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Oxidation Half-Reaction of Aqueous Nucleosides and Nucleotides via Photoelectron Spectroscopy Augmented by ab Initio Calculations
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SYSNO ASEP 0443310 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Oxidation Half-Reaction of Aqueous Nucleosides and Nucleotides via Photoelectron Spectroscopy Augmented by ab Initio Calculations Author(s) Schroeder, C. A. (US)
Pluhařová, Eva (UOCHB-X) RID
Seidel, R. (US)
Schroeder, W. P. (US)
Faubel, M. (DE)
Slavíček, P. (CZ)
Winter, B. (DE)
Jungwirth, Pavel (UOCHB-X) RID, ORCID
Bradforth, S. E. (US)Number of authors 9 Source Title Journal of the American Chemical Society. - : American Chemical Society - ISSN 0002-7863
Roč. 137, č. 1 (2015), s. 201-209Number of pages 9 s. Language eng - English Country US - United States Keywords DNA damage ; photoelectron spectroscopy ; DNA charge migration 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 000348483500046 EID SCOPUS 84921038760 DOI 10.1021/ja508149e Annotation Oxidative damage to DNA and hole transport between nucleobases in oxidized DNA are important processes in lesion formation for which surprisingly poor thermodynamic data exist, the relative ease of oxidizing the four nucleobases being one such example. Theoretical simulations of radiation damage and charge transport in DNA depend on accurate values for vertical ionization energies (VIEs), reorganization energies, and standard reduction potentials. Liquid-jet photoelectron spectroscopy can be used to directly study the oxidation half-reaction. The VIEs of nucleic acid building blocks are measured in their native buffered aqueous environment. The experimental investigation of purine and pyrimidine nucleotides, nucleosides, pentose sugars, and inorganic phosphate demonstrates that photoelectron spectra of nucleotides arise as a spectral sum over their individual chemical components; that is, the electronic interactions between each component are effectively screened from one another by water. Electronic structure theory affords the assignment of the lowest energy photoelectron band in all investigated nucleosides and nucleotides to a single ionizing transition centered solely on the nucleobase. Thus, combining the measured VIEs with theoretically determined reorganization energies allows for the spectroscopic determination of the one-electron redox potentials that have been difficult to establish via electrochemistry. 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 2016 Electronic address http://pubs.acs.org/doi/10.1021/ja508149e
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