Qualitative and Quantitative Metabolite Comparison of Grain, Persimmon, and Apple Vinegars with Antioxidant Activities

Fermented vinegars have been highlighted globally for their health benefits. The benefits can differ according to the type of vinegar; therefore, we investigated the differences of 15 grain (GV), 10 persimmon (PV), and 14 apple vinegars (AV) using integrated non-targeted and targeted metabolome analyses. We profiled non-volatile and volatile metabolites using gas chromatography time-of-flight mass spectrometry (GC-TOF-MS), ultra-high-performance liquid chromatography–orbitrap–tandem mass spectrometry, and headspace–solid-phase microextraction–GC-TOF-MS. Among the 132 identified metabolites, 73 non-volatile and 40 volatile metabolites showed significant differences across the three vinegar types. Amino acids, hydroxy fatty acids, phenolic compounds, aldehydes, pyrazines, and sulfides were abundant in GV. Some phenolic compounds, alcohols, and esters were abundant in PV, whereas carbohydrates, flavonoids, and terpenoids were abundant in AV, contributing to nutrients, tastes, and flavors. Bioactivity assays revealed that GV showed notable antioxidant activity, whereas PV and AV had the highest total phenolic and flavonoid contents, respectively. Through quantitative analysis, we revealed that acetic acid, propionic acid, butanoic acid, lactic acid, and alanine were major components in the three types of vinegar, although their composition was different in each vinegar. Our comprehensive qualitative and quantitative metabolite comparison provides insights into the differences among the three vinegar types, classified according to their raw materials.