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Experimental and theoretical studies of dissociative electron attachment to metabolites oxaloacetic and citric acids

  • In this contribution the dissociative electron attachment to metabolites found in aerobic organisms, namely oxaloacetic and citric acids, was studied both experimentally by means of a crossed-beam setup and theoretically through density functional theory calculations. Prominent negative ion resonances from both compounds are observed peaking below 0.5 eV resulting in intense formation of fragment anions associated with a decomposition of the carboxyl groups. In addition, resonances at higher energies (3–9 eV) are observed exclusively from the decomposition of the oxaloacetic acid. These fragments are generated with considerably smaller intensities. The striking findings of our calculations indicate the different mechanism by which the near 0 eV electron is trapped by the precursor molecule to form the transitory negative ion prior to dissociation. For the oxaloacetic acid, the transitory anion arises from the capture of the electron directly into some valence states, while, for the citric acid, dipole- or multipole-bound statesIn this contribution the dissociative electron attachment to metabolites found in aerobic organisms, namely oxaloacetic and citric acids, was studied both experimentally by means of a crossed-beam setup and theoretically through density functional theory calculations. Prominent negative ion resonances from both compounds are observed peaking below 0.5 eV resulting in intense formation of fragment anions associated with a decomposition of the carboxyl groups. In addition, resonances at higher energies (3–9 eV) are observed exclusively from the decomposition of the oxaloacetic acid. These fragments are generated with considerably smaller intensities. The striking findings of our calculations indicate the different mechanism by which the near 0 eV electron is trapped by the precursor molecule to form the transitory negative ion prior to dissociation. For the oxaloacetic acid, the transitory anion arises from the capture of the electron directly into some valence states, while, for the citric acid, dipole- or multipole-bound states mediate the transition into the valence states. What is also of high importance is that both compounds while undergoing DEA reactions generate highly reactive neutral species that can lead to severe cell damage in a biological environment.show moreshow less

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Author details:Janina KopyraORCiD, Paulina WierzbickaORCiD, Adrian Tulwin, Guillaume Thiam, Ilko BaldORCiDGND, Franck RabilloudORCiD, Hassan Abdoul-CarimeORCiD
DOI:https://doi.org/10.3390/ijms22147676
ISSN:1422-0067
Title of parent work (English):International Journal of Molecular Sciences (IJMS)
Publisher:MDPI
Place of publishing:Basel
Publication type:Article
Language:English
Date of first publication:2021/06/07
Publication year:2021
Release date:2021/10/18
Tag:citric acid; dissociative electron attachment; mass spectrometry; negative ions; oxaloacetic acid
Volume:22
Issue:14
Article number:7676
Number of pages:14
Funding institution:Universität Potsdam
Funding number:PA 2021_072
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
DDC classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Peer review:Referiert
Grantor:Publikationsfonds der Universität Potsdam
Publishing method:Open Access / Gold Open-Access
License (German):License LogoCC-BY - Namensnennung 4.0 International
External remark:Zweitveröffentlichung in der Schriftenreihe Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe ; 1156
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