Molecular mechanism for metal-independent production of hydroxyl radicals by hydrogen peroxide and halogenated quinones.

Abstract:

:We have shown previously that hydroxyl radicals (HO*) can be produced by H2O2 and halogenated quinones, independent of transition metal ions; however, the underlying molecular mechanism is still unclear. In the present study, using the electron spin resonance secondary radical spin-trapping method, we found that tetrachloro-1,4-benzoquinone (TCBQ), but not its corresponding semiquinone anion radical, the tetrachlorosemiquinone anion radical (TCSQ*-), is essential for HO* production. The major reaction product between TCBQ and H2O2 was identified by electrospray ionization quadrupole time-of-flight mass spectrometry to be the ionic form of trichlorohydroxy-1,4-benzoquinone (TrCBQ-OH), and H2O2 was found to be the source and origin of the oxygen atom inserted into the reaction product TrCBQ-OH. On the basis of these data, we propose that HO* production by H2O2 and TCBQ is not through a semiquinone-dependent organic Fenton reaction but rather through the following mechanism: a nucleophilic attack of H2O2 to TCBQ, forming a trichlorohydroperoxyl-1,4-benzoquinone (TrCBQ-OOH) intermediate, which decomposes homolytically to produce HO*. This represents a mechanism of HO* production that does not require redox-active transition metal ions.

authors

Zhu BZ,Kalyanaraman B,Jiang GB

doi

10.1073/pnas.0704030104

subject

Has Abstract

pub_date

2007-11-06 00:00:00

pages

17575-8

issue

45

eissn

0027-8424

issn

1091-6490

pii

0704030104

journal_volume

104

pub_type

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