Detection and quantitation of frauds in the authentication of cranberry-based extracts by UHPLC-HRMS (Orbitrap) polyphenolic profiling and multivariate calibration methods

Abstract

UHPLC-HRMS (Orbitrap) polyphenolic profiling was applied to the characterization, classification and authentication of cranberry-based natural and pharmaceutical products. 53 polyphenolic standards were characterized to build a user accurate mass database which was then proposed to obtain UHPLC-HRMS polyphenolic profiles by means of ExactFinderTM software. Principal component analysis results showed a good sample discrimination according to the fruit employed. Regarding cranberry-based pharmaceuticals, discrimination according to the presentation format (syrup, sachets, capsules, etc.) was also observed due to the enhancement of some polyphenols by purification and preconcentration procedures. Procyanidin A2 and homogenistic, sinapic, veratric, cryptochlorogenic and caffeic acids showed to be important polyphenols to achieve cranberry-based products discrimination against the other studied fruits. Partial least square regression allowed the determination of adulterant percentages in cranberry-fruit samples. Very satisfactory results, with adulteration quantification errors lower than 6.0% were obtained even at low adulteration levels.