DNA lesion can facilitate base ionization: vertical ionization energies of aqueous 8-oxoguanine and its nucleoside and nucleotide

0437492 - ÚOCHB 2015 RIV US eng J - Journal Article
Palivec, Vladimír - Pluhařová, Eva - Unger, I. - Winter, B. - Jungwirth, Pavel
DNA lesion can facilitate base ionization: vertical ionization energies of aqueous 8-oxoguanine and its nucleoside and nucleotide.
Journal of Physical Chemistry B. Roč. 118, č. 48 (2014), s. 13833-13837. ISSN 1520-6106. E-ISSN 1520-5207
R&D Projects: GA ČR GBP208/12/G016
Institutional support: RVO:61388963
Keywords : 8-oxoguanine * aqueous solution * ionization * ab initio calculations * photoelectron spectroscopy
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.302, year: 2014

8-Oxoguanine is one of the key products of indirect radiation damage to DNA by reactive oxygen species. Here, we describe ionization of this damaged nucleobase and the corresponding nucleoside and nucleotide in aqueous phase, modeled by the nonequilibrium polarizable continuum model, establishing their lowest vertical ionization energies of 6.8-7.0 eV. We thus confirm that 8-oxoguanine has even lower ionization energy than the parental guanine, which is the canonical nucleobase with the lowest ionization energy. Therefore, it can act as a trap for the cationic hole formed by ionizing radiation and thus protect DNA from further radiation damage. We also model using time-dependent density functional theory and measure by liquid jet photoelectron spectroscopy the valence photoelectron spectrum of 8-oxoguanine in water. We show that the calculated higher lying ionization states match well the experiment which, however, is not sensitive enough to capture the electron signal corresponding to the lowest ionization process due to the low solubility of 8-oxoguanine in water.
Permanent Link: http://hdl.handle.net/11104/0241229