DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio

Abstract

Here, a new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section (Ω), a quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio (m/z), a two-dimensional Ω – m/z space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D Ω – m/z space. Species of the same chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the Ω – m/z space.more » Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [1];  [3];  [3];  [1];  [2];  [1];  [1]
  1. Aerodyne Research Inc., Billerica, MA (United States)
  2. Univ. of Colorado, Boulder, CO (United States); Cooperative Institute for Research in Environmental Sciences, Boulder, CO (United States)
  3. TOFWERK, Thun (Switzerland)
Publication Date:
Research Org.:
Univ. of Colorado, Boulder, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1360106
Grant/Contract Number:  
SC0011105
Resource Type:
Accepted Manuscript
Journal Name:
Atmospheric Chemistry and Physics (Online)
Additional Journal Information:
Journal Name: Atmospheric Chemistry and Physics (Online); Journal Volume: 16; Journal Issue: 20; Journal ID: ISSN 1680-7324
Publisher:
European Geosciences Union
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Xuan, Krechmer, Jordan E., Groessl, Michael, Xu, Wen, Graf, Stephan, Cubison, Michael, Jayne, John T., Jimenez, Jose L., Worsnop, Douglas R., and Canagaratna, Manjula R. A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio. United States: N. p., 2016. Web. doi:10.5194/acp-16-12945-2016.
Zhang, Xuan, Krechmer, Jordan E., Groessl, Michael, Xu, Wen, Graf, Stephan, Cubison, Michael, Jayne, John T., Jimenez, Jose L., Worsnop, Douglas R., & Canagaratna, Manjula R. A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio. United States. https://doi.org/10.5194/acp-16-12945-2016
Zhang, Xuan, Krechmer, Jordan E., Groessl, Michael, Xu, Wen, Graf, Stephan, Cubison, Michael, Jayne, John T., Jimenez, Jose L., Worsnop, Douglas R., and Canagaratna, Manjula R. Wed . "A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio". United States. https://doi.org/10.5194/acp-16-12945-2016. https://www.osti.gov/servlets/purl/1360106.
@article{osti_1360106,
title = {A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio},
author = {Zhang, Xuan and Krechmer, Jordan E. and Groessl, Michael and Xu, Wen and Graf, Stephan and Cubison, Michael and Jayne, John T. and Jimenez, Jose L. and Worsnop, Douglas R. and Canagaratna, Manjula R.},
abstractNote = {Here, a new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section (Ω), a quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio (m/z), a two-dimensional Ω – m/z space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D Ω – m/z space. Species of the same chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the Ω – m/z space. Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.},
doi = {10.5194/acp-16-12945-2016},
journal = {Atmospheric Chemistry and Physics (Online)},
number = 20,
volume = 16,
place = {United States},
year = {Wed Oct 19 00:00:00 EDT 2016},
month = {Wed Oct 19 00:00:00 EDT 2016}
}

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

Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Application of a universal force field to organic molecules
journal, December 1992

  • Casewit, C. J.; Colwell, K. S.; Rappe, A. K.
  • Journal of the American Chemical Society, Vol. 114, Issue 25
  • DOI: 10.1021/ja00051a041

A two-dimensional volatility basis set – Part 2: Diagnostics of organic-aerosol evolution
journal, January 2012

  • Donahue, N. M.; Kroll, J. H.; Pandis, S. N.
  • Atmospheric Chemistry and Physics, Vol. 12, Issue 2
  • DOI: 10.5194/acp-12-615-2012

Metabolic profiling by ion mobility mass spectrometry (IMMS)
journal, December 2007


Peer Reviewed: Ion Mobility Spectrometers in National Defense
journal, November 2004

  • Eiceman, G. A.; Stone, J. A.
  • Analytical Chemistry, Vol. 76, Issue 21
  • DOI: 10.1021/ac041665c

Chemical standards in ion mobility spectrometry
journal, January 2010

  • Fernández-Maestre, Roberto; Harden, Charles Steve; Ewing, Robert Gordon
  • The Analyst, Vol. 135, Issue 6
  • DOI: 10.1039/b915202d

High resolution ion mobility-mass spectrometry for separation and identification of isomeric lipids
journal, January 2015

