Quantifying Binding of Ethylene Oxide–Propylene Oxide Block Copolymers with Lipid Bilayers

Block copolymers composed of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) have been widely used in cell membrane stabilization and permeabilization. To explore the mechanism of interaction between PPO–PEO block copolymers and lipid membranes, we have investigated how polymer structure influences the polymer–lipid bilayer association by varying the overall molecular weight, the hydrophobic and hydrophilic block lengths, and the end-group structure systematically, using 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) unilamellar liposomes as model membranes. Pulsed-field-gradient NMR (PFG-NMR) was employed to probe polymer diffusion in the absence and presence of liposomes. The echo decay curves of free polymers in the absence of liposomes are single exponentials, indicative of simple translational diffusion, while in the presence of liposomes, the decays are biexponential, with the slower decay corresponding to polymers bound to liposomes. The binding percentage of polymer to the lipo...