title: On the electron affinity of cytosine in bulk water and at hydrophobic aqueous interfaces.
abstract: In the past one possible mechanism of DNA damage in bulk water has been attributed to the presence of hydrated electrons in water. Recently, one important property of hydrated electrons, namely their binding energy, was reported to be smaller at hydrophobic interfaces than in bulk aqueous solution. This possibly opens up new reaction possibilities with different solutes such as the DNA at hydrophobic, aqueous interfaces. Here, we use QM/MM molecular dynamics simulation to study how the molecular environment at the vacuum-water interface and in the bulk alters the electron affinity of cytosine being a characteristic part of the DNA. The electron affinity at the interface is closer to the corresponding binding energy of the partially hydrated electron. The increased energy resonance makes the electron capture process more probable and suggests that hydrated electrons at hydrophobic interfaces may be more reactive than the fully hydrated ones. Additionally, we found that the relaxation of the anionic form after electron attachment also induces a proton transfer from the surrounding solvent that was confirmed by comparison with the experimental reduction potential.
authors.affiliation: Departamento de Físico-Química, Facultad de Ciencias Químicas, Universidad de Concepción, Concepción, Chile, evohringer@udec.cl.
authors.forename: Esteban
authors.initials: E
authors.lastname: Vöhringer-Martinez
authors.forename: Ciro
authors.initials: C
authors.lastname: Dörner
authors.forename: Bernd
authors.initials: B
authors.lastname: Abel
mesh_terms: D003596:Cytosine / Q000737:chemistry*; D004249:DNA Damage; D004583:Electrons; D004735:Energy Transfer; D057927:Hydrophobic and Hydrophilic Interactions; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D011522:Protons; D015203:Reproducibility of Results; D013329:Structure-Activity Relationship; D013499:Surface Properties; D014618:Vacuum; D014867:Water / Q000737:chemistry*
chemical_list: D011522:Protons; D014867:Water; D003596:Cytosine