Crystal engineering: exploiting variation of sulfur oxidation for the control of the solid state structure of organosulfur compounds

This thesis is focused on the design and synthesis of a diverse range of novel organosulfur compounds (sulfides, sulfoxides and sulfones), with the objective of studying their solid state properties and thereby developing an understanding of how the molecular structure of the compounds impacts upon their solid state crystalline structure. In particular, robust intermolecular interactions which determine the overall structure were investigated. These synthons were then exploited in the development of a molecular switch. Chapter One provides a brief overview of crystal engineering, the key hydrogen bonding interactions utilized in this work and also a general insight into “molecular machines” reported in the literature of relevance to this work. Chapter Two outlines the design and synthetic strategies for the development of two scaffolds suitable for incorporation of terminal alkynes, organosulfur and ether functionalities, in order to investigate the robustness and predictability of the S=O•••H-C≡C- and S=O•••H-C(α) supramolecular synthons. Crystal structures and a detailed analysis of the hydrogen bond interactions observed in these compounds are included in this chapter. Also the biological activities of four novel tertiary amines are discussed. Chapter Three focuses on the design and synthesis of diphenylacetylene compounds bearing amide and sulfur functionalities, and the exploitation of the N-H•••O=S interactions to develop a “molecular switch”. The crystal structures, hydrogen bonding patterns observed, NMR variable temperature studies and computer modelling studies are discussed in detail. Chapter Four provides the overall conclusions from chapter two and chapter three and also gives an indication of how the results of this work may be developed in the future. Chapter Five contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of the NCI (National Cancer Institute) biological test results are included in the appendix.

Assessing the impulse control of violent offenders using computer-based cognitive performance tasks

The topic of this thesis is impulsivity. The meaning and measurement of impulse control is explored, with a particular focus on forensic settings. Impulsivity is central to many areas of psychology; it is one of the most common diagnostic criteria of mental disorders and is fundamental to the understanding of forensic personalities. Despite this widespread importance there is little agreement as to the definition or structure of impulsivity, and its measurement is fraught with difficulty owing to a reliance on self-report methods. This research aims to address this problem by investigating the viability of using simple computerised cognitive performance tasks as complementary components of a multi-method assessment strategy for impulse control. Ultimately, the usefulness of this measurement strategy for a forensic sample is assessed. Impulsivity is found to be a multifaceted construct comprised of a constellation of distinct sub-dimensions. Computerised cognitive performance tasks are valid and reliable measures that can assess impulsivity at a neuronal level. Self-report and performance task methods assess distinct components of impulse control and, for the optimal assessment of impulse control, a multi-method battery of self-report and performance task measures is advocated. Such a battery is shown to have demonstrated utility in a forensic sample, and recommendations for forensic assessment in the Irish context are discussed.