profiles indicate that active carbon behaves as a dispersion agent and the supported metal is dispersed in a disordered phase rather than as a stoichiometric compound. The hydrogen consumed in the reduction indicates that the metal residues are present in monovalent and divalent forms. High-temperature reduction peaks were also observed and are explained on the basis of metal-surface interactions and the porosity of the active carbon. Nitrogen adsorption reveals that the active carbon porosity decreases due to progressive closure of the pores when metals are supported on the surface of active carbon.     

纳米Ni－B非晶态合金的催化性质研究

纳米Ｎｉ－Ｂ非晶态合金的催化性质研究杨军,崔黎丽,邓景发（复旦大学化学系,第二军医大学药学院,上海,２００４３３）关键词纳米材料,非晶态合金,催化性质纳米非晶材料融合了纳米晶与非晶材料的特性,既有很高的表面原子比,又呈高度几何无序状态。与普通非晶材料...     

Modeling Steroid 5alpha-reductase and Characterizing Its Potential Active Sites

Steroid 5alpha-reductase of human is an enzyme in the biosynthetic pathway from testosterone (T) to dihydrotestosterone (DHT). Up to now, no crystal structure of this enzyme has been reported. However, knowledge of the tertiary structure and possible active sites is essential for understanding the catalysis mechanism and for the design of inhibitors. A model with putative active sites has been created and evaluated by using homology modeling and molecular docking techniques based on the bioinformatics knowledge. The homology model is optimized in Swiss PDB Viewer with MM method and substrate structures before docking are also optimized on HF/6-31G. The active site for the docking of NADP, T, DHT and Finasteride is located near the N-terminus of enzyme. Four active amino acids in the active site are identified as Ala26, Arg53, Arg176 and Lys177. Reaction procedure, binding pattern of active sites, the types of weak interaction and so on are also discussed.     

Oxidative Dehydrogenation on Nanocarbon: Intrinsic Catalytic Activity and Structure–Function Relationships

Physical and chemical insights into the nature and quantity of the active sites and the intrinsic catalytic activity of nanocarbon materials in alkane oxidative dehydrogenation (ODH) reactions are reported using a novel in situ chemical titration process. A study on the structure–function relationship reveals that the active sites are identical both in nature and function on various nanocarbon catalysts. Additionally, the quantity of the active sites could be used as a metric to normalize the reaction rates, and thus to evaluate the intrinsic activity of nanocarbon catalysts. The morphology of the nanocarbon catalysts at the microscopic scale exhibits a minor influence on their intrinsic ODH catalytic activity. The number of active sites calculated from the titration process indicates the number of catalytic centers that are active (that is, working) under the reaction conditions.     

等离子体聚合成膜中的活性粒子模拟分析

针对等离子体聚合成膜实验中的活性粒子的能量及空间分布问题,运用电磁场理论和Ｍｏｎｔｅ Ｃａｒｌｏ方法模拟分析氢、氧、氮直流辉光放电等离子体中的活性粒子的运动,得出其能量分布图和空间密度分布图,并与离子活性能量范围相比较,从而得出结论：在氢、氧等离子体中有足够多的活性离子可以参与和单体分子的物理化学反应,成膜较快;在氮等离子体中,达到活性粒子能量范围的离子相当少,成膜较慢。     

Active Centers for the Stereospecific Polymerization of Methyl Methacrylate by Organomagnesium Compounds

New evidence on the polymerization kinetics of methyl methacrylate and molar mass distributions is presented which together with earlier work on the stereochemistry of the polymerization of α,β-dideuteroacrylates shows that these are not typical anionic polymerizations. The persistence and stability of the active centers, together with evidence that the α-carbon of the monomer assumes the tetrahedral configuration it takes in the polymer chain as it becomes the active chain end, suggests that the active centers are covalent magnesium-carbon bonds. Existing hypotheses about the mechanism of steric control in homogeneous polymerizations are examined. Kinetic evidence confirms that complexing of the monomer to the active center does occur. However, intramolecular complexing of the penultimate or antepenultimate chain carbonyl group to the metal is not a prerequisite for isotactic polymerization though it may be involved in controlling the in-chain configuration of the β-carbon. Gel-permeation chromatography shows that in some systems more than one active center operates independently. These centers are established in the initiation stages and persist. The proportions of active centers of different reactivity and stereo-specificity are determined by conditions prevailing during initiation and it is these that primarily determine the structure of the polymers formed. Evidence is reported that confirms this.     

