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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)
DOI PMC
Open Access Green möglich sobald Postprint bei der ZB eingereicht worden ist.
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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Publikationstyp Artikel: Journalartikel
Dokumenttyp Wissenschaftlicher Artikel
Korrespondenzautor
Schlagwörter 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
Zeitschrift Journal of the American Society for Mass Spectrometry
Quellenangaben Band: 34, Heft: 8, Seiten: 1632-1646 Artikelnummer: , Supplement: ,
Verlag Elsevier
Verlagsort 1155 16th St, Nw, Washington, Dc 20036 Usa
Nichtpatentliteratur Publikationen
Begutachtungsstatus Peer reviewed
Institut(e) Cooperation Group Comprehensive Molecular Analytics (CMA)
Förderungen German Research Foundation (DFG)
Horizon 2020 program