Abstract
AbstractElectrospray ionization mass spectrometry (ESI‐MS) is a powerful method for sequencing peptides. A novel fragmentation pattern with the loss of a neutral fragment of 45 Da was observed with the dipeptides, tripeptides, tetrapeptides and pentapeptides containing phenylalanine or histidine residues. A novel rearrangement reaction with the extrusion of a formamide piece was studied and the rearrangement mechanism was proposed and confirmed by deuterium labeling experiments with ESI‐MS and high‐resolution mass spectrometry. These findings are potentially helpful in identifying the specific sequence pattern in the peptide sequencing.
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