UPLC-Q-TOF-MS/MS结合对照药材法快速筛查硫磺熏蒸商品人参

该研究建立了UPLC-Q-TOF-MS/MS结合自制对照药材的硫磺熏蒸人参快速筛查方法。采用道地药材通过常规程序制备硫磺熏蒸人参对照药材,应用UPLC-Q-TOF-MS/MS发现和鉴定硫磺熏蒸人参对照药材8个特征成分,选择质谱响应较高的25-hydroxyl-Re sulfate作为标志物,研究其质谱裂解,选取丰度较高的特征离子m/z 879.44作为提取离子,再通过优化质谱条件提高特征离子m/z 879.44质谱响应值,提高筛查方法灵敏度。应用所建立的方法筛查了来源于不同地区的21份商品生晒参,有9份样品化学轮廓与硫磺熏蒸人参对照药材相似,且都检测到25-hydroxyl-Re sulfate的特征离子m/z 879.44,表明近43%商品生晒参是硫磺熏蒸品。同时采用2010年版《中国药典》附录方法测定21批药材中二氧化硫残留,结果一致。与二氧化硫残留检测方法相比,该方法选择性更强、更快速,可为人参质量控制提供有效辅助手段。

Development of UPLC-Q-TOF-MS/MS combined with reference herb approach to rapidly screen commercial sulfur-fumigated ginseng

An ultra-performance liquid chromatography-quadrupole/time of flight mass spectrometry(UPLC-Q-TOF-MS/MS) combined with reference herb method was developed to rapidly screen commercial sulfur-fumigated ginseng. Sulfur-fumigated ginseng reference herb was prepared using genuine ginseng by conventional procedure. Then the reference sulfur-fumigated ginseng sample was analyzed by UPLC-Q-TOF-MS/MS to identify characteristic marker components. 25-hydroxyl-Re sulfate with higher abundance was selected as marker compound from 8 characteristic components identified in sulfur-fumigated ginseng reference herb. The fragmentation of 25-hydroxyl-Re sulfate was extensively investigated, fragment ion m/z 879.44 with higher intensity was chosen as the characteristic ion of sulfur-fumigated ginseng. The response of ion m/z 879.44 was improved by optimizing the MS conditions so that this ion could be used as the characteristic marker ion for screening purpose in ion extracting screening mode. The established approach was successfully applied to inspect 21 commercial ginseng samples collected from different cities in China. It was found that the chemical profiles of 9 samples were similar to that of sulfur-fumigated ginseng reference herb, and the characteristic ion m/z 879.44 of 25-hydroxyl-Re sulfate was also detected in these samples, suggesting that there were nearly 43% ginseng samples analyzed being sulfur-fumigated. This finding agreed well with the results of sulfur dioxide residues of these 21 commercial ginseng samples determined with the method documented in Chinese Pharmacopeia. Compared with the method documented in Chinese Pharmacopeia, the proposed approach is more rapid and specific for screening sulfur-fumigated ginseng. SFDA of China should strengthen the enforcement to prohibit ginseng being sulfur-fumigated, so that ginseng and it preparations could be effectively and safely benefit to the health of human beings.