Fate of model complexes with monocopper center towards the functional properties of type 2 and type 3 copper oxidases,JBIC Journal of Biological Inorganic Chemistry

当前位置： X-MOL 学术 › J. Biol. Inorg. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Fate of model complexes with monocopper center towards the functional properties of type 2 and type 3 copper oxidases
JBIC Journal of Biological Inorganic Chemistry ( IF 2.7 ) Pub Date : 2021-01-06 , DOI: 10.1007/s00775-020-01837-5
Mariappan Murali ₁ , Velusamy Sathya ₁ , Balasubramaniam Selvakumaran ₁

Affiliation

Abstract

Green colored mononuclear copper(II) complexes viz. [Cu(L)(bpy)](ClO₄) (1) or [Cu(L)(phen)](ClO₄) (2) (where H(L) is 2-((2-dimethylamino)ethyliminomethyl)naphthol) show distorted square pyramidal (4 + 1) geometry with CuN₄O 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.

Graphic abstract

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.

中文翻译：

具有单铜中心的模型复合物对 2 型和 3 型铜氧化酶功能特性的影响

摘要

绿色单核铜（II）配合物即。[Cu(L)(bpy)](ClO ₄ ) ( 1 ) 或 [Cu(L)(phen)](ClO ₄ ) ( 2 )（其中 H(L) 是 2-((2-二甲氨基）乙基亚氨基甲基）萘酚）显示扭曲的方形金字塔 (4 + 1) 几何形状和 CuN ₄O 发色团。自组装分子缔合的存在表明二聚体的形成。由于底物的结合，溶液中的二聚体性质得以保留，促进底物和 Cu(II) 活性位点之间的空间匹配，这有利于电子转移。有趣的是，这两种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催化氧化为脱氢抗坏血酸或苄胺催化氧化为苯醛或邻苯二酚到邻苯二酚。-醌从而模拟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，催化活性是有效的，甚至优于许多双核铜 (II) 配合物。