| 基于Cyclam衍生物的单核金属配合物的结构及核酸酶活性 |
| Structural Characterization and Artificial Nuclease Activity of Transition Metal Complexes of Cyclam Derivatives |
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| 摘要: 以1,8-二甲基-1,4,8,11-四氮杂环十四烷为原料,以N,N'-二叔丁氧羰基-2-甲璜酰氧基-1,3-二氨基丙烷为烷基化试剂,合成了cyclam衍生物:1,8-二(N,N'-二叔丁氧羰基-1,3-二氨基异丙基)-4,11-二甲基-1,4,8,11-四氮杂环十四烷(L1);及其对应的系列单核金属配合物,Zn(L1)Cl2(1),Ni(L1)Cl2(2)和Cu(L1)Cl2(3);核磁结果表明,L1为C2对称结构,且cyclam环上每一个亚甲基碳上的2个氢化学不等价;利用2D[1H,15N]HSQC对比配体配位前后N-H化学位移的变化,确定配合物的结构是金属与配体cyclam环上的4个氮原子配位;利用变温核磁1HNMR和13CNMR,结合2D[1H,15N]HSQC核磁共振波谱表明,配合物1在溶液中主要以两种构型并存,并主要以trans-Ⅲ构型存在.此外,用凝胶电泳研究了配体与单核金属配合物对超螺旋pBR322质粒DNA切割活性;实验结果表明,配合物3在抗坏血酸存在的条件下具有核酸酶活性,而配体(L1),配合物1和配合物2在实验条件下,无论是氧化切割还是水解切割都显阴性. |
| 关键词: Cyclam衍生物 单核金属配合物 构型 人工核酸酶 |
| 基金项目: 国家自然科学基金(No.21131003)资助项目. |
| Abstract: Acyclam-based ligand: tetratert-butyl ((4,11-dimethyl-1,4,8,11-tetraazacyclotetradecane-1,8-diyl)bis (propane-3,2,1-triyl)) tetracarbamatev (L1), and its metal complexes [Zn(L1)Cl2] (1), [Ni(L1)Cl2] (2) and [Cu(L1)Cl2] (3) were designed and synthesized. L1 has a C2 symmetrical structure and the 1H chemical shift of the same carbon was different because of the influence of cyclam ring. The metal binding site of the L1 was confirmed by 2D [1H, 15N] HSQC by comparing the chemical shift of N of the branched chains of the ligand that of with the corresponding metal complex. The co-existence of two configuration was characterized by 13C VT NMR combined with 2D [1H, 15N] HSQC NMR and trans-Ⅲ was confirmed to be the main configuration for complex 1. The cleavage activity of the ligand L1 and the complexes 1~3 was investigated in detail under physiological conditions. Agarose gel electrophoresis experiments showed that the complex 3 possesses interesting nuclease activity in the present of ascorbate; No matter the hydrolysis or oxidation, the ligand L1 and complex 1, and 2 were negative to DNA at the experimental conditions. |
| Keywords: cyclam derivatives mono-metal complex configuration artificial nuclease |
| 投稿时间：2014-08-11 修订日期：2014-10-24 |
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| 李志喜,胡明,刘超,杨晓亮.基于Cyclam衍生物的单核金属配合物的结构及核酸酶活性[J].无机化学学报,2015,31(1):127-132. |
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