Structural characterization of glutaminergic blocker spider toxins by high‐energy collision charge‐remote fragmentations

Spider venom gland stores various glutaminergic blockers such as acylpolyamines, besides proteins and peptides. A method is described for structure determination of these acylpolyamines using fast‐atom bombardment and four‐sector tandem mass spectrometry. The collision‐induced dissociation (CID) spectra of protonated molecular ions of synthetic model compounds show only a small number of weak, sequence‐related product ions. But, unlike the CID spectra of [M + H] + ions, dissociation of sodium‐attached molecular ions leads to charge‐remote fragmentations and provides intense sequence‐related product ions.