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具有单铜中心的模型配合物的命运与 2 型和 3 型铜氧化酶的功能特性有关。

Fate of model complexes with monocopper center towards the functional properties of type 2 and type 3 copper oxidases.

机构信息

Coordination and Bioinorganic Chemistry Research Laboratory, Department of Chemistry, National College (Autonomous), Tiruchirappalli, Tamil Nadu, 620 001, India.

出版信息

J Biol Inorg Chem. 2021 Feb;26(1):67-79. doi: 10.1007/s00775-020-01837-5. Epub 2021 Jan 6.

Abstract

Green colored mononuclear copper(II) complexes viz. Cu(L)(bpy) (1) or Cu(L)(phen) (2) (where H(L) is 2-((2-dimethylamino)ethyliminomethyl)naphthol) show distorted square pyramidal (4 + 1) geometry with CuNO chromophore. The existence of self-assembled molecular associations indicates the formation of the dimer. Dimeric nature in solution is retained due to the binding of the substrate, encourages steric match between substrate and Cu(II) active site, which favors electron transfer. Interestingly, both the complexes exhibit high-positive redox potential. Therefore, the presence of self-assembled molecular association along with the positive redox potential enhances the catalytic oxidation of ascorbic acid to dehydroascorbic acid or benzylamine to benaldehyde or catechol to o-quinone thereby model the functional properties of type 2 and type 3 copper oxidases. Notably, catalytic activity is effective when compared with other reported mononuclear copper(II) complexes and even superior to many binuclear copper(II) complexes. Existence of self-assembled molecular association in solution along with high-positive redox potential favors electron transfer process in mononuclear copper(II) complexes and models the functional properties of type 2 and type 3 copper oxidases.

摘要

绿色单核铜(II)配合物,即 Cu(L)(bpy)(1)或Cu(L)(phen)(2)(其中 H(L) 是 2-((2-二甲氨基)乙基亚氨基甲基)萘酚),具有扭曲的四方锥(4+1)几何形状,CuNO 发色团。自组装分子缔合的存在表明形成了二聚体。由于底物的结合,溶液中二聚体的性质得以保留,这鼓励了底物和 Cu(II)活性位点之间的空间匹配,有利于电子转移。有趣的是,这两个配合物都表现出高正氧化还原电位。因此,自组装分子缔合的存在以及正氧化还原电位增强了抗坏血酸向脱氢抗坏血酸、苯甲胺向苯甲醛或儿茶酚向邻醌的催化氧化,从而模拟了 2 型和 3 型铜氧化酶的功能特性。值得注意的是,与其他报道的单核铜(II)配合物相比,催化活性更有效,甚至优于许多双核铜(II)配合物。溶液中自组装分子缔合的存在以及高正氧化还原电位有利于单核铜(II)配合物中的电子转移过程,并模拟了 2 型和 3 型铜氧化酶的功能特性。

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