Investigation of liquid chromatography quadrupole time-of-flight mass spectrometry performance for identification and determination of hydroxylated stilbene antioxidants in wine

The performance of liquid chromatography (LC) followed by quadrupole time-of-flight (QTOF) mass spectrometry (MS) for the determination of hydroxylated stilbene compounds in red and white wine samples is assessed. When combined with a solid-phase extraction step, LC–QTOF-MS allowed the selective determination of five target compounds (trans- and cis-resveratrol, trans-piceatannol, trans-piceid and trans-pterostilbene) attaining limits of quantification between 3 and 20 ng mL−1 and providing linear responses up to 4000 ng mL−1. Recoveries, established against standards prepared in methanol, varied between 93% and 115%. The distribution of the above species in wine is illustrated with the analysis of 15 samples. Trans-pterostilbene remained undetected in samples, whereas trans-piceid and trans-resveratrol maximum concentrations exceed the 6000 ng mL−1 level. Values for trans-piceatannol and cis-resveratrol ranged from non detected to 600 ng mL−1, and from 11 to more than 3200 ng mL−1, respectively. Accurate MS and MS/MS scan spectra were used to investigate the existence of reduced (dihydro) and oxidized (dehydro) forms of resveratrol and picetannol in the processed samples. Dihydro derivatives appeared, as free compounds, in 100% (dihydro-piceatannol) and 40% (dihydro-resveratrol) of the samples. On the other hand, dehydro derivatives were noticed as conjugated (glycosylated) species, with detection frequencies of 100% and 47% for dehydro-glucosyl-resveratrol and dehydro-glucosyl-piceatannol, respectively. Above findings confirm the suitability of LC–QTOF-MS for the comprehensive study of hydroxylated stilbene antioxidants in wine samples.