The electronic structure of FeV-cofactor in vanadium-dependent nitrogenase.

Chemical Science
Zhi-Yong YangLance C Seefeldt

Abstract

The electronic structure of the active-site metal cofactor (FeV-cofactor) of resting-state V-dependent nitrogenase has been an open question, with earlier studies indicating that it exhibits a broad S = 3/2 EPR signal (Kramers state) having g values of ∼4.3 and 3.8, along with suggestions that it contains metal-ions with valencies [1V3+, 3Fe3+, 4Fe2+]. In the present work, genetic, biochemical, and spectroscopic approaches were combined to reveal that the EPR signals previously assigned to FeV-cofactor do not correlate with active VFe-protein, and thus cannot arise from the resting-state of catalytically relevant FeV-cofactor. It, instead, appears resting-state FeV-cofactor is either diamagnetic, S = 0, or non-Kramers, integer-spin (S = 1, 2 etc.). When VFe-protein is freeze-trapped during high-flux turnover with its natural electron-donating partner Fe protein, conditions which populate reduced states of the FeV-cofactor, a new rhombic S = 1/2 EPR signal from such a reduced state is observed, with g = [2.18, 2.12, 2.09] and showing well-defined 51V (I = 7/2) hyperfine splitting, aiso = 110 MHz. These findings indicate a different assignment for the electronic structure of the resting state of FeV-cofactor: S = 0 (or integer-sp...Continue Reading

References

Sep 1, 1966·Proceedings of the National Academy of Sciences of the United States of America·W A Bulen, J R LeComte
Jan 1, 1993·Annual Review of Nutrition·R H Burris, G P Roberts
Oct 24, 2001·Inorganic Chemistry·Philip L. W. Tregenna-PiggottHans-Ueli Güdel
Nov 7, 1996·Chemical Reviews·Barbara K. Burgess, David J. Lowe
Feb 28, 2002·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·E KrahnA Müller
Mar 20, 2003·Journal of Bacteriology·Carmen Rüttimann-JohnsonPaul W Ludden
Mar 1, 1965·Proceedings of the National Academy of Sciences of the United States of America·W A BULENJ R LECOMTE
Dec 25, 2003·Molecular Biology and Evolution·Jason RaymondRobert E Blankenship
Sep 17, 2005·Proceedings of the National Academy of Sciences of the United States of America·Yilin HuMarkus W Ribbe
Jan 19, 2008·Nature·Nicolas Gruber, James N Galloway
May 30, 2009·Proceedings of the National Academy of Sciences of the United States of America·Chi Chung LeeMarkus W Ribbe
Feb 4, 2010·Journal of the American Chemical Society·Dmitriy LukoyanovBrian M Hoffman
Nov 19, 2011·Science·Thomas SpatzalOliver Einsle
Apr 20, 2013·Biochimica Et Biophysica Acta·Lance C SeefeldtDennis R Dean
Sep 26, 2013·Proceedings of the National Academy of Sciences of the United States of America·Zhi-Yong YangLance C Seefeldt
Jan 29, 2014·Chemical Reviews·Brian M HoffmanLance C Seefeldt
Jan 1, 2015·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Ragnar BjornssonSerena DeBeer
Mar 15, 2016·Nature Communications·Thomas SpatzalOliver Einsle
Dec 9, 2016·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Daniel SippelOliver Einsle
Feb 6, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Julian A ReesSerena DeBeer
Jul 12, 2017·Nature Chemical Biology·Daniel Sippel, Oliver Einsle
Mar 31, 2018·Science·Daniel SippelOliver Einsle
May 5, 2018·The Journal of Biological Chemistry·Emilio Jimenez-VicenteDennis R Dean
Aug 11, 2018·Accounts of Chemical Research·Lance C SeefeldtDennis R Dean
Mar 9, 2019·The Journal of Biological Chemistry·Emilio Jimenez-VicenteDennis R Dean
Jan 25, 2020·Chemical Reviews·Stefan BurénLuis M Rubio
Jan 31, 2020·Chemical Reviews·Hannah L Rutledge, F Akif Tezcan
Mar 5, 2020·Chemical Reviews·Andrew J JasniewskiYilin Hu
Mar 17, 2020·Chemical Reviews·Lance C SeefeldtBrian M Hoffman
Mar 24, 2020·Chembiochem : a European Journal of Chemical Biology·Maame A Addo, Patricia C Dos Santos
Apr 3, 2020·Chemical Reviews·Casey Van StappenSerena DeBeer
Jun 17, 2020·Chemical Reviews·Oliver Einsle, Douglas C Rees
Jul 15, 2020·Annual Review of Microbiology·Caroline S Harwood

❮ Previous
Next ❯

Citations

Oct 14, 2021·Chembiochem : a European Journal of Chemical Biology·Niels N Oehlmann, Johannes G Rebelein

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.