Discrimination of Apple Liqueurs (Nalewka) Using a Voltammetric Electronic Tongue, UV-Vis and Raman Spectroscopy

The capability of a phthalocyanine-based voltammetric electronic tongue to analyze strong alcoholic beverages has been evaluated and compared with the performance of spectroscopic techniques coupled to chemometrics. Nalewka Polish liqueurs prepared from five apple varieties have been used as a model of strong liqueurs. Principal Component Analysis has demonstrated that the best discrimination between liqueurs prepared from different apple varieties is achieved using the e-tongue and UV-Vis spectroscopy. Raman spectra coupled to chemometrics have not been efficient in discriminating liqueurs. The calculated Euclidean distances and the k-Nearest Neighbors algorithm (kNN) confirmed these results. The main advantage of the e-tongue is that, using PLS-1, good correlations have been found simultaneously with the phenolic content measured by the Folin–Ciocalteu method (R(2) of 0.97 in calibration and R(2) of 0.93 in validation) and also with the density, a marker of the alcoholic content method (R(2) of 0.93 in calibration and R(2) of 0.88 in validation). UV-Vis coupled with chemometrics has shown good correlations only with the phenolic content (R(2) of 0.99 in calibration and R(2) of 0.99 in validation) but correlations with the alcoholic content were low. Raman coupled with chemometrics has shown good correlations only with density (R(2) of 0.96 in calibration and R(2) of 0.85 in validation). In summary, from the three holistic methods evaluated to analyze strong alcoholic liqueurs, the voltammetric electronic tongue using phthalocyanines as sensing elements is superior to Raman or UV-Vis techniques because it shows an excellent discrimination capability and remarkable correlations with both antioxidant capacity and alcoholic content—the most important parameters to be measured in this type of liqueurs.