Functional Plasticity of Microbial Siderophores in Iron- and Boron-Rich Niches

Siderophores are high-affinity iron-chelating metabolites that underpin microbial survival in iron-limited environments and play central roles in metal homeostasis, ecological competition, and pathogenesis. Traditionally viewed as dedicated Fe(III) scavengers, siderophores are now recognized as structurally and functionally versatile coordination agents whose donor-set architectures—particularly catecholate and α-hydroxycarboxylate motifs—permit conditional interactions beyond iron. In iron- and boron-rich niches, especially marine and mildly alkaline systems where borate availability increases, certain siderophores are chemically capable of forming reversible borate complexes through cis-diol coordination. Although Fe(III) exhibits substantially higher thermodynamic affinity and remains the primary biological target, boron binding represents a predictable secondary property arising from shared oxygen-donor chemistry. This dynamic interplay allows siderophores to cycle between iron-bound, boron-bound, and apo states depending on local redox conditions, pH, and metal availability. Here, we synthesize current knowledge on the structural classes of microbial siderophores, their transport and regulatory mechanisms, and emerging evidence for boron coordination within catecholate and carboxylate systems. By integrating coordination chemistry with microbial ecology, we propose an expanded model in which siderophores function not only as iron acquisition molecules but also as modulators of boron speciation and environmental sensing. This functional plasticity positions siderophores at the intersection of iron and boron biogeochemical cycles and highlights new directions for understanding microbial adaptation in complex metal-rich environments.