Theoretical studies of the ultrafast deactivation mechanism of 8-oxo-guanine on the S1 and S2 electronic states in gas phase.

Abstract

The 8-oxo-deoxyguanosine is the most abundant specie of the DNA oxidative damage. Despite the deleterious effects such as gene mutation it may cause, the 8-oxodG was also reported to have beneficial effect such as repairing the nearby cyclobutane pyrimidine dimer (CPD) after photoexcitation. Due to its strong biological relevance, the photoinduced excited state dynamics behavior of 8-oxo-deoxyguanosine is of particular interest. In this work, a theoretical investigation by combination of complete active space self-consistent field (CASSCF) ab initio calculations and on-the-fly nonadiabatic dynamics simulations are implemented to provide intrinsic deactivation mechanism of its free base 8-oxoguanine after being excited to the S1 and S2 states. Two minimum energy conical intersections (MECIs) characterized by the C3-puckered motion with attractive chiral character are located, which contribute appreciably to the S1 state deactivation process. When the system is being excited to the S2 state directly, a S2→S1→S0 two-step decay pattern is proposed. A nearly planar S2/S1 intersection plays a significant role in the S2→S1 decay process. The subsequent S1 state relaxation process is also dominated by the C3-puckered deformation motion. One decay time is estimated to be 704fs, which compares well with the experimental observation of 0.9±0.1ps in solvents. Particular illustration is the fact that the MECIs configurations we located bear an exceptional resemblance with previous reported thymine, cytosine and guanine, suggesting that the current work could lend support for better understanding of the non-natural nucleobases and derivatives.