Understanding
the details of DNA damage caused by high-energy particles
or photons is complicated by the multitude of reactive species, arising
from the ionization and dissociation of H2O, DNA, and protein.
In this work, oligonucleotides (ODNs) are irradiated with a beam of
low-energy electrons of 1.3 to 2.3 eV, which can only induce damage
via the decay of shape resonances into various dissociative electron
attachment channels. Using LC–MS/MS analysis, the major products
are the release of nonmodified nucleobases (NB; Cyt ≫ Thy ∼
Ade > Gua). Additional damage includes 5,6-dihydropyrimidines (dHT
> dHU) and eight nucleosides with modified sugar moieties consisting
of 2′,3′- and 2′,5′-dideoxynucleosides
(ddG > ddA ∼ ddC > ddT). The distribution of products
is remarkably
different in a 16-mer ODN compared to that observed previously with
thymidylyl-(3′-5′)-thymidine. This difference is explained
by electron delocalization occurring within a sufficiently long strand,
the DEA theory of O’Malley, and recent time-dependent density
functional theory calculations.