'Green' approaches for chemical synthesis

Synthetic polymers and polymeric materials have become ubiquitous with our daily lives. However, their production often relies on non-environmentally friendly chemical processes, based upon fossil fuel derived energy and toxic organic solvents. With the growing concern for the environmental impact of polymeric material, a transition towards more sustainable and ‘green’ polymer synthesis approaches are necessary. Reversible-deactivation radical polymerisations (RDRPs) processes, particularly atom transfer radical polymerisation (ATRP), pave the way towards more sustainable and practically less demanding polymerisation methods. Atom transfer radical polymerisation (ATRP) is a ‘controlled/living’ technique which enables the synthesise of polymers with well-defined macromolecular characteristics and complex architectures. Advances in this method have enabled polymerisation to proceed with low concentrations of transition metals and often in ‘green’ aqueous conditions. One such advancement is Activators Regenerated by Electron Transfer (ARGET) ATRP. However, conventional ARGET ATRP typically requires a continuous supply of a reducing agents. This study seeks to overcome these challenges by either reducing sugars coupling electrogenic bacteria with ARGET ATRP. Such an approach enables the synthesis of biocompatible polymers in aqueous media, while also investigating correlations between the electrochemical activity of the bacteria and the resulting polymer quality. To investigate this hypothesis, ARGET ATRP was carried out with both gram-negative and gram-positive microorganisms to polymerise the hydrophilic monomer, oligo(ethylene glycol) methyl ether methacrylate (OEGMA500). The gram-negative bacteria, Shewanella loihica (S. loihica) and Pseudomonas aeruginosa (P. aeruginosa), and gram-positive bacteria L. monocytogenes demonstrated the ability to facilitate polymerisation with high monomer conversions of 100, 81, and 88% respectively. ARGET ATRP was also performed using ascorbic acid (AA) as the reducing agent to allow direct comparison with state-of-the-art systems. A substantial and sustained negative redox potential ( Eh > −400 mV for 16 h) was measured for both S. loihica and L. monocytogenes, demonstrating the promising potential of these bacteria to effectively modulate the equilibrium of the ATRP reactions for controlled polymer synthesis. In addition, the capacity of reducing sugars to drive controlled ATRP reactions was also evaluated. Reducing sugars, such as glucose, cellobiose and lactose, are often employed as carbon sources to grow electrogenic bacteria. Complete monomer conversion was observed for glucose- and cellobiose-mediated ARGET ATRP. Future work will focus on further optimising these reactions with electrogenic bacteria under aerobic conditions, and using reducing sugars from food waste as alternative/sustainable carbon sources

The Guinness family and the shaping of Dublin 1868-1927

This dissertation examines the role the Guinness family played in the shaping of Dublin between the death of Sir Benjamin Lee Guinness in 1868 and the passing of his youngest son, Edward Cecil Guinness, 1st Earl of Iveagh, in 1927. It looks at how the Guinnesses impacted both the city and the county of Dublin not only physically but across the spheres of culture, industry, philanthropy, politics, public health, society, and religion. It is reductive and one dimensional to see the Guinnesses simply as generous fringe figures who selflessly applied their income from making beer to alleviate the malaise that surrounded them. Generous they were and the family did ameliorate the difficult living conditions for many of their fellow citizens, but they were not acting on the fringes. They were major players who worked to place themselves at the centre of the Irish establishment. Their philanthropic initiatives should also be seen as vehicles to achieve their own ambitions and shape public opinion. They were major political actors, often working behind the scenes to maintain the status quo. The rise of threats from within, including Irish nationalism, agitation for land reform, and triumphal Catholicism, mixed with an infiltration of external influences such as leftwing ideologies in the form is socialism and syndicalism combined to bring the Guinness’s world crashing down. The irony is that even as the Guinness family were working to ensconce themselves firmly within the Protestant Ascendancy that world was already slipping away. The central argument of this thesis is that the Guinnesses tried to arrest this decline of by using Dublin as a bulwark, and that even after the achievement of Irish independence in 1922 they aVempted to salvage as many remnants of Ireland’s ancient régime as they could2025-10-23 JG: Author's signature removed from PD

Hauntology: Neoliberalism, State-Keynesianism, and Repressed Contradictions in Post-1980 Anglo-American Fiction

