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. Fifty three polyphenolic standards were characterized to build a user-accurate mass database which was then proposed to obtain UHPLC-HRMS polyphenolic profiles by means of ExactFinder 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 homogentisic, sinapic, veratric, cryptochlorogenic, and caffeic acids showed to be important polyphenols to achieve cranberry-based products discrimination against the other studied fruits. Partial least-squares 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.

Authentication of the Origin, Variety and Roasting Degree of Coffee Samples by Non-Targeted HPLC-UV Fingerprinting and Chemometrics. Application to the Detection and Quantitation of Adulterated Coffee Samples

“…Each adulteration level ( Figure 1) was prepared by quintuplicate obtaining a total of 55 sample extracts for each adulteration case. Similar calibration designs were used successfully elsewhere for predicting adulteration amounts [31,32]. Levels in this design were chosen to be realistic from the point of view of the authentication, since higher adulterant percentages could be of interest in fraudulent practices to obtain bigger illicit profits.…”

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

“…As can be seen, remarkable differences in both signal profile and relative abundances are obtained, depending on the origin of the samples. As a first approach, chromatographic sample raw data was then processed with the TraceFinder TM software (Thermo Fisher Scientific) to obtain the corresponding targeted-UHPLC-HRMS polyphenolic profiles, by using an accurate mass database of 53 polyphenols and phenolic compounds that were previously characterized [27]. A threshold signal of 1.0 × 10 5 was established in the screening software to consider a positive match for a given polyphenolic compound in the analyzed samples.…”

“…At present, there are several methods for the determination of polyphenolic and phenolic compounds, such as global assays for the evaluation of the total content by colorimetric or fluorimetric methods, or more specific ones, based on separation by capillary electrophoresis, liquid chromatography, and gas chromatography. However, liquid chromatography with UV or electrochemical detection, or that coupled with mass spectrometry is nowadays the technique of choice [17,[23][24][25][26][27][28][29][30][31][32]. However, the great chemical diversity among this family of compounds and the range of concentrations in which they can be found make liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) the most effective technique.…”

“…However, the great chemical diversity among this family of compounds and the range of concentrations in which they can be found make liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) the most effective technique. Among these, time-of-flight (TOF) and Orbitrap analyzers are the most frequently employed for the characterization, identification, and determination of polyphenolic and phenolic compounds in food, including paprika products [25,27,31]. Liquid chromatography with UV and mass spectrometric detection are also typically employed in the determination of capsaicinoid compounds in pepper and pepper-processed products [14,[33][34][35][36][37][38][39].…”

“…For this purpose, a total of 126 paprika samples belonging to La Vera PDO, Murcia PDO (Spain), and the Czech Republic were analyzed through the proposed methodology, after applying a simple sample extraction procedure utilizing water:acetonitrile 20:80 (v/v) as an extractant agent. As a first approach, 53 polyphenols and phenolic compounds were monitored using the TraceFinder TM software v3.3 (Thermo Fisher Scientific, San José, CA, USA), employing a previously established accurate mass database [27], and the obtained peak signal profiles were used as sample chemical descriptors for PCA and PLS-DA. Then, to improve sample classification, especially for the La Vera paprika samples, capsaicinoid profiling by monitoring 12 compounds was also employed as sample chemical descriptors, together with the polyphenolic and phenolic acid profiles, for PCA and PLS-DA.…”