A microscopic study of structural and electronic properties of functionalized silicon surfaces based on first-principles

Surface modification of silicon with organic monolayers tethered to the surface by different linkers is an important process in realizing future (opto-)electronic devices. Understanding the role played by the nature of the linking group and the chain length on the adsorption structures and electronic properties of these assemblies is vital to advance this technology. This Thesis is a study of such properties and contributes in particular to a microscopic understanding of induced changes in the work function of experimentally studied functionalized silicon surfaces. Using first-principles density functional theory (DFT), at the first step, we provide predictions for chemical trends in the work function of hydrogenated silicon (111) surfaces modified with various terminations. For nonpolar terminating atomic species such as F, Cl, Br, and I, the change in the work function is directly proportional to the amount of charge transferred from the surface, thus relating to the difference in electronegativity of the adsorbate and silicon atoms. The change is a monotonic function of coverage in this case, and the work function increases with increasing electronegativity. Polar species such as −TeH, −SeH, −SH, −OH, −NH2, −CH3, and −BH2 do not follow this trend due to the interaction of their dipole with the induced electric field at the surface. In this case, the magnitude and sign of the surface dipole moment need to be considered in addition to the bond dipole to generally describe the change in work function. Compared to hydrogenated surfaces, there is slight increase in the work function of H:Si(111)-XH, where X = Te, Se, and S, whereas reduction is observed for surfaces covered with −OH, −CH3, and −NH2. Next, we study the hydrogen passivated Si(111) surface modified with alkyl chains of the general formula H:Si–(CH2)n–CH2 and H:Si–X–(CH2)n–CH3, where X = NH, O, S and n = (0, 1, 3, 5, 7, 9, 11), at half coverage. For (X)–Hexyl and (X)–Dodecyl functionalization, we also examined various coverages up to full monolayer grafting in order to validate the result of half covered surface and the linker effect on the coverage. We find that it is necessary to take into account the van der Waals interaction between the alkyl chains. The strongest binding is for the oxygen linker, followed by S, N, and C, irrespective of chain length. The result revealed that the sequence of the stability is independent of coverage; however, linkers other than carbon can shift the optimum coverage considerably and allow further packing density. For all linkers apart from sulfur, structural properties, in particular, surface-linker-chain angles, saturate to a single value once n > 3. For sulfur, we identify three regimes, namely, n = 0–3, n = 5–7, and n = 9–11, each with its own characteristic adsorption structures. Where possible, our computational results are shown to be consistent with the available experimental data and show how the fundamental structural properties of modified Si surfaces can be controlled by the choice of linking group and chain length. Later we continue by examining the work function tuning of H:Si(111) over a range of 1.73 eV through adsorption of alkyl monolayers with general formula -[Xhead-group]-(CnH2n)-[Xtail-group], X = O(H), S(H), NH(2). The work function is practically converged at 4 carbons (8 for oxygen), for head-group functionalization. For tail-group functionalization and with both head- and tail-groups, there is an odd-even effect in the behavior of the work function, with peak-to-peak amplitudes of up to 1.7 eV in the oscillations. This behavior is explained through the orientation of the terminal-group's dipole. The shift in the work function is largest for NH2-linked and smallest for SH-linked chains and is rationalized in terms of interface dipoles. Our study reveals that the choice of the head- and/or tail-groups effectively changes the impact of the alkyl chain length on the work function tuning using self-assembled monolayers and this is an important advance in utilizing hybrid functionalized Si surfaces. Bringing together the understanding gained from studying single type functionalization of H:Si(111) with different alkyl chains and bearing in mind how to utilize head-group, tail-group or both as well as monolayer coverage, in the final part of this Thesis we study functionalized H:Si(111) with binary SAMs. Aiming at enhancing work function adjustment together with SAM stability and coverage we choose a range of terminations and linker-chains denoted as –X–(Alkyl) with X = CH3, O(H), S(H), NH(2) and investigate the stability and work function of various binary components grafted onto H:Si(111) surface. Using binary functionalization with -[NH(2)/O(H)/S(H)]-[Hexyl/Dodecyl] we show that work function can be tuned within the interval of 3.65-4.94 eV and furthermore, enhance the SAM’s stability. Although direct Si-C grafted SAMs are less favourable compared to their counterparts with O, N or S linkage, regardless of the ratio, binary functionalized alkyl monolayers with X-alkyl (X = NH, O) is always more stable than single type alkyl functionalization with the same coverage. Our results indicate that it is possible to go beyond the optimum coverage of pure alkyl functionalized SAMs (50%) by adding a linker with the correct choice of the linker. This is very important since dense packed monolayers have fewer defects and deliver higher efficiency. Our results indicate that binary anchoring can modify the charge injection and therefore bond stability while preserving the interface electronic structure.

