Efficient extraction and sensitive LC-MS quantification of hydroxytyrosol in wine, oil and plasma

Hydroxytyrosol (HT) possesses significant biological activity. However, the methodologies for its quantification always suffered from low sensitivity, intricate treatment and high sample consumption. Here, we presented the very first attempt for specific extraction of HT through cis-diol recognition mechanism. By using easily prepared zirconia as dispersive solid phase extraction medium, HT from small amount of wine (10 μL), oil (20 mg) and plasma (100 μL) was efficiently purified within ten minutes. Coupled with LC-MS/MS analysis, the method limit of detection (LOD) could reach 1 ng/mL in wine, 0.5 μg/kg in oil and 0.1 ng/mL in plasma. Profited by this superior method, HT analysis was successfully performed in diverse wine and oil products as well as human plasma samples after intake of extra virgin olive oil. In addition, we further confirmed the endogenous HT was undetectable from routine human plasma even after upgrading the detection sensitivity through post isonicotinoyl chloride derivatization.