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The rate of interaction between H 2 O 2  and the DNA -Cu (I) complex increases with pH and with salt (NaCl) concentration, suggesting that HO 2  -  is involved. The pH dependence can be fitted, assuming k(DNA - Cu(I) + H 2 O 2 ) = 1 м  -1  s-1 and k (DNA -Cu(I) + HO 2  - ) = 10 5  м -1  s -1  (at low salt concentrations). These interactions cause DNA damage, probably due to the for­mation of  · OH radicals near the site of Cu(I) fixation at DNA bases. About 70% of the inter­mediates DNA  · OH , formed by free  · OH radicals, were found capable of reducing Cu(II) to regenerate DNA -Cu (I); thus a (limited) reaction chain involving “reductive propagation” by DNA  · OH species appears feasible upon reaction of H 2 O 2  with DNA -Cu (I).  · OH-induced in­termediates of poly(C) are more efficient (about 80%), those of poly(A) and poly(G) are less efficient (about 38%), in reducing Cu(II). Certain organic buffers, particulary HEPES and PIPES, promote autoxidation in DNA /Cu (II)/H 2 O 2  systems, and it is shown that  · OH-induced buffer intermediates as well as secondary stable buffer products can engage in “reductive propagation” of redox cycles.

The Interaction between Hydrogen Peroxide and the DNA -Cu (I) Complex: Effects of pH and Buffers