UPLC-Q-TOF-MS分析不同产地泥附子化学成分的差异

Analysis on characteristic constituents of crude Aconitum carmichaelii in different regions based on UPLC-Q-TOF-MS

附子是我国毒性中药的代表品种,具有较高的药用价值,同时也具有一定的安全风险。随着城市化进程的推进及产业转移升级,逐渐形成了传统道地产区与新兴产区并存的局面。不同产区在地理分布、生态环境及生长周期等方面的差异性,可能导致附子种内化学成分的变异,进而影响品质和疗效。然而,有关不同产区附子的化学特征成分尚缺少深入研究。应用超高效液相色谱-四级杆飞行时间质谱(UPLC-Q-TOF-MS)方法对比分析传统不同产地附子的化学成分差异。结果表明,采用无监督的主成分分析(PCA),汉中附子与道地的江油附子成分相似,明显不同于新兴产区的布拖与巍山附子;运用偏最小二乘判别分析(PLS-DA),筛选发现7个主要差异化合物,其中新乌头碱与附子灵在布拖附子与巍山附子中含量较高,而次乌头碱、尼奥林、卡米查林、宋果灵等在江油附子与汉中附子中含量较高;结合各成分的毒性强弱,发现次乌头碱与新乌头碱是区分江油附子与布拖附子、巍山附子的关键毒性成分,江油附子毒性低于布拖附子与巍山附子。江油附子较低的毒性有利于保障临床用药安全,可能是附子道地性形成的重要原因之一。上述研究结果为从次生代谢产物多样性角度揭示附子道地性的形成机制提供了新的参考数据。

As a representative variety of hypertoxic herbs,aconite has a very high medicinal value but certain security risks. With the advance of urbanization and industrial transfer and upgrading,traditional geo-authentic regions and emerging regions have gradually coexisted. However,there are significant differences in the geographical distribution,ecological environment and growing cycle in these areas,which may cause intraspecific variations in chemical components,and then affect herb quality and clinical efficacy. Furthermore,there was still lack of in-depth study on characteristic constituents of aconite genuineness. In this paper,an UPLC-Q-TOF-MS was used to investigate the chemical ingredients in Jiangyou aconite,Hanzhong aconite,Butuo aconite and Weishan aconite. The results suggested that using unsupervised PCA method,Jiangyou aconite was similar with Hanzhong aconite in chemical ingredients,but significantly different from ones in emerging regions. Using PLS-DA method,seven characteristic constituents were identified,in which Butuo aconite and Weishan aconite had higher contents of mesaconitine and fuziline,while Jiangyou aconite and Hanzhong aconite had higher contents of hypaconitine,neoline,carmichaeline,and songorine. Based on basic toxicity of each ingredient,we can find that hypaconitine and mesaconitine were the key toxicity factors to distinguish Jiangyou aconite,Butuo aconite,and Weishan aconite. The toxicity of geo-authentic Jiangyou aconite was lower than that of Butuo aconite and Weishan aconite. The lower toxicity in geo-authentic Jiangyou aconite was beneficial for ensuring clinical drug safety,which may be one of the important reasons for the formation of genuine aconite. These results provide new reference data to reveal the formation mechanism of genuine aconite from the perspective of plant secondary metabolite diversity.