Exploring the scope and utility of dynamic covalent chemistry within polymeric nanoparticles

PhD ThesisDynamic covalent chemistry encompasses reversible bond forming reactions which proceed under equilibrium control, where the position of the equilibria are sensitive to changes in environment, and which are often able to undergo component exchange. These virtues provide polymeric nanoparticles incorporating dynamic covalent bonds with the ability to reconfigure or change their structural properties in response to stimuli. In Chapter 1 we critically discuss and evaluate the current state of the art whereby polymer chemists have exploited dynamic covalent bonds within responsive and adaptive polymeric nanoparticles. Chapter 2 describes the synthesis and study of a chemoresponsive polymeric micelle. In this work, aldehyde and alkoxyamine endfunctionalized polymers are shown to link together through a single oxime bond and then self-assemble into micellar aggregates. The chemoresponsive nature of these micellar aggregates is expressed when their disassembly is triggered through the addition of a small molecule alkoxyamine. Chemoresponsive core cross-linked star and nanogel nanoparticles which contain multiple imine cross-links are presented in Chapter 3. These imine linkages are utilized to facilitate the self-assembly process of the nanoparticles, which display chemoresponsive disassembly upon the addition of a small molecule amine. Chapter 4 describes the preparation of core cross-linked star polymers which are both pH-responsive and thermoresponsive. The pH-responsive nature is imparted through the pH-responsiveness of multiple imine linkages, and their thermoresponsive nature arises on account of the thermoresponsive polymer chains contained within their cores. In Chapter 5 nanoparticles possessing pH-responsive imine and redox-responsive disulfide cross-links have been developed where the simultaneous application of both low pH and a reducing agent is required to trigger their disassembly. It is shown that the application of either low pH or a reducing agent does not trigger disassembly. The research presented throughout this dissertation confirms the great potential of dynamic covalent chemistry in the development of stimuliresponsive polymeric nanoparticles