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Leguto, A.J.; Smith, M.A.; Morgada, M.N.; Zitare, U.A.; Murgida, D.H.; Lancaster, K.M.; Vila, A.J. "Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes" (2019) Journal of the American Chemical Society. 141(3):1373-1381
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Abstract:

Cu A is a binuclear copper site acting as electron entry port in terminal heme-copper oxidases. In the oxidized form, Cu A is a mixed valence pair whose electronic structure can be described using a potential energy surface with two minima, σ u ∗ and π u , that are variably populated at room temperature. We report that mutations in the first and second coordination spheres of the binuclear metallocofactor can be combined in an additive manner to tune the energy gap and, thus, the relative populations of the two lowest-lying states. A series of designed mutants span σ u ∗/π u energy gaps ranging from 900 to 13 cm -1 . The smallest gap corresponds to a variant with an effectively degenerate ground state. All engineered sites preserve the mixed-valence character of this metal center and the electron transfer functionality. An increase of the Cu-Cu distance less than 0.06 Å modifies the σ u /π u energy gap by almost 2 orders of magnitude, with longer distances eliciting a larger population of the π u state. This scenario offers a stark contrast to synthetic systems, as model compounds require a lengthening of 0.5 Å in the Cu-Cu distance to stabilize the π u state. These findings show that the tight control of the protein environment allows drastic perturbations in the electronic structure of Cu A sites with minor geometric changes. © 2018 American Chemical Society.

Registro:

Documento: Artículo
Título:Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes
Autor:Leguto, A.J.; Smith, M.A.; Morgada, M.N.; Zitare, U.A.; Murgida, D.H.; Lancaster, K.M.; Vila, A.J.
Filiación:Instituto de Biología Molecular y Celular de Rosario (IBR), Departamento de Química Biológica, Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, CONICET, Rosario, 2000, Argentina
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, United States
Instituto de Química Física de Los Materiales Medio Ambiente y Energía, Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, CONICET, Buenos Aires, 1428, Argentina
Palabras clave:Binary alloys; Copper; Electronic structure; Energy gap; Ground state; Potential energy; Quantum chemistry; Coordination sphere; Electron transfer; Electronic perturbations; Engineered site; Geometric changes; Heme-copper oxidase; Orders of magnitude; Synthetic systems; Copper alloys; copper ion; Article; chemical binding; chemical interaction; chemical modification; chemical parameters; chemical structure; electron transport; energy; geometry; mutation; structure analysis
Año:2019
Volumen:141
Número:3
Página de inicio:1373
Página de fin:1381
DOI: http://dx.doi.org/10.1021/jacs.8b12335
Título revista:Journal of the American Chemical Society
Título revista abreviado:J. Am. Chem. Soc.
ISSN:00027863
CODEN:JACSA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v141_n3_p1373_Leguto

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Citas:

---------- APA ----------
Leguto, A.J., Smith, M.A., Morgada, M.N., Zitare, U.A., Murgida, D.H., Lancaster, K.M. & Vila, A.J. (2019) . Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes. Journal of the American Chemical Society, 141(3), 1373-1381.
http://dx.doi.org/10.1021/jacs.8b12335
---------- CHICAGO ----------
Leguto, A.J., Smith, M.A., Morgada, M.N., Zitare, U.A., Murgida, D.H., Lancaster, K.M., et al. "Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes" . Journal of the American Chemical Society 141, no. 3 (2019) : 1373-1381.
http://dx.doi.org/10.1021/jacs.8b12335
---------- MLA ----------
Leguto, A.J., Smith, M.A., Morgada, M.N., Zitare, U.A., Murgida, D.H., Lancaster, K.M., et al. "Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes" . Journal of the American Chemical Society, vol. 141, no. 3, 2019, pp. 1373-1381.
http://dx.doi.org/10.1021/jacs.8b12335
---------- VANCOUVER ----------
Leguto, A.J., Smith, M.A., Morgada, M.N., Zitare, U.A., Murgida, D.H., Lancaster, K.M., et al. Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes. J. Am. Chem. Soc. 2019;141(3):1373-1381.
http://dx.doi.org/10.1021/jacs.8b12335