Related Experiment Video
Updated: May 1, 2026

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Reversible [4Fe-3S] cluster morphing in an O(2)-tolerant [NiFe] hydrogenase
Stefan Frielingsdorf1, Johannes Fritsch2, Andrea Schmidt3
11] Institut für Biologie-Mikrobiologie, Humboldt-Universität zu Berlin, Berlin, Germany. [2] Institut für Chemie, Sekr. PC14, Technische Universität Berlin, Berlin, Germany.
Certain [NiFe] hydrogenases resist oxygen damage, allowing hydrogen utilization in aerobic environments. This resilience stems from a unique [4Fe-3S] cluster that undergoes redox-dependent transformations, facilitating electron transfer.
Area of Science:
- Biochemistry
- Bioenergetics
- Enzyme mechanisms
Background:
- Hydrogenases are crucial enzymes for H(2) metabolism.
- Most hydrogenases are oxygen-sensitive, limiting their application.
- Some [NiFe] hydrogenases exhibit remarkable oxygen tolerance.
Purpose of the Study:
- Investigate the mechanism of oxygen tolerance in membrane-bound [NiFe] hydrogenases.
- Characterize the role of the unique [4Fe-3S] cluster in oxygen tolerance.
- Elucidate the redox-dependent transformations of the [4Fe-3S] cluster.
Main Methods:
- Multidisciplinary approach combining biochemical and biophysical techniques.
- Spectroscopic analysis of the [4Fe-3S] cluster.
- Structural and functional characterization of the enzyme.
Main Results:
- The [4Fe-3S] cluster undergoes redox-dependent iron swapping.
- An oxygen ligand reversibly binds to an iron atom in the cluster.
- This oxygen binding is linked to a conserved histidine residue essential for H(2) oxidation.
- Transformations resemble those of nitrogenase P-cluster.
Conclusions:
- The unique [4Fe-3S] cluster is key to oxygen tolerance in [NiFe] hydrogenases.
- Redox-dependent cluster transformations facilitate electron transfer and oxygen resistance.
- The findings provide insights into enzyme adaptation for aerobic H(2) utilization.
More Related Videos
11:27Single-Molecule Förster Resonance Energy Transfer Methods for Real-Time Investigation of the Holliday Junction Resolution by GEN1
Published on: September 18, 2019
05:51Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
Published on: July 19, 2019
Related Concept Videos
[3,3] Sigmatropic Rearrangement of 1,5-Dienes: Cope Rearrangement
Thermal Sigmatropic Reactions: Overview
Sigmatropic shifts are classified based on an order term [i, j ], where i and j indicate the number of atoms across which each end of the σ bond migrates. Below are examples of a [3,3] sigmatropic shift in...
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration