Tailored Synthesis of Intelligent Polymer Nanocapsules: An Investigation of Controlled Permeability and pH-Dependent Degradability

In this study, we present a new route to synthesize an intelligent polymer nanocapsule with an ultrathin membrane based on surface-initiated reversible addition-fragmentation chain-transfer polymerization. The key concept of our report is to use pH-responsive polydiethylaminoethylmethacrylate as a main membrane-generating component and a degradable disulfide bond to cross-link the membrane. The permeability of membrane, tuned by adjusting pH and using different lengths of the cross-linkers, was proven by showing a dramatic swelling behavior of the nanocapsules with the longest cross linker from 560 nm at pH 8.0 to 780 nm at pH 4.0. Also due to the disulfide cross linker degradation of the capsules using GSH as reducing agent was achieved which is further significantly promoted at pH 4.0. Using a, rather long-chain dithiol cross-linker, the synthesized nanocapsules demonstrated a good permeability allowing that an enzyme myoglobin can be postencapsulated, where the pH controlled enzyme activity by switching membrane permeability was also shown.