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铝离子促进的甲基化对苯二酚衍生物的自由基清除反应。

Aluminium ion-promoted radical-scavenging reaction of methylated hydroquinone derivatives.

机构信息

Quantitative RedOx Sensing Team (QRST), Department of Basic Medical Sciences for Radiation Damages, National Institute of Radiological Sciences (NIRS), National Institutes for Quantum and Radiological Science and Technology (QST), Inage-ku, Chiba 263-8555, Japan.

Division of Oxidative Stress Research, Showa Pharmaceutical University, Machida, Tokyo 194-8543, Japan.

出版信息

Org Biomol Chem. 2016 Aug 16;14(33):7956-61. doi: 10.1039/c6ob01470d.

Abstract

The effect of the aluminium ion (Al(3+)) on the scavenging reaction of a 2,2-diphenyl-1-picrylhydrazyl radical (DPPH˙), as a reactivity model of reactive oxygen species, with hydroquinone (QH2) and its methylated derivatives (MenQH2, n = 1-4) was investigated using stopped-flow and electrochemical techniques in a hydroalcoholic medium. The second-order rate constants (k) for the DPPH˙-scavenging reaction of the hydroquinones increased with the increasing number of methyl substituents. Upon addition of Al(3+), the k values significantly increased depending on the concentration of Al(3+). Such an accelerating effect of Al(3+) on the DPPH˙-scavenging rates of the hydroquinones results from the remarkable positive shift of the one-electron reduction potential (Ered) of DPPH˙ in the presence of Al(3+). These results demonstrate that Al(3+), a strong Lewis acid, can act as a radical-scavenging promoter by stabilising the one-electron reduced species of the radical, although Al(3+) is reported not only to act as a pro-oxidant but also to strongly interact with biomolecules, showing toxicities.

摘要

采用停流和电化学技术在水醇介质中研究了铝离子(Al(3+))对 2,2-二苯基-1-苦基肼自由基(DPPH˙)清除反应的影响,DPPH˙是活性氧物种的反应性模型,研究对象为对苯二酚(QH2)及其甲基化衍生物(MenQH2,n = 1-4)。苯二酚的 DPPH˙清除反应的二级速率常数(k)随甲基取代基数量的增加而增加。加入 Al(3+)后,k 值取决于 Al(3+)的浓度,显著增加。Al(3+)对苯二酚 DPPH˙清除速率的这种加速作用源于 DPPH˙的单电子还原电势(Ered)在 Al(3+)存在下显著正向移动。这些结果表明,尽管 Al(3+) 不仅被报道为氧化剂,而且还与生物分子强烈相互作用,表现出毒性,但作为一种强路易斯酸,Al(3+) 可以通过稳定自由基的单电子还原物种来充当自由基清除促进剂。

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