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Toward understanding the ionization mechanism of matrix‐assisted ionization using mass spectrometry experiment and theory

  • Matrix‐assisted ionization (MAI) mass spectrometry does not require voltages, a laser beam, or added heat to initiate ionization, but it is strongly dependent on the choice of matrix and the vacuum conditions. High charge state distributions of nonvolatile analyte ions produced by MAI suggest that the ionization mechanism may be similar to that of electrospray ionization (ESI), but different from matrix‐assisted laser desorption/ionization (MALDI). While significant information is available for MAI using mass spectrometers operating at atmospheric and intermediate pressure, little is known about the mechanism at high vacuum. Eleven MAI matrices were studied on a high‐vacuum time‐of‐flight (TOF) mass spectrometer using a 266 nm pulsed laser beam under otherwise typical MALDI conditions. Detailed comparisons with the commonly used MALDI matrices and theoretical prediction were made for 3‐nitrobenzonitrile (3‐NBN), which is the only MAI matrix that works well in high vacuum whenMatrix‐assisted ionization (MAI) mass spectrometry does not require voltages, a laser beam, or added heat to initiate ionization, but it is strongly dependent on the choice of matrix and the vacuum conditions. High charge state distributions of nonvolatile analyte ions produced by MAI suggest that the ionization mechanism may be similar to that of electrospray ionization (ESI), but different from matrix‐assisted laser desorption/ionization (MALDI). While significant information is available for MAI using mass spectrometers operating at atmospheric and intermediate pressure, little is known about the mechanism at high vacuum. Eleven MAI matrices were studied on a high‐vacuum time‐of‐flight (TOF) mass spectrometer using a 266 nm pulsed laser beam under otherwise typical MALDI conditions. Detailed comparisons with the commonly used MALDI matrices and theoretical prediction were made for 3‐nitrobenzonitrile (3‐NBN), which is the only MAI matrix that works well in high vacuum when irradiated with a laser. Screening of MAI matrices with good absorption at 266 nm but with various degrees of volatility and laser energies suggests that volatility and absorption at the laser wavelength may be necessary, but not sufficient, criteria to explain the formation of multiply charged analyte ions. 3‐NBN produces intact, highly charged ions of nonvolatile analytes in high‐vacuum TOF with the use of a laser, demonstrating that ESI‐like ions can be produced in high vacuum. Theoretical calculations and mass spectra suggest that thermally induced proton transfer, which is the major ionization mechanism in MALDI, is not important with the 3‐NBN matrix at 266 nm laser wavelength. 3‐NBN:analyte crystal morphology is, however, important in ion generation in high vacuum. The 3‐NBN MAI matrix produces intact, highly charged ions of nonvolatile compounds in high‐vacuum TOF mass spectrometers with the aid of ablation and/or heating by laser irradiation, and shows a different ionization mechanism from that of typical MALDI matrices.zeige mehrzeige weniger

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Metadaten
Autoren/innen:C. Lee, E. D. Inutan, J. L. Chen, M. M. Mukeku, Steffen Weidner, S. Trimpin, C.-K. Ni
Dokumenttyp:Zeitschriftenartikel
Veröffentlichungsform:Verlagsliteratur
Sprache:Englisch
Titel des übergeordneten Werkes (Englisch):Rapid Communications in Mass Spectrometry
Jahr der Erstveröffentlichung:2019
Organisationseinheit der BAM:6 Materialchemie
6 Materialchemie / 6.3 Strukturanalytik
Verlag:John Wiley & Sons
Ausgabe/Heft:Special Issue Research Article
Erste Seite:1
Letzte Seite:10
DDC-Klassifikation:Naturwissenschaften und Mathematik / Chemie / Analytische Chemie
Freie Schlagwörter:Ionization; MALDI-TOF MS; Mechanism
Themenfelder/Aktivitätsfelder der BAM:Analytical Sciences
Analytical Sciences / Spurenanalytik und chemische Zusammensetzung
DOI:https://doi.org/10.1002/rcm.8382
Verfügbarkeit des Dokuments:Datei im Netzwerk der BAM verfügbar ("Closed Access")
Datum der Freischaltung:07.10.2019
Referierte Publikation:Ja
Datum der Eintragung als referierte Publikation:25.11.2019