Oxidation of DNA represents a major pathway of genetic mutation. We have applied infrared spectroscopy in 77 K glass with supporting density functional theory (DFT) calculations (EDF1/6-31+G*) to provide an IR signature of the guanine radical cation G+̇, formed as a result of 193 nm photoionization of DNA. Deprotonation of this species to produce the neutral radical G(-H)̇ does not occur in 77 K glass. DFT calculations indicate that the formation of G+̇ within the double helix does not significantly perturb the geometry of the G/C pair, even though there is a significant movement of the N1 proton away from G toward C. However, this is in stark contrast to drastic changes that are expected if full deprotonation of G/C occurs, producing the G(-H)̇/C pair. These results are discussed in light of solution-phase time-resolved IR spectroscopic studies and demonstrate the power of IR to follow dynamics of DNA damage in natural environments.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry