Sandbox Reserved 496: Difference between revisions

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'''β subunit reactions'''
'''β subunit reactions'''


C-cluster (CODH activity): CO2 + 2H<sup>+</sup> + 2e-  ↔  CO + H2O
C-cluster (CODH activity): CO2 + 2H<sup>+</sup> + 2e<sup>-</sup> ↔  CO + H2O


B- and D-clusters: electron transfer
B- and D-clusters: electron transfer
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'''α subunit reactions'''
'''α subunit reactions'''


A-cluster (ACS activity): CH3-Co(III)-CFeSP + CO + HSCoA  ↔  CH3-CO-SCoA +  Co(I)-CFeSP + H+
A-cluster (ACS activity): CH3-Co(III)-CFeSP + CO + HSCoA  ↔  CH3-CO-SCoA +  Co(I)-CFeSP + H<sup>+</sup>




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[[Image:C_cluster.JPG|frame|Proposed mechanism for CODH activity in the C-cluster. <ref name="CN"/>]]
[[Image:C_cluster.JPG|frame|Proposed mechanism for CODH activity in the C-cluster. <ref name="CN"/>]]


In the proposed catalytic action of the C-cluster, CO first binds the Ni ion followed by deprotonation of the Fe-bound water to yield a reactive hydroxide which promotes nucleophilic attack of CO by the hydroxide.  Next, the Ni-COOH intermediate is deprotonated to Ni-COO- which allows release of CO2 as the C-cluster is reduced to a new redox state.  Then, electrons are shuttled between the B- and D-clusters to reoxidize the C-cluster to its original redox state <ref name="CN"/>.  This catalytic cycle is of course operated in reverse to reduce CO2 to CO and allow subsequent production of acetyl-CoA .
In the proposed catalytic action of the C-cluster, CO first binds the Ni ion followed by deprotonation of the Fe-bound water to yield a reactive hydroxide which promotes nucleophilic attack of CO by the hydroxide.  Next, the Ni-COOH intermediate is deprotonated to Ni-COO<sup>-</sup> which allows release of CO2 as the C-cluster is reduced to a new redox state.  Then, electrons are shuttled between the B- and D-clusters to reoxidize the C-cluster to its original redox state <ref name="CN"/>.  This catalytic cycle is of course operated in reverse to reduce CO2 to CO and allow subsequent production of acetyl-CoA .


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