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

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 CuII Br 2 /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. File list (2)download file view on ChemRxiv One-pot PhotoATR-PISA_Macromolecules_Final.docx (2.88 MiB) download file view on ChemRxiv Supporting Information_PhotoATR-PISA _Macromolecule...

Orthogonal synthesis and modification of polymer materials

“…Polymerization induced self‐assembly (PISA) has attracted a lot of attention recently due to the unique ability to form polymer NPs in situ at high solids concentration 209–217 . Via this method, polymeric nano‐objects with tunable morphology, size and surface chemistry can be prepared.…”

Bottom‐Up versus Top‐Down Strategies for Morphology Control in Polymer‐Based Biomedical Materials

“…Reversible addition-fragmentation chain transfer (RAFT) polymerization, with the ability to produce precise molecular weight polymers, with low polydispersity, superb utility in aqueous systems, and suitability for a large range of monomer classes has been the polymerization method of choice for PISA systems. [64][65][66][67][69][70][71] In stating this, other controlled polymerization methods have also successfully been used to produce PISA nanoparticles including atom transfer radical polymerization (ATRP), [72][73][74] nitroxide-mediated radical polymerization (NMP), [75][76][77][78] living anionic polymerisation, [79] and ring opening metathesis polymerization (ROMP). [18,19,68,80,81] The main prerequisite is the ability to polymerize an insoluble polymer block from soluble monomers utilizing a macroinitiator in a specific antisolvent.…”

“…[18,19,68,80,81] The main prerequisite is the ability to polymerize an insoluble polymer block from soluble monomers utilizing a macroinitiator in a specific antisolvent. [74] PISA is an exciting method for the production of polymeric nanomaterials at high solid content and has been utilized to realize a vast array of different morphologies (Figure 4), [67] however, typically micelles, rods, worms, and vesicles are observed. [82] The utility of PISA for controlling nanomaterial size and shape for biomedical applications was thoroughly reviewed by Davis and co-workers, in 2018, [11] hence in this section, we will provide a highlight of recent works making use of PISA for the synthesis of biomedical materials.…”

Playing construction with the monomer toy box for the synthesis of multi‐stimuli responsive copolymers by reversible deactivation radical polymerization protocols

“…Sarkar et al 184 exploited disulfide crosslinking to stabilize nanocapsules obtained by reversible complexation mediated polymerization in PISA conditions, thus allowing further chemical manipulation (hydrolysis and reduction) without disrupting the nanocapsule morphology. Shahrokhinia et al 185 applied a photoATRP‐PISA protocol using ppm levels of a copper catalyst at ambient temperature to obtain dual‐responsive (pH and redox) crosslinkable nanoaggregates. (Table 2)…”