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Introduction Steviol glycosides from Stevia rebaudiana Bertoni exhibit high sweetening power, and their composition influences both the intensity and the temporal dynamics of perceived gustatory sensations. Objective This study investigated, through multivariate analysis, relationships between Time–Intensity (TI) sensory responses and chromatographic composition of commercial stevia sweeteners in vegan chocolate mousse. Methodology TI analysis of sweetness and bitterness was conducted by a trained panel (n = 9), with three independent repetitions, using SensoMaker software. Five commercial stevia sweeteners (S1–S5), previously adjusted by magnitude estimation to sweetness equivalent to 10% sucrose (0.0449%, 0.0584%, 0.0564%, 0.1477%, and 0.0282%, respectively), were evaluated. Maximum intensity (Imax) and area under the curve (AreaS) were extracted from the temporal curves. Rebaudiosides A, D, M, and C, rubusoside (R), and stevioside (S) were quantified by HPLC (n = 3). Sensory and chromatographic data were integrated using Principal Component Analysis (PCA). Results PCA explained 67.2% of the total variance (PC1 = 36.4%; PC2 = 30.8%) and revealed distinct sensory–chemical profiles among the commercial sweeteners. S5, the sweetener with the highest relative sweetening potency, was mainly associated with rebaudioside A (RA), whereas S4, with the lowest relative sweetening potency, was associated with R, rebaudioside M, S, and bitterness-related parameters, particularly maximum bitterness intensity (ImaxB). S2 was more closely associated with rebaudioside C and the TI sweetness parameters ImaxS and AreaS, indicating greater maximum sweetness intensity and overall sweetness response over time. S3 showed a closer association with rebaudioside D (RD), while S1 remained near the center of the multivariate space, with a tendency toward the RA/RD-related profile. Conclusions Integrating TI and HPLC data revealed distinct sensory–chemical profiles among commercial stevia sweeteners. Relative sweetening potency did not correspond directly to maximum sweetness intensity, highlighting the value of multivariate analysis for characterizing differences in sensory performance.
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