DFT STUDY ON METAL CATIONIZATION AND O6-PROTONATION ON 2′-DEOXYGUANOSINE CONFIGURATION: CHANGES ON SUGAR PUCKERING AND STRENGTH OF THE N-GLYCOSIDIC BOND

Abstract

Density functional theory (DFT) calculations were performed at the B3LYP/6-311++G (d, p) level to determine coordination geometries, absolute metal ion affinities, and free energies for all possible complexation stable products formed by monovalent metal cations including Li+ , Na+ , K+ with the nucleoside 2′-Deoxyguanosine. All computations indicate that the metal ion affinity (MIA) decreases on going from Li+ to Na+ and K+ for 2′-Deoxyguanosine. For example, the affinities for the metal ions described above are 75.2, 57.3, 43.4 kcal/mol, respectively. Furthermore, the influence of metal cationization and O6 protonation on the strength of the N-glycosidic bond, torsion angles and angle of pseudorotation (P) have been studied. With respect to the results, it has been found that metal binding significantly change the values of the phase angle of pseudorotation (P) in the sugar unit of these nucleosides but, O6 -protonation do not significantly change the values of the torsion angles and angle of pseudorotation (P). In all modified forms, the length of the C1'–N9 bond increases. The Mulliken population analysis and natural bond orbital (NBO) analysis on atomic charges have been carried out on the optimized geometries.