High-resolution mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY(2024)
摘要
The plant secondary metabolite families of coumarin and 4-hydroxy coumarin have a broad pharmacological spectrum ranging from antibacterial to anticancer properties. One prominent member of this substance class is the synthetic but naturally inspired anticoagulant drug and rodenticide warfarin (coumadin). A vast number of publications focus on the identification of warfarin and its major cytochrome P450-mediated phase I metabolites by liquid chromatography (LC) with mass spectrometry (MS) and tandem mass spectrometric (MS/MS) detection techniques. For the first time, electron ionization (EI) induced high-resolution quadrupole time-of-flight mass spectrometric (HR-qToF-MS) data of in-liner derivatized warfarin and selected hydroxylated species is provided in this study as an alternative to LC-MS/MS approaches. Furthermore, the characteristic fragments and fragmentation pathways of the analyzed methyl ethers are concluded. The obtained data of analytical standards, specific deuterated and 13C-labeled compounds prove inductive cleavage of the acyl or acetonyl side chain, methyl migration, and H-migration, along with consequential inductive cleavage as predominant fragmentation routes. Based on the HR-spectral data, commonalities and differences between the analyzed compounds and fragment groups were evaluated with future applicability in structure elucidation and spectra prediction of related compounds.
更多查看译文
关键词
High -resolution mass spectrometry,Warfarin,Hydroxy warfarin,Methyl migration,Electron impact ionization,Fragmentation pathway
AI 理解论文
溯源树
样例
生成溯源树,研究论文发展脉络
Chat Paper
正在生成论文摘要