Synthesis, characterization, antitumor activity of nickel(Ⅱ) and cobalt (Ⅱ) complexes of 2,2''''-diamino-4,4''''-bithiazole and their interaction with dGMP

New complexes,of bis(2,2'-diamino-4,4'-bithiazole)sulfate nickel(Ⅱ) and bis(2,2'-diami-no-4,4'-bithiazole)sulfate cobalt(Ⅱ),have been prepared.The complexes were characterized by infrared and UV-Vis spectroscopy,1H NMR,elemental analyses and molar conductivity.The effect of these complexes on the DNA synthesis of sarcoma 180 cells has been studied by the technique of isotopic liquid scintillation.The results indicated that complexes show ability to inhibit DNA synthesis of the tumor cells.In order to provide a molecular basis for understanding the biological effects,the probe,[trana-en2Os(η2-H2)](CF3SO3)2 (en,ethylenediamine) as a monitor was first used to explore interaction of the complexes with 2'-deoxyguanosine-5'-monophosphate (dGMP).     

Influence of acid treatments of carbon nanotube precursors on Ni/CNT in the synthesis of carbon nanotubes

The Ni/CNT catalyst was fabricated by directly dipping carbon nanotube precursors refluxed in 4 M of nitric acid into Ni electroless plating bath, and used to synthesize new carbon nanotubes. The experimental results indicate that the duration of acid-treatment of carbon nanotubes precursors exerts a great influence on the catalysis of Ni/CNT in the synthesis of carbon nanotubes and hence the structures of the new carbon nanotubes. When the carbon nanotubes precursors were refluxed for 0.5 h in 4 M of nitric acid, bamboo-shaped carbon nanotubes (BSCNT) or Y junction carbon nanotubes in the carbon products were obtained. As the duration of acid-treatment of carbon nanotubes precursors increased to 6 h, the as-prepared Ni/CNT displayed higher activity, and the carbon nanotube products were high pure without any Y junction structure or any separation layers in hollow.     

Degradation thermique et etude vibrationnelle de MII(NH4)4(P3O9)2x4H2O(M II=Cu2+, Ni2+, Co2+)

We have studied the thermal behaviour under atmospheric pressure of isotypic tetrahydrate cyclotriphosphates M^II(NH₄)₄(P₃O₉)₂x4H₂O (M ^II=Cu, Ni and Co), between 25 and 1400°C, by X-ray diffraction, thermal analyses (TG and DTA) and infrared spectrometry. This study shows that the series of the compounds M^II(NH₄)₄(P₃O₉)₂x4H₂O (M ^II=Cu, Ni and Co) after elimination of water, in two different stages, and ammonia leads, at 400°C to cyclotetraphosphate M₂ ^IIP₄O₁₂ crystallized and to a thermal residue with a formula H₄P₄O₁₂ which undergoes under a thermal degradation by evolving water and pentoxide phosphorus. The kinetic characteristics of the dehydration and elimination of ammonia have been determinated. The vibrational spectra of Cu(NH₄)₄(P₃O₉)₂x4H₂O were examined and interpreted, in the domain of the valency frequencies, on the basis of the crystalline structure of its isotypic compound Co(NH₄)₄(P₃O₉)₂x4H₂O whose cycle has the site symmetry C₁, of our results of the calculation of the IR frequencies and the successive isotopic substitutions of the equivalent atoms (3P, 3Oi and 6Oe belonging to the P₃Oi₃Oe₆ ring) of the P₃O₉ ³⁻ cycle with high symmetry D_3h. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal decomposition study on mixed ligand thymine complexes of divalent nickel(II) with dianions of some dicarboxylic acids

