Comparison of the positive and negative ion electrospray mass spectra of some small peptides containing pyroglutamate

The positive ion electrospray mass spectra of [M+H](+) and the negative ion electrospray mass spectra of [M-H](-) ions of selected pyroglutamate containing peptides both provide sequencing data. The negative ion spectra show the normal alpha and beta backbone cleavages in addition to delta and gamma backbone cleavages initiated by the side chains of Glu and Phe residues. For example, the [M-H](-) ion of pGlu Pro Gln Val Phe Val-NH(2) shows delta and gamma peaks at m/z 224 (delta, Gln3), 244 (gamma, Phe4), 451 (delta, Phe4), 471 (gamma, Gln3). Some of the negative ion spectra show unusual grandaughter peaks that originate by alpha and beta, or delta and gamma backbone cleavages of a beta(1) cleavage ion.