Factors controlling the site of protonation of the one electron adduct of cytosine and its derivatives

Podmore, I.D.; Malone, M.E.; Symons, M.C.R.; Cullis, P.M.; Dalgarno, B.G.

Journal of the Chemical Society Faraday Transactions 87(22): 3647-3652

1991


DOI: 10.1039/ft9918703647
Accession: 007341618

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Abstract
Exposure of cystosine and derivatives thereof to 60Co .gamma.-rays at 77 K in a range of aqueous solutions (H2O or D2O) at 77 K gave EPR spectra assigned to the corresponding radical anions. These spectra comprise either doublet or triplet hyperfine features due to one or two protons. Triplet features observed using H2O media become doublets using D2O media. Well defined triplet spectra were observed using lithium chloride glasses and methanol-water glasses. Using frozen aqueous solutions which give phase-separated solids, spectra ranging from doublets via mixtures to triplets were obtained, depending on the derivative used. It is suggested that the first formed radical anions are rapidly protonated either on the ring nitrogen [N(3)] or on the amino nitrogen. In the former, there is no extra splitting from the added proton and a major doublet is observed because of hyperfine coupling to the C(6) proton [C(6)-H]. In the latter case, the proton is thought to add along a path normal to the plane of the ring so that overlap with the SOMO is maximized, and there is a large hyperfine coupling. Coupling to the other two amino protons is too small to resolve under these conditions. The fact that the -N(CH3)2 derivative gives a doublet rather than a triplet supports the postulate that the -NH2 group is indeed protonated in the triplet species. For the acqueous-methanol glasses, on annealing, this extra doublet splitting is lost irreversibly, probably because rotation of the -NH3+ group sets in, making the three protons equivalent. As has been shown by Bernhard and co-workers, certain oligomers which give C.- centers on irradiation give rise to doublets only in H2O glasses. Hence N(3)-protonation is favoured in polymeric systems. Reasons for differences, and the importance of these results in relation to DNA are discussed.

Factors controlling the site of protonation of the one electron adduct of cytosine and its derivatives