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Comparative electronic structures of nitrogenase FeMoco and FeVco

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dc.contributor Háskóli Íslands
dc.contributor University of Iceland
dc.contributor.author Rees, Julian A.
dc.contributor.author Bjornsson, Ragnar
dc.contributor.author Kowalska, Joanna K.
dc.contributor.author Lima, Frederico A.
dc.contributor.author Schlesier, Julia
dc.contributor.author Sippel, Daniel
dc.contributor.author Weyhermüller, Thomas
dc.contributor.author Einsle, Oliver
dc.contributor.author Kovacs, Julie A.
dc.contributor.author DeBeer, Serena
dc.date.accessioned 2018-01-10T13:07:13Z
dc.date.available 2018-01-10T13:07:13Z
dc.date.issued 2017
dc.identifier.citation Rees, J. A., Bjornsson, R., Kowalska, J. K., Lima, F. A., Schlesier, J., Sippel, D., . . . DeBeer, S. (2017). Comparative electronic structures of nitrogenase FeMoco and FeVco. Dalton Transactions, 46(8), 2445-2455. doi:10.1039/C7DT00128B
dc.identifier.uri https://hdl.handle.net/20.500.11815/520
dc.description.abstract An investigation of the active site cofactors of the molybdenum and vanadium nitrogenases (FeMoco and FeVco) was performed using high-resolution X-ray spectroscopy. Synthetic heterometallic iron–sulfur cluster models and density functional theory calculations complement the study of the MoFe and VFe holoproteins using both non-resonant and resonant X-ray emission spectroscopy. Spectroscopic data show the presence of direct iron–heterometal bonds, which are found to be weaker in FeVco. Furthermore, the interstitial carbide is found to perturb the electronic structures of the cofactors through highly covalent Fe–C bonding. The implications of these conclusions are discussed in light of the differential reactivity of the molybdenum and vanadium nitrogenases towards various substrates. Possible functional roles for both the heterometal and the interstitial carbide are detailed.
dc.description.sponsorship This work was supported by the European Research Council (ERC) under the European Union’s Seventh Framework Programme (FP/2007–2013) ERC Grant Agreement number 615414 (S. D.) and the ERC N-ABLE project (O. E.). Funding was also provided by the Deutsche Forschungsgemeinschaft grants EI-520/7 and RTG1976 (O. E.), the NIH (R01-GM45881 to J. A. K.), and by the Max-Planck–Gesellschaft (S. D., R. B., J. K. K., and F. A. L.). J. A. R. was funded by a graduate study scholarship from the German Academic Exchange Service (DAAD). R. B. acknowledges support from the Icelandic Research Fund, Grant No. 141218051 and the University of Iceland Research Fund. Matthias Gschell and Florian Schneider are thanked for preparing the extracted FeMoco, and Tabea Hamann is thanked for providing samples of the molybdenum cubane. Stefan Hugenbruch, Benjamin Van Kuiken, Rebeca Gómez Castillo, and Anselm Hahn are thanked for assistance with data collection. The ESRF and CHESS are also acknowledged for providing beamtime, and Sara Lafuerza and Pieter Glatzel at beamline ID-26 (ESRF) and Kenneth D. Finkelstein at beamline C-1 (CHESS) are gratefully acknowledged for technical assistance with measurements. CHESS is supported by the National Science Foundation and the National Institutes of Health/National Institute of General Medical Sciences under NSF award DMR-133220. Open Access funding provided by the Max Planck Society.
dc.format.extent 2445-2455
dc.language.iso en
dc.publisher Royal Society of Chemistry (RSC)
dc.relation "info:eu-repo/grantAgreement/EC/FP7/615414"
dc.relation.ispartofseries Dalton Transactions;46(8)
dc.rights info:eu-repo/semantics/openAccess
dc.subject Inorganic Chemistry
dc.subject Ólífræn efnafræði
dc.subject Spectroscopy
dc.subject Litrófsgreining
dc.subject Efnasambönd
dc.title Comparative electronic structures of nitrogenase FeMoco and FeVco
dc.type info:eu-repo/semantics/article
dcterms.license This article is licensed under a Creative Commons Attribution 3.0 Unported Licence
dc.description.version Peer Reviewed
dc.identifier.journal Dalton Transactions
dc.identifier.doi 10.1039/C7DT00128B
dc.relation.url http://pubs.rsc.org/en/content/articlepdf/2017/DT/C7DT00128B
dc.contributor.department Raunvísindastofnun (HÍ)
dc.contributor.department Science Institute (UI)
dc.contributor.department Raunvísindadeild (HÍ)
dc.contributor.department Faculty of Physical Sciences (UI)
dc.contributor.school Verkfræði- og náttúruvísindasvið (HÍ)
dc.contributor.school School of Engineering and Natural Sciences (UI)

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