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) |