Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes
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 tempera...
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2019
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v141_n3_p1373_Leguto http://hdl.handle.net/20.500.12110/paper_00027863_v141_n3_p1373_Leguto |
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paper:paper_00027863_v141_n3_p1373_Leguto2023-06-08T14:22:54Z Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes 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 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. 2019 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v141_n3_p1373_Leguto http://hdl.handle.net/20.500.12110/paper_00027863_v141_n3_p1373_Leguto |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
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 |
| spellingShingle |
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 Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes |
| topic_facet |
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 |
| description |
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. |
| title |
Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes |
| title_short |
Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes |
| title_full |
Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes |
| title_fullStr |
Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes |
| title_full_unstemmed |
Dramatic Electronic Perturbations of Cu A Centers via Subtle Geometric Changes |
| title_sort |
dramatic electronic perturbations of cu a centers via subtle geometric changes |
| publishDate |
2019 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v141_n3_p1373_Leguto http://hdl.handle.net/20.500.12110/paper_00027863_v141_n3_p1373_Leguto |
| _version_ |
1768543922668175360 |