栀子饮片质量分析研究

目的： 建立了栀子、炒栀子、焦栀子中3个有效成分京尼平龙胆二糖苷、栀子苷、西红花苷Ⅰ的含量测定方法及高效液相色谱指纹图谱，利用高效液相色谱串联电喷雾高分辨质谱（ESI-MS/MS）对特征峰进行指认，对栀子、炒栀子、焦栀子的水煎液与甲醇提取液中各成分的含量进行比较研究。 方法： 采用液相色谱法，使用Kromasil 100-5C₁₈（4.6 mm×250 mm，5 μm）色谱柱，以乙腈（A）-0.5%甲酸溶液（B）为流动相，梯度洗脱（0~15 min，5%A→20%A；15~27 min，20%A→27%A；27~33 min，27%A→33%A；33~38 min，33%A；38~45 min，33%A→38%A），流速1 mL·min^-1，检测波长为切换波长（0~20 min，240 nm，测定京尼平龙胆二糖苷，栀子苷；20~45 min，440 nm，测定西红花苷Ⅰ），柱温30 ℃；质谱采用负离子模式。 结果： 建立了栀子、炒栀子、焦栀子的指纹图谱及其药效成分的含量测定方法；指认8个特征峰，分别为山栀苷、羟异栀子苷、京尼平龙胆二糖苷、栀子苷、西红花苷Ⅰ、西红花苷Ⅱ、西红花苷Ⅲ及西红花酸的色谱峰。确定了栀子饮片、炒栀子及焦栀子的药效成分及其水煎液与甲醇提取液药效成分的含量变化规律。 结论： 所建立的指纹图谱分析方法，可识别栀子、炒栀子、焦栀子样品。栀子经炮制后，环烯醚萜苷类成分京尼平龙胆二糖苷、栀子苷及色素类成分西红花苷Ⅰ含量减少。栀子、炒栀子、焦栀子样品水煎液与甲醇提取液中各成分的含量呈下降变化趋势。

Objective: To establish the HPLC fingerpri nt and the determination of genipin-1-β-D-gentiobioside,geniposide,crocin-Ⅰ of Gardeniae Fructus,Gardeniae Fructus(stir-baked),Gardeniae Fructus Preparatus,identify the compound of peaks in fingerprints by ESI-MS/MS,and compare the water decoction and the methanol extract of Gardeniae Fructus,Gardeniae Fructus (stir-baked),and Gardeniae Fructus Preparatus. Methods: The analysis was performed on a Kromasil 100-5C₁₈column (4.6 mm×250 mm,5 μm),the mobile phase was acetonitrile (A) - 0.5% formic acid water (B) with gradient elution mode (0-15 min,5%A→20%A;15-27 min,20%A→27%A;27-33 min,27%A→33%A;33-38 min,33%A;38-45 min,33%A→38%A), at the flow rate of 1 mL·min^-1, the detection was set at 240 nm (0-20 min) for genipin-1-β-D-gentiobioside,geniposide) and 440 nm (20-45 min) for crocin-Ⅰ,the column temperature was 30 ℃. Results: The fingerprint and the method for determination were established.Eight common peaks were identified by ESI-MS/MS which were shanzhiside,gardenoside,genipin-1-β-D-gentiobioside,geniposide,crocin-Ⅰ,crocin-Ⅱ,crocin-Ⅲ and crocin acid.The effective components of Gardeniae Fructus,Gardeniae Fructus (stir-baked) and Gardeniae Fructus Preparatus were determined.And the change rules of effective components between the water solution and the methanol extract were completed. Conclusion: The method established in this experiment is able to recognize the three kinds of Gardeniae Fructus.Being processed by different methods,the contents of genipin-1-β-D-gentiobioside,geniposide,crocin-Ⅰ declined gradually.The developmental tendency of the contents of the water solution and the methanol extract is also downward.