Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 24, Pages 9744-9750Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202002647
Keywords
enzymes; EPR spectroscopy; molybdenum; reaction mechanisms; reduction
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Funding
- JSPS [18H02070]
- RIKEN, Japan
- [NRF-2017M3D1A1039380]
- Grants-in-Aid for Scientific Research [18H02070] Funding Source: KAKEN
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Nitrate is a pervasive aquatic contaminant of global environmental concern. In nature, the most effective nitrate reduction reaction (NRR) is catalyzed by nitrate reductase enzymes at neutral pH, using a highly-conserved Mo center ligated mainly by oxo and thiolate groups. Mo-based NRR catalysts mostly function in organic solvents with a low water stability. Recently, an oxo-containing molybdenum sulfide nanoparticle that serves as an NRR catalyst at neutral pH was first reported. Herein, in a nanoparticle-catalyzed NRR system a pentavalent Mo-V(=O)S-4 species, an enzyme mimetic, served as an active intermediate for the NRR. Potentiometric titration analysis revealed that a redox synergy among Mo-V-S, S radicals, and Mo-V(=O)S-4 likely play a key role in stabilizing Mo-V(=O)S-4, showing the importance of secondary interactions in facilitating NRR. The first identification and characterization of an oxo- and thiolate-ligated Mo intermediates pave the way to the molecular design of efficient enzyme mimetic NRR catalysts in aqueous solution.
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