TDDFT Study on Excited-State Hydrogen Bonding of 2′-Deoxyguanosine in H2O Solution

Abstract

The mono and dihydrated complexes of 2′-deoxyguanosine have been used to elucidate the importance of the 2′-hydroxy group in the hydration. Density functional theory and time-dependent density functional theory methods were performed to investigate the ground-and excited-state hydrogen bonding properties of 2′-deoxyguanosine-water (2′-dG-W) and 2′-deoxyguanosine-2water (2′-dG-2W). Infrared spectra, geometric optimizations, frontier molecular orbitals and Mulliken charges have also been studied. The results demonstrated that the excited-state intramolecular hydrogen bonding dynamics of complexes 2′-dG-W and 2′-dG-2W behaves differently upon photoexcitation, while their intermolecular hydrogen bonding dynamics behaves similarly. Moreover, the significant weakening of the intermolecular hydrogen bond O4⋯H1–N1 and the formation of the new strong hydrogen bond O4⋯H3–N2 in the 2′-dG-2W upon photoexcitation were due to the geometric structure bending of guanine and the rigidity of related molecules. In addition, the charge transfer properties were theoretically investigated by analysis of molecular orbital.