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Vanadium is a biologically ultramicrotrace transition metal which can be found both in anionic and cationic forms with oxidation states ranging from 1 to +5 (I–V). The cationic forms of vanadium complexes with oxidation state +4 (IV) have been shown to modulate the cellular redox potential, regulate enzymatic phosphorylation, and exert pleiotrophic effects in multiple biological systems by catalyzing the generation of reactive oxygen species (ROS) in cellular and cell-free systems. Vanadium species are present in several proteins including bromoperoxidase and nitrogenase being essential for their catalytic activity. Moreover, the ability of vanadium to assume various oxidation states contributes to the versatility of this metal in biological systems and allows its interaction with different biomolecules.