After the initial chapter (a general introduction to the relevant field) each following chapter contains an introductory section that gives relevant background information. The thesis of a whole consists of two general parts: firstly the synthetic development of functionalised cubic cage complexes; secondly the development of the host-guest chemistry of the Ward group's cubic cage, specifically concerned with the trapping, catalysed hydrolysis, and predicted binding of chemical warfare agent simulants.
Chapter 1: Introduction
This chapter consists of a brief history and general introduction to the supramolecular chemistry field. This starts with discussion of self-assembly and molecular interactions used. Principles behind the design of coordination-chemistry driven assemblies and key examples are introduced. Finally the various Ward group cages are discussed along with the recently published host-guest applications for the cubic cages (HA and HW).
Chapter 2: Synthesis
The chapter focuses on the synthetic development of ligands to yield a cage complex soluble in non-polar solvents such as dichloromethane, using a range of different routes, similar to those for HA and HW.
Chapter 3: Binding of Chemical Warfare Agent Simulants
This chapter introduces chemical warfare agents. The history, usage and related working involving G-series nerve agent simulants is discussed before HA and HW are used to bind a series of alkyl phosphonates (size and shape related simulants).
Chapter 4: Catalysed Destruction of Dichlorvos
Dichlorvos, a pesticide with similar chemical properties to G-series nerve agents, is bound in the cubic cage and then the cage catalysed hydrolysis is investigated. After finding some complications with HW, a different cubic cage host (HD) is used instead and gives a 500-fold rate enhancement for the hydrolysis of dichlorvos.
Chapter 5: Predicting Guest Binding
This final chapter delves into using a protein docking program (GOLD) to predict the binding affinities of a range of aliphatic ketones. While previous work has successfully predicted binding constants for rigid guests, improvement to the scoring function was required to predict the binding of flexible ketones. After improving the prediction of binding, the experimental binding affinities for the newly bound ketones and the series of alkyl phosphonates from chapter 3 closely matched those calculated.
