Observation of solvent effects on abundance of polyhydrogen adducts (M + nH)+ in fast atom bombardment mass spectrometry.

The formation of polyhydrogen adducts of peptide molecules during fast atom bombardment (FAB) mass spectrometry (MS) is shown to be matrix dependent. FAB/MS analyses completed in glycerol solvent produced higher than expected peak intensities at m/z corresponding to (M + 2)+, (M + 3)+, and (M + 4)+ when the contributions of all stable isotopes present in the sample are included. Analysis of the same peptides in thioglycerol by positive or negative ion FAB yielded peak intensity distributions for the protonated molecule which matched those predicted from the natural abundance of stable isotopes. These findings suggest that thioglycerol should be the FAB matrix in analyses of peptides when determination of elemental or isotopic composition is desired.