Thermal decomposition of mixed ligand thymine (2,4-dihydroxy-5-methylpyrimidine) complexes of divalent Ni(II) with aspartate, glutamate and ADA (N-2-acetamido)iminodiacetate dianions was monitored by TG, DTG and DTA analysis in static atmosphere of air. The decomposition course and steps of complexes [Ni(C₅H₆N₂O₂)(C₄H₅NO₄)²⁻(H₂O)₂]·H₂O, [Ni(C₅H₆N₂O₂)(C₅H₇NO₄)²⁻(H₂O)₂]·H₂O and [Ni(C₅H₆N₂O₂)(C₆H₈N₂O₅)²⁻(H₂O)₂]·1.5H₂O were analyzed. The final decomposition products are found to be the corresponding metal oxides. The kinetic parameters namely, activation energy (E*), enthalpy (ΔH*), entropy (ΔS*) and free energy change of decomposition (ΔG*) are calculated from the TG curves using Coats–Redfern and Horowitz–Metzger equations. The stability order found for these complexes follows the trend aspartate > ADA > glutamate.     

α-Al2O3纳米粒子对Co-Ni合金异常共沉积电化学行为的影响

为了研究在电化学复合共沉积过程中,惰性纳米粒子和金属离子、电极表面的相互作用,以及由此产生的对合金电化学共沉积行为的影响.本文从两个吸附过程出发: 电解液中的金属离子和H＋在纳米粒子表面的吸附；纳米粒子迁移到阴极表面,在电极表面的吸附.采用Zeta电势和稳态极化以及电化学交流阻抗（EIS）研究了纳米Al2O3粒子和电解液中的金属离子，和电极表面的相互作用,进而分析了纳米粒子对Co2＋和Ni2＋还原沉积的影响规律.通过对阻抗数据的拟合,讨论了Al2O3纳米粒子对等效电路中各物理参数的影响.在H＋和不同金属离子在纳米粒子上发生竞争吸附的基础上,提出了纳米粒子和合金共沉积的可能反应历程.     

用Xα方法对CH4在Ni(Ⅲ)表面吸附解离反应的理论研究

用Ｘ_α方法对ＣＨ_４在Ｎｉ（Ⅲ）表面吸附解离反应的理论研究马晨生,马理,杨忠志（吉林大学理论化学研究所,长春,１３００２３）关键词ＣＨ_４／Ｎｉ（Ⅲ）吸附体系,原子簇模型,ＣＨ_４／Ｍｉ_７,ＭＳ－Ｘ_α－ＳＣＦ方法甲烷在Ｎｉ表面的催化重整反应在工业和国...     

A Novel Carbon Nanotube-Supported NiP Amorphous Alloy Catalyst and Its Hydrogenation Activity

A carbon nanotube-supported NiP amorphous catalyst (NiP/CNT) was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.     

表面电沉积Ni—La2O3复合镀层的Fe26Cr1Mo不锈钢的氧化行为研究

Ｆｅ２６Ｃｒ１Ｍｏ不锈钢在９００℃氧化时，生成的氧化层在冷却过程中大量剥落，经表面共电沉积ＮｉＬａ２Ｏ３复合镀层后，抗热循环能力明显提高。     

铂配位的腺嘌呤质子化的理论研究

用量子化学从头算研究一系列平面四方金属配体作用于腺嘌呤N₇位点对其质子化的影响。计算结果表明气相中，配合物质子化能力主要受长程静电效应影响，不同金属离子的影响差别甚微。综合考虑极性溶剂影响后长程静电效应影响显著降低。NBO电荷布居分析表明质子化位点电子云密度的变化直接影响该位点质子化能力。     

纳米尺寸团簇NinZrn(n=3～5)的几何结构与成键规律研究

根据化学键理论与拓扑原理，设计了团簇NinZrn(n=3-5)的可能几何构型，并用从头算方法进行构型优化，结果表明，由NiZr组成的团簇原子间的Zr-Zr和Zr-Ni键明显较强，而Ni-Ni的成键较弱，并发与NinZrn(n=3-5)团簇电子性质与有机烯烃分子等瓣相似，原子之间的成键按照强弱相间的规则分布。