Sol-gel-derived graphite organosilicate composite electrodes bulk-modified with Keggin-type alpha-germanomolybdic acid

A novel inorganic-organic hybrid material incorporating graphite powder and Keggin-type alpha -germanomolybdic acid (GeMo12) in methyltrimethoxysilane-based gels has been produced by the sol-gel technique and used to fabricate a chemically bulk-modified electrode. GeMo12 acts as a catalyst, graphite powder ensures conductivity by percolation, the silicate provides a rigid porous backbone, and the methyl groups endow hydrophobicity and thus limit the wetting section of the modified electrode. The GeMo12-modified graphite organosilicate composite electrode was characterized by cyclic and square-wave voltammetry. The modified electrode shows a high electrocatalytic activity toward the reduction of bromate, nitrite and hydrogen peroxide in acidic aqueous solution. In addition, the chemically-modified electrode has some distinct advantages over the traditional polyoxometalate-modified electrodes, such as long-term stability and especially repeatability of surface-renewal by simple mechanical polishing.

Oxidation of NADH by dopamine incorporated in lipid film cast onto a glassy carbon electrode

Stable lipid film was made by casting lipid in chloroform onto a glassy carbon electrode. This model of a biological membrane was used to investigate the oxidation of dihydronicotinamide adenine dinucleotide (NADH) by dopamine. After this electrode had been immersed in dopamine solution for 10 h, it was found that some dopamine had been incorporated in the film. The cyclic voltammogram was obtained for the oxidation of 2.0 X 10(-3) mol 1(-1) NADH with dopamine incorporated in the films. All electrochemical experiments were performed in 0.005 mol 1(-1) phosphate buffer (pH 7.0) containing 0.1 mol 1(-1) NaCl without oxygen. The oxidation current increased gradually with successive sweeps and reached steady state. It was a different phenomenon from previous results. The anodic overpotential was reduced by about 130 mV compared with that obtained at a bare glassy carbon electrode. The diffusion coefficient for 2.0 X 10(-3) mol 1(-1) NADH was 6.7 X 10(-6) cm(2) s(-1). (C) 1999 Elsevier Science S.A. All rights reserved.

Syntheses of indenyl lanthanide derivatives and the molecular structures of [(C9H7)(2)PrCl(THF)](2) and [(C9H7)(3)La(THF)]

The reaction of anhydrous PrCl3 with Na(C9H7) in 1.2 mole ratio in THF gives [(C9H7)(2)PrCl(THF)](2)1. 1 crystallized in monoclinic system, space group P2(1)/c with a = 7.808(2), b = 17.796(6), c = 14.070(4) Angstrom, beta = 93.97(2)degrees, V= 1950.3(9) Angstrom(3), Dcalcd = 1.63 g/cm(3) and Z = 2. Each Pr ion is surrounded by two indenyl, two Cl and one THF in a roughly trigonal bipyramid arrangement with average Pr-C(ring) and Pr-Cl distances of 2.81 and 2.84 Angstrom. The reaction of LaCl3 with Na(C9H7) in 1:3 mole ratio gives (C9H7)(3)LaTHF 2, which crystallizes in the monoclinic space group P2(1)/a with unit cell constants a = 21.871(8), b = 10.585(3), c = 23.652(7) Angstrom,beta = 114.62(2)degrees, V = 4977.9 Angstrom(3) and Z = 8. (C) 1997 Elsevier Science S.A.

A STUDY OF CATALYTIC PROPERTIES OF PEROVSKITE-TYPE OXIDES LAMNYCO1-YO3 .1. THE RELATIONSHIP BETWEEN THE TYPE OF OXYGEN SPECIES AND THE CATALYTIC PROPERTY IN AMMONIA OXIDATION

The type of oxygen species in perovskite-type oxides LaMnyCo1-yO3 (y = 0.0, 0.1, 0.3, 0.5, 0.7, 0.9, 1.0) has been studied by means of XRD, XPS and TPD. The catalytic activity in ammonia oxidation was also investigated. It was found that there were three desorption peaks in TPD curve corresponding to three types of oxygen species (alpha, beta, beta'). The desorption temperatures were 293 K less-than-or-equal-to T(alpha) less-than-or-equal-to 773 K, 773 K less-than-or-equal-to T(beta) less-than-or-equal-to K and T(beta') greater-than-or-equal-to 1073 K respectively. The relationship among the composition, structure and the catalytic property of.the catalyst was correlated and could be explainned with a model based on solid defect reaction and the interaction between Co and Mn ions. The adsorption strength and quantity of a oxygen are proportional to the catalytic activity. The, result indicates that the synergetic effect between B-site ions seems to the benefit of the ammonis oxidation reaction.

