PuSH - Publication Server of Helmholtz Zentrum München: Vacuum laser photoionization inside the C-trap of an orbitrap mass spectrometer: Resonance-enhanced multiphoton ionization high-resolution mass spectrometry.

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Kösling, P.* ; Rüger, C.P.* ; Schade, J.* ; Fort, K.L.* ; Ehlert, S.* ; Irsig, R.* ; Kozhinov, A.N.* ; Nagornov, K.O.* ; Makarov, A.* ; Rigler, M.* ; Tsybin, Y.O.* ; Walte, A.* ; Zimmermann, R.

Vacuum laser photoionization inside the C-trap of an orbitrap mass spectrometer: Resonance-enhanced multiphoton ionization high-resolution mass spectrometry.

Anal. Chem. 93, 9418–9427 (2021)

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

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State-of-the-art mass spectrometry with ultraviolet (UV) photoionization is mostly limited to time-of-flight (ToF) mass spectrometers with 1000-10 000 m/Δm mass resolution. However, higher resolution and higher spectral dynamic range mass spectrometry may be indispensable in complex mixture characterization. Here, we present the concept, implementation, and initial evaluation of a compact ultrahigh-resolution mass spectrometer with gas-phase laser ionization. The concept is based on direct laser photoionization in the ion accumulation and ejection trap (C-trap) of an Orbitrap mass spectrometer. Resonance-enhanced multiphoton ionization (REMPI) using 266 nm UV pulses from a frequency-quadrupled Nd:YAG laser was applied for selective and efficient ionization of monocyclic and polycyclic aromatic hydrocarbons. The system is equipped with a gas inlet for volatile compounds and a heated gas chromatography coupling. The former can be employed for rapid system m/z-calibration and performance evaluation, whereas the latter enables analysis of semivolatile and higher-molecular-weight compounds. The capability to evaluate complex mixtures is demonstrated for selected petrochemical materials. In these experiments, several hundred to over a thousand compounds could be attributed with a root-mean-square mass error generally below 1 ppm and a mass resolution of over 140 000 at 200 m/z. Isobaric interferences could be resolved, and narrow mass splits, such as 3.4 mDa (SH₄/C₃), are determined. Single laser shots provided limits of detection in the 20-ppb range for p-xylene and 1,2,4-trimethylbenzene, similar to compact vacuum REMPI-ToF systems.

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Publication type Article: Journal article

Document type Scientific Article

Corresponding Author

Keywords Polycyclic Aromatic-hydrocarbons; Single-photon Ionization; Atmospheric-pressure Photoionization; Electron-impact Ionization; Real-time Analysis; Chemical-ionization; Gas-chromatography; Thermal-analysis; Crude Oils; Online

ISSN (print) / ISBN 0003-2700

e-ISSN 1520-6882

Journal Analytical Chemistry

Quellenangaben Volume: 93, Issue: 27, Pages: 9418–9427

Publisher American Chemical Society (ACS)

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 Helmholtz International Lab. aeroHEALTH
EUROSTARS project