M. Chanon et al., Is O-1(2) alone sufficient for DNA cleavage? Possible involvement of paramagnetic intermediates, RES CHEM IN, 25(7), 1999, pp. 633-644
It is proposed that singlet dioxygen reacting with guanosine or deoxyguanos
ine part of nucleotides does not, by itself, cause DNA cleavage. The strand
break originates at the endoperoxide stage whenever this link evolves into
a O-centered radical. The O-centered radical is then in a good spatial pos
ition to abstract an hydrogen intramolecularly from the ribose or desoxyrib
ose part of the nucleotide. The carbon centered radical thus formed on the
sugar part may lead to strand break either by a p-scission mechanism or by
an homolytically induced solvolysis. High pH could also induce cleavage aft
er the endoperoxide stage via a base catalyzed ring chain protomerism.