Ryan Paul, Hynes Michael J
Department of Chemistry, National University of Ireland, Galway, Ireland.
J Inorg Biochem. 2008 Jan;102(1):127-36. doi: 10.1016/j.jinorgbio.2007.07.041. Epub 2007 Aug 10.
The kinetics and mechanisms of the reactions of a pseudo-first order excess of iron(III) with the flavonoids quercetin and morin have been investigated in aqueous solution at 25 degrees C and an ionic strength of 0.5M. Mechanisms have been proposed which account satisfactorily for the kinetic data. The data are consistent with a mechanism in which the metal:ligand complex formed initially on reaction of iron(III) with the ligand subsequently decomposes through an electron transfer step. Morin forms a 1:1 metal:ligand complex while quercetin forms a 2:1 metal:ligand complex. Both ligands showed evidence for the involvement of the iron hydroxo dimer Fe2(OH)2(4+) in the complex formation reaction at the hydroxy-carbonyl moiety. The iron(III) assisted decomposition of the initial iron(III) complex formed was also investigated and the rate constants evaluated. Both the complex formation and subsequent electron transfer reactions of iron(III) with these ligands were monitored using UV-visible spectrophotometry. All of the suggested mechanisms and calculated rate constants are supported by calculations carried out using global analysis of time dependant spectra.
在25℃和离子强度为0.5M的水溶液中,研究了过量的拟一级铁(III)与黄酮类化合物槲皮素和桑色素反应的动力学及反应机理。已提出的反应机理能够令人满意地解释动力学数据。这些数据与一种机理相符,即铁(III)与配体反应最初形成的金属-配体络合物随后通过电子转移步骤分解。桑色素形成1:1的金属-配体络合物,而槲皮素形成2:1的金属-配体络合物。两种配体均显示出在羟基-羰基部分的络合反应中,铁羟基二聚体Fe2(OH)2(4+)参与反应的证据。还研究了铁(III)对最初形成的铁(III)络合物的分解作用,并评估了速率常数。利用紫外-可见分光光度法监测了铁(III)与这些配体的络合形成及随后的电子转移反应。所有提出的反应机理和计算得到的速率常数都得到了使用时间相关光谱全局分析进行的计算的支持。