超高效液相色谱-四极杆静电场轨道阱高分辨质谱法测定米炒人参炮制前后皂苷成分及其裂解规律的研究  

Determination of saponin components and their cleavage laws in rice-fried ginseng before and after concoction by ultra performance liquid chromatography-quadrupole-orbitrap-mass spectrometry

作　　者：王艺霏 陈晶 马启风 张淼 罗健顺 高红梅[1] WANG Yi-Fei;CHEN Jing;MA Qi-Feng;ZHANG Miao;LUO Jian-Shun;GAO Hong-Mei(School of Pharmacy,Changchun University of Chinese Medicine,Changchun 130117,China)

机构地区：[1]长春中医药大学药学院,长春130117

出　　处：《食品安全质量检测学报》2024年第8期235-245,共11页Journal of Food Safety and Quality

基　　金：2023年全国中药特色技术传承人才培训项目(T20234832005)。

摘　　要：目的建立超高效液相色谱-四极杆静电场轨道阱高分辨质谱法(ultra performance liquid chromatography-quadrupole-orbitrap-mass spectrometry,UPLC-Q-Orbitrap-MS)检测米炒人参炮制前后皂苷成分的方法,并研究其裂解规律。方法采用Supelco C18色谱柱,以乙腈-0.1%甲酸水溶液梯度洗脱,应用电喷雾离子源,负离子全扫描模式采集一、二级质谱数据,扫描范围为150~2000 m/z。结合质谱数据库及相关文献信息,运用X Calibur2.2软件对米炒人参中皂苷类成分进行鉴定。以6种人参皂苷Re、Rg_(1)、Rb_(1)、Rc、Rb_(2)、Rb_(3)进行模拟炮制,确定皂苷类成分裂解产物,明确皂苷成分的裂解规律。结果从人参中检测出14个成分,鉴定出13种人参皂苷成分;米炒人参中检测出23个成分,鉴定出20种人参皂苷成分。通过比较人参米炒前后的皂苷类成分,发现米炒人参中存在人参中未检测到的8种稀有人参皂苷20(S)-Rg_(2)、20(S)-Rh_(1)、20(R)-Rh_(1)、F_(2)、20(S)-Rg_(3)、20(R)-Rg_(3)、20(S)-Rs_(3)、20(R)-Rs_(3)。模拟炮制结果表明,人参皂苷Re脱去C-20糖基,转化为稀有人参皂苷20(S)-Rg_(2);人参皂苷Rg_(1)脱去C-20位糖基,转化为稀有人参皂苷20(S)-Rh_(1)、20(R)-Rh_(1);人参皂苷Rb_(1)、Rb_(2)、Rb_(3)、Rc脱去C-20或C-3位糖基,转化为稀有人参皂苷20(S)-Rg_(3)、20(R)-Rg_(3)或F_(2)。结论人参经米炒后,稀有人参皂苷成分增加,产生的稀有皂苷为原型皂苷发生苷键裂解而获得,模拟炮制可作为其裂解规律研究的有效方法。Objective To establish a method for determination of saponin components in rice-fried ginseng before and after concoction by ultra performance liquid chromatography-quadrupole-orbitrap-mass spectrometry,and study their cleavage laws.Methods A Supelco C18 column was used with gradient elution of acetonitrile-0.1%formic acid aqueous solution,and an electrospray ionization was applied to collect the primary and secondary mass spectrometry data in negative-ion full-scan mode,with a scanning range of 150-2000 m/z.Combined with the information from the mass spectrometry database and the related literatures,the identification of the saponin constituents in rice fried ginseng was carried out by using the X Calibur 2.2 software was used to identify the saponin components in ginseng fried in rice.Six ginsenosides Re,Rg_(1),Rb_(1),Rc,Rb_(2) and Rb_(3) were used to simulate processing,to determine the cleavage products of the saponin-like components and to clarify the cleavage laws of the saponin components.Results Fourteen components were detected and 13 kinds of ginsenoside components were identified from ginseng;23 kinds of components were detected and 20 kinds of ginsenoside components were identified from rice-fried ginseng.By comparing the ginsenoside components of ginseng before and after rice-frying,it was found that 8 kinds of rare ginsenosides 20(S)-Rg_(2),20(S)-Rh_(1),20(R)-Rh_(1),F_(2),20(S)-Rg_(3),20(R)-Rg_(3),20(S)-Rs_(3) and 20(R)-Rs_(3),which were not detected in ginseng,were found in the rice-fried ginseng.The results of simulated processing indicated that the ginsenosides Re was converted to the rare ginsenoside 20(S)-Rg_(2) by removing the C-20 sugar group;the ginsenoside Rg_(1) was converted to the rare ginsenosides 20(S)-Rh_(1),20(R)-Rh_(1) by removing the sugar group at the C-20 position;and the ginsenosides Rb_(1),Rb_(2),Rb_(3),Rc were converted to the rare ginsenosides 20(S)-Rg_(3),20(R)-Rg_(3) or F_(2) by removing the sugar group at the C-20 or C-3 position.Conclusion Rare ginsenoside components incr

关 键 词：米炒人参 超高效液相色谱-四极杆静电场轨道阱高分辨质谱法 人参皂苷 模拟炮制 裂解规律 

分 类 号：O657.63[理学—分析化学] R284.1[理学—化学]