Synthesis,structure and stereochemistry of diiodide complexes (E)[(η5-t-BuC5H3)Fe(CO)2I]2 (E = Me2Si,Me2SiSiMe2, and Me2SiOSiMe2)

Reactions of diiron complexes (E)[⁵-t-BuC₅H₃)Fe(CO)]₂(-CO)₂ [E = Me₂Si (1), Me₂SiSiMe₂ (2), and Me₂SiOSiMe₂ (3)] with iodine in CHCl₃ yielded diiodide complexes (E)[⁵-t-BuC₅H³)Fe(CO)₂I]₂ [E=Me₂Si (5), Me₂SiSiMe₂ (6), and Me₂SiOSiMe₂ (7)]. Like (1–3), complexes (5–7) also exists as mixtures of cis and trans isomers even though the Fe–Fe bond in (1–3) has been cleaved. When the pure isomers (1–3) reacted with iodine respectively in CHCl₃, the cis isomers (1c–3c) yielded only the cis products (5c–7c), whereas the trans isomers (1t–3t) yielded only the trans isomers (5t–7t). This indicates that iodination of bridged diiron complexes is stereospecific. Similar treatment of trans-(Me₂Si)[{⁵-t-(heptyl)C₅H₃}Fe(CO)]₂(-CO)₂ (4t) with iodine gave only the trans product (Me_2Si)[{⁵-t-(heptyl)C₅H₃}Fe(CO)₂I]₂ (8t). The molecular structure of (5t) was determined by X-ray diffraction.     

杂原子HMS介孔分子筛的催化脱氢和加氢脱硫性能

ＭＣＭ４１［１］和ＨＭＳ［２］等介孔分子筛对大分子的扩散阻力较小且具有良好的热稳定性,特别是在合成中可以直接将各种杂原子引入骨架,从而调变其催化性能,因此目前介孔分子筛在催化中的应用引起了各国研究者的广泛兴趣．Ｔｉ,Ｚｒ,Ｖ,Ｃｒ,Ｍｎ,Ｃｕ和Ｆｅ...     

Capacity of Bacillus thuringiensis S-layer protein displaying polyhistidine peptides on the cell surface

S-layer protein of Bacillus thuringiensis strain CTC was used as the carrier protein to display polyhistidine (poly[6His]) peptides on the cell surface. Poly(6His) _n was fused with S-layer protein at two different sites, inserting just downstream of the S-layer protein homologous domain (slh) and replacing the non-slh region of S-layer protein, respectively. The two series chimeric proteins were both expressed by crystal negative B. thuringiensis strain 4Q7 and strain 171, respectively, as shown by sodium dodecyl sulfate polyacrylamide gel electrophoresis. The recombinant B. thuringiensis cells gained Ni²⁺- and Cd²⁺-binding ability and had a capacity to display up to nine copies of poly(6His). The Cd²⁺ adsorption quantity of the recombinant strain with the strongest adsorption ability was twice that of the host strain.     

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     

雪松烯的光氧化反应研究

以次甲基兰为光敏剂, 甲醇为溶剂, 用通氧光照产生的单重态氧与雪松烯反应,产物只有一种。用元素分析、红外光谱。核磁共振谱、质谱以及高压液相色谱等方法测定了产物的分子结构。并讨论了光氧化反应的动力学控制和立体效应。     

六氟丙烯等离子体聚合机理研究

<正> 在以前的工作中,我们曾应用色谱-质谱(GC-MS)及顺磁共振(ESR)等方法研究了四氟乙烯和三氟氯乙烯等离子体聚合过程中气体冷凝物的组成及结构,提出自由基引发聚合反应机理。本文用类似方法研究六氟丙烯(HFP)等离子体气体冷凝物的组成与结构和冷凝物的ESR信号及其从低温到高温的变化规律,证实了自由基的稳定性并提出气相聚合反应机理。     

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.     

Simultaneous Determination of Dopamine and Ascorbic Acid at a Triazole Self-Assembled Monolayer-Modified Gold Electrode

A 3-amino-5-mercapto-1,2,4-triazole (TA) self-assembled monolayer-modified gold electrode (TA SAM/Au) is characterized by X-ray photoelectron spectroscopy, A.C. impedance, cyclic voltammetry, chronoamperometry and chronocoulometry. The TA SAM/Au exhibited good promotion of the electrochemical oxidation of dopamine. Some electrochemical parameters of dopamine such as electron transfer number, exchange current density, standard heterogeneous rate constant, diffusion coefficient, etc., were measured by different electrochemical methods. The peak currents of dopamine were linearly dependent on its concentration in the range of 1.5 × 10⁻⁶–1.0 × 10⁻⁴ mol L⁻¹, with a detection limit of 5.0 × 10⁻⁷ mol L⁻¹. The oxidative peak potentials of dopamine and ascorbic acid were well separated at about 190 ± 10 mV in pH 2.0 BR buffers at TA SAM/Au, the oxidation peak current increases approximately linearly with increasing concentration of both dopamine and ascorbic acid in the concentration range of 9.98 × 10⁻⁶–4.54 × 10⁻⁴ mol L⁻¹. It can be used for simultaneous determination of dopamine and ascorbic acid.     

Ritter Reaction of 1‐Aryl‐1‐Fluoro‐2‐Haloethanes

Fluorinated phenethyl bromides 1,2 , and 3 , prove to be totally inert under Ritter reaction conditions in the presence of either SnCl₄ or AgNO₃, due to the strong deactivation by the gem‐difluoro unit. Subjecting 2‐bromo‐1‐fluoro‐1‐phenylethane to SnCl₄ in MeCN at elevated temperatures led to formation of 2‐methyl‐4‐phenyl‐4,5‐dihydrooxazole.     

Synthesis and Crystal Structure of Complex of Sodium Perrhenate with Tetraethyl p-tert-Butylcalix[4]arene Tetraacetate

Recently,theconformationofthecalixarenehasbeenshowntobeimportantincontrollingtheseIectivityofthereceptor.Forexample,sodiumioncouldbeboundverystronglybyesterderivativesofcalix[4]areneintheconeconformationl.Wehavefoundthatinthepresenceofcertainamountofsodiumion,microamountofReO4-canbequantitativelyextractedintol,2-dichloroethanebytheligandtetraethylp-tert-butylcalix[4]arenetetraacetate(L).ItshowsthatthepresenceofNa inaqueoussolutioncanpromotetheformationofhydrophobiccomplex[NaL] .ReO'-whichc…