Narratives in early Irish law tracts

This thesis presents a study of the 112 narratives collected from the Corpus Iuris Hibernici. The selection of narratives is based on criteria informed by modern narratological theories. The significant presence of narratives in early Irish law tracts appears at odds with the normal conception of law texts as consisting solely of provisions, and therefore needs to be accounted for. Since no systematic study has been conducted of these legal narratives, this thesis serves as an introduction by giving firstly an index of narratives and secondly a categorisation of them in terms of distribution, dates and functions. It then carries out a general analysis of the relationship between legal narratives and early Irish literature, and a selected case study of the relationship between legal narratives and the legal institutions in the context of which the narratives are located. It has become clearer, with the progress of argument, that the use of narratives was an integral part of legal writing in medieval Ireland; and the narratives, though having many idiosyncratic features of themselves, are profoundly connected with the learned tradition at large. The legal narratives reveal the intellectual background and compositional concerns of medieval Irish jurists, and they formed a crucial part of the effort to accommodate law tracts into the dynamic tradition of senchas. Two appendices are included at the end: one consists of translations of 34 narratives from the index, and the other is a critical edition of one of the narratives discussed in detail, together with translations of some relevant passages.

Investigations into the cellular and molecular changes in the amygdala in models of temporal lobe epilepsy and maternal immune activation

The amygdala is a limbic structure that is involved in many of our emotions and processing of these emotions such as fear, anger and pleasure. Conditions such as anxiety, autism, and also epilepsy, have been linked to abnormal functioning of the amygdala, owing to improper neurodevelopment or damage. This thesis investigated the cellular and molecular changes in the amygdala in models of temporal lobe epilepsy (TLE) and maternal immune activation (MIA). The kainic acid (KA) model of temporal lobe epilepsy (TLE) was used to induce Ammon’s-horn sclerosis (AHS) and to investigate behavioural and cytoarchitectural changes that occur in the amygdala related to Neuropeptide Y1 receptor expression. Results showed that KA-injected animals showed increased anxiety-like behaviours and displayed histopathological hallmarks of AHS including CA1 ablation, granule cell dispersion, volume reduction and astrogliosis. Amygdalar volume and neuronal loss was observed in the ipsilateral nuclei which was accompanied by astrogliosis. In addition, a decrease in Y1 receptor expressing cells in the ipsilateral CA1 and CA3 sectors of the hippocampus, ipsi- and contralateral granule cell layer of the dentate gyrus and ipsilateral central nucleus of the amygdala was found, consistent with a reduction in Y1 receptor protein levels. The results suggest that plastic changes in hippocampal and/or amygdalar Y1 receptor expression may negatively impact anxiety levels. Gamma-aminobutyric acid (GABA) is the main inhibitory neurotransmitter in the brain and tight regulation and appropriate control of GABA is vital for neurochemical homeostasis. GABA transporter-1 (GAT-1) is abundantly expressed by neurones and astrocytes and plays a key role in GABA reuptake and regulation. Imbalance in GABA homeostasis has been implicated in epilepsy with GAT-1 being an attractive pharmacological target. Electron microscopy was used to examine the distribution, expression and morphology of GAT-1 expressing structures in the amygdala of the TLE model. Results suggest that GAT-1 was preferentially expressed on putative axon terminals over astrocytic processes in this TLE model. Myelin integrity was examined and results suggested that in the TLE model myelinated fibres were damaged in comparison to controls. Synaptic morphology was studied and results suggested that asymmetric (excitatory) synapses occurred more frequently than symmetric (inhibitory) synapses in the TLE model in comparison to controls. This study illustrated that the amygdala undergoes ultrastructural alterations in this TLE model. Maternal immune activation (MIA) is a risk factor for neurodevelopmental disorders such as autism, schizophrenia and also epilepsy. MIA was induced at a critical window of amygdalar development at E12 using bacterial mimetic lipopolysaccharide (LPS). Results showed that MIA activates cytokine, toll-like receptor and chemokine expression in the fetal brain that is prolonged in the postnatal amygdala. Inflammation elicited by MIA may prime the fetal brain for alterations seen in the glial environment and this in turn have deleterious effects on neuronal populations as seen in the amygdala at P14. These findings may suggest that MIA induced during amygdalar development may predispose offspring to amygdalar related disorders such as heightened anxiety, fear impairment and also neurodevelopmental disorders.

