Enantiomeric Separation of Triacylglycerols Consisting of Three Different Fatty Acyls and Their Chiral Chromatographic Elution Behavior
: Zhang, Yuqing; Kalpio, Marika; Haraldsdóttir, Hafdís; Gudmundsson, Haraldur G.; Haraldsson, Gudmundur G.; Sigurjónsson, Svanur; Kristinsson, Björn; Linderborg, Kaisa M.; Yang, Baoru
Publisher: American Chemical Society
: 2024
: Analytical Chemistry
: Analytical chemistry
: Anal Chem
: 96
: 34
: 13936
: 13943
: 0003-2700
: 1520-6882
DOI: https://doi.org/10.1021/acs.analchem.4c02513(external)
: https://pubs.acs.org/doi/full/10.1021/acs.analchem.4c02513(external)
: https://research.utu.fi/converis/portal/detail/Publication/457573844(external)
Chromatographic separation of triacylglycerol (TG) enantiomers is a highly challenging task of analytical chemistry because of the similar physicochemical properties. The analysis of chiral TGs is crucial for improving the knowledge of lipid biochemistry and for understanding the nutritional properties of fats and oils. Thus, this study aimed to systematically investigate the chiral resolution of TGs consisting of three different fatty acyls (FAs). Thirty-three asymmetric TG enantiopairs, including 49 synthesized enantiopure TGs and racemic TGs, were analyzed with a recycling chiral HPLC system. Twenty-six enantiopairs were successfully separated. Overall, having both unsaturated and saturated FAs in the outer positions or a difference in carbon chain length between two saturated FAs at the outer positions favored the separation of enantiomers. The retention time at separation correlated negatively with the sn-3 carbon number of the early eluting enantiomer and positively with the carbon number difference between sn-1 and sn-3. When the samples were studied in separate groups based on unsaturation and regioisomers, both the acyl carbon number and the degree of unsaturation of FAs in all three positions influenced the separation and elution behavior of chiral TGs, indicating an active role of both intermolecular interactions and steric hindrances. This is the first systematic study of the chiral separation of TGs consisting of three different FAs using a large number of enantiopairs. The novel findings on the behavior of TG enantiomers in a chiral environment provide important guidance and reference for a stereospecific study of the chemistry and biochemistry of natural lipids.
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This work was funded by the Research Council of Finland(Decision No. 310982, Chiral lipids in chiral nature: a novelstrategy for regio- and stereospecific research of human milkand omega-3 lipids; Decision No. 356891, Structures andfunctions of chiral lipids: a stereospecific & multiomicsapproach) and by the Finland−China Food and HealthNetwork. The personal grant from the Turku UniversityFoundation and the funding support from the DoctoralProgramme in Technology at the Graduate School of theUniversity of Turku are acknowledged
