Rapid quality assessment of Radix Aconiti Preparata using direct analysis in real time mass spectrometry
实时直接分析质谱（DART）在制川乌快速质量控制中的应用
Hongbin Zhu, Chunyan Wang, Yao Qi, Fengrui Song, Zhiqiang Liu, Shuying Liu
Changchun Center of Mass Spectrometry & Chemical Biology Laboratory, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
University of Chinese Academy of Sciences, Beijing 100039, China
朱洪彬1,2，刘 舒1,2，宋凤瑞1* 刘志强1，刘淑莹1
（ 1. 中国科学院长春应用化学研究所，长春质谱中心，吉林长春 130022； 2. 中国科学院研究生部，北京 100049）
This study presents a novel and rapid method to identify chemical markers for the quality control of Radix Aconiti Preparata, a world widely used traditional herbal medicine. In the method, the samples with a fast extraction procedure were analyzed using direct analysis in real time mass spectrometry (DART MS) combined with multivariate data analysis. At present, the quality assessment approach of Radix Aconiti Preparata was based on the two processing methods recorded in Chinese Pharmacopoeia for the purpose of reducing the toxicity of Radix Aconiti and ensuring its clinical therapeutic efficacy. In order to ensure the safety and effectivity in clinical use, the processing degree of Radix Aconiti should be well controlled and assessed. In the paper, hierarchical cluster analysis and principal component analysis were performed to evaluate the DART MS data of Radix Aconiti Preparata samples in different processing times. The results showed that the well processed Radix Aconiti Preparata, unqualified processed and the raw Radix Aconiti could be clustered reasonably corresponding to their constituents. The loading plot shows that the main chemical markers having the most influence on the discrimination amongst the qualified and unqualified samples were mainly some monoester diterpenoid aconitines and diester diterpenoid aconitines, i.e. benzoylmesaconine, hypaconitine, mesaconitine, neoline, benzoyl hypaconine, benzoylaconine, fuziline, aconitine and 10-OH-mesaconitine. The established DART MS approach in combination with multivariate data analysis provides a very flexible and reliable method for quality assessment of toxic herbal medicine.
由于制川乌的炮制程度直接关系到其在临床应用中的安全、有效，因此，控制、检测其炮制程度是制川乌质量标准研究的重要方面。本研究采用新型的质谱离子化技术，对中国药典中制川乌的快速质量控制方法进行了研究。经快速简单处理后的样品直接用于实时直接分析质谱（DART MS）分析，并结合化学计量学方法对其 DART MS 指纹图谱进行评价。通过系统聚类分析（HCA）和主成分分析（PCA）对不同炮制时间制川乌的DART MS指纹图谱的评价，确定了制川乌质量控制的化学标志性物质。结果表明，通过 DART MS 结合化学计量学分析能够对合格的制川乌、不合格制川乌以及生川乌进行鉴别。主成分分析载荷图结果表明，制川乌质量控制的主要化学标志物为苯甲酰新乌头原碱，次乌头碱，新乌头碱，尼奥灵，苯甲酰次乌头原碱，苯甲酰乌头原碱，附子灵，乌头碱和 10-OH-新乌头碱。本研究证明实时直接分析质谱技术（DART MS）快速可靠，直接通过谱图分析或结合化学计量学方法可以应用于制川乌的快速质量控制。
