Low-temperature trapping of N2 reduction reaction intermediates in nitrogenase MoFe protein–CdS quantum dot complexes

Pellows, Lauren M.; Vansuch, Gregory E.; Chica, Bryant; Yang, Zhi-Yong; Ruzicka, Jesse L.; Willis, Mark A.; Clinger, Andrew; Brown, Katherine A.; Seefeldt, Lance C.; Peters, John W.; Dukovic, Gordana; Mulder, David W.; King, Paul W.

doi:10.1063/5.0170405

Title: Low-temperature trapping of N₂ reduction reaction intermediates in nitrogenase MoFe protein–CdS quantum dot complexes

Journal Article · Wed Dec 20 00:00:00 EST 2023 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/5.0170405· OSTI ID:2281543

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University of Colorado, Boulder, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Utah State University, Logan, UT (United States)
Washington State University, Pullman, WA (United States)
Washington State University, Pullman, WA (United States); University of Oklahoma, Norman, OK (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); University of Colorado, Boulder, CO (United States)

The biological reduction of N₂ to ammonia requires the ATP-dependent, sequential delivery of electrons from the Fe protein to the MoFe protein of nitrogenase. It has been demonstrated that CdS nanocrystals can replace the Fe protein to deliver photoexcited electrons to the MoFe protein. Herein, light-activated electron delivery within the CdS:MoFe protein complex was achieved in the frozen state, revealing that all the electron paramagnetic resonance (EPR) active E-state intermediates in the catalytic cycle can be trapped and characterized by EPR spectroscopy. Prior to illumination, the CdS:MoFe protein complex EPR spectrum was composed of a S = 3/2 rhombic signal (g = 4.33, 3.63, and 2.01) consistent with the FeMo-cofactor in the resting state, E₀. Illumination for sequential 1-h periods at 233 K under 1 atm of N₂ led to a cumulative attenuation of E₀ by 75%. This coincided with the appearance of S = 3/2 and S = 1/2 signals assigned to two-electron (E₂) and four-electron (E₄) reduced states of the FeMo-cofactor, together with additional S = 1/2 signals consistent with the formation of E₆ and E₈ states. Simulations of EPR spectra allowed quantification of the different E-state populations, along with mapping of these populations onto the Lowe–Thorneley kinetic scheme. The outcome of this work demonstrates that the photochemical delivery of electrons to the MoFe protein can be used to populate all of the EPR active E-state intermediates of the nitrogenase MoFe protein cycle.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2281543

Report Number(s):: NREL/JA-2700-87499; MainId:88274; UUID:c9c1cf16-1b32-4c80-8a26-dce34cba9bda; MainAdminID:71551

Journal Information:: Journal of Chemical Physics, Vol. 159, Issue 23; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
ammonia
biohybrid
catalysis
electron paramagnetic resonance spectroscopy
N2 reduction
nanocrystal
nitrogenase
solar energy

Title: Low-temperature trapping of N2 reduction reaction intermediates in nitrogenase MoFe protein–CdS quantum dot complexes

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Title: Low-temperature trapping of N₂ reduction reaction intermediates in nitrogenase MoFe protein–CdS quantum dot complexes