Proton diffusion across membranes of vesicles of poly(styrene-b-acrylic acid) diblock copolymers

A study of proton diffusion across membranes of block copolymer vesicles in dilute solution is described. The vesicles were formed by the self-assembly of a diblock copolymer of poly(styrene-b-acrylic acid) (PS(310)-b-PAA(36), where the numbers represent the degree of polymerization for individual blocks). A pH gradient was created across the vesicle membrane with the interior pH (pH(in)) of ca. 2.9 and the exterior pH (pH(out)) of ca. 8.5. The permeability of the polystyrene (PS) membrane was tuned by the addition of different amounts of dioxane (0-40 wt %) to the external aqueous solution. Proton concentrations in the solution outside of the vesicles were followed by monitoring the spectrum of a pH-sensitive fluorescent dye, namely 8-hydroxypyrene-1,3,6-trisulfonate. After the start of the experiment, the proton concentrations increase linearly with the square root of time, while the slopes of the lines increase with dioxane content. To calculate the diffusion coefficients of the protons across the vesicular membrane, the concentration data were fitted using a model, which describes the diffusion of species across the membrane of a reservoir. The apparent diffusion coefficient (D*, which equals the true diffusion coefficient multiplied by the partition coefficient of protons between PS and water) increases from 1.1 x 10(-18) cm(2)/s at 7 wt % dioxane in the external solution to 1.2 x 10(-14) cm(2)/s at 40 wt %. The increase of D* with dioxane content is related to its plasticization of the PS membrane, which can be used as a gating mechanism.