Determining the relative amounts of positional isomers in complex mixtures of triglycerides using reversed-phase high-performance liquid chromatography-tandem mass spectrometry

Lipids
Michael Malone, Jason J Evans

Abstract

A reversed-phase HPLC-tandem mass spectrometry (RP-HPLC-MS-MS) method was refined for the positional analysis of complex mixtures of TAG. This method has the advantages of speed, ease of automation, and specificity over traditional digestion-based methods for the positional analysis of TAG. Collision-induced dissociation (CID) of ammoniated TAG in an ion-trap mass spectrometer produced spectra that were dependent on the FA position. Dominant DAG fragments were formed from the loss of a FA moiety from the ammoniated TAG species. The loss of FA in the outer positions was favored over their loss in the central position. The combination of RP-HPLC and CID produced spectra that were free of the isotope effects that can complicate spectral interpretation in existing methods. The combination also provided selectivity based on the chromatographic fractionation of TAG, in addition to the selectivity inherent in the CID process. Proof-of-concept experiments were performed with binary mixtures of TAG from the SOS/SSO, OSO/OOS, and the PSO/POS/SPO positional isomer systems (where S is 18:0, stearic acid; O is 18:1 (cis-9), oleic acid; and P is 16:0, palmitic acid). Plots of fractional DAG fragment intensities vs. fractional composition of ...Continue Reading

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Citations

Oct 25, 2012·Journal of Lipid Research·Kornél NagyOlivier Schafer
May 29, 2014·Journal of the American Society for Mass Spectrometry·J Stuart GrossertJeremy E Melanson
Sep 16, 2008·Analytica Chimica Acta·Nicole Zehethofer, Devanand M Pinto
Jun 13, 2015·Free Radical Biology & Medicine·Marco FazzariFrancisco J Schopfer
Nov 9, 2004·Journal of Mass Spectrometry : JMS
Jun 26, 2007·Rapid Communications in Mass Spectrometry : RCM·Heidi LeskinenHeikki Kallio
Sep 26, 2007·Rapid Communications in Mass Spectrometry : RCM·Robert GakwayaJason J Evans
Sep 4, 2010·Rapid Communications in Mass Spectrometry : RCM·Lisandra Cubero HerreraJeremy E Melanson
Oct 26, 2005·Journal of Chromatography. a·Josef CvackaIrena Valterová
Oct 2, 2020·Rapid Communications in Mass Spectrometry : RCM·Louis RamaleyJeremy E Melanson
Jul 3, 2021·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Zhiqian Liu, Simone Rochfort

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