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Title: Dissociative electron attachment to the gas-phase nucleobase hypoxanthine

Abstract

We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C{sub 5}H{sub 4}N{sub 4}O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp − H) anion (C{sub 5}H{sub 3}N{sub 4}O{sup −}) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp − NH){sup −}, C{sub 4}H{sub 3}N{sub 4}{sup −}/C{sub 4}HN{sub 3}O{sup −}, C{sub 4}H{sub 2}N{sub 3}{sup −}, C{sub 3}NO{sup −}/HC(HCN)CN{sup −}, OCN{sup −}, CN{sup −}, and O{sup −}. Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA tomore » Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.« less

Authors:
 [1]; ;  [2];  [1];  [1]
  1. Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556 (United States)
  2. Institut für Ionenphysik und Angewandte Physik, and Center for Molecular Biosciences Innsbruck (CMBI), Leopold-Franzens Universität Innsbruck, Technikerstr. 25, A-6020 Innsbruck (Austria)
Publication Date:
OSTI Identifier:
22415953
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 21; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ADENINES; ANIONS; BOUND STATE; CALCULATION METHODS; DEHYDROGENATION; DIPOLES; ELECTRON ATTACHMENT; ELECTRONS; EV RANGE; HYDROCYANIC ACID; HYPOXANTHINE; MASS SPECTRA; PRECURSOR; RADIATION EFFECTS

Citation Formats

Dawley, M. Michele, Tanzer, Katrin, Denifl, Stephan, Carmichael, Ian, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, Ptasińska, Sylwia, and Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556. Dissociative electron attachment to the gas-phase nucleobase hypoxanthine. United States: N. p., 2015. Web. doi:10.1063/1.4921388.
Dawley, M. Michele, Tanzer, Katrin, Denifl, Stephan, Carmichael, Ian, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, Ptasińska, Sylwia, & Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556. Dissociative electron attachment to the gas-phase nucleobase hypoxanthine. United States. https://doi.org/10.1063/1.4921388
Dawley, M. Michele, Tanzer, Katrin, Denifl, Stephan, Carmichael, Ian, Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, Ptasińska, Sylwia, and Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556. Sun . "Dissociative electron attachment to the gas-phase nucleobase hypoxanthine". United States. https://doi.org/10.1063/1.4921388.
@article{osti_22415953,
title = {Dissociative electron attachment to the gas-phase nucleobase hypoxanthine},
author = {Dawley, M. Michele and Tanzer, Katrin and Denifl, Stephan and Carmichael, Ian and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556 and Ptasińska, Sylwia and Department of Physics, University of Notre Dame, Notre Dame, Indiana 46556},
abstractNote = {We present high-resolution measurements of the dissociative electron attachment (DEA) to isolated gas-phase hypoxanthine (C{sub 5}H{sub 4}N{sub 4}O, Hyp), a tRNA purine base. The anion mass spectra and individual ion efficiency curves from Hyp were measured as a function of electron energy below 9 eV. The mass spectra at 1 and 6 eV exhibit the highest anion yields, indicating possible common precursor ions that decay into the detectable anionic fragments. The (Hyp − H) anion (C{sub 5}H{sub 3}N{sub 4}O{sup −}) exhibits a sharp resonant peak at 1 eV, which we tentatively assign to a dipole-bound state of the keto-N1H,N9H tautomer in which dehydrogenation occurs at either the N1 or N9 position based upon our quantum chemical computations (B3LYP/6-311+G(d,p) and U(MP2-aug-cc-pVDZ+)) and prior studies with adenine. This closed-shell dehydrogenated anion is the dominant fragment formed upon electron attachment, as with other nucleobases. Seven other anions were also observed including (Hyp − NH){sup −}, C{sub 4}H{sub 3}N{sub 4}{sup −}/C{sub 4}HN{sub 3}O{sup −}, C{sub 4}H{sub 2}N{sub 3}{sup −}, C{sub 3}NO{sup −}/HC(HCN)CN{sup −}, OCN{sup −}, CN{sup −}, and O{sup −}. Most of these anions exhibit broad but weak resonances between 4 and 8 eV similar to many analogous anions from adenine. The DEA to Hyp involves significant fragmentation, which is relevant to understanding radiation damage of biomolecules.},
doi = {10.1063/1.4921388},
url = {https://www.osti.gov/biblio/22415953}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 21,
volume = 142,
place = {United States},
year = {2015},
month = {6}
}