Pro-oxidant activity of aluminum: promoting the Fenton reaction by reducing Fe(III) to Fe(II).
Pro-oxidant activity of aluminum: promoting the Fenton reaction by reducing Fe(III) to Fe(II).
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DOI：
10.1016/j.jinorgbio.2012.09.008
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发表时间：
2012-12
影响因子：
3.9
通讯作者：
F. Ruipérez;J. Mujika;J. Ugalde;C. Exley;X. López
中科院分区：
文献类型：
--
作者：
F. Ruipérez;J. Mujika;J. Ugalde;C. Exley;X. López
铝-超氧化物复合物的可能性，以减少Fe（III）的Fe（II），促进氧化损伤，通过芬顿反应，研究使用高精度从头计算方法和密度泛函理论结合溶剂化连续方法来模拟散装溶剂的影响。研究发现，Al-超氧化物与Fe（III）生成Fe（II）的氧化还原反应是放热的。此外，在Al-超氧化物络合物中的超氧自由基离子的电子损失导致分子氧从铝的自发解离，因此回收Al 3+六水合络合物。如在以前的研究中所示，这种复合物再次倾向于稳定另一个超氧化物分子，这表明在Al（III）存在下增加Fe（II）浓度的催化循环。Al（OH）2+和Al（OH）2+水解物种的结果相似。我们的工作加强了这样一种想法，即铝在生物系统中的存在可能会导致一个重要的促氧化活性通过超氧化物形成机制。
The possibility for an Al-superoxide complex to reduce Fe(III) to Fe(II), promoting oxidative damage through the Fenton reaction, is investigated using highly accurate ab initio methods and density functional theory in conjunction with solvation continuum methods to simulate bulk solvent effects. It is found that the redox reaction between Al-superoxide and Fe(III) to produce Fe(II) is exothermic. Moreover, the loss of an electron from the superoxide radical ion in the Al-superoxide complex leads to a spontaneous dissociation of molecular oxygen from aluminum, recovering therefore an Al3+hexahydrated complex. As demonstrated in previous studies, this complex is again prone to stabilize another superoxide molecule, suggesting a catalytic cycle that augments the concentration of Fe(II) in the presence of Al(III). Similar results are found for Al(OH)2+and Al(OH)2+hydrolytic species. Our work reinforces the idea that the presence of aluminum in biological systems could lead to an important pro-oxidant activity through a superoxide formation mechanism.