Alignment and photooxidation dynamics of a perylene diimide chromophore in lipid bilayers†

We present a method of enabling photochemical reactions in water by using biomimetic, water-soluble liposomes and a specifically functionalized perylene diimide chromophore. Linking two flexible saturated C4-alkyl chains with terminal positively charged trimethylammonium groups to the rigid perylene diimide core yielded [1]²⁺ allowing for its co-assembly at the lipid bilayer interface of DOPG liposomes (DOPG = 1,2-dioleoyl-sn-glycero-3-phospho-(1′-rac-glycerol)) with a preferred orientation and in close proximity to the water interface. According to molecular dynamics simulations the chromophore aligns preferably parallel to the membrane surface which is supported by confocal microscopy. Irradiation experiments with visible light and in the presence of a negatively charged, water-soluble oxidant were slower in the DOPG-membrane than under acetonitrile–water reaction conditions. The generated radical species was characterized by EPR spectroscopy in an acetonitrile–water mixture and associated to the DOPG-membrane. Time-resolved emission studies revealed a static quenching process for the initial electron transfer from photoexcited [1]²⁺ to the water soluble oxidant. The findings presented in this study yield design principles for the functionalization of lipid bilayer membranes which will be relevant for the molecular engineering of artificial cellular organelles and nano-reactors based on biomimetic vesicles and membranes.