Star polymers have tremendous potential as viscosity modifiers and cargo carriers. Efforts have been directed towards synthesizing star polymers with reversible core structures to facilitate degradation and cargo release. Common strategies utilize dynamic-covalent linkages as well as non-dynamic degradable linkers but limited focus has been placed on utilizing functional groups that can be modified to tune the degradation behavior. This work utilizes reversible-addition-fragmentation chain transfer (RAFT) polymerization, photoiniferter polymerization, and imine chemistry to tailor the degradation profile of amphiphilic star polymers for cargo loading and release. We utilize three different imine derivatives: oximes, semicarbazones, and hydrazones as the core-crosslinker to generate core-crosslinked star polymers via an arm-first approach. The efficiency of conversion from arms to stars could be controlled through the relative stoichiometric ratios of cross-linker and chain transfer agent (CTA). When subjected to acidic aqueous conditions, a reversion from stars to arms was observed, and the degradation and release varied based on hydrolytic stability of the imine crosslinker.

Imine core-crosslinked stars for tunable degradation and release

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