Triple three-dimensional MS/MS spectrum facilitates quantitative ginsenosides-targeted sub-metabolome characterization in notoginseng  

作　　者：Ke Zhang Jinru Jia Ting Li Wenjing Liu Pengfei Tu Jian-Bo Wan Jun Li Yuelin Song 

机构地区：[1]Modern Research Center for Traditional Chinese Medicine,Beijing Research Institute of Chinese Medicine,Beijing University of Chinese Medicine,Beijing 100029,China [2]SCIEX China,Beijing 100015,China [3]School of Pharmacy,Henan University of Chinese Medicine,Zhengzhou 450046,China [4]State Key Laboratory of Quality Research in Chinese Medicine,Institute of Chinese Medical Sciences,University of Macao,Taip1,Macao 999078,China

出　　处：《Acta Pharmaceutica Sinica B》2024年第9期4045-4058,共14页药学学报（英文版）

基　　金：the National Natural Science Foundation of China(No.81973444);National Administration of Traditional Chinese Medicine High level Key Discipline Construction Project of Traditional Chinese MedicinedChemistry of Chinese Materia Medica.

摘　　要：Although serving as the workhorse,MS/MS cannot fully satisfy the analytical requirements of quantitative sub-metabolome characterization.Because more information intrinsically correlates to more structural and concentration clues,here,efforts were devoted to comprehensively tracing and deciphering MS/MS behaviors through constructing triple three-dimensional(3×3D)-MS/MS spectrum.Ginsenosides-targeted metabolomics of notoginseng,one of the most famous edible medicinal plants,was employed as a proof-of-concept.Serial authentic ginsenosides were deployed to build the correlations between 3×3D-MS/MS spectra and structure/concentration features.Through assaying ginsenosides with progressive concentrations using QTOF-MS to configure 1st 3D spectrum,the generations of MS1 spectral signals,particularly multi-charged multimer anions,e.g.,[2Me2H]^(2-) and[2M+2HCOO]^(2-) ions,relied on both concentration and the amount of sugar chains.By programming progressive collision energies to the front collision cell of Qtrap-MS device to gain 2^(nd) 3D spectrum,optimal collision energy(OCE)corresponding to the glycosidic bond fission was primarily correlated with the masses of precursor and fragment ions and partially governed by the glycosidation site.The quantitative relationships between OCEs and masses of precursor and fragment ions were utilized to build large-scale quantitative program for ginsenosides.After applying progressive exciting energies to the back collision chamber to build 3^(rd) 3D spectrum,the fragment ion and the decomposition product anion exhibited identical dissociation trajectories when they shared the same molecular geometry.After ginsenosides-focused quantitative metabolomics,significant differences occurred for sub-metabolome amongst different parts of notoginseng.The differential ginsenosides were confirmatively identified by applying the correlations between 3×3D-MS/MS spectra and structures.Together,3×3D-MS/MS spectrum covers all MS/MS behaviors and dramatically facilitates sub-metabolome character

关 键 词：Quantitative submetabolome characterization GINSENOSIDES Structural identification Notoginseng Full exciting energy ramp-MS3 spectrum 

分 类 号：R28[医药卫生—中药学]