| Summary: | Glucose, fructose and sucrose are sugars with known physiological effects, and their consumption has impact on the human health, also having an important effect on food sensory attributes. The analytical methods routinely used for identification and quantification of sugars in foods, like liquid chromatography and visible spectrophotometry have several disadvantages, like longer analysis times, high consumption of chemicals and the need for pretreatments of samples. To overcome these drawbacks, in this work, a potentiometric electronic tongue built with two identical multi-sensor systems of 20 cross-selectivity polymeric sensors, coupled with multivariate calibration with feature selection (a simulated annealing algorithm) was applied to quantify glucose, fructose and sucrose, and the total content of sugars as well. Standard solutions of ternary mixtures of the three sugars were used for multivariate calibration purposes, according to an orthogonal experimental design (multilevel fractional factorial design) with or without ionic background (KCl solution). The quantitative models’ predictive performance was evaluated by cross-validation with K-folds (internal validation) using selected data for training (selected with the K-means algorithm) and by external validation using test data. Overall, satisfactory predictive quantifications were achieved for all sugars and total sugar content based on subsets comprising 16 or 17 sensors. The test data allowed us to compare models’ predictions values and the respective sugar experimental values, showing slopes varying between 0.95 and 1.03, intercept values statistically equal to zero (<i>p</i>-value ≥ 0.05) and determination coefficients equal to or greater than 0.986. No significant differences were found between the predictive performances for the quantification of sugars using synthetic solutions with or without KCl (1 mol L<sup>−1</sup>), although the adjustment of the ionic background allowed a better homogenization of the solution’s matrix and probably contributed to an enhanced confidence in the analytical work across all of the calibration working range.
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