4R0V

[FeFe]-hydrogenase Oxygen Inactivation is Initiated by the Modification and Degradation of the H cluster 2Fe Subcluster

Summary for 4R0V

• Entry DOI: 10.2210/pdb4r0v/pdb
• Related: 3C8Y 3lx4
• Descriptor: Fe-hydrogenase, IRON/SULFUR CLUSTER, CHLORIDE ION, ... (5 entities in total)
• Functional Keywords: hyda1 monomer, fes cluster, h-cluster, [fefe]-hydrogenase, oxidoreductase, cys oxidation, s-hydroxycysteine, cysteine-s-dioxide, [2fe2s] cluster
• Biological source: Chlamydomonas reinhardtii
• Total number of polymer chains: 2
• Total formula weight: 111563.33

Authors

Swanson, S.D.,Ratzloff, M.W.,Mulder, D.W.,Artz, J.H.,Ghose, S.,Hoffman, A.,White, S.,Zadvornyy, O.A.,Broderick, J.B.,Bothner, B.,King, P.W.,Peters, J.W. (deposition date: 2014-08-01, release date: 2015-01-28, Last modification date: 2024-11-20)

Primary citation

Swanson, K.D.,Ratzloff, M.W.,Mulder, D.W.,Artz, J.H.,Ghose, S.,Hoffman, A.,White, S.,Zadvornyy, O.A.,Broderick, J.B.,Bothner, B.,King, P.W.,Peters, J.W.
[FeFe]-Hydrogenase Oxygen Inactivation Is Initiated at the H Cluster 2Fe Subcluster.
J.Am.Chem.Soc., 137:1809-1816, 2015

PubMed Abstract: The [FeFe]-hydrogenase catalytic site H cluster is a complex iron sulfur cofactor that is sensitive to oxygen (O2). The O2 sensitivity is a significant barrier for production of hydrogen as an energy source in water-splitting, oxygenic systems. Oxygen reacts directly with the H cluster, which results in rapid enzyme inactivation and eventual degradation. To investigate the progression of O2-dependent [FeFe]-hydrogenase inactivation and the process of H cluster degradation, the highly O2-sensitive [FeFe]-hydrogenase HydA1 from the green algae Chlamydomonas reinhardtii was exposed to defined concentrations of O2 while monitoring the loss of activity and accompanying changes in H cluster spectroscopic properties. The results indicate that H cluster degradation proceeds through a series of reactions, the extent of which depend on the initial enzyme reduction/oxidation state. The degradation process begins with O2 interacting and reacting with the 2Fe subcluster, leading to degradation of the 2Fe subcluster and leaving an inactive [4Fe-4S] subcluster state. This final inactive degradation product could be reactivated in vitro by incubation with 2Fe subcluster maturation machinery, specifically HydF(EG), which was observed by recovery of enzyme activity.

PubMed: 25579778
DOI: 10.1021/ja510169s

Experimental method

X-RAY DIFFRACTION (2.29 Å)