【作者】 鲁晓明； 姜凌； 毛希安； 叶朝辉； 卢景芬；

【Author】 Xiaoming Lu~(a*) Ling Jang~b Xi’an Mao~b Chaohui Ye~b Jingfen Lu~c a Department of Chemistry,Capital Normal University,Beijing,100037,China b Wuhan Institute of Physics and Mathematics,Chinese Academy of Sciences,Wuhan,430071,China c Key laboratory of Natural and Bimemic drug,Perkin University,Beijing,100083,China

【机构】 首都师范大学化学系； 波谱与原子分子物理国家重点实验室(中国科学院武汉物理与数学研究所)； 北京大学医学部天然药物与仿生药物国家重点实验室；

【摘要】 <正>钼、钨氧转移酶在生物体系的氮、硫和碳的天然循环过程中起着极其重要催化作用,因而各类钼、钨氧转移酶活性结构因子的仿生合成以及催化机理研究成为热点。本文仿生合成了系列配合物（NH₂CH₂CH₂NH₃）₃[Mo^VO₂（O₂C₆H₄）₂],（NH₂CH₂CH₂NH₃）_2．5更多还原

【Abstract】 Complexes（NH₂CH₂CH₂NH₃）₃[Mo^ⅤO₂（O₂C₆H₄）₂]1,（NH₂CH₂CH₂NH₃）_2.5 [Mo_0.5^ⅤW_0.5^ⅥO₂（O₂C₆H₄）₂]₂ and（NH₂CH₂CH₂NH₃）₂[W^ⅥO₂（O₂C₆H₄）₂]3 are synthesized and studied comparably on their interaction with ATP by NMR spectroscopy in physiological solution and their DNA cleavage activities.The central molybdenum and tungsten ions of the complexes present as M（Ⅴ）in freshly prepared D₂O solution but undergo oxidation from M（Ⅴ）to M（Ⅵ）when the complexes are mixed with ATP in physiological D₂O solution.ATP offers the advantage of appreciable stability and promotion to the oxidation of M（Ⅴ）to M（Ⅵ）and therefore the hydrolysis of catecholato ligand.The catecholato ligand of the complexes exhibit different hydrolysis rate either in the solution containing M（Ⅴ）or M（Ⅵ）.No chemical shift changes are observed in ¹H,¹³C,³¹p and ¹⁵N of ATP when it is mixed with the complexes in solution,indicating that no catecholatometaI-ATP adducts are formed.Complex 1 possesses fairly good activity on DNA cleavage while complex 2 and 3 are less effective.It is worthy to note that the effectiveness of DNA cleavage is relation to the hydrolysis rates of catecholate ligand positively so it can be deduced that the mechanism of the DNA cleavage of the complexes is probably the intercalation into the base-pairs of DNA via the planar aromatic ring of catechol molecules.更多还原