  • Groessl, M.; Graf, S.; Knochenmuss, R.
  • The Analyst, Vol. 140, Issue 20
  • DOI: 10.1039/C5AN00838G

Fragmentation pathways of negative ions produced by electrospray ionization of acyclic dicarboxylic acids and derivatives
journal, November 2005

  • Grossert, J. Stuart; Fancy, Paul D.; White, Robert L.
  • Canadian Journal of Chemistry, Vol. 83, Issue 11
  • DOI: 10.1139/v05-214

Avogadro: an advanced semantic chemical editor, visualization, and analysis platform
journal, August 2012

  • Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.
  • Journal of Cheminformatics, Vol. 4, Issue 1
  • DOI: 10.1186/1758-2946-4-17

A simplified description of the evolution of organic aerosol composition in the atmosphere: VAN KREVELEN DIAGRAM OF ORGANIC AEROSOL
journal, April 2010

  • Heald, C. L.; Kroll, J. H.; Jimenez, J. L.
  • Geophysical Research Letters, Vol. 37, Issue 8
  • DOI: 10.1029/2010GL042737

Electrospray Ionization Ion Mobility Spectrometry of Amino Acids:  Ion Mobilities and a Mass−Mobility Correlation
journal, July 2004

  • Johnson, Paul V.; Kim, Hugh I.; Beegle, Luther W.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 27
  • DOI: 10.1021/jp0492117

Ion mobility-mass spectrometry
journal, January 2008

  • Kanu, Abu B.; Dwivedi, Prabha; Tam, Maggie
  • Journal of Mass Spectrometry, Vol. 43, Issue 1
  • DOI: 10.1002/jms.1383

Resistive Glass IM-TOFMS
journal, November 2010

  • Kaplan, Kimberly; Graf, Stephan; Tanner, Christian
  • Analytical Chemistry, Vol. 82, Issue 22
  • DOI: 10.1021/ac1017259

Electrospray Ionization Ion Mobility Spectrometry of Carboxylate Anions:  Ion Mobilities and a Mass−Mobility Correlation
journal, September 2005

  • Kim, Hugh I.; Johnson, Paul V.; Beegle, Luther W.
  • The Journal of Physical Chemistry A, Vol. 109, Issue 35
  • DOI: 10.1021/jp051274h

Experimental and Theoretical Investigation into the Correlation between Mass and Ion Mobility for Choline and Other Ammonium Cations in N 2
journal, March 2008

  • Kim, Hyungjun; Kim, Hugh I.; Johnson, Paul V.
  • Analytical Chemistry, Vol. 80, Issue 6
  • DOI: 10.1021/ac701888e

Ion mobility spectrometry–mass spectrometry (IMS–MS) for on- and offline analysis of atmospheric gas and aerosol species
journal, January 2016

  • Krechmer, Jordan E.; Groessl, Michael; Zhang, Xuan
  • Atmospheric Measurement Techniques, Vol. 9, Issue 7
  • DOI: 10.5194/amt-9-3245-2016

Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol
journal, January 2011

  • Kroll, Jesse H.; Donahue, Neil M.; Jimenez, Jose L.
  • Nature Chemistry, Vol. 3, Issue 2
  • DOI: 10.1038/nchem.948

Collision cross section calculations for polyatomic ions considering rotating diatomic/linear gas molecules
journal, November 2014

  • Larriba-Andaluz, Carlos; Hogan, Christopher J.
  • The Journal of Chemical Physics, Vol. 141, Issue 19
  • DOI: 10.1063/1.4901890

Mapping the human plasma proteome by SCX-LC-IMS-MS
journal, July 2007

  • Liu, Xiaoyun; Valentine, Stephen J.; Plasencia, Manolo D.
  • Journal of the American Society for Mass Spectrometry, Vol. 18, Issue 7
  • DOI: 10.1016/j.jasms.2007.04.012

Mobilities of polyatomic ions in gases: core model
journal, February 1972

  • Mason, E. A.; O'Hara, H.; Smith, F. J.
  • Journal of Physics B: Atomic and Molecular Physics, Vol. 5, Issue 2
  • DOI: 10.1088/0022-3700/5/2/011

Ion mobility–mass spectrometry: a new paradigm for proteomics
journal, February 2005

