Induction of strand breaks in polyribonucleotides and DNA by the sulphate radical anion: role of electron loss centres as precursors of strand breakage.

The interaction of the sulphate radical anion, SO4.-, with the polyribonucleotides, poly U and poly C, in deaerated, aqueous solutions at pH 7.5 results in strand breakage (sb) with efficiencies of 57 and 23%, respectively, determined by time resolved laser light scattering (TRLS). Most sb are produced within 70 microseconds, the risetime of the detection system. Oxygen inhibits the induction of sb in poly U and poly C by SO4.- through its interaction with a radical precursor to sb. In contrast, the interaction of SO4.- with poly A and single stranded DNA does not lead to significant strand breakage (< or = 5% efficiency). From optical studies, the interaction of poly A and poly G with SO4.- radicals yields predominantly the corresponding one electron oxidized base radicals. With poly C and poly U, it is proposed that the SO4.- radical interacts predominantly by addition to the base moiety to produce the C(5)-yl and C(6)-yl sulphate radical adducts which react with oxygen. These base adducts subsequently interact with the sugar-phosphate moiety by H-atom abstraction to yield C(2)' sugar radicals with rate constants in the range 1.3-1.7 x 10(5) s-1. It is proposed that the C(2)' sugar radical leads to strand breakage within 70 microseconds, in competition with its transformation into the C(1)'-sugar radical involving base release. From optical studies on the interaction of SO4.- with double stranded DNA, it is suggested that the predominant radical species produced in DNA is the one-electron oxidized radical of guanine, consistent with positive charge migration in DNA. Since the efficiency of SO4.- to induce sb in single stranded DNA is low, it is concluded that the one-electron oxidized guanine radical does not effectively induce strand breakage in DNA.