目的 建立当归Angelica sinensis和欧当归Levisticum officinal药材的指纹图谱,结合化学计量学方法寻找二者的成分差异,从而为建立欧当归掺伪当归的鉴别方法提供依据。方法 采用UPLC法建立指纹图谱,色谱柱为Waters CortecsT3柱(100mm×2.1mm,1.6μm);流动相为0.1%甲酸乙腈溶液-0.1%甲酸水溶液,梯度洗脱;体积流量为0.4mL/min;柱温35℃;检测波长为210nm。采用相似度评价、主成分分析(principal component analysis,PCA)和层次聚类分析(hierarchical cluster analysis,HCA)对2种药材的指纹图谱进行评价,寻找2者的成分差异。采用UPLC-MS/MS及NMR波谱等技术对主要差异性成分进行鉴定。结果 从当归和欧当归指纹图谱中分别识别出23个和19个共有峰,与当归指纹图谱共有模式相比,当归样品组内有3批样品相似度较低,为0.59~0.80,其余样品相似度均大于0.99,而欧当归与之相比,相似度在0.53~0.94,且组内差异较大。PCA和HCA结果显示,当归和欧当归可明显分为2组,对区分贡献较大的色谱峰有6个,鉴定为色氨酸、阿魏酸、E-藁本内酯、欧当归内酯A异构体、绿原酸和法卡林二醇,其中后2种成分在欧当归中含量较高,其余成分在当归中含量较高。结论 建立的UPLC指纹图谱结合化学计量学评价方法,简便可行,可有效区分当归和欧当归并揭示其差异性成分,为当归的质量控制及掺伪欧当归鉴别方法<建立提供依据。同时首次从欧当归中分离得到法卡林二醇,该化合物为欧当归区别于当归的主要成分。

Objective To establish the fingerprints of Danggui (Angelica sinensis) and Oudanggui (Levisticum officinale), and find their differential components using chemometrics methods, thus providing a foundation for identifying the two herbs. Methods A UPLC method was applied to establish the fingerprints. Chromatographic separation was performed on Waters Cortecs T3 column (100 mm×2.1 mm, 1.6 μm). The mobile phase consisting of 0.1% formic acid acetonitrile solution-0.1% formic acid aqueous solution were adopted for gradient elution with the flow rate of 0.4 mL/min. The column temperature was 35 ℃, and the detection wavelength was at 210 nm. The fingerprints of A. sinensis and L. officinale were evaluated by similarity evaluation, principal component analysis (PCA) and hierarchical cluster analysis (HCA), to find their differential components. At the same time, the main differential components were identified by UPLC-MS/MS and NMR methods. Results A total of 23 and 19 common peaks were determined from the fingerprints of A. sinensis and L. officinale, respectively. Within A. sinensis group, the similarity of three batches of samples was low, in the range of 0.59—0.80 compared to the common pattern, while the rest was greater than 0.99. Within L. officinale group, the similarity of samples varied greatly, in the range of 0.53—0.94. PCA and HCA results showed that the samples of A. sinensis and L. officinale could be clearly divided into two groups. Six chromatographic peaks contributed significantly to the distinction of the two herbs, which were identified as tryptophan, ferulic acid, E-ligustilide, isomer of levistilide A, chlorogenic acid and falcarindiol, with the latter two being higher in L. officinale and the remaining being higher in A. sinensis. Conclusion The established UPLC fingerprints combined with the chemometrics method was simple and feasible, which could effectively distinguish A. sinensis and L. officinal as well as reveal their differential components, providing a basis for quality control of A. sinensis and for establishing the adulteration identification method of L. officinal impersonating A. sinensis. Meanwhile, falcarindiol was isolated from L. officinale for the first time, which is the main component of L. officinaele that distinguishes it from A. sinensis.

R286.2