Collision‐induced dissociation of three groups of hydroxamate siderophores: ferrioxamines, ferrichromes and coprogens/fusigens

The behaviour of a series of hydroxamate siderophores – microbially produced iron complexes – was investigated using electrospray ionisation mass spectrometry (ESI‐MS). Three groups of iron hydroxamate siderophores, namely the ferrioxamines, ferrichromes and coprogens/fusigens, were separated by high‐performance liquid chromatography (HPLC) prior to ESI and MS 2 fragmentation. For the majority of the siderophores, both protonated molecules and sodium adducts were observed. The most abundant ion was selected for collision‐induced fragmentation. Potential fragmentation mechanisms are postulated and discussed. Fragmentation patterns differed between siderophore groups; however, common fragmentation patterns were observed for siderophore ions within the groups examined. Cleavage frequently occurred at carbon–nitrogen or carbon–oxygen bonds. Fragmentation of the ions also involved cleavage of iron–oxygen bonds and transfer of the charge to iron. Copyright © 2008 John Wiley & Sons, Ltd.