Theoretical and electrochemical study of the mechanism of anthraquinone-mediated one-electron reduction of oxygen: the involvement of adducts of dioxygen species to anthraquinones
1997
Anthraquinone derivatives, which are an important class of
anticancer drugs, possess the ability to mediate the transfer of one
electron to molecular oxygen to form the superoxide anion radical, which
results in their undesirable peroxidating and, further, cardiotoxic
properties. In this paper one-electron reduction of
dioxygen–anthraquinone systems was studied using electrochemical and
theoretical methods. Cyclic voltammetry (CV) experiments performed on
dimethyl sulfoxide and dimethylformamide solutions of selected
anthraquinones suggest that anthraquinones bearing hydroxy groups or their
semiquinones interact remarkably with molecular oxygen; this is manifested
as a shift of anthraquinone-reduction potential towards more positive
values in the presence of oxygen. This phenomenon can be explained by the
assumption that anthraquinone reduction is accompanied with oxygen addition
to form hydroperoxide anion radicals, which can be formed by anthraquinones
possessing proton-donor (e.g. hydroxy) groups only; the calculated
(using the ab initio, DFT and semiempirical PM3 methods, with
1-hydroxynaphthoquinone and model anthraquinone derivatives as model
compounds) enthalpies of this process are greater than those of
anthraquinone reduction alone.
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