THE INFLUENCES OF OXIDATION AND CATIONIZATION ON THE N-GLYCOSIDIC BOND STABILITY OF 8-OXO-2′-DEOXYADENOSINE — A THEORETICAL STUDY

Abstract

This work is an attempt to evaluate theoretically the influences of oxidation and cationization on the N-glycosidic bond stability and the proton and sodium affinities on 8-oxo-2′-deoxyadenosine (8-oxodA) by using the density functional theory (DFT) B3LYP with basis set 6-31++G(d,p). This work shows that the cation attachment to 8-oxodA may modify the equilibrium geometry and bond dissociation. In all modified forms, the length of the N9–C1′ bond in which there is no intramolecular interaction, i.e. O8–H(Na)⋯O4′, increases relative to the neutral system 8-oxodA but that of others decreases. The analysis for the proton and sodium affinity energies indicates that the N1 and N3 atoms are the favorable sites for proton while the N1 atom is the favorable site for Na+. From the dissociation energies of the N-glycosidic bond, it has been found that the homolytic dissociation becomes more difficult upon introducing positive charge in the base ring. In contrast, these systems favor the heterolytic dissociation significantly. The influence is most prominent with the monocation obtained by O8 cationization.