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  • Title: Pro-oxidant activity of aluminum: promoting the Fenton reaction by reducing Fe(III) to Fe(II).
    Author: Ruipérez F, Mujika JI, Ugalde JM, Exley C, Lopez X.
    Journal: J Inorg Biochem; 2012 Dec; 117():118-23. PubMed ID: 23085591.
    Abstract:
    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 Al(3+) 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.
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