Iron-molybdenum cofactor composition

Nelson, M. J., Levy, M. A., and Orme-Johnson, W. H. (1983). Metal and sulphur composition of iron-molybdenum cofactor of nitrogenase. Proc. Natl. Acad. Sci. USA 80 147-50. 

Nitrogenase, which catalyzes the reduction of N2 to two molecules of NH3, has a different molybdenum -iron cofactor (FeMo-co). It can be obtained by acid denaturation of the very oxygen-labile iron-molybdenum protein of nitrogenase followed by extraction with d i methyl formamide.655,656 The coenzyme is a complex Fe-S-Mo cluster also containing homocitrate with a composition MoFe7S9-homocitrate (see Fig. 24-3). Nitrogenase and this coenzyme are considered further in Chapter 24. 

One type of the constituent metallocenters in the MoFe protein has the properties of a somewhat independent structural entity. This component, referred to as the FeMo cofactor (FeMo-co), was first identified by Shah and Brill (1977) as the stable metallocluster extracted from acid-denatured MoFe protein. The FeMo-co was able to fully activate a defective protein in the extracts of mutant strain UW45, a protein which subsequently was shown to contain the P clusters but not the EPR-active center. The isolated cofactor accounted for the total S = t system observed by EPR and Mdssbauer spectroscopies of the holo-MoFe protein (Rawlings et al., 1978). Elemental analysis indicated a composition of Mo Fee-8 Se-g for the cofactor, which, if there are two FeMo-co s per a2 2> accounts for all the molybdenum and approximately half the iron in active enzyme (Nelson etai, 1983). Although FeMo-co has been extensively studied [reviewed in Burgess (1990)] the structure remains enigmatic. To date, all attempts to crystallize the cofactor have failed. This is possibly due to the instability and resultant heterogeneity of the cofactor when removed from the protein. Also, there is a paucity of appropriate models for spectral comparison (see Coucouvanis, 1991, for a recent discussion). Final resolution of this elusive structure may require its determination as a component of the holoprotein. 

Some elements are essential to the composition or function of the body. Since the body is mostly water, hydrogen and oxygen are obviously essential elements. Carbon (C) is a component of all life molecules, including proteins, lipids, and carbohydrates. Nitrogen (N) is in all proteins. The other essential nonmetals are phosphorus (P), sulfur (S), chlorine (Cl), selenium (Se), fluorine (F), and iodine (I). The latter two are among the essential trace elements that are required in only small quantities, particularly as constituents of enzymes or as cofactors (nonprotein species essential for enzyme function). The metals present in macro amounts in the body are sodium (Na), potassium (K), and calcium (Ca). Essential trace elements are chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), copper (Cu), zinc (Zn), magnesium (Mg), molybdenum (Mo), nickel (Ni), and perhaps more elements that have not yet been established as essential. 

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