Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.770585
Title: Binuclear complexes as quantitative imaging agents
Author: Hill, Leila
ISNI:       0000 0004 7653 4631
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2018
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Abstract:
This thesis explores the synthesis of and subsequent use of mono- and binuclear lanthanide complexes in their binding to biologically endogenous dianions. Chapter 1 outlines the properties of the lanthanides with a focus on their chemical and photophysical behaviour and self-assembly involving lanthanide-containing complexes. Medical applications are also discussed. Chapter 2 sets the scene for anion binding with lanthanide complexes by establishing the fundamentals and thermodynamics of their interactions with dicarboxylate species. In this chapter, the focus is on the use of luminescence spectroscopy to explore the nature of self-assemblies and establish the role of local and remote structural variations (in concert with solvation effects) in tuning binding affinity for dicarboxylate guests. Chapter 3 covers the synthesis and characterisation of a set of binuclear lanthanide complexes of ligands in which m-xylyl derivatives bridge two DO3A-derived domains. Chapter 4 describes the synthesis and characterisation of mononuclear complexes. These exhibit greater structural variation than the m-xylyl systems, containing the DO3A core with pendent benzyl, propargyl and coumarin groups. Chapter 5 discusses the synthesis and characterisation of two binuclear naphthyl complexes, in which 2,6- and 2,7- substituents are used to form the bridge between the two DO3Ayl domains. Chapter 6 extends the synthesis of the style of binuclear complex described in Chapter 3 by coupling the amino derivative to the longer wavelength sensitiser acridone. Chapter 7 provides an overview of the binding studies performed in this thesis with mono- and binuclear host complexes to an array of anionic guests, outlining and comparing methods for using luminescence and NMR to explore guest binding events. Chapter 8 considers specifically binding to species from the glycolytic pathway and to the similar chain-length carboxylate species tartrate and lactate. These studies reveal that the dianionic species in the pathway can act as bridging ligands, and that differences in structure and photophysics can give rise to selective responses from different guests. Chapter 9 evaluates binding to endogenous and non-biological phosphate species, both by luminescence measurements and phosphorus NMR. Chapter 10 focuses on binding to and interactions with catechol species including dopamine. In these systems, the relative instability of catechols in solution combines with inner filter effects to present challenges to method development. Chapter 11 lays out the conclusions reached over the course of this work and suggests possible opportunities for further work. Chapter 12 contains experimental procedures and techniques for processing data.  A series of appendices provide supplementary information to the core thesis, including a reference to the molecular structures of host complexes and guest anions in this thesis, X-ray crystallography data, and published papers.
Supervisor: Faulkner, Stephen Sponsor: Cancer Research UK
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.770585  DOI: Not available
Keywords: spectroscopy and molecular structure ; inorganic chemistry ; Chemistry ; supramolecular chemistry ; physical sciences
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