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An investigation into the surface-based host-guest chemistry of an octanuclear coordination cage
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Ludden, Michael (2021) An investigation into the surface-based host-guest chemistry of an octanuclear coordination cage. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3766426
Abstract
An investigation into the surface-based host-guest chemistry of an octanuclear coordination cage
Chapter 1 – The first chapter of this work provides an overview of the subject area, including the history of supramolecular chemistry from its inception to the present day. The design and synthesis of coordination cages is also described, including the forces behind self-assembly and examples of applications that cages have been used for. The chapter concludes with a timeline of the work conducted by the Ward group, contextualising the work undertaken within this thesis.
Chapter 2 – This chapter covers the factors behind the water solubility of Ward group cages, specifically the octanuclear cubic cage [M8L12]16+. Anion exchange studies have been carried out to determine the conversion from BF4⁻ anions to other anions such as Cl⁻, NO3⁻ and HCO3⁻. The effect of altering the anionic composition of the cage on the catalysis of nitrobenzisoxazole to 2-cyano-4-nitrophenolate was also investigated, which revealed distinct differences in reaction rate depending on the nature of the anion.
Chapter 3 – Having determined that different anions will bind to the cage with varying affinities, a fluorescence displacement assay was developed to allow association constants to be calculated for a wide range of anions binding to the cage’s exterior surface, ranging from simple inorganic anions such as fluoride to larger organic anions e.g., gluconate. The stoichiometry of binding for anionic fluorophores such as fluorescein and hydroxypyrene tris-sulfonate to the cage’s exterior was also investigated.
Chapter 4 – With the knowledge that surface-bound fluorophores could be displaced, a colourimetric sensor for guest binding was designed using both cavity- and surfacebound fluorophores. This sensor is able to produce a different colour response depending on whether the analyte molecule binds on the inside or outside of the cage (or both) and can distinguish between these three different modes of binding.
Chapter 5 – A novel mixed-metal cage [Cr4Co4L12](Cl)20 was synthesised and subsequent guest-binding studies were carried out to investigate whether the higher charge of this complex would affect the binding constants of previously used fluorophore guest molecules e.g. fluorescein.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Coordination compounds, Catalysis, Anions, Chemical kinetics, Binding sites (Biochemistry), Supramolecular chemistry | ||||
Official Date: | September 2021 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Ward, Michael D. | ||||
Format of File: | |||||
Extent: | various pagings : illustrations | ||||
Language: | eng |
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