天然产物研究与开发 ›› 2025, Vol. 37 ›› Issue (11): 2018-2027.doi: 10.16333/j.1001-6880.2025.11.005 cstr: 32307.14.1001-6880.2025.11.005

• 研究论文 • 上一篇    下一篇

香橼及其易混淆品UPLC指纹图谱建立及6个成分含量测定研究

郑舒宁1,2,齐  红3,林墁怡4,周彦君4,张  英1,2,吴孟华1,2,曹  晖1,2,马志国1,2*   

  1. 1暨南大学岭南传统中药研究中心,广州 510632;2国家中药现代化工程技术研究中心 岭南资源分中心,广州 510632;3济南市食品药品检验检测中心,250102;4暨南大学药学院,广州510632
  • 出版日期:2025-11-27 发布日期:2025-11-26
  • 基金资助:
    全国名老中医药专家传承工作室(国中医药人教函[2022]75号);2023年度国家药品标准制修订研究课题(2023Z03)

UPLC fingerprints and content determination of six components of Citri Fructus and its adulterants 

ZHENG Shu-ning1,2,QI Hong3,LIN Man-yi4,ZHOU Yan-jun4,ZHANG Ying1,2,WU Meng-hua1,2,CAO Hui1,2,MA Zhi-guo1,2*   

  1. 1Research Center for Traditional Chinese Medicine of Lingnan,Jinan University,Guangzhou 510632,China;2National Engineering Research Center for Modernization of Traditional Chinese Medicine Lingnan Resources Branch,Guangzhou 510632,China;3Jinan Institute for Food and Drug Control,Jinan 250102,China; 4Jinan University College of Pharmacy,Guangzhou 510632,China
  • Online:2025-11-27 Published:2025-11-26

摘要:

通过建立香橼的UPLC指纹图谱及多成分含量测定方法,为香橼及其易混淆品的鉴别提供依据。采用UPLC建立香橼及其易混淆品的指纹图谱,并采用相似度进行评价;然后针对6个主要成分开展含量测定研究,将所获得结果导入SIMCA软件进行正交偏最小二乘判别分析(Orthogonal partial least squares discriminant analysis, OPLS-DA)评价香橼与其易混淆品的差异。结果显示,香橼的两个基原品种(枸橼、香圆)及其易混淆品佛手、柚幼果的指纹图谱之间均存在差异,其中枸橼与易混淆品佛手指纹图谱相似,但枸橼中的2号、3号峰未在佛手中检测到,且佛手中9号峰(5,7-二甲氧基香豆素)峰面积远高于枸橼;香圆与易混淆品柚幼果指纹图谱相似,但香圆中的9号峰在柚幼果中未检测到,柚幼果中的5号、7号、8号峰在香圆中未检测到。共有峰的差异可以有效区分枸橼、香圆及其易混淆品。新西兰牡荆苷、柚皮苷、野漆树苷、橙皮苷、地奥司明、5,7-二甲氧基香豆素的6个成分在各自质量浓度范围内线性关系良好(r≥0.999 0),加样回收率均在98.90%~106.0%,相对标准偏差均小于2.2%。柚幼果中的柚皮苷平均含量(98.280 mg/g)略高于香圆(85.770 mg/g),佛手中的5,7-二甲氧基香豆素平均含量(1.160 mg/g)明显高于枸橼(0.080 mg/g)。四个品种可通过建立的OPLS-DA模型进行有效区分。本研究所建立的方法操作简单,重复性好,可为香橼质量标准建立提供更全面的依据。

关键词: 香橼, UPLC, 含量测定, 指纹图谱, 化学计量学

Abstract:

To establish a method for UPLC fingerprints and multi-component quantitation of Citri Fructus (CF) and provide a basis for distinguishing CF from its adulterants, UPLC was employed to construct fingerprints of CF and its adulterants with similarity evaluation. Additionally, content determination of six major components was conducted, and the results were analyzed using orthogonal partial least squares discriminant analysis (OPLS-DA) via SIMCA software to evaluate differences between CF and its adulterants. The results revealed distinct differences in the fingerprints of the two original varieties of CF: Citrus medica fruit (CMF) and Citrus wilsonii fruit (CWF), and its adulterants: Citri Sarcodactylis fruit (CSF) and Citrus grandis immature fruit (CGF). Although the fingerprints of CMF and CSF were similar, peaks 2 and 3 in CMF were absent in CSF, while peak 9 (5,7-dimethoxycoumarin) in CSF exhibited a significantly higher peak area compared to CMF. CWF and CGF shared similarities in their UPLC fingerprints, but peak 9 in CWF was undetected in CGF, and peaks 5, 7 and 8 in CGF were absent in CWF. These differences in common peaks effectively distinguished CMF, CWF, and their adulterants. Six components including vicenin Ⅱ, naringin, rhoifolin, hesperidin, diosmin and 5,7-dimethoxycoumarin demonstrated excellent linear relationships (r ≥ 0.999 0) within their respective concentration ranges. The recovery rates ranged from 98.90% to 106.0%, with relative standard deviations below 2.2%. The average content of naringin in CGF (98.280 mg/g) was slightly higher than that in CWF (85.770 mg/g), while the average content of 5,7-dimethoxycoumarin in CSF (1.160 mg/g) was significantly higher than that in CMF (0.080 mg/g). The four varieties were effectively differentiated using the established OPLS-DA model. The developed method in this study is straightforward, reproducible, and provides a comprehensive foundation for establishing quality standards for CF.

Key words: Citri Fructus, UPLC, Content determination, Fingerprint, Chemometrics

中图分类号:  R932