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一个d-过渡金属和一个镧系元素的异双核配合物（f-过渡金属）离子有效水解各种磷酸二酯，并为人工限制性内切酶的开发提供有用的信息。双核CuLn和CuCu及单核Ln和Cu配合物（Ln=镧系元素（III））是使用通过2，6-二甲酰基-4-甲基苯酚和1，3-二氨基丙烷在2：1摩尔比，2，6-二甲酰基-4-甲基苯酚：乙二胺：二乙烯三胺= 2：1：1摩尔比，2，6-二甲酰基-4-甲基苯酚：乙二胺：1，3-二氨基-2-丙醇= 2：1：1摩尔比，考察了它们对4-硝基苯磷酸酯（NPP）的水解性能。双核CuLn和单核Ln配合物具有水解活性。前者的活性高于后者。另一方面，水解的双核铜铜和单核铜配合物没有显着承认。这些观察结果表明，异金属CuLn核心参与水解（d-过渡金属和f-金属离子的合作效应）。在此，仅观察到由于作为产物的4-硝基苯酚盐而产生的HPLC峰，这表明反应仅是水解的而没有发生氧化还原反应。发现大环侧链上的-NH-和-OH基团在水解中起重要作用。此外，还研究了双（4-硝基苯基）磷酸酯的水解反应。

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.