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Title: Interactions of 1-Methylimidazole with UO₂(CH₃CO₂)₂ and UO₂(NO₃)₂: Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The first definitive high-resolution single-crystal X-ray structure for the coordination of the 1-methylimidazole (Meimid) ligand to UO₂(Ac)₂ (Ac =CH₃CO₂) is reported. The crystal structure evidence is confirmed by IR, Raman, and UV-vis spectroscopic data. Direct participation of the nitrogen atom of the Meimid ligand in binding to the uranium center is confirmed. Structural analysis at the DFT (B3LYP) level of theory showed a conformational difference of the Meimid ligand in the free gas-phase complex versus the solid state due to small energetic differences and crystal packing effects. Energetic analysis at the MP2 level in the gas phase supported stronger Meimid binding over H₂2O binding to both UO₂(Ac)₂ and UO₂(NO₃)₂. In addition, self-consistent reaction field COSMO calculations were used to assess the aqueous phase energetics of combination and displacement reactions involving H₂O and Meimid ligands to UO₂R₂ (R ) Ac, NO₃). For both UO₂(NO₃)₂ and UO₂(Ac)₂, the displacement of H₂O by Meimid was predicted to be energetically favorable, consistent with experimentalmore » results that suggest Meimid may bind uranyl at physiological pH. Also, log(Knitrate/KAc) calculations supported experimental evidence that the binding stoichiometry of the Meimid ligand is dependent upon the nature of the reactant uranyl complex. These results clearly demonstrate that imidazole binds to uranyl and suggest that binding of histidine residues to uranyl could occur under normal biological conditions.« less

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
921817
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society, 129(3):526-536; Journal Volume: 129; Journal Issue: 3
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ATOMS; CRYSTAL STRUCTURE; HISTIDINE; IMIDAZOLES; NITROGEN; RESIDUES; STOICHIOMETRY; UNIVERSE; URANIUM; Environmental Molecular Sciences Laboratory

Citation Formats

Gutowski, Keith E., Cocalia, Violina A., Griffin, Scott T., Bridges, Nicholas J., Dixon, David A., and Rogers, Robin D. Interactions of 1-Methylimidazole with UO₂(CH₃CO₂)₂ and UO₂(NO₃)₂: Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion. United States: N. p., 2007. Web. doi:10.1021/ja064592i.
Gutowski, Keith E., Cocalia, Violina A., Griffin, Scott T., Bridges, Nicholas J., Dixon, David A., & Rogers, Robin D. Interactions of 1-Methylimidazole with UO₂(CH₃CO₂)₂ and UO₂(NO₃)₂: Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion. United States. doi:10.1021/ja064592i.
Gutowski, Keith E., Cocalia, Violina A., Griffin, Scott T., Bridges, Nicholas J., Dixon, David A., and Rogers, Robin D. Wed . "Interactions of 1-Methylimidazole with UO₂(CH₃CO₂)₂ and UO₂(NO₃)₂: Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion". United States. doi:10.1021/ja064592i.
@article{osti_921817,
title = {Interactions of 1-Methylimidazole with UO₂(CH₃CO₂)₂ and UO₂(NO₃)₂: Structural, Spectroscopic, and Theoretical Evidence for Imidazole Binding to the Uranyl Ion},
author = {Gutowski, Keith E. and Cocalia, Violina A. and Griffin, Scott T. and Bridges, Nicholas J. and Dixon, David A. and Rogers, Robin D.},
abstractNote = {The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The first definitive high-resolution single-crystal X-ray structure for the coordination of the 1-methylimidazole (Meimid) ligand to UO₂(Ac)₂ (Ac =CH₃CO₂) is reported. The crystal structure evidence is confirmed by IR, Raman, and UV-vis spectroscopic data. Direct participation of the nitrogen atom of the Meimid ligand in binding to the uranium center is confirmed. Structural analysis at the DFT (B3LYP) level of theory showed a conformational difference of the Meimid ligand in the free gas-phase complex versus the solid state due to small energetic differences and crystal packing effects. Energetic analysis at the MP2 level in the gas phase supported stronger Meimid binding over H₂2O binding to both UO₂(Ac)₂ and UO₂(NO₃)₂. In addition, self-consistent reaction field COSMO calculations were used to assess the aqueous phase energetics of combination and displacement reactions involving H₂O and Meimid ligands to UO₂R₂ (R ) Ac, NO₃). For both UO₂(NO₃)₂ and UO₂(Ac)₂, the displacement of H₂O by Meimid was predicted to be energetically favorable, consistent with experimental results that suggest Meimid may bind uranyl at physiological pH. Also, log(Knitrate/KAc) calculations supported experimental evidence that the binding stoichiometry of the Meimid ligand is dependent upon the nature of the reactant uranyl complex. These results clearly demonstrate that imidazole binds to uranyl and suggest that binding of histidine residues to uranyl could occur under normal biological conditions.},
doi = {10.1021/ja064592i},
journal = {Journal of the American Chemical Society, 129(3):526-536},
number = 3,
volume = 129,
place = {United States},
year = {Wed Jan 24 00:00:00 EST 2007},
month = {Wed Jan 24 00:00:00 EST 2007}
}