目的 基于HPLC指纹图谱技术和统计学分析方法,比较和评价常山柚橙Citrus aurantium 'Changshan-huyou'未成熟的干燥果实(衢枳壳)与不同栽培变种酸橙间质量的一致性与差异性。方法 使用Extend XDB C₁₈色谱柱(250 mm×4.6 mm,5 μm),检测波长330 nm,以乙腈-0.1%甲酸水溶液为流动相进行梯度洗脱,体积流量1.0 mL/min,柱温为30℃。通过聚类分析(cluster analysis,CA)和主成分分析(principal component analysis,PCA)对35批样品的指纹图谱进行评价。结果 建立的酸橙枳壳的指纹图谱共有模式获得24个共有峰,并指认出12个目标化合物。13批衢枳壳样品的相似度结果范围0.920~0.947,质量一致性好,不同基原枳壳相似度结果为0.127~0.990,质量差异大。CA将衢枳壳均与酸橙枳壳聚为一类,朱栾和部分黄皮酸橙单独聚为一类,结合PCA获得区分不同基原枳壳的差异性标志物,其中9个已知化合物分别为葡萄内酯水合物、川陈皮素、柚皮苷、桔皮素、木犀草素、新橙皮苷、芸香柚皮苷、橙皮苷、柚皮素。结论 研究表明衢枳壳的化学成分与酸橙枳壳相似度高,且药材质量一致性好,药材质量优于朱栾和塘橙,推荐作为《中国药典》的枳壳植物基原之一。同时应增加区分不同基原枳壳的关键化合物作为指标成分,以全面准确的评价和控制枳壳药材质量。

Objective The fingerprint and statistical analysis were determined to compared and evaluate the quality consistency and difference between Citrus aurantium 'Changshan-huyou' immature dry fruit (Qu Aurantii Fructus) and different C. aurantium cultivars. Methods HPLC analysis was performed on Extend XDB C₁₈ column (250 mm × 4.6 mm, 5 μm), the detection wavelength was set at 330 nm, using acetonitrile-0.1% aqueous formic acid aqueous solution as mobile phase for gradient elution, the flow rate was 1 mL/min, the column temperature was maintained at 30℃. The fingerprints of 35 batches of samples were evaluated by cluster analysis (CA) principal component analysis (PCA). Results The established fingerprint common pattern of C. aurantium Aurantii Fructus samples obtained 24 common peaks and identified 12 target compounds. The similarity results of 13 batches of Qu Aurantii Fructus ranged from 0.920 to 0.947 with good quality consistency, while the similarity results of different original plant species of Aurantii Fructus ranged from 0.127 to 0.990 with great quality differences. Through CA, Qu Aurantii Fructus and C. aurantium Aurantii Fructus were clustered into one category, C. aurantium 'Chuluan' and partial C. aurantium 'Huangpi' were clustered into one category. The different markers of Aurantii Fructus with different original plant species were obtained by PCA, among which nine known compounds were glucolactone hydrate, nobiletin, naringin, tangeretin, luteolin, neohesperidin, Yunxiang naringin, hesperidin, naringenin) that caused the quality differences between samples. Conclusion Research showed that Qu Aurantii Fructus had high similarity of chemical composition with C. aurantium, had good consistency in medicinal material quality, which was batter than C. aurantium 'Tangcheng' and C. aurantium 'Chuluan'. Qu Aurantii Fructu can be used as one of the original plans of Aurantii Fructus in Chinese Pharmacopoeia. At the same time, adding the key compound s which distinguish different original plant species of Aurantii Fructus as the target ingredients to evaluate the quality of Aurantii Fructus correctly and thoroughly.

浙江省科技厅分析测试项目（LGC22H280007）；浙江省药品监督管理局项目（2023020）；浙江省市场监督管理局雏鹰计划项目（ZC2021A028）