Note to users. If you're seeing this message, it means that your browser cannot find this page's style/presentation instructions -- or possibly that you are using a browser that does not support current Web standards. Find out more about why this message is appearing, and what you can do to make your experience of our site the best it can be.

Science 6 September 2002:
Vol. 297. no. 5587, pp. 1696 - 1700
DOI: 10.1126/science.1073877
Prev | Table of Contents | Next

Reports

Nitrogenase MoFe-Protein at 1.16 Å Resolution: A Central Ligand in the FeMo-Cofactor

Oliver Einsle,12 F. Akif Tezcan,2 Susana L. A. Andrade,12 Benedikt Schmid,2 Mika Yoshida,12 James B. Howard,3 Douglas C. Rees12*

A high-resolution crystallographic analysis of the nitrogenase MoFe-protein reveals a previously unrecognized ligand coordinated to six iron atoms in the center of the catalytically essential FeMo-cofactor. The electron density for this ligand is masked in structures with resolutions lower than 1.55 angstroms, owing to Fourier series termination ripples from the surrounding iron and sulfur atoms in the cofactor. The central atom completes an approximate tetrahedral coordination for the six iron atoms, instead of the trigonal coordination proposed on the basis of lower resolution structures. The crystallographic refinement at 1.16 angstrom resolution is consistent with this newly detected component being a light element, most plausibly nitrogen. The presence of a nitrogen atom in the cofactor would have important implications for the mechanism of dinitrogen reduction by nitrogenase.

1 Howard Hughes Medical Institute,
2 Division of Chemistry and Chemical Engineering, California Institute of Technology, Mail Code 147-75CH, Pasadena, CA 91125, USA.
3 Department of Biochemistry, University of Minnesota, Minneapolis, MN 55455, USA.
*   To whom correspondence should be addressed. E-mail: dcrees{at}caltech.edu

