Tang Yu, Han Zhu, Zhang Han, Che Li, Liao Genjie, Peng Jun, Lin Yu, Wang Yi
Pharmaceutical Informatics Institute, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, China; Innovation Institute for Artificial Intelligence in Medicine of Zhejiang University, Hangzhou 310018, China.
Pharmaceutical Informatics Institute, College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058, China.
J Pharm Biomed Anal. 2023 May 10;228:115320. doi: 10.1016/j.jpba.2023.115320. Epub 2023 Mar 1.
A new approach is developed for the reliable classification of Calculus bovis along with the identification of willfully contaminated C. bovis species and the quantification of unclaimed adulterants. Guided by a principal component analysis, NMR data mining achieved a near-holistic chemical characterization of three types of authenticated C. bovis, including natural C. bovis (NCB), in vitro cultured C. bovis (Ivt-CCB), and artificial C. bovis (ACB). In addition, species-specific markers used for quality evaluation and species classification were confirmed. That is, the content of taurine in NCB is near negligible, while choline and hyodeoxycholic acid are characteristic for identifying Ivt-CCB and ACB, respectively. Besides, the peak shapes and chemical shifts of H-25 of glycocholic acid could assist in the recognition of the origins of C. bovis. Based on these discoveries, a set of commercial NCB samples, macroscopically identified as problematic species, was examined with deliberately added sugars and outliers discovered. Absolute quantification of the identified sugars was realized by qHNMR using a single, nonidentical internal calibrant (IC). This study represents the first systematic study of C. bovis metabolomics via an NMR-driven methodology, which advances the toolbox for quality control of TCM and provides a more definitive reference point for future chemical and biological studies of C. bovis as a valuable materia medica.
开发了一种新方法，用于牛黄的可靠分类，同时识别故意污染的牛黄种类以及对未申报掺假物进行定量。在主成分分析的指导下，核磁共振数据挖掘实现了对三种经鉴定的牛黄的近乎全面的化学表征，包括天然牛黄（NCB）、体外培养牛黄（Ivt - CCB）和人工牛黄（ACB）。此外，还确定了用于质量评估和种类分类的物种特异性标志物。也就是说，天然牛黄中牛磺酸的含量几乎可以忽略不计，而胆碱和猪去氧胆酸分别是鉴定体外培养牛黄和人工牛黄的特征成分。此外，甘氨胆酸H - 25的峰形和化学位移有助于识别牛黄的来源。基于这些发现，对一组宏观上被鉴定为有问题种类的市售天然牛黄样品进行了检查，发现了故意添加的糖类和异常值。使用单一的、不同的内标（IC）通过定量核磁共振（qHNMR）实现了对鉴定出的糖类的绝对定量。本研究代表了通过核磁共振驱动方法对牛黄代谢组学的首次系统研究，它推进了中药质量控制的工具箱，并为牛黄作为一种珍贵药材的未来化学和生物学研究提供了更明确的参考点。