On the choice of active space orbitals in MCSCF calculations

We describe a procedure which may be used to aid selection of the active space in multiconfigurational self-consistent field (MCSCF) calculations for general chemical systems. Starting from a restricted Hartree-Fock calculation, we define a hierarchy of interacting virtual orbitals for every occupied orbital. The most strongly interacting orbitals are then taken to constitute the active space in a configuration interaction (CI) calculation. The natural orbital occupation numbers obtained from the CI calculation are then used to choose the active space to be used in a subsequent MCSCF calculation. We illustrate our method on a number of systems (Li₂, B₂, C₂, carbonyl oxide and the transition state for oxidation of H₂S by dioxirane). In all these cases, ‘intuitive’ active spaces are inadequate, as are active spaces derived from the natural orbitals of unrestricted Hartree-Fock calculations.     

1-辛烯Ziegler-Natta聚合的活性中心多分散性——分子量分布及动力学的研究

本文通过对TiCl_3-Al(C_2H_5)_3聚合1-辛烯产物的双峰型分子量分布曲线用Schulz函数进行拟合、分峰处理,发现这种双峰型分布中的高分子量峰部分由一种活性中心生成,低分子量峰部分则由至少两种活性中心生成.将不同转化率时聚辛烯的分子量分布分峰拟合数据与聚合速率、活性中心数等测定数据相结合,得到了高分子量和低分子量两部分产物相应的活性中心上各自的动力学参数(增长速率常数、活性中心数、链转移常数等)及各自的聚合速率曲线,从而证实了多种活性中心的存在、它们催化特性的差异及与聚合物分子量分布增宽的关系.     

Catalysis by gold dispersed on supports: the importance of cationic gold

There are many examples of catalysis in solution by cationic complexes of gold, and recent results, reviewed here in this critical review, demonstrate that cationic gold species on oxide and zeolite supports are also catalytically active, for reactions including ethylene hydrogenation and CO oxidation. The catalytically active gold species on supports are evidently not restricted to isolated mononuclear gold complexes, but include gold clusters, which for at least some reactions are more active than the mononuclear complexes and for some reactions less active. Fundamental questions remain about the nature of cationic gold in supported catalysts, such as the nature of the cationic gold clusters and the nature of gold atoms at metal-support interfaces (88 references).     

Ni2P加氢脱硫催化剂

环境法规对硫氧化物脱出的限制日益严格以及原油品质的不断下降,使得有必要研发高效的加氢脱硫催化剂。Ni2P由于具有优异的加氢脱硫活性和稳定性,引起了广泛的关注。本文综述了Ni2P加氢脱硫催化剂的特性、反应活性相、制备方法、改进和加氢脱硫活性等方面的研究进展。在Ni2P中存在两种不同的初始活性位,四面体几何构型的Ni(1)初始活性位在加氢脱硫反应中参与直接脱硫反应,四方锥几何构型的Ni(2)初始活性位则与催化剂的高加氢活性有关。在加氢脱硫反应中,催化剂表面生成的NixSyP相被认为是真正的活性相。制备Ni2P的方法主要是程序升温还原和液相合成。载体、助剂和络合剂对Ni2P活性相的形成和催化剂的活性有重要影响。相比于商用硫化物催化剂,Ni2P催化剂对噻吩、二苯并噻吩和4,6-二甲基二苯并噻吩均表现出更高的加氢脱硫活性。     

Diffusion-influenced reactions of particles with several active sites

The main concern of the present work is consideration of sterically specific liquid-phase reactions in the case where one of the reactants has several active sites. In kinematic approximation we derived compact formulas for partial rate constants of individual active sites. Reaction rates are expressed via the kinetic rate constants and convolutions of the free Green functions over reaction zones. These results are valid for arbitrary geometry of reactants and active sites. Effects of mutual influence of the active sites were studied, their simple estimate was proposed.     