This thesis will apply a Marxist, world-ecological framework to the study of the aesthetic mode of hauntology in post-1980 Anglo-American fiction. I argue that hauntology is an aesthetic mode which arises in fiction set within core regions of the capitalist world-system. I contend that hauntological fiction is characterised by a historically specific form of haunting, in which the era of neoliberal conditions is haunted by the period of state-Keynesianism. Hauntological novels are typified by a return to the mid-century from a post-1980 perspective, and this attachment to the mid-century mediates unresolved contradictions. I focus on a number of contradictions, including: the contradiction between capitalism’s promotion of individual self-interest versus the conditions required for total social reproduction; the contradiction between capitalism’s claims to legal equality and freedom versus capitalism’s reliance on forms of inequality and economic coercion; and the contradiction between capitalism’s drive for exponential growth versus ecological limits. Crucially, haunting in hauntological fiction occurs not only from the past but also from the future, particularly from the threat of the impending climate crisis which exposes the unsustainability of both state-Keynesianism and neoliberalism. I argue that reading hauntological fiction can provide an opportunity to re-narrate the mid-century, avoiding conceptions of the relationship between state-Keynesianism and neoliberalism as one of pure rupture or pure continuity. The way in which the mid-century continues to haunt neoliberalism in these novels speaks to how neoliberalism did not simply emerge in opposition to, but built upon, the affects, subjectivities, and institutions created by state-Keynesianism. Simultaneously, hauntological fiction offers an insight into how the affective experience of the transition from state-Keynesianism to neoliberalism was one of rupture and can shed light on how perceptions of a clean break between the two orders have generated a mindset of declinism

Development of a High-Average Radiance Soft X-ray Light Source

This thesis presents the iterative development of a table-top (TT) laser-produced plasma (LPP) light source optimised for high average radiance in the soft x-ray (SXR) region. The system employed a solid molybdenum target and exhibited peak emission within the water window (WW) region. Plasma generation was driven by a diode-pumped λ = 1064 nm Nd:YAG laser delivering 5 ns pulses (full width at half maximum, FWHM) with an energy of 37.5 mJ at a repetition rate of 1 kHz. Focusing these pulses with a 100 mm lens produced LPP SXR emission diameters (averaged over 100 shots) of approximately 22 μm and 13 μm (FWHM) along the horizontal and vertical axes, respectively, corresponding to an estimated radiance of 5×10¹⁰ photons/s/mm²/mrad² at 2.74 nm and 0.1% relative bandwidth (BW). This prototype addresses key challenges in solid target light-source development and paves the way for a design capable of achieving radiance up to two orders of magnitude greater. Realising this increase requires relatively straightforward improvements to the focusing optics and target stability. The compact design relies on helium buffer gas as the primary debris mitigation mechanism to protect nearby optical components. This approach necessitated the integration of a 100 nm thick silicon nitride membrane (SNM), positioned in close proximity to the LPP, to serve as a helium-vacuum interface transmissive to SXR radiation. To shield both the SNM and the laser focusing lens from particulate debris, a set of novel components was developed to manipulate particle trajectories through interaction with high-velocity gas flows. These components were designed using a three-dimensional (3D) particle drag force model, coupled with computational fluid dynamics (CFD) simulations of the surrounding environment. The final configuration demonstrated stable collection of SXRs from the LPP, transmitted through the SNM at a 2.7° collection angle, over a continuous 4 hour period. This duration represents a substantial fraction of the expected daily operational cycle for TT light sources intended for imaging, patterning, and spectroscopy applications

What is the Problem of Dual Diagnosis Represented to be in Sharing the Vision?

