6533b825fe1ef96bd128328c
RESEARCH PRODUCT
Proton coupled electron transfer of ubiquinone Q2 incorporated in a self-assembled monolayer.
Rita Meunier-prestCelia LemmerMarcel Bouvetsubject
Aqueous mediumChemistrySurface PropertiesUbiquinoneAnalytical chemistryGeneral Physics and AstronomyWaterSelf-assembled monolayerElectronHydrogen-Ion ConcentrationElectrochemistryElectron TransportReaction rate constantCoenzyme Q – cytochrome c reductaseMonolayerElectrochemistryThermodynamicsGoldPhysical and Theoretical ChemistryProton-coupled electron transferProtonsOxidation-Reductiondescription
We present a complete study of the reduction of ubiquinone Q(2) (UQ(2)) in simpler aqueous medium, over a pH range of 2.5 to 12.5. The short isoprenic chain ubiquinones (UQ(2)) were incorporated in a self-assembled monolayer. Under these conditions, the global 2e(-) electrochemical reaction can be described on the basis of a nine-member square scheme. The thermodynamic constants of the system were determined. The global 2e(-) process is controlled by the uptake of the second electron. The elementary electrochemical rate constants obtained by fitting of the experimental rate constant were k(s4) = 1.5 s(-1) for QH˙(+)(2)↔ QH(2), k(s5) = 1.5 s(-1) for QH˙↔ QH(-) and k(s6) = 1 s(-1) for Q˙(-)↔ Q(2-). The three electrochemical reactions QH˙(+)(2)↔ QH(2), QH˙↔ QH(-) and Q˙(-)↔ Q(2-) are successively involved when increasing the pH. Protonations can occur or not, before or after the electron uptake and the reaction paths are, from low to high pH: e(-), H(+)e(-), e(-)H(+), H(+)e(-)H(+), H(+)e(-) and e(-)H(+).
year | journal | country | edition | language |
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2011-06-29 | Physical chemistry chemical physics : PCCP |