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Reactivity, Mechanism, and Assembly of the Alternative Nitrogenases

Journal Article · · Chemical Reviews

Biological nitrogen fixation is catalyzed by the enzyme nitrogenase, which facilitates the cleavage of the relatively inert triple bond of N2. Nitrogenase is most commonly associated with the molybdenum–iron cofactor called FeMoco or the M-cluster, and it has been the subject of extensive structural and spectroscopic characterization over the past 60 years. In the late 1980s and early 1990s, two “alternative nitrogenase” systems were discovered, isolated, and found to incorporate V or Fe in place of Mo. These systems are regulated by separate gene clusters; however, there is a high degree of structural and functional similarity between each nitrogenase. Limited studies with the V- and Fe-nitrogenases initially demonstrated that these enzymes were analogously active as the Mo-nitrogenase, but more recent investigations have found capabilities that are unique to the alternative systems. In this review, we will discuss the reactivity, biosynthetic, and mechanistic proposals for the alternative nitrogenases as well as their electronic and structural properties in comparison to the well-characterized Mo-dependent system. Studies over the past 10 years have been particularly fruitful, though key aspects about V- and Fe-nitrogenases remain unexplored.

Research Organization:
Univ. of California, Irvine, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0014470; SC0016510
OSTI ID:
1802675
Journal Information:
Chemical Reviews, Journal Name: Chemical Reviews Journal Issue: 12 Vol. 120; ISSN 0009-2665
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Structural insights into a protein-bound iron-molybdenum cofactor precursor journal January 2006
A methyldiazene (HNNCH3)-derived species bound to the nitrogenase active-site FeMo cofactor: Implications for mechanism journal November 2006
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Connecting nitrogenase intermediates with the kinetic scheme for N2 reduction by a relaxation protocol and identification of the N2 binding state journal January 2007
Unique features of the nitrogenase VFe protein from Azotobacter vinelandii journal May 2009
NifEN-B complex of Azotobacter vinelandii is fully functional in nitrogenase FeMo cofactor assembly journal May 2011
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Comparative Biochemical Characterization of the Iron-Only Nitrogenase and the Molybdenum Nitrogenase from Rhodobacter Capsulatus journal March 1997
A late methanogen origin for molybdenum-dependent nitrogenase: A late methanogen origin for Mo-nitrogenase journal April 2011
Biological nitrogen fixation by alternative nitrogenases in boreal cyanolichens: importance of molybdenum availability and implications for current biological nitrogen fixation estimates journal September 2016
Proterozoic Ocean Chemistry and Evolution: A Bioinorganic Bridge? journal August 2002
Structure of a Cofactor-Deficient Nitrogenase MoFe Protein journal April 2002
Nitrogenase MoFe-Protein at 1.16 A Resolution: A Central Ligand in the FeMo-Cofactor journal September 2002
Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center journal July 2003
Nitrogenase Complexes: Multiple Docking Sites for a Nucleotide Switch Protein journal August 2005
Vanadium Nitrogenase Reduces CO journal August 2010
Structure of Precursor-Bound NifEN: A Nitrogenase FeMo Cofactor Maturase/Insertase journal January 2011
Structural Basis for Methyl Transfer by a Radical SAM Enzyme journal April 2011
X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase Iron-Molybdenum Cofactor journal November 2011
Extending the Carbon Chain: Hydrocarbon Formation Catalyzed by Vanadium/Molybdenum Nitrogenases journal August 2011
N2 Reduction and Hydrogenation to Ammonia by a Molecular Iron-Potassium Complex journal November 2011
Evidence for Interstitial Carbon in Nitrogenase FeMo Cofactor journal November 2011
Radical SAM-Dependent Carbon Insertion into the Nitrogenase M-Cluster journal September 2012
A Radical Route for Nitrogenase Carbide Insertion journal September 2012
Ligand binding to the FeMo-cofactor: Structures of CO-bound and reactivated nitrogenase journal September 2014
Crystallographic structure of the nitrogenase iron protein from Azotobacter vinelandii journal September 1992
Structural models for the metal centers in the nitrogenase molybdenum-iron protein journal September 1992
A nitrogen pressure of 50 atmospheres does not prevent evolution of hydrogen by nitrogenase journal June 1984
The nitrogenase FeMo-cofactor and P-cluster pair: 2.2 A resolution structures journal May 1993
A bound reaction intermediate sheds light on the mechanism of nitrogenase journal March 2018
Characterization of Diazotrophs Containing Mo-Independent Nitrogenases, Isolated from Diverse Natural Environments journal March 2008
Culture-Independent Characterization of a Gene Responsible for Nitrogen Fixation in the Symbiotic Microbial Community in the Gut of the Termite Neotermes koshunensis journal November 1999
Transcriptional Profiling of Nitrogen Fixation in Azotobacter vinelandii journal July 2011
Interactions among substrates and inhibitors of nitrogenase. journal January 1975
Purification of a second alternative nitrogenase from a nifHDK deletion strain of Azotobacter vinelandii. journal January 1988
Nucleotide sequence and mutational analysis of the structural genes (anfHDGK) for the second alternative nitrogenase from Azotobacter vinelandii. journal February 1989
Construction and characterization of an Azotobacter vinelandii strain with mutations in the genes encoding flavodoxin and ferredoxin I. journal June 1989
Identification of an alternative nitrogenase system in Rhodospirillum rubrum. journal September 1991
Nucleotide sequence and mutational analysis of the vnfENX region of Azotobacter vinelandii journal December 1991
The nifY product of Klebsiella pneumoniae is associated with apodinitrogenase and dissociates upon activation with the iron-molybdenum cofactor. journal January 1993
Purification and characterization of the alternative nitrogenase from the photosynthetic bacterium Rhodospirillum rubrum journal March 1996
Functional Genomic Analysis of Three Nitrogenase Isozymes in the Photosynthetic Bacterium Rhodopseudomonas palustris journal November 2005
Insights into Hydrocarbon Formation by Nitrogenase Cofactor Homologs journal April 2015
Characterization of an M-Cluster-Substituted Nitrogenase VFe Protein journal March 2018
Biosynthesis of the Metalloclusters of Nitrogenases journal June 2016
Mechanism of Mo-Dependent Nitrogenase journal June 2009
Distribution of nitrogen fixation and nitrogenase-like sequences amongst microbial genomes journal January 2012
Genome-wide transcriptome profiling of nitrogen fixation in Paenibacillus sp. WLY78 journal March 2016
Bacterial Alternative Nitrogen Fixation Systems journal January 1988
An Alternative Path for the Evolution of Biological Nitrogen Fixation journal January 2011
New insights into the evolutionary history of biological nitrogen fixation journal January 2013
Diversity and Activity of Alternative Nitrogenases in Sequenced Genomes and Coastal Environments journal February 2017
The Fe Protein: An Unsung Hero of Nitrogenase journal February 2018
Regulation of Three Nitrogenase Gene Clusters in the Cyanobacterium Anabaena variabilis ATCC 29413 journal December 2014
Catalysis-dependent selenium incorporation and migration in the nitrogenase active site iron-molybdenum cofactor journal December 2015

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