Journal of the American Chemical Society, Vol.120, No.45, 11548-11553, 1998
Efficient oxidation of 2 '-deoxyguanosine by Mn-TMPyP/KHSO5 to imidazolone dIz without formation of 8-oxo-dG
Oxidation of 2'-deoxyguanosine dG with the chemical nuclease Mn-TMPyP/KHSO5 leads within one minute to a nearly quantitative amount of 2-amino-5-[(2-deoxy-beta-D-erythro-pentofuranosyl)amino]-4H-imidazol-4-one (dIz or imidazolone for short) (90%) in a non-oxygen-dependent pathway arid without formation of 8-oxo-dG. This new mechanism of dIz formation involves,as a crucial first step, the abstraction of two electrons from guanine by a high-valent porphyrin-Mn(V)=O species, leading to the dG(+) cation instead of the classical dG(.+) radical cation. We describe also the. oxidation of imidazolone into the corresponding imidazolone N-oxide in the presence of KHSO5.
Keywords:POTASSIUM MONOPERSULFATE, PORPHYRIN COMPLEX, NUCLEASE ACTIVITY;ELECTRON-TRANSFER, AQUEOUS-SOLUTION, RADICAL CATIONS, DNA;NUCLEOSIDES, CLEAVAGE, GUANINE