States of play: Irish childhoods, race and belonging

This thesis explores the meaning-making practices of migrant and non-migrant children in relation to identities, race, belonging and childhood itself in their everyday lives and in the context of ‘normalizing’ discourses and spaces in Ireland. The relational, spatial and institutional contexts of children’s worlds are examined in the arenas of school, home, family, peer groups and consumer culture. The research develops a situated account of children’s complex subject positions, belongings and exclusions, as negotiated within discursive constructs, emerging in the ‘in-between’ spaces explored with other children and with adults. As a peripheral EU area both geographically and economically, Ireland has traditionally been a country of net emigration. This situation changed briefly in the late 1990s to early 2000s, sparking broad debate on Ireland’s perceived ‘new’ ethnic, cultural and linguistic diversity arising from the arrival of migrant people both from within and beyond the EU as workers and as asylum seekers, and drawing attention to issues of race, identity, equality and integration in Irish society. Based in a West of Ireland town where migrant children and children of migrants comprise very small minorities in classroom settings, this research engages with a particular demographic of children who have started primary school since these changes have occurred. It seeks to represent the complexities of the processes which constitute children’s subjectivities, and which also produce and reproduce race and childhood itself in this context. The role of local, national and global spaces, relational networks and discursive currents as they are experienced and negotiated by children are explored, and the significance of embodied, sensory and affective processes are integrated into the analysis. Notions of the functions and rhetorics of play and playfulness (Sutton-Smith 1997) form a central thread that runs throughout the thesis, where play is both a feature of children’s cultural worlds and a site of resistance or ‘thinking otherwise’. The study seeks to examine how children actively participate in (re)producing definitions of both childhood and race arising in local, national and global spaces, demonstrating that while contestations of the boundaries of childhood discourses are contingently successful, race tends to be strongly reiterated, clinging to bodies and places and compromising belonging. In addition, it explores how children access belongings through agentic and imaginative practices with regard to peer and family relationships, particularly highlighting constructions of home, while also illustrating practices of excluding children positioned as unintelligible, including the role of silences in such situations. Finally, drawing on teachers’ understandings and on children’s playful micro-level negotiations of race, the study argues that assumptions of childhood innocence contribute to justifying depoliticised discourses of race in the early primary school years, and also tend to silence children’s own dialogues with this issue. Central throughout the thesis is an emphasis on the productive potentials of children’s marginal positioning in processes of transgressing definitional boundaries, including the generation of post-race conceptualisations that revealed the borders of race as performative and fluid. It suggests that interrupting exclusionary raced identities in Irish primary schools requires engagement with children’s world-making practices and the multiple resources that inform their lives.

A critical realist examination of the inhibitors of double loop learning in an agile adoption

