Preparation and electrochemistry of azobenzene self-assembled monolayers on gold--long range tunneling and end-group hydrogen bonding effect

A series of thiol-functionalied azobenzene derivatives (RAzoCnSH: R=H for n=3-6, abbreviated as AzoCnSH; R=CH(3)CONH for n=4, abbreviated as aaAzoC4SH) on gold electrodes were prepared and their self-assembly and electrochemical properties were studied by cyclic voltammetry. They all formed uniform and reproducible self-assembled monolayers (SAMs) on gold and showed well-behaved voltammetric responses in aqueous solution. Both the length of the alkyl chain spacer and the H-bonding of the end acetamino group had effects on the stability and the electrochemical kinetics of the SAMs, and the effect of the H-bonding was dominant. The surface coverage of the SAMs (AzoCnSH) is gradually increased with an increase of the alkyl chain spacer length, whereas the presence of the terminal acetamino group leads to a greater increase of the surface coverage. At a low scan rate, voltammetric responses corresponding to an irreversible two-electron, two-proton reduction/oxidation of the trans-azobenzene redox center were obtained in the range of +300 mV and -800 mV, which exhibited very large peak-to-peak splitting. At a high scan rate of 500 mV/s, two steps of reversible one-electron, one-proton reduction/oxidation corresponding to the cis-isomer in azobenzene-thiol SAMs (n is odd) was clearly observed between +300 and -200 mV. The apparent electron-transfer rate is decreased with increasing distance between the azobenzene redox center and the gold electrode. The existence of the end acetamino group which restricted the conformational change during the redox process also led to a decrease of the standard rate constant, and this restriction effect is more predominant than the distance effect.     

N－亚硝基化合物的结构／致癌活性的三维构效关系研究

用比较力场分析研究了Ｎ－亚硝基化合物的结构与致癌活性的关系，考察了网络结构和探针原子对结果的影响．结果表明，立体效应和静电作用场是描述其致癌活性和进行结构性能关系研究的最重要的结构参数。     

Theoretical investigation of the decarbonylation of acetaldehyde by Fe+ and Cr+.

We report a comprehensive theoretical study on the decarbonylation of acetaldehyde by Fe+ and Cr+. Various intermediates, transition states, and products involved in the decarbonylation reactions are fully optimized at the B3LYP/6-311+G(2df,2pd) level of theory. The potential energy surfaces (PESs) corresponding to [M,O,C2,H4]+(M=Cr and Fe) are examined in detail using B3LYP and CCSD(T) methods, respectively. The validity of these theoretical methods is calibrated with respect to the available thermochemical data. Calculations suggest that the Cr+ mediated decarbonylation of acetaldehyde takes place in four steps on the sextet surface: encounter complexation, C-C activation, aldehyde H-shift, and nonreactive dissociation, in good accordance with the Co+ mediated decarbonylation of acetaldehyde [Zhao, Zhang, Guo, Wu, Lu, Chem. Phys. Lett. 2005, 414, 28], while for the Fe+/acetaldehyde system decarbonylation can occur on both the quartet and the sextet PESs. The quartet pathway, which experiences spin-orbit coupling between the two surfaces, is energetically more favorable; whereas along the sextet decarbonylation coordinate several high-energy barriers are revealed. The theoretical results are compared with the experimental product kinetic energy and angular distributions of decarbonylation of acetaldehyde by Fe+ and Cr+ measured using a crossed-beam technique [Sonnenfroh, Farrar, J. Am. Chem. Soc. 1986, 108, 3521].     

Mesoporous silica nanospheres with the ability of photo-driven releasing sandela 803 for the application to wallpaper

Mesoporous silica nanospheres loaded with sandela 803 (S803@MS-S) are prepared for application to wallpaper. The nano-fragrance has high encapsulation efficiency and property of photo-driven release.     

流动注射化学发光法测定甲氨蝶呤

研究了甲醛增强高锰酸钾与甲氨蝶呤的化学发光反应，由此建立了一种测定甲氨蝶呤的流动性注射化学发光分析法，方法的检出限为３．４×１０＾－９ｇ／ｍＬ，相对标准偏差为１．１％（２．０×１０＾－６ｇ／ｍＬ甲氨蝶呤，ｎ＝１１）线性范围为１．０×１０＾－８～１．０×１０＾－５ｇ／ｍＬ。该法已用于甲氨蝶呤针剂及片剂中甲氨蝶呤含量的测定。     

Mo－Cu－S原子簇化合物［Mo_2Cu_6S_6（SCMe_3）_2（O）_

基于标题簇合物的快原子质谱研究，提出该二簇合物在质谱过程中的可能断裂途径及其簇骼转换的相关性。     

Electrochemical reduction and voltammetric determination of metronidazole at a nanomaterial thin film coated glassy carbon electrode

Simple and sensitive electrochemical method for the determination of metronidazole, based on a nanostructured film coated glassy carbon electrode (GCE), is described. Multi-walled carbon nanotubes (MWNT) was dispersed into water in the presence of a hydrophobic surfactant to give very stable and homogeneous MWNT suspension, and a MWNT-film coated GCE was achieved via evaporating solvent. Metronidazole yields a well-defined reduction peak whose potential is −0.71 V at the MWNT-film coated GCE in pH 9.0 Britton-Robinson buffer. Compared with bare GCE, the MWNT-film modified GCE significantly enhances the reduction peak current of metronidazole. All the experimental parameters were optimized for the determination of metronidazole. The detection limit is 6×10⁻⁹ mol/l at 2 min accumulation. This method has been successfully used to determine metronidazole in the drugs. Furthermore, results obtained by the proposed method have been compared with spectrophotometric method.     

微波照射合成不对称1，4－二氢吡啶的研究

微波照射合成不对称１，４－二氢吡啶的研究张雅文，沈宗旋，潘备，杨海康，陆新华，陆澄容（苏州大学化学系苏州２１５００６）关键词缩合，二氢吡啶，微波Ｈａｎｔｚｓｃｈ合成是制备１，４－二氢吡啶的经典方法。这一合成的改进方法之一是３－氨基巴豆酸酯与醛和乙酰乙...     

液相色谱专家系统中柱系统推荐规则的建立和验证

把分子结构和分子、离子静电作用力作为影响溶质保留值和选择性的基本点,提出了液相色谱专家系统柱系统推荐的基本规则,由此可以从溶质所包含的基团或官能团的信息进行色谱柱系统推荐。为了验证这些规则的正确性,应用几类常用的或典型的样品从分子结构通道进行液相色谱柱系统推荐,获得满意的结果。