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Trinuclear Metal Complexes Based on 1,10-Phenanthroline Derivates as Catalysts for Cleavage of a RNA-Model Substrate

机译:基于1,10-菲咯啉衍生物的三核金属配合物作为裂解RNA模型底物的催化剂

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摘要

Two multidentate ligands 2,9-di [6'-(2"-hydroxyl -3"-methoxyphenyl) -n-2',5'-diazahexyl ] -1,10-phenanthroline (LA) and 2,9 -di ( 6'-α-phenol-n-2', 5' -diazahexyl) - 1,10 - phenanthroline ( LB ) were synthesized and fully characterized. Protonation of the ligands and the stability of the complexes of the ligands with divalent metal ions were investigated. The trinuclear metal complexes [ Cu (Ⅱ) and Zn (Ⅱ)] of the ligands were studied, as catalysts, for the transphosphorylation of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate(HPNP). The second-order rate constants of HPNP-hydrolysis catalyzed by M3L and M3LH-1 were obtained, which indicated that Zn3LBH-1 was the most efficient catalyst among them. The proposed mechanisms included the activation of the substrate via binding to the metal ions and intramolecular nucleophilic attack by the deprotonated C2-hydroxyl of HPNP.
机译:两个多齿配体2,9-di [6'-(2“-羟基-3”-甲氧基苯基)-n-2',5'-二氮杂己基] -1,10-菲咯啉(LA)和2,9 -di(合成并充分表征了6'-α-苯酚-n-2',5'-二氮杂己基)-1,10-菲咯啉(LB)。研究了配体的质子化以及配体与二价金属离子的配合物的稳定性。研究了配体的三核金属配合物[Cu(Ⅱ)和Zn(Ⅱ)]作为催化剂,用于RNA模型底物2-羟丙基-对硝基苯基磷酸酯(HPNP)的转磷酸作用。得到了M3L和M3LH-1催化的HPNP水解的二级速率常数,表明Zn3LBH-1是其中最有效的催化剂。拟议的机制包括通过结合金属离子激活底物,以及HPNP去质子化的C2-羟基对分子内亲核的攻击。

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