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

Benoit Couturaud,Rachel K O'Reilly,Panagiotis G Georgiou,Maria C Arno,Jeffrey C Foster,Spyridon Varlas,Joseph R Jones

doi:10.1002/marc.201800460

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.

Highlights

Polymer-based stimuli-responsive materials have been the subject of significant and sustained research owing to their potential for a range of applications, e.g., drug delivery, sensing, smart coatings.[1]
We report the first example of using Pentafluorophenyl methacrylate (PFMA) as the core-forming block for reversible addition-fragmentation chaintransfer (RAFT)-mediated Polymerization-induced self-assembly (PISA) conducted in DMSO
We noted that our initial attempts to prepare PPFMA homopolymers in DMSO via RAFT resulted in macroscopic precipitation

Summary

Introduction

Polymer-based stimuli-responsive materials have been the subject of significant and sustained research owing to their potential for a range of applications, e.g., drug delivery, sensing, smart coatings.[1]. We report the first example of using PFMA as the core-forming block for RAFT-mediated PISA conducted in DMSO.

Results

Conclusion