Abstract
The electronebulization of a cobalt(II)/cysteine(Cys) mixture in water/methanol (50/50) produced mainly cobalt‐cationized species. Three main groups of the Co‐cationized species can be distinguished in the ESI‐MS spectrum: (1) the cobalt complexes including the cysteine amino acid only (they can be singly charged, for example, [Co(Cys)~n~− H]^+^ with n = 1–3 or doubly charged such as [Co + (Cys)~2~]^2+^); (2) the cobalt complexes with methanol: [Co(CH~3~OH)~n~− H]^+^ with n = 1–3, [Co(CH~3~OH)~4~]^2+^; and (3) the complexes with the two different types of ligands: [Co(Cys)(CH~3~OH) − H]^+^. Only the singly charged complexes were observed. Collision‐induced dissociation (CID) products of the [Co(Cys)~2~]^2+^, [Co(Cys)~2~ − H]^+^ and [Co(Cys) − H]^+^ complexes were studied as a function of the collision energy, and mechanisms for the dissociation reactions are proposed. These were supported by the results of deuterium labelling experiments and by density functional theory calculations. Since [Co(Cys) − H]^+^ was one of the main product ions obtained upon the CID of [Co(Cys)~2~]^2+^ and of [Co(Cys)~2~ − H]^+^ under low‐energy conditions, the fragmentation pathways of [Co(Cys) − H]^+^ and the resulting product ion structures were studied in detail. The resulting product ion structures confirmed the high affinity of cobalt(II) for the sulfur atom of cysteine. Copyright © 2007 John Wiley & Sons, Ltd.