title: On the electron transfer mechanism between cytochrome C and metal electrodes. Evidence for dynamic control at short distances.
abstract: Cytochrome c was coordinatively bound to self-assembled monolayers of pyridine-terminated alkanethiols on Au and Ag electrodes. The mechanism of heterogeneous electron transfer of the immobilized protein was investigated by cyclic voltammetry and time-resolved surface-enhanced resonance Raman spectroelectrochemistry. The temperature, distance, and overpotential dependencies of the electron transfer rates indicate a change of mechanism from a tunneling controlled reaction at long distances (thicker films) to a solvent/protein friction controlled reaction at smaller distances (thinner films).
authors.affiliation: Chemistry Department, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
authors.forename: Hongjun
authors.initials: H
authors.lastname: Yue
authors.forename: D
authors.initials: D
authors.lastname: Khoshtariya
authors.forename: D H
authors.initials: DH
authors.lastname: Waldeck
authors.forename: J
authors.initials: J
authors.lastname: Grochol
authors.forename: P
authors.initials: P
authors.lastname: Hildebrandt
authors.forename: D H
authors.initials: DH
authors.lastname: Murgida
mesh_terms: D000465:Algorithms; D000818:Animals; D045304:Cytochromes c / Q000737:chemistry*; D004553:Electric Conductivity; D004563:Electrochemistry; D004566:Electrodes; D004579:Electron Transport; D004583:Electrons; D006736:Horses; D008670:Metals / Q000737:chemistry*; D010084:Oxidation-Reduction; D012997:Solvents / Q000737:chemistry; D013059:Spectrum Analysis, Raman; D013696:Temperature; D013816:Thermodynamics; D014783:Viscosity
chemical_list: D008670:Metals; D012997:Solvents; D045304:Cytochromes c