Semi‐Fluorinated Methacrylates: A Class of Versatile Monomers for Polymerization‐Induced Self‐Assembly

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.

Section: Methodsmentioning

confidence: 98%

Section: Methodsmentioning

confidence: 99%

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

Couturaud

Georgiou

Varlas

et al. 2018

“…Alcoholic RAFT dispersion polymerizations of 2-(perfluorobutyl)ethyl methacrylate (FBEMA), 2-(perfluorohexyl) ethyl methacrylate (FHEMA), and 2-(perfluorooctyl)ethyl methacrylate (FOEMA) were investigated. [73] PISA of FBEMA in ethanol resulted in the production of spheres, worm-like micelles, and vesicles depending on the DP of PFBEMA and the solids content. In contrast, PISA of FHEMA (which has a higher fluorine content than FBEMA) resulted solely in spheres regardless of the DP of FHEMA.…”

Section: Controlling Particle Sizementioning

confidence: 99%

“…To this end, in a recent report, a series of semi‐fluorinated methacrylates was systematically assessed for their applicability to PISA. Alcoholic RAFT dispersion polymerizations of 2‐(perfluorobutyl)ethyl methacrylate (FBEMA), 2‐(perfluorohexyl)ethyl methacrylate (FHEMA), and 2‐(perfluorooctyl)ethyl methacrylate (FOEMA) were investigated . PISA of FBEMA in ethanol resulted in the production of spheres, worm‐like micelles, and vesicles depending on the DP of PFBEMA and the solids content.…”

Section: Raft Dispersion Polymerizationmentioning

confidence: 99%

Controlling Nanomaterial Size and Shape for Biomedical Applications via Polymerization‐Induced Self‐Assembly

Khor

Quinn

Whittaker

et al. 2018

145

136

Rapid developments in the polymerization-induced self-assembly (PISA) technique have paved the way for the environmentally friendly production of nanoparticles with tunable size and shape for a diverse range of applications. In this feature article, the biomedical applications of PISA nanoparticles and the substantial progress made in controlling their size and shape are highlighted. In addition to early investigations into drug delivery, applications such as medical imaging, tissue culture, and blood cryopreservation are also described. Various parameters for controlling the morphology of PISA nanoparticles are discussed, including the degree of polymerization of the macro-CTA and core-forming polymers, the concentration of macro-CTA and core-forming monomers, the solid content of the final products, the solution pH, the thermoresponsitivity of the macro-CTA, the macro-CTA end group, and the initiator concentration. Finally, several limitations and challenges for the PISA technique that have been recently addressed, along with those that will require further efforts into the future, will be highlighted.

“…For a typical PISA process, a solvophilic homopolymer is chain extended with a second monomer to form an amphiphilic block copolymer that undergoes in situ self‐assembly to produce nanoparticles in one pot . Therefore, PISA represents an extremely versatile, efficient, and cost‐effective approach toward fabrication of block copolymer nanoparticles . Introducing stimuli‐responsive functional groups to PISA system provides a convenient route to stimuli‐responsive polymer nanoparticles.…”

Section: Introductionmentioning

confidence: 99%

CO₂‐Breathing Polymer Assemblies via One‐Pot Sequential RAFT Dispersion Polymerization

Zeng

Huo

Yan

et al. 2018

Self Cite

ABC triblock copolymer assemblies with reversible "breathing" behaviors based on poly[oligo(ethylene glycol) methyl ether methacrylate]-b-poly(benzyl methacrylate)-b-poly[2-(diethylamino)ethyl methacrylate] (POEGMA-b-PBnMA-b-PDEA) are fabricated via one-pot sequential reverisble addition-fragmentation chain transfer dispersion polymerization. Using a POEGMA as the macromolecular chain transfer agent, chain extension with BnMA and DEA is conducted in ethanol, where PBnMA acts as the core-forming block, and the PDEA block endows the solvophilicity and CO -responsiveness. With the increment of the DP of PBnMA, the morphology of the assemblies evolves from spheres to worms, and to vesicles, while it degenerates from conglutinated vesicles to spheres as the DP of PDEA increases. After replacing ethanol with water, the morphologies of these assemblies remain unchanged, while their size decreases due to the collapse of the hydrophobic PDEA chains. Interestingly, due to the protonation and deprotonation of PDEA blocks, both the spheres and vesicles manifest a reversible expansion/shrinkage upon alternative CO /Ar stimulation, exhibiting distinctive breathing feature.