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We have investigated the impact of increasing concentration of imidazolium-based ionic liquids ([CnMIM]+[Br]-) on the structural integrity of large unilamellar vesicles (LUVs) made of pure phosphatidylcholine (PC) and phosphatidylglycerol (PG) lipids. Calcein based dye leakage assays were used to monitor the permeability of LUVs in the presence of ionic liquids. As the ionic liquid concentration approaches the critical micelle value, vesicle fusion occurs resulting in unexpected quenching which is accompanied by rapid dye leakage due to