Light-Driven Hydrogen Evolution by Nickel-Substituted Rubredoxin.
Michael J StevensonSean C MarguetCamille R SchneiderHannah S ShafaatPublished in: ChemSusChem (2017)
An enzymatic system for light-driven hydrogen generation has been developed through covalent attachment of a ruthenium chromophore to nickel-substituted rubredoxin (NiRd). The photoinduced activity of the hybrid enzyme is significantly greater than that of a two-component system and is strongly dependent on the position of the ruthenium phototrigger relative to the active site, indicating a role for intramolecular electron transfer in catalysis. Steady-state and time-resolved emission spectra reveal a pathway for rapid, direct quenching of the ruthenium excited state by nickel, but low overall turnover numbers suggest initial electron transfer is not the rate-limiting step. This approach is ideally suited for detailed mechanistic investigations of catalysis by NiRd and other molecular systems, with implications for generation of solar fuels.
Keyphrases
- electron transfer
- reduced graphene oxide
- oxide nanoparticles
- molecular docking
- carbon nanotubes
- metal organic framework
- visible light
- energy transfer
- genome wide
- hydrogen peroxide
- gene expression
- gold nanoparticles
- bone mineral density
- single cell
- nitric oxide
- density functional theory
- molecular dynamics simulations
- body composition