Abstract
The reactions of sulphonyl peroxyl radicals with DNA and its components at low temperatures are investigated through use of electron spin resonance spectroscopy. Radiolysis of cysteine sulphinic acid solution in oxygenated aqueous 5 moldm- 3 LiCl glass has been employed to generate sulphonyl peroxyl radicals, CysSO 2OO. The mechanism of production is a two-step process involving the oxidation of the sulphinate (CysSO 2-) to the sulphonyl radical (CysSO 2) by radiolytically produced Cl 2- followed by oxygen addition to CysSO2. Sulphonyl peroxyls are shown to be reactive towards DNA and nucleotides in low temperature glasses, giving rise to carbon-based peroxyl radicals. However, of the DNA bases only thymine was found to react readily. The thymine methyl group contains a relatively weak C-H bond which makes it easily abstractable. DNA nucleosides and nucleotides are likely attacked by CysSO 2OO by abstraction from the sugar C-H bonds. The C(1) position of deoxyribose ring of model nucleosides is suggested to be a preferred site for attack at low temperatures. The reaction with double-stranded DNA at higher temperatures may occur at the more accessible C(4) position. CysSO 2OO is also shown to react with a number of methyl substituted uracils, producing the highly persistent 5- oxouracil-6-yl radicals. The reaction mechanism proposed involves the addition of CysSO 2OO to pyrimidine 5,6- double bonds followed by elimination of cysteine sulphonic acid.