Proton-coupled electron-transfer reactions at a distance in DNA duplexes: Kinetic deuterium isotope effect

Kinetic solvent isotope effects on the electron-transfer kinetics associated with the oxidation of guanine by a 2-aminopurine (2AP) neutral radical separated by 2 or 3 thymine, or 6 adenine residues on the same. strand in 15-mer double-stranded oligonucleotides in H2O or D2O were measured. The evolution in time of the oxidized form of guanine, the neutral radical G(-H)(.), and the electron acceptor, the neutral 2AP(-H)(.) radical, were followed directly by a spectroscopic laser pulse-induced transient absorption technique on a 1-200 mus time scale. About 70-100% of this one-electron-transfer reaction occurs on this relatively slow time scale in the three oligonucleotide duplexes studied. The rate constants of formation of G(-H)(.) in the oligonucleotides are larger in H2O than in D2O by a factor of 1.3-1.7. This kinetic isotope effect suggests that the electron-transfer reaction from G to 2AP(-H) is coupled to a deprotonation of G(.+), and a protonation of 2AP(-), the primary products of the electron-transfer reaction. Thus, electron-transfer reactions occurring at a distance in these DNA duplexes can be considered in terms of proton-coupled electron-transfer reactions.