Photoelectron spectroscopic studies of 5-halouracil anions

Journal Article · Thu Jan 06 23:00:00 EST 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3525623· OSTI ID:21559970

Radisic, Dunja; Ko, Yeon Jae; Nilles, John M; Stokes, Sarah T; Bowen, Kit H ^[1]; Sevilla, Michael D ^[2]; Rak, Janusz ^[3]

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1. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218 (United States)
2. Department of Chemistry, Oakland University, Rochester, Michigan 48309 (United States)
3. Department of Chemistry, University of Gdansk, 80-952 Gdansk (Poland)

The parent negative ions of 5-chlorouracil, UCl{sup -} and 5-fluorouracil, UF{sup -} have been studied using anion photoelectron spectroscopy in order to investigate the electrophilic properties of their corresponding neutral halouracils. The vertical detachment energies (VDE) of these anions and the adiabatic electron affinities (EA) of their neutral molecular counterparts are reported. These results are in good agreement with the results of previously published theoretical calculations. The VDE values for both UCl{sup -} and UF{sup -} and the EA values for their neutral molecular counterparts are much greater than the corresponding values for both anionic and neutral forms of canonical uracil and thymine. These results are consistent with the observation that DNA is more sensitive to radiation damage when thymine is replaced by halouracil. While we also attempted to prepare the parent anion of 5-bromouracil, UBr{sup -}, we did not observe it, the mass spectrum exhibiting only Br{sup -} fragments, i.e., 5-bromouracil apparently underwent dissociative electron attachment. This observation is consistent with a previous assessment, suggesting that 5-bromouracil is the best radio-sensitizer among these three halo-nucleobases.

• OSTI ID: 21559970
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 134; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTANT EFFECTS ON LIVING ORGS. AND BIOL. MAT.
ACCURACY
AFFINITY
ANIONS
AZINES
BROMINE IONS
CHARGED PARTICLES
DNA
ELECTRON ATTACHMENT
ELECTRON SPECTROSCOPY
HETEROCYCLIC COMPOUNDS
HYDROXY COMPOUNDS
IONIZING RADIATIONS
IONS
MASS SPECTRA
NUCLEIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PHOTOELECTRON SPECTROSCOPY
PYRIMIDINES
RADIATION EFFECTS
RADIATIONS
REAGENTS
SENSITIZERS
SPECTRA
SPECTROSCOPY
THYMINE
URACILS