This thesis critically analyses the role of Ireland’s national mental health policy, Sharing the Vision (Government of Ireland, 2020), in shaping a public healthcare issue known as dual diagnosis. In the thesis, I undertake a scoping review of the literature to explore how dual diagnosis is defined and problematised. Afterwards, I deploy a poststructuralist approach that rests on a form of governmentality theory to examine how Sharing the Vision produces dual diagnosis in particular ways, primarily through the use of problems. Drawing on the analytical framework known as the ‘What’s the Problem Represented to be? (WPR) approach (Bacchi, 2009), I examine the ways in which Sharing the Vision represents the problem of dual diagnosis; the medical, rationalist and neo-liberal discourses that belie these representations; and the silences that are an effect of these representations; closing off other ways of imagining dual diagnosis. Though the object of this thesis is government policy, the concern is for the conceptualisation of dual diagnosis, and the implications particular representations have on the lives of people that are affected. The thesis contributes to a gap both in the critical analysis of the concept of dual diagnosis (Iudici et al., 2020) and the absence of such an analysis in the Irish context. The research aims to support and inform dialogue on dual diagnosis in Ireland, pointing to the way in which this issue is contested and challenged

Dynamic gene regulatory network construction from high-throughput time-course data

The rapid advancement of high-throughput genomic technologies has created many opportunities to analyze gene expression and gain insights into complex biological processes. In particular, time-course gene expression data has become important for understanding the dynamic response of biological systems and for constructing and analyzing dynamic gene regulatory networks (GRNs) that denote the interaction between genes. However, the analysis of time-course gene expression data presents numerous statistical and computational challenges due to the high dimensionality of the data and substantial measurement error. This thesis addresses several of these challenges in the context of constructing and analyzing GRNs by developing four novel statistical methodologies aimed at improving the pre-processing of time-course data, clustering in both temporal and spatial contexts, and the statistical analysis of samples of GRNs

Titian, Giulio Romano, and the Legacy of the Caesars Reconstructing Federico II Gonzaga’s Camerino dei Cesari at the Palazzo Ducale in Mantua

The research presented in this thesis provides fresh insights into the richness and complexity of Titian and Giulio Romano’s work for one of the major decorative cycles of the Italian renaissance, the Camerino dei Cesari at the Ducal Palace in Mantua (1536-1540). The thesis will begin by exploring the artistic tradition of depictions of uomini illustri as a genre and how this was developed into a propaganda tool in the North Italian courts. The research explores previously undeveloped links, and parallels, between the Camerino and Mantegna’s anticipatory monument to Gonzaga immortality, the Camera degli Sposi (1465 -1474). The political context of this major commission is then considered from the point of view of all the key players: Federico II Gonzaga, Duke of Mantua; the Holy Roman Emperor, Charles V; Titian; and Giulio Romano. Attention will then turn to new and comprehensive digital reconstructions of the Camerino’s lost decorative scheme. These have been developed to a new standard of accuracy, drawing on visual material and actual paintings from the visual scheme previously thought lost, but rediscovered by the author. These include an equestrian painting of Julius Caesar in a private collection in England and an album of sixteenth-century drawings after Titian’s eleven portraits of the Caesars by their first and prolific copyist, Bernardino Campi. These reconstructions, and a close examination of Andreasi’s drawings, have revealed previously unseen details which suggest new interpretations of the scheme’s iconography within the context of the wealth and political ambitions of the Gonzaga family. The research also sheds new light on the source material available to the artists and how this was applied in the development of the decorative scheme. The context of how this material was interpreted and understood in the sixteenth century is considered. The thesis also considers the heritage of these works as part of a more general appraisal of the Camerino’s significant artistic legacy: Titian’s portrayals of the Caesars for the Camerino constitute some of the most copied and imitated paintings in European art of the early modern period

Computational Modelling and Experimental Development of Novel Liquid Air Energy Storage Systems

As the planet shifts towards sustainable energy, the need for efficient, scalable, and geographically flexible energy storage solutions is paramount. LAES systems, characterized by their geographical independence, long lifespan, and potential for leveraging existing industrial infrastructure, are emerging as a viable solution to this challenge. The research presented in this thesis encompasses the development and analysis of innovative approaches to enhance the efficiency and integration capabilities of LAES systems. A significant focus is placed on the novel concept of using packed beds for the direct liquefaction and regasification of air, aiming to improve the energy performance of the system. A comprehensive model, formulated and refined using data from various sources, is introduced to evaluate this concept. Experimental investigations, including the development of a packed bed experimental pilot rig, demonstrate the conceptual viability of this approach. The performance of the packed bed system, particularly in terms of energy efficiency, is critically assessed. Additionally, the thesis explores the integration of cryogenic CO2 capture in packed beds within LAES systems. A new model for cryogenic CO2 capture is developed. A parametric study using this model investigates the impact of a number of parameters on the performance of this cryogenic CO2 capture system. Building on these findings, the thesis finally proposes an innovative LAES system which integrates the packed bed model developed in this thesis into an LAES system. This packed bed LAES integrated system shows potential for high round-trip efficiency of up to 76%, and its modular nature makes it suitable for integration with external cold energy sources, such as LNG regasification terminals

