Scalable 1D and 2D polymer-based nanoparticles via crystallization-driven self-assembly

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dc.contributor.authorEllis, Charlotte Emily
dc.contributor.supervisorManners, Ian
dc.date.accessioned2022-04-21T20:34:08Z
dc.date.copyright2022en_US
dc.date.issued2022-04-21
dc.degree.departmentDepartment of Chemistry
dc.degree.levelDoctor of Philosophy Ph.D.en_US
dc.description.abstractSelf-assembly is ubiquitous in nature. A diverse range of materials with exceptional properties are accessed from a limited number of sub-units, through controlling structural order on all length-scales. Achieving the same level of control to access functional materials akin to those in nature is a key challenge in chemistry. Self-assembly of block copolymers (BCPs) offers a valuable bottom-up route, governed by non-covalent interactions, to access ordered assemblies on the nanoscale. Anisotropic nanostructures, such as one- and two-dimensional (1D and 2D) micelle morphologies, are of particular interest for various applications including those in biomedicine, catalysis, optoelectronics, and materials engineering. Crystallization-driven self-assembly (CDSA) of BCPs containing a crystallizable core-forming segment presents a robust route to preparing 1D and 2D micelles. Significantly, the use of pre-existing seed micelles in a process termed living CDSA allows access to 1D and 2D nanostructures of controlled size and low size-dispersity. Although CDSA protocols represent powerful tools for the formation controlled 1D and 2D nanostructures, key challenges associated with scale-up of these processes remain. In most cases, increasing the concentration at which living CDSA is performed results in competitive self-nucleation, compromising micelle size-control and dispersity. Living polymerization-induced crystallization-driven self-assembly (PI-CDSA) has been presented as a promising alternative route to accessing scalable 1D micelles. In this case, the polymerization, self-assembly, and seeded growth of a BCP containing a crystallizable core-forming segment occur in situ. However, the scope of living PI-CDSA is currently limited to the use of polyferrocenylsilane (PFS)-based BCPs. Owing to the diverse range of crystalline core chemistries compatible with CDSA protocols, and therefore various promising applications of 1D and 2D micelles, scale-up is essential to facilitate their further investigation and application. The work presented in this thesis focusses on upscaling the preparation and processing of controlled 1D and 2D micelles with a crystalline core. The scalable preparation of low dispersity 2D platelet micelles by living CDSA of a charge-terminated PFS homopolymer with surfactant counteranions is presented in Chapter 2. Here, fundamental insight into the effects of living CDSA concentration on platelet dimensions, structure fidelity, and aggregation behaviour is provided. In Chapter 3, the scope of living PI-CDSA is extended to access scalable length-controlled low dispersity 1D nanofibers containing a biodegradable poly(fluorenetrimethylenecarbonate) (PFTMC) crystalline core. PFTMC-based 1D fibers are of interest for biomedical applications, hence, in this work, it is demonstrated that living PI-CDSA can be used to prepare fibers exhibiting biologically-relevant lengths at scalable concentrations. In Chapter 4, the scalable formation of low dispersity 1D micelles by living CDSA of a PFS-based BCP in a continuous flow setup is explored. Processing of 1D micelles into microfibers using simple, low cost, and high throughput electrospinning techniques is demonstrated in Chapter 5. Finally, Chapter 6 summarises the contribution of this thesis to improving the scalability of CDSA protocols and provides future directions for this work.en_US
dc.description.embargo2023-04-12
dc.description.scholarlevelGraduateen_US
dc.identifier.bibliographicCitationEllis, C. E.; Fukui, T.; Cordoba, C.; Blackburn, A.; Manners, I. Towards Scalable, Low Dispersity, and Dimensionally Tunable 2D Platelets Using Living Crystallization-Driven Self-Assembly. Polym. Chem. 2021, 12 (25), 3650–3660.en_US
dc.identifier.urihttp://hdl.handle.net/1828/13866
dc.languageEnglisheng
dc.language.isoenen_US
dc.rightsAvailable to the World Wide Weben_US
dc.subjectblock copolymersen_US
dc.subjectpolymersen_US
dc.subject1D nanoparticlesen_US
dc.subject2D nanoparticlesen_US
dc.subject1D micellesen_US
dc.subject2D micellesen_US
dc.subjectcrystallization-driven self-assemblyen_US
dc.subjectpolymerization-induced self-assemblyen_US
dc.subjectscalablilityen_US
dc.subjectcontinuous flowen_US
dc.subjectelectrospinningen_US
dc.subjectcoaxial electrospinningen_US
dc.titleScalable 1D and 2D polymer-based nanoparticles via crystallization-driven self-assemblyen_US
dc.typeThesisen_US

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