Trolox的抗氧化活性:了解非血红素金属蛋白模型μ -氧-二铁(III)配合物氧化Trolox的机制途径

IF 1.8 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR
Bula Singh
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引用次数: 0

摘要

水溶性维生素E类似物Trolox-C (TXC)与μ -氧-二铁配合物[Fe(III)2(μ -O)(phen)4(H2O)2]Cl4⋅5H2O(1,phen = 1,10-菲罗啉)的反应导致酚类抗氧化剂的单电子氧化,中间形成一个苯氧基自由基,并积累一个醌类终产物。这些氧化反应与酸性缓冲介质(pH 4.0-5.8)中复合物1的单个还原有关,Trolox根据一级反应动力学定量还原1。每个1分子接受来自Trolox的2e -并还原为铁蛋白[Fe(phen)3]2+。氧化后,Trolox产生Trolox醌。在反应介质中,由于连续脱质子,1与[Fe(III)2(µ-O)(phen)4(H2O)(OH)]3+ (1a)和[Fe(III)2(µ-O)(phen)4(OH)2]2+ (1b)平衡存在(pKa分别为3.71和5.28)。动力学分析表明反应阶为1 <;1 & lt;1 b。机制可能性表明,虽然1、1a和1b是由ET机制减少的。我们认为,通过质子抽离,桥接的µ-氧基的初始活化导致了更高的1b反应活性。介质离子强度没有变化,表明一种阳离子与其他中性电荷之间的反应。正动力学同位素效应(kH/kD <;1)表示在配合物1中发生平衡前质子化步骤。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Anti -Oxidant Activity of Trolox: Understanding the Mechanistic Pathway of Oxidation of Trolox by µ-Oxo-Diiron(III) Complex, a Model of Non-Heme Metalloprotein

Anti -Oxidant Activity of Trolox: Understanding the Mechanistic Pathway of Oxidation of Trolox by µ-Oxo-Diiron(III) Complex, a Model of Non-Heme Metalloprotein

The reaction of Trolox-C (TXC), a water-soluble vitamin E analog, with µ-oxo-diiron complex [Fe(III)2(µ-O)(phen)4(H2O)2]Cl4⋅5H2O(1, phen = 1,10-phenanthroline) entailed one-electron oxidations of the phenolic antioxidant with intermediate formation of a phenoxyl radical and accumulation of a quinone end product. These oxidation reactions were linked to individual reductions of complex 1 in acidic buffer media (pH 4.0–5.8), Trolox quantitatively reduces 1 following a first-order reaction kinetics. Each molecule of 1 accepts 2e from Trolox and is reduced to ferroin, [Fe(phen)3]2+. On oxidation, Trolox produces Trolox quinone. In reaction media, due to successive deprotonations, 1 exists in equilibrium with the species [Fe(III)2(µ-O)(phen)4(H2O)(OH)]3+ (1a) and [Fe(III)2(µ-O)(phen)4(OH)2]2+ (1b) (pKa = 3.71 and 5.28 respectively). The kinetic analyses suggest for an unusual reactivity order as 1 < 1a < 1b. The mechanistic possibilities suggest that while 1, 1a, and 1b are reduced by an ET mechanism. We believe that the initial activation of the bridging µ-oxo group by a proton abstraction results in the higher reactivity of 1b. No variations in media ionic strength suggests for the reaction between one cationic species with other neutral charge species. Positive kinetic isotope effect (kH/kD < 1) indicates for a pre-equilibrium protonation step occur in complex 1.

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来源期刊
Russian Journal of Inorganic Chemistry
Russian Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
3.10
自引率
38.10%
发文量
237
审稿时长
3 months
期刊介绍: Russian Journal of Inorganic Chemistry is a monthly periodical that covers the following topics of research: the synthesis and properties of inorganic compounds, coordination compounds, physicochemical analysis of inorganic systems, theoretical inorganic chemistry, physical methods of investigation, chemistry of solutions, inorganic materials, and nanomaterials.
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