Archbishop William King (1650-1729) and the Constitution of Church and State

Accepted Version

Synthesis of iminophosphine and phosphinoiminol cyclometallated Pt (II) and Pt (IV) chloro complexes and studies into their biological and photophysical properties

This thesis focuses on the synthesis and analysis of novel chloride based platinum complexes derived from iminophosphine and phosphinoamide ligands, along with studies on their reactivity towards substitution and oxidation reactions. Also explored here are the potential applications of these complexes for biological and luminescent purposes. Chapter one provides an extensive overview of platinum coordination chemistry with examples of various mixed donor ligands along with the history of platinum anticancer therapy. It also looks at metals in medicine, both for biological functions as well as for therapeutic purposes and gives a background to some other applications for platinum complexes. Chapter two outlines the design and synthetic strategies employed for the development of novel platinum (II) chloride complexes from iminophosphine and phosphinoamide ligands. Also reported is the cyclometallation of these complexes to form stable tridentate mixed donor platinum (II) compounds. In Chapter three the development of a direct method for displacing a chloride from a platinum metal centre with a desired phosphine is reported. Numerous methods for successful oxidation of the platinum (II) complexes will also be explored, leading to novel platinum (IV) complexes being reported here also. The importance of stabilisation of the displaced anion, chloride, by the solvent system will also be discussed in this chapter. Chapter four investigates the reactivity of the platinum (II) complexes towards two different biomolecules to form novel platinum bio-adducts. The potential application of the platinum (II) cyclometallates as chemotherapeutics will also be explored here using in-vitro cancer cell testing. Finally, luminescence studies are also reported here for the ligands and platinum complexes reported in chapter two and three to investigate potential applications in this field also. Chapter five provides a final conclusion and an overall summary of the entire project as well as identifying key areas for future work.

Assessment of primary energy conversions of oscillating water columns. II. Power take-off and validations

This is the second part of the assessment of primary energy conversions of oscillating water columns (OWCs) wave energy converters. In the first part of the research work, the hydrodynamic performance of OWC wave energy converter has been extensively examined, targeting on a reliable numerical assessment method. In this part of the research work, the application of the air turbine power take-off (PTO) to the OWC device leads to a coupled model of the hydrodynamics and thermodynamics of the OWC wave energy converters, in a manner that under the wave excitation, the varying air volume due to the internal water surface motion creates a reciprocating chamber pressure (alternative positive and negative chamber pressure), whilst the chamber pressure, in turn, modifies the motions of the device and the internal water surface. To do this, the thermodynamics of the air chamber is first examined and applied by including the air compressibility in the oscillating water columns for different types of the air turbine PTOs. The developed thermodynamics is then coupled with the hydrodynamics of the OWC wave energy converters. This proposed assessment method is then applied to two generic OWC wave energy converters (one bottom fixed and another floating), and the numerical results are compared to the experimental results. From the comparison to the model test data, it can be seen that this numerical method is capable of assessing the primary energy conversion for the oscillating water column wave energy converters.

Frederick Douglass and Ireland, 1845: The "Vertiginous Twist[s]" of an Irish Encounter

Frederick Douglas was a reader of and writer on the nineteenth-century political and social texts and contexts of oppression, which he experienced at home and witnesed while in Ireland and Britain, 1845-47. This thesis is unique in its identification of several surprising lacunae in the research and critical evaluation of Frederick Douglass’ activities of reading and writing and the texts and contexts that supported these activities. This thesis takes Douglass’ relationship with Ireland and the Irish as its starting point, and offers several moments in the transnational space engendered by Douglass’ readerly and writerly experience of the transatlantic axes of Ireland, Britain and America. This thesis draws upon archival research to recover information regarding Douglass’ trip and subjects his reading and writing on Ireland and the Irish to the critical rigours of narratolgical, cultural and discourse analysis. One lacuna is Douglass’ favourite and neglected school primer, the Columbian Orator, which Douglass signified upon across his autobiographical project. The speech by the Irish patriot and exile, Arthur O’Connor, included in the Orator, is crucial to Douglass’ understanding and expression of justice and equality. Genette’s narratological analysis gives theoretical traction to the ways in which, in his autobiographical representations of his British trip, Douglass recalibrates his autobiographies to reflect his changing perspectives on his life and work. Contrary to popular assumptions, Douglass did, in two letters to Garrison address and comment on Irish poverty. This thesis interrogates the strategic anglophilia of these letters. While the World’s Temperance Convention (WTC) refused to discuss African- American slavery, analysis of Douglass’ speech in Covent Garden and of the paratextual apparatus of the published proceedings of the WTC demonstrates the impossibility of separating these closely interrelated reform causes. When a newly discovered poem from Waterford that admonished the city for its disregard for Douglass’ message is juxtaposed with an uncomfortable moment in Cork, we understand that Douglass became a pawn to bolster sectarian rivalries between nationalist and establishment factions. Though Douglass believed imperial politics was the best vehicle for modernity, he recognised that it had failed Ireland: consequently, in Thoughts and Recollections of a Trip to Ireland (1886), he advocates for Home Rule for Ireland.