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What do matrix‐assisted laser desorption/ionization mass spectra reveal about ionization mechanisms?
Author(s) -
Papantonakis Michael R.,
Kim Jun,
Hess Wayne P.,
Haglund Richard F.
Publication year - 2002
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.318
Subject(s) - chemistry , ionization , atmospheric pressure laser ionization , ambient ionization , mass spectrum , matrix assisted laser desorption electrospray ionization , mass spectrometry , analyte , ion , excited state , ion source , soft laser desorption , laser , photoionization , spectral line , matrix (chemical analysis) , chemical ionization , analytical chemistry (journal) , desorption , matrix assisted laser desorption/ionization , atomic physics , electron ionization , chromatography , optics , physics , organic chemistry , adsorption , astronomy
We present ion mass spectra obtained by matrix‐assisted laser desorption/ionization for analytes of ∼1000 Da across the largest range of wavelengths and pulse durations to date. The matrix used in all cases was 2,5‐dihydroxybenzoic acid. Based on the data and fundamentals of laser–material interactions, we evaluated the plausibility of discriminating among such ion formation mechanisms as multiphoton ionization and excited‐state ionization from mass spectra alone. Some previously proposed mechanisms appear unlikely for the matrix–analyte systems that we studied, casting doubt on their general applicability. Moreover, although analysis of mass spectra can apparently exclude certain mechanisms, it cannot establish which of several competing mechanisms is actually operative. This is particularly true with respect to variations in pulse duration and wavelength. Copyright © 2002 John Wiley & Sons, Ltd.