基于UPLC-Q/TOF-MS分析淫羊藿炮制前后黄酮组分的变化规律

Analysis changes of Epimedii Folium’s flavonoids before and after processing based on UPLC-Q/TOF-MS

目的基于UPLC-Q/TOF-MS技术建立淫羊藿炮制前后指纹图谱,对其全成分进行分析并找出标志性化学成分,以明确淫羊藿炮制前后黄酮组分的变化规律。方法采用UPLC-Q/TOF-MS技术,在正离子模式下采集淫羊藿生品及炮制品样品数据,并在此基础上根据正交-偏最小二乘判别分析(OPLS-DA)整体探究9个不同产地、批次的淫羊藿炮制前后化学成分的差异。结果从淫羊藿生品及炮制品中寻找并鉴定出9个标志性化学成分,即8-乙烯-山柰酚、淫羊藿素、淫羊藿次苷I、淫羊藿素-3-O-葡萄糖苷、异戊醇基箭藿苷B、1,3-异戊二烯基朝藿定C、1,3-异戊二烯基-箭藿苷B-7-O-葡萄糖醛酸、3-O-(4-乙酰氧基)鼠李糖-2-O-(间二乙酰氧基)葡萄糖-淫羊藿苷及其同分异构体。结论淫羊藿炮制后黄酮组分结构发生变化,次级糖苷增加,多级糖苷减少,淫羊藿黄酮组分总体向低糖苷组分转化,进一步阐明了淫羊藿加热炮制后黄酮组分的变化规律。

Objective Based on UPLC-Q/TOF-MS technology, the fingerprint of Epimedium koreanum before and after processing was established to analyze the whole composition and find out the iconic chemical composition to clarify the change rule of flavonoids. Methods The data of E. koreanum raw and processed products were collected in positive ion mode using UPLC-Q/TOF-MS technology, and orthogonal partial least least squares-discriminant analysis(OPLS-DA) method was used to explore the differences in chemical composition of E. koreanum before and after processing in nine different origins and batches. Results Nine iconic chemical constituents from E. koreanum raw and processed products were found and identified, including 8-ethylene-kaempferol, icaritin, icariin I, icartin-3-O-glucoside, isoamyl alcohol sagittatoside B, 1,3-prenyl epimedin C, 1,3-prenyl-sagittatoside B-7-O-glucuronic acid, 3-O-((4-acetoxy) rhamnose-2-O-(m-2 acetoxy) glucose) icariin and its isomers. Conclusion The structures of E. koreanum’s flavonoids changed after the processing, the secondary glycosides of flavonoids increased, the polyglycosides decreased, and the flavonoids were generally converted to low glycoside components, which further clarified the change rule of E. koreanum’s flavonoids after processing.