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Generation of ion-bound solvent clusters as reactant ions in dopant-assisted APPI and APLI.
Anal. Bioanal. Chem. 405, 6933-51 (2013)
We provide experimental and theoretical evidence that the primary ionization process in the dopant-assisted varieties of the atmospheric pressure ionization methods atmospheric pressure photoionization and atmospheric pressure laser ionization in typical liquid chromatography-mass spectrometry settings is--as suggested in the literature--dopant radical cation formation. However, instead of direct dopant radical cation-analyte interaction--the broadly accepted subsequent step in the reaction cascade leading to protonated analyte molecules--rapid thermal equilibration with ion source background water or liquid chromatography solvents through dopant ion-molecule cluster formation occurs. Fast intracluster chemistry then leads to almost instantaneous proton-bound water/solvent cluster generation. These clusters interact either directly with analytes by ligand switching or association reactions, respectively, or further downstream in the intermediate-pressure regions in the ion transfer stages of the mass spectrometer via electrical-field-driven collisional decomposition reactions finally leading to the predominantly observed bare protonated analyte molecules [M + H](+).
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Publikationstyp
Artikel: Journalartikel
Dokumenttyp
Wissenschaftlicher Artikel
ISSN (print) / ISBN
1618-2642
e-ISSN
1618-2650
Zeitschrift
Analytical and Bioanalytical Chemistry
Quellenangaben
Band: 405,
Heft: 22,
Seiten: 6933-51
Verlag
Springer
Verlagsort
Heidelberg
Nichtpatentliteratur
Publikationen
Begutachtungsstatus
Peer reviewed