压力可调光离串联离子迁移谱法研究二元体系的质子转移反应。

IF 3.1 2区 化学 Q2 BIOCHEMICAL RESEARCH METHODS
Yiqian Xu, Qimu Yang, Yi Yu, Xuesong Zhang, Manman Pan, Dandan Jiang, Yuying Dong, Peng Gao, Lei Hua, Chuang Chen, Haiyang Li
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引用次数: 0

摘要

利用离子迁移率谱法(IMS)或质谱法研究和控制电离源内的离子-分子反应有助于开发先进的电离源和新的分析技术。在这项研究中,开发了一种压力可调的光电离串联离子迁移谱仪(PI-tandem-IMS),用于研究双分析物体系中高质子亲和(PA)离子被低质子亲和分子去质子化的异常质子转移反应所引起的电离抑制。研究了甲苯-丙酮和甲苯-乙醇体系中的质子转移反应机理。实验结果表明,ln(SX2H+·K0(T+)/ST+·K0(X2H+) + 1)与反应物浓度的平方(cX2)和压力的立方(p3)呈线性相关。基于此,在甲苯-丙酮和甲苯-乙醇体系中质子结合二聚体的生成被认为是一个三分子过程。计算了不同温度下甲苯-丙酮和甲苯-乙醇体系的反应速率系数k, Arrhenius图显示速率系数均与温度呈负相关,表明温度升高抑制了质子转移反应。在313.15 K时,甲苯-丙酮体系和甲苯-乙醇体系的K值分别为2.2 × 10-26 cm6/s和5.2 × 10-28 cm6/s,表明丙酮对甲苯电离的抑制作用高于乙醇。此外,降低压力或增加反应区电场强度对质子转移反应有抑制作用,说明pi -串联IMS是了解电离源中离子-分子反应的良好工具。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Pressure-Tunable Photoionization Tandem Ion Mobility Spectrometry for Investigating Proton Transfer Reactions of Binary Systems.

Investigating and manipulating the ion-molecule reactions within the ionization source of ion mobility spectrometry (IMS) or mass spectrometry can contribute to developing advanced ionization sources and novel analytical techniques. In this study, a pressure-tunable photoionization tandem ion mobility spectrometer (PI-tandem-IMS) was developed to investigate the ionization suppression caused by unusual proton transfer reactions in dual-analyte systems in which high proton affinity (PA) ions are deprotonated by low PA molecules. The proton transfer reaction mechanisms in the toluene-acetone and toluene-ethanol systems were studied. The experimental results showed the linear correlation between the ln(SX2H+·K0(T+)/ST+·K0(X2H+) + 1) and the square of the reactant concentration cX2, as well as the cubic power of the pressure p3. Based on this, the generation of the proton-bound dimers in the toluene-acetone and toluene-ethanol systems was assigned as a termolecular process. The reaction rate coefficients k of the toluene-acetone and toluene-ethanol systems were calculated at different temperatures, and the Arrhenius plot showed that rate coefficients were both negatively correlated with temperature, implying that elevated temperatures suppress the proton transfer reaction. At 313.15 K, the calculated k values for the toluene-acetone and the toluene-ethanol systems were 2.2 × 10-26 cm6/s and 5.2 × 10-28 cm6/s, respectively, suggesting a higher inhibitory effect of acetone on toluene ionization than that of ethanol. Besides, the suppressive effect of reducing the pressure or increasing the reaction region electric field strength on proton transfer reactions was shown, which demonstrated the PI-tandem IMS was a good tool for understanding ion-molecule reactions in the ionization source.

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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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