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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Catalytic dioxygenation of flavonol by M-II-complexes (M = Mn, Fe, Co, Ni, Cu and Zn) - mimicking the M-II-substituted quercetin 2,3-dioxygenase
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Catalytic dioxygenation of flavonol by M-II-complexes (M = Mn, Fe, Co, Ni, Cu and Zn) - mimicking the M-II-substituted quercetin 2,3-dioxygenase

机译:M-II-络合物(M = Mn,Fe,Co,Ni,Cu和Zn)对黄酮醇的催化双加氧作用-模拟M-II-取代的槲皮素2,3-二加氧酶

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摘要

In order to get insights into the metal ion effects and the carboxylate effects on enzymatic activity, a series of the carboxylate ligand supported transition metal complexes [(ML)-L-II(OAc)] (M = Mn (1), Fe (2), Co (3), Ni (4), Cu (5) and Zn (6); LH = 2-{[bis-(pyridin-2-ylmethyl)amino]methyl}-4-methoxy benzoic acid) were synthesized and characterized as structural and functional models for the active sites of various M-II-substituted resting quercetin 2,3-dioxygenases (2,3-QD). Their structures, spectroscopic features, redox properties, as well as the catalytic reactivity toward the substrate flavonol and O-2 have been investigated in detail. The model complexes show higher enzymatic reactivities in the catalytic dioxygenation (oxidative ring opening) of the substrate flavonol at lower temperatures (55-100 degrees C), presumably caused by the carboxylate group in the supporting model ligand, which could lower the redox potential of the bound substrate flavonolate by electron donation. The catalytic reactivity of [(ML)-L-II(OAc)] exhibits notable differences and it is in a metal ion dependent order of Co (3) > Ni (4) > Zn (6) > Fe (2) > Mn (1) > Cu (5). The differences in the reactivities among them could be ascribed to the redox potential of the bound substrate flavonolate, which was drastically influenced by the metal ions via tuning the electron density of flavonolate, providing important insights into the metal ion effects and the carboxylate effects on the enzymatic activity of various M-II-substituted 2,3-QD. Our model complexes [(ML)-L-II(OAc)] are the first examples of a series of structural and functional models of various M-II-substituted resting 2,3-QD.
机译:为了深入了解金属离子作用和羧酸盐对酶活性的影响,一系列羧酸盐配体支持的过渡金属配合物[(ML)-L-II(OAc)](M = Mn(1),Fe( 2),Co(3),Ni(4),Cu(5)和Zn(6); LH = 2-{[双-(吡啶-2-基甲基)氨基]甲基} -4-甲氧基苯甲酸)合成并表征为各种M-II取代的静息槲皮素2,3-二加氧酶(2,3-QD)活性位点的结构和功能模型。详细研究了它们的结构,光谱特征,氧化还原性质以及对底物黄酮醇和O-2的催化反应性。模型配合物在较低温度(55-100摄氏度)下底物黄酮醇的催化双加氧反应(氧化开环)中显示较高的酶反应性,可能是由支持模型配体中的羧酸根引起的,可能会降低通过电子给予结合的底物黄酮酸酯。 [(ML)-L-II(OAc)]的催化反应性表现出显着差异,并且其金属离子依赖性顺序为Co(3)> Ni(4)> Zn(6)> Fe(2)> Mn (1)>铜(5)。它们之间反应性的差异可归因于结合的黄酮磺酸盐的底物的氧化还原电势,通过调节黄酮磺酸盐的电子密度,金属离子对金属离子的影响极大,从而提供了对金属离子效应和羧酸盐对苯甲酸的影响的重要见解。各种M-II-取代的2,3-QD的酶活性。我们的模型复合物[(ML)-L-II(OAc)]是各种M-II取代的静置2,3-QD的一系列结构和功能模型的第一个示例。

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