Parahydrogen-enhanced magnetic resonance identification of intermediates in [Fe]-hydrogenase catalysis
Abstract Hydrogenases are widespread metalloenzymes used for the activation and production of molecular hydrogen. Understanding the catalytic mechanism of hydrogenases can help to establish industrial (bio)catalytic hydrogen production and conversion. Here we show the observation of so-far undetectable intermediates of [Fe]-hydrogenase in its catalytic cycle. We observed these intermediates by applying a signal-enhancing NMR technique based on parahydrogen. Molecular hydrogen occurs as orthohydrogen or parahydrogen, depending on its nuclear spin state. We found that catalytic conversion of parahydrogen by the [Fe]-hydrogenase leads to notably enhanced NMR signals (parahydrogen-induced polarization, PHIP). The observed signals encode information about how the [Fe]-hydrogenase binds hydrogen during catalysis. Our data support models of the catalytic mechanism that involve the formation of a hydride at the iron centre. Moreover, PHIP enabled studying the binding kinetics. This work demonstrates the hitherto unexploited power of PHIP to study catalytic mechanisms of hydrogenases.
Authors
- Seigo Shima (ORCID: https://orcid.org/0000-0003-1872-8705)
- Alexander A. Auer (ORCID: https://orcid.org/0000-0001-6012-3027)
- Gangfeng Huang (ORCID: https://orcid.org/0000-0002-4115-284X)
- Andrey N. Pravdivtsev (ORCID: https://orcid.org/0000-0002-8763-617X)
- Christian Griesinger (ORCID: https://orcid.org/0000-0002-1266-4344)
- Stefan Glöggler (ORCID: https://orcid.org/0000-0003-3354-6141)
- Jan‐Bernd Hövener (ORCID: https://orcid.org/0000-0001-7255-7252)
- Frank Neese (ORCID: https://orcid.org/0000-0003-4691-0547)
- Christoph Riplinger (ORCID: https://orcid.org/0000-0002-0166-6272)
- Georgi L. Stoychev (ORCID: https://orcid.org/0000-0002-3408-5749)
- Lukas Kaltschnee (ORCID: https://orcid.org/0000-0002-3530-8000)
- Manuel Gehl (ORCID: https://orcid.org/0000-0001-5846-9539)
- Maximilian Keitel
Institutions
- Christian-Albrechts-Universität zu Kiel (DE)
- Max-Planck-Institut für Kohlenforschung (DE)
- Clinical Research Center Kiel (DE)
- Max Planck Institute for Terrestrial Microbiology (DE)
- Max Planck Institute for Multidisciplinary Sciences (DE)
Publication Details
- Journal
- Nature Catalysis
- Published
- 2024-12-13
- DOI
- https://doi.org/10.1038/s41929-024-01262-w
- Citations
- 11
- Primary Topic
- Metalloenzymes and iron-sulfur proteins
- Type
- article
- Field-Weighted Citation Impact
- 1.13
Funders
- Deutsche Forschungsgemeinschaft
- Bundesministerium für Bildung und Forschung
- Max-Planck-Gesellschaft
- European Regional Development Fund