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Title: Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses

Abstract

One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival timemore » distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Central Analytical Research Facility, Insitutue for Future Environments, Queensland University of Technology, Brisbane, Queensland 4000, Australia
  2. Biological Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
  3. School of Medicine, University of Wollongong, Wollongong, New South Wales 2522, Australia
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1422288
Report Number(s):
PNNL-SA-129778
Journal ID: ISSN 0003-2700; 49531; 400412000
DOE Contract Number:
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Analytical Chemistry; Journal Volume: 90; Journal Issue: 2
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Poad, Berwyck L. J., Zheng, Xueyun, Mitchell, Todd W., Smith, Richard D., Baker, Erin S., and Blanksby, Stephen J. Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses. United States: N. p., 2017. Web. doi:10.1021/acs.analchem.7b04091.
Poad, Berwyck L. J., Zheng, Xueyun, Mitchell, Todd W., Smith, Richard D., Baker, Erin S., & Blanksby, Stephen J. Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses. United States. doi:10.1021/acs.analchem.7b04091.
Poad, Berwyck L. J., Zheng, Xueyun, Mitchell, Todd W., Smith, Richard D., Baker, Erin S., and Blanksby, Stephen J. Thu . "Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses". United States. doi:10.1021/acs.analchem.7b04091.
@article{osti_1422288,
title = {Online Ozonolysis Combined with Ion Mobility-Mass Spectrometry Provides a New Platform for Lipid Isomer Analyses},
author = {Poad, Berwyck L. J. and Zheng, Xueyun and Mitchell, Todd W. and Smith, Richard D. and Baker, Erin S. and Blanksby, Stephen J.},
abstractNote = {One of the most significant challenges in contemporary lipidomics lies in the separation and identification of lipid isomers that differ only in site(s) of unsaturation or geometric configuration of the carbon-carbon double bonds. While analytical separation techniques including ion mobility spectrometry (IMS) and liquid chromatography (LC) can separate isomeric lipids under appropriate conditions, conventional tandem mass spectrometry cannot provide unequivocal identification. To address this challenge, we have implemented ozone-induced dissociation (OzID) in-line with LC, IMS and high resolution mass spectrometry. Modification of an IMS- capable quadrupole time-of-flight mass spectrometer was undertaken to allow the introduction of ozone into the high-pressure trapping ion funnel region preceding the IMS cell. This enabled the novel LC-OzID-IMS-MS configuration where ozonolysis of ionized lipids occurred rapidly (10 ms) without prior mass-selection. LC-elution time alignment combined with accurate mass and arrival time extraction of ozonolysis products facilitated correlation of precursor and product ions without mass-selection (and associated reductions in duty cycle). Unsaturated lipids across 11 classes were examined using this workflow in both positive and negative ion modalities and in all cases the positions of carbon-carbon double bonds were unequivocally assigned based on predictable OzID transitions. Under these conditions geometric isomers exhibited different IMS arrival time distributions and distinct OzID product ion ratios providing a means for discrimination of cis/trans double bonds in complex lipids. The combination of OzID with multidimensional separations shows significant promise for facile profiling of unsaturation patterns within complex lipidomes.},
doi = {10.1021/acs.analchem.7b04091},
journal = {Analytical Chemistry},
number = 2,
volume = 90,
place = {United States},
year = {Thu Dec 21 00:00:00 EST 2017},
month = {Thu Dec 21 00:00:00 EST 2017}
}