RAFT Emulsion Polymerization as a Platform to Generate Well‐Defined Biocompatible Latex Nanoparticles

Abstract

Current approaches to generate core-shell nanoparticles for biomedical applications are limited by factors such as synthetic scalability and circulatory desorption of cytotoxic surfactants. Developments in controlled radical polymerization, particularly in dispersed states, represent a promising method of overcoming these challenges. In this work, well-defined PEGylated nanoparticles are synthesized using reversible addition fragmentation chain transfer emulsion polymerization to control particle size and surface composition and were further characterized with light scattering, electron microscopy, and size exclusion chromatography. Importantly, the nanoparticles are found to be tolerated both in vitro and in vivo, without the need for any purification after particle synthesis. Pharmacokinetic and biodistribution studies in mice, following intraperitoneal injection of the nanoparticles, reveal a long (>76 h) circulation time and accumulation in the liver.

Bilayer‐Templated Two‐Dimensional RAFT Polymerization for Directed Assembly of Polymer Nanostructures

“…Among modern controlled/living radical polymerization methods, RAFT has emerged as a promising technique due to its versatility and simplicity and because the polymer is free from the contamination of metal catalysts . It was recently used to produce polymer nanostructures with different shapes . A common drawback of “living” free radical polymerization methods includes slow reaction rates in bulk solution due to the need to keep the concentration of radicals relatively low compared to the concentration of a mediating agent (for example, RAFT or degenerative chain transfer) in order to limit the biradical termination.…”

Alcohol mediated degenerate chain transfer controlled cationic polymerisation of para-alkoxystyrene

“…The advancement of macromolecular synthesis has enabled the creation of complex architectures and functional materials. [1][2][3][4][5][6][7] Although controlled radical polymerisation methods have dominated this area in general, 8,9,14 materials generated by cationic polymerisation offer unique properties that are not readily accessible by radical chemistry. 10,11 In contrast, controlled cationic polymerisation has gained less attention, due to the synthetic challenge in controlling the highly reactive propagating cationic species that often leads to more side reactions.…”

A study on the preparation of alkyne functional nanoparticlesviaRAFT emulsion polymerisation

“…Diblock macro-RAFT agent (TMS-Alkyne-O-P[(PEGA)12-b-(n-BA)12]) synthesis was indeed successful with TMS-Alkyne-PEsBTC (Figure 1a, Table 1, Figure S8) without significant molar mass deviation or low molar mass shoulders in the SEC chromatograms. However, the nanoparticles prepared using previously established RAFT emulsion polymerisation conditions 38 , with TMS-Alkyne-O-P[(PEGA)12-b-(n-BA)12] had a large PDi (0.235) and the dissolved polymers displayed broad molar mass distributions (Ð = 6.51) (Figure 2a, Figure 2f, Table 2). We suspected that the lack of electrostatic stabilisation, was the main cause of this instability, while the hydrophobicity of the trimethylsilyl end-group exacerbated this effect.…”

“…28 It has previously shown that RAFT emulsion polymerisation can be used to introduce carboxylic, [29][30][31][32][33][34][35] polysulfonated 36, 37 and biocompatible surfaces. 38 As of yet, this technique has not been used to produce any other surface functionality, including alkynes. Our aim in this work was therefore to introduce functional alkyne groups on the surface of nanoparticles, by performing RAFT emulsion polymerisations with alkyne functional macro-RAFT agents.…”