川楝子中柠檬苦素类成分的HPLC-ELSD指纹谱分析

目的：建立高效液相色谱-蒸发光散射方法，分析川楝子中柠檬苦素类成分的指纹谱，并测定1-去乙酰基尼泊里宁 B的含量。方法：采用YMC-Pack C₁₈（150 mm×4.6 mm，5 μm）色谱柱，以流动相甲醇-水-四氢呋喃（55：40：5）进行洗脱，流速1.0 mL·min^-1，柱温25 ℃；采用蒸发光散射检测器，漂移管温度93.0 ℃，载气流速2.3 L·min^-1。结果：川楝子中主要含有1-去乙酰基尼泊里宁B（1）、尼泊里宁B（2）、尼泊里宁A（3）、1-顺芷酰基尼泊里宁A（4）、川楝素（5）等柠檬苦素类成分，化合物2~5存在不同程度互变异构现象；1-去乙酰基尼泊里宁B的线性范围为2.324~19.36 μg（r=0.9996），平均加样回收率为96.98%，RSD为2.6%。结论：建立的方法符合方法学验证要求，可用于川楝子中柠檬苦素类成分的分析。指纹谱分析结果表明，尼泊里宁型化合物是川楝子中的主要成分；川楝子炮制后指标成分含量有所降低；样品中指标成分含量差异较大。

Objective: To establish a fingerprint analysis method for limonoids in Fructus Toosendan by high performance liquid chromatography-evaporative light scattering detection (HPLC-ELSD),and to determine the content of 1-deacetylnimbolinin B. Methods: A YMC-Pack C₁₈ column (150 mm×4.6 mm,5 μm) was applied;the mobile phase consisted of methanol-water-THF (55:40:5);the flow rate was 1.0 mL·min^-1;the column temperature was 25 ℃;the drift tube temperature of ELSD was set at 93.0 ℃,and the flow rate of air was 2.3 L·min^-1. Results: 1-Deacetylnimbolinin B (1) and other four tautomeric limonoids,nimbolinin B (2),nimbolinin A (3),1-O-tigloyl-1-O-deacetyl-nimbolinin B (4) and toosendanin (5) were assigned in HPLC chromatogram of Fructus Toosendan;as for 1-deacetylnimbolinin B,the linear detection range was 2.324-19.36 μg (r=0.9996);the average recovery was 96.98% and the relative standard deviation was 2.6%. Conclusion: This method conforms to the method validation requirements,and can be used for determination and analysis of limonoids in Fructus Toosendan.Fingerprint analysis showed that nimbolinin compound is the main component in Fructus toosendan;after processing,the marker components content reduces,while the index component content of samples varies greatly.