title: H2O3 as a reactive oxygen species: formation of 8-oxoguanine from its reaction with guanine.
abstract: Reaction of guanine with H2O3 in the absence and presence of a water molecule leading to the formation of 8-oxoguanine (8-oxoG) was investigated. Initial calculations were performed using imidazole (Im) as a model for the five-membered ring of guanine. The reactant, intermediate, and product complexes as well as transition states were obtained in gas phase at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels of theory. In all the cases, except for the reactions involving imidazole, single-point energy calculations were performed in gas phase at the MP2/AUG-cc-pVDZ level of theory. Solvation calculations in aqueous media were carried out using the polarizable continuum model (PCM) of the self-consistent reaction field (SCRF) theory. Vibrational frequency analysis and intrinsic reaction coordinate (IRC) calculations were performed to ensure that the transition states connected the reactant and product complexes properly. Zero-point energy (ZPE)-corrected total energies and Gibbs free energies at 298.15 K in gas phase and aqueous media were obtained. When a reaction of H2O3 in place of H2O2 with guanine is considered, the major barrier energy which is encountered at the first step is almost halved showing that H2O3 would be much more reactive than H2O2. Considering the reaction schemes investigated here and the observed fact that H2O3 is dissociated easily under ambient conditions, it appears that H2O3 would serve as an effective reactive oxygen species.
authors.affiliation: Department of Physics, Banaras Hindu University, Varanasi, 221 005, India.
authors.forename: P K
authors.initials: PK
authors.lastname: Shukla
authors.forename: P C
authors.initials: PC
authors.lastname: Mishra
mesh_terms: D003198:Computer Simulation; D006147:Guanine / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry*; D007093:Imidazoles / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D010087:Oxides / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D017382:Reactive Oxygen Species / Q000737:chemistry*
chemical_list: D007093:Imidazoles; D010087:Oxides; D017382:Reactive Oxygen Species; C470086:dihydrogen trioxide; D006147:Guanine; D010100:Oxygen