{[Sm_2(Gly)_6(H_2O)_4](ClO_4)_6(H_2O)_5}_n的合成和晶体结构

本文合成了标题配合物,对其红外光谱进行了研究.测定了配合物的晶体结构,结果表明,晶体属三斜晶系,P1空间群,单胞参数:α=11.549(2)(?),b=14.122(3)(?),c=15.654(?),α=97.01(2)°,β=102.70(2)°,γ=105.43(2)°,V=2355.94(0.87)(?)~3,Z=2.晶体结构是采用Patterson法和差值Fourier合成解出.经全矩阵最小二乘法修正,最后偏差因子R=0.0337,R_w=0.0364.晶体中甘氨酸与Sm原子的结合方式有三种:第一种甘氨酸的羧基离子以螯合桥式与Sm原子配位;第二种甘氨酸以羧基桥式与同一单元的两个Sm原子配位;第三种甘氨酸以酸基桥式连结两个相邻单元中的相邻Sm原子而形成一维无限长链结构.此外,每个Sm原子还与两个水分子成键,其配位数为9.

钙钛石型复合氧化物催化剂LaMn_yCo_(1-y)O_3的催化性能研究——Ⅰ.在氨氧化反应中氧的形态和催化性能的关系

用XRD,XPS和TPD等手段研究了钙钛石(ABO_3)型复合氧化物催化剂LaMn_yCo_(1-y)O_3中氧的形态;研究了催化剂在氨氧化反应中的活性,发现这类氧化物中存在三种形态的氧种(α,β,β’).它们所对应的脱附温度分别为293K≤T_α≤773K,773K≤T_β≤1073K,T_β’≥1073K.研究了它们与催化剂组成、结构及催化性能之间的关系,并用缺陷化学反应和B位离子之间的相互作用模型进行了解释.α氧的吸附强度和吸附量与催化活性成正比关系.B位离子之间的协同作用有利于氨氧化反应的进行.

SYNTHESIS, PROPERTIES AND MOLECULAR-STRUCTURE OF 5-COORDINATE N,N-DIBENZYLDITHIOCARBAMATE COMPLEXES OF TITANOCENE, ZIRCONOCENE AND HAFNOCENE

The five complexes (RC5H4)2M(S2CNBz2)Cl (R = H, CH3; M = Ti, Zr, Hf; Bz = CH2C6H5) have been prepared by the reaction of (RC5H4)2MCl2 with anhydrous sodium salts of dibenzyldithiocarbamate in refluxing CH2Cl2. These complexes have been characterized by elemental analysis, IR and H-1 NMR. X-ray crystal structure determination of Cp2Zr(S2CNBZ2)Cl shows the molecule has a five-coordinate bent metallocene geometry in which the zirconium atom is attached to two eta-5-C5H5 groups, one bidentate dibenzyldithiocarbamate ligand and one chlorine [Zr-Cl, 2.549(1) angstrom; Zr-S, 2.734(1), 2.667(1); Cl-Zr-S, 137.6(1)-degrees and 73.3(1)-degrees; S-Zr-S, 64.3(1)-degrees]. The catalytic system Cp2Ti (S2CNBZ2)Cl-NaH exhibits high initial catalytic activity of hydrogenation of hexene-1 under mild conditions.

几种溴化改性聚烯烃的富氧性能

研究了聚(4-甲基戊烯-1)、有规及无规聚丙烯的溴化反应。反应以自由基机理进行,溴取代主要发生在主链上的叔氢原子上。溴化反应改变了三种聚合物的溶解和物理性能。溴化产物的透氧系数 P_(v_2)下降,分离系数α_(O(?)N)有所提高,有可能满足某些特殊气体分离膜的要求。

土壤中常量元素的X射线荧光光谱测定

本文介绍了以低压聚乙烯垫底、镶边、粉末直接压片、X荧光谱定量测定土壤中常量元素的方法。用逐步回归法选择影响元素,并以散射内标与经验系数相结合校正基体效应,同时对“经验系数法”和“基本参数与经验系数结合法”进行了比较。

Cytoglobosins A-G, Cytochalasans from a Marine-Derived Endophytic Fungus, Chaetomium globosum QEN-14

Financial support from the Ministry of Science and Technology of China (2010CB833802 and 2007AA09Z446) and from the National Science Foundation of China (30910103914) is gratefully acknowledged.

Characterization of amphioxus GDF8/11 gene, an archetype of vertebrate MSTN and GDF11

MSTN, also known as growth and differentiation factor 8 (GDF8), and GDF11 are members of the transforming growth factor-beta (TGF-beta) subfamily. They have been thought to be derived from one ancestral gene. In the present study, we report the isolation and characterization of an invertebrate GDF8/11 homolog from the amphioxus (Branchiostoma belcheri tsingtauense). The amphioxus GDF8/11 gene consists of five exons flanked by four introns, which have two more exons and introns than that of other species. In intron III, a possible transposable element was identified. This suggested that this intron might be derived from transposon. The amphioxus GDF8/11 cDNA encodes a polypeptide of 419 amino acid residues. Phologenetic analysis shows that the GDF8/11 is at the base of vertebrate MSTNs and GDF11s. This result might prove that the GDF8/11 derived from one ancestral gene and the amphioxus GDF8/11 may be the common ancestral gene, and also the gene duplication event generating MSTN and GDF11 occurred before the divergence of vertebrates and after or at the divergence of amphioxus from vertebrates. Reverse transcriptase polymerase chain reaction results showed that the GDF8/11 gene was expressed in new fertilized cell, early gastrulation, and knife-shaped embryo, which was different from that in mammals. It suggested that the GDF8/11 gene might possess additional functions other than regulating muscle growth in amphioxus.

