Low-energy electron-induced decomposition of 5-trifluoromethanesulfonyl-uracil: a potential radiosensitizer

J. Ameixa , E. Arthur-Baidoo , R. Meissner , Samanta Makurat , Witold Kozak , Kamila Butowska , F. Ferreira da Silva , Janusz Rak , S. Denifl

Abstract

5-trifluoromethanesulfonyl-uracil (OTfU), a recently proposed radiosensitizer, is decomposed in the gas-phase by attachment of low-energy electrons. OTfU is a derivative of uracil with a triflate (OTf) group at the C5-position, which substantially increases its ability to undergo effective electron-induced dissociation. We report a rich assortment of fragments formed upon dissociative electron attachment (DEA), mostly by simple bond cleavages (e.g., ehydrogenation or formation of OTf−). The most favorable DEA channel corresponds to the formation of the triflate anion alongside with the reactive uracil-5-yl radical through the cleavage of the O–C5 bond, particularly at about 0 eV. Unlike for halouracils, the parent anion was not detected in our experiments. The experimental findings are accounted by a comprehensive theoretical study carried out at the M06-2X/aug-cc-pVTZ level. The latter comprises the thermodynamic thresholds for the formation of the observed anions calculated under the experimental conditions (383.15 K and 3×10−11atm). The energy-resolved ion yield of the dehydrogenated parent anion, (OTfU–H)−, is discussed in terms of vibrational Feshbach resonances arising from the coupling between the dipole bound state and vibrational levels of the transient negative ion. We also report the mass spectrum of the cations obtained through ionization of OTfU by electrons with a kinetic energy of 70 eV. The current study endorses OTfU as a potential radiosensitizer agent with possible applications in radio-chemotherapy.
Author J. Ameixa
J. Ameixa,,
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, E. Arthur-Baidoo
E. Arthur-Baidoo,,
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, R. Meissner
R. Meissner,,
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, Samanta Makurat (FCh / DPCh / LBS)
Samanta Makurat,,
- Laboratory of Biological Sensitizers
, Witold Kozak (FCh / DPCh / LBS)
Witold Kozak,,
- Laboratory of Biological Sensitizers
, Kamila Butowska (IFB)
Kamila Butowska ,,
- Intercollegiate Faculty of Biotechnology UG
, F. Ferreira da Silva
F. Ferreira da Silva,,
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, Janusz Rak (FCh / DPCh / LBS)
Janusz Rak,,
- Laboratory of Biological Sensitizers
, S. Denifl
S. Denifl,,
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Journal seriesJournal of Chemical Physics, ISSN 0021-9606 [1089-7690], (A 35 pkt)
Issue year2018
Vol149
No16
Pages1-9
Publication size in sheets0.5
DOIDOI:10.1063/1.5050594
URL https://doi.org/10.1063/1.5050594
Languageen angielski
Score (nominal)35
ScoreMinisterial score = 35.0, 06-11-2018, ArticleFromJournal
Ministerial score (2013-2016) = 35.0, 06-11-2018, ArticleFromJournal
Publication indicators WoS Impact Factor: 2016 = 2.965 (2) - 2016=2.907 (5)
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