能量分辨质谱区分与检测人参皂苷同分异构体20(S)-Rf和Rg_(1)  

Differentiation and Investigation of Ginsenoside Isomers 20(S)-Rf and Rg_(1) by Energy-resolved Mass Spectrometry

作　　者：赵幻希 李卓[2] 赵孟雅 田璐 肖禹圣 王震寰 越皓 修洋 ZHAO Huanxi;LI Zhuo;ZHAO Mengya;TIAN Lu;XIAO Yusheng;WANG Zhenhuan;YUE Hao;XIU Yang(Jilin Ginseng Academy,Changchun University of Chinese Medicine,Changchun 130117,China;Affiliated Hospital of Changchun University of Chinese Medicine,Changchun 130021,China)

机构地区：[1]长春中医药大学吉林省人参科学研究院,长春130117 [2]长春中医药大学附属医院,长春130021

出　　处：《高等学校化学学报》2023年第4期45-51,共7页Chemical Journal of Chinese Universities

基　　金：吉林省科技发展计划项目(批准号:YDZJ202201ZYTS261,20210204098YY,20200201093JC)资助。

摘　　要：将连续变化的碰撞能量与串联质谱相结合,建立了能量分辨质谱(Energy-resolved mass spectrometry,ERMS)分析方法用以区分和检测人参皂苷同分异构体20(S)-Rf和Rg_(1).ERMS将子离子与母离子强度的比值定义为强度分数(Intensity fraction,IF),两个子离子强度的比值定义为强度比(Intensity ratio,IR),并通过IF和IR分别对连续变化的碰撞能量作图建立特征碎片离子的IF和IR曲线.虽然20(S)-Rf和Rg_(1)的串联质谱图无明显差异,但是多元统计分析结果显示其特征碎片离子[M-Glc-H]-,[M-2Glc-H]-和[M-2Glc-C_(6)H_(12)-H]-的IF和IR曲线差异显著,有明显的区分边界,可以直接区分20(S)-Rf和Rg_(1).进一步利用ERMS实时分析了原人参三醇型皂苷生物转化产物中20(S)-Rf和Rg_(1)的相对摩尔含量.结果表明,ERMS不需液相色谱分离即可实现20(S)-Rf和Rg_(1)的快速区分和相对含量检测.An energy-resolved mass spectrometry(ERMS)method was developed for the differentiation and investi⁃gation of ginsenoside isomers 20(S)-Rf and Rg_(1) by combining continuously varied collision energy with tandem mass spectrometry.The ratio of product ion intensity to its precursor ion intensity was defined as intensity fraction(IF),whereas the ratio of two product ion intensities was defined as intensity ratio(IR).IF and IR were plotted against the continuously varied collision energy to establish the IF and IR curves,respectively.Although the tandem mass spectra of ginsenoside isomers 20(S)-Rf and Rg_(1) were almost identical,multivariate statistical analysis showed significant differences in the IF and IR profiles of their characteristic fragment ions[M−Glc−H]‒,[M−2Glc−H]‒,and[M−2Glc−C_(6)H_(12)−H]‒with distinct differentiation boundaries that could directly distinguish 20(S)-Rf and Rg_(1).The relative molar contents of 20(S)-Rf and Rg_(1) in the biotransformation products of protopanaxtriol-type ginsenosides were further analyzed in real time using ERMS.All the results showed that ERMS enables the rapid differentiation and relative content monitoring of 20(S)-Rf and Rg_(1) without the separation by liquid chromatography.

关 键 词：能量分辨质谱 同分异构体 人参皂苷20(S)-Rf 人参皂苷RG1 相对定量分析 

分 类 号：O657[理学—分析化学]