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