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Oxidation state changes and electron flow in enzymatic catalysis and electrocatalysis through Wannier-function
Patrick H-L Sit1, Federico Zipoli, Jia Chen
1Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA. hsit@princeton.edu
Chemistry (Weinheim an Der Bergstrasse, Germany)
|September 10, 2011
Summary
A new method using optimally localized orbitals (OLOs) accurately determines oxidation states and electron flow in metalloenzyme catalysis. This approach aids in understanding complex redox reactions in enzymes like superoxide reductase (SOR) and electrocatalysts.
Area of Science:
- Inorganic Chemistry
- Biochemistry
- Computational Chemistry
Background:
- Transition-metal atoms are central to redox reactions in metalloenzymes and electrocatalysts.
- Understanding oxidation state changes is crucial for elucidating catalytic mechanisms.
Purpose of the Study:
- Introduce a novel, generally applicable local method for determining oxidation states (OSs) and associated electronic changes.
- Analyze the catalytic mechanisms of superoxide reductase (SOR) and a hydrogen-producing electrocatalyst ([FeS(2)]/[FeFe](P)).
Main Methods:
- Utilizing optimally localized orbitals (OLOs) to compute local oxidation states.
- Analyzing electron flow and bonding changes during catalytic cycles.
- Applying the OLO method to specific metalloenzyme and electrocatalyst systems.
Main Results:
- Successfully determined oxidation states of Fe atoms and ligands in SOR and the [FeS(2)]/[FeFe](P) model.
- Quantified changes in bonding and electron flow during substrate reduction.
- Demonstrated the method's utility in analyzing under-coordinated Fe sites.
Conclusions:
- Optimally localized orbitals (OLOs) provide a powerful tool for interpreting redox reaction mechanisms.
- The method facilitates first-principles computation-based analysis of complex catalytic processes.
- This approach enhances the understanding of electron transfer in biological and artificial catalytic systems.
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