Iridoid Glycosides as Key Discriminators of Cranberry (Vaccinium macrocarpon) Cultivars Revealed by UHPLC-HRAM-MSn
Ping Geng1, Jianghao Sun1, Pei Chen1
1U.S. Department of Agriculture, Methods and Application of Food Composition Laboratory, Beltsville Human Nutrition Research Center, Agricultural Research Service, Beltsville, MD 20705, United States.
Background:
Cranberry (Vaccinium macrocarpon) contains diverse hydrophilic phytochemicals, but their compositional profiles and cultivar-specific variation have not been comprehensively characterized.
Objective:
The objective of this study was to profile hydrophilic metabolites in cranberry cultivars and identify constituents that differentiate among cultivars.
Methods:
Water-eluted fractions of Sephadex® LH-20-separated cranberry extracts from six cultivars (Crimson Queen, Demoranville, Haines, Mullica Queen, Stevens, and Welker) were analyzed using ultra-HPLC-high-resolution accurate-mass tandem mass spectrometry (UHPLC-HRAM-MSn). Metabolites were annotated based on accurate mass and MS2 fragmentation data and comparison with literature reports. Sparse partial least-squares discriminant analysis (sPLS-DA) was applied to assess classification performance and identify discriminative features.
Results:
Thirty-nine putative hydrophilic metabolites were identified, including hydroxycinnamic acid hexose derivatives, anthocyanins, hydroxycinnamoylquinic acids, and a distinct group of iridoid glycosides. Vaccinoside and several coumaroyl-substituted monotropein derivatives were structurally characterized in cranberry for the first time. sPLS-DA identified iridoid glycosides as key discriminators, with higher abundance observed in the Welker cultivar.
Conclusion:
Cranberry cultivars contain previously unreported iridoid glycosides that contribute to chemotaxonomic differentiation. These results expand current knowledge of cranberry hydrophilic phytochemistry and support the relevance of iridoid glycosides as cultivar-informative metabolites.
Highlights:
This study characterizes the highly polar, water-eluted fraction of six cranberry cultivars using UHPLC-HRAM-MSn analysis, resulting in the putative identification of 39 compounds, including a prominent series of iridoid glycosides.
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