Read the Full Text


THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Stepwise formation of P-cluster in nitrogenase MoFe protein.
C. C. Lee, M. A. Blank, A. W. Fay, J. M. Yoshizawa, Y. Hu, K. O. Hodgson, B. Hedman, and M. W. Ribbe (2009)
PNAS 106, 18474-18478
   Abstract »    Full Text »    PDF »
Catalytic activities of NifEN: Implications for nitrogenase evolution and mechanism.
Y. Hu, J. M. Yoshizawa, A. W. Fay, C. C. Lee, J. A. Wiig, and M. W. Ribbe (2009)
PNAS 106, 16962-16966
   Abstract »    Full Text »    PDF »
Unique features of the nitrogenase VFe protein from Azotobacter vinelandii.
C. C. Lee, Y. Hu, and M. W. Ribbe (2009)
PNAS 106, 9209-9214
   Abstract »    Full Text »    PDF »
A newly discovered role for iron-sulfur clusters.
P. C. Dos Santos and D. R. Dean (2008)
PNAS 105, 11589-11590
   Full Text »    PDF »
From the Cover: Metal trafficking for nitrogen fixation: NifQ donates molybdenum to NifEN/NifH for the biosynthesis of the nitrogenase FeMo-cofactor.
J. A. Hernandez, L. Curatti, C. P. Aznar, Z. Perova, R. D. Britt, and L. M. Rubio (2008)
PNAS 105, 11679-11684
   Abstract »    Full Text »    PDF »
Evolutionary Persistence of the Molybdopyranopterin-Containing Sulfite Oxidase Protein Fold.
G. J. Workun, K. Moquin, R. A. Rothery, and J. H. Weiner (2008)
Microbiol. Mol. Biol. Rev. 72, 228-248
   Abstract »    Full Text »    PDF »
Evidence for nifU and nifS Participation in the Biosynthesis of the Iron-Molybdenum Cofactor of Nitrogenase.
D. Zhao, L. Curatti, and L. M. Rubio (2007)
J. Biol. Chem. 282, 37016-37025
   Abstract »    Full Text »    PDF »
In vitro synthesis of the iron molybdenum cofactor of nitrogenase from iron, sulfur, molybdenum, and homocitrate using purified proteins.
L. Curatti, J. A. Hernandez, R. Y. Igarashi, B. Soboh, D. Zhao, and L. M. Rubio (2007)
PNAS 104, 17626-17631
   Abstract »    Full Text »    PDF »
Expression and Association of Group IV Nitrogenase NifD and NifH Homologs in the Non-Nitrogen-Fixing Archaeon Methanocaldococcus jannaschii.
C. R. Staples, S. Lahiri, J. Raymond, L. Von Herbulis, B. Mukhophadhyay, and R. E. Blankenship (2007)
J. Bacteriol. 189, 7392-7398
   Abstract »    Full Text »    PDF »
Dinitrogen Dissociation on an Isolated Surface Tantalum Atom.
P. Avenier, M. Taoufik, A. Lesage, X. Solans-Monfort, A. Baudouin, A. de Mallmann, L. Veyre, J.-M. Basset, O. Eisenstein, L. Emsley, et al. (2007)
Science 317, 1056-1060
   Abstract »    Full Text »    PDF »
P-cluster maturation on nitrogenase MoFe protein.
Y. Hu, A. W. Fay, C. C. Lee, and M. W. Ribbe (2007)
PNAS 104, 10424-10429
   Abstract »    Full Text »    PDF »
Structure of the non-redox-active tungsten/[4Fe:4S] enzyme acetylene hydratase.
G. B. Seiffert, G. M. Ullmann, A. Messerschmidt, B. Schink, P. M. H. Kroneck, and O. Einsle (2007)
PNAS 104, 3073-3077
   Abstract »    Full Text »    PDF »
Purification of a NifEN Protein Complex That Contains Bound Molybdenum and a FeMo-Co Precursor from an Azotobacter vinelandii {Delta}nifHDK Strain.
B. Soboh, R. Y. Igarashi, J. A. Hernandez, and L. M. Rubio (2006)
J. Biol. Chem. 281, 36701-36709
   Abstract »    Full Text »    PDF »
Nitrogen Fixation Special Feature: Inner-sphere two-electron reduction leads to cleavage and functionalization of coordinated dinitrogen.
L. P. Spencer, B. A. MacKay, B. O. Patrick, and M. D. Fryzuk (2006)
PNAS 103, 17094-17098
   Abstract »    Full Text »    PDF »
From the Cover: Nitrogen Fixation Special Feature: FeMo cofactor maturation on NifEN.
Y. Hu, M. C. Corbett, A. W. Fay, J. A. Webber, K. O. Hodgson, B. Hedman, and M. W. Ribbe (2006)
PNAS 103, 17119-17124
   Abstract »    Full Text »    PDF »
From the Cover: Nitrogen Fixation Special Feature: Nitrogenase Fe protein: A molybdate/homocitrate insertase.
Y. Hu, M. C. Corbett, A. W. Fay, J. A. Webber, K. O. Hodgson, B. Hedman, and M. W. Ribbe (2006)
PNAS 103, 17125-17130
   Abstract »    Full Text »    PDF »
Nitrogen Fixation Special Feature: Catalytic reduction of dinitrogen to ammonia at a single molybdenum center.
W. W. Weare, X. Dai, M. J. Byrnes, J. M. Chin, R. R. Schrock, and P. Muller (2006)
PNAS 103, 17099-17106
   Abstract »    Full Text »    PDF »
Nitrogen Fixation Special Feature: A methyldiazene (HNNCH3)-derived species bound to the nitrogenase active-site FeMo cofactor: Implications for mechanism.
