The first dinuclear copper(II) and zinc(II) complexes containing novel Bis-TACN: syntheses, structures, and DNA cleavage activities.
The first dinuclear copper(II) and zinc(II) complexes containing novel Bis-TACN: syntheses, structures, and DNA cleavage activities.
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DOI：
10.1039/b615148e
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发表时间：
2007-02
影响因子：
4
通讯作者：
Jing Qian;W. Gu;Hui Liu;Feng-Xian Gao;Li Feng;Shi‐Ping Yan;D. Liao;P. Cheng
中科院分区：
文献类型：
--
作者：
Jing Qian;W. Gu;Hui Liu;Feng-Xian Gao;Li Feng;Shi‐Ping Yan;D. Liao;P. Cheng
两个新的双核配合物[Cu（2）（L）].（ClO（4））（2）（1）和[Zn（2）（L）]。（ClO（4））（2）（2）{L = 1（4），5（4）-二甲基-1（2），5（2）-二羟基-1（1，3），5（1，3）-二苯-3（1，4），7（1，4）-二-1，4，7-三氮杂环壬烷}的合成和晶体结构表征。1的阳离子[Cu（2）（L）]（2+）结构与2的阳离子[Zn（2）（L）]（2+）结构相似。中心离子由L的二苯氧桥连，并位于接近完美的正方形金字塔几何形状中。1和2的晶体在三斜晶系空间群P1。这两种复合物在生理pH和温度下，在活化剂的存在下有效地促进质粒DNA的切割。在巯基乙醇存在下，配合物1的拟米氏动力学参数k（cat）= 1.61 h（-1），K（m）= 1.35 × 10（-5）M;在过氧化氢存在下，配合物2的拟米氏动力学参数k（cat）= 2.48 h（-1），K（m）= 5.5 × 10（-5）M。通过加入标准自由基清除剂研究了质粒DNA切割的机理。双核Zn（II）/H（2）O（2）体系的DNA裂解反应是一种水解机制。
Two novel binuclear complexes [Cu(2)(L)].(ClO(4))(2) (1) and [Zn(2)(L)].(ClO(4))(2) (2) were synthesized and crystallographically characterized {L = 1(4),5(4)-dimethyl-1(2),5(2)-dihydroxy-1(1,3),5(1,3)-dibenzene-3(1,4),7(1,4)-di-1,4,7-triazacyclononane}. The cation [Cu(2)(L)](2+) structure of 1 is similar to that of [Zn(2)(L)](2+) of 2. The central ion is bridged by the di-phenoxo of L and lies in a close to perfect square pyramidal geometry. 1 and 2 crystallize in the triclinic space group P1. The two complexes effectively promote the cleavage of plasmid DNA in the presence of activating agents at physiological pH and temperature. The pseudo-Michaelis-Menten kinetic parameters k(cat) = 1.61 h(-1), K(m) = 1.35 x 10(-5) M for complex 1 in the presence of mercaptoethanol; k(cat) = 2.48 h(-1), K(m) = 5.5 x 10(-5)M for complex 2 in the presence of hydrogen peroxide were obtained. The mechanism of plasmid DNA cleavage was studied by adding standard radical scavengers. DNA cleavage reaction by the binuclear Zn(II)/H(2)O(2) system is a hydrolytic mechanism.