液相色谱-线性离子阱-静电场轨道阱高分辨质谱测定蜂胶中9种黄酮类物质

Rapid Screening and Accurate Mass Confirmation of 9 Flavonoids in Propolis by High Resolution LC-LTQ-Orbitrap Mass Spectrometry

本文利用线性离子阱-静电场轨道阱（LTQ-Orbitrap）高分辨质谱,配合全自动筛选应用软件ToxID可以对大量数据进行高通量分析的特点,建立了蜂胶中杨梅酮、乔松素、芹菜素、苛因、山奈素、高良姜素、槲皮素、芦丁、桑黄素9种黄酮类物质的快速筛选和确证方法。样品使用无水乙醇提取,采用Waters xselect HSS T3色谱柱（100×3.0mm,3.5μm）,以乙腈-0.1%乙酸溶液为流动相,FT正离子扫描模式进行质谱检测,外标法定量。结果表明,该方法对以上除杨梅酮外8种黄酮类化合物的线性范围为0.5-50μg/mL,杨梅酮的线性范围为1.0-50μg/mL,相关系数（r）均大于0.99。在625mg/kg、1 250mg/kg、2 500mg/kg 3个添加水平的回收率为78.7%-93.3%,相对标准偏差为7.10%-12.65%。

A high performance liquid chromatography（HPLC）method combined with full-scan accurate linear ion trap-orbitrap mass spectrometry（LTQ-Orbitrap）was established to detect rutin,myricetin,quercetin,kaempferol,apigenin,pinocembrin,chrysin and galangin contents in propolis.The propolis were extracted with absolute ethyl alcohol.The LC separation was performed on a column of Waters xselect HSS T3（100×3.0 mm,3.5μm）with acetonitrile and 0.1% acetic acid solution as the mobile phase.The analyte was detected by FT positive mode.The calibration curves showed good linearity within the concentration range of 0.5-50μg/mL for all the analytes except myricetin（1.0-50μg/mL）.The average recoveries of 9compounds ranged from 78.7%to 93.3%at the spiked levels of 625mg/kg,1 250mg/kg and 2 500mg/kg,respectively with the relative standard deviations（RSDs）less than 12.65%.