From the results, it is evident that the Cu(I)-PLs performed at least equally well as the CuI powder or the Cu-ligand catalyst. Furthermore, as expected, the reaction toward Rufinamide (employing propiolamide) was considerably faster than the reaction to product 2 with phenylacetylene. Only the Cu(I)-PLs experiment with water as co-solvent was not successful. This may be caused by the increased solvent polarity that makes the bilayer membrane less accessible to reagents. After the reaction was completed, the reaction mixture was cooled down to r.t. (around 10 mins) and gratifyingly, for all reactions performed in pure ACN, the product crystallized out and could be conveniently collected from the bottom of the reaction vials. This demonstrates a good agreement with the COSMO-RS prediction. Furthermore, based on analysis of Entry 6, the polymersomes were effectively retrieved in the ACN layer. In case of Rufinamide, due to the faster reaction time and lower solubility compared to 2 , product precipitation already occurred after 2 minutes during reaction and only 15 mins were needed for full conversion from R1. However, the Rufinamide crystals were contaminated to some extent with polymersomes. This could be circumvented by addition of ACN after the reaction to wash and filter the polymersomes out. In Entry 10, the isolated Rufinamide yield was 93%, with 4% of product retained in the organic layer. In addition, although the conversions in DMSO were high, no product precipitated at r.t. and Cu(I)-PLs were not observed by TEM after the reaction.