title: Hydrogen abstraction by photoexcited benzophenone: consequences for DNA photosensitization.
abstract: We report a computational investigation of the hydrogen abstraction (H-abstraction) induced by triplet benzophenone ((3)BP) on thymine nucleobase and backbone sugar. The chemical process is studied using both high level multiconfigurational perturbation and density functional theory. Both methods show good agreement in predicting small kinetic barriers. Furthermore the behavior of benzophenone in DNA is simulated using molecular dynamics and hybrid quantum mechanics/molecular mechanics methods. The accessibility of benzophenone to the labile hydrogens within B-DNA is demonstrated, as well as the driving force for this reaction. We evidence a strong dependence of the H-abstraction with the non-covalent BP-DNA interaction mode, and a reaction that is less favorable when embedded in DNA than for the isolated system.
authors.affiliation: Université de Lorraine - Nancy, Theory-Modeling-Simulation SRSMC, Vandoeuvre-les-Nancy, France. antonio.monari@univ-lorraine.fr and CNRS, Theory-Modeling-Simulation SRSMC, Vandoeuvre-les-Nancy, France.
authors.forename: Marco
authors.initials: M
authors.lastname: Marazzi
authors.affiliation: Instituto de Ciencia Molecular, Universitat de Valencia, Valencia, Spain. daniel.roca@uv.es.
authors.forename: Meilani
authors.initials: M
authors.lastname: Wibowo
authors.affiliation: Université de Lorraine - Nancy, Theory-Modeling-Simulation SRSMC, Vandoeuvre-les-Nancy, France. antonio.monari@univ-lorraine.fr and CNRS, Theory-Modeling-Simulation SRSMC, Vandoeuvre-les-Nancy, France.
authors.forename: Hugo
authors.initials: H
authors.lastname: Gattuso
authors.affiliation: Ecole Normale Supérieure de Lyon and CNRS, Laboratoire de Chimie, Lyon, France.
authors.forename: Elise
authors.initials: E
authors.lastname: Dumont
authors.affiliation: Instituto de Ciencia Molecular, Universitat de Valencia, Valencia, Spain. daniel.roca@uv.es.
authors.forename: Daniel
authors.initials: D
authors.lastname: Roca-Sanjuán
authors.affiliation: Université de Lorraine - Nancy, Theory-Modeling-Simulation SRSMC, Vandoeuvre-les-Nancy, France. antonio.monari@univ-lorraine.fr and CNRS, Theory-Modeling-Simulation SRSMC, Vandoeuvre-les-Nancy, France.
authors.forename: Antonio
authors.initials: A
authors.lastname: Monari
mesh_terms: D001577:Benzophenones / Q000737:chemistry*; D003198:Computer Simulation; D004247:DNA / Q000737:chemistry / Q000528:radiation effects*; D006859:Hydrogen / Q000737:chemistry*; D008027:Light; D056004:Molecular Dynamics Simulation
chemical_list: D001577:Benzophenones; C047723:benzophenone; D006859:Hydrogen; D004247:DNA