紫草素及去氧紫草素的ESI离子阱质谱裂解分析  

Fragmentation analysis of shikonin and deoxyshikonin by electron spray ionization mass spectrometry

作　　者：周滔[1] 夏彬彬[1] 秦春雨[1] 白露[1] 徐平湘[1] 薛明[1] 

机构地区：[1]首都医科大学基础医学院药理学系,生物医学检测技术与仪器北京实验室,北京100069

出　　处：《分析试验室》2015年第1期12-17,共6页Chinese Journal of Analysis Laboratory

基　　金：国家自然科学基金项目(81173121);北京市自然科学基金;北京市教委重点项目(KM201110025024)资助

摘　　要：应用电喷雾离子阱多级质谱技术对紫草素及其活性衍生物去氧紫草素的结构和质谱裂解规律进行比较研究,并在负离子模式下解析了紫草素的主要特征碎片离子及其裂解规律。紫草素负离子模式下的主要碎片为m/z 287,269,259,218,190及173;其中,碎片m/z 218是其特征峰,碎片m/z 269和m/z 259均可进一步裂解为m/z 241,碎片m/z 190为m/z 259和m/z 218的共同产物离子;此外,碎片m/z 190和m/z 173均可进一步裂解为m/z 162。去氧紫草素负离子模式下主要裂解为碎片m/z 271、253、228和203;其中,碎片m/z253是其特征峰。紫草素和去氧紫草素均能发生过渡态氢重排β-裂解和连续的CO中性丢失。Electrospray ionization multistage tandem mass spectrometry （ESI-MS^n） was used to analyze the chemical structure and main fragmentation pathways of shikonin and its active analogue deoxyshikonin. The maincharacteristic fragment ions and demonstrated in negative mode. fragmentation pathways of shikonin and deoxyshikonin were elucidated and The main fragment ions m/z 287, 269, 259, 218, 190 and 173 were obtained from the ESI-MS/MS spectrum of shikonin, and the characteristic fragment ion was m/z 218. The fragment ions m/z 269 and m/z 259 could further form the product ion m/z 241, the fragment ion m/z 190 was the common product ion of m/z 259 and m/z 218, and the fragment ions m/z 218 and m/z 190 formed the ion m/z 175. The fragment m/z 271, 253, 228 and 203 were discovered in the ESI-MS/MS spectrum of deoxyshikonin, and the ion peak m/z 253 was the characteristic fragment. The hydrogen rearrangement β-cleavage pattern in transition state and the continuous neutral loss of CO existed in both compounds. These results provided significant information for the structural modification, pharmacological activities and in vivo drug metabolic research of shikonin and deoxyshikonin.

关 键 词：紫草素 去氧紫草素 电喷雾离子阱多级质谱(ESI-MS^n) 裂解规律 

分 类 号：O657.63[理学—分析化学]