title: Analysis of structure-function relationships in cytochrome c oxidase and its biomimetic analogs via resonance Raman and surface enhanced resonance Raman spectroscopies.
abstract: Cytochrome c oxidase (CcO) catalyzes the four electron reduction of molecular oxygen to water while avoiding the formation of toxic peroxide; a quality that is of high relevance for the development of oxygen-reducing catalysts. Resonance Raman spectroscopy has been used since many years as a technique to identify electron transfer pathways in cytochrome c oxidase and to identify the key intermediates in the catalytic cycle. This information can be compared to artificial systems such as modified heme-copper enzymes, molecular heme-copper catalysts or CcO/electrode complexes in order to shed light into the reaction mechanism of these non-natural systems. Understanding the structural commonalities and differences of CcO with its non-natural analogs is of great value for designing efficient oxygen-reducing catalysts. In this review therefore Raman spectroscopic measurements on artificial heme-copper enzymes and model complexes are summarized and compared to the natural enzyme cytochrome c oxidase. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems.
authors.affiliation: Department of Chemistry PC 14, Technische Universitaet Berlin, Strasse des 17. Juni 135, 10623 Berlin, Germany. Electronic address: inez.weidinger@tu-berlin.de.
authors.forename: Inez M
authors.initials: IM
authors.lastname: Weidinger
mesh_terms: D032701:Biomimetics / Q000379:methods; D002384:Catalysis; D003300:Copper / Q000737:chemistry / Q000378:metabolism; D004579:Electron Transport; D003576:Electron Transport Complex IV / Q000737:chemistry* / Q000378:metabolism*; D006418:Heme / Q000737:chemistry / Q000378:metabolism; D008958:Models, Molecular; D010100:Oxygen / Q000737:chemistry / Q000378:metabolism; D013059:Spectrum Analysis, Raman / Q000379:methods; D013329:Structure-Activity Relationship
chemical_list: D006418:Heme; D003300:Copper; D003576:Electron Transport Complex IV; D010100:Oxygen
keywords: Biomimetic complex; Cytochrome c oxidase; Oxo intermediate; Oxygen reduction; Resonance Raman; Surface enhanced Raman spectroscopy