The structure and properties of 12-heteropolyacid of molybdenum and tungsten (H3PMo6W6O40) solvated by dimethyl ether

The crystal structure of H3PMo6W6O40 3C2H6O was determined by X-ray crystallography and refined to R = 0.0698 based on 2279 observed reflections to give unit cell parameters a = 16.48(2)Angstrom, c = 25.205(5)Angstrom , gamma = 120 degrees, hexagonal, space group R (3) over bar. The organic solvent molecules were characterized also by IR, H NMR spectra. Weak interaction existed between the organic solvent and the heteropoly acid in the secondary structure. The novel compound showed different behaviours in solubility, oxidizability and photosensitivity in comparison with classical dodeca heteropolyacid of molybdenum and tungsten. (C) 1998 Elsevier Science B.V.

4-羟基偶氮苯与6-氯-5,12-萘并萘醌反应产物的NMR分析

无水碳酸钾存在下6-氯-5,12-萘并萘醌与4-羟基偶氮苯在干燥DMF中反应的主要产物在某些反应条件下不是6[4-(苯基偶氮基)苯氧基]-5,12-萘并萘醌(1)。该未知反应产物2经核磁共振方法研究证实是6-(N,N-二甲氨基)-5,12-萘并萘醌。本文对化合物2的~1H-和~(13)C化学位移、偶合信息和结构作了详细归属,并推测其反应进程,实验结果表明,化合物2是由化合物1与溶剂DMF反应生成。

Probe beam deflection combined with cyclic voltammetry studies of C-60-modified electrode film

C-60 films, prepared by solution casting, were studied by means of in situ probe beam deflection (PBD) combined with cyclic voltammetry (CV). PBD is a powerful technique for investigation of phenomena at the electrode/electrolyte interface in acetonitrile with quaternary ammonium and alkali metal salts as supporting electrolytes. In tetra-n-butylammonium (TBA(+)) salt solution, a stable CV can be obtained during the first two reduction/reoxidation waves. On reduction, injection of cations to maintain charge balance and dissolution of small amount of C-60(-) (TEA(+)) and/or C-60(2-) (TBA(+))(2) are detected. During the reoxidation process ejection of cations and injection of anions occur simultaneously, especially for the second reoxidation wave. In the case where TBABr is the supporting electrolyte, the accompanied behavior is more complicated than in TBABF(4), TBAClO(4), and TBAPF(6) solutions. A small pair of prewaves in CV are proposed due to oxidation/reduction of C-60 domains but not dissolution/redeposition of C-60 film. Extending the potential scan range to the third reduction wave, no apparent corresponding reoxidation wave is related to the third reduction wave, the electroactivity of the film disappears rapidly and dissolution of C-60 film is observed. In tetraethylammonium (TEA(+)) and NAClO(4) solutions, the electrochemistry of the C-60 films is unstable, and potential scans lead to dissolution of flaking of the film.

Studies on morphology and crystallization of polypropylene/polyamide 12 blends

Scanning electron microscopy (SEM) and an image analyser are used to study morphologies of the fractured surface, etched by hot phenol, of polypropylene/maleated polypropylene/polyamide 12 PP/PP-MA/PA12) = 65/10/25 blend and PP-MA/PA12 = 75/25 blend. The particle dimension and its distribution of PA12 dispersed phase in these blends are much lower and narrower than that of the PP/PA12. blends. Especially, most of the particles in the PP-MA/PA12 = 75/25 blend are smaller than 0.1 mu m. The effect of the morphology of PP/PA12 blends on their crystallization behaviour is studied using differential scanning calorimetry and SEM. PA12 dispersed phase coarsens during annealing in the PP/PP-MA/PA12 = 65/10/25 blend. The mechanism of coarsening of the PA12 dispersed phase is a coalescence process. The intense mixing between the PP component and the PA12 component through reaction of PP-MA and PA12 leads to a change of dynamic mechanical behaviour of the components. A separation method is used to separate the polyolefin parts (precipitated from hot phenol), from PA12 parts (hot phenol filtrate). Of PP/PP-MA/PA12 = 65/10/25 blend, infra-red measurements and elementary analysis show that the precipitate has a lower PA12 content than the feed, whereas the filtrate has a higher PA12 content. From PP-MA/PA12 = 75/25 blend, PA12 contents in the precipitate and the filtrate are the same as in the feed. This implies that all PA12 has reacted with all PP-MA in the latter case while not in the former case. Using the method of interface exposure, interfacial reaction of PP-MA with PA12 is studied by X-ray photoelectron spectrometry (X.p.s.). Copyright (C) 1996 Elsevier Science Ltd.

