Encyclopedia of Metalloproteins

2013 Edition
| Editors: Robert H. Kretsinger, Vladimir N. Uversky, Eugene A. Permyakov

Cobalt-containing Enzymes

Reference work entry
DOI: https://doi.org/10.1007/978-1-4614-1533-6_71

Synonyms

Introduction

Among the metals of the first transition series,  cobalt (Co) is next to iron (Fe) and exhibits three oxidation states (+1, +2, and +3) much like its congener iron (+2, +3, and +4). However, unlike iron, it is present in a relatively small number of enzymes and cofactors (Kobayashi and Shimizu 1999). In addition, it does not participate in oxygen activation, a process that iron frequently takes part in. In the +3 oxidation state,  cobalt enjoys high crystal field stabilization energy (CFSE) in several coordination geometries. Significantly, high stability arises when Co3+ exists in spin-paired (low-spin) electronic configuration within an octahedral coordination environment of strong ligands. Such stability often makes the Co3+center resistant to substitution processes such as exchange of a bound water molecule for the substrate. Such a center however can serve as a...

This is a preview of subscription content, log in to check access.

References

  1. Arakawa T, Kawano Y et al (2006) Structure of thiocyanate hydrolase: a new nitrile hydratase family protein with a novel five-coordinate cobalt(III) center. J Mol Biol 366:1497–1509CrossRefPubMedGoogle Scholar
  2. Arakawa T, Kawano Y et al (2009) Structural basis for catalytic activation of thiocyanate hydrolase involving metal-ligated cysteine modification. J Am Chem Soc 131:14838–14843CrossRefPubMedGoogle Scholar
  3. Banerjee R (2003) Radical carbon skeleton rearrangements: catalysis by coenzyme B12-dependent mutases. Chem Rev 103:2083–1094CrossRefPubMedGoogle Scholar
  4. Banerjee R, Ragsdale S (2003) The many faces of vitamin B12 catalysis by cobalamin-dependent enzymes. Annu Rev Biochem 72:209–247CrossRefPubMedGoogle Scholar
  5. Harrop T, Mascharak P (2004) Fe(III) and Co(III) centers with carboxamido nitrogen and modified sulfur coordination: lessons learned from nitrile hydratase. Acc Chem Res 37:253–260CrossRefPubMedGoogle Scholar
  6. Kobayashi M, Shimizu S (1998) Metalloenzyme nitrile hydratase: structure, regulation, and application to biotechnology. Nat Biotechnol 16:733–736CrossRefPubMedGoogle Scholar
  7. Kobayashi M, Shimizu S (1999) Cobalt proteins. Eur J Biochem 261:1–9CrossRefPubMedGoogle Scholar
  8. Ludwig M, Mathews R (1997) Structure-based perspectives on B12-dependent enzymes. Annu Rev Biochem 66:269–313CrossRefPubMedGoogle Scholar
  9. Mascharak P (2002) Structural and functional models of nitrile hydratase. Coord Chem Rev 225:201–214CrossRefGoogle Scholar
  10. Mathews R (2001) Cobalamin-dependent methytransferases. Acc Chem Res 34:681–689CrossRefGoogle Scholar
  11. Miyanaga A, Fushinobu S et al (2001) Crystal structure of cobalt-containing nitrile hydratase. Biochem Biophys Res Commun 288:1169–1174CrossRefPubMedGoogle Scholar
  12. Nordlund P, Reichard P (2006) Ribonucleotide reductase. Ann Rev Biochem 75:681–706CrossRefPubMedGoogle Scholar
  13. Shibata N, Tamagaki H et al (2010) Crystal structure of ethanolamine ammonia-lyase complexes with coenzyme B12 analogs and substrates. J Biol Chem 285:26484–26493CrossRefPubMedGoogle Scholar
  14. Sintchak M, Arjara G, Kellogg B, Stubbe J, Drennan C (2002) The crystal structure of class II ribonucleotide reductase reveals how an allosterically regulated monomer mimics a dimer. Nat Struct Biol 9:293–300CrossRefPubMedGoogle Scholar
  15. Stubbe J, van der Donk W (1998) Protein radicals in enzyme catalysis. Chem Rev 98:705–762CrossRefPubMedGoogle Scholar
  16. Thomä N, Evans P et al (2000) Protection of radical intermediates at the active site of adenosylcobalamin-dependent methylmalonyl-CoA mutase. Biochemistry 39:9213–9221CrossRefPubMedGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2013

Authors and Affiliations

  1. 1.Department of ChemistryUniversity of GeorgiaAthensUSA
  2. 2.Department of Chemistry and BiochemistryUniversity of CaliforniaSanta CruzUSA