On the electron affinity of cytosine in bulk water and at hydrophobic aqueous interfaces
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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.
KeywordsCytosine QM/MM Electron affinity
E. V.-M. thanks FONDECYT for financial support provided by Proyecto 11121179, CONICYT, Departamento de Relaciones Internacionales “Programa de Cooperación Científica Internacional” CONICYT/DFG-607 and grant ICM No 120082. B. A. thanks the Deutsche Forschungsgemeinschaft (DFG) for financial support (AB 63/12-1).
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