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

Katherine A. Brown; Derek F. Harris; Molly B. Wilker; Andrew Rasmussen; Nimesh Khadka; Hayden Hamby; Stephen Keable; Gordana Dukovic; John W. Peters; Lance C. Seefeldt; Paul W. King

doi:10.1126/science.aaf2091

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

Katherine A. Brown
, Derek F. Harris
, Molly B. Wilker
, Andrew Rasmussen
, Nimesh Khadka
, Hayden Hamby
, Stephen Keable
, Gordana Dukovic
, John W. Peters
, Lance C. Seefeldt
, Paul W. King

Research output: Contribution to journal › Article › peer-review

819 Scopus citations

Abstract

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-Œ-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.

Original language	English
Pages (from-to)	448-450
Number of pages	3
Journal	Science
Volume	352
Issue number	6284
DOIs	https://doi.org/10.1126/science.aaf2091
State	Published - Apr 22 2016
Externally published	Yes

Funding

K.A.B. and P.W.K. were supported by a Laboratory Directed Research and Development Program seed project at the National Renewable Energy Laboratory for CdS:MoFe protein photochemical H2 production experiments, and by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences; and the U.S. Department of Energy under Contract no. DE-AC36-08-GO28308 with the National Renewable Energy Laboratory for CdS:MoFe protein biohybrid N2 reduction experiments. M.B.W., H.H., and G.D. conducted .

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@article{ca61da6107ef492e92133e93657db6c0,

title = "Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid",

abstract = "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-{\OE}-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.",

author = "Brown, \{Katherine A.\} and Harris, \{Derek F.\} and Wilker, \{Molly B.\} and Andrew Rasmussen and Nimesh Khadka and Hayden Hamby and Stephen Keable and Gordana Dukovic and Peters, \{John W.\} and Seefeldt, \{Lance C.\} and King, \{Paul W.\}",

year = "2016",

month = apr,

day = "22",

doi = "10.1126/science.aaf2091",

language = "English",

volume = "352",

pages = "448--450",

journal = "Science",

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publisher = "American Association for the Advancement of Science",

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T1 - Light-driven dinitrogen reduction catalyzed by a CdS:nitrogenase MoFe protein biohybrid

AU - Brown, Katherine A.

AU - Harris, Derek F.

AU - Wilker, Molly B.

AU - Rasmussen, Andrew

AU - Khadka, Nimesh

AU - Hamby, Hayden

AU - Keable, Stephen

AU - Dukovic, Gordana

AU - Peters, John W.

AU - Seefeldt, Lance C.

AU - King, Paul W.

PY - 2016/4/22

Y1 - 2016/4/22

N2 - 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-Œ-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.

AB - 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-Œ-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.

UR - https://www.scopus.com/pages/publications/84964765886

U2 - 10.1126/science.aaf2091

DO - 10.1126/science.aaf2091

M3 - Article

C2 - 27102481

AN - SCOPUS:84964765886

SN - 0036-8075

VL - 352

SP - 448

EP - 450

JO - Science

JF - Science

IS - 6284

ER -

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

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