The Bioinorganic Chemistry of Vanadium

Abstract

Vanadium is a trace element that plays an important, perhaps essential and general role in the regulation of enzymatic phosphorylations. Several forms of life, including the fly agaric toadstool (Amanita muscaria) and certain sea squirts (ascidians), are able to concentrate vanadium. In other organisms vanadium is part of the active site of some enzymes. Well-studied examples are the nitrogen-fixing bacterium Azotobacter and various seaweeds that use vanadate-dependent peroxidases to synthesize halogenated organic compounds. Despite its importance as a "biometal" both in primitive, prokaryotic organisms (Azotobacter) and in the highly organized ascidians, which represent an early stage in the evolution of vertebrates, the bioinorganic chemistry of vanadium is still in its infancy. Just as young, but undergoing explosive development, is the chemistry of model compounds for vanadium-containing biomolecules, a domain of the bioinorganic coordination chemist, who almost daily discovers compounds with new and surprising structural features. This article reviews this fascinating area of bioinorganic chemistry.

Synthesis, Characterization and Crystal Structure of a Novel Decavanadate Salt, [V0.50(H2O)5]2[H2(V10O28)]·4(H2O)

“…[1][2][3][4][5][6][7] In recent years, the interest to the chemistry of oxovanadates has grown considerably. 8 The increasing interest is mainly owing to the role of vanadium in several biological processes such as the regulation of glucose level in the blood of diabetic animals and patients.…”

“…8 The increasing interest is mainly owing to the role of vanadium in several biological processes such as the regulation of glucose level in the blood of diabetic animals and patients. 3,4,[9][10][11][12][13][14][15][16][17] Moreover, decavanadate and oxovanadates have many biological activities and been successfully used for the comprehension of several biochemical processes. 18 Other interest for vanadium oxides is sourced from their potential uses as secondary cathode materials, both catalysis and electronics.…”

Model studies related to vanadium biochemistry: recent advances and perspectives

“…Although numerous biochemical and physiological functions have been suggested for this element, and despite the amount of the knowledge so far accumulated, vanadium still does not have a clearly defined role in the higher forms of life. [1][2][3][4][5] The best evidence for a biological role of vanadium comes from bacteria (the so-called alternative nitrogenases in which vanadium replaces molybdenum in the FeMocofactor of some Azotobacter species) [4][5][6][7] and from plants (vanadium-dependent haloperoxidases found in some algae, lichens and fungi). 4,5,8,9 On the other hand, experiments with laboratory animals have shown that vanadium deprivation enhances abortion rates, reduces milk levels during lactation and produces thyroidal disorders.…”

“…10 Like molybdenum, vanadium occupies an exceptional position among the bioelements because both, anionic and cationic forms can participate in biological processes. 3,5,11,12 In its anionic forms (vanadates(V)), it resembles phosphates, but in its cationic forms -mainly as VO 2+ -it behaves like a typical transition metal ion, which competes with other metal cations in coordination with biogenic ligands or compounds. This duality, together with the facility with which it changes oxidation states and coordination environments, may be responsible for the very peculiar and somewhat unparalleled behavior of this biometal.…”

“…5,12 Aspects of the coordination chemistry of vanadium relevant to its presence and activity in biological systems have been recently reviewed. [2][3][4][11][12][13][14] In this account we will present some of our recent results of studies on model systems related to aspects of the biochemistry of vanadium and those of other research groups working in this field.…”