  • McLean, John A.; Ruotolo, Brandon T.; Gillig, Kent J.
  • International Journal of Mass Spectrometry, Vol. 240, Issue 3
  • DOI: 10.1016/j.ijms.2004.10.003

Structural Information from Ion Mobility Measurements:  Effects of the Long-Range Potential
journal, January 1996

  • Mesleh, M. F.; Hunter, J. M.; Shvartsburg, A. A.
  • The Journal of Physical Chemistry, Vol. 100, Issue 40
  • DOI: 10.1021/jp961623v

Loss of H 2 and CO from protonated aldehydes in electrospray ionization mass spectrometry: Loss of H 2 and CO from protonated aldehydes
journal, July 2014

  • Neta, Pedatsur; Simón-Manso, Yamil; Liang, Yuxue
  • Rapid Communications in Mass Spectrometry, Vol. 28, Issue 17
  • DOI: 10.1002/rcm.6968

Absolute scale determination for photoabsorption spectra and the calculation of molecular properties using dipole sum-rules
journal, October 1997


Multiphase Chemistry at the Atmosphere–Biosphere Interface Influencing Climate and Public Health in the Anthropocene
journal, February 2015

  • Pöschl, Ulrich; Shiraiwa, Manabu
  • Chemical Reviews, Vol. 115, Issue 10
  • DOI: 10.1021/cr500487s

Real time pharmaceutical reaction monitoring by electrospray ion mobility-mass spectrometry
journal, February 2013

  • Roscioli, Kristyn M.; Zhang, Xing; Li, Shelly X.
  • International Journal of Mass Spectrometry, Vol. 336
  • DOI: 10.1016/j.ijms.2012.12.004

General atomic and molecular electronic structure system
journal, November 1993

  • Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A.
  • Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363
  • DOI: 10.1002/jcc.540141112

An exact hard-spheres scattering model for the mobilities of polyatomic ions
journal, October 1996


Modeling ionic mobilities by scattering on electronic density isosurfaces: Application to silicon cluster anions
journal, March 2000

  • Shvartsburg, Alexandre A.; Liu, Bei; Jarrold, Martin F.
  • The Journal of Chemical Physics, Vol. 112, Issue 10
  • DOI: 10.1063/1.481042

Improved Momentum-Transfer Theory for Ion Mobility. 1. Derivation of the Fundamental Equation
journal, November 2012

  • Siems, William F.; Viehland, Larry A.; Hill, Herbert H.
  • Analytical Chemistry, Vol. 84, Issue 22
  • DOI: 10.1021/ac301779s

A functional group oxidation model (FGOM) for SOA formation and aging
journal, January 2013


Evaluation of Hadamard Transform Atmospheric Pressure Ion Mobility Time-of-Flight Mass Spectrometry for Complex Mixture Analysis
journal, January 2014

  • Zhang, Xing; Knochenmuss, Richard; Siems, William F.
  • Analytical Chemistry, Vol. 86, Issue 3
  • DOI: 10.1021/ac403435p

Formation and evolution of molecular products in α-pinene secondary organic aerosol
journal, November 2015

  • Zhang, Xuan; McVay, Renee C.; Huang, Dan D.
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 46
  • DOI: 10.1073/pnas.1517742112

Time-resolved molecular characterization of organic aerosols by PILS + UPLC/ESI-Q-TOFMS
journal, April 2016


Works referencing / citing this record:

A parallelized molecular collision cross section package with optimized accuracy and efficiency
journal, January 2019

  • Ieritano, Christian; Crouse, Jeff; Campbell, J. Larry
  • The Analyst, Vol. 144, Issue 5
  • DOI: 10.1039/c8an02150c

Novel pathway of SO 2 oxidation in the atmosphere: reactions with monoterpene ozonolysis intermediates and secondary organic aerosol
journal, January 2018

  • Ye, Jianhuai; Abbatt, Jonathan P. D.; Chan, Arthur W. H.
  • Atmospheric Chemistry and Physics, Vol. 18, Issue 8
  • DOI: 10.5194/acp-18-5549-2018

Molecular characterization of alkyl nitrates in atmospheric aerosols by ion mobility mass spectrometry
journal, January 2019

  • Zhang, Xuan; Zhang, Haofei; Xu, Wen
  • Atmospheric Measurement Techniques, Vol. 12, Issue 10
  • DOI: 10.5194/amt-12-5535-2019