Ionization Patterns and Chemical Reactivity of Cytosine‐Guanine Watson‐Crick Pairs

Abstract

Gas‐phase and aqueous vertical ionization potentials, vIPgas and vIPaq respectively and measurements of the molecular electrostatic and local ionization maps calculated at the DFT/B3LYP‐D3/ 6‐311+G** level of theory and the C‐PCM reaction field model for single‐ and double‐stranded CpG and 5MeCpG pairs show that the vIPaq for single‐ and double‐stranded pairs of C‐G and 5MeC‐G are practically the same, in the range of 5.79 to 5.81 eV. The aqueous adiabatic ionization potentials for single‐stranded CpG and 5MeCpG are 5.52 eV and 5.51 eV respectively and they reflect the nuclear reorganization that takes place after the abstraction of the electron. The aqueous adiabatic ionization energy values that correspond to the CpG+. radical cation and the hydrated electron, e‐, , being at infinite distance, adIPaq + Vo, are 3.92 eV and 3.91 eV respectively with (Vo = ‐1.6 eV) Analysis of data suggest that the HOMO‐LUMO energy gap in the hard/soft‐acid/base (HSAB) concept cannot be used a priori to determine the effect of cytosine methylation on the guanine enhanced oxidative damage in DNA.