The original solution to the high failure rate of software development projects was the imposition of an engineering approach to software development, with processes aimed at providing a repeatable structure to maintain a consistency in the ‘production process’. Despite these attempts at addressing the crisis in software development, others have argued that the rigid processes of an engineering approach did not provide the solution. The Agile approach to software development strives to change how software is developed. It does this primarily by relying on empowered teams of developers who are trusted to manage the necessary tasks, and who accept that change is a necessary part of a development project. The use of, and interest in, Agile methods in software development projects has expanded greatly, yet this has been predominantly practitioner driven. There is a paucity of scientific research on Agile methods and how they are adopted and managed. This study aims at addressing this paucity by examining the adoption of Agile through a theoretical lens. The lens used in this research is that of double loop learning theory. The behaviours required in an Agile team are the same behaviours required in double loop learning; therefore, a transition to double loop learning is required for a successful Agile adoption. The theory of triple loop learning highlights that power factors (or power mechanisms in this research) can inhibit the attainment of double loop learning. This study identifies the negative behaviours - potential power mechanisms - that can inhibit the double loop learning inherent in an Agile adoption, to determine how the Agile processes and behaviours can create these power mechanisms, and how these power mechanisms impact on double loop learning and the Agile adoption. This is a critical realist study, which acknowledges that the real world is a complex one, hierarchically structured into layers. An a priori framework is created to represent these layers, which are categorised as: the Agile context, the power mechanisms, and double loop learning. The aim of the framework is to explain how the Agile processes and behaviours, through the teams of developers and project managers, can ultimately impact on the double loop learning behaviours required in an Agile adoption. Four case studies provide further refinement to the framework, with changes required due to observations which were often different to what existing literature would have predicted. The study concludes by explaining how the teams of developers, the individual developers, and the project managers, working with the Agile processes and required behaviours, can inhibit the double loop learning required in an Agile adoption. A solution is then proposed to mitigate these negative impacts. Additionally, two new research processes are introduced to add to the Information Systems research toolkit.

Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies.

The Celtic dragon slayer - a literary analysis of Tochmarc Emire in connection with Tristan et Iseut

As Celtic scholars have long noted, the medieval Irish tale Tochmarc Emire “The Courtship of Emer” is heavily indebted to other medieval Irish texts. In this tale of courtship and otherworldly quests, the Irish hero Cú Chulainn must prove himself worthy of the hand of the noblewoman Emer. Among his overseas adventures, Cú Chulainn rescues a princess from three attackers of the Fomoire. This episode may represent the only medieval Irish example of AT300 “The Dragon Slayer”, a story pattern known from classical models such as the stories of Perseus and Andromeda; and Hercules and Hesione. Moreover, in the company of Cú Chulainn we find a character otherwise unknown to Irish tradition by the name of Drust mac Seirb. This has led scholars to argue that Tochmarc Emire may preserve a Celtic precursor of the Continental Tristan legend, seeing in Drust the Pictish origin of the character Tristan, himself a famous dragon slayer. In this interdisciplinary dissertation, a number of questions are addressed. If the redactor of Tochmarc Emire drew on material from outside Irish tradition, what does this tell us about medieval Irish concepts of literature and genre? Further, what evidence do we have for tracing the origin of the Continental Tristan legend back to Pictland, and what explanation might we offer for a putative Pictish prince featuring in an Irish Dragon Slayer story? Finally, what place does the Dragon Slayer episode occupy within Tochmarc Emire and can we find other narratives, Celtic or classical or other, fitting the pattern of AT300, which may strengthen the link between Tochmarc Emire and Tristan?

The impact of first pregnancy and delivery on pelvic floor dysfunction

Background: The first childbirth has the greatest impact on a woman’s pelvic floor when major changes occur. The aim of this study was to comprehensively describe pelvic floor dysfunction (PFD) in young nulliparous women, and its correlation with postnatal pathology. Methods: A prospective study was performed at Cork University Maternity Hospital, Ireland. Initially 1484 nulliparous women completed the validated Australian Pelvic Floor Questionnaire at 15 weeks’ gestation and repeatedly at one year postnatally (N=872). In the second phase, at least one year postnatally, 202 participants without subsequent pregnancies attended the clinical follow up which included: pelvic organ prolapse quantification, a 3D-Transperineal ultrasound scan and collagen level assessment. Results: A high pre-pregnancy prevalence of various types of PFD was detected, which in the majority of cases persisted postnatally and included multiple types of PFD. The first birth had a negative impact on severity of pre-pregnancy symptoms in <15% of cases. Apart from prolapse, vaginal delivery, including instrumental delivery did not increase the risk of PFD symptoms, where as Caesarean section was protective for all types of PFD. The first birth had a bigger impact on pre-existing symptoms of overactive bladder compared to stress urinary incontinence. Pelvic organ prolapse is extremely prevalent in young primiparous women, however usually it is low grade and asymptomatic. Congenital factors and high collagen type III levels play an important role in the aetiology of pelvic organs prolapse. Levator ani trauma is present in one in three women after the first pregnancy and delivery. Conclusion: The main damage to the pelvic floor most likely occurs due to an undiagnosed congenital intrinsic weakness of the pelvic floor structures. PFD is highly associated with first childbirth, however it seems that pregnancy and delivery are contributing factors only which unmask the congenital intrinsic weakness of the pelvic floor support.

