Computation of Oxidation Potentials of Solvated Nucleobases by Static and Dynamic Multilayer Approaches
EntityUAM. Departamento de Química
PublisherAmerican Chemical Society
10.1021/acs.jcim.2c00234Journal of Chemical Information and Modeling 62.14 (2022): 3365–3380
ISSN1549-9596 (print); 1549-960X (online)
Funded byWe acknowledge the generous allocation of computer time at the Centro de Computación Científica at the Universidad Autónoma de Madrid (CCC-UAM). This work was partially supported by the MICINN, Spanish Ministry of Science and Innovation, Projects PID2019-110091GB-I00 and PID2020- 117806GA-I00 funded by MCIN/AEI/10.13039/ 501100011033, and the “María de Maeztu” (CEX2018- 000805-M) Program for Centers of Excellence in R&D. J.J.N. and G.C. acknowledge the Comunidad de Madrid for funding through the Attraction of Talent Program (Grant ref 2018-T1/BMD-10261). N.A.O. acknowledges the Comunidad de Madrid and European Social Fund for funding through the Programa Operativo de Empleo Juvenil y la Iniciativa de Empleo Juvenil. J.L.T. acknowledges the FPU19/02292 grant from the Spanish Ministry of Education and Vocational Training
Rights© 2022 The Authors
Esta obra está bajo una Licencia Creative Commons Atribución 4.0 Internacional.
The determination of the redox properties of nucleobases is of paramount importance to get insight into the charge-transfer processes in which they are involved, such as those occurring in DNA-inspired biosensors. Although many theoretical and experimental studies have been conducted, the value of the one-electron oxidation potentials of nucleobases is not welldefined. Moreover, the most appropriate theoretical protocol to model the redox properties has not been established yet. In this work, we have implemented and evaluated different static and dynamic approaches to compute the one-electron oxidation potentials of solvated nucleobases. In the static framework, two thermodynamic cycles have been tested to assess their accuracy against the direct determination of oxidation potentials from the adiabatic ionization energies. Then, the introduction of vibrational sampling, the effect of implicit and explicit solvation models, and the application of the Marcus theory have been analyzed through dynamic methods. The results revealed that the static direct determination provides more accurate results than thermodynamic cycles. Moreover, the effect of sampling has not shown to be relevant, and the results are improved within the dynamic framework when the Marcus theory is applied, especially in explicit solvent, with respect to the direct approach. Finally, the presence of different tautomers in water does not affect significantly the one-electron oxidation potentials
Files in this item
Google Scholar:Lucía Tamudo, Jesús - Cárdenas, Gustavo - Anguita Ortiz, Nuria - Díaz-Tendero Victoria, Sergio - Nogueira, Juan J.
This item appears in the following Collection(s)
Showing items related by title, author, creator and subject.