The reduction potential of the slipped GC base pair in one-electron oxidized duplex DNA.

Redox equilibrium between the low potential aniline radical cation and the guanine in the GC base pair of duplex DNA has been established using pulse radiolysis. We relate the measurement of a radical one-electron reduction potential, E-0 ', of 1.01 +/- 0.03 V to the perturbation of the GC base pair to accommodate the neutral guanyl radical in an energetically more stable 'slipped' structure. The formation of the 'slipped' structure is exothermic by -11.4 kcal mol(-1) as calculated by DFT, which is inline with our experimental results.