Hyperbranched molecular nanocapsules: comparison of the hyperbranched architecture with the perfect linear analogue.

The results of a comparative study of hyperbranched, partially esterified polyglycerols with their linear polyglycerol analogues with respect to molecular encapsulation and phase transfer are reported. Two hyperbranched polyglycerol samples with molecular weights of 3000 and 8000 g/mol (Mw/Mn = 1.3), respectively, have been partially esterified using palmitoyl chloride. The same modification was applied to the structurally analogous linear polyglycerol (3000 g/mol). A detailed UV-vis study correlated with viscosity experiments demonstrated that only the hyperbranched core-shell structures form "nanocapsules", leading to the encapsulation of polar guest molecules. The results underline the crucial role of the hyperbranched topology and the resulting solution conformation for supramolecular guest encapsulation and phase transfer. The unusually compact ("collapsed") structure assumed by the hyperbranched core-shell amphiphiles in apolar media is responsible for the formation of a hydrophilic compartment, capable of irreversibly taking up guest molecules.