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Sitosterol Thermo-oxidative Degradation Leads to the Formation of Dimers, Trimers and Oligomers: A Study Using Combined Size Exclusion Chromatography/Mass Spectrometry

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Lipids

Abstract

Phytosterols are recognized as functional food components with cholesterol reducing properties in humans. The formation of phytosterol oligomers as a result of the thermo-oxidative degradation of sitosterol is shown to occur. The existence of oligomers is demonstrated by size exclusion chromatography (SEC) and confirmed by combined SEC-atmospheric pressure chemical ionization mass spectrometry (SEC/APCI-MS). A speculative structure for the sitosterol dimer with 3,7′ linkage is proposed consistent with data from tandem mass spectrometry and exact mass measurements. Higher molecular weight species arising from the formation of trimers or higher oligomers are seen in the mass spectra. Fragments of sitosterol formed by thermo-oxidative processes are also shown to oligomerize and their common structural characteristics are demonstrated by tandem mass spectrometry. The results presented provide evidence for the possible formation of oligomeric species involving sterols in addition to those known for acylglycerides in vegetable oils subjected to extreme oxidative stress such as in frying.

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Abbreviations

APCI:

Atmospheric pressure chemical ionization

ELSD:

Evaporative light scattering detector

ESI:

Electrospray ionization

HPLC:

High pressure liquid chromatography

LC/MS:

Liquid chromatography–mass spectrometry

SEC:

Size exclusion chromatography

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Acknowledgments

This work was financed by the State Committee for Scientific Research, grant # N312 071 32/3209, by the Alberta Value Added Corporation, the Agriculture Funding Consortium project #2006F018R; project #2009FO32R supported by the Agriculture and Food Council of Canada and the Alberta Agricultural Research Institute, and by an NSERC Discovery Grant (to J.M. Curtis).

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Authors and Affiliations

  1. Faculty of Food Science and Nutrition, Poznan University of Life Sciences, Poznan, Poland

    Magdalena Rudzinska

  2. Department of Agricultural, Food and Nutritional Science, University of Alberta, Edmonton, Canada

    Yuan Yuan Zhao & Jonathan M. Curtis

  3. Department of Chemistry and Biochemistry, University of Lethbridge, Lethbridge, AB, T1K 3M4, Canada

    Roman Przybylski

Authors
  1. Magdalena Rudzinska
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  2. Roman Przybylski
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  3. Yuan Yuan Zhao
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  4. Jonathan M. Curtis
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Correspondence to Roman Przybylski.

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Rudzinska, M., Przybylski, R., Zhao, Y.Y. et al. Sitosterol Thermo-oxidative Degradation Leads to the Formation of Dimers, Trimers and Oligomers: A Study Using Combined Size Exclusion Chromatography/Mass Spectrometry. Lipids 45, 549–558 (2010). https://doi.org/10.1007/s11745-010-3433-0

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  • DOI: https://doi.org/10.1007/s11745-010-3433-0

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