Observation of large multimers in the electrospray ionization mass spectrometry of peptides

Large multimeric ions were detected from electrospray ionization (ESI) mass spectrometry of peptides, using a quadrupole mass spectrometer of standard mass range. Multimers, up to heptamers, were seen for angiotensin I; and multimers, up to pentamers, were observed for renin substrate. The appearance of the multimeric species could be controlled by manipulation of sampling conditions in the ESI interface. The relevance of the observation of large multimers to proposed mechanisms of ESI is discussed. Implications of the observation of large multimers to efforts to deduce higher order structure of biomolecules from ESI mass spectrometric experiments are also noted.