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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: The new hydrolyzate of aconitine was found by HPLC-MSn combined with quantum chemistry calculations. Methods: HPLC-MSn method using gradient elution, mass spectrometry with positive ion mode. The possible product structures were calculated at the B3LYP / 6-31G (d) level using density functional theory. Results: It was found by HPLC-MSn that aconitine was hydrolyzed to give a compound with molecular ion peak of 482, which was presumed to be dehydrated aconitine. The results of quantum chemical calculation showed that only the products with elimination reaction at C8 and C15 had the lowest energy Conformational analysis revealed that the compound having a molecular ion peak of 482 is a dehydrated aconitine base having a C15 carbonyl group. CONCLUSION: Aconitine was first hydrolyzed to form dehydrated aconitine, suggesting two new hydrolysis pathways of aconitine hydrolysis.