The present paper describes general principles of redox catalysis and redox regulation in two diverse systems. The first is microbial metabolism of CO by the Wood–Ljungdahl pathway, which involves the conversion of CO or H2/CO2 into acetyl-CoA, which then serves as a source of ATP and cell carbon. The focus is on two enzymes that make and utilize CO, CODH (carbon monoxide dehydrogenase) and ACS (acetyl-CoA synthase). In this pathway, CODH converts CO2 into CO and ACS generates acetyl-CoA in a reaction involving Ni·CO, methyl-Ni and acetyl-Ni as catalytic intermediates. A 70 Å (1 Å=0.1 nm) channel guides CO, generated at the active site of CODH, to a CO ‘cage’ near the ACS active site to sequester this reactive species and assure its rapid availability to participate in a kinetically coupled reaction with an unstable Ni(I) state that was recently trapped by photolytic, rapid kinetic and spectroscopic studies. The present paper also describes studies of two haem-regulated systems that involve a principle of metabolic regulation interlinking redox, haem and CO. Recent studies with HO2 (haem oxygenase-2), a K+ ion channel (the BK channel) and a nuclear receptor (Rev-Erb) demonstrate that this mode of regulation involves a thiol–disulfide redox switch that regulates haem binding and that gas signalling molecules (CO and NO) modulate the effect of haem.
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Conference Article|
May 22 2012
Redox, haem and CO in enzymatic catalysis and regulation
Stephen W. Ragsdale;
Stephen W. Ragsdale
1
*Department of Biological Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A.
1To whom correspondence should be addressed (emailsragsdal@umich.edu).
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Li Yi;
Li Yi
*Department of Biological Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A.
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Güneş Bender;
Güneş Bender
*Department of Biological Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A.
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Nirupama Gupta;
Nirupama Gupta
*Department of Biological Chemistry, University of Michigan, Ann Arbor, MI 48109, U.S.A.
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Yan Kung;
Yan Kung
†Departments of Chemistry and Biology, Massachusetts Institute of Technology, 16-573A, 77 Massachusetts Avenue, Cambridge, MA 02139, U.S.A.
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Lifen Yan;
Lifen Yan
‡Department of Chemistry, University of California, Davis, Davis, CA 95616, U.S.A.
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Troy A. Stich;
Troy A. Stich
‡Department of Chemistry, University of California, Davis, Davis, CA 95616, U.S.A.
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Tzanko Doukov;
Tzanko Doukov
§Stanford Synchrotron Radiation Lightsource, Menlo Park, CA 94025, U.S.A.
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Lars Leichert;
Lars Leichert
∥Department of Molecular, Cellular, and Developmental Biology, University of Michigan, Ann Arbor, MI 48109, U.S.A.
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Paul M. Jenkins;
Paul M. Jenkins
¶Department of Pharmacology, University of Michigan, Ann Arbor, MI 48109, U.S.A.
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Christopher M. Bianchetti;
Christopher M. Bianchetti
**Department of Biochemistry, University of Wisconsin-Madison, Madison, WI 53706, U.S.A.
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Simon J. George;
Simon J. George
‡Department of Chemistry, University of California, Davis, Davis, CA 95616, U.S.A.
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Stephen P. Cramer;
Stephen P. Cramer
‡Department of Chemistry, University of California, Davis, Davis, CA 95616, U.S.A.
††Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, U.S.A.
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R. David Britt;
R. David Britt
‡Department of Chemistry, University of California, Davis, Davis, CA 95616, U.S.A.
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Ursula Jakob;
Ursula Jakob
∥Department of Molecular, Cellular, and Developmental Biology, University of Michigan, Ann Arbor, MI 48109, U.S.A.
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Jeffrey R. Martens;
Jeffrey R. Martens
¶Department of Pharmacology, University of Michigan, Ann Arbor, MI 48109, U.S.A.
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George N. Phillips, Jr;
George N. Phillips, Jr
**Department of Biochemistry, University of Wisconsin-Madison, Madison, WI 53706, U.S.A.
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Catherine L. Drennan
Catherine L. Drennan
†Departments of Chemistry and Biology, Massachusetts Institute of Technology, 16-573A, 77 Massachusetts Avenue, Cambridge, MA 02139, U.S.A.
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Publisher: Portland Press Ltd
Received:
March 15 2012
Online ISSN: 1470-8752
Print ISSN: 0300-5127
© The Authors Journal compilation © 2012 Biochemical Society
2012
Biochem Soc Trans (2012) 40 (3): 501–507.
Article history
Received:
March 15 2012
Citation
Stephen W. Ragsdale, Li Yi, Güneş Bender, Nirupama Gupta, Yan Kung, Lifen Yan, Troy A. Stich, Tzanko Doukov, Lars Leichert, Paul M. Jenkins, Christopher M. Bianchetti, Simon J. George, Stephen P. Cramer, R. David Britt, Ursula Jakob, Jeffrey R. Martens, George N. Phillips, Catherine L. Drennan; Redox, haem and CO in enzymatic catalysis and regulation. Biochem Soc Trans 1 June 2012; 40 (3): 501–507. doi: https://doi.org/10.1042/BST20120083
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