Why do the abundances of ions generated by MALDI look thermally determined?

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Title
Why do the abundances of ions generated by MALDI look thermally determined?
Author(s)
Y J Bae; J C Choe; Jeong Hee Moon; M S Kim
Bibliographic Citation
Journal of American Society for Mass Spectrometry, vol. 24, no. 11, pp. 1807-1815
Publication Year
2013
Abstract
In a previous study (J. Mass Spectrom. 48, 299-305, 2013), we observed that the abundance of each ion in a matrix-assisted laser desorption ionization (MALDI) spectrum looked thermally determined. To find out the explanation for the phenomenon, we estimated the ionization efficiency and the reaction quotient (QA) for the autoprotolysis of matrix, M + M → [M + H] + + [M - H]-, from the temperature-controlled laser desorption ionization spectra of α-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB). We also evaluated the equilibrium constants (KA) for the autoprotolysis at various temperatures by quantum chemical calculation. Primary ion formation via various thermal models followed by autoprotolysis-recombination was compatible with the observations. The upper limit of the effective temperature of the plume where autoprotolysis- recombination occurs was estimated by equating QA with the calculated equilibrium constant. [
Keyword
AutoprotolysisMALDIPrimary ion formationRecombinationThermal determination
ISSN
1044-0305
Publisher
Amer Chem Soc
DOI
http://dx.doi.org/10.1007/s13361-013-0717-7
Type
Article
Appears in Collections:
Division of Biomedical Research > Disease Target Structure Research Center > 1. Journal Articles
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