skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Modulation of Active Site Electronic Structure by the Protein Matrix to Control [NiFe] Hydrogenase Reactivity

Abstract

Control of the reactivity of the nickel center of the [NiFe] hydrogenase and other metalloproteins commonly involves outer coordination sphere ligands that act to modify the geometry and physical properties of the active site metal centers. We carried out a combined set of classical molecular dynamics and quantum/classical mechanics calculations to provide quantitative estimates of how dynamic fluctuations of the active site within the protein matrix modulate the electronic structure at the catalytic center. Specifically we focused on the dynamics of the inner and outer coordination spheres of the cysteinate-bound Ni–Fe cluster in the catalytically active Ni-C state. There are correlated movements of the cysteinate ligands and the surrounding hydrogen-bonding network, which modulate the electron affinity at the active site and the proton affinity of a terminal cysteinate. On the basis of these findings, we hypothesize a coupling between protein dynamics and electron and proton transfer reactions critical to dihydrogen production.

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1167638
Report Number(s):
PNNL-SA-103780
47484; KC0304020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP, 16(43):24026-24033
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP, 16(43):24026-24033
Country of Publication:
United States
Language:
English
Subject:
[NiFe] hydrogenase; Environmental Molecular Sciences Laboratory

Citation Formats

Smith, Dayle MA, Raugei, Simone, and Squier, Thomas C. Modulation of Active Site Electronic Structure by the Protein Matrix to Control [NiFe] Hydrogenase Reactivity. United States: N. p., 2014. Web. doi:10.1039/c4cp03518f.
Smith, Dayle MA, Raugei, Simone, & Squier, Thomas C. Modulation of Active Site Electronic Structure by the Protein Matrix to Control [NiFe] Hydrogenase Reactivity. United States. https://doi.org/10.1039/c4cp03518f
Smith, Dayle MA, Raugei, Simone, and Squier, Thomas C. 2014. "Modulation of Active Site Electronic Structure by the Protein Matrix to Control [NiFe] Hydrogenase Reactivity". United States. https://doi.org/10.1039/c4cp03518f.
@article{osti_1167638,
title = {Modulation of Active Site Electronic Structure by the Protein Matrix to Control [NiFe] Hydrogenase Reactivity},
author = {Smith, Dayle MA and Raugei, Simone and Squier, Thomas C.},
abstractNote = {Control of the reactivity of the nickel center of the [NiFe] hydrogenase and other metalloproteins commonly involves outer coordination sphere ligands that act to modify the geometry and physical properties of the active site metal centers. We carried out a combined set of classical molecular dynamics and quantum/classical mechanics calculations to provide quantitative estimates of how dynamic fluctuations of the active site within the protein matrix modulate the electronic structure at the catalytic center. Specifically we focused on the dynamics of the inner and outer coordination spheres of the cysteinate-bound Ni–Fe cluster in the catalytically active Ni-C state. There are correlated movements of the cysteinate ligands and the surrounding hydrogen-bonding network, which modulate the electron affinity at the active site and the proton affinity of a terminal cysteinate. On the basis of these findings, we hypothesize a coupling between protein dynamics and electron and proton transfer reactions critical to dihydrogen production.},
doi = {10.1039/c4cp03518f},
url = {https://www.osti.gov/biblio/1167638}, journal = {Physical Chemistry Chemical Physics. PCCP, 16(43):24026-24033},
number = ,
volume = ,
place = {United States},
year = {Tue Sep 30 00:00:00 EDT 2014},
month = {Tue Sep 30 00:00:00 EDT 2014}
}