Blackman, Lewis D. (2017) Understanding the formation and responsive behavior of aqueous polymer self-assemblies. PhD thesis, University of Warwick.

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Abstract

This thesis explores the self-assembly and responsive behavior of block copolymer amphiphiles in aqueous solution. In Chapter 1, an overview of the modern synthetic methods used for preparing such materials will be given, as well as the parameters governing block copolymer self-assembly in solution. An introduction into polymerization-induced self-assembly will be given, as well as an overview of stimuli- responsive polymers and polymer self-assemblies. Finally, an outline of the analytical techniques used throughout this thesis for studying polymer self-assemblies will be given.

Chapter 2 will introduce thermoresponsive polymers, which can respond to changes in temperature, before investigating the solution behavior of a series of thermoresponsive polymer self-assemblies. These micelles have a tunable average number of chains per particle and will used as a platform to investigate the thermoresponsive behavior of the system using a range of complementary solution-based characterization techniques.

Chapter 3 will build on the knowledge gained in the previous chapter and will explore the effects of factors such as the glass transition temperature and hydrogen bonding ability on the thermoresponsive behavior of such systems. This will give an insight into the reversibility of thermoresponsive phase transitions, more generally, and provide a unique tool with which to probe structure-property relationships in stimuli-responsive self- assemblies.

Chapter 4 will uncover the differences between the two initiation pathways for polymerization-induced self-assembly, thermally and photoinitiated, discussed in this Chapter. Isothermal non-equilibrium phase diagrams will be constructed using thermally initiated and photoinitiated polymerization-induced self-assembly. The effects of light intensity on the formed nano-objects will be investigated as well as the effect of post synthetic light irradiation, both are aspects that have not been widely explored in the literature.

Chapter 5 will explore the use of polymerization-induced self-assembly to prepare selectively permeable biohybrid vesicular nanoreactors. Functional proteins with fluorescent or enzymatic capabilities will be encapsulated inside hollow polymersomes and the selective permeability of the membrane will be demonstrated. A clinically relevant therapeutic protein will also be investigated as the encapsulated species and the formed nanoreactors’ ability to prevent cancer cell proliferation will be validated. The non-covalent, yet protective nature of this protein compartmentalization will also provide several distinct advantages over covalent attachment of poly(ethylene glycol), the current state-of-the-art for this clinical therapeutic.

Finally, Chapter 6 will summarize the conclusions gained from the research herein, as well as offer some insights into possible areas of new research directed by the findings detailed in this thesis.

Item Type:	Thesis or Dissertation (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Amphiphiles, Self-assembly (Chemistry), Block copolymers, Polymerization
Official Date:	9 December 2017
Dates:	Date Event 9 December 2017 UNSPECIFIED
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	O'Reilly, Rachel K. ; Gibson, Matthew I.
Extent:	xxxiii, 255 leaves : illustrations, charts.
Language:	eng

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