Journal of The American Society for Mass Spectrometry

, Volume 30, Issue 9, pp 1700–1712 | Cite as

The Establishment of Tandem Mass Spectrometric Fingerprints of Phytosterols and Tocopherols and the Development of Targeted Profiling Strategies in Vegetable Oils

  • Kang Jiang
  • George Gachumi
  • Asmita Poudel
  • Bryn Shurmer
  • Zafer Bashi
  • Anas El-AneedEmail author
Research Article


Phytosterols and tocopherols are essential for plant biochemistry, and they possess beneficial health effects for humans. Evaluating the tandem mass spectrometric (MS/MS) behavior of phytosterols and tocopherols is needed for the development of a qualitative and quantitative method for these biologically active plant metabolites. Herein, the MS/MS dissociation behavior of phytosterols and tocopherols is elucidated to establish generalized MS/MS fingerprints. MS/MS and multistage (MS3) analysis revealed common fragmentation behavior among the four tested phytosterols, namely β-sitosterol, stigmasterol, campesterol, and brassicasterol. Similar analysis was conducted for the tocopherols (i.e., alpha (α), beta (β), gamma (γ), and delta (δ)). As such, a universal MS/MS fragmentation pathway for each group was successfully established for the first time. Based on the generalized MS/MS fragmentation behavior of phytosterols, diagnostic product ions were chosen for the development of profiling methods for over 20 naturally occurring phytosterols. A precursor ion scan-triggered-enhanced product ion scan (PIS-EPI) method was established. Due to enhanced chromatographic peaks, multiple ion monitoring-triggered-enhanced product ion scan (MIM-EPI) was employed for confirmation. The screening approach was applied successfully to identify blinded samples obtained from standard mixtures as well as sesame and olive oils. The oil samples contain other phytosterols, and their successful identification indicates that, the generalized MS/MS fragmentation behavior is applicable to various structures of phytosterols. A similar approach was attempted for tocopherols and was only hindered by the low concentration of these bioactive metabolites present in the oil samples.


MS/MS fingerprints Phytosterols Tocopherols Profiling Precursor ion scan Multiple ion monitoring PIS-EPI MIM-EPI Vegetable oil 



Funding for this project is provided by an Agriculture Development Fund, Ministry of Agriculture, Government of Saskatchewan, Canada. The QTRAP 6500 was acquired via a Western Economic Diversification Canada grant. Mr. Jiang acknowledges scholarship joint funding from the Beijing Institute of Technology and the University of Saskatchewan. The authors would like to thank Ms. Deborah Michel for training Mr. Kang on the QTRAP instrument.

Supplementary material

13361_2019_2242_MOESM1_ESM.docx (740 kb)
ESM 1 (DOCX 739 kb)


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Copyright information

© American Society for Mass Spectrometry 2019

Authors and Affiliations

  1. 1.College of Pharmacy and NutritionUniversity of SaskatchewanSaskatoonCanada
  2. 2.Government of CanadaCanadian Food Inspection AgencySaskatoonCanada

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