Oxidation–Reduction Reactions

Oxidation–reduction reactions in nature are usually catalysed by enzymes classified broadly as oxidoreductases. These enhance the rate of electron transfer from an oxidizable substrate, typically a hydrogen donor, to a reducible acceptor.

Keywords: oxidoreductases; dehydrogenases; reductases; oxidases; oxygenases; peroxidases; haem systems; catalases; pyridine nucleotides; flavins

Figure 1. Stereospecific hydride ion transfer to/from the nicotinamide moiety in NAD(P)-dependent oxidoreductases.
Figure 2. Biological redox states of flavocoenzymes with pKa values for interconversions of free species.
Figure 3. Catalytic mechanism of a typical NADPH-dependent flavoprotein disulfide reductase with the intermediacy of a flavin C(4a)-thio adduct.
Figure 4. Principal redox participants in the flow of electrons from metabolism of substrates to mitochondrial oxidative phosphorylation.
Scheme 1.
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 References
    book Creighton DJ and Murthy NSRK (1990) "Stereochemistry of enzyme-catalyzed reactions at carbon". In: Sigman DS and Boyer PD (eds) The Enzymes, vol. XIX, Mechanisms of Catalysis, pp. 323–421. New York: Academic Press.
    book Decker K (1991) "Covalent flavoproteins". In: Müller F (ed) Chemistry and Biochemistry of Flavoenzymes, vol. II, pp. 343–375. Boca Raton, FL: CRC Press.
    book Dolphin D, Poulson R and Avamovic O (eds) (1987) Pyridine Nucleotide Coenzymes, parts A and B. New York: Wiley-Interscience.
    Ghisla S and Massey V (1989) Mechanisms of flavoprotein-catalyzed reactions. European Journal of Biochemistry 181: 1–17.
    book IUBMB (1992) Enzyme Nomenclature. San Diego: Academic Press.
    Janes SM, Mu D, Wemmer D et al. (1990) A new redox cofactor in eukaryotic enzymes: 6-hydroxydopa at the active site of bovine serum amine oxidase. Science 248: 981–987.
    Kemal C, Chan TW and Bruice TC (1977) Reaction of 3O2 with dihydroflavins. I. N3,5-Dimethyl-1,5-dihydrolumiflavin and 1,5-dihydroisoalloxazines. Journal of the American Chemical Society 99: 7272–7286.
    book Lehninger AL, Nelson DL and Cox MM (1993) Principles of Biochemistry, chap. 18, pp. 542–594. New York: Worth Publishers.
    Lesk AM (1995) NAD-binding domains of dehydrogenases. Current Opinion in Structural Biology 5(6): 775–783.
    Massey V (1994) Activation of molecular oxygen by flavins and flavoproteins. Journal of Biological Chemistry 269: 22459–22462.
    book McCormick DB (1996) "Coenzymes, biochemistry of". In: Meyers RA (ed.) Encyclopedia of Molecular Biology and Molecular Medicine, pp. 396–406. New York: VCH Publishers.
    Scrutton NS (1994) Alpha/beta barrel evolution and the molecular assembly of enzymes: emerging trends in the flavin oxidase/dehydrogenase family. Bioessays 16(2): 115–122.
    book Segel GH (1975) Biochemical Calculations, 2nd edn, pp. 414–415. New York: Wiley.
    book Stankovich MT (1991) "Redox properties of flavins and flavoproteins". In: Müller F (ed.) Chemistry and Biochemistry of Flavoenzymes, vol. I, pp. 401–425. Boca Raton, FL: CRC Press.
    book Stevenson KJ, Massey V and Williams CH Jr (eds) (1996) Flavins and Flavoproteins 1996. Calgary: University of Calgary Press.
    Trumpower BL and Gennis RB (1994) Energy transduction by cytochrome complexes in mitochondrial and bacterial respiration: the enzymology of coupling electron transfer reactions to transmembrane proton translocation. Annual Reviews of Biochemistry 63: 675–716.
    Tsukihara T, Asyama H, Yamashita E et al. (1996) The whole structure of the 13-subunit oxidized cytochrome c oxidase at 2.8 Å. Science 272(5265): 1136–1144.
    book Walsh C (1979) Enzymatic Reaction Mechanisms, pp. 349–521. San Francisco: WH Freeman.
 Further Reading
    book Creighton DJ and Murthy NSRK (1990) "Stereochemistry of enzyme-catalyzed reactions at carbon". In: Sigman DS and Boyer PD (eds) The Enzymes, vol. XIX, Mechanisms of Catalysis, pp. 323–421. New York: Academic Press.
    book Dolphin D, Poulson R and Avamovic O (eds) (1987) Pyridine Nucleotide Coenzymes, parts A and B. New York: Wiley-Interscience.
    book Lehninger AL, Nelson DL and Cox MM (1993) Principles of Biochemistry, chap. 18, pp. 542–594. New York: Worth Publishers.
    book McCormick DB (1996) "Coenzymes, biochemistry of". In: Meyers RA (ed.) Encyclopedia of Molecular Biology and Molecular Medicine, pp. 396–406. New York: VCH Publishers.
    book Müller F (ed.) (1991) Chemistry and Biochemistry of Flavoenzymes, vols I and II. Boca Raton, FL: CRC Press.
    book Walsh C (1979) Enzymatic Reaction Mechanisms, pp. 349–521. San Francisco: WH Freeman.
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McCormick, Donald B(May 2003) Oxidation–Reduction Reactions. In: eLS. John Wiley & Sons Ltd, Chichester. http://www.els.net [doi: 10.1038/npg.els.0000610]