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International Journal of Molecular Sciences
Article . 2022 . Peer-reviewed
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Electron Attachment to 5-Fluorouracil: The Role of Hydrogen Fluoride in Dissociation Chemistry

Authors: Eugene Arthur-Baidoo; Gabriel Schöpfer; Milan Ončák; Lidia Chomicz-Mańka; Janusz Rak; Stephan Denifl;

Electron Attachment to 5-Fluorouracil: The Role of Hydrogen Fluoride in Dissociation Chemistry

Abstract

We investigate dissociative electron attachment to 5-fluorouracil (5-FU) employing a crossed electron-molecular beam experiment and quantum chemical calculations. Upon the formation of the 5-FU− anion, 12 different fragmentation products are observed, the most probable dissociation channel being H loss. The parent anion, 5-FU−, is not stable on the experimental timescale (~140 µs), most probably due to the low electron affinity of FU; simple HF loss and F− formation are seen only with a rather weak abundance. The initial dynamics upon electron attachment seems to be governed by hydrogen atom pre-dissociation followed by either its full dissociation or roaming in the vicinity of the molecule, recombining eventually into the HF molecule. When the HF molecule is formed, the released energy might be used for various ring cleavage reactions. Our results show that higher yields of the fluorine anion are most probably prevented through both faster dissociation of an H atom and recombination of F− with a proton to form HF. Resonance calculations indicate that F− is formed upon shape as well as core-excited resonances.

Keywords

Anions, STABILIZATION, 5-HALOURACILS, Electrons, electron attachment, Article, Hydrofluoric Acid, MECHANISMS, ATOMS, electron attachment; 5-fluorouracil; anion; hydrogen fluoride, REARRANGEMENT REACTIONS, AFFINITIES, 5-fluorouracil, BASIS-SETS, RADIOSENSITIZATION, hydrogen fluoride, LOW-ENERGY ELECTRONS, 5-fluorouracyl, anion, przyłączenie elektronu, fluorowodór, DNA-DAMAGE, Fluorouracil, Hydrogen

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    11
    popularity
    This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
    Top 10%
    influence
    This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
    Average
    impulse
    This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
    Top 10%
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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
11
Top 10%
Average
Top 10%
Green
gold