title: Metal speciation in health and medicine represented by iron and vanadium.
abstract: The influence of metals in biology has become more and more apparent within the past century. Metal ions perform essential roles as critical scaffolds for structure and as catalysts in reactions. Speciation is a key concept that assists researchers in investigating processes that involve metal ions. However, translation of the essential area across scientific fields has been plagued by language discrepancies. To rectify this, the IUPAC Commission provided a framework in which speciation is defined as the distribution of species. Despite these attempts, contributions from inorganic chemists to the area of speciation have not fully materialized in part because the past decade's contributions focused on technological advances, which are not yet to the stage of measuring speciation distribution in biological solutions. In the following, we describe how speciation influences the area of metals in medicine and how speciation distribution has been characterized so far. We provide two case studies as an illustration, namely, vanadium and iron. Vanadium both has therapeutic importance and is known as a cofactor for metalloenzymes. In addition to being a cation, vanadium(V) has analogy with phosphorus and as such is a potent inhibitor for phosphorylases. Because speciation can change the metal's existence in cationic or anionic forms, speciation has profound effects on biological systems. We also highlight how speciation impacts iron metabolism, focusing on the rather low abundance of biologically relevant iron cation that actually exists in biological fluids. fluids. Furthermore, we point to recent investigations into the mechanism of Fenton chemistry, and that the emerging results show pH dependence. The studies suggest formation of Fe(IV)-intermediates and that the generally accepted mechanism may only apply at low pH. With broader recognition toward biological speciation, we are confident that future investigations on metal-based systems will progress faster and with significant results. Studying metal complexes to explore the properties of a potential "active species" and further uncovering the details associated with their specific composition and geometry are likely to be important to the action.
authors.affiliation: Department of Chemistry, Colorado State University , Fort Collins, Colorado 80523, United States.
authors.forename: Debbie C
authors.initials: DC
authors.lastname: Crans
authors.forename: Kellie A
authors.initials: KA
authors.lastname: Woll
authors.forename: Kestutis
authors.initials: K
authors.lastname: Prusinskas
authors.forename: Michael D
authors.initials: MD
authors.lastname: Johnson
authors.forename: Eugenijus
authors.initials: E
authors.lastname: Norkus
mesh_terms: D000818:Animals; D003067:Coenzymes / Q000737:chemistry / Q000378:metabolism; D006801:Humans; D006868:Hydrolysis; D007501:Iron / Q000097:blood / Q000737:chemistry* / Q000378:metabolism* / Q000493:pharmacokinetics; D008670:Metals / Q000737:chemistry / Q000378:metabolism / Q000493:pharmacokinetics; D014639:Vanadium / Q000737:chemistry* / Q000378:metabolism*
chemical_list: D003067:Coenzymes; D008670:Metals; D014639:Vanadium; D007501:Iron