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通过质谱和电子顺磁共振光谱法检测和表征水自由基阳离子

Detection and Characterization of Water Radical Cations by Mass Spectrometry and Electron Paramagnetic Resonance Spectroscopy.

作者信息

Zhang Xiaoping, Duan Minmin, Chingin Konstantin, Balabin Roman, Liu Lijuan, Zhang Xinglei, Chen Huanwen

机构信息

Jiangxi Key Laboratory for Mass Spectrometry and Instrumentation, East China University of Technology, Nanchang 330013, P. R. China.

The Jiangxi Province Key Laboratory for Diagnosis, Treatment, and Rehabilitation of Cancer in Chinese Medicine, Jiangxi University of Chinese Medicine, Nanchang 330004, P. R. China.

出版信息

Anal Chem. 2025 Jul 29;97(29):16004-16010. doi: 10.1021/acs.analchem.5c03067. Epub 2025 Jun 24.

DOI:10.1021/acs.analchem.5c03067
PMID:40552371
Abstract

Water radical cations (HO) serve as key reactive intermediates in fundamental chemical processes, atmospheric chemistry, and energy-related applications due to their high reactivity and ability to initiate diverse chemical reactions. In this study, we investigated the generation of water dimer radical cations (/ 36, (HO)) and their reaction products with different substrates using multiple soft ionization techniques. Our comprehensive analytical platform incorporates corona discharge ionization (CDI), electrospray ionization (ESI), dielectric barrier discharge ionization (DBDI), and microwave plasma torch (MPT), coupled with complementary mass analyzers, including ion trap, Orbitrap, and quadrupole time-of-flight (Q-TOF) mass spectrometers. To confirm the formation of (HO), we employed a multitechnique verification strategy combining high-resolution mass spectrometry (MS), isotope labeling technique, tandem MS, and electron paramagnetic resonance (EPR) spectroscopy. The stabilization and reactivity of HO were also examined by using different substrates.

摘要

水自由基阳离子(HO)由于其高反应活性和引发多种化学反应的能力,在基础化学过程、大气化学以及与能源相关的应用中作为关键的反应中间体。在本研究中,我们使用多种软电离技术研究了水二聚体自由基阳离子(/ 36,(HO))的生成及其与不同底物的反应产物。我们的综合分析平台包括电晕放电电离(CDI)、电喷雾电离(ESI)、介质阻挡放电电离(DBDI)和微波等离子体炬(MPT),并与包括离子阱、轨道阱和四极杆飞行时间(Q-TOF)质谱仪在内的互补质量分析器联用。为了确认(HO)的形成,我们采用了一种多技术验证策略,结合高分辨率质谱(MS)、同位素标记技术、串联质谱和电子顺磁共振(EPR)光谱。还通过使用不同底物研究了HO的稳定性和反应活性。

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