Origins of the proton in the generation of protonated polymers and peptides in matrix-assisted laser desorption/ionization

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Abstract
In this paper, various possible sources of protons for protonation of polymer and peptide molecules under matrix-assisted laser desorption/ionization conditions were studied by using a deuterium labeling method. It was demonstrated that exchangeable protons from either carboxylic acid or hydroxyl groups of the matrix were important, but not essential, for protonation of the analyte. For a nitroanthracene matrix, the non-exchangeable protons from the matrix and the exchangeable protons from the solvent (and possibly from the analyte) were also shown to contribute protons for the formation of protonated molecule-ions.

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