Charge-state shifting of individual multiply-charged ions of bovine albumin dimer and molecular weight determination using an individual-ion approach.

Ion-molecule reactions of individual multiply-protonated ions of bovine albumin dimer, formed from electrospray ionization, have been studied using a Fourier transform ion cyclotron resonance mass spectrometer. Upon reaction of ammonia with a group of individual ions, charge-state shifting was observed due to proton transfer. Repeated additions of ammonia during remeasurements of the same ion population were observed to induce multiple-step charge-state shifts. Charge-state-dependent reactivity, as well as nonstatistical behavior in reactivity, was observed due to the small ion population. The molecular weights of individual ions whose charge state shifted during reaction were determined with an accuracy of 67 ppm, the first example of using an individual-ion approach to the determination of molecular weight for a large biopolymer. The molecular weight distribution of a group of ions can be determined with a precision related to the number of ions examined and the weight heterogeneity of the sample. We obtained the molecular weight for eight individual ions from which a molecular weight of 133,320 +/- 210 Da was calculated for bovine albumin dimer.