Front-face fluorescence excitation-emission matrices in combination with three-way chemometrics for the discrimination and prediction of phenolic response to vineyard agronomic practices

•PARAFAC, LDA and DA-UPLS discriminated between irrigated and non-irrigated grapes.•PARAFAC, LDA and DA-UPLS discriminated between high and low crop load.•The resveratrol concentration predictions were better applying UPLS.•The PARAFAC results for catechin and epicatechin were comparable with LC results.•Resveratrol, catechin and epicatechin concentrations increased with irrigation. Phenolic extracts from cv Tempranillo grapes subjected to water stress and irrigation treatment, both of them with high and low crop load, were analyzed by front-face fluorescence. Excitation-emission matrices (EEMs) were analyzed by means of unsupervised parallel factor analysis (PARAFAC), PARAFAC supervised by linear discriminant analysis, and discriminant unfolded partial least-squares. All algorithms allowed to differentiate between water stress and irrigation grape samples when the fluorescence maxima region of catechin and epicatechin, and resveratrol was considered. A central composite design was employed for the calibration of catechin, epicatechin and resveratrol. Resveratrol was quantified by U-PLS in both, irrigated and water stressed samples, and levels between 3.46 ± 0.22 and 4.67 ± 0.08 μg mL−1 and 2.43 ± 0.60 and 3.03 ± 0.10 μg mL−1, respectively, were found. PARAFAC only allowed the determination of the sum of catechin plus epicatechin (R2 = 0.9397). The determination of total catechin plus epicatechin by means of PARAFAC was successfully validated by liquid chromatography.