Microarray‐Based Detection of Dye‐Labeled DNA by SERRS Using Particles Formed by Enzymatic Silver Deposition

The growing interest in DNA diagnostics is addressed today by microarrays with fluoresence detection. In our approach, we utilize spatially defined arrays of short oligonucleotides on a modified glass surface. Surface enhanced resonance Raman scattering (SERRS) is used to obtain molecularly specific spectra of the Raman‐active dye‐labeled DNA. Nanoparticles produced by enzymatic silver deposition are used as SERS‐active substrate. They grow directly on the modified oligonucleotides and only in the spatially defined areas on the chip. Furthermore, they potentially offer several advantages for SERS detection. The nanoparticles are characterized and their ability for use as SERS‐ and SERRS‐active substrate is estimated. Three different Raman‐active dyes are investigated for their potential for involvement in sequence specific DNA analysis.     

Computer simulation of active layers in the electric double layer supercapacitor: Optimization of active layer charging modes and structure,calculation of overall characteristics

The structure and functioning modes of active layers in an electric double layer capacitor (EDLC) with an aqueous electrolyte are simulated by means of a computer. A model of active layers prepared from activated carbon materials is proposed, percolation estimates are performed and effective ionic conductivities are calculated. The polarization of active layers includes a sequence of two charging processes: first, galvanostatic and then potentiostatic. The proposed program of calculations involves mutual matching and optimization of seven parameters characterizing the active layer and conditions of charging processes. According to calculations, galvanostatic polarization of wide pores in the EDLC biporous active layer up to the limiting potential followed by potentiostatic polarization of fine pores allows the capacity C _sp = 246 F/g and the energy W _sp = 107 kJ/kg to be obtained in fractions of second.     

Binary Mixtures in Linear Convection Arrays

We numerically investigated the dynamics of a mixture of finite-size active and passive disks in a linear array of two-dimensional convection rolls. The interplay of advection and steric interactions produces a number of interesting effects, like the stirring of a passive colloidal fluid by a small fraction of slow active particles, or the separation of the mixture active and passive colloidal fractions by increasing the motility of the active one, which eventually clusters in stagnation areas along the array walls. These mechanisms are quantitatively characterized by studying the dependence of the diffusion constants of the active and passive particles on the parameters of the active mixture fraction.     

1-辛烯Ziegler-Natta聚合的活性中心多分散性——分子量分布及动力学的研究

 本文通过对TiCl₃-Al(C₂H₅)₃聚合1-辛烯产物的双峰型分子量分布曲线用Schulz函数进行拟合、分峰处理,发现这种双峰型分布中的高分子量峰部分由一种活性中心生成,低分子量峰部分则由至少两种活性中心生成.将不同转化率时聚辛烯的分子量分布分峰拟合数据与聚合速率、活性中心数等测定数据相结合,得到了高分子量和低分子量两部分产物相应的活性中心上各自的动力学参数(增长速率常数、活性中心数、链转移常数等)及各自的聚合速率曲线,从而证实了多种活性中心的存在、它们催化特性的差异及与聚合物分子量分布增宽的关系.     

Optimizing Weights of Platinum in the Active Layer of the Cathode of a Hydrogen–Oxygen Fuel Cell with a Solid Polymer Electrolyte

The active layer of the cathode of a hydrogen–oxygen fuel cell with a solid polymer electrolyte is computer simulated. The active mass of the electrode consists of substrate grains (agglomerates of carbon particles with Pt particles embedded into them) and grains of a solid polymer electrolyte (Nafion). The substrate grains presumably contain hydrophobic pores, which facilitate the oxygen penetration into the active mass. A calculation of characteristics of such an electrode focuses on the optimization of platinum weights. The principal parameters of the system are concentration and size of grains of substrate and Nafion, Pt concentration in substrate grains, average diameter of hydrophobic pores in substrate grains, and the electrode polarization. The optimum, at a given electrode polarization, electrochemical activity of the active layer, its thickness, and the platinum weight are calculated. A link between these quantities and principal parameters of the active layer is revealed.