目的：建立了超高效液相色谱-串联质谱（UPLC-MS/MS）测定多种棘豆属植物中苦马豆素含量的分析方法。方法：样品经1% 甲酸甲醇溶液超声提取,活性炭固相萃取小柱净化,用甲醇-1% 甲酸水溶液梯度洗脱;采用CAPCELL PAK C18色谱柱（100 mm×2.1 mm,2 μm）分离,流动相为1% 甲酸水溶液（A）-甲醇（B）,梯度洗脱（0~0.5 min,90%A;0.5~3 min,90%A → 5%A）,流速0.3 mL·min-1,柱温30 ℃ ;质谱分析采用电喷雾电离,在多反应监测（MRM）模式下,正离子扫描。结果：苦马豆素质量浓度在0.25~25 μg·L-1 范围内线性良好（r=0.999 8）;加样回收率为114.5%,RSD（n=6）≤ 5.0%,定量下限为0.003 μg·g-1。采用该方法对32批不同产地、不同品种的棘豆样品中的苦马豆素进行测定,含量在0.004~107.301 μg·g-1 范围内。同时进一步考察了镰形棘豆、轮叶棘豆和黄花棘豆根、茎、叶中苦马豆素的含量,苦马豆素的含量由高到低顺序均为叶、茎、根。结论：该方法快捷、灵敏、准确、可靠,可用于棘豆中苦马豆素的定量、定性。
Objective: To establish a method for quantitative determination of swainsonine in Oxytropis of different origins and varieties using solid-phase extration（SPE） followed by ultra high performance liquid chromatography-tandem mass spectrometry（UPLC-MS/MS）. Methods: The samples were ultrasonic extracted by methanol containing 1%（v/v） formic acid,purified by activated carbon column,gradient elution with methanoL-1% formic acid aqueous solution,separated on CAPCELL PAK C18（100 mm×2.1 mm,2 μm） chromatographic column, quantified in a UPLC-MS/MS system in multiple reaction monitoring mode,and identified on the basis of product ion abundance ratios as well as characteristic fragments in enhanced product ion spectra UPLC-MS/MS system in multiple reaction monitoring mode. Results: There was a good linearity in the concentration range of 0.25-25 μg·L-1（r=0.999 8）. The average recovery of swainsonine was 114.5% with RSD less than or equal to 5.0%. The minimum quantitative limit was 0.003 μg·g-1. The proposed method has been applied to 32 batches of Oxytropis of different origins and varieties,and the swainsonine contents were 0.004-107.301 μg·g-1. Meanwhile,the contents of swainsonine in roots,stems and leaves of Oxytropis falcate Bunge,Oxytropis chiliophylla Royle and Oxytropis ochrocephala Bunge were further determined,respectively. The contents of swainsonine in leaves were higher than that in stems,and the contents of swainsonine in stems were higher than that in roots. Conclusion: The method is simple,rapid,sensitive,accurate and can be used for the analysis of swainsonine in Oxytropis.
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