Optimised crystal morphologies for active pharmaceutical ingredients and related studies

The majority of active pharmaceutical ingredients (APIs) are crystalline solids in their pure forms. Crystalline solids have definable morphologies, i.e. shape and size. Crystal morphology is determined by both the internal structure of the crystals and external factors during growth from solution. The morphology of a crystal batch can affect key processes during manufacturing. Companies generally accept whatever morphology the manufacturing process provides and deal with any subsequent problems by costly trouble‒shooting. Rational design of optimised morphologies for crystalline pharmaceutical solids would be a very significant technical and commercial advance. Chapter one introduces the concept of crystal nucleation and growth. The phenomenon of polymorphism alongside the causes and impact is discussed. A summary of the scope of instrumentation used in the investigation of crystal polymorphism and morphology, including crystal size distribution (CSD), is also included. Chapter two examines the research carried out during an exploration of the optimum crystallisation parameters of phenacetin. Following a morphological study, the impact this induces on particle density and flow properties is examined. The impact of impurities on the crystallisation properties of phenacetin is investigated. Significantly, the location of impurities within individual crystals is also studied. The third chapter describes an industrial collaboration looking at the resolution and polymorphic study of trometamol and lysine salts of ketoprofen and 2‒phenylpropionic acid (2‒PPA). Chapter four incorporates a solid state study on three separate compounds: 2‒chloro‒4‒nitroaniline, 4‒hydroxy‒N‒phenylbenzenesulfonamide and N‒acetyl‒D‒glucosamine‒6‒O‒sulfate. 2‒Chloro‒4‒nitroaniline and 4‒hydroxy‒N‒phenylbenzenesulfonamide both produced interesting, extreme morphologies which warranted further investigation as part of a collaborative study. Following a summarisation of results in chapter five, chapter six contains the full experimental details, incorporating spectral and other analytical data for all compounds synthesised during the course of the research.

Public evaluations of novel food technologies: a qualitative citizen-scientist deliberative discourse approach

This qualitative research expands understanding of how information about a range of Novel Food Technologies (NFTs) is used and assimilated, and the implications of this on the evolution of attitudes and acceptance. This work enhances theoretical and applied understanding of citizens’ evaluative processes around these technologies. The approach applied involved observations of interactive exchanges between citizens and information providers (i.e. food scientists), during which they discussed a specific technology. This flexible, yet structured, approach revealed how individuals construct meaning around information about specific NFTs. A rich dataset of 42 ‘deliberate discourse’ and 42 postdiscourse transcripts was collected. Data analysis encompassed three stages: an initial descriptive account of the complete dataset based on the top-down bottom-up (TDBU) model of attitude formation, followed by inductive and deductive thematic analysis across the selected technology groups. The hybrid thematic analysis undertaken identified a Conceptual Model, which represents a holistic perspective on the influences and associated features directing ‘sense-making’ and ultimate evaluations around the technology clusters. How individuals make sense of these technologies is shaped by: their beliefs, values and personal characteristics; their perceptions of power and control over the application of the technology; and, the assumed relevance of the technology and its applications within different contexts. These influences form the frame for the creation of sense-making around the technologies. Internal negotiations between these influences are evident and evaluations are based on the relative importance of each influence to the individual, which tend to contribute to attitude ambivalence and instability. The findings indicate the processes of forming and changing attitudes towards these technologies are: complex; dependent on characteristics of the individual, technology, application and product; and, impacted by the nature and forms of information provided. Challenges are faced in engaging with the public about these technologies, as levels of knowledge, understanding and interest vary.

