Biopolymer and carbon nanotubes interface prepared by self-assembly for studying the electrochemistry of microperoxidase-11

Stable films of biopolymer chitosan and carbon nanotubes were prepared by a layer-by-layer self-assembly technique. Atomic force microscopy, scanning electron microscopy, cyclic voltammetry, and UV-vis spectroscopy were used to characterize the film assembly. Atomic force microscopy and scanning electron microscopy showed that an even, stable film was formed. The UV-vis spectroscopy and cyclic voltammetry study indicated the uniform growth of the film. The property of the self-assembled multilayer film in promoting protein electron transfer was demonstrated by incorporating microperoxidase-11 in the film. Microperoxidase-11 in the multilayer film could transfer electrons with the electrode indicating that carbon nanotubes could wire the protein to the electrode. The electrocatalytic activity of the microperoxidase-11 containing multilayer film-modified electrode toward H(2)O(2) and O(2) was investigated. The results showed that along with the increase in the assembled layers the electrocatalytic reduction potentials of H(2)O(2) and O(2) shifted positively. The prepared multilayer film of chitosan and carbon nanotubes containing protein was a sensitive interface for electrocatalytic study.     

Synthesis, structure and fluorescence of a novel diarylethene

The photochromic diarylethene, 1,2-bis(2-methyl-5-(2-(1,3-dithiolpentane))-thien-3-yl)perfluorocyclopentene (BMDTP), has been synthesized in high yield and its structure was determined by X-ray crystallographic analysis. The compound undergoes a photochromic reaction both in solution and in the single crystalline phase. In addition, its fluorescence property in solution is discussed.     

电沉积AuInSe2半导体薄膜上的电化学振荡现象

研究了电沉积制得的ＡｕＩｎＳｅ２半导体薄膜上过氧化氢阴极还原过程中产生的电化学振荡行为，对影响该振荡行为的一些因素如半导体薄膜的后处理、溶液组成、传质、光照、化学浸渍作用等进行了分析，同时采用外界周期性光照和外接小幅度正弦波电位来调节振荡频率，为金铟硒半导体薄膜发展成为光电传感器件提供了一定的理论与实践基础．     

Homogeneous rare earth coordination catalysts for copolymerization of styrene with acrylonitrile

The study on homogeneous rare earth coordination catalysts, LnL₃-Al(i-Bu)₃-CCl₄, for the copolymerization of styrene with acrylonitrile has been successfully carried out for the first time. Some features and kinetic behavior of copolymerization of styrene with acrylonitrile by Nd(P₂₀₄)₃-Al(i-Bu)₃-CCl₄ system are described. The catalyst sites appear to possess both coordinate anionic and free radical characteristics. The catalytic activity of various rare earth elements in Ln(P₂₀₄)₃ and ligands in NdL₃ for the copolymerization have the following order, respectively: Yb > Er > Tb ～ Tm > Ho > Ce > Lu ～ Sm ～ La > Pr > Nd, and Nd(naph)₃ > Nd(P₂₀₄)₃ ～ Nd(P₅₀₇)₃ > Nd(acac)₃·3H₂O. An alternating-rich copolymer of styrene-acrylonitrile with a high softening point (195–230°C) was obtained by the LnL₃-Al(i-Bu)₃-CCl₄ systems in toluene at 80°C.     

二苯并噻吩亚砜的单晶结构及其π-π堆积作用理论研究

采用X射线衍射法测定二苯并噻吩亚砜单晶结构,发现晶体中二苯并噻吩亚砜分子以反平行三明治式的结构Ⅲ和反平行位移式的结构Ⅳ两种堆砌方式交替堆砌形成有序π-π堆积晶体。二苯并噻吩亚砜单晶结构属于三斜型,空间群为P1,晶体参数为:a=0.84712nm,b=0.94137nm,c=1.20380nm,α=97.866°,β=106.2630°,γ=96.437°,V=0.9014nm3,R1(全部数据)=0.0348和ωR2(全部数据)=0.0814。利用BHandH/6-31 G**方法计算了二苯并噻吩亚砜分子间的π-π堆积作用,Ⅲ和Ⅳ堆砌模式的π-π堆积效应作用能相当大,其计算值分别为-36.06kJ/mol和-39.83kJ/mol,电荷分布表明正负电荷匹配是稳定晶体π-π堆积体系的重要因素。     

Improving MCM‐41 as a Nitrosamines Trap through a One‐Pot Synthesis

Copper oxide was incorporated into MCM‐41 by a one‐pot synthesis under acidic conditions to prepare a new mesoporous nitrosamines trap for protection of the environment. The resulting composites were characterized by XRD, N₂ adsorption–desorption, and H₂ temperature‐programmed reduction techniques, and their adsorption capabilities were assessed in the gaseous adsorption of N‐nitrosopyrrolidine (NPYR). The adsorption isotherms were consistent with the Freundlich equation. The copper salt was deposited onto MCM‐41 during the evaporation stage and was fixed on the host in the calcination process that followed. MCM‐41 was able to capture NPYR in air below 373 K but not at 453 K. Loading of copper oxide on MCM‐41 greatly improved its adsorption capability at elevated temperatures. The influence of the incorporation of copper into MCM‐41 samples and the adsorption behavior of these samples are discussed in detail.     

