目的 研究6种乌头类生物碱（乌头碱、次乌头碱、中乌头碱、苯甲酰乌头原碱、苯甲酰次乌头原碱、苯甲酰中乌头原碱）的质谱裂解途径。方法 采用高效液相色谱串联四级杆飞行时间质谱（HPLC-Q-TOF-MS）对该类化合物进行分析。结果 在正离子模式下，乌头类生物碱的主要裂解途径是连续丢失CH₃OH与H₂O。双酯型生物碱也可以在C-8位置断裂，失去CH₃COOH分子形成明显的特征碎片离子，从而实现与单酯型生物碱的区分。结论 此质谱裂解途径可为乌头类生物碱的结构鉴定提供依据，采用HPLC-Q-TOF-MS技术可以高效地分析中药中乌头类生物碱类化学成分，有利于化合物的分析和鉴定。

Objective To study the fragmentation pathways of six aconitine-type alkaloids (aconitine, hypaconitine, mesaconitine, benzoylaconitine, benzoylhypaconitine, and benzoylmesaconitine) in mass spectra (MS). Methods The samples were analyzed by liquid chromatography-tandem quadrupole time-of-flight mass spectrometry (HPLC-Q-TOF-MS). Results In positive mode, The typical fragmentation pathways of the six aconitine-type alkaloids were mainly continuous loss of CH₃OH and H₂O. The characteristic fragmentation pathway of diester-diterpene type aconitine was losing an acetic acid molecule from C-8 position; However this fragmentation could not be observed in MS of mono-ester aconitine alkaloids. Conclusion The study on fragmentation pathways could be adopted for the structural identification of the six aconitine-type alkaloids.

国家重点基础研究发展计划（973）项目（2015CB554405）