Studies on epidemiology and co-morbidities of adult Attention Deficit Hyperactive disorder in (ADHD) in northwest area of Ireland

This thesis is an endeavour to examine epidemiology of Adult ADHD in people attending mental health services in northwest area of Ireland. In addition, it examined mental health comorbidities including personality disorders, functionality, and quality of life in adults newly diagnosed with ADHD in their adult life. Further the association of childhood symptoms as they measured with the retrospective scale Wender Utah Rating Scale (WURS) with specific mental health disorders in adulthood (including ADHD) was explored. Finally, a new scale was developed and psychometrically tested which allows for the clinician routinely to measure clinical outcomes from interventions at individual level as well as overall outcomes of the service. The major findings of those studies where that there is a considerable number of undiagnosed or misdiagnosed ADHD cases among people attending adult mental health services (prevalence 16.1%). A meta-analysis of four similar studies shows a pooled prevalence of 16.31%. Also, the number of comorbid mental disorders in people with ADHD was higher compared to those without ADHD, and those with ADHD had significantly higher rates of depression and recurrent depression compared to those without. In the same line regarding personality disorders (PDs) the majority of those with ADHD had at least one comorbid PD the most common being the Dependent PD, followed by Depressive PD. Additionally, in terms of functionality and quality of life, those diagnosed with ADHD had significantly poorer functionality and lower quality of life compared to those with similar symptomatology but without ADHD diagnosis. Moreover, it was found that there was an association between certain childhood behaviours classified by WURS and later diagnosis in adulthood with ADHD, personality disorders, and substance abuse. Finaly, the new ADHD Clinical Outcome Scale (ACOS) tested in a sample of 148 participants, and it was found with high internal consistency (83%), high Inter-rater reliability (87%), good concurrent validity with Weiss Functional Impairment Rating Scale, 48%, and Adult ADHD Quality of Life Questionnaire (57%) and it was sensitive to clinical changes. The above results of the studies which included in this thesis, had a major impact on the design and development of a new adult ADHD service in national level, and influenced the guidelines proposed in the Model of Care from the National Clinical Programme for Adult ADHD. In addition, at the local level the place where this research was carried out was the first where an ADHD tertiary clinic developed under the auspices of the National Clinical Programme

Reading the Global City: New York, London and the Capitalist World-System in the Late Neoliberal Novel

This thesis examines works of fiction written in the wake of the 2008/11 financial crash which take the global city as a setting from which to interrogate capitalist relations of combined and uneven development and the cultural, ideological and spatial means through which these relations are obscured. These novels mediate critical responses to Fredric Jameson’s concept of “cognitive mapping,” which calls for a pedagogical aesthetic that would “enable a situational representation on the part of the individual subject to… the ensemble of society’s structures as a whole” (1991: 51). I contend that this preoccupation represents a characteristic current of critique in the “late neoliberal novel,” in which crisis precipitates the (re-) emergence of the horizon of totality in cultural productions. The thesis is divided into four chapters. The first analyses Tom McCarthy’s Satin Island (2015) as a work thematising the ideological, mediatory role played by particular forms of urban and global space in the (re-) production of “false consciousness” in post-Fordist cores, while the second examines Ben Lerner’s 10:04 (2014) in relation to its pursuit of an immanent form of cognitive mapping that seeks to overcome these epistemological and ideological conditions. In Chapter Four, Teju Cole’s Open City (2011) is analysed in relation to its counterhegemonic readings of urban space, revealing the repressed violence – past and present, local and global – in which the global city is implicated. Finally, Rachel Kushner’s The Flamethrowers (2014) is analysed as an engagement with the ascent of neoliberalism and its attendant cultural logic in 1970s New York, addressing the structural role played by artists in the resolution of Fordist crisis in both concrete urban and broad cultural terms in order to address the dialectical entanglements of subjectivity, art, space and totality