目的 建立四季三黄片制剂的HPLC指纹图谱,对特征峰进行指认,并与相同色谱条件下原药材HPLC指纹图谱进行谱峰匹配研究。方法 对3个厂家10个批次的样品进行HPLC指纹图谱相似性评价并与原药材进行谱峰匹配,样品采用甲醇超声提取(100 kHz,30 min,25 ℃),采用高效液相色谱法-二极管阵列检测,检测波长254 nm,流动相为甲醇-0.1%磷酸水溶液,梯度洗脱,体积流量0.8 mL/min,柱温25 ℃,以夹角余弦和相关系数为测度计算其相似度,采用SPSS 16.0软件进行聚类分析。结果 10批样品色谱图中有19个共有峰,其中第1、2、4、17、18号峰分别是栀子苷、盐酸小檗碱、黄芩苷、大黄素和大黄酚,大黄、黄芩、栀子、黄柏与四季三黄片分别有11、6、2、1个色谱峰匹配,9号峰为大黄和黄芩所共有。各批样品的夹角余弦、相关系数均大于0.9,聚类分析表明四季三黄片样品可大致聚为3类。结论 建立的四季三黄片制剂及药材谱峰匹配指纹图谱为其鉴别和质量评价提供了有效的方法。

Objective To establish high performance liquid chromatography (HPLC) fingerprints of Siji Sanhuang Tablets (SST) and study the characteristic peaks identification and preparations-medicinal materials peak pattern matching. Methods Similarity on 10 batches of SST from three manufacturers was estimated, and peak pattern matching of the original medicine was conducted. Sample extraction with methanol in ultrasonic condition (100 kHz, 30 min, 25 ℃) was carried out. HPLC-Diode Array Detector methods were developed to determine, detection wave length was set at 254 nm, HPLC mobile phase consisted of methanol-0.1% phosphoric acid aqueous solution (gradient elute), volume flow-rate was delivered at 0.8 mL/min, and column temperature was kept at 25 ℃. Similarity measures such as included angle cosine and correlation coefficient were tested. Ten batches of samples were analyzed by SPSS 16.0. Results The results showed that 19 common peaks were defined, the peaks No. 1, 2, 4, 17, and 18 were geniposide, berberine hydrochloride, baicalin, emodin, and chrysophanol, respectively, and peak pattern matching showed that SST had 11, 6, 2, and 1 matching peaks with Rhei Radix et Rhizoma, Scutellariae Radix, Gardeniae Fructus, and Phellodendri chinensis Cortex, respectively. The peak No. 9 belonged to Rhei Radix et Rhizoma and Scutellariae Radix. The fingerprint similarity among the samples were all over 0.9. All the samples were classified into three categories. Conclusion Peak matching fingerprints of preparations-medicinal materials established provide the effective methods for the identification and the quality control of SST.

河北省中医药管理局科研计划项目(2013078);张家口市科学技术研究与发展指导计划项目(1021097D)