Intramolecular and Intermolecular Hole Delocalization Rules the Reducer Character of Isolated Nucleobases and Homogeneous Single-Stranded DNA

24 February 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


The use of DNA strands as nanowires or electrochemical biosensors requires a deep understanding of charge transfer processes along the strand, as well as of the redox properties. These properties are computationally assessed in detail throughout this study. By applying molecular dynamics and hybrid QM/continuum and QM/QM/continuum schemes, the vertical ionization energies, adiabatic ionization energies, vertical attachment energies, one-electron oxidation potentials, and delocalization of the hole generated upon oxidation have been determined for nucleobases in their free form and as part of a pure single-stranded DNA. We show that the reducer ability of the isolated nucleobases is explained by the intramolecular delocalization of the positively charged hole, while the enhancement of the reducer character when going from aqueous solution to the strand correlates very well with the intermolecular hole delocalization. Our simulations suggest that the redox properties of DNA strands can be tuned by playing with the balance between intramolecular and intermolecular charge delocalization.


One-electron oxidation potential
Hole Delocalization
Molecular Dynamics
Marcus Theory

Supplementary materials

Supporting Information for Hole Delocalization Regulates the Reducer Character of Isolated Nucleobases and DNA Strands
-One-electron oxidation potentials for nucleosides and nucleotides. -Probability distributions of the vertical attachment energies. -Charge delocalization analysis after vertical attachment.


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