Unusual Fragmentations of Silylated Polyfluoroalkyl Compounds Induced by Electron Ionization

IF 2.7 2区 化学 Q2 BIOCHEMICAL RESEARCH METHODS
Yufang Zheng*, Edward P. Erisman, Weihua Ji, Stephen E. Stein and William E. Wallace, 
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引用次数: 0

Abstract

Per- and polyfluoroalkyl substances (PFAS) are environmentally persistent compounds that present analytical challenges due to their stability and low concentrations. In this study, electron ionization (EI) mass spectra of trimethylsilyl (TMS) derivatized fluorinated alcohols and carboxylic acids were examined to improve PFAS identification in the NIST Mass Spectral Reference Library. In contrast with the spectra of unsubstituted alcohol TMS compounds featuring losses of hydrocarbons, fluorinated alcohol TMS derivatives are characterized by the losses of fluorinated silyl groups. For example, a previously unreported [M–111]+ ion was consistently observed in compounds containing three methylene groups between the hydroxyl group and the first CF2 unit. Detailed quality assurance analysis using a suite of NIST software tools along with high-resolution TOF-MS confirmed the origin and elemental composition of these ions. MS2 experiments and full scan of TMS derivatives of fluorinated alcohols with varying numbers of methylene groups investigations suggest the formation of a five-membered ring intermediate as a key feature in this unique fragmentation pathway. These findings improve our understanding of PFAS fragmentation and support more accurate compound identification in analytical workflows.

电子电离诱导的硅基化多氟烷基化合物的异常碎片化。
全氟烷基和多氟烷基物质(PFAS)是环境持久性化合物,由于其稳定性和低浓度,给分析带来了挑战。为了提高NIST质谱参考库中PFAS的鉴定水平,本研究对三甲基硅基(TMS)衍生化氟化醇和羧酸的电子电离(EI)质谱进行了研究。与未取代醇TMS化合物的光谱特征为烃类损失相比,氟化醇TMS衍生物的特征是氟化硅基的损失。例如,在羟基和第一个CF2单元之间含有三个亚甲基的化合物中,一直观察到以前未报道的[M-111]+离子。使用一套NIST软件工具以及高分辨率TOF-MS进行详细的质量保证分析,确认了这些离子的来源和元素组成。MS2实验和具有不同亚甲基数量的氟化醇衍生物的TMS全扫描研究表明,五元环中间体的形成是这一独特裂解途径的关键特征。这些发现提高了我们对PFAS碎片的理解,并支持在分析工作流程中更准确地识别化合物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
5.50
自引率
9.40%
发文量
257
审稿时长
1 months
期刊介绍: The Journal of the American Society for Mass Spectrometry presents research papers covering all aspects of mass spectrometry, incorporating coverage of fields of scientific inquiry in which mass spectrometry can play a role. Comprehensive in scope, the journal publishes papers on both fundamentals and applications of mass spectrometry. Fundamental subjects include instrumentation principles, design, and demonstration, structures and chemical properties of gas-phase ions, studies of thermodynamic properties, ion spectroscopy, chemical kinetics, mechanisms of ionization, theories of ion fragmentation, cluster ions, and potential energy surfaces. In addition to full papers, the journal offers Communications, Application Notes, and Accounts and Perspectives
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