Epitaxial crystallization in the sPP/nylon-12 semicrystalline polymer system

The epitaxial crystallization behaviour of syndiotactic polypropylene (sPP) on highly oriented nylon-12 substrates has been investigated by means of transmission electron microscopy. The results obtained from bright field electron microscopy and electron diffraction indicate that sPP crystals grow epitaxially on the oriented nylon-12 substrate with their c-axes +/- 37 degrees apart from the chain axis of the nylon-12 substrate. The contact planes of the sPP crystals are the (100) lattice planes. Moreover, the epitaxial crystallization of nylon-12 on highly oriented sPP substrates from a dilute solution in cyclohexanone has also been studied using optical microscopy. The results show that the nylon-12 crystals grow epitaxially on the oriented sPP substrate with the oriented nylon-12 lamellae forming large, anisotropic domains. Copyright (C) 1996 Elsevier Science Ltd.

LaSrNiO4-lambda with K2NiF4 structure - A highly active catalyst for direct decomposition of nitrogen monoxide

A series of perovskite-like mixed oxides La(2-x)Sr(x)MO(4+lambda) (M=Cu, Co,Ni; x=0,1) was prepared and characterized using X-ray powder diffraction. The catalytic properties of these catalysts in NO decomposition were tested. The results showed that LaSrNiO4-lambda with K2NiF4 structure is very active and stable for the decomposition of NO.

Relationship between the structure and catalytic activity of La2-xSrxNiO4-lambda(0<=x<=1) mixed oxides for NH3 oxidation

A series of samples having the composition of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) were prepared and used as catalysts for NH3 oxidation. It was found that the La and oxygen vacancies exist in the La2-xSrxNiO4-lambda(0 less than or equal to x less than or equal to 1). The unit cell volume decreases with the increase of x. For bath c and a parameters there appeared a turning point at x = 0.5. Doping with a lower valence cation Sr2+ in the case of La2NiO4 resulted in an increase of Ni3+, consequently the formation of oxygen vacancies, the increase of reducing ability and the increase of catalytic activity. In the oxygen TPD of La2-xSrxNiO4(0 less than or equal to x less than or equal to 1) appeared three peaks, the alpha' peak at about 400K was attributed to the surplus oxygen desorption, the a peak at 700K which approaches to a maxium at x = 0.6 was attributed to the oxygen adsorbed at oxygen vacancies. The beta peak at about 1000K which depends closely on the x and favors the catalytic activity was attributed to the reduction of Ni3+. The catalytic activity of La-2-x SrxNiO4 mixed oxides in the NH3 oxidation in general could be attributed to the extent of the redox reaction: 2Ni(2+) + O-2 + V-0(..) reversible arrow 2Ni(3+) + 20(-) where V-0(..) representes the oxygen vacancies and O- the oxygen species adsorbed at the vacancies.

High-yield Synthesis and Extraction of Gd@C-2n

Endohedral metallofullerene Gd@C-2n were synthesized with high-yield using the carbon-arc discharge method of activating the Gd2O3-containing graphite anode in situ and back-burning technique. A series of Gd@C-2n for 2n from 70 to 96 were effectively extracted by toluene at high-temperature and under high-pressure condition. Gd@C-82, Gd@C-74 were considered to be fairly stable and soluble metallofullerene species.

