skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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)
OSTI Identifier:
1474073
Alternate Identifier(s):
OSTI ID: 1378423
Grant/Contract Number:  
FC02-04ER15533
Resource Type:
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 = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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

  • Ernst, M.; Matochik, J. A.; Heishman, S. J.
  • Proceedings of the National Academy of Sciences, Vol. 98, Issue 8
  • DOI: 10.1073/pnas.061369098

Electron impact fragmentation of pyrrole molecules studied by fluorescence emission spectroscopy
journal, September 2011

  • Wasowicz, Tomasz; Linert, Ireneusz; Lachowicz, Izabela
  • Photonics Letters of Poland, Vol. 3, Issue 3
  • DOI: 10.4302/plp.2011.3.07

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

  • Śmiałek, Małgorzata A.; MacDonald, Michael A.; Ptasińska, Sylwia
  • The European Physical Journal D, Vol. 70, Issue 2
  • DOI: 10.1140/epjd/e2016-60673-0

Dipole-bound negative ions: Collisional destruction and blackbody-radiation-induced photodetachment
journal, December 2003

  • Suess, L.; Liu, Y.; Parthasarathy, R.
  • The Journal of Chemical Physics, Vol. 119, Issue 24
  • DOI: 10.1063/1.1628215

VUV photoionisation of free azabenzenes: Pyridine, pyrazine, pyrimidine, pyridazine and s-triazine
journal, August 2008

  • Vall-llosera, G.; Coreno, M.; Erman, P.
  • International Journal of Mass Spectrometry, Vol. 275, Issue 1-3
  • DOI: 10.1016/j.ijms.2008.05.019

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

  • Barbosa, Alessandra S.; Pastega, Diego F.; Bettega, Márcio H. F.
  • Physical Review A, Vol. 88, Issue 2
  • DOI: 10.1103/physreva.88.022705

Electronic excitation and ionization spectra of azabenzenes: Pyridine revisited by the symmetry-adapted cluster configuration interaction method
journal, March 2001

  • Wan, Jian; Hada, Masahiko; Ehara, Masahiro
  • The Journal of Chemical Physics, Vol. 114, Issue 12
  • DOI: 10.1063/1.1351880

A snapshot of smokers after lung and colorectal cancer diagnosis: Smoking After Cancer Diagnosis
journal, January 2012

  • Park, Elyse R.; Japuntich, Sandra J.; Rigotti, Nancy A.
  • Cancer, Vol. 118, Issue 12
  • DOI: 10.1002/cncr.26545

Resonances in Electron Impact on Diatomic Molecules
journal, July 1973


Molecular rearrangement reactions in the gas phase triggered by electron attachment
journal, January 2013

  • Ómarsson, Benedikt; Bjarnason, Elías H.; Haughey, Sean A.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 13
  • DOI: 10.1039/c3cp44320e

Experimental and theoretical study of the metastable decay of negatively charged nucleosides in the gas phase
journal, January 2011

  • Flosadóttir, Helga Dögg; Jónsson, Hannes; Sigurdsson, Snorri Th.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 33
  • DOI: 10.1039/c1cp21298b

Electrostatic and stereoelectronic interaction impacts on the structural properties and isomerization reactions of methyl isocyanide and its trihalo-analogs
journal, August 2015

  • Atabaki, Hooshang; Nori-Shargh, Davood; Momen-Heravi, Mohamad
  • Structural Chemistry, Vol. 27, Issue 3
  • DOI: 10.1007/s11224-015-0653-1

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


Solvent Dependent Assembly of Lanthanide Metallacrowns Using Building Blocks with Incompatible Symmetry Preferences
journal, June 2014

  • Jankolovits, Joseph; Kampf, Jeff. W.; Pecoraro, Vincent L.
  • Inorganic Chemistry, Vol. 53, Issue 14
  • DOI: 10.1021/ic500832u

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

  • Deutsch, Joseph; Hegedus, Lajos; Greig, Nigel H.
  • Journal of Chromatography B: Biomedical Sciences and Applications, Vol. 579, Issue 1
  • DOI: 10.1016/0378-4347(92)80366-x

Electron Scattering from Pyridine
journal, April 2014

  • Sieradzka, A.; Blanco, F.; Fuss, M. C.
  • The Journal of Physical Chemistry A, Vol. 118, Issue 33
  • DOI: 10.1021/jp503665a

A benchmark study of electronic excitation energies, transition moments, and excited-state energy gradients on the nicotine molecule
journal, December 2014

  • Egidi, Franco; Segado, Mireia; Koch, Henrik
  • The Journal of Chemical Physics, Vol. 141, Issue 22
  • DOI: 10.1063/1.4903307

