Lookup NU author(s): Michael Bracchi,
Dr Gema Dura,
Dr David Fulton
This is the authors' accepted manuscript of an article that has been published in its final definitive form by Royal Society of Chemistry, 2019.
For re-use rights please refer to the publisher's terms and conditions.
© 2019 The Royal Society of Chemistry. Dynamic covalent bonds can be utilized to endow polymer-based structures, such as nanoparticles or hydrogel networks, with the abilities to adapt their structures or compositions in response to an external stimuli. In this work we investigate the potential of aromatic thiols, which because they exhibit vastly different reactivities, pK a 's and nucleophilicities in comparison to aliphatic thiols, present an alternative reversible thiol/disulfide system for utilization within polymer-based structures. We demonstrate that water-soluble arylthiol pendant-functional random copolymers capable of forming dynamic disulfide bonds can be prepared and show how they can be cross-linked into polymeric nanoparticles and hydrogel networks through the formation of disulfide cross-links which can then be cleaved to reafford the initial aromatic thiol-functionalized polymers. We highlight how careful control of reaction conditions is required to drive the self-assembly of these polymers into nanoparticles in a process which is predominately under kinetic control. The potential of these arylthiol appended polymers to be utilized within a more complex orthogonal dynamic covalent polymer system also featuring polymer chains cross-linked through reversible imine bond formation was also investigated. This work expands the utility of aromatic disulfides in dynamic polymer systems and will broaden the range and versatility of dynamic covalent disulfide-based materials available to researchers in the fields of nanochemistry and functional materials.
Author(s): Bracchi ME, Dura G, Fulton DA
Publication type: Article
Publication status: Published
Journal: Polymer Chemistry
Print publication date: 14/03/2019
Online publication date: 30/01/2019
Acceptance date: 27/01/2019
Date deposited: 02/04/2019
ISSN (print): 1759-9954
ISSN (electronic): 1759-9962
Publisher: Royal Society of Chemistry
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