Journal
JOURNAL OF MASS SPECTROMETRY
Volume 47, Issue 8, Pages 995-1003Publisher
WILEY
DOI: 10.1002/jms.3027
Keywords
MALDI; electron transfer; matrix; secondary reaction; 9; 10-diphenylanthracene; endothermic
Funding
- National Science Foundation [CHE-1058764]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1058764] Funding Source: National Science Foundation
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The most common secondary-ionization mechanism in positive ion matrix-assisted laser desorption/ionization (MALDI) involves a proton transfer reaction to ionize the analyte. Peptides and proteins are molecules that have basic (and acidic) sites that make them susceptible to proton transfer. However, non-polar, aprotic compounds that lack basic sites are more difficult to protonate, and creating charged forms of this type of analyte can pose a problem when conventional MALDI matrices are employed. In this case, forming a radical molecular ion through electron transfer is a viable alternative, and certain matrices may facilitate the process. In this work, we investigate the performance of a newly developed electron-transfer secondary reaction matrix: 9,10-diphenylanthracene (9,10-DPA). The use of 9,10-DPA as matrix for MALDI analysis has been tested using several model compounds. It appears to promote ionization through electron transfer in a highly efficient manner as compared to other potential matrices. Thermodynamic aspects of the observed electron transfers in secondary-ionization reactions were also considered, as was the possibility for kinetically controlled/endothermic, electron-transfer reactions in the MALDI plume. Copyright (c) 2012 John Wiley & Sons, Ltd.
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