Targeted UHPLC–HRMS (Orbitrap) Polyphenolic and Capsaicinoid Profiling for the Chemometric Characterization and Classification of Paprika with Protected Designation of Origin (PDO) Attributes

Society’s interest in the quality of food products with certain attributes has increased, the attribute of a Protected Designation of Origin (PDO) being an effective tool to guarantee the quality and geographical origin of a given food product. In Spain, two paprika production areas with PDO (La Vera and Murcia) are recognized. In the present work, targeted UHPLC-HRMS polyphenolic and capsaicinoid profiling through the TraceFinder(TM) screening software, using homemade accurate mass databases, was proposed as a source of chemical descriptors, to address the characterization, classification, and authentication of paprika. A total of 126 paprika samples from different production regions—Spain (La Vera PDO and Murcia PDO) and the Czech Republic, each including different flavor varieties, were analyzed. UHPLC-HRMS polyphenolic profiles showed to be good chemical descriptors to achieve paprika classification and authentication, based on the production region, through principal component analysis and partial least squares regression-discriminant analysis, with classification rates of 82%, 86%, and 100% for La Vera PDO, Murcia PDO, and the Czech Republic, respectively. In addition, a perfect classification was also accomplished among the flavor varieties for the Murcia PDO and Czech Republic samples. By employing the UHPLC-HRMS polyphenolic and capsaicinoid profiles as chemical descriptors, acceptable discrimination among La Vera PDO flavor varieties was also achieved.