Materials:All the experiments were performed under inert conditions. THF and toluene were dried over Na and used fresh distilled.Hyperbranched polyethyleneimine (PEI) with a DB around 60% 1 and a molecular weight around 5 kD were supplied as a water solution 2 .Prior to use water was evaporated under vacuum at 80°C for several hours. 2H,2H,3H,3H-perfluoroundecaonoic acid was purchased from Fluorus and Poly(hexafluoropropylene oxide) monocarboxylic acid, chloro terminated from Aldrich. The monocarbonyl acide terminated polydimethylsiloxane and the 3,6,9,12-tetraoxotridecanoic acid were synthesized as described in the literature. 3,4 Other reagents were commercially available and used without any further purification.Typical procedure for the synthesis of unimolecular micelles with a hydrophobic shell: PEI-NHCOCH 2 CH 2 C 8 F 17 , 1. The 2H,2H,3H,3H-perfluoroundecaonoic acid (1.06g, 2.16mmol) dissolved in THF (10mL) is added slowly to a solution of carbonyldiimidazol (338mg, 2.09mmol) in THF (10mL). The reaction is stirred for 1h at room temperature. An argon stream is used to displace remaining CO 2 . Then the mixture is transferred to a schlenk containing the hyperbranched polymer PEI (293mg, 2.09mmol terminal amino groups). The reaction is heated at 40°C over night. The solvent is reduced to 10mL and 50mL water are added. The white precipitate is isolated and washed with water several times. After drying under high vacuum, the product is obtained as a white powder (480mg, 83% yield).
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