Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid

Brown, K. A.; Harris, D. F.; Wilker, M. B.; Rasmussen, A.; Khadka, N.; Hamby, H.; Keable, S.; Dukovic, G.; Peters, J. W.; Seefeldt, L. C.; King, P. W.

doi:10.1126/science.aaf2091

Title: Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid

Journal Article · Thu Apr 21 00:00:00 EDT 2016 · Science

DOI:https://doi.org/10.1126/science.aaf2091· OSTI ID:1249160

Brown, K. A.; Harris, D. F.; Wilker, M. B.; Rasmussen, A.; Khadka, N.; Hamby, H.; Keable, S.; Dukovic, G.; Peters, J. W.; Seefeldt, L. C.; King, P. W.

The splitting of dinitrogen (N2) and reduction to ammonia (NH3) is a kinetically complex and energetically challenging multistep reaction. In the Haber-Bosch process, N2 reduction is accomplished at high temperature and pressure, whereas N2 fixation by the enzyme nitrogenase occurs under ambient conditions using chemical energy from adenosine 5'-triphosphate (ATP) hydrolysis. We show that cadmium sulfide (CdS) nanocrystals can be used to photosensitize the nitrogenase molybdenum-iron (MoFe) protein, where light harvesting replaces ATP hydrolysis to drive the enzymatic reduction of N2 into NH3. The turnover rate was 75 per minute, 63% of the ATP-coupled reaction rate for the nitrogenase complex under optimal conditions. Inhibitors of nitrogenase (i.e., acetylene, carbon monoxide, and dihydrogen) suppressed N2 reduction. The CdS:MoFe protein biohybrids provide a photochemical model for achieving light-driven N2 reduction to NH3.

Cite

Export

Save

Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Biological Electron Transfer and Catalysis (BETCy)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC36-08GO28308; SC0012518

OSTI ID:: 1249160

Report Number(s):: NREL/JA-2700-65820

Journal Information:: Science, Vol. 352, Issue 6284; Related Information: Science; ISSN 0036-8075

Publisher:: AAAS

Country of Publication:: United States

Language:: English

References (26)

