Simplification of product ion spectra derived from multiply charged parent ions via ion/ion chemistry.

High-mass multiply charged ions fragment to yield a mixture of products of varying mass and charge. When the measurement of mass-to-charge ratio is used to determine products ion mass, product ion charge must first be established. To minimize charge-state ambiguity in product ion spectra derived from multiply charged parent ions, product ions have been subjected to proton-transfer reactions with oppositely charged ions to reduce product ion charge states largely to +1. This procedure greatly simplifies the interpretation of product ion spectra derived from multiply charged ions. Illustrative data are presented for the +4 and +3 parent ions derived from electrospray of melittin and the +12 to +4 parent ions of bovine ubiquitin, whereby product ions were formed in a conventional quadrupole ion trap tandem mass spectrometry experiment. Data are also shown for product ion mixtures derived from interface-induced dissociation of multiply charged ions derived from bovine ubiquitin, tuna cytochrome c, bovine cytochrome c, and equine cytochrome c. The use of ion/ion chemistry to simplify product ion spectra derived from multiply charged parent ions significantly extends the size range of macromolecules for which the quadrupole ion trap can derive structural information.