Trace analysis of icariin in human serum with dansyl chloride derivatization after oral administration of Epimedium decoction by liquid chromatography tandem mass spectrometry

Epimedium herbs are a type of complex traditional Chinese medicine (TCM) with high estrogenic bioactivity. The Epimedium herbal decoction mixture contains many compounds including icariin that can exert potent effects on numerous physiological processes related to human health. An ultrasensitive liquid chromatography tandem mass spectrometric (LC–MS/MS) method has been developed to determine trace levels of icariin in human serum with dansyl chloride derivatization after oral administration of the Epimedium herbal decoctions. The dansyl-icariin showed an intense protonated molecular ion at m/z 910. The collision-induced dissociation of this ion formed a distinctive product at m/z 764, corresponding to a characteristic removal of a rhamnose sugar moiety of icariin. The selected reaction monitoring, based on the m/z 910 → 764 transition, was highly specific and ultrasenstive for icariin in human serum samples. The lower limit of quantitation was 10 pg/mL icariin spiked into blank serum. The ranges of coefficients of variation for interday assays and intraday assays were 0–15.0% and 1.1–17.5%, respectively, for a wide linear range from 10 pg/mL to 4 ng/mL. This method was successfully applied to measure trace levels of icariin in a human serum after oral administration of Epimedium decoction within 48 h for the first time.