Encapsulation and release by star‐shaped block copolymers as unimolecular nanocontainers

Abstract A five‐arm star‐shaped poly(ethylene oxide) (PEO) with terminal bromide groups was used as a macroinitiator for the atom transfer radical polymerization of tert ‐butyl acrylate ( t BA), resulting in five‐arm star‐shaped poly(ethylene oxide)‐ block ‐poly( tert ‐butyl acrylate) block copolymers. The polymerization proceeded in a controlled way using a copper(I)bromide/pentamethyl diethylenetriamine catalytic system in acetonitrile as solvent. The hydrolysis of the t BA blocks of the amphiphilic star‐shaped PEO‐ b ‐P t BA block copolymer resulted in dihydrophilic star structures. The encapsulation of the star‐block copolymers and their release properties in acid environment have been followed by UV‐spectroscopy and color changes, using the dye methyl orange as a hydrophilic guest molecule. Characterization of the structures has been done by 1 H NMR, size exclusion chromatography, MALDI‐TOF, and differential scanning calorimetry. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 650–660, 2008