Energy-resolved Mass Spectrometry-Strengthened Structural Identification and Empirical Justification of Glucuronidation Metabolites for Chrysophanol and Physcion
10.19756/j.issn.0253-3820.241455
- VernacularTitle:能量分辨质谱法准确鉴定大黄酚和大黄素甲醚葡萄糖醛酸化代谢产物结构及实验验证
- Author:
Xiao-Yun LI
1
;
Hang-Yun HE
;
Mao-Dong WANG
;
Yu-Xuan ZHOU
;
Hui JIN
;
Qian WANG
;
Yue-Lin SONG
Author Information
1. 北京中医药大学北京中医药研究院,北京 102488;北京中医药大学中药学院,北京 102488
- Keywords:
Chrysophanol;
Physcion;
Glucuronides;
Energy-resolved mass spectrometry;
Bond dissociation energy
- From:
Chinese Journal of Analytical Chemistry
2025;53(4):652-659,中插29-中插30
- CountryChina
- Language:Chinese
-
Abstract:
Chrysophanol(Chr)and physcion(Phy)are primary active ingredients of a well-known traditional Chinese medicine namely rhubarb(Chinese name:Dahuang),and their glucuronides have been revealed as the dominant forms presenting in rats after oral administration.Either Chr or Phy has two glycosylation sites,resulting in a pair of positional isomers for glucuronides of either compound(CG1&CG2 and PG1&PG2).To confirmatively identify these glucuronides,energy-resolved mass spectrometry(ER-MS)was used to pursue the fragmentation trajectories of the targeted fragment ions,and the resultant breakdown graphs that were described by the optimal collision energy(OCE)were expected to exhibit the differences of glycosidic bond cleavage between the isomers.Quantum chemical calculation was thereafter conducted to produce the bond dissociation energy(BDE)of the glycosidic bonds.The isomers were unambiguously identified through applying the positive correlation rule between OCE and BDE.Fortunately,the glucuronides of Chr and Phy in vivo were observed through liver microsomes incubationin vitro.ER-MS was utilized to collect the Gaussian-shaped breakdown graphs in response to the neutral loss of 176 Da,and the absolute values of OCE were compared between positional isomers.The results revealed that CG1(-32.31 eV)>CG2(-31.61 eV),and nonetheless,PG1(-30.00 eV)Chr-8-GluA(-48.787 kJ/mol),and nonetheless,Phy-1-GluA(-48.672 kJ/mol)
