Vanadium biological roles

The sea squirts or tunicates are fascinating marine creatures, their name being derived from the tunic made of cellulosic material that surrounds the body of the animal. In 1911, Henze discovered vanadium in the blood of Phallusia mammillata C.343 He later found the same with other ascidians (a class of tunicates). In vanadium-accumulating species, most vanadium is located in the vacuoles—vanadophores—of certain types of blood cells—the vanadocytes. The concentration in the vanadophore can be as high as 1M and this value must be compared with concentrations of the order of 2 x 10-8 M for vanadium in sea water.344 Kustin et al. have reviewed the work done to understand the efficient accumulation and the possible biological roles of the metal.345... 

Other forms of vanadium have been implicated in the stimulation of the plasma membrane vanadate-dependent NAD(P)H oxidation reaction. Decavanadate has been shown to be a more potent stimulator of the vanadate-dependent NADH oxidation activity than added orthovanadate [30,31], Interestingly, decavanadate reductase activity has been found to be an alternative activity of an NADP-specific isocitrate dehydrogenase [32], Diperoxovanadium derivatives have also been shown to be involved in this type of reaction [33,34], Decavanadate may play a role in the biological role of vanadium, as it is found in yeast cells growing in the presence of orthovanadate [8] and is a potent inhibitor of phosphofructokinase-1, the control step of glycolysis, and other metabolic reactions [35],... 

Historically, vanadium has received little attention from biochemists. In the past four years, however, the interaction of this element with biological systems has become the focus of intense study in numerous laboratories throughout the world. Many biochemical and physiological effects of this essential metal are now known and new ones are being discovered almost monthly. Despite these recently discovered phenomena, the role of vanadium in vivo remains an open question. The potency of this element at extremely low concentrations, typical of those found in many tissues, is particularly relevant to a possible function. As is the case with most essential metals, vanadium in all probability will be shown to have more than one biological role. 

Underivatized ( )-tunichrome An-1 was synthesized recently on a semi-preparative scale 163). Its availability will help to clarify the biological role of tunichromes, including their interactions with vanadium. 

Oxidation of sulfides catalyzed by haloperoxidases has been reviewed [74]. The natural biological role of haloperoxidases is to catalyze oxidation of chloride, bromide, or iodide by hydrogen peroxide. Three classes of haloperoxidases have been identified (i) those without a prosthetic group, found in bacteria, (ii) heme-containing peroxidases such as chloroperoxidase (CPO), and (iii) vanadium-containing peroxidases. 

The quality of the experimental evidence for nutritional essentiality varies widely for the ultratrace elements. The evidence for the essentiality of three elements, iodine, molybdenum and selenium, is substantial and noncontroversial specific biochemical functions have been defined for these elements. The nutritional importance of iodine and selenium are such that they have separate entries in this encyclopedia. Molybdenum, however, is given very little nutritional attention, apparently because a deficiency of this element has not been unequivocally identified in humans other than individuals nourished by total parenteral nutrition or with genetic defects causing disturbances in metabolic pathways involving this element. Specific biochemical functions have not been defined for the other 15 ultratrace elements listed above. Thus, their essentiality is based on circumstantial evidence, which most often is that a dietary deprivation in an animal model results in a suboptimal biological function that is preventable or reversible by an intake of physiological amounts of the element in question. Often the circumstantial evidence includes an identified essential function in a lower form of life, and biochemical actions consistent with a biological role or beneficial action in humans. The circumstantial evidence for essentiality is substantial for arsenic, boron, chromium, nickel, silicon, and vanadium. The evidence for essentiality for the... 

In some plants and animals, vanadium can reach high concentrations. The vanadium content of marine plants and invertebrate animals usually ranks above that of land plants, insects and vertebrates. An investigation done by Bertrand revealed that a species of mushroom. Amanita muscaria, contained more than 100 ppm of the element [7]. The biologic role of vanadium played was not deciphered but Bertrand did note that vanadium did not seem to be derived from the soil in which the mushroom grew. Table 6 shows the vanadium content in some investigated plants and animals. 

Orvig, C. Thompson, K. H. Battell, M. McNeill, J. H. Metal Ions in Biological Systems Vanadium and its Role in Life In Metal Ions in Biological Systems, Sigel, H. Sigel, A. Eds. Marcel Dekker New York, 1995 Vol. 31, p 575. 

The potentially serious aspects of vanadium pollution, the function of biologically occurring enzyme systems, the role of vanadium on the function of numerous enzymes, and the associated role in the insulin-mimetic vanadium compounds are inextricably linked. The key to our understanding all such functionality relies on understanding the basic chemistry that underlies it. This chemistry is determined to a significant extent by the V(IV) and V(V) oxidation states but clearly is not restricted to these states. Indeed, the redox interplay between the vanadium oxidation states can be a critical aspect of the biological functionality of vanadium, particularly in enzymes such as the vanadium-dependent nitrogenases, where redox reactions are the basis of the enzyme functionality. 

Extrapolating from well-characterized enzymatic inhibition in test tubes, numerous mechanistic ideas concerning the in vivo effects of vanadium compounds have been advanced. The effects of vanadium compounds as transition-state analogs of certain enzymes with a phosphoprotein intermediate in their reaction scheme is proposed to account for the action of vanadium [11] in many biological systems. Unfortunately, it is often difficult to determine if the inhibition observed in the test tube occurs in vivo. For example, although vanadate is a potent inhibitor of plasma membrane ion pumps (such as the sodium potassium ATPase) in the test tube, it is difficult to determine if these pumps are actually inhibited in animals exposed to vanadium compounds. Currently, the role of vanadium compounds as protein phosphatase (PTP) inhibitors is believed to be related to the metabolic effects of this... 

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