Gated electron transfer of cytochrome c6 at biomimetic interfaces: a time-resolved SERR study

The electron shuttle heme protein Cyt-c6 from the photosynthetic cyanobacterium Nostoc sp. PCC 7119 was immobilized on nanostructured Ag electrodes coated with SAMs that mimic different possible interactions with its natural reaction partner PSI. The structure, redox potential, and electron-transfer...

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Detalhes bibliográficos
Autores: Kranich, Anja, Naumann, Hendrik, Molina Heredia, Fernando P., Moore, H. Justin, Lee, T. Randall, Lecomte, Sophie, Nuñez de la Rosa, Eduardo Miguel, Hildebrandt, Peter, Murgida, Daniel Horacio
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2009
País:Argentina
Recursos:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositório:CONICET Digital (CONICET)
Idioma:inglês
OAI Identifier:oai:ri.conicet.gov.ar:11336/75275
Acesso em linha:http://hdl.handle.net/11336/75275
Access Level:Acceso aberto
Palavra-chave:Citocromos
Redox Proteins
Raman
Protein Dynamics
https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descrição
Resumo:The electron shuttle heme protein Cyt-c6 from the photosynthetic cyanobacterium Nostoc sp. PCC 7119 was immobilized on nanostructured Ag electrodes coated with SAMs that mimic different possible interactions with its natural reaction partner PSI. The structure, redox potential, and electron-transfer dynamics of the SAM-Cyt-c6 complexes were investigated by TR-SERR spectroelectrochemistry. It is shown that the heterogeneous electron-transfer process is gated both in electrostatic and hydrophobic-hydrophilic complexes. At long tunneling distances, the reaction rate is controlled by the tunneling probability, while at shorter distances or higher driving forces, protein dynamics becomes the rate-limiting event.