Complexation of hydroxamate-based siderophores with cobalt(II/III): growth inhibitory effect of cobalt(III)-desferricoprogen complex on fungi

Abstract

Solution equilibrium results for Co(II) and Co(III) complexes of two natural hydroxamate-based siderophores, the exocyclic desferricrocin (DFR) and the endocyclic triacetylfusarinine (TAF) are presented. The three hydroxamate chelating functions of TAF were found to complete the octahedral coordination sphere of a Co(II) ion in stepwise processes, but following the coordination of two hydroxamates of DFR practically in one step, the third function, most probably because of sterical reasons, remained uncoordinated. A comparison with corresponding results for the previously studied acyclic desferrioxamine B (DFB) and desferricoprogen (DFC) provided some information about the effects of the molecular framework of siderophores on their cobalt-binding ability. The oxidation of the central metal ion under basic conditions and investigation of the cobalt(III) complexes by cyclic voltammetry were also made. Compared to Fe(III), by several orders of magnitude, higher stability complexes were formed with Co(III). The possibility of any effect of the Co(III)-siderophore complex on microbial Fe(III) uptake was tested by investigation of the antifungal effect of Co(III)-DFC in comparison with that of CoCl2 on two fungi cultures, Penicillium brevicompactum and Aspergillus fumigatus.