Proton transfer reactions of matrix-assisted laser desorption/ionization matrix monomers and dimers

Articles

Abstract

The gas-phase basicities of monomeric and dimeric deprotonated ferulic and sinapic acids, common matrix-assisted laser desorption/ionization (MALDI) matrices, were determined. A new bracketing method based on structure-reactivity correlations was developed for deriving gas-phase basicities from reaction efficiencies. The matrix dimer anions were found to be significantly less basic than the monomer anions, by about 115 kJ/mol. The low basicity of the dimer anion can qualitatively be explained by resonance stabilization. The energies for proton transfer from dimers to monomers are therefore about 1.2 eV lower than for proton transfer between monomers. For the MALDI process, proton transfer reactions involving matrix dimers provide a low energy pathway for matrix and analyte ion formation.

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Copyright information

© American Society for Mass Spectrometry 1999

Authors and Affiliations

  1. 1.Department of Chemistry, Swiss Federal Institute of Technology (ETH)Universitätstrasse 16ZürichSwitzerland

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