High-throughput fingerprinting of hydrolysable tannins in wine and oak wood using in-source fragmentation on QTOF and QQQ platforms

Hydrolysable tannins, including ellagitannins and gallotannins, influence a wine's sensory and antioxidant properties, particularly through oak aging. However, their quantification is hindered by structural diversity, low concentrations, and interference from other phenolics. This study introduces hydrolysable tannin fragmentation fingerprinting (H-TFF), a novel and rapid liquid chromatography–mass spectrometry method that leverages in-source fragmentation to quantify and tentatively identify hydrolysable tannins in wine and oak wood. Developed and validated on quadrupole time-of-flight and triple quadrupole platforms, native-state quantification is achieved without acid hydrolysis. Ellagitannin concentrations strongly correlated with those obtained by acid hydrolysis (r ' 0.92), and gallotannin analysis achieved adequate cross-platform agreement despite interference from galloylated condensed tannins. By preserving chromatographic resolution, H-TFF enables distributional insights for tentative identification, and when integrated with condensed tannin fingerprinting, it enhances wine differentiation based on the oak treatment and tannin composition. Overall, H-TFF provides efficient, information-rich tannin analysis within 6 min.