Simultaneous determination of 11 aconitum alkaloids in human serum and urine using liquid chromatography–tandem mass spectrometry

A liquid chromatography–tandem mass spectrometry method was developed and validated for simultaneous determination of four aconitines (aconitine, mesaconitine, hypaconitine, jesaconitine) and seven of their hydrolysis products (benzoylmesaconine, benzoylhypaconine, 14-O-anisoylaconine, benzoylaconine, aconine, mesaconine, hypaconine) in human serum and urine samples. Extraction was undertaken using a mixed-mode cation-exchange cartridge (OASIS MCX), and D5-aconitine was used as an internal standard. Separation of aconitum alkaloids was carried out using an L-column ODS with the mobile phase consisting of 10 mM ammonium formate and methanol. The intra- and inter-day precisions were 0.3% to 9.9% and 3.2% to 12.8%, respectively. Intra- and inter-day accuracies were −14.1% to 7.3%, and −10.6% to 8.3%, respectively. The limit of detection and limit of quantification of analytes were 0.04–0.38 ng/mL and 0.12–1.15 ng/mL respectively. This method was applied in an autopsy case and successfully detected aconitines and their metabolites as well as some anti-psychiatric drugs.