The mediation of redox reactions through bilayer lipid membranes was studied. With an appropriate choice of electron acceptors the redox process can be limited either by the chemical reaction rate between the mediator and the reactants or by the shuttle frequency of the mediator through the membrane. Both modes were demonstrated for redox reactions mediated by 2,6 dichlorobenzoquinone (DCBQ) and by alpha-tocopherol with ascorbate entrapped inside vesicles using ferricyanide (a mild oxidant) or hexachloroiridate (a strong oxidant) in the external solution. The redox processes were reaction rate-limited and diffusion-limited for ferricyanide and hexachloroiridate, respectively. The kinetics of the redox processes in the diffusion- and the reaction rate-limited modes allows the determination of the shuttle frequencies and of the interfacial reaction rates of the mediators, respectively. The shuttle frequencies of DCBQ and alpha-tocopherol were approximately 8 and 0.08 s-1, respectively, in L-alpha-dipalmitoyl phosphatidylcholine (DPPC) cholesterol vesicles at 25 degrees C. Interfacial reaction rates between the mediators and ferricyanide were about two- and tenfold lower compared with bulk reaction rates for DCBQ (water) and tocopherol (50% ethanol solution), respectively, i.e., tocopherol is relatively less accessible to aqueous oxidants at the membrane interface. Tocopherol and oxidized tocopherol are reversible hydrophobic redox couples that interact very rapidly with strong oxidants. In both modes of mediation DCBQ was more effective than alpha-tocopherol.

Neutral quinones rapidly equilibrate across the lipid bilayer, hereby rendering the photoeffects seen in pigmented bilayers sensitive to the redox properties at both interfaces. The lack of photoeffect by quinones themselves and their apparent quenching reactions with aqueous acceptors is thus explained. An aqueous donor is needed on one side to break the symmetry and to allow vectorial electron transfer to be recorded. It is concluded that the neutral quinone accumulates on the polar side of the interface with respect to the hydrophobic pigment. The system may allow the study of kinetics of proton transfer accompanying the redox reactions of the quinones.