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

本工作的目的是合成由d过渡金属和镧系（f过渡金属）离子组成的异双核配合物，有效地水解各种磷酸二酯，并为人工限制性内切酶的开发提供有用的信息。在今年,双核的CuLn CuCu单核Ln和铜复合物(Ln =镧系元素(III))是合成使用dinucleating重点通过2的凝结,6-diformyl-4-methylphenol, 3-diaminopropane 2: 1克分子比,2,6-diformyl-4-methylphenol,乙二胺和二乙撑三胺2:1:1摩尔比率,和2,6-diformyl-4-methylphenol,乙二胺和1,2 3-diamino-2-propanol: 1:研究了它们对4-硝基苯基磷酸（NPP）的水解性能。双核CuLn和单核Ln配合物对水解具有活性。前者的活性高于后者。另一方面，双核Cu和单核Cu配合物的水解作用不明显。这些观察结果表明，异质金属CuLn核参与了水解（d-过渡金属和f-金属离子的协同作用）。这里只观察到4-硝基苯酚作为产物的一个HPLC峰，说明该反应仅为水解反应，未发生氧化还原反应。发现大环侧链上的nh和oh基团在水解过程中起重要作用。此外，还研究了一些d-f异核配合物对二（4-硝基苯基）磷酸的水解。

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.