Acid-Degradable Core-Crosslinked Micelles Prepared from Thermosensitive Glycopolymers Synthesized via RAFT Polymerization

A thermoresponsive block copolymer, namely poly(acryloyl glucosamine)‐block‐poly(N‐isopropylacryamide) (PAGA180‐b‐PNIPAAM350) was simultaneously self‐assembled and crosslinked in aqueous medium via RAFT polymerization at 60 °C to afford core‐crosslinked micelles exhibiting a glycopolymer corona and a PNIPAAM stimuli‐responsive core. An acid‐labile crosslinking agent, 3,9‐divinyl‐2,4,8,10‐tetraoxaspiro[5.5]undecane, was employed to generate thermosensitive and acid‐degradable core‐shell nanoparticles. Stable against degradation at pH = 6 and 8.2, the resulting core crosslinked micelles readily hydrolyzed into well‐defined free block copolymers at lower pH (30 min and 12 h respectively at pH = 2 and 4).