Poly(Pentafluorophenyl Methacrylate)‐Based Nano‐Objects Developed by Photo‐PISA as Scaffolds for Post‐Polymerization Functionalization

Abstract

The preparation of a functional fluorine-containing block copolymer using reversible addition-fragmentation chain-transfer dispersion polymerization in DMSO as a "platform/scaffold" is explored. The nanostructures, comprised of poly(ethyleneglycol)-b-poly(pentafluorophenyl methacrylate) or PEG-b-P(PFMA), are formulated via photo-initiated polymerization-induced self-assembly (PISA) followed by post-polymerization modification using different primary amines. A combination of light scattering and microscopy techniques are used to characterize the resulting morphologies. It is found that upon varying the degree of polymerization of the core-forming block of PFMA, only uniform spheres (with textured surfaces) are obtained. These nanostructures are subsequently modified by cross-linking using a non-responsive and a redox-responsive diamine, thus imparting stability to the particles in water. In response to intracellular glutathione (GSH) concentration, destabilization of the micelles occurs as evidenced by dynamic light scattering. The well-defined size, inherent reactivity of the nanoparticles toward nucleophiles, and GSH-responsiveness of the nanospheres make them ideal scaffolds for drug delivery to intracellular compartments with reductive environments.

Reactive and Functional Nanoobjects by Polymerization‐Induced Self‐Assembly

“…Reactive and functional nanoobjects are now targeted, taking advantage of the simplicity of implementation, the morphological variety, and the functional group tolerance of most PISA systems. This is clearly showcased in the present special issue on PISA . The aim of the present review is to gather and discuss most of the literature on the synthesis of reactive/functional nanoobjects by PISA up to May 2018.…”

Polymerization‐Induced Self‐Assembly

“…They notably showed that these particles out‐performed heparin and linear PAMPS in cellular proliferation, while keeping a low toxicity. Such low cytotoxicity was also briefly demonstrated for the above‐mentioned particles prepared by the O'Reilly's group . The potential and limits of PISA‐derived particles for biomedical applications are in fact well assessed in the review article of Hong, Pan et al .…”

“…The potential of light to control PISA is also demonstrated in the works of Tan et al . and O'Reilly et al . to photo‐control RAFT‐mediated dispersion polymerizations.…”

“…As such, in the work of Wang, Matyjaszewski, and co‐workers, reporting on the simultaneous ARGET ATRP PISA (in dispersion) and the in‐situ crosslinking through ring opening of glycidyl methacrylate (GMA), only spherical particles were obtained. Two additional contributions propose alternative strategies to crosslink the core of the block copolymer particles: O'Reilly et al . propose the polymerization of pentafluorophenyl methacrylate (PFMA) as a core monomer yielding spherical particles, which could be successfully crosslinked after polymerization by the addition of diamines in a dry solvent (DMSO) to avoid side reactions.…”

Reactive Precursor Particles as Synthetic Platform for the Generation of Functional Nanoparticles, Nanogels, and Microgels

“…The concept of crosslinking of self‐assembled block copolymers was further extended by O'Reilly and co‐workers who used polymerization‐induced self‐assembly (PISA) via RAFT polymerization to prepare (PEG‐ b ‐PPFPMA) nanostructures . These structures were then stabilized via postpolymerization modification of the active esters of the core forming block with nonresponsive or redox‐responsive diamines …”