目的 采用HPLC指纹图谱与化学计量学相结合、UPLC-MS/MS测定多黄酮成分含量的方法，测定不同产地陈皮质量，为其鉴别和质量控制提供依据。方法 采用HPLC-DAD指纹图谱检测并结合“中药色谱指纹图谱相似度评价系统（2012A版）”建立6个产区，49个不同批次陈皮药材（S1～S49）指纹图谱，并进行相似度评价和共有峰确认，结合聚类分析（hierarchical clustering analysis，HCA）、主成分分析（principal component analysis，PCA）、正交偏最小二乘法-判别分析（orthogonal partial least-squares discrimination analysis，OPLS-DA）等化学计量学综合分析。采用UPLC-MS/MS法建立了8个黄酮类成分柚皮素、柚皮苷、木犀草苷、川陈皮素、橙皮素、橙皮苷、橘皮素和芸香柚皮苷的含量测定方法对60批7个产地陈皮药材进行评价。结果 建立了49批不同产地陈皮药材的指纹图谱，相似度为0.864～0.999，共标定了11个共有峰，HCA分析49批陈皮明显分为4类；PCA得到5个主成分的累积方差贡献率为92.748%；OPLS-DA表明8、7、10和11号峰可能是影响陈皮药材质量的差异标志物；含量测定结果表明不同产地陈皮中黄酮类含量存在显著差异，广东新会以川陈皮素和橘皮素为主要标志成分，四川荷花池以木犀草苷为差异性成分，江西樟树以柚皮素和柚皮苷为差异性成分，广西玉林则以橙皮素、橙皮苷和芸香柚皮苷为主，重庆云阳以川陈皮素和橙皮苷为主。结论 建立了稳定性强的不同产地陈皮HPLC指纹图谱和8个黄酮类UPLC-MS/MS定量测定方法，结合化学计量学可用于陈皮药材综合评价和质量控制。

Objective To determine the quality of Citrus reticulata from different production areas by combining HPLC fingerprinting with chemometrics and UPLC-MS/MS to provide a basis for its identification and quality control. Methods The fingerprints of 49 batches of C. reticulata from six production areas (S1—S49) were established using HPLC-DAD fingerprinting combined with the “Similarity Evaluation System for Chromatographic Fingerprinting in Chinese Medicine (2012A version)”, and similarity evaluation and common peaks were confirmed. Hierarchical clustering analysis (HCA), principal component analysis (PCA) and orthogonal partial least-squares-discrimination analysis (OPLS-DA). discrimination analysis (OPLS-DA) and other chemometric syntheses. A UPLC-MS/MS method was developed for the determination of eight flavonoid components “naringenin, naringin, luteoloside, nobiletin, hesperitin, hesperidin, tangeretin, narirutin” in 60 batches of C. reticulata from seven origins. Results The fingerprint profiles of 49 batches of C. reticulata from different origins were established with similarities of 0.864—0.999. Eleven common peaks were identified, HCA analysis of 49 batches of C. reticulata was divided into four categories; PCA obtained a cumulative variance contribution of 92.748% for the five principal components; OPLA-DA indicated that peak 8, peak 7, peak 10 and peak 11 might be the differential markers affecting the quality of C. reticulata; and the results of content determination showed that there were significant differences in flavonoid contents in C. reticulata from different origins, with nobiletin and tangeretin as the main marker components in Xinhui, Guangdong, luteoloside as the differential component in Hehuachi, Sichuan, naringenin and naringin as the differential in Zhangshu, Jiangxi, and metabolites, and Guangxi Yulin was dominated by hesperitin, hesperidin and narirutin, and Chongqing Yunyang was dominated by nobiletin and hesperidin; Conclusion Stable HPLC fingerprints of C. reticulata from different origins and quantitative determination of eight flavonoids by UPLC-MS/MS were established, which can be used for a comprehensive evaluation and quality control of C. reticulata herbs in combination with chemometrics.

R286.2

国家自然科学基金资助项目（81874337）；国家自然科学基金资助项目（81891014）；国家重点研发计划项目（2017YFC1700701）；中国中医科学院重点领域（ZZ10-027）