高分辨质谱法阐明甲基化华法林和选定羟基化物种的电子电离诱导碎片途径

IF 1.6 3区 化学 Q3 PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
W.J. von Törne , L. Steinhäuser , U.-A. Klyk-Seitz , C. Piechotta
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引用次数: 0

摘要

香豆素和 4-羟基香豆素的植物次生代谢物家族具有广泛的药理作用,从抗菌到抗癌。这类物质的一个重要成员是人工合成但天然激发的抗凝血药物和杀鼠剂华法林(coumadin)。大量文献集中于通过液相色谱法(LC)、质谱法(MS)和串联质谱法(MS/MS)检测技术鉴定华法林及其主要细胞色素 P450 介导的 I 期代谢物。作为液相色谱-质谱/串联质谱检测方法的一种替代方法,本研究首次提供了线内衍生华法林和选定羟基化物种的电子电离(EI)诱导高分辨率四极杆飞行时间质谱(HR-qToF-MS)数据。此外,还总结了所分析甲基醚的特征碎片和碎片路径。分析标准、特定氚标记和 13C 标记化合物所获得的数据证明,酰基或丙酮侧链的感应裂解、甲基迁移和 H 迁移以及随之而来的感应裂解是主要的碎裂途径。根据 HR 光谱数据,评估了所分析的化合物和片段组之间的共性和差异,以便将来用于相关化合物的结构阐释和光谱预测。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

High-resolution mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species

High-resolution mass spectrometric elucidation of electron ionization induced fragmentation pathways of methylated warfarin and selected hydroxylated species

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.

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来源期刊
CiteScore
3.60
自引率
5.60%
发文量
145
审稿时长
71 days
期刊介绍: The journal invites papers that advance the field of mass spectrometry by exploring fundamental aspects of ion processes using both the experimental and theoretical approaches, developing new instrumentation and experimental strategies for chemical analysis using mass spectrometry, developing new computational strategies for data interpretation and integration, reporting new applications of mass spectrometry and hyphenated techniques in biology, chemistry, geology, and physics. Papers, in which standard mass spectrometry techniques are used for analysis will not be considered. IJMS publishes full-length articles, short communications, reviews, and feature articles including young scientist features.
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