Electron loss from N-(2-mercaptopropionyl) glycine (PSH) gave an EPR detectable radical anion, PS-.SP(-). When the PSH derivative was frozen in aqueous DNA solutions to 77 K and exposed to ionizing radiation, normal damage to the DNA was detected by EPR spectroscopy. However, on annealing above 77 K, central EPR features for the DNA base radical cations and anions gave central features assigned to PS-.SP(-) sigma*-radical anions, together with outer features for 5-6-dihydro-5-thymyl radicals, TH.. It is proposed that on freezing, the PSH molecules are constrained into a glassy region around the DNA, and that, on annealing, electron donation gives PS. radicals, with loss of quanine radical-cations, G(.+). The PS. radicals were not detectable, but on reaction with another PSH molecule, gave good EPR spectra for PS-.SP(-) radical-anions. These results indicate that PSH had little effect on the yield of the other base radicals C(.-)/T(.-). Also, growth of TH. radicals, formed from protonated thymine radical-anions, T(.-), were detected. We conclude that the primary effect of PSH is to capture the G(.+) centers, and thus could either prevent or repair radiation damage to DNA.

The heterocyclic structure of the pyrazoline obtained from reaction of 2,4-pentanedione with 4-methyl-3-thiosemicarbazide has been confirmed by X-ray crystallography. Reactions of the pyrazoline with CuII and ZnII have been probed by EPR and NMR spectroscopies respectively. The results suggest that the pyrazoline undergoes ring-opening back to the bis-thiosemicarbazone upon coordination to the transition metal, accompanied by oxidation of the central methylene group when the reactions are carried out under air.