Reactions in Nitroimidazole Triggered by Low‐Energy (0–2 eV) Electrons: Methylation at N1‐H Completely Blocks Reactivity |
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| Authors: | Katrin Tanzer Dr Linda Feketeová Benjamin Puschnigg Prof?Dr Paul Scheier Prof?Dr Eugen Illenberger Prof?Dr Stephan Denifl |
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| Institution: | 1. Institut für Ionenphysik und Angewandte Physik and Center of Molecular Biosciences, Leopold Franzens Universit?t Innsbruck, Technikerstrasse 25, 6020 Innsbruck (Austria);2. ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Chemistry and Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, 30 Flemington Road, Victoria 3010 (Australia);3. Present address: CNRS/IN2P3, UMR5822, Institut de Physique Nucléaire de Lyon, 69622 Villeurbanne (France);4. Institut für Chemie und Biochemie‐Physikalische und Theoretische Chemie, Freie Universit?t Berlin, Takustrasse 3, 14195 Berlin (Germany) |
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| Abstract: | Low‐energy electrons (LEEs) at energies of less than 2 eV effectively decompose 4‐nitroimidazole (4NI) by dissociative electron attachment (DEA). The reactions include simple bond cleavages but also complex reactions involving multiple bond cleavages and formation of new molecules. Both simple and complex reactions are associated with pronounced sharp features in the anionic yields, which are interpreted as vibrational Feshbach resonances acting as effective doorways for DEA. The remarkably rich chemistry of 4NI is completely blocked in 1‐methyl‐4‐nitroimidazole (Me4NI), that is, upon methylation of 4NI at the N1 site. These remarkable results have also implications for the development of nitroimidazole based radiosensitizers in tumor radiation therapy. |
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| Keywords: | gas‐phase reactions low‐energy electrons mass spectrometry metastable compounds reaction mechanisms |
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