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1H NMR和13C NMR,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p BR322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。
A cyclam-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 the1 H chemical shift of the same carbon was different because of the influence of cyclam ring.The metal binding site of the L1 was confirmed by2 D [^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^13 C 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 2were negative to DNA at the experimental conditions.
出处
《无机化学学报》
SCIE
CAS
CSCD
北大核心
2015年第1期127-132,共6页
Chinese Journal of Inorganic Chemistry
基金
国家自然科学基金(No.21131003)资助项目
