Enhanced photoinduced electron transfer at the surface of charged lipid bilayers

Photocatalytic systems often suffer from poor quantum yields due to fast charge recombination: The energy-wasting annihilation of the photochemically created charge-separated state. In this report, we show that the efficiency of photoinduced electron transfer from a sacrificial electron donor to positively charged methyl viologen, or to negatively charged 5,5'-dithiobis(2-nitrobenzoate), increases dramatically upon addition of charged phospholipid vesicles if the charge of the lipids is of the same sign as that of the electron acceptor. Centrifugation and UV/Vis titration experiments showed that the charged photosensitizers adsorb at the liposome surface, that is, where the photocatalytic reaction takes place. The increased photoelectron transfer efficiency in the presence of charged liposomes has been ascribed to preferential electrostatic interactions between the photosensitizer and the membrane, which prevents the formation of photosensitizer-electron-acceptor complexes that are inactive towards photoreduction. Furthermore, it is shown that the addition of liposomes results in a decrease in photoproduct inhibition, which is caused by repulsion of the reduced electron acceptor by the photocatalytic site. Thus, liposomes can be used as a support to perform efficient photocatalysis; the charged photoproducts are pushed away from the liposomes and represent "soluble electrons" that can be physically separated from the place where they were generated.