Allium ursinum and poisonous adulterants Convallaria majalis and Arum maculatum were used as a model for detection of adulterants in edible plant. A. ursinum samples were spiked with C. majalis and A. maculatum to mimic adulteration. Metabolomic fingerprinting of all samples was performed using 1H NMR spectroscopy, and the resulting data sets were subjected to multivariate data analysis. As a result of this analysis, signals of adulterants were extracted from the data, and the structures of biomarkers of adulteration from partially purified samples were elucidated using 2D NMR and LC-MS techniques. Thus, isovitexin and vicenin II, azetidine-2-carboxylic acid, and trigonelline indicated adulteration of A. ursinum samples with C. majalis. Isovitexin was also recognized to be an indicator of adulteration of A. ursinum with A. maculatum. In conclusion, the case study of A. ursinum suggested that plant metabolomics approach could be utilized for identification of low molecular weight biomarkers of adulteration in edible plants.
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