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  • Accepted Manuscript: One-electron oxidation of ds(5′-GGG-3′) and ds(5′-G(8OG)G-3′) and the nature of hole distribution: a density functional theory (DFT) study
Title: One-electron oxidation of ds(5′-GGG-3′) and ds(5′-G(8OG)G-3′) and the nature of hole distribution: a density functional theory (DFT) study
Of particular interest in radiation-induced charge transfer processes in DNA is the extent of hole localization immediately after ionization and subsequent relaxation. To address this, we considered double stranded oligomers containing guanine (G) and 8-oxoguanine (8OG), i.e. , ds(5′-GGG-3′) and ds(5′-G8OGG-3′) in B-DNA conformation. Using DFT, we calculated a variety of properties, viz. , vertical and adiabatic ionization potentials, spin density distributions in oxidized stacks, solvent and solute reorganization energies and one-electron oxidation potential ( E 0 ) in the aqueous phase. Calculations for the vertical state of the -GGG- cation radical showed that the spin was found mainly (67%) on the middle G. However, upon relaxation to the adiabatic -GGG- cation radical, the spin localized (96%) on the 5′-G, as observed in experiments. Hole localizations on the middle G and 3′-G were higher in energy by 0.5 kcal mol −1 and 0.4 kcal mol −1 , respectively, than that of 5′-G. In the -G8OGG- cation radical, the spin localized only on the 8OG in both vertical and adiabatic states. The calculated vertical ionization potentials of -GGG- and -G8OGG- stacks were found to be lower than that of the vertical ionization potential of a single G in DNA. The calculated more » E 0 values of -GGG- and -G8OGG- stacks are 1.15 and 0.90 V, respectively, which owing to stacking effects are substantially lower than the corresponding experimental E 0 values of their monomers (1.49 and 1.18 V, respectively). SOMO to HOMO level switching is observed in these oxidized stacks. Consequently, our calculations predict that local double oxidations in DNA will form triplet diradical states, which are especially significant for high LET radiations. « less
Authors:
; ; ;
Award ID(s):
1920110
Publication Date:
NSF-PAR ID:
10286737
Journal Name:
Physical Chemistry Chemical Physics
Volume:
22
Issue:
9
Page Range or eLocation-ID:
5078 to 5089
ISSN:
1463-9076
Sponsoring Org:
National Science Foundation
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