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Cu(II)-Induced oxidation of catechols (dopa, dopamine and epinephrine) to yield indolic aminochromes is speeded up by at least two orders of magnitude upon addition of DNA. This effect was observed both in aerobic and anaerobic solutions, indicating that it is not due to the reductive activation of oxygen with formation of O 2  ·-  and H 2 O 2  as oxidant. It is suggested that the unfavourable redox equilibrium of the catechol-Cu(II) complex, ROH-Cu(II) ⇄ Cu(I) + RO ·  + H + , to yield Cu(I) and semiquinone, is efficiently driven to the right by DNA due to formation of the strong DNA-Cu(I) complex, for which a stability constant of K ≈ 2×10 9  м -1  has been estimated previously. Absorbance changes characteristic to the formation of DNA-Cu(I) appear in fact concomitantly with the 480 nm absorption of aminochrome, derived from the semiquinone RO · . Cu(II)-Induced oxidation of ascorbate and o-phenylenediamine (leading to 2,3-diaminophenazine) was also speeded up by almost two orders of magnitude in presence of DNA. The observed activation of redox reactions of copper in the vicinity of DNA may have important implications with respect to the toxicological properties of certain bioreductive endogenous and xenobiotic compounds.

Cu(II)-Induced Oxidation of Catechols, Ascorbate and o-Phenylenediamine is Promoted by DNA