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Title: Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine

Abstract

Dissociative electron attachment to nicotine, pyridine, and N-methyl-pyrrolidine was studied in the gas phase in order to assess their stability with respect to low-energy electron interactions. Anion yield curves for different products at electron energies ranging from zero to 15 eV were measured, and the molecular fragmentation pathways were proposed. Nicotine does not form a stable parent anion or a dehydrogenated anion, contrary to other biological systems. However, we have observed complex dissociation pathways involving fragmentation at the pyrrolidine side accompanied by isomerization mechanisms. Combining structure optimization and enthalpy calculations, performed with the Gaussian09 package, with the comparison with a deuterium-labeled N-methyl-d3-pyrrolidine allowed for the determination of the fragmentation pathways. In contrast to nicotine and N-methylpyrrolidine, the dominant pathway in dissociative electron attachment to pyridine is the loss of hydrogen, leading to the formation of an [M-H] - anion. The presented results provide important new information about the stability of nicotine and its constituent parts and contribute to a better understanding of the fragmentation mechanisms and their effects on the biological environment.

Authors:
 [1];  [2];  [3];  [3]
  1. Univ. of Notre Dame, IN (United States). Radiation Lab.
  2. Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Medical Imaging, College of Medicine
  3. Univ. of Notre Dame, IN (United States). Radiation Lab., and Dept. of Physics
Publication Date:
Research Org.:
Univ. of Notre Dame, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1474073
Alternate Identifier(s):
OSTI ID: 1378423
Grant/Contract Number:  
FC02-04ER15533
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 9; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ryszka, Michal, Alizadeh, Elahe, Li, Zhou, and Ptasińska, Sylwia. Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine. United States: N. p., 2017. Web. doi:10.1063/1.4994679.
Ryszka, Michal, Alizadeh, Elahe, Li, Zhou, & Ptasińska, Sylwia. Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine. United States. doi:10.1063/1.4994679.
Ryszka, Michal, Alizadeh, Elahe, Li, Zhou, and Ptasińska, Sylwia. Tue . "Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine". United States. doi:10.1063/1.4994679. https://www.osti.gov/servlets/purl/1474073.
@article{osti_1474073,
title = {Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine},
author = {Ryszka, Michal and Alizadeh, Elahe and Li, Zhou and Ptasińska, Sylwia},
abstractNote = {Dissociative electron attachment to nicotine, pyridine, and N-methyl-pyrrolidine was studied in the gas phase in order to assess their stability with respect to low-energy electron interactions. Anion yield curves for different products at electron energies ranging from zero to 15 eV were measured, and the molecular fragmentation pathways were proposed. Nicotine does not form a stable parent anion or a dehydrogenated anion, contrary to other biological systems. However, we have observed complex dissociation pathways involving fragmentation at the pyrrolidine side accompanied by isomerization mechanisms. Combining structure optimization and enthalpy calculations, performed with the Gaussian09 package, with the comparison with a deuterium-labeled N-methyl-d3-pyrrolidine allowed for the determination of the fragmentation pathways. In contrast to nicotine and N-methylpyrrolidine, the dominant pathway in dissociative electron attachment to pyridine is the loss of hydrogen, leading to the formation of an [M-H]- anion. The presented results provide important new information about the stability of nicotine and its constituent parts and contribute to a better understanding of the fragmentation mechanisms and their effects on the biological environment.},
doi = {10.1063/1.4994679},
journal = {Journal of Chemical Physics},
number = 9,
volume = 147,
place = {United States},
year = {Tue Sep 05 00:00:00 EDT 2017},
month = {Tue Sep 05 00:00:00 EDT 2017}
}

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Works referenced in this record:

Surface Analysis under Ambient Conditions Using Plasma-Assisted Desorption/Ionization Mass Spectrometry
journal, August 2007

  • Ratcliffe, Lucy V.; Rutten, Frank J. M.; Barrett, David A.
  • Analytical Chemistry, Vol. 79, Issue 16, p. 6094-6101
  • DOI: 10.1021/ac070109q