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

Palivec, Vladimír; Pluhařová, Eva; Unger, I.; Winter, B.; Jungwirth, Pavel

doi:https://dx.doi.org/10.1021/jp5111086

Number of the records: 1

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

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SYSNO ASEP	0437492
Document Type	J - Journal Article
R&D Document Type	Journal Article
Subsidiary J	Článek ve WOS
Title	DNA lesion can facilitate base ionization: vertical ionization energies of aqueous 8-oxoguanine and its nucleoside and nucleotide
Author(s)	Palivec, Vladimír (UOCHB-X)_ORCID Pluhařová, Eva (UOCHB-X)_RID Unger, I. (DE) Winter, B. (DE) Jungwirth, Pavel (UOCHB-X)_{RID, ORCID}
Number of authors	5
Source Title	Journal of Physical Chemistry B. - : American Chemical Society - ISSN 1520-6106 Roč. 118, č. 48 (2014), s. 13833-13837
Number of pages	5 s.
Language	eng - English
Country	US - United States
Keywords	8-oxoguanine ; aqueous solution ; ionization ; ab initio calculations ; photoelectron spectroscopy
Subject RIV	CF - Physical ; Theoretical Chemistry
R&D Projects	GBP208/12/G016 GA ČR - Czech Science Foundation (CSF)
Institutional support	UOCHB-X - RVO:61388963
UT WOS	000345891500006
EID SCOPUS	84915764488
DOI	10.1021/jp5111086
Annotation	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.
Workplace	Institute of Organic Chemistry and Biochemistry
Contact	asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418
Year of Publishing	2015

Number of the records: 1