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Chemical Ionization Mass Spectrometry: History
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Contributor: Helena Kang

Gas-phase ion–molecule reactions between analyte molecules and a reagent-gas plasma constitute chemical ionization (CI) mass spectrometry. In the classical form, a reagent gas such as methane, isobutane, or ammonia is ionized by electrons; the resulting reagent ions transfer a proton, hydride, or charge to the analyte, producing even-electron ions with less fragmentation than electron ionization [1]. Atmospheric-pressure chemical ionization (APCI) and desorption APCI extend the same ion–molecule chemistry to an atmospheric corona or related discharge, so that the ionization step remains chemical rather than purely photonic or electrospray-based [2]. Negative-ion CI uses electron-capture or proton-abstraction reagent ions and is a polarity variant of the same concept [3]. Conceptual boundaries exclude electron ionization, electrospray ionization, and photoionization, each of which generates ions by a different primary process. Essential features are a reagent-ion population, a pressure regime that permits ion–molecule collisions, and a mass analyzer that records the resulting analyte ions, often after chromatographic introduction [4].

  • chemical ionization
  • ion–molecule reaction
  • APCI
  • reagent gas

Metabolomics and Mass Spectrometry Studies • Molecular Biology • Biochemistry, Genetics and Molecular Biology • Life Sciences

References

  1. Jonathan W. Martin; Derek C. G. Muir; Cheryl A. Moody; David A. Ellis; Wai Chi Kwan; Keith R. Solomon; Scott A. Mabury; Collection of Airborne Fluorinated Organics and Analysis by Gas Chromatography/Chemical Ionization Mass Spectrometry. Anal. Chem. 2002, 74, 584-590, 10.1021/ac015630d.
  2. Shuiping Yang; Jianhua Ding; Jian Zheng; Bin Hu; Jianqiang Li; Huanwen Chen; Zhiquan Zhou; Xiaolin Qiao; Detection of Melamine in Milk Products by Surface Desorption Atmospheric Pressure Chemical Ionization Mass Spectrometry. Anal. Chem. 2009, 81, 2426-2436, 10.1021/ac900063u.
  3. Jian-Liang Zhao; Guang-Guo Ying; Li Wang; Ji-Feng Yang; Xiao-Bing Yang; Li-Hua Yang; Xu Li; Determination of phenolic endocrine disrupting chemicals and acidic pharmaceuticals in surface water of the Pearl Rivers in South China by gas chromatography–negative chemical ionization–mass spectrometry. Sci. Total. Environ. 2009, 407, 962-974, 10.1016/j.scitotenv.2008.09.048.
  4. Michal Holčapek; Pavel Jandera; Petr Zderadička; Lucie Hrubá; Characterization of triacylglycerol and diacylglycerol composition of plant oils using high-performance liquid chromatography–atmospheric pressure chemical ionization mass spectrometry. J. Chromatogr. A 2003, 1010, 195-215, 10.1016/s0021-9673(03)01030-6.
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