Synthesis of photo- and pH-responsive composite nanoparticles using a two-step controlled radical polymerization method

We present a versatile synthetic method for photo- and pH-sensitive composite nanoparticles using a combined use of reversible addition-fragmentation chain transfer (RAFT) and atom transfer radical polymerization (ATRP). Crosslinked nanoparticles of a random copolymer composed of methyl methacrylate (MMA), 4-vinylbenzyl chloride (VBC) and divinylbenzene (DVB) were first synthesized using RAFT miniemulsion polymerization in aqueous solution. This was followed by solvent exchange through extraction and dialysis that allowed the nanoparticles to be transferred to and highly swollen in an organic solvent (anisole or THF). By dissolving a monomer of a stimuli-responsive polymer in the solution, subsequent ATRP grafting polymerization could be initiated by halide groups on the swollen nanoparticle, resulting in larger composite nanoparticles. Photosensitive poly(1-pyrenylmethyl methacrylate) (PPyMA) and pH-sensitive poly(dimethylaminoethyl methacrylate) (PDMAEMA) were incorporated in the composite nanoparticles, and their photo- and pH-responsive behaviors were investigated. With this method, monomers soluble in organic solvents can be used in conjunction with emulsion polymerization in aqueous solution to design functional composite nanoparticles.