title: Reaction electronic flux and its role in DNA intramolecular proton transfers.
abstract: Proton transfer reactions present a key step in many biological and chemical processes. Here, we focused on the electronic changes in the proton transfer reactions of the four DNA bases. In combination with the previous structural analysis the reaction electronic flux together with local descriptors as the Hirshfeld-I charges allow us to identify chemical events and rationalize the underlying reaction mechanism. Our results show that imine-enamine in adenine and citosyne, and keto-enol tautomerizations in thymine and guanine have different reaction mechanisms. The former involve net structural rearrangements driven by favoured electrostatic interactions between the proton and the acceptor atom whereas the keto-enol tautomerizations require electronic changes reflected in the reaction electronic flux and changes in the NBO bond orders which favour the proton transfer reaction.
authors.affiliation: Milennium Nucleous of Chemical Processes and Catalysis (CPC), Santiago, Chile.|QTC, Departamento de Químico Física, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860, Macul, Santiago, Chile.
authors.forename: Rocío
authors.initials: R
authors.lastname: Durán
authors.affiliation: QTC, Departamento de Químico Física, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860, Macul, Santiago, Chile.|Departamento de Físico-Química, Facultad de Ciencias Químicas, Universidad de Concepción, Concepción, Chile.
authors.forename: Esteban
authors.initials: E
authors.lastname: Vöhringer-Martinez
authors.affiliation: Milennium Nucleous of Chemical Processes and Catalysis (CPC), Santiago, Chile.|QTC, Departamento de Químico Física, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860, Macul, Santiago, Chile.
authors.forename: Alejandro
authors.initials: A
authors.lastname: Toro-Labbé
authors.affiliation: Milennium Nucleous of Chemical Processes and Catalysis (CPC), Santiago, Chile. bherrera@uc.cl.|QTC, Departamento de Químico Física, Pontificia Universidad Católica de Chile, Av. Vicuña Mackenna 4860, Macul, Santiago, Chile. bherrera@uc.cl.
authors.forename: Bárbara
authors.initials: B
authors.lastname: Herrera
mesh_terms: D000225:Adenine / Q000737:chemistry; D000465:Algorithms; D003596:Cytosine / Q000737:chemistry; D004247:DNA / Q000737:chemistry*; D004583:Electrons; D006147:Guanine / Q000737:chemistry; D007097:Imines / Q000737:chemistry; D007536:Isomerism; D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D011522:Protons; D055672:Static Electricity; D013941:Thymine / Q000737:chemistry
chemical_list: D007097:Imines; D011522:Protons; D006147:Guanine; D003596:Cytosine; D004247:DNA; D000225:Adenine; D013941:Thymine
keywords: Proton transfers; Reaction electronic flux; Reaction force