目的 基于HPLC指纹图谱与化学计量学探究白芍Paeoniae Radix Alba酒炙前后化学成分的差异性，筛选差异性标志物，为探究白芍酒炙前后炮制机制及建立质量控制标准提供参考。方法 采用HPLC建立白芍饮片酒炙前后指纹图谱，标定共有峰并进行指认与相似度评价，以白芍饮片酒炙前后共有峰峰面积为指标，运用层次聚类分析（hierarchical cluster analysis，HCA）、主成分分析（principal component analysis，PCA）和正交偏最小二乘-判别分析（orthogonal partial least squares- discriminant analysis，OPLS-DA）等方法对白芍酒炙前后进行区分，并筛选出差异性标志物进行定量分析。结果 生白芍与酒白芍HPLC指纹图谱相似度较高，但其酒炙前后峰面积有所差异；HCA与PCA可明显把生白芍与酒白芍分为2类，表明白芍酒炙前后化学成分存在一定差异；根据OPLS-DA分析筛选出峰1（没食子酸）、2（氧化芍药苷）、3、7（芍药苷）、8（没食子酰芍药苷）为酒炙前后主要差异性标志物；对其中可指认且含量较高的3个差异性标志物进行定量研究，结果显示，白芍经酒炙后没食子酸含量显著性增加，芍药苷、没食子酰芍药苷含量显著性减少，HCA可明显把白芍与酒白芍分为2类，进一步证实了选择该3种成分作为白芍酒炙前后差异性标志物的合理性。结论 白芍酒炙前后差异性标志物的研究可以为完善白芍与酒白芍饮片的质量控制和品质评价提供参考。

Objective Based on HPLC fingerprinting and chemometrics, we investigated the differences in chemical composition of Baishao (Paeoniae Radix Alba) with wine before and after processing, and screened the difference markers to provide reference for exploring the mechanism of the preparation of Paeoniae Radix Alba with wine before and after processing and establishing quality control standards. Methods HPLC was used to establish fingerprints of Paeoniae Radix Alba prepared slices before and after wine processing, to identify common peaks and evaluate the similarity. The peak areas of peaks shared before and after wine processing of Paeoniae Radix Alba prepared slices were used as indicators, and orthogonal partial least squares-discriminant analysis (OPLS-DA), principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to differentiate Paeoniae Radix Alba before and after wine processing. The above methods were used to differentiate between before and after wine processing of Paeoniae Radix Alba, and the differential markers were screened for quantitative analysis. Results The HPLC fingerprints of Paeoniae Radix Alba and wine-processed Paeoniae Radix Alba were similar, but their peak areas before and after wine roasting were different; HCA and PCA can clearly divide Paeoniae Radix Alba and wine-processed Paeoniae Radix Alba into two categories, indicating that there are some differences in the chemical composition of Paeoniae Radix Alba before and after wine processing; Peak 1 (gallic acid), 2 (oxidized paeoniflorin), 3, 7 (paeoniflorin) and 8 (gallic acyl paeoniflorin) were screened according to OPLS-DA analysis as markers of variability Paeoniae Radix Alba herbal pair with wine before and after processing; A quantitative study of three of these identifiable and high differential markers showed that the content of gallic acid was significantly increased and paeoniflorin and gallic acyl paeoniflorin were significantly decreased in Paeoniae Radix Alba prepared slices after wine processing. HCA could clearly divide Paeoniae Radix Alba prepared slices into two categories with wine-processed Paeoniae Radix Alba prepared slices, further confirming the rationality of selecting these three components as markers of the differences between Paeoniae Radix Alba prepared slices before and after wine processing. Conclusion The study on the differential markers of Paeoniae Radix Alba herbal pair with wine before and after processing can provide a reference for improving the quality control and quality evaluation of the prepared slices of Paeoniae Radix Alba and wine-processed Paeoniae Radix Alba.

R283.6

国家重点研发计划（2019YFC1711505）；安徽省重点研发项目（202104h04020029）；亳州市科技重大项目专项（bzzd2020002）；基于血清代谢组学变化的白芍酒炙增效机制研究（YJS20210491）