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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4994679· OSTI ID:1474073
 [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
+ Show Author Affiliations

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.

Research Organization:
Univ. of Notre Dame, IN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
FC02-04ER15533
OSTI ID:
1474073
Alternate ID(s):
OSTI ID: 1378423
Journal Information:
Journal of Chemical Physics, Vol. 147, Issue 9; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

References (51)

Dual role of nicotine in addiction and cognition: A review of neuroimaging studies in humans journal September 2014
E-Cigarettes: A Scientific Review journal May 2014
Electron-transmission study of the temporary anion states of substituted pyridines journal January 1983
Effect of nicotine on brain activation during performance of a working memory task journal March 2001
Electron impact fragmentation of pyrrole molecules studied by fluorescence emission spectroscopy journal September 2011
Transplacental transfer and biotransformation studies of nicotine in the human placental cotyledon perfused in vitro journal November 1998
Photoelectron and threshold photoelectron valence spectra of pyridine journal February 2016
Dipole-bound negative ions: Collisional destruction and blackbody-radiation-induced photodetachment journal December 2003
VUV photoionisation of free azabenzenes: Pyridine, pyrazine, pyrimidine, pyridazine and s-triazine journal August 2008
Selenium, carbon monoxide and water as a new reduction system: Reductive cleavage of disulfides and diselenides to thiols and selenols journal January 1987
Study of triplet states and short-lived negative ions by means of electron impact spectroscopy journal January 1989
Shape resonances in the elastic scattering of slow electrons by pyridine journal August 2013
Electronic excitation and ionization spectra of azabenzenes: Pyridine revisited by the symmetry-adapted cluster configuration interaction method journal March 2001
A snapshot of smokers after lung and colorectal cancer diagnosis: Smoking After Cancer Diagnosis journal January 2012
Resonances in Electron Impact on Diatomic Molecules journal July 1973
Molecular rearrangement reactions in the gas phase triggered by electron attachment journal January 2013
Experimental and theoretical study of the metastable decay of negatively charged nucleosides in the gas phase journal January 2011
Electrostatic and stereoelectronic interaction impacts on the structural properties and isomerization reactions of methyl isocyanide and its trihalo-analogs journal August 2015
Rapid Sensitization of Physiological, Neuronal, and Locomotor Effects of Nicotine: Critical Role of Peripheral Drug Actions journal June 2013
Brain Activity in Cigarette Smokers Performing a Working Memory Task: Effect of Smoking Abstinence journal July 2005
The B Vitamins Nicotinamide (B3) and Riboflavin (B2) Stimulate Metamorphosis in Larvae of the Deposit-Feeding Polychaete Capitella teleta: Implications for a Sensory Ligand-Gated Ion Channel journal November 2014
Solvent Dependent Assembly of Lanthanide Metallacrowns Using Building Blocks with Incompatible Symmetry Preferences journal June 2014
Electron-induced damage of DNA and its components: Experiments and theoretical models journal November 2011
Electron-impact and chemical ionization detection of nicotine and cotinine by gas chromatography—mass spectrometry in rat plasma and brain journal August 1992
Electron Scattering from Pyridine journal April 2014
A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule journal December 2014
Electron attachment to the DNA bases adenine and guanine and dehydrogenation of their anionic derivatives: Density functional study journal January 2007
Effects of acute smoking on brain activity vary with abstinence in smokers performing the N-Back Task: A preliminary study journal December 2006
Modeling risk factors for nicotine and other drug abuse in the preclinical laboratory journal October 2009
Free-Base and Protonated Nicotine in Electronic Cigarette Liquids and Aerosols journal July 2015
Pharmacological and Chemical Effects of Cigarette Additives journal November 2007
Temporary negative ions and electron affinities of benzene and N ‐heterocyclic molecules: pyridine, pyridazine, pyrimidine, pyrazine, and s ‐triazine journal March 1975
Surface Analysis under Ambient Conditions Using Plasma-Assisted Desorption/Ionization Mass Spectrometry journal August 2007
Electron energy-loss spectroscopy of excited states of the pyridine molecules journal April 2016
Production of low-energy electrons by ionizing radiation journal August 2007
Molecular adsorption study of nicotine and caffeine on single-walled carbon nanotubes from first principles journal August 2013
Effects of Tobacco Smoking and Nicotine on Cancer Treatment journal October 2012
Collision-induced fragmentation pathways including odd-electron ion formation from desorption electrospray ionisation generated protonated and deprotonated drugs derived from tandem accurate mass spectrometry journal January 2006
Dissociative electron attachment to gas-phase N-methylformamide journal May 2014
Subcorneal Pustular Dermatosis journal April 1963
Depression and nicotine: Preclinical and clinical evidence for common mechanisms journal November 2001
Recent advances in understanding nicotinic receptor signaling mechanisms that regulate drug self-administration behavior journal October 2011
One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure journal November 2014
Comparison and Assessment of Electron Cross Sections for Monte Carlo Track Structure Codes journal August 1999
Associative and dissociative electron attachment by SF 6 and SF 5 Cl journal January 1988
Does nicotine improve cognitive function? journal August 1994
He I Ultraviolet Photoelectron Spectroscopy of Benzene and Pyridine in Supersonic Molecular Beams Using Photoelectron Imaging journal April 2011
Biomolecular Damage Induced by Ionizing Radiation: The Direct and Indirect Effects of Low-Energy Electrons on DNA journal April 2015
The effect of nicotine onin vitro sperm motion characteristics journal March 1995
Formation of CN ( B 2 Σ + ) radicals in the vacuum-ultraviolet photodissociation of pyridine and pyrimidine molecules journal February 2014
Characterization of Neutral Radicals from a Dissociative Electron Attachment Process journal August 2017

Cited By (4)

Selecting and identifying gas-phase protonation isomers of nicotineH + using combined laser, ion mobility and mass spectrometry techniques journal January 2019
Low-energy electron collisions with proline and pyrrolidine: A comparative study journal February 2018
Cross sections for electron collision with pyridine [C 5 H 5 N] molecule journal September 2018
Cross sections for electron collision with pyridine [C$_{5}$H$_{5}$N] molecule text January 2018

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