芳香胺中质子化位点的捕获离子迁移率和红外离子光谱联合研究

IF 2.7 2区 化学 Q2 BIOCHEMICAL RESEARCH METHODS
Laura Finazzi, Lara van Tetering, Jelle L. Schuurman, Jonathan Martens, Giel Berden and Jos Oomens*, 
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引用次数: 0

摘要

芳香胺在气相中的质子化位点一直存在很大的争议,因为它涉及到胺氮较高的电负性与融合芳香环较好的电荷离域能力之间的微妙竞争。先前的研究已经明确地表明,特别是通过离子迁移率测量,根据离子源中的实验条件,包括电压设置和喷雾源中使用的溶剂类型,很容易观察到高能量的互变异构体。在这里,我们使用离子迁移率和离子光谱相结合的方法,重点研究离子迁移率分离后的互变异构体结构,特别是质子化的1-氨基萘和1-氨基蒽。我们采用了一个大气压化学电离(APCI)源,带有直接插入探针以避免任何溶剂影响,安装在FTICR质谱仪上,该质谱仪具有捕获离子迁移率(TIMS)单元和对离子的光学访问,使用红外实验自由电子激光器(FELIX)进行红外(IR)多光子解离光谱。TIMS分析确实揭示了N-和c -质子化物质的存在,但在ICR细胞中记录的红外光谱也表明,在TIMS分离后质子的动员和打乱发生了。我们计算研究了重异构化的能量学,并通过实验探索了TIMS分离后的离子活化。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Combined Trapped Ion Mobility and Infrared Ion Spectroscopy Study of Protonation Sites in Aromatic Amines

The protonation site of aromatic amines in the gas phase has been under substantial debate, as it involves a subtle competition between the higher electronegativity of the amine nitrogen and the better charge delocalization ability of the fused aromatic rings. Previous studies have unambiguously shown, especially by ion mobility measurements, that higher-energy tautomers are easily observed depending on the experimental conditions in the ion source, including voltage settings and the type of solvent used in spray sources. Here, we use a combination of ion mobility and ion spectroscopy and focus on the tautomeric structure after ion mobility separation, in particular for protonated 1-aminonaphthalene and 1-aminoanthracene. We employ an atmospheric pressure chemical ionization (APCI) source, with a direct insertion probe to avoid any solvent influence, mounted on an FTICR mass spectrometer with a trapped ion mobility (TIMS) unit and optical access to the ions to perform infrared (IR) multiple-photon dissociation spectroscopy using the Free-Electron Laser for Infrared eXperiments (FELIX). TIMS analysis indeed reveals the presence of both N- and C-protonated species, but the IR spectra recorded in the ICR cell also suggest that mobilization and scrambling of the proton occur after TIMS separation. We computationally investigate the energetics of tautomerization and experimentally explore ion activation after TIMS separation.

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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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