B. M. Barney, D. Lukoyanov, T.-C. Yang, D. R. Dean, B. M. Hoffman, and L. C. Seefeldt (2006)
PNAS 103, 17113-17118
   Abstract »    Full Text »    PDF »
Nitrogen Fixation Special Feature: How many metals does it take to fix N2? A mechanistic overview of biological nitrogen fixation.
J. B. Howard and D. C. Rees (2006)
PNAS 103, 17088-17093
   Abstract »    Full Text »    PDF »
Molecular Insights into Nitrogenase FeMoco Insertion: TRP-444 OF MoFe PROTEIN {alpha}-SUBUNIT LOCKS FeMoco IN ITS BINDING SITE.
Y. Hu, A. W. Fay, B. Schmid, B. Makar, and M. W. Ribbe (2006)
J. Biol. Chem. 281, 30534-30541
   Abstract »    Full Text »    PDF »
From the Cover: NifB-dependent in vitro synthesis of the iron-molybdenum cofactor of nitrogenase.
L. Curatti, P. W. Ludden, and L. M. Rubio (2006)
PNAS 103, 5297-5301
   Abstract »    Full Text »    PDF »
Structural insights into a protein-bound iron-molybdenum cofactor precursor.
M. C. Corbett, Y. Hu, A. W. Fay, M. W. Ribbe, B. Hedman, and K. O. Hodgson (2006)
PNAS 103, 1238-1243
   Abstract »    Full Text »    PDF »
The onset and early evolution of life.
M. J. Russell and A. J. Hall (2006)
Geological Society of America Memoirs 198, 1-32
   Abstract »    Full Text »    PDF »
Nitrogenase reactivity with P-cluster variants.
Y. Hu, M. C. Corbett, A. W. Fay, J. A. Webber, B. Hedman, K. O. Hodgson, and M. W. Ribbe (2005)
PNAS 102, 13825-13830
   Abstract »    Full Text »    PDF »
100th Anniversary Special Paper: * > On Hydrothermal Convection Systems and the Emergence of Life.
M. J. Russell, A. J. Hall, A. J. Boyce, and A. E. Fallick (2005)
Economic Geology 100, 419-438
   Abstract »    Full Text »    PDF »
Catalytic reduction of dinitrogen to ammonia at well-defined single metal sites.
R. R Schrock (2005)
Phil Trans R Soc A 363, 959-969
   Abstract »    Full Text »    PDF »
Structural basis of biological nitrogen fixation.
D. C Rees, F Akif Tezcan, C. A Haynes, M. Y Walton, S. Andrade, O. Einsle, and J. B Howard (2005)
Phil Trans R Soc A 363, 971-984
   Abstract »    Full Text »    PDF »
Identification of a nitrogenase FeMo cofactor precursor on NifEN complex.
Y. Hu, A. W. Fay, and M. W. Ribbe (2005)
PNAS 102, 3236-3241
   Abstract »    Full Text »    PDF »
Maturation of Nitrogenase: a Biochemical Puzzle.
L. M. Rubio and P. W. Ludden (2005)
J. Bacteriol. 187, 405-414
   Full Text »    PDF »
Characterization of Azotobacter vinelandii nifZ Deletion Strains: INDICATION OF STEPWISE MoFe PROTEIN ASSEMBLY.
Y. Hu, A. W. Fay, P. C. Dos Santos, F. Naderi, and M. W. Ribbe (2004)
J. Biol. Chem. 279, 54963-54971
   Abstract »    Full Text »    PDF »
Substrate Interaction at an Iron-Sulfur Face of the FeMo-cofactor during Nitrogenase Catalysis.
B. M. Barney, R. Y. Igarashi, P. C. Dos Santos, D. R. Dean, and L. C. Seefeldt (2004)
J. Biol. Chem. 279, 53621-53624
   Abstract »    Full Text »    PDF »
Localization of a Catalytic Intermediate Bound to the FeMo-cofactor of Nitrogenase.
R. Y. Igarashi, P. C. Dos Santos, W. G. Niehaus, I. G. Dance, D. R. Dean, and L. C. Seefeldt (2004)
J. Biol. Chem. 279, 34770-34775
   Abstract »    Full Text »    PDF »
Comparison of Iron-Molybdenum Cofactor-deficient Nitrogenase MoFe Proteins by X-ray Absorption Spectroscopy: IMPLICATIONS FOR P-CLUSTER BIOSYNTHESIS.
M. C. Corbett, Y. Hu, F. Naderi, M. W. Ribbe, B. Hedman, and K. O. Hodgson (2004)
J. Biol. Chem. 279, 28276-28282
   Abstract »    Full Text »    PDF »
Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center.
D. V. Yandulov and R. R. Schrock (2003)
Science 301, 76-78
   Abstract »    Full Text »    PDF »
The Interface Between the Biological and Inorganic Worlds: Iron-Sulfur Metalloclusters.
D. C. Rees and J. B. Howard (2003)
Science 300, 929-931
   Abstract »    Full Text »    PDF »
Bioinorganic Chemistry Special Feature: Biological inorganic chemistry at the beginning of the 21st century.
H. B. Gray (2003)
PNAS 100, 3563-3568
   Abstract »    Full Text »    PDF »
Bioinorganic Chemistry Special Feature: Speculative synthetic chemistry and the nitrogenase problem.
S. C. Lee and R. H. Holm (2003)
PNAS 100, 3595-3600
   Abstract »    Full Text »    PDF »


To Advertise     Find Products

Science. ISSN 0036-8075 (print), 1095-9203 (online)