Reactions at Surfaces: From Atoms to Complexity (Nobel Lecture) Ertl, Gerhard Angewandte Chemie International Edition, Vol. 47, Issue 19 https://doi.org/10.1002/anie.200800480	journal	April 2008
Artificial Photosynthesis for Sustainable Fuel and Chemical Production Kim, Dohyung; Sakimoto, Kelsey K.; Hong, Dachao Angewandte Chemie International Edition, Vol. 54, Issue 11 https://doi.org/10.1002/anie.201409116	journal	January 2015
Synthesis of ammonia directly from air and water at ambient temperature and pressure Lan, Rong; Irvine, John T. S.; Tao, Shanwen Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep01145	journal	January 2013
Mechanism of Nitrogen Fixation by Nitrogenase: The Next Stage Hoffman, Brian M.; Lukoyanov, Dmitriy; Yang, Zhi-Yong Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr400641x	journal	January 2014
Nitrogenase and nitrogenase reductase associate and dissociate with each catalytic cycle. Hageman, R. V.; Burris, R. H. Proceedings of the National Academy of Sciences, Vol. 75, Issue 6 https://doi.org/10.1073/pnas.75.6.2699	journal	June 1978
Is Mo Involved in Hydride Binding by the Four-Electron Reduced (E ₄ ) Intermediate of the Nitrogenase MoFe Protein? Lukoyanov, Dmitriy; Yang, Zhi-Yong; Dean, Dennis R. Journal of the American Chemical Society, Vol. 132, Issue 8 https://doi.org/10.1021/ja910613m	journal	March 2010
Identification of a Key Catalytic Intermediate Demonstrates That Nitrogenase Is Activated by the Reversible Exchange of N ₂ for H ₂ Lukoyanov, Dmitriy; Yang, Zhi-Yong; Khadka, Nimesh Journal of the American Chemical Society, Vol. 137, Issue 10 https://doi.org/10.1021/jacs.5b00103	journal	March 2015
Uncoupling Nitrogenase: Catalytic Reduction of Hydrazine to Ammonia by a MoFe Protein in the Absence of Fe Protein-ATP Danyal, Karamatullah; Inglet, Boyd S.; Vincent, Kylie A. Journal of the American Chemical Society, Vol. 132, Issue 38 https://doi.org/10.1021/ja1067178	journal	September 2010
Fe Protein-Independent Substrate Reduction by Nitrogenase MoFe Protein Variants Danyal, Karamatullah; Rasmussen, Andrew J.; Keable, Stephen M. Biochemistry, Vol. 54, Issue 15 https://doi.org/10.1021/acs.biochem.5b00140	journal	April 2015
ATP- and Iron−Protein-Independent Activation of Nitrogenase Catalysis by Light Roth, Lauren E.; Nguyen, Joey C.; Tezcan, F. Akif Journal of the American Chemical Society, Vol. 132, Issue 39 https://doi.org/10.1021/ja1071866	journal	October 2010
ATP-Uncoupled, Six-Electron Photoreduction of Hydrogen Cyanide to Methane by the Molybdenum–Iron Protein Roth, Lauren E.; Tezcan, F. Akif Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja303265m	journal	May 2012
Semiconductor Clusters, Nanocrystals, and Quantum Dots Alivisatos, A. P. Science, Vol. 271, Issue 5251, p. 933-937 https://doi.org/10.1126/science.271.5251.933	journal	February 1996
Controlled Assembly of Hydrogenase-CdTe Nanocrystal Hybrids for Solar Hydrogen Production Brown, Katherine A.; Dayal, Smita; Ai, Xin Journal of the American Chemical Society, Vol. 132, Issue 28 https://doi.org/10.1021/ja101031r	journal	July 2010
Characterization of Photochemical Processes for H ₂ Production by CdS Nanorod–[FeFe] Hydrogenase Complexes Brown, Katherine A.; Wilker, Molly B.; Boehm, Marko Journal of the American Chemical Society, Vol. 134, Issue 12 https://doi.org/10.1021/ja2116348	journal	March 2012
Electronic wave functions in semiconductor clusters: experiment and theory Brus, Louis The Journal of Physical Chemistry, Vol. 90, Issue 12, p. 2555-2560 https://doi.org/10.1021/j100403a003	journal	June 1986
Charge Transfer Dynamics between Photoexcited CdS Nanorods and Mononuclear Ru Water-Oxidation Catalysts Tseng, Huan-Wei; Wilker, Molly B.; Damrauer, Niels H. Journal of the American Chemical Society, Vol. 135, Issue 9 https://doi.org/10.1021/ja400178g	journal	February 2013
Changes in the Midpoint Potentials of the Nitrogenase Metal Centers as a Result of Iron Protein−Molybdenum-Iron Protein Complex Formation ^† Lanzilotta, William N.; Seefeldt, Lance C. Biochemistry, Vol. 36, Issue 42 https://doi.org/10.1021/bi9715371	journal	October 1997
Acetylene reduction by nitrogen-fixing preparations from Clostridium pasteurianum Dilworth, M. J. Biochimica et Biophysica Acta (BBA) - General Subjects, Vol. 127, Issue 2 https://doi.org/10.1016/0304-4165(66)90383-7	journal	October 1966
Acetylene as a competitive inhibitor of N-2 fixation. Schollhorn, R.; Burris, R. H. Proceedings of the National Academy of Sciences, Vol. 58, Issue 1 https://doi.org/10.1073/pnas.58.1.213	journal	July 1967
Nitrogenase Winter, H. C.; Burris, R. H. Annual Review of Biochemistry, Vol. 45, Issue 1 https://doi.org/10.1146/annurev.bi.45.070176.002205	journal	June 1976
Oxidation of Good’s buffers by hydrogen peroxide Zhao, Guanghua; Chasteen, N. Dennis Analytical Biochemistry, Vol. 349, Issue 2 https://doi.org/10.1016/j.ab.2005.10.005	journal	February 2006
Synthesis and Micrometer-Scale Assembly of Colloidal CdSe/CdS Nanorods Prepared by a Seeded Growth Approach Carbone, Luigi; Nobile, Concetta; De Giorgi, Milena Nano Letters, Vol. 7, Issue 10 https://doi.org/10.1021/nl0717661	journal	October 2007
Experimental Determination of the Extinction Coefficient of CdTe, CdSe, and CdS Nanocrystals Yu, W. William; Qu, Lianhua; Guo, Wenzhuo Chemistry of Materials, Vol. 15, Issue 14, p. 2854-2860 https://doi.org/10.1021/cm034081k	journal	July 2003
One-Pot Synthesis of Highly Luminescent CdSe/CdS Core−Shell Nanocrystals via Organometallic and “Greener” Chemical Approaches ^† Mekis, Ivo; Talapin, Dmitri V.; Kornowski, Andreas The Journal of Physical Chemistry B, Vol. 107, Issue 30 https://doi.org/10.1021/jp0278364	journal	July 2003
Photocatalytic Hydrogen Production with Tunable Nanorod Heterostructures Amirav, Lilac; Alivisatos, A. Paul The Journal of Physical Chemistry Letters, Vol. 1, Issue 7 https://doi.org/10.1021/jz100075c	journal	March 2010
Catalytic and Biophysical Properties of a Nitrogenase Apo-MoFe Protein Produced by a n ifB -Deletion Mutant of Azotobacter v inelandii ^† Christiansen, Jason; Goodwin, Paul J.; Lanzilotta, William N. Biochemistry, Vol. 37, Issue 36 https://doi.org/10.1021/bi981165b	journal	September 1998

Similar Records

Hole-scavenging in photo-driven N₂ reduction catalyzed by a CdS-nitrogenase MoFe protein biohybrid system

Journal Article · Tue Jan 09 00:00:00 EST 2024 · Journal of Inorganic Biochemistry · OSTI ID:1249160

Clinger, Andrew; Yang, Zhi-Yong; Pellows, Lauren M.; +5 more

Mechanism of Nitrogenase H ₂ Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

Journal Article · Fri Sep 15 00:00:00 EDT 2017 · Journal of the American Chemical Society · OSTI ID:1249160

Khadka, Nimesh; Milton, Ross D.; Shaw, Sudipta; +6 more

Energy Transduction in Nitrogenase

Journal Article · Tue Sep 18 00:00:00 EDT 2018 · Accounts of Chemical Research · OSTI ID:1249160

Seefeldt, Lance C.; Hoffman, Brian; Peters, John W.; +4 more

Related Subjects

09 BIOMASS FUELS
37 INORGANIC, ORGANIC, PHYSICAL, AND ANAYLYTICAL CHEMISTRY
CdS nanorod:MoFe protein complex
photocatalyze
reduction of N2 into NH3

Title: Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid

Citation Formats

References (26)

Similar Records

Related Subjects