Phosphate diesters and DNA hydrolysis by dinuclear Zn(II) complexes featuring a disulfide bridge and H-bond donors

Phosphate diesters and DNA hydrolysis by dinuclear Zn(II) complexes featuring a disulfide bridge and H-bond donors
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DOI:
10.1016/j.tet.2010.01.050
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发表时间:
2010-03-20
期刊:
影响因子:
2.1
通讯作者:
Mancin, Fabrizio
Mancin, Fabrizio
中科院分区:
化学3区
文献类型:
--
作者:
Lombardo, Valentina;Bonomi, Renato;Mancin, Fabrizio

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双核配体1基于双-合成了2-氨基-吡啶基-6-甲基)胺(BAPA)金属键合单元,并研究了其作为磷酸二酯水解催化剂的催化性能。BAPA的Zn(II)配合物能引发金属离子与氢原子之间的相互作用,并能催化磷酸二酯的水解。研究了双核配合物1 Zn(II)(2)与双对-对研究了亚磷酸硝基苯酯和质粒DNA的复合物,并与没有二硫键或没有提供氢键的氨基的参考复合物进行了比较。复合物使两种底物的裂解速率显著加速,并伴有BNP的显著差异,二硫桥的存在不会导致预期作为更好预组织结果的两种金属离子的协同作用的改善。从另一方面来说。在DNA的情况下,配合物1 Zn(II)(2)比相应的没有二硫键的参考物反应性更强。因此,不同的配位必须由一种良好的催化剂来实现,用于切割两种底物。此外,与DNA的结合研究表明,在配合物中存在两种金属离子或吡啶氨基。而不是二硫键,导致复合物对该底物的亲和力增强(C)2010 Elsevier Ltd保留所有权利
The dinuclear ligand 1 based on the bis-(2-amino-pyridinyl-6-methyl)amine (BAPA) metal binding unit and featuring a two-atom disulfide bridge was synthesized and studied as hydrolytic catalysts for phosphate diesters The Zn(II) complexes of BAPA ale known to elicit the cooperation between the metal ion and the hydrogen-bond donating amino groups to greatly increase the late of cleavage of phosphate diesteis The reactivity of the dinuclear complex 1 Zn(II)(2) toward bis-p-nitrophenyl phosphite and plasmid DNA was investigated and compared with that of reference complexes devoid of the disulfide bridge or of the hydrogen-bond donating amino groups The dimetallic Zn(II) complex produces remarkable accelerations of the rate of cleavage of both the substrates accompanied by significant differences in the case of BNP, the presence of the disulfide bridge does not lead to the improvement of the cooperative action of the two metal ions expected as the result of better preorganization. On the other hand. in the case of DNA the complex 1 Zn(II)(2) is much more reactive that the corresponding reference devoid of the disulfide bridge Hence, different requisites Must be fulfilled by 1 good catalyst for the cleavage of the two substrates Moreover, binding Studies with DNA indicated that the presence of two metal ions in file complex or of the pyridine amino groups. but not of the disulfide bridge, results into all enhanced affinity of the complexes toward this substrate (C) 2010 Elsevier Ltd All rights reserved