Positive and negative ions of the amino acid histidine formed in low-energy electron collisions

Rebecca Meißner, Linda Feketeová, Andreas Bayer, Johannes Postler, Paulo Limão-Vieira, Stephan Denifl

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Histidine is an aromatic amino acid crucial for the biological functioning of proteins and enzymes. When biological matter is exposed to ionising radiation, highly energetic particles interact with the surrounding tissue which leads to efficient formation of low-energy electrons. In the present study, the interaction of low-energy electrons with gas-phase histidine is studied at a molecular level in order to extend the knowledge of electron-induced reactions with amino acids. We report both on the formation of positive ions formed by electron ionisation and negative ions induced by electron attachment. The experimental data were complemented by quantum chemical calculations. Specifically, the free energies for possible fragmentation reactions were derived for the τ and the π tautomer of histidine to get insight into the structures of the formed ions and the corresponding neutrals. We report the experimental ionisation energy of (8.48 ± 0.03) eV for histidine which is in good agreement with the calculated vertical ionisation energy. In the case of negative ions, the dehydrogenated parent anion is the anion with the highest mass observed upon dissociative electron attachment. The comparison of experimental and computational results was also performed in view of a possible thermal decomposition of histidine during the experiments, since the sample was sublimated in the experiment by resistive heating of an oven. Overall, the present study demonstrates the effects of electrons as secondary particles in the chemical degradation of histidine. The reactions induced by those electrons differ when comparing positive and negative ion formation. While for negative ions, simple bond cleav ages prevail, the observed fragment cations exhibit partly restructuring of the molecule during the dissociation process.

Original languageEnglish
Pages (from-to)802-816
Number of pages15
JournalJournal Of Mass Spectrometry
Issue number10
Publication statusPublished - 1 Oct 2019


  • amino acids
  • anions
  • cleavage reactions
  • ionisation potentials
  • mass spectrometry


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