Comparative electronic structures of nitrogenase FeMoco and FeVco
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...
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Royal Society of Chemistry (RSC)
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Online Access: | https://hdl.handle.net/20.500.11815/520 https://doi.org/10.1039/C7DT00128B |
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ftopinvisindi:oai:opinvisindi.is:20.500.11815/520 2024-09-15T18:14:35+00:00 Comparative electronic structures of nitrogenase FeMoco and FeVco Rees, Julian A. Bjornsson, Ragnar Kowalska, Joanna K. Lima, Frederico A. Schlesier, Julia Sippel, Daniel Weyhermüller, Thomas Einsle, Oliver Kovacs, Julie A. DeBeer, Serena Raunvísindastofnun (HÍ) Science Institute (UI) Raunvísindadeild (HÍ) Faculty of Physical Sciences (UI) Verkfræði- og náttúruvísindasvið (HÍ) School of Engineering and Natural Sciences (UI) Háskóli Íslands University of Iceland 2017 2445-2455 https://hdl.handle.net/20.500.11815/520 https://doi.org/10.1039/C7DT00128B en eng Royal Society of Chemistry (RSC) "info:eu-repo/grantAgreement/EC/FP7/615414" Dalton Transactions;46(8) http://pubs.rsc.org/en/content/articlepdf/2017/DT/C7DT00128B 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 https://hdl.handle.net/20.500.11815/520 Dalton Transactions doi:10.1039/C7DT00128B info:eu-repo/semantics/openAccess Inorganic Chemistry Ólífræn efnafræði Spectroscopy Litrófsgreining Efnasambönd info:eu-repo/semantics/article 2017 ftopinvisindi https://doi.org/20.500.11815/52010.1039/C7DT00128B 2024-07-09T03:01:56Z 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. 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 ... Article in Journal/Newspaper Iceland Opin vísindi (Iceland) Dalton Transactions 46 8 2445 2455 |
institution |
Open Polar |
collection |
Opin vísindi (Iceland) |
op_collection_id |
ftopinvisindi |
language |
English |
topic |
Inorganic Chemistry Ólífræn efnafræði Spectroscopy Litrófsgreining Efnasambönd |
spellingShingle |
Inorganic Chemistry Ólífræn efnafræði Spectroscopy Litrófsgreining Efnasambönd Rees, Julian A. Bjornsson, Ragnar Kowalska, Joanna K. Lima, Frederico A. Schlesier, Julia Sippel, Daniel Weyhermüller, Thomas Einsle, Oliver Kovacs, Julie A. DeBeer, Serena Comparative electronic structures of nitrogenase FeMoco and FeVco |
topic_facet |
Inorganic Chemistry Ólífræn efnafræði Spectroscopy Litrófsgreining Efnasambönd |
description |
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. 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 ... |
author2 |
Raunvísindastofnun (HÍ) Science Institute (UI) Raunvísindadeild (HÍ) Faculty of Physical Sciences (UI) Verkfræði- og náttúruvísindasvið (HÍ) School of Engineering and Natural Sciences (UI) Háskóli Íslands University of Iceland |
format |
Article in Journal/Newspaper |
author |
Rees, Julian A. Bjornsson, Ragnar Kowalska, Joanna K. Lima, Frederico A. Schlesier, Julia Sippel, Daniel Weyhermüller, Thomas Einsle, Oliver Kovacs, Julie A. DeBeer, Serena |
author_facet |
Rees, Julian A. Bjornsson, Ragnar Kowalska, Joanna K. Lima, Frederico A. Schlesier, Julia Sippel, Daniel Weyhermüller, Thomas Einsle, Oliver Kovacs, Julie A. DeBeer, Serena |
author_sort |
Rees, Julian A. |
title |
Comparative electronic structures of nitrogenase FeMoco and FeVco |
title_short |
Comparative electronic structures of nitrogenase FeMoco and FeVco |
title_full |
Comparative electronic structures of nitrogenase FeMoco and FeVco |
title_fullStr |
Comparative electronic structures of nitrogenase FeMoco and FeVco |
title_full_unstemmed |
Comparative electronic structures of nitrogenase FeMoco and FeVco |
title_sort |
comparative electronic structures of nitrogenase femoco and fevco |
publisher |
Royal Society of Chemistry (RSC) |
publishDate |
2017 |
url |
https://hdl.handle.net/20.500.11815/520 https://doi.org/10.1039/C7DT00128B |
genre |
Iceland |
genre_facet |
Iceland |
op_relation |
"info:eu-repo/grantAgreement/EC/FP7/615414" Dalton Transactions;46(8) http://pubs.rsc.org/en/content/articlepdf/2017/DT/C7DT00128B 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 https://hdl.handle.net/20.500.11815/520 Dalton Transactions doi:10.1039/C7DT00128B |
op_rights |
info:eu-repo/semantics/openAccess |
op_doi |
https://doi.org/20.500.11815/52010.1039/C7DT00128B |
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Dalton Transactions |
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46 |
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8 |
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2445 |
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2455 |
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1810452355207921664 |