Nietzsche and Montaigne: cheerful naturalism

The influence of the Essays of Michel de Montaigne on the thought of Friedrich Nietzsche has, hitherto, received scant scholarly attention. The aim of this thesis is to address this lacuna in the literature by making evident the importance of the Essays to the development of Nietzsche’s philosophy. I argue that, in order to fully appreciate Nietzsche’s thought, it must be recognized that, from the beginning to the end of his philosophical life, Montaigne was for him a thinker of the deepest personal and philosophical significance. Against the received scholarly opinion, which would see Montaigne as influential only for Nietzsche’s middle works, I contend that the Essays continue to be a key inspiration for Nietzsche even into his late and final works. Montaigne, with his cheerful affirmation of life, his experimental mode of philosophizing, and his resolutely naturalized perspective, was an exemplar for Nietzsche as a philosopher, psychologist, sceptic and naturalist. The Essays not only stimulated Nietzsche’s thinking on questions to do with morality, epistemology and the nature of the soul but also informed his conception of the ideal philosophical life. Moreover, to explore the Essays from a Nietzschean viewpoint, allows the drawing out of the more radical aspects of Montaigne’s thought, while to probe Montaigne’s impact on Nietzsche, provides insight into the trajectory of Nietzsche’s philosophy as he broke free from romantic pessimism and embraced the naturalism that would guide his works from Human, All Too Human onward.

Chamber investigations of atmospheric mercury oxidation chemistry

Mercury is a potent neurotoxin even at low concentrations. The unoxidised metal has a high vapour pressure and can circulate through the atmosphere, but when oxidised can deposit and be accumulated through the food chain. This work aims to investigate the oxidation processes of atmospheric Hg0(g). The first part describes efforts to make a portable Hg sensor based on Cavity Enhanced Absorption Spectroscopy (CEAS). The detection limit achieved was 66 ngm−3 for a 10 second averaging time. The second part of this work describes experiments carried out in a temperature controlled atmospheric simulation chamber in the Desert Research Institute, Reno, Nevada, USA. The chamber was built around an existing Hg CRDS system that could measure Hg concentrations in the chamber of<100 ngm−3 at 1 Hz enabling reactions to be followed. The main oxidant studied was bromine, which was quantified with a LED based CEAS system across the chamber. Hg oxidation in the chamber was found to be mostly too slow for current models to explain. A seven reaction model was developed and tested to find which parameters were capable of explaining the deviation. The model was overdetermined and no unique solution could be found. The most likely possibility was that the first oxidation step Hg + Br →HgBr was slower than the preferred literature value by a factor of two. However, if the more uncertain data at low [Br2] was included then the only parameter that could explain the experiments was a fast, temperature independent dissociation of HgBr some hundreds of times faster than predicted thermolysis or photolysis rates. Overall this work concluded that to quantitatively understand the reaction of Hg with Br2, the intermediates HgBr and Br must be measured. This conclusion will help to guide the planning of future studies of atmospheric Hg chemistry.

Multi-parametric metabolic assessment of cells under stress conditions

Glycolysis, glutaminolysis, the Krebs cycle and oxidative phosphorylation are the main metabolic pathways. Exposing cells to key metabolic substrates (glucose, glutamine and pyruvate); investigation of the contribution of substrates in stress conditions such as uncoupling and hypoxia was conducted. Glycolysis, O2 consumption, O2 and ATP levels and hypoxia inducible factor (HIF) signalling in PC12 cells were investigated. Upon uncoupling with FCCP mitochondria were depolarised similarly in all cases, but a strong increase in respiration was only seen in the cells fed on glutamine with either glucose or pyruvate. Inhibition of glutaminolysis reversed the glutamine dependant effect. Differential regulation of the respiratory response to FCCP by metabolic environment suggests mitochondrial uncoupling has a potential for substrate-specific inhibition of cell function. At reduced O2 availability (4 % and 0 % O2), cell bioenergetics and local oxygenation varied depending on the substrate composition. Results indicate that both supply and utilisation of key metabolic substrates can affect the pattern of HIF-1/2α accumulation by differentially regulating iO2¬, ATP levels and Akt/Erk/AMPK pathways. Inhibition of key metabolic pathways can modulate HIF regulatory pathways, metabolic responses and survival of cancer cells in hypoxia. Hypoxia leads to transcriptional activation, by HIF, of pyruvate dehydrogenase (PDH) kinase which phosphorylates and inhibits PDH, a mitochondrial enzyme that converts pyruvate into acetyl-CoA. The levels of PDH (total and phosphorylated), PDH kinase and HIF-1α were analysed in HCT116 and HCT116 SCO2-/- (deficient in complex IV of the respiratory chain) grown under 20.9 % and 3 % O2. Data indicate that regulation of PDH can occur in a manner independent of the HIF-1/PDH kinase 1 axis, mitochondrial respiration and the demand for acetyl-CoA. Collectively these results can be applied to many diseases; reduced nutrient supply and O2 during ischemia/stroke, hypoglycaemia in diabetes mellitus and cancer associated changes in uncoupling protein expression levels.

