One hundred eighty-two authentic potato samples ( Solanum tuberosum) of known variety were collected from various German regions in 2016 and 2017. Samples were extracted with a liquid-liquid-extraction protocol that included isopropanol, methanol, and water in order to focus on lipophilic metabolites. The analysis of nonpolar extracts was performed using an UPLC-IMS-QToF-MS system; data sets obtained were evaluated via multivariate data analysis. A selection of 14 key metabolites with a significant difference in their abundance profiles was identified. This set of markers contained four hydroxylated glucocerebrosides, two phosphoinositols, one phosphocholine, and seven acylated sterol glucosides based on stigmasterol and β-sitosterol, which primarily enable the varietal discrimination. Fragments and neutral losses commonly appearing within one class or subclass of lipids were summarized within a new database that included ion mobility data. The performance of the approach was verified with twenty-nine commercial potato samples.
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