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PhotoATRP Induced Self-Assembly (PhotoATR-PISA) Enables Simplified Synthesis of Responsive Polymer Nanoparticles in One-Pot

submitted on 22.09.2020, 14:58 and posted on 23.09.2020, 11:59 by Ali Shahrokhinia, Randall Scanga, Priyanka Biswas, James Reuther

ABSTRACT: Photo-controlled atom transfer radical polymerization (PhotoATRP) was implemented, for the first time, to accomplish polymerization induced self-assembly (PISA) mediated by UV light (λ = 365 nm) using ppm levels (ca. < 20 ppm) of copper catalyst at ambient temperature. Using CuIIBr2/tris(pyridin-2-ylmethyl)amine (TPMA) catalyst systems, PISA was per-formed all in one-pot starting from synthesis of solvophilic poly(oligo(ethylene oxide) methyl ether methacrylate) (POEGMA) blocks to core-crosslinked nanoparticles (NPs) utilizing poly(glycidyl methacrylate) (PGMA) and N,N-cystamine bismethacrylamide (CBMA) as the solvophobic copolymer and crosslinking agent, respectively. Sequential chain-extensions were performed for PGMA demonstrating capabilities for accessing multi-block copolymers with temporal control via switching the UV light on and off. Further, core-crosslinking of PISA nanoparticles was performed via the slow incorporation of the CBMA enabling one-pot crosslinking during the PISA process. Finally, the disulfide installed in the CBMA core-crosslinks allowed for the stimuli-triggered dissociation of nanoparticles using DL-dithiothreitol at acidic pH.


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University of Massachusetts Lowell



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