Citizenship education in Irish secondary schools: the influence of curriculum content, school culture and stakeholder perspectives

This research interrogates the status of citizenship education in Irish secondary schools. The following questions are examined: How does school culture impact on citizenship education? What value is accorded to the subjects, Civic, Social and Political Education (CSPE) and Social, Personal and Health Education (SPHE)? To what extent are the subjects of both the cognitive and non-cognitive curricula affirmed? The importance of these factors in supporting the social, ethical, personal, political and emotional development of students is explored. The concept of citizenship is dynamic and constantly evolving in response to societal change. Society is increasingly concerned with issues such as: globalisation; cosmopolitanism; the threat of global risk; environment sustainability; socio-economic inequality; and recognition/misrecognition of new identities and group rights. The pedagogical philosophy of Paulo Freire which seeks to educate for the conscientisation and humanisation of the student is central to this research. Using a mixed methods approach, data on the insights of students, parents, teachers and school Principals was collected. In relation to Irish secondary school education, the study reached three main conclusions. (1) The educational stakeholders rate the subjects of the non-cognitive curriculum poorly. (2) The subjects Civic, Social and Political education (CSPE), and Social, Personal and Health Education (SPHE) command a low status in the secondary school setting. (3) The day-to-day school climate is influenced by an educational philosophy that is instrumentalist in character. Elements of school culture such as: the ethic of care; the informal curriculum; education for life after school; and affirmation of teachers, are not sufficiently prioritised in supporting education for citizenship. The research concludes that the approach to education for citizenship needs to be more robust within the overall curriculum, and culture and ethos of the Irish education system.

Subterfuge-safe trust management for delegation of permissions in open environments

Open environments involve distributed entities interacting with each other in an open manner. Many distributed entities are unknown to each other but need to collaborate and share resources in a secure fashion. Usually resource owners alone decide who is trusted to access their resources. Since resource owners in open environments do not have a complete picture of all trusted entities, trust management frameworks are used to ensure that only authorized entities will access requested resources. Every trust management system has limitations, and the limitations can be exploited by malicious entities. One vulnerability is due to the lack of globally unique interpretation for permission specifications. This limitation means that a malicious entity which receives a permission in one domain may misuse the permission in another domain via some deceptive but apparently authorized route; this malicious behaviour is called subterfuge. This thesis develops a secure approach, Subterfuge Safe Trust Management (SSTM), that prevents subterfuge by malicious entities. SSTM employs the Subterfuge Safe Authorization Language (SSAL) which uses the idea of a local permission with a globally unique interpretation (localPermission) to resolve the misinterpretation of permissions. We model and implement SSAL with an ontology-based approach, SSALO, which provides a generic representation for knowledge related to the SSAL-based security policy. SSALO enables integration of heterogeneous security policies which is useful for secure cooperation among principals in open environments where each principal may have a different security policy with different implementation. The other advantage of an ontology-based approach is the Open World Assumption, whereby reasoning over an existing security policy is easily extended to include further security policies that might be discovered in an open distributed environment. We add two extra SSAL rules to support dynamic coalition formation and secure cooperation among coalitions. Secure federation of cloud computing platforms and secure federation of XMPP servers are presented as case studies of SSTM. The results show that SSTM provides robust accountability for the use of permissions in federation. It is also shown that SSAL is a suitable policy language to express the subterfuge-safe policy statements due to its well-defined semantics, ease of use, and integrability.