四逆汤煎煮过程中乌头类生物碱的溶出和水解平衡

目的 研究四逆汤中乌头类生物碱的溶出平衡和水解平衡。方法 利用电喷雾质谱分析，比较了制附子、四逆汤、四逆汤药渣和含有3种双酯型生物碱的混合对照品体系中的乌头碱类二萜生物碱。结果 在煎煮过程中双酯型生物碱溶解并发生水解反应，而脂类生物碱则难溶于水。乌头碱、中乌头碱、次乌头碱水溶性相近，但是次乌头碱在水中的热稳定性更高，C19二萜骨架上C3取代基(—OH或—H)的变化影响生物碱的稳定性。结论四逆汤中的乌头碱类生物碱的种类及含量由其溶解性和化学稳定性共同决定。

Stripping and hydrolyzing balance of aconitic alkaloids in processing of Sini Decoction

Object To study the stripping and hydrolyzing balance of aconitic alkaloids in Sini Decoction. Methods Sini Decoction, the prepared aconite roots that had been concocted with liquorice and dried ginger, the residue of Sini Decoction and the mixed reference substance system contained three kind of diester diterpenoid alkaloids (DDAs) were analyzed by electrospray ionization mass spectrometry (ESI-MS) respectively. Results The results showed that the DDAs were solved and reduced by hydrolysis reaction, and the lipo-alkaloids were difficult to be soluted in the Decoction. The further study for the system of three DDAs including aconitine, mesaconitine and hypaconitine indicated that the solubility of DDAs was similar, but hypaconitine was more stable in boiling water, which suggested that the change of C 3-substitute (-OH or -H) on diterpenoid skeleton would influence the stability of DDAs evidently. Conclusion The content of aconitic alkaloids in Sini Decoction and its variety depend on both their solubility and chemical stability.