Geomorphic and hydrodynamic responses in salt marsh-tidal creek systems, Jiangsu, China

Salt marsh-tidal creek systems as a coastal geomorphological unit represent an important natural resource. The present study on Jiangsu salt marshes, eastern China, shows that variations in tidal current velocities in salt marsh creeks are controlled by the local tidal wave characteristics and the bed slope and elevation of the salt marshes and creeks. Likewise, the tidal currents modify the geomorphology of the salt marsh-tidal creek systems by transporting sediments and causing erosion/deposition. Storm events, which appear to have cyclical changes in their intensity relating to sunspot activities, can affect the geomorphic evolution of such systems. Further, in response to accelerated sea-level rise, accretional rates on salt marshes may increase. The tidal creeks have the function of transporting water and sediment onto the salt marsh surface; further, the energy of tidal currents and waves are dissipated within the salt marsh-tidal creek system. Hence, this coastal system has a potential value for coastal protection.

Representation of microscale ocean wavenumber spectrum correct to the second order

In this paper, the analytical representations of four wave source functions in high-frequency spectrum range are given on the basis of ocean wave theory and dimensional analysis, and the perturbation method is used to solve the governing equations of ocean wave high-frequency spectrum on the basis of the temporally stationary and locally homogeneous scale relations of microscale wave. The microscale ocean wavenumber spectrum correct to the second order has an explicit structure, its first order part represents the equilibrium between different source functions, and its second order part represents the contribution of microscale wave propagation.

黄槿内生真菌赤散囊菌及红海榄的次生代谢产物及其生物活性研究

由于生长环境的特殊性，红树林及其内生真菌的代谢产物在化学类型和生物活性方面都具有多样性，因此对其代谢产物的研究引起了人们越来越多的关注。本论文以菌丝体生物量、代谢产物量等指标及薄层色谱分析、高效液相色谱分析、抗菌活性测试等筛选手段对来源于我国海南红树植物的九株内生真菌在四种不同液体培养基上的静置发酵产物进行了综合评价，并从中选择了来源于半红树植物黄槿（Hibiscus tiliaceus）的内生真菌G2——赤散囊菌（Eurotium rubrum）进行了30 L规模发酵（采用PDB培养基）和次生代谢产物的研究，对分离得到的部分化合物进行了初步的生物活性评价。此外，本论文还对海南真红树植物红海榄（Rhizophora stylosa Griff.）的化学成分进行了研究，并对分离得到的部分化合物进行了二苯代苦味酰自由基（DPPH）清除活性的评价。 采用常规的硅胶柱层析、Sephadex LH-20柱层析、反相硅胶柱层析、制备薄层层析（pTLC）、重结晶等分离手段，分离纯化得到单体化合物。综合运用现代波谱技术 (IR、UV、MS、1D-NMR 和 2D-NMR) 以及与标准品或文献比对鉴定单体化合物的结构。从G2菌丝体和发酵液的合并提取物中鉴定了45个化合物的结构，其中13个为新化合物，结构类型包括6个苯甲醛类化合物（ER1*~ER6*）、4个蒽醌类化合物（ER15*~ ER18*）和3个含吲哚的二酮哌嗪生物碱类化合物（ER27*~ER29*）。 对以上分离鉴定的部分单体化合物进行了DPPH自由基清除活性、拒食杀虫活性、抗细菌活性以及体外细胞毒活性的初步评价。新化合物ER15*和三个已知化合物ER20、ER39和ER40都表现很强的DPPH自由基清除活性。化合物ER15*还表现较好的拒食杀虫活性，而化合物ER5*和ER18*不但没有杀虫活性，反而能促进幼虫的生长。所测试的化合物只有ER15*和ER18*表现出微弱的抗金黄色葡萄球菌活性。所测试的化合物对A-549、HL-60和P-388细胞株均未表现出有意义的体外细胞毒活性。 从红海榄枝条的提取物中分离鉴定了29个化合物，其中2个为新化合物，包括1个三萜酯（RS1*）和1个黄烷醇类化合物（RS12*）；另有1个三萜酯（RS5）和1个黄烷醇类化合物（RS11）作为新的天然产物被分离鉴定。 对从红海榄提取物乙酸乙酯相和正丁醇相分离得到的部分单体化合物进行了DPPH自由基清除活性的研究。黄烷醇类化合物RS16和RS17显示最强的活性。另外，实验结果说明黄烷醇类化合物的DPPH自由基清除活性与其分子中所含的羟基数目有一定关系，而且若芳香环上有多个邻位酚羟基，则该化合物的活性将增强。本论文实验结果为海南红海榄植物资源的利用提供了化学成分及抗氧化活性方面的科学依据。