A triple-quadrupole spectrometer has been used to study proton-transfer reactions of multiply charged ions generated by electrospray ionization. Doubly and triply charged ions generated from the peptides Arg-Lys-Glu-Val-Tyr and Met-Lys-bradykinin, respectively, were found to undergo proton-transfer reactions with ammonia molecules contained in the RF-only quadrupole collision-gas cell of the spectrometer. With horse-heart myoglobin in the source, ions having charges of 20+, 19+, 16+ and 14+ were selected in turn by the first quadrupole and their proton-transfer reactions with ammonia investigated. For each ion, numerous product ions were detected having charges (n-1)+, (n-2)+, (n-3)+ ... where n was the charge on the reacting parent ion. The possibility of using the experimental technique to measure approximately the proton affinities of multiply charged ions is discussed. Also, a procedure is outlined for identifying the charge states of product ions resulting from collision-induced dissociation of multiply charged ions.
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