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金属酚类配合物的自由基清除和催化活性

Radical scavenging and catalytic activity of metal-phenolic complexes.

作者信息

Mahal Harbir S, Kapoor Sudhir, Satpati Ashis K, Mukherjee Tulsi

机构信息

Radiation and Photochemistry Division, Analytical Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400085, India.

出版信息

J Phys Chem B. 2005 Dec 22;109(50):24197-202. doi: 10.1021/jp0549430.

Abstract

A series of metal-ligand complexes were prepared by the reaction of various metal ions, namely, Cu(II), Mn(II), or Fe(II) with phenolic derivatives of [catechol, chlorogenic acid (CGA), n-propyl gallate (nPG), 3-hydroxy anthranilic acid, resveratrol, and rutin] and characterized by UV-vis spectroscopy. The metal/ligand complexing ratio and complexation constants have been determined. The complexes were probed for their reactivity toward various free radicals (e aq-, CO2*-, and O2*-). Pulse radiolysis studies showed that the one-electron reduction of metal/phenol complexes by CO2*- radicals was metal-centered, and this was confirmed by the formation of an initial adduct with CO2*- radicals. Rate constants for the scavenging of superoxide anions with metal complexes ranged between 10(7)-10(9) dm3 mol(-1) s(-1) and those for the reaction of e aq- with the metal complexes were in the range of (1-5) x 10(9) dm3 mol(-1) s(-1), depending on the pH of the solution. Cyclic and differential pulse voltammetric studies showed that the reduction potential of the complexes are found to range between -0.022 to 0.45 V vs normal hydrogen electrode.

摘要

通过各种金属离子(即Cu(II)、Mn(II)或Fe(II))与[儿茶酚、绿原酸(CGA)、没食子酸正丙酯(nPG)、3-羟基邻氨基苯甲酸、白藜芦醇和芦丁]的酚类衍生物反应制备了一系列金属-配体配合物,并通过紫外-可见光谱对其进行了表征。确定了金属/配体的络合比和络合常数。研究了这些配合物对各种自由基(水合电子e aq-、二氧化碳负离子CO2* -和超氧阴离子O2* -)的反应活性。脉冲辐解研究表明,CO2* -自由基对金属/酚配合物的单电子还原是以金属为中心的,这一点通过与CO2* -自由基形成初始加合物得到了证实。金属配合物清除超氧阴离子的速率常数在10(7)-10(9) dm3 mol(-1) s(-1)之间,而e aq-与金属配合物反应的速率常数在(1 - 5)×10(9) dm3 mol(-1) s(-1)范围内,这取决于溶液的pH值。循环伏安法和差分脉冲伏安法研究表明,相对于标准氢电极,配合物的还原电位在-0.022至0.45 V之间。

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