为了测定铁皮石斛中的吡咯里西啶生物碱（pyrrolizidine alkaloids，PAs）的含量，该研究建立了固相萃取结合超高效液相色谱-串联质谱法同时测定铁皮石斛中16种不饱和PAs的分析方法。样品经0.05 mol/L硫酸甲醇提取、MCX固相萃取小柱纯化富集，以甲醇和0.005 mol/L甲酸铵-0.1%甲酸水溶液为流动相，Waters ACQUITY UPLC BEH C18柱梯度洗脱分离，采用电喷雾正离子、多反应监测模式进行采集，基质匹配外标法定量。结果表明，该方法中16种PAs在0.5~20 μg/L范围内线性关系良好，相关系数均大于0.99；检出限为0.06~0.11 μg/kg，定量限为0.23~0.35 μg/kg；在0.5、1.0、10 μg/kg加标水平下，平均回收率范围在75.38%~110.27%之间，相对标准偏差为2.61%~7.43%。采用此方法对20份市售铁皮石斛中的PAs进行测定，结果显示，12份样品中检出7-乙酰石松胺，含量为1.02~6.54 μg/kg。该方法操作简便且具有良好的灵敏度和准确性，适合铁皮石斛中PAs的快速确证和定量分析。

In order to determine the content of pyrrolizidine alkaloids (PAs) in Dendrobium officinale Kimura et Migo, an analytical method for the simultaneous determination of 16 kinds of unsaturated PAs in Dendrobium officinale Kimura et Migo by solid phase extraction combined with ultra performance liquid chromatography-tandem mass spectrometry was established in this study. Samples were extracted with 0.05 mol/L sulfuric acid methanol, purified and enriched by MCX solid-phase extraction cartridge. The mobile phases were methanol and 0.005 mol/L of ammonium formate - 0.1% of formic acid solution. The separation was performed on a Waters ACQUITY UPLC BEH C18 column with gradient elution. The electrospray positive ion and multi-reaction monitoring mode were used for acquisition, and matrix matching external standard method was used for quantification. The results showed that the linear range of 16 kinds of PAs in this method was 0.5~20 μg/L, and the correlation coefficients were all greater than 0.99. The limits of detection were 0.06~0.11 μg/kg, and the limits of quantification were 0.23~0.35 μg/kg. At the spiked levels of 0.5, 1.0 and 10 μg/kg, the average recoveries ranged from 75.38% to 110.27%, with the relative standard deviations ranging from 2.61% to 7.43%. This method was used to determine the PAs in 20 Dendrobium officinale Kimura et Migo samples commercially available. The results showed that 7-acetyllycopsamine was detected in 12 samples with the content ranging from 1.02~6.54 μg/kg. The method is simple, sensitive and accurate, and is suitable for rapid confirmation and quantitative analysis of PAS in Dendrobium officinale Kimura et Migo.

中国热带农业科学院基本科研业务费专项资金（1630122017020）；农业农村部农产品质量安全监管（风险评估）专项（GJFP20210502；GJFP20210503；GJFP2020003）；海南省自然科学基金项目（219QN290）