Electron attachment to the DNA bases adenine and guanine and dehydrogenation of their anionic derivatives: Density functional study
journal, January 2007

  • Xie, Hujun; Cao, Zexing
  • International Journal of Quantum Chemistry, Vol. 107, Issue 5
  • DOI: 10.1002/qua.21252

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

  • Rabinoff, Michael; Caskey, Nicholas; Rissling, Anthony
  • American Journal of Public Health, Vol. 97, Issue 11
  • DOI: 10.2105/ajph.2005.078014

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

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

  • Petros, William P.; Younis, Islam R.; Ford, James N.
  • Pharmacotherapy: The Journal of Human Pharmacology and Drug Therapy, Vol. 32, Issue 10
  • DOI: 10.1002/j.1875-9114.2012.01117

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

  • Laje, Rene P.; Berman, Joshua A.; Glassman, Alexander H.
  • Current Psychiatry Reports, Vol. 3, Issue 6
  • DOI: 10.1007/s11920-001-0040-z

Recent advances in understanding nicotinic receptor signaling mechanisms that regulate drug self-administration behavior
journal, October 2011

  • Tuesta, Luis M.; Fowler, Christie D.; Kenny, Paul J.
  • Biochemical Pharmacology, Vol. 82, Issue 8
  • DOI: 10.1016/j.bcp.2011.06.026

One-photon mass-analyzed threshold ionization (MATI) spectroscopy of pyridine: Determination of accurate ionization energy and cationic structure
journal, November 2014

  • Lee, Yu Ran; Kang, Do Won; Kim, Hong Lae
  • The Journal of Chemical Physics, Vol. 141, Issue 17
  • DOI: 10.1063/1.4900569

Comparison and Assessment of Electron Cross Sections for Monte Carlo Track Structure Codes
journal, August 1999

  • Uehara, Shuzo; Nikjoo, Hooshang; Goodhead, Dudley T.
  • Radiation Research, Vol. 152, Issue 2
  • DOI: 10.2307/3580095

Associative and dissociative electron attachment by SF 6 and SF 5 Cl
journal, January 1988

  • Fenzlaff, Marita; Gerhard, Rolf; Illenberger, Eugen
  • The Journal of Chemical Physics, Vol. 88, Issue 1
  • DOI: 10.1063/1.454646

Does nicotine improve cognitive function?
journal, August 1994

  • Rusted, J.; Graupner, L.; O'Connell, N.
  • Psychopharmacology, Vol. 115, Issue 4
  • DOI: 10.1007/bf02245580

He I Ultraviolet Photoelectron Spectroscopy of Benzene and Pyridine in Supersonic Molecular Beams Using Photoelectron Imaging
journal, April 2011

  • Liu, Suet-Yi; Alnama, Koutayba; Matsumoto, Jun
  • The Journal of Physical Chemistry A, Vol. 115, Issue 14
  • DOI: 10.1021/jp1098574

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

  • Reddy, Anupama; Sood, Ajay; Rust, Philip F.
  • Journal of Assisted Reproduction and Genetics, Vol. 12, Issue 3
  • DOI: 10.1007/bf02211802

Formation of CN ( B 2 Σ + ) radicals in the vacuum-ultraviolet photodissociation of pyridine and pyrimidine molecules
journal, February 2014

  • Wasowicz, Tomasz J.; Kivimäki, Antti; Coreno, Marcello
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 47, Issue 5
  • DOI: 10.1088/0953-4075/47/5/055103

Characterization of Neutral Radicals from a Dissociative Electron Attachment Process
journal, August 2017


    Works referencing / citing this record:

    Selecting and identifying gas-phase protonation isomers of nicotineH + using combined laser, ion mobility and mass spectrometry techniques
    journal, January 2019

    • Marlton, Samuel J. P.; McKinnon, Benjamin I.; Ucur, Boris
    • Faraday Discussions, Vol. 217
    • DOI: 10.1039/c8fd00212f

    Selecting and identifying gas-phase protonation isomers of nicotineH + using combined laser, ion mobility and mass spectrometry techniques
    journal, January 2019

    • Marlton, Samuel J. P.; McKinnon, Benjamin I.; Ucur, Boris
    • Faraday Discussions, Vol. 217
    • DOI: 10.1039/c8fd00212f

    Low-energy electron collisions with proline and pyrrolidine: A comparative study
    journal, February 2018

    • Barbosa, Alessandra Souza; Freitas, Thiago Corrêa; Bettega, M. H. F.
    • The Journal of Chemical Physics, Vol. 148, Issue 7
    • DOI: 10.1063/1.5008748

    Cross sections for electron collision with pyridine [C 5 H 5 N] molecule
    journal, September 2018