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  Structure–Spectroscopy Correlations for Intermediate Q of Soluble Methane Monooxygenase: Insights from QM/MM Calculations

Schulz, C. E., Castillo, R. G., Pantazis, D. A., DeBeer, S., & Neese, F. (2021). Structure–Spectroscopy Correlations for Intermediate Q of Soluble Methane Monooxygenase: Insights from QM/MM Calculations. Journal of the American Chemical Society, 143(17), 6560-6577. doi:10.1021/jacs.1c01180.

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 Urheber:
Schulz, Christine E.1, Autor           
Castillo, Rebeca G.2, Autor
Pantazis, Dimitrios A.1, Autor           
DeBeer, Serena2, Autor           
Neese, Frank3, Autor           
Affiliations:
1Research Group Pantazis, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541711              
2Research Department DeBeer, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023871              
3Research Department Neese, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_2541710              

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 Zusammenfassung: The determination of the diiron core intermediate structures involved in the catalytic cycle of soluble methane monooxygenase (sMMO), the enzyme that selectively catalyzes the conversion of methane to methanol, has been a subject of intense interest within the bioinorganic scientific community. Particularly, the specific geometry and electronic structure of the intermediate that precedes methane binding, known as intermediate Q (or MMOHQ), has been debated for over 30 years. Some reported studies support a bis-μ-oxo-bridged Fe(IV)2O2 closed-core conformation Fe(IV)2O2 core, whereas others favor an open-core geometry, with a longer Fe–Fe distance. The lack of consensus calls for a thorough re-examination and reinterpretation of the spectroscopic data available on the MMOHQ intermediate. Herein, we report extensive simulations based on a hybrid quantum mechanics/molecular mechanics approach (QM/MM) approach that takes into account the complete enzyme to explore possible conformations for intermediates MMOHox and MMOHQ of the sMMOH catalytic cycle. High-level quantum chemical approaches are used to correlate specific structural motifs with geometric parameters for comparison with crystallographic and EXAFS data, as well as with spectroscopic data from Mössbauer spectroscopy, Fe K-edge high-energy resolution X-ray absorption spectroscopy (HERFD XAS), and resonance Raman 16O–18O difference spectroscopy. The results provide strong support for an open-core-type configuration in MMOHQ, with the most likely topology involving mono-oxo-bridged Fe ions and alternate terminal Fe-oxo and Fe-hydroxo groups that interact via intramolecular hydrogen bonding. The implications of an open-core intermediate Q on the reaction mechanism of sMMO are discussed.

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Sprache(n): eng - English
 Datum: 2021-01-312021-04-222021-05-05
 Publikationsstatus: Erschienen
 Seiten: 18
 Ort, Verlag, Ausgabe: -
 Inhaltsverzeichnis: -
 Art der Begutachtung: Expertenbegutachtung
 Identifikatoren: DOI: 10.1021/jacs.1c01180
 Art des Abschluß: -

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Titel: Journal of the American Chemical Society
  Andere : JACS
  Kurztitel : J. Am. Chem. Soc.
Genre der Quelle: Zeitschrift
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Ort, Verlag, Ausgabe: Washington, DC : American Chemical Society
Seiten: - Band / Heft: 143 (17) Artikelnummer: - Start- / Endseite: 6560 - 6577 Identifikator: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870