固定波长同步荧光光谱参数的理论计算

基于荧光激发光谱和发射光谱对波长呈高斯分布的设定,本文推导出固定波长同步荧光光谱峰峰值位置、相对强度和半峰宽度等3个主要光谱参数的理论计算式。所提出的计算式应用于若干荧光物质光谱参数的计算,并和实测值、文献计算值作了对照。结果表明,和文献计算方法相比,本法与所研究物质的实际光谱参数较为接近,可为固定波长同步荧光光谱参数的理论计算提供一有效方法。     

希土元素与三甲胺氧化物配合物的制备及光谱性质

尽管文献报道了三甲胺氧化物与Mn、Co、Ni、Zn、Cd、Cu等多种离子在有机溶剂中形成较稳定的配合物。但对其金属配合物的研究远不如芳香族杂环化合物那样引起人们广泛的注意。本文研究了它与希土元素形成配合物的合成和光谱性质。     

γ-irradiation of polypropylene in vacuum and in air

Polypropylene films were irradiated with ⁶⁰Co γ-rays in vacuum or in air and stored in air. Just after irradiation, the concentration of carbonyl group of the sample irradiated in air only increased with dose. The concentrations of both samples increased with storage time. The more the absorbed doses, the higher the increasing rates. The increasing rate of the concentration of carbonyl group during irradiation in air was higher than those during storage in air. Just after irradiation, the tensile strengths and the elongations of the both samples somewhat increased with dose at the doses less than 5 Mrad, but decreased at doses more than 13 Mrad. The tensile strength and the elongation of the sample irradiated in air decreased with storage time. Those of the sample irradiated in vacuum also decreased with storage time but the decreasing rates were much smaller than those in the sample irradiated in air. The gel fractions of the samples irradiated in vacuum and annealed in vacuum were somewhat higher than those irradiated in vacuum and not annealed. To elucidate high oxidation rate in the sample irradiated in air during and after irradiation, reaction mechanisms were discussed. To clarify the difference of mechanical properties between the samples irradiated in vacuum and in air, the effect of crosslink was considered, together with the oxidation.     

Investigation on the chain-to-chain and chain-to-open-framework transformations of two one-dimensional aluminophosphate chains

Using ethylenediamine as a template, two one-dimensional (1-D) aluminophosphate compounds [AlP(2)O(8)H][NH(3)CH(2)CH(2)NH(3)] (1) and [AlP(2)O(8)][NH(3)CH(2)CH(2)NH(3)][NH(4)] (2) have been prepared from a gel system: 1.0:x:y:44 Al(i-PrO)(3)-H(3)PO(4)-en-EG (x = 3.0-9.0, y = 1.0-11.0). Compound 1 consists of edge-sharing four-membered ring (MR) chains, denoted as AlPO-ESC, and compound 2 consists of corner-sharing 4-MR chains, denoted as AlPO-CSC. The molar ratio of en:H(3)PO(4) in the starting gel has an important influence on the final product. If en:H(3)PO(4) > or = 1, AlPO-CSC is obtained, while if en:H(3)PO(4) < 1, AlPO-ESC is formed. These two chains can transform to each other upon addition of some extra amount of en or H(3)PO(4) to the reaction mixture in which AlPO-ESC or AlPO-CSC is crystallized. On the basis of XRD and (27)Al and (31)P MAS NMR analyses, a possible chain-to-chain transformation mechanism is proposed. The corner-sharing 4-MR chains of AlPO-CSC, as well as the edge-sharing 4-MR chains of AlPO-ESC can be assembled to 3-D open-framework compound NiAlP(2)O(8).C(2)N(2)H(9) through Ni(2+) cations. It is noted that AlPO-CSC remains in the structure of NiAlP(2)O(8).C(2)N(2)H(9). It is believed that AlPO-ESC might be first transformed to AlPO-CSC followed by the assembly to 3-D open-framework of NiAlP(2)O(8).C(2)N(2)H(9) through Ni(2+) cations.