title: Gated electron transfer of cytochrome c6 at biomimetic interfaces: a time-resolved SERR study.
abstract: The electron shuttle heme protein Cyt-c(6) 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-c(6) 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.
authors.affiliation: Institut für Chemie, Technische Universität Berlin. Str. des 17. Juni 135, Sekr. PC, 14, D10623-Berlin, Germany.
authors.forename: Anja
authors.initials: A
authors.lastname: Kranich
authors.forename: Hendrik
authors.initials: H
authors.lastname: Naumann
authors.forename: Fernando P
authors.initials: FP
authors.lastname: Molina-Heredia
authors.forename: H Justin
authors.initials: HJ
authors.lastname: Moore
authors.forename: T Randall
authors.initials: TR
authors.lastname: Lee
authors.forename: Sophie
authors.initials: S
authors.lastname: Lecomte
authors.forename: Miguel A
authors.initials: MA
authors.lastname: de la Rosa
authors.forename: Peter
authors.initials: P
authors.lastname: Hildebrandt
authors.forename: Daniel H
authors.initials: DH
authors.lastname: Murgida
mesh_terms: D001665:Binding Sites; D032701:Biomimetics; D045365:Cytochromes c6 / Q000737:chemistry* / Q000235:genetics; D004583:Electrons; D007700:Kinetics; D008954:Models, Biological; D009154:Mutation; D046937:Nostoc / Q000201:enzymology*; D013059:Spectrum Analysis, Raman; D013499:Surface Properties
chemical_list: D045365:Cytochromes c6