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.2012 Aug;47(8):995-1003.
doi: 10.1002/jms.3027.

9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions

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9,10-Diphenylanthracene as a matrix for MALDI-MS electron transfer secondary reactions

M Nazim Boutaghou et al. J Mass Spectrom.2012 Aug.

Abstract

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 © 2012 John Wiley & Sons, Ltd.

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