Infrared characterization of the guanine radical cation: finger printing DNA damage

J Phys Chem B. 2010 Mar 18;114(10):3660-7. doi: 10.1021/jp9106958.


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 N(1) 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.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cations / chemistry*
  • DNA / chemistry
  • DNA Damage*
  • Guanine / chemistry*
  • Nucleic Acid Conformation
  • Spectrophotometry, Infrared


  • Cations
  • Guanine
  • DNA