Synthesis and application of polymeric micelles assembled from pentafluorophenyl ester-containing amphiphilic block copolymers

Abstract

Functionalizable pentafluorophenyl ester (PFP)-based polymer precursors, namely poly(pentafluorophenyl acrylate) (PPFPA) and poly(pentafluorophenyl metharylate) (PPFPMA), and zwitterionic poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) are the two polymers having extremely different solubility. It is therefore almost impossible to synthesize their block copolymers in a controlled manner by the conventional approach. Herein, we demonstrated, for the first time, that the synthesis and in situ formation of nanoassemblies of their diblock copolymer can be done via polymerization-induced self-assembly (PISA) using reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization. PMPC was synthesized as the first block and further employed as a macro chain transfer agent (PMPC Macro-CTA) for the synthesis of the PFP-based polymer as a second block. Synthesized using an appropriate range of copolymer composition and solid concentration, in situ self-assembled nanostructures of the diblock copolymers were evaluated by dynamic light scattering and transmission electron microscopy. To demonstrate the functionalizability of the core-forming block of PFP-based polymer precursor, the nanoparticles were subjected to post-polymerization modification with nucleophilic modifiers yielding nanostructures bearing multifunctionality that may be applicable for a wide range of applications.