目的 建立同时测定蒺藜中槲皮素、山柰酚、异鼠李素、白杨素、蒺藜皂苷、蒺藜皂苷K、蒺藜皂苷D、蒺藜呋甾皂苷B、蒺藜苷元、海柯皂苷元、薯蓣皂苷元和替告皂苷元含量的方法，探索主成分分析（PCA）、正交偏最小二乘法-判别分析（OPLS-DA）及灰色关联度分析（GRA）模型在蒺藜质量差异评价中的应用。方法 采用HPLC法，以乙腈-0.05%磷酸为流动相，梯度洗脱；检测波长为360、203 nm；通过对多指标成分含量结果进行PCA、OPLS-DA分析，同时建立GRA模型，综合分析不同产地蒺藜质量差异。结果 方法学验证结果均符合《中国药典》要求； 12种成分在各自范围内线性关系良好（r＞0.999），平均加样回收率（n＝9）在96.92%～100.18%（RSD＜2.0%）。PCA、OPLS-DA分析显示蒺藜苷元、异鼠李素、山柰酚和槲皮素是影响蒺藜产品质量的主要潜在标志物。GRA相对关联度0.339 7～0.597 1，蒺藜质量存在一定产地差异。结论 HPLC同时测定蒺藜中12个成分，简便可靠，PCA、OPLS-DA和GRA可用于不同产地蒺藜质量差异分析。

Objective To establish a method for the simultaneous determination of quercetin, kaempferol, isorhamnetin, chrysin, tribuloside, terrestrosin K, terrestrosin D, terrestroside B, (25R) -spirost-4-ene-3, 12-dione, hecogenin, diosgenin and tigogenin in Tribuli Fructus, and to explore the application of principal component analysis (PCA), orthogonal partial least squares-discriminant analysis (OPLS-DA) and grey relational analysis (GRA) in the quality difference evaluation of Tribuli Fructus. Method HPLC method was used with acetonitrile as mobile phase A and 0.05% phosphate acid solution as mobile phase B in gradient elution mode; the detection wavelengths were 360 and 203 nm. Through the chemometric analysis of the results of multi-index component content, the GRA model was established to comprehensively analysis the quality differences of Tribuli Fructus from different producing areas. Results The results of methodological verification were in line with the requirements of Chinese Pharmacopoeia; There were good linear relationships (r > 0.999) when the 12 components were in their respective ranges, and the average recovery rate (n = 9) were 96.92%—100.18% (RSD < 2.0%). Chemometric analysis showed that (25R) -spirost-4-ene-3, 12-dione, isorhamnetin, kaempferol and quercetin were the main potential markers affecting the quality of Tribuli Fructus. The relative correlation degree of GRA were 0.3397—0.5971, and there was a certain difference between producing areas of Tribuli Fructus. Conclusion The HPLC method can simultaneously determine the 12 components in Tribuli Fructus, which is simple and practical, PCA, OPLS-DA and GRA can be used to analyze the quality differences of Tribuli Fructus from different producing areas.

R284.1

甘肃省科技计划（自筹经费-自然科学基金）项目（编号23JRRA1595）