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Characterization of Wax Esters by Electrospray Ionization Tandem Mass Spectrometry: Double Bond Effect and Unusual Product Ions

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Lipids

Abstract

A series of different types of wax esters (represented by RCOOR′) were systematically studied by using electrospray ionization (ESI) collision-induced dissociation tandem mass spectrometry (MS/MS) along with pseudo MS3 (in-source dissociation combined with MS/MS) on a quadrupole time-of-flight (Q-TOF) mass spectrometer. The tandem mass spectra patterns resulting from dissociation of ammonium/proton adducts of these wax esters were influenced by the wax ester type and the collision energy applied. The product ions [RCOOH2]+, [RCO]+ and [RCO−H2O]+ that have been reported previously were detected; however, different primary product ions were demonstrated for the three wax ester types including: (1) [RCOOH2]+ for saturated wax esters, (2) [RCOOH2]+, [RCO]+ and [RCO−H2O]+ for unsaturated wax esters containing only one double bond in the fatty acid moiety or with one additional double bond in the fatty alcohol moiety, and (3) [RCOOH2]+ and [RCO]+ for unsaturated wax esters containing a double bond in the fatty alcohol moiety alone. Other fragments included [R′]+ and several series of product ions for all types of wax esters. Interestingly, unusual product ions were detected, such as neutral molecule (including water, methanol and ammonia) adducts of [RCOOH2]+ ions for all types of wax esters and [R′−2H]+ ions for unsaturated fatty acyl-containing wax esters. The patterns of tandem mass spectra for different types of wax esters will inform future identification and quantification approaches of wax esters in biological samples as supported by a preliminary study of quantification of isomeric wax esters in human meibomian gland secretions.

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Abbreviations

APCI:

Atmospheric pressure chemical ionization

CI:

Chemical ionization

CID:

Collision induced dissociation

EI:

Electron ionization

ESI:

Electrospray ionization

MRM:

Multiple-reaction monitoring

MS/MS:

Tandem mass spectrometry

MS3 (MS/MS/MS):

Multi-stage tandem mass spectrometry

Pseudo MS3 :

In source dissociation combined with MS/MS

Q-TOF:

Quadrupole time-of-flight

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Acknowledgments

The authors thank NIH for funding (grant number: NEI R01EY015519) and Jeremy Keirsey at the Campus Chemical Instrument Center of the Ohio State University for proofreading and critical comments.

Author information

Author notes

  1. Jianzhong Chen & Kelly K. Nichols

    Present address: School of Optometry, The University of Alabama at Birmingham, Birmingham, AL, 35294-0010, USA

  2. Kari B. Green

    Present address: Department of Chemistry, University of Florida, Gainesville, FL, 32611, USA

Authors and Affiliations

  1. Applied Biotechnology Branch, Air Force Research Laboratory, Dayton, OH, 45433, USA

    Jianzhong Chen

  2. Mass Spectrometry and Proteomics Facility, The Ohio State University, Columbus, OH, 43210, USA

    Jianzhong Chen & Kari B. Green

  3. College of Optometry, University of Houston, Houston, TX, 77204, USA

    Kelly K. Nichols

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  1. Jianzhong Chen
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Correspondence to Jianzhong Chen.

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Chen, J., Green, K.B. & Nichols, K.K. Characterization of Wax Esters by Electrospray Ionization Tandem Mass Spectrometry: Double Bond Effect and Unusual Product Ions. Lipids 50, 821–836 (2015). https://doi.org/10.1007/s11745-015-4044-6

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