Manganese biochemistry

The importance of manganese for bacteria, such as that of Ni and to a lesser extent Co, as we saw in the last chapter, is considerable. Of course, as we will see shortly, it is also important in the tetranuclear Mn cluster that is involved in oxygen production in photosynthetic plants, algae and cyanobacteria, as well as in a number of mammalian enzymes such as arginase and mitochondrial superoxide dismutase. Most of manganese biochemistry can be explained on the one hand by its redox activity, and on the other by its analogy to Mg2+ (reviewed in Yocum and Pecoraro, 1999). 

We begin this overview of manganese biochemistry with a brief account of its role in the detoxification of free radicals, before considering the function of a dinuclear Mn(II) active site in the important eukaryotic urea cycle enzyme arginase. We then pass in review a few microbial Mn-containing enzymes involved in intermediary metabolism, and conclude with the very exciting recent results on the structure and function of the catalytic manganese cluster involved in the photosynthetic oxidation of water. 

The major role of manganese in biology is in oxygen production by photosynthetic plants, algae, and cyanobacteria. It is also involved in a number of mammalian enzymes like arginase and mitochondrial superoxide dismutase and it also plays an important role in microbial metabolism. Most of manganese biochemistry can be... 

M.S. Lah, M.M. Dixon, K.A. Pattridge, W.C. Stallings, J.A. Fee, and M.L. Ludwig, Structure-function in Escherichia coli iron superoxide dismutase comparisons with the manganese enzyme from Thermus thermophilus. Biochemistry. 34, 1646-1660 (1995). 

Bulbring E, T omita T 1969 Effect of calcium, barium and manganese on the action of adrenaline in the smooth muscle of the guinea-pig taenia coli. Proc R Soc Lond B Biol Sci 172 121-136 Marchant JS, Taylor CW 1998 Rapid activation and partial inactivation of inositol trisphosphate receptors by inositol trisphosphate. Biochemistry 37 11524-11533 Somlyo AV, Horiuti K, Trentham DR, Kitazawa T, Somlyo AP 1992 Kinetics of Ca2+ release and contraction induced by photolysis of caged D-myo-inositol 1,4,5-trisphosphate in smooth muscle the effects of heparin, procaine, and adenine nucleotides. J Biol Chem 267 22316-22322... 

Weiss, R. Gold, A. Trautwein, A. X. Terner, J. High-valent iron and manganese complexes of porphyrins and related macrocycles, The Porphyrin Handbook. Volume 4. Biochemistry and Binding Activation of Small Molecules , Eds. Kadish, . M. Smith, . M. Guilard, R. Academic Press San Diego, 2000, pp. 65-96. 

Lin, Y. Nageswara Rao, B.D. Structural characterization of adenine nucleotides bound to Escherichia coli adenylate kinase. 2. P and C Relaxation measurements in the presence of cobalt(II) and manganese(ll). Biochemistry, 39, 3647-3655 (2000)... 

Keen CL, Lonnerdal B, Hurley LS (1984) Manganese. In Frieden E (ed) Biochemistry of the Essential Ultratrace Elements. Plenum, New York p 89-132... 

Heavy metals. The most common heavy-metal pollutants are arsenic, cadmium, chromium, copper, nickel, lead, and mercury. Some metals, such as manganese, iron, copper, and zinc, are essential micronutrients. Each type of heavy metal in its own way affects water ecosystem biochemistry and can accumulate in bottom deposits and in the biomass of living elements. 

Sundaramoorthy M, Youngs HL, Gold MH et al (2005) High-resolution crystal structure of manganese peroxidase substrate and inhibitor complexes. Biochemistry 44 6463-6470... 

Ruiz-Duenas FJ, Morales M, Perez-Boada M et al (2007) Manganese oxidation site in Pleurotus eryngii versatile peroxidase A site-directed mutagenesis, kinetic and crystallographic study. Biochemistry 46 66-77... 

Reading NS, Aust SD (2001) Role of disulfide bonds in the stability of recombinant manganese peroxidase. Biochemistry 40 8161-8168... 

Youngs HL, Gelpke MDS, Li DM et al (2001) The role of Glu39 in Mn-II binding and oxidation by manganese peroxidase from Phanerochaete chrysosporium. Biochemistry 40 2243-2250... 

Wariishi H, Akileswaran L, Gold MH (1988) Manganese peroxidase from the basidiomycete Phanerochaete chrysosporium spectral characterization of the oxidized states and the catalytic cycle. Biochemistry 27 5365-5370... 

Stich TA, Yeagle GJ, Service RF, Debus RJ, Britt RD. Ligation of Dl-His332 and Dl-Aspl70 to the manganese cluster of photosystem II from Synechocystis assessed by multifrequency pulse EPR spectroscopy. Biochemistry. 2011 50(34) 7390-404. 

Hou, J.-M., Boichenko, V.A., Diner, B.A., Mauzerall, D. (2001) Thermodynamics of electron transfer in oxygenic photosynthetic reaction centers Volume change, enthalpy, and entropy of electron transfer reactions in manganese-depleted photosystem II core complexes, Biochemistry 40(24), 7117-7125. 

Meinike, C., Sole, A., Pospisil, P., Dau, H. (2000) does the structure of the water-oxidizing Photosystem II-Manganese complex at room temperature differ from its low-temperature structure A comparative X-ray absorption study, Biochemistry 39, (24)... 

M2. MacMillan-Crow, L. A., Crow, J. P., and Thompson, J. A., Peroxynitrite-mediated inactivation of manganese superoxide dismutase involves nitration and oxidation of critical tyrosine residues. Biochemistry 37, 1613-1622 (1998). 

Watanabe, T., Katayama, S., Enoki, M., Honda, Y. Kuwahara, M. (2000). Formation of acyl radical in lipid peroxidation of linoleic acid by manganese-dependent peroxidase from Ceriporiopsis subvermispora and Bjerkandera adusta. European Journal of Biochemistry, 267, 4222-31. 

Sutherland, G. R. J., and Aust, S. D., 1997, Thermodynamics of binding of the distal calcium to manganese peroxidase, Biochemistry 36 8567n8573. 

Wilcox, S. K., Putnam, C. D., Sastry, M., Blankenship, J., Chazin, W. J., McRee, D. E., and Goodin, D. B., 1998, Rational design of a functional metalloenzyme introduction of a site for manganese binding and oxidation into a heme peroxidase, Biochemistry 37 16853nl6862. 

Jiang W, Hoffart LM, Krebs C, Bollinger JM Jr. A man-ganese(IV)/iron(IV) intermediate in assembly of the manganese (IV)/Iron(in) cofactor of chlamydia trachomatis rihonucleotide reductase. Biochemistry 2007 46 8709-8716. 

Y. Hsieh, Y. Guan, C. Tu, P.J. Bratt, A. Angerhofer, J.R. Lepock, M.J. Hickey, J.A. Tainer, H.S. Nick, and D.N. Silverman. 1998. Probing the active site of human manganese superoxide dismutase The role of glutamine 143 Biochemistry 37 4731-4739. (PubMed)... 

Perhaps the most important area of biochemistry in which ESR is used is the study of metalloproteins. Transition metals in certain oxidation and spin states have unpaired electrons, are paramagnetic, and in many cases are amenable to ESR spectroscopy. The most commonly found transition metals in biological systems are iron, copper, molybdenum, cobalt, and manganese. The remainder, including metals such as vanadium and... 

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