高效液相色谱-质谱联用结合量子化学计算发现乌头碱一新水解产物  

Studies on new hydrolysate of aconitine using HPLC-MS^n and quantum chemistry calculation

作　　者：谭鹏[1] 刘永刚[1] 关君[1] 李飞[1] 董玲[1] 乔延江[1] 

机构地区：[1]北京中医药大学,北京100102

出　　处：《中国中药杂志》2011年第15期2099-2101,共3页China Journal of Chinese Materia Medica

基　　金：国家自然科学基金项目(30901959);国家重点基础研究发展计划(973)项目(2009CB522800)

摘　　要：目的:高效液相色谱-质谱/质谱(HPLC-MSn)结合量子化学计算发现乌头碱的新水解产物。方法:HPLC-MSn方法采用梯度洗脱,质谱用正离子模式。采用密度泛函方法,在B3LYP/6-31G(d)水平上,对可能的产物结构进行计算。结果:通过HPLC-MSn的检测发现乌头碱水解产生分子离子峰为482的化合物,推测结构为脱水乌头原碱,量子化学计算结果只有C8位和C15位发生消除反的产物得到了最低能量构象,分析推测分子离子峰为482的化合物为C15位羰基的脱水乌头原碱。结论:首次发现乌头碱加热水解生成脱水乌头原碱,推测了乌头碱水解的两条新水解途径。Objective： To study the new hydrolysate of aconitine using HPLC-MSn and quantum chemistry calculation. Method： The HPLC method was applied in gradient elution program and the mass spectrometry was in positive ion mode. Geometries of the possible hydmlysates were optimized at DFT/6-31G（d） level. Result： The new hydrolysate was found and its proto- nated molecularions was at m/z 482. The quantum chemistry calculation results show that the product of elimination reations at C8 and C15 got the lowest energy conformation. The compound at m/z 482 was deduced to be the hydrolysate of carbony at C15. Conclusion： Delydration aconine was detected for the first time and the new hydrdysis pathways of aconitine in water were deduced.

关 键 词：HPLC—MSn 量子化学 乌头碱 脱水乌头原碱 水解 

分 类 号：R284[医药卫生—中药学]