Proton Transfer of Guanine Radical Cations Studied by Time-Resolved Resonance Raman Spectroscopy Combined with Pulse Radiolysis

TLDR: The oxidation of guanine (G) is studied by using transient absorption and time-resolved resonance Raman spectroscopies combined with pulse radiolysis to demonstrate the pH dependence and the increase in the bonding order of pyrimidine (Pyr) and imidazole rings.

Abstract: The oxidation of guanine (G) is studied by using transient absorption and time-resolved resonance Raman spectroscopies combined with pulse radiolysis. The transient absorption spectral change demonstrates that the neutral radical of G (G•(−H+)), generated by the deprotonation of G radical cation (G•+), is rapidly converted to other G radical species. The formation of this species shows the pH dependence, suggesting that it is the G radical cation (G•+)′ formed from the protonation at the N7 of G•(−H+). On one hand, most Raman bands of (G•+)′ are up-shifted relative to those of G, indicating the increase in the bonding order of pyrimidine (Pyr) and imidazole rings. The (G•+)′ exhibits the characteristic CO stretching mode at ∼1266 cm–1 corresponding to a C–O single bond, indicating that the unpaired electron in (G•+)′ is localized on the oxygen of the Pyr ring.