Controllable Self-Assembly of Amphiphilic Tadpole-Shaped Polymer Single-Chain Nanoparticles Prepared through Intrachain Photo-cross-linking

We report the use of intramolecular cross-linking chemistry as a tool to control the self-assembly of amphiphilic diblock copolymers (di-BCPs). Two amphiphilic di-BCPs of poly(N,N′-dimethylacrylamide)-block-polystyrene (PDMA-b-PS) with photo-cross-linkable cinnamoyl groups in either hydrophobic or hydrophilic blocks were prepared using reversible addition–fragmentation chain transfer polymerization. Intramolecular photo-cross-linking of cinnamoyl groups led to the formation of tadpole-shaped polymer single-chain nanoparticles (SCNPs) consisting of a self-collapsed block as the “head” and an un-cross-linked block as the “tail”. When intramolecular photo-cross-linking was carried out in hydrophobic PS blocks, a clear morphological transition from branched cylindrical micelles (for the linear di-BCP) to completely spherical micelles at a dimerization degree of ∼63% was observed. A pattern of morphological transitions from cylindrical micelles to spherical micelles is observed through stepwise downsizing the ...