Reactive Polymorphic Nanoparticles: Preparation via Polymerization-induced Self-assembly and Post-synthesis Thiol–para-Fluoro Core Modification

Busatto, Nicolas, Van Luc, Stolojan, Vlad, Shaw, M, Keddie, Joseph and Roth, Peter (2018) Reactive Polymorphic Nanoparticles: Preparation via Polymerization-induced Self-assembly and Post-synthesis Thiol–para-Fluoro Core Modification Macromolecular Rapid Communications.

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Abstract

The use of 2,3,4,5,6-pentafluorobenzyl methacrylate (PFBMA) as a core-forming monomer in ethanolic RAFT dispersion polymerization formulations is presented. Poly[poly(ethylene glycol) methyl ether methacrylate] (pPEGMA) macromolecular chain transfer agents were chain extended with PFBMA leading to nanoparticle formation via polymerization-induced self-assembly (PISA). pPEGMA-pPFBMA particles exhibited the full range of morphologies (spheres, worms, and vesicles) including pure and mixed phases. Worm phases formed gels that underwent a thermo-reversible degelation and morphological transition to spheres (or spheres and vesicles) upon heating. Post-synthesis, the pPFBMA cores were modified through thiol–para-fluoro substitution reactions in ethanol using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the base. For monothiols, conversions were 64% (1-octanethiol) and 94% (benzyl mercaptan). Spherical and worm-shaped nano-objects were core cross-linked using 1,8-octanedithiol, which prevented their dissociation in non-selective solvents. For a temperature-responsive worm sample, cross-linking additionally resulted in the loss of the temperature-triggered morphological transition. The use of the reactive monomer PFBMA in PISA formulations presents a simple method to prepare well-defined nano-objects similar to those produced with non-reactive monomers (e.g. benzyl methacrylate) and to retain morphologies independent of solvent and temperature.

Item Type:	Article
Divisions :	Faculty of Engineering and Physical Sciences > Chemistry
Authors :	Name Email ORCID Busatto, Nicolas, Van Luc n.busatto@surrey.ac.uk Stolojan, Vlad V.Stolojan@surrey.ac.uk Shaw, M Keddie, Joseph J.Keddie@surrey.ac.uk Roth, Peter p.roth@surrey.ac.uk
Date :	2018
DOI :	10.1002/marc.201800346
Copyright Disclaimer :	This is the peer reviewed version of an article which has been published in final form at: https://onlinelibrary.wiley.com/doi/abs/10.1002/marc.201800346. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Uncontrolled Keywords :	Thiol–para-fluoro reaction, nanoparticle cross-linking, temperature-responsiveness, PISA, postpolymerization modification
Depositing User :	Melanie Hughes
Date Deposited :	12 Jun 2018 16:30
Last Modified :	04 Jul 2019 02:08
URI:	http://epubs.surrey.ac.uk/id/eprint/847040

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