Electrochemical microreactor combined with mass spectrometry for online oxidation and real-time detection of alkaloids.

The main purpose of the present study was to investigate the prototypes and oxidation products of alkaloids with the use of an online electrochemistry/quadrupole time-of-flight mass spectrometry system. The metabolism of oxidative phase I and II was simulated in an electrochemical reaction cell. The metabolic processes for coptisine and jatrorrhizine were simulated in a thin-layer cell fitted with a glassy carbon working electrode, while the metabolic processes for berberine and palmatine were simulated by using a boron-doped diamond working electrode. By using the new experimental system, dehydrogenation, demethylation, methylation, hydroxylation, and the formation of two hydroxylation adducts were detected by applying different potentials to the electrochemical cell. The online reaction with glutathione yielded different covalent glutathione adducts. The results obtained from the electrochemical simulation were found to be in good accordance with those reported previously in vivo, showing that electrochemistry/mass spectrometry is an effective tool for studying metabolic reactions for various complex components. Moreover, analysis of alkaloids in liver microsomes by liquid chromatography coupled with mass spectrometry confirmed the possibility of using an electrochemistry technique to simulate the metabolism of target compounds.