Dinuclear Complexes Comprising a d-Transition Metal Ion and a Lanthanide Ion as Model Compounds with Nuclease-like Functions

包含d-过渡金属离子和镧系离子的双核配合物作为具有核酸酶样功能的模型化合物

基本信息

批准号：
10640537
负责人：
SAKAMOTO Masatomi
金额：
$ 2.37万
依托单位：
Yamagata University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1998
资助国家：
日本
起止时间：
1998 至 2000
项目状态：
已结题

项目摘要

The purpose of this work is to synthesize heterodinuclear complexes comprising a d-transition metal and a lanthanide (f-transition metal) ions effectively hydrolyzing various phosphate diesters and to give useful informations for the development of the artificial restriction enzymes.In this year, dinuclear CuLn and CuCu and mononuclear Ln and Cu complexes (Ln= lanthanide(III)) were synthesized using dinucleating macrocycles obtained by the condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane in the 2 : 1 molar ratio, 2,6-diformyl-4-methylphenol, ethylenediamine and diethylenetriamine in the 2 : 1 : 1 molar ratio, and 2,6-diformyl-4-methylphenol, ethylenediamine and 1,3-diamino-2-propanol in the 2 : 1 : 1 molar ratio, and their hydrolytic properties toward 4-nitrophenylphosphate (NPP) were investigated. Dinuclear CuLn and mononuclear Ln complexes were active for the hydrolysis. The activitiy of the former was higher than that of the latter. On the other hand, hydrolysis by the dinuclear CuCu and mononuclear Cu complexes was not significantly recognized. These observations suggest that the heterometal CuLn core takes part in the hydrolysis (cooperation effect of a d-transition metal and a f-metal ions). Here, only a HPLC peak due to 4-nitrophenolate as a product was observed, indicating that the reaction is only hydrolytic and the redox reaction does not occur. The-NH-and-OH groups on the lateral chain of macrocyles were found to play an important role in the hydrolysis. Furthermore, the hydrolysis of bis(4-nitrophenyl)phosphate was also investigated using some d-f heteronuclear complexes.

这项工作的目的是合成构成构成D型金属和灯笼的灯笼（F-转移金属）离子的异质综合络合物，有效地水解了各种磷酸盐二分钟，并为人工限制酶的开发提供了有用的信息。 synthesized using dinucleating macrocycles obtained by the condensation of 2,6-diformyl-4-methylphenol and 1,3-diaminopropane in the 2 : 1 molar ratio, 2,6-diformyl-4-methylphenol, ethylenediamine and diethylenetriamine in the 2 : 1 : 1 molar ratio, and 2,6-diformyl-4-methylphenol,在2：1：1摩尔比中，乙二胺和1,3-二氨基-2-丙醇及其水解特性及其对4-硝基苯基磷酸（NPP）的特性进行了研究。双核CULN和单核LN复合物进行水解活性。前者的活动高于后者。另一方面，尚未明显识别出双核CUCU和单核Cu复合物的水解。这些观察结果表明，异源CULN核心参与水解（D-转换金属和F-金属离子的合作效应）。在这里，仅观察到由于4硝基苯甲酸盐而引起的HPLC峰，表明该反应仅是水解，并且不会发生氧化还原反应。发现大环侧链上的NH和-OH基团在水解中起着重要作用。此外，还使用一些D-F型异核复合物研究了双（4-硝基苯基）磷酸盐的水解。