Abstract

The first‐ and second‐generation well‐defined thermal and enzymatic dual‐stimuli responsive amphiphilic linear‐dendritic block copolymers (LDBCs) based on hydrophilic linear poly(N‐vinylcaprolactam) (PNVCL) and a hydrophobic Fmoc‐terminated dendron derived from an aliphatic polyester of 2, 2′‐dimethylolpropionic acid (bis‐MPA) have been synthesized via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization of N‐vinylcaprolactam (NVCL) and “chain‐first” strategy. The copolymers were characterized by 1H NMR spectra and gel permeation chromatograph (GPC) analyses, showing controlled molecular weight and narrow molecular weight distribution (PDI ≤1.27). They self‐assemble in water into vesicles that are able to disrupt and release encapsulated cargos upon papain treatment. Their thermal‐responsive property was highly dependent on the generation and concentration of copolymers, and enzyme‐responsive behavior was affected by the generation of dendritic aliphatic polyester block. Moreover, papain influenced the thermal‐responsive behavior of the copolymers. Such smart copolymers could be efficiently used in drug delivery systems or biosensors.

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