巴戟天中环烯醚萜苷和蒽醌在电喷雾离子源负离子模式下的质谱裂解行为  

Fragmentation Behavior for Iridoid Glucosides and Anthraquinones in Morinda officinalis by ESI-Q-TOF MS/MS in Negative Ion Mode

作　　者：赵祥升 杨美华[2] 吴海峰[2] 舒晓燕[3] ZHAO Xiang-sheng1 , YAN G Mei-hua2, WU Hai-feng2, SHU Xiao-yan3(1. Hainan Branch Institute o f Medicinal Plant Development, Chinese Academy of Medical Sciences XPeking Union Medical College, Haikou 571100,China;2. Institute o f Medicinal Plant Development, Chinese A cademy of MedicalSciencss XPeking Union Medical College, B eijing 100193,China;3. Colege of L ife Scienee and Engineering,Southwest University o f Scienee and Gechnology, M ianyang 621010, Chin)

机构地区：[1]中国医学科学院药用植物研究所海南分所,海南海口571100 [2]中国医学科学院药用植物研究所,北京100193 [3]西南科技大学生命科学与工程学院,四川绵阳621010

出　　处：《质谱学报》2018年第3期342-350,共9页Journal of Chinese Mass Spectrometry Society

基　　金：国家自然科学基金(81603398;21402162);海南省重点研发计划项目(ZDYF2016174)资助

摘　　要：利用电喷雾-四极杆-飞行时间串联质谱(ESI-Q-TOF MS/MS)技术,在负离子模式下,探讨巴戟天中4种环烯醚萜苷和2种蒽醌成分的质谱裂解途径。通过[M-H]-获得化合物的相对分子质量信息,进一步对[M-H]-进行碰撞诱导解离,获得相应化合物的裂解途径。结果表明,环烯醚萜苷主要的裂解途径是首先脱去母环上的功能基团,如中性丢失H_2O、CO_2、CH_3COOH和糖单元等部分;其次是二氢吡喃环和糖环的断裂,m/z113、101为环烯醚萜苷母环断裂的特征碎片离子。蒽醌类化合物的裂解行为是连续失去CO,也可以失去CO_2。这些质谱裂解行为的研究有助于环烯醚萜苷和蒽醌类化合物的结构解析,也可为其他同类化合物的鉴定提供依据。Morinda officinalis, the dried root of Morinda officinalis How, is commonlyused as a traditional Chinese medicine for the treatment of impotence and osteoporosisin clinical theraphy, and this effect is supposed to be attributed to iridoid glyco-side and anthraquinone c o m p o u n d s . Recent years, liquid chromatography coupled withhigh resolution mass spectrometry wa s widely used for the identification of componentsfrom traditional Chinese medicine based on the fragmentation pathways of main c o m p o nents.H o w e v e r , reports on the fragmentation pathway of main ingredients in M-officinaliswere limited. Therefore, in this paper, the fragmentation pathways of 4 iridoidglycosides （monotropein, deacetyla sperulosidic acid, asperulosidic acid and asperuloside）and 2 anthraquinones （rubiadin-l-methyl ether and rubiadin） in M-offic in a lwere investigated using electrospray ionization quadrupole time-of-flight tandem massspectrometry （ESI-Q-TOFMS/MS） in negative ion m o d e . T h e deprotonated [ M -H ]-were observed by E S -M S , from which the molecular weights were deduced. The coliisioninduced dissociation （CID） data of [ M -H ]- ions provided fragmentation informationof the compounds of interest. T h e main and typical fragmentation pathway of iridoidglycosides were neutral losses of H2O, CO2 , CH3COOH and glucosidic units.Mean while , the cleavages of dihydropyranoid and sugar ring were also observed. common fragment ions of m/ z 113, lOl were the characteristic ions for the cleavages ofdihydropyranoid. T h e fragmentation process of anthraquinones w as continual loss of C Ofollowed by dissociation of CO2. T h e experimental results indicated that the fragmentationbehavior of iridoid glycosides and anthraquinones was reasonable and could providethe basis for their structures elucidation and identification.

关 键 词：巴戟天 电喷雾-四极杆-飞行时间串联质谱(ESI-Q-TOFMS/MS)环烯醚萜苷 蒽醌 裂解行为 

分 类 号：O657.63[理学—分析化学]