气相酯化反应的高效催化剂──活性炭固载的杂多酸（HPA／C）

在气－固反应体系中研究了固载在活性炭上的硅钨（ＳｉＷ_（１２））和磷钨（ＰＷ_（１２））杂多酸在合成乙酸乙酯和乙酸丁酯中的催化性能。实验结果表明，反应温度、空间速度和反应物的配比均对催化活性有明显影响，并且，负载催化剂表面酸量与酯化反应活性之间存在着相应的顺变关系。催化剂在较低反应温度和相当大的流速下具有较高的酯化活性，且性能稳定，有一定的应用前景。

STUDIES ON STATES OF CYTOCHROME-C MOLECULES IN AQUOUS SOLUTIONS USING SYNCHRONOUS FLUORESCENCE SPECTROSCOPY

The states of cytochrome C molecules in aquous solution were studied with synchronous fluorescence spectroscopy, It was found that the synchronous fluorescent spectra of cytochrome C were contributed by tyrosine and tryptophan residues separately at Delta lambda = 20 nm and Delta lambda = 80 nm, The peak position in synchronous fluorescent spectra of tyrosine residues in cytochrome C molecule does not change with its concentration, but that of tryptophan residue changes with its concentration, Only one peak at 340.0 nm was observed in the dilute solution of cytochrome C, With increasing the concentration of cytochrome C, a new peak at 304. 0 nm appeared. The peak at 340.0 nm disappeared and only one peak at 304.0 nm was observed at a higher concentration of cytochrome C, It may originate from the change of aggregation states of cytochrome C molecules and it was considered that the peak at 340.0 nm was attributed to the monomer and peak at 304.0 nm was due to the dimmer or oligomers. When urea was added into cytochrome C solution in which both monomer and dimmer or oligomers exist, cytochrome C molecules do not denature in the range of the specific concentrations of urea. The concentration of monomer of cytochrome C molecules increased and that of aggregation slates decreased by adding urea, Therefore, the synchronous fluorescence spectroscopy can be used to identify monomer and aggregation states of cytochrome C molecules.

用同步荧光光谱法定量测定细胞色素C

采用同步荧光光谱技术研究了细胞色素C(Cyt C)的同步荧光光谱特性,发现在波长差Δλ=20nm时表现为酪氨酸(Tyr)残基的荧光峰,在Δλ=80nm时为色氨酸(Try)残基的荧光峰。同时考察了浓度对Cyt C同步荧光光谱的影响,为Cyt C的定量测定打下基础。

细胞色素C的电化学行为研究

本文评述了细胞色素C电化学研究的发展概况,重点介绍了细胞色素C在促进剂作用下的电化学行为、促进荆种类、影响促进作用的因素及促进机理。

促进剂与细胞色素c中赖氨酸残基相互作用的研究

促进剂与细胞色素ｃ中赖氨酸残基相互作用的研究曲晓刚，菊，周成立，陆天虹，董绍俊（中国科学院长春应用化学研究所，电分析化学开放实验室，长春，１３００２２）关键词细胞色素ｃ，促进剂，同步荧光光谱Ｈｉｌｌ小组［１］发现４，４＇－联吡啶能促进细胞色素ｃ（ｃｙ...

谷胱甘肽与稀土离子作用的~(13)C NMR研究

本文利用顺磁稀土离子的诱导化学位移变化的性质,研究了多官能团配体谷胱甘肽(GSH)与稀土的配位作用.在水溶液中GSH通过分子两端的羧基负离子与稀土形成遥爪配位结构.谷氨酸端和甘氨酸端羧基与Eu~(3+)的配位稳定常数分别为12.5±0.1L/mol和100.0±0.5L/mol.从~(13)C化学位移的pH变化曲线求得谷氨酸端和甘氨酸端羧基解离的pK_a值分别为2.20±0.02和3.50±0.04.对Dy~(3+)、Ho~(3+)、Er~(3+)、Tm~(3+)和 Yb~(3+)作用下,GSH的~(13)C位移数据分析表明,配体与这些离子形成同构的配合物,分子两端羧基均可能以双齿形式与稀土配位.