The development of a simple HPLC-UV method towards the evaluation of Spanish paprika’s phenolic profile and their discrimination based on the former is reported herein. The approach is based on C18 reversed-phase chromatography to generate characteristic fingerprints, in combination with linear discriminant analysis (LDA) to achieve their classification. To this aim, chromatographic conditions were optimized so as to achieve the separation of major phenolic compounds already identified in paprika. Paprika samples were subjected to a sample extraction stage by sonication and centrifugation; extracting procedure and conditions were optimized to maximize the generation of enough discriminant fingerprints. Finally, chromatograms were baseline corrected, compressed employing fast Fourier transform (FFT), and then analyzed by means of principal component analysis (PCA) and LDA to carry out the classification of paprika samples. Under the developed procedure, a total of 96 paprika samples were analyzed, achieving a classification rate of 100% for the test subset (n = 25).
This work reports the applicability of a voltammetric sensor array able to quantify the content of 2,4-dinitrophenol, 4-nitrophenol, and picric acid in artificial samples using the electronic tongue (ET) principles. The ET is based on cyclic voltammetry signals, obtained from an array of metal disk electrodes and a graphite epoxy composite electrode, compressed using discrete wavelet transform with chemometric tools such as artificial neural networks (ANNs). ANNs were employed to build the quantitative prediction model. In this manner, a set of standards based on a full factorial design, ranging from 0 to 300 mg·L−1, was prepared to build the model; afterward, the model was validated with a completely independent set of standards. The model successfully predicted the concentration of the three considered phenols with a normalized root mean square error of 0.030 and 0.076 for the training and test subsets, respectively, and r ≥ 0.948.
Herein we investigate the usage of principal component analysis (PCA) and canonical variate analysis (CVA), in combination with the F factor clustering metric, for the a priori tailored selection of the optimal sensor array for a given electronic tongue (ET) application. The former allows us to visually compare the performance of the different sensors, while the latter allows us to numerically assess the impact that the inclusion/removal of the different sensors has on the discrimination ability of the ET. The proposed methodology is based on the measurement of a pure stock solution of each of the compounds under study, and the posterior analysis by PCA/CVA with stepwise iterative removal of the sensors that demote the clustering when retained as part of the array. To illustrate and assess the potential of such an approach, the quantification of paracetamol, ascorbic acid, and uric acid mixtures were chosen as the study case. Initially, an array of eight different electrodes was considered, from which an optimal array of four sensors was derived to build the quantitative ANN model. Finally, the performance of the optimized ET was benchmarked against the results previously reported for the analysis of the same mixtures, showing improved performance.