PuSH - Publication Server of Helmholtz Zentrum München: Detailed comparison of Xenon APPI (9.6/8.4 eV), Krypton APPI (10.6/10.0 eV), APCI, and APLI (266 nm) for gas chromatography high resolution mass spectrometry of standards and complex mixtures.

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Neumann, A.* ; Tiemann, O.* ; Hansen, H.J.* ; Rüger, C.* ; Zimmermann, R.

Detailed comparison of Xenon APPI (9.6/8.4 eV), Krypton APPI (10.6/10.0 eV), APCI, and APLI (266 nm) for gas chromatography high resolution mass spectrometry of standards and complex mixtures.

J. Am. Soc. Mass Spectrom. 34, 1632-1646 (2023)

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Open Access Green as soon as Postprint is submitted to ZB.

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Photoionization schemes for mass spectrometry, either by laser or discharge lamps, have been widely examined and deployed. In this work, the ionization characteristics of a xenon discharge lamp (Xe-APPI, 9.6/8.4 eV) have been studied and compared to established ionization schemes, such as atmospheric pressure chemical ionization, atmospheric pressure photoionization with a krypton discharge lamp (Kr-APPI, 10.6/10 eV) and atmospheric pressure laser ionization (266 nm). Addressing the gas-phase ionization behavior has been realized by gas chromatography coupled to high-resolution mass spectrometry without the usage of a dopant. For standard substances, it has been found that Xe-APPI is able to ionize a broad range of polycyclic aromatic hydrocarbons as well as their heteroatom-containing and alkylated derivatives. However, thiol and ester compounds could not be detected. Moreover, Xe-APPI revealed a high tendency to generate oxygenated artifacts, most likely due to a VUV absorption band of oxygen at 148 nm. Beneficially, almost no chemical background, commonly caused by APCI or Kr-APPI due to column blood, plasticizers or impurities, is observed. This advantage is noteworthy for evolved gas analysis without preseparation or for chromatographic coelution. For the complex mixtures, Xe-APPI revealed the predominant generation of radical cations via direct photoionization with a high selectivity toward aromatic core structures with low alkylation. Interestingly, both Xe-APPI and Kr-APPI could sensitively detect sterane cycloalkanes, validated by gas chromatographic retention. The narrowly ionized chemical space could let Xe-APPI find niche applications, e.g., for strongly contaminated samples to reduce the background.

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Publication type Article: Journal article

Document type Scientific Article

Corresponding Author

Keywords Atmospheric Pressure Ionization ; Gas Chromatography ; Mass Spectrometry ; Photoionization ; Polycyclic Aromatic Hydrocarbons; Atmospheric-pressure Photoionization; Polycyclic Aromatic-hydrocarbons; Chemical-ionization; Electrospray-ionization; Laser Ionization; Thermal-degradation; Selective Detection; Ion-source; Petroleum; Ms

e-ISSN 1044-0305

Journal Journal of the American Society for Mass Spectrometry

Quellenangaben Volume: 34, Issue: 8, Pages: 1632-1646

Publisher Elsevier

Publishing Place 1155 16th St, Nw, Washington, Dc 20036 Usa

Non-patent literature Publications

Reviewing status Peer reviewed

Institute(s) Cooperation Group Comprehensive Molecular Analytics (CMA)

Grants German Research Foundation (DFG)
Horizon 2020 program