Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes
In this paper we present a combined experimental and theoretical study of the heterogeneous electron transfer reaction of cytochrome c electrostatically adsorbed on metal electrodes coated with monolayers of 6-mercaptohexanoic acid. Molecular dynamics simulations and pathways calculations show that...
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| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_00134686_v54_n22_p4963_Paggi |
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todo:paper_00134686_v54_n22_p4963_Paggi2023-10-03T14:11:02Z Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes Paggi, D.A. Martín, D.F. Kranich, A. Hildebrandt, P. Martí, M.A. Murgida, D.H. Cytochrome c Molecular dynamics Protein electron transfer Self-assembled monolayers SERR Coated electrodes Cytochrome c Direct monitoring Electron transfer Electron transfer rates Electron-transfer rate constants Electronic coupling Heterogeneous electron transfer Metal electrodes Molecular dynamics simulations Protein dynamics SERR Surface enhanced resonance Theoretical study Time-resolved Tunnelling probability Adsorption Coated wire electrodes Electrodes Electron transitions Molecular dynamics Molecular orientation Rate constants Reaction kinetics Self assembled monolayers Dynamics In this paper we present a combined experimental and theoretical study of the heterogeneous electron transfer reaction of cytochrome c electrostatically adsorbed on metal electrodes coated with monolayers of 6-mercaptohexanoic acid. Molecular dynamics simulations and pathways calculations show that adsorption of the protein leads to a broad distribution of orientations and, thus, to a correspondingly broad distribution of electron transfer rate constants due to the orientation-dependence of the electronic coupling parameter. The adsorbed protein exhibits significant mobility and, therefore, the measured reaction rate is predicted to be a convolution of protein dynamics and tunnelling probabilities for each orientation. This prediction is confirmed by time-resolved surface enhanced resonance Raman which allows for the direct monitoring of protein (re-)orientation and electron transfer of the immobilised cytochrome c. The results provide a consistent explanation for the non-exponential distance-independence of electron transfer rates usually observed for proteins immobilized on electrodes. © 2009 Elsevier Ltd. All rights reserved. Fil:Martí, M.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Murgida, D.H. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00134686_v54_n22_p4963_Paggi |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Cytochrome c Molecular dynamics Protein electron transfer Self-assembled monolayers SERR Coated electrodes Cytochrome c Direct monitoring Electron transfer Electron transfer rates Electron-transfer rate constants Electronic coupling Heterogeneous electron transfer Metal electrodes Molecular dynamics simulations Protein dynamics SERR Surface enhanced resonance Theoretical study Time-resolved Tunnelling probability Adsorption Coated wire electrodes Electrodes Electron transitions Molecular dynamics Molecular orientation Rate constants Reaction kinetics Self assembled monolayers Dynamics |
| spellingShingle |
Cytochrome c Molecular dynamics Protein electron transfer Self-assembled monolayers SERR Coated electrodes Cytochrome c Direct monitoring Electron transfer Electron transfer rates Electron-transfer rate constants Electronic coupling Heterogeneous electron transfer Metal electrodes Molecular dynamics simulations Protein dynamics SERR Surface enhanced resonance Theoretical study Time-resolved Tunnelling probability Adsorption Coated wire electrodes Electrodes Electron transitions Molecular dynamics Molecular orientation Rate constants Reaction kinetics Self assembled monolayers Dynamics Paggi, D.A. Martín, D.F. Kranich, A. Hildebrandt, P. Martí, M.A. Murgida, D.H. Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes |
| topic_facet |
Cytochrome c Molecular dynamics Protein electron transfer Self-assembled monolayers SERR Coated electrodes Cytochrome c Direct monitoring Electron transfer Electron transfer rates Electron-transfer rate constants Electronic coupling Heterogeneous electron transfer Metal electrodes Molecular dynamics simulations Protein dynamics SERR Surface enhanced resonance Theoretical study Time-resolved Tunnelling probability Adsorption Coated wire electrodes Electrodes Electron transitions Molecular dynamics Molecular orientation Rate constants Reaction kinetics Self assembled monolayers Dynamics |
| description |
In this paper we present a combined experimental and theoretical study of the heterogeneous electron transfer reaction of cytochrome c electrostatically adsorbed on metal electrodes coated with monolayers of 6-mercaptohexanoic acid. Molecular dynamics simulations and pathways calculations show that adsorption of the protein leads to a broad distribution of orientations and, thus, to a correspondingly broad distribution of electron transfer rate constants due to the orientation-dependence of the electronic coupling parameter. The adsorbed protein exhibits significant mobility and, therefore, the measured reaction rate is predicted to be a convolution of protein dynamics and tunnelling probabilities for each orientation. This prediction is confirmed by time-resolved surface enhanced resonance Raman which allows for the direct monitoring of protein (re-)orientation and electron transfer of the immobilised cytochrome c. The results provide a consistent explanation for the non-exponential distance-independence of electron transfer rates usually observed for proteins immobilized on electrodes. © 2009 Elsevier Ltd. All rights reserved. |
| format |
JOUR |
| author |
Paggi, D.A. Martín, D.F. Kranich, A. Hildebrandt, P. Martí, M.A. Murgida, D.H. |
| author_facet |
Paggi, D.A. Martín, D.F. Kranich, A. Hildebrandt, P. Martí, M.A. Murgida, D.H. |
| author_sort |
Paggi, D.A. |
| title |
Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes |
| title_short |
Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes |
| title_full |
Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes |
| title_fullStr |
Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes |
| title_full_unstemmed |
Computer simulation and SERR detection of cytochrome c dynamics at SAM-coated electrodes |
| title_sort |
computer simulation and serr detection of cytochrome c dynamics at sam-coated electrodes |
| url |
http://hdl.handle.net/20.500.12110/paper_00134686_v54_n22_p4963_Paggi |
| work_keys_str_mv |
AT paggida computersimulationandserrdetectionofcytochromecdynamicsatsamcoatedelectrodes AT martindf computersimulationandserrdetectionofcytochromecdynamicsatsamcoatedelectrodes AT kranicha computersimulationandserrdetectionofcytochromecdynamicsatsamcoatedelectrodes AT hildebrandtp computersimulationandserrdetectionofcytochromecdynamicsatsamcoatedelectrodes AT martima computersimulationandserrdetectionofcytochromecdynamicsatsamcoatedelectrodes AT murgidadh computersimulationandserrdetectionofcytochromecdynamicsatsamcoatedelectrodes |
| _version_ |
1807316539803697152 |