Analysis of Oligomer Proanthocyanidins in Different Barley Genotypes Using High-Performance Liquid Chromatography–Fluorescence Detection–Mass Spectrometry and Near-Infrared Methodologies

Proanthocyanidins are a class of polyphenols present in many foodstuffs (i.e., tea, cocoa, berries, etc.) that may reduce the risk of several chronic diseases. Barley, with sorghum, rice, and wheat, are the only cereals that contain these compounds. Because of that, two barley genotypes, named waxy and non-waxy, were analyzed by normal-phase high-performance liquid chromatography–fluorescence detection–mass spectrometry (NP-HPLC–FLD–MS). Total proanthocyanidin content ranged between 293.2 and 652.6 μg/g of flour. Waxy samples reported the highest content (p < 0.05) of proanthocyanidins. Dimer compounds were the principal proanthocyanidin constituents of barley samples. Moreover, the possibility to use near-infrared (NIR) spectroscopy as a rapid method to discriminate between waxy and non-waxy samples and to predict quantitatively proanthocyanidins in barley samples was evaluated. Partial least squares (PLS) models were built to predict the proanthocyanidin constituent, obtaining determination coefficients (R2) ranging from 0.92 to 0.97, in test set validation. Because of that, this study highlights that NIR spectroscopy technology with multivariate calibration analysis could be successfully applied as a rapid method to determine proanthocyanidin content in barley.