Abstract
Desferrioxamine (DEF) is a trihydroxamate siderophore typical of those produced by bacteria and fungi for the purpose of scavenging Fe^3+^ from environments where the element is in short supply. Since this class of molecules has excellent chelating properties, reaction with metal contaminants such as actinide species can also occur. The complexes that are formed can be mobile in the environment. Because the natural environment is extremely diverse, strategies are needed for the identification of metal complexes in aqueous matrices having a high degree of chemical heterogeneity, and electrospray ionization mass spectrometry (ESI‐MS) has been highly effective for the characterization of siderophore–metal complexes. In this study, ESI‐MS of solutions containing DEF and either UO~2~^2+^, Fe^3+^ or Ca^2+^ resulted in generation of abundant singly charged ions corresponding to [UO~2~(DEF − H)]^+^, [Fe(DEF − 2H)]^+^ and [Ca(DEF − H)]^+^. In addition, less abundant doubly charged ions were produced. Mass spectrometry/mass spectrometry (MS/MS) studies of collision‐induced dissociation (CID) reactions of protonated DEF and metal–DEF complexes were contrasted and rationalized in terms of ligand structure. In all cases, the most abundant fragmentation reactions involved cleavage of the hydroxamate moieties, consistent with the idea that they are most actively involved with metal complexation. Singly charged complexes tended to be dominated by cleavage of a single hydroxamate, while competitive fragmentation between two hydroxamate moieties increased when the doubly charged complexes were considered. Rupture of amide bonds was also observed, but these were in general less significant than the hydroxamate fragmentations. Several lower abundance fragmentations were unique to the metal examined: abundant loss of H~2~O occurred only for the singly charged UO~2~^2+^ complex. Further, NH~3~ was eliminated only from the singly charged Fe^3+^ complex; this and fragmentation of CC and CN bonds derived from neither the hydroxamate nor the amide groups suggested that Fe^3+^ insertion reactions were competing with ligand complexation. In no experiments were coordinating solvent molecules observed, attached either to the intact complexes or to the fragment ions, which indicated that both intact DEF and its fragments were occupying all of the coordination sites around the metal centers. This conclusion was based on previous experiments that showed that undercoordinated UO~2~^2+^ and Fe^3+^ readily added H~2~O and methanol in the ESI quadrupole ion trap mass spectrometer that was used in this study. Copyright © 2004 John Wiley & Sons, Ltd.