6 resultados para the Third

em CORA - Cork Open Research Archive - University College Cork - Ireland


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In this paper, The radio Frequency (RF) Monitoring and Measurement of the Environmental Research Institute (ERI) located in Cork city will be monitored and analyzed in both the Zigbee (2.44 GHz) and the industrial, scientific and medical (ISM 433 MHz). The main objective of this survey is to confirm what the noise and interferences threat signals exist in these bands. It was agreed that the surveys would be carried out in 5 different rooms and areas that are candidates for the Wireless Sensors deployments. Based on the carried on study, A Zigbee standard Wireless Sensor Network (WSN) will be developed employing a number of motes for sensing number of signals like temperature, light and humidity beside the RSSI and battery voltage monitoring. Such system will be used later on to control and improve indoor building climate at reduced costs, remove the need for cabling and both installation and operational costs are significantly reduced.

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The research described in this thesis focuses, principally, on synthesis of stable α-diazosulfoxides and investigation of their reactivity under various reaction conditions (transition-metal catalysed, photochemical, thermal and microwave) with a particular emphasis on the reactive intermediates and mechanistic aspects of the reaction pathways involved. In agreement with previous studies carried out on these compounds, the key reaction pathway of α-diazosulfoxides was found to be hetero-Wolff rearrangement to give α-oxosulfine intermediates. However, a competing reaction pathway involving oxygen migration from sulfur to oxygen was also observed. Critically, isomerisation of α-oxosulfine stereoisomers was observed directly by 1H NMR spectroscopy in this work and this observation accounts for the stereochemical outcomes of the various cycloaddition reactions, whether carried out with in situ trapping or with preformed solutions of sulfines. Furthermore, matrix isolation experiments have shown that electrocyclisation of α-oxosulfines to oxathiiranes takes place and this verifies the proposed mechanisms for enol and disulfide formation. The introductory chapter includes a brief literature review of the synthesis and reactivity of α-diazosulfoxides prior to the commencement of research in this field by the Maguire group. The Wolff rearrangement is also discussed and the characteristic reactions of a number of reactive intermediates (sulfines, sulfenes and oxathiiranes) are outlined. The use of microwave-assisted organic synthesis is also examined, specifically, in the context of α-diazocarbonyl compounds as substrates. The second chapter describes the synthesis of stable monocyclic and bicyclic lactone derivatives of α-diazosulfoxides from sulfide precursors according to established experimental procedures. Approaches to precursors of ketone and sulfimide derivatives of α-diazosulfoxides are also described. The third chapter examines the reactivity of α-diazosulfoxides under thermal, microwave, rhodium(II)-catalysed and photochemical conditions. Comparison of the results obtained under thermal and microwave conditions indicates that there was no evidence for any effect, other than thermal, induced by microwave irradiation. The results of catalyst studies involving several rhodium(II) carboxylate and rhodium(II) carboxamidate catalysts are outlined. Under photochemical conditions, sulfur extrusion is a significant reaction pathway while under thermal or transition metal catalysed conditions, oxygen extrusion is observed. One of the most important observations in this work was the direct spectroscopic observation (by 1H NMR) of interconversion of the E and Z-oxosulfines. Trapping of the α-oxosulfine intermediates as cycloadducts by reaction with 2,3-dimethyl-1,3-butadiene proved useful both synthetically and mechanistically. As the stereochemistry of the α-oxosulfine is retained in the cycloadducts, this provided an ideal method for characterisation of this key feature. In the case of one α-oxosulfine, a novel [2+2] cycloaddition was observed. Preliminary experiments to investigate the reactivity of an α-diazosulfone under rhodium(II) catalysis and microwave irradiation are also described. The fourth chapter describes matrix isolation experiments which were carried out in Rühr Universität, Bochum in collaboration with Prof. Wolfram Sander. These experiments provide direct spectroscopic evidence of an α-oxosulfine intermediate formed by hetero-Wolff rearrangement of an α-diazosulfoxide and subsequent cyclisation of the sulfine to an oxathiirane was also observed. Furthermore, it was possible to identify which stereoisomer of the α-oxosulfine was present in the matrix. A preliminary laser flash photolysis experiment is also discussed. The experimental details, including all spectral and analytical data, are reported at the end of each chapter. The structural interpretation of 1H NMR spectra of the cycloadducts, described in Chapter 3, is discussed in Appendix I.

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The dissertation proposes that one of the more fruitful ways of interpreting Burke's work is to evaluate him as an oral performer rather than a literary practitioner and it argues that in his voice can be heard the modulations of the genres and conventions of oral composition of eighteenth-century Gaelic Ireland. The first chapter situates Burke in the milieu of the Gaelic landed class of eighteenth-century Ireland. The next chapter examines how the rich oral culture of the Munster Gaelic gentry, where Burke spent his childhood days, was to provide a lasting influence on the form and content of Burke's work. His speeches on the British constitution are read in the context of the historical and literary culture of the Jacobites, specifically the speculum principis, Párliament na mBán. The third chapter surveys the tradition of Anglo-Irish theoretical writings on oratory and discusses how Burke is aligned with this school. The focus is on how Burke's thought and practice, his 'idioms', might be understood as being mediated through the criterion of orality rather than literature. The remaining chapters discuss Burke's politics and performance in the light of Gaelic cultural practices such as the rituals of the courts of poetry, the Warrant Poems or Barántas; the performance of funeral laments and elegies, Caoineadh, the laments for the fallen nobility, Marbhna na daoine uaisle, the satires and the political vision allegories of Munster, Aislingí na Mumhan; to show how they provide us with a remarkable context for discussing Burke's poetical-political performance. In hearing Burke's voice through the body of Gaelic culture our understanding of Burke's position in the wider world of the eighteenth century (and hence his meaning) is profoundly affected.

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The concept of police accountability is not susceptible to a universal or concise definition. In the context of this thesis it is treated as embracing two fundamental components. First, it entails an arrangement whereby an individual, a minority and the whole community have the opportunity to participate meaningfully in the formulation of the principles and policies governing police operations. Second, it presupposes that those who have suffered as victims of unacceptable police behaviour should have an effective remedy. These ingredients, however, cannot operate in a vacuum. They must find an accommodation with the equally vital requirement that the burden of accountability should not be so demanding that the delivery of an effective police service is fatally impaired. While much of the current debate on police accountability in Britain and the USA revolves around the issue of where the balance should be struck in this accommodation, Ireland lacks the very foundation for such a debate as it suffers from a serious deficit in research and writing on police generally. This thesis aims to fill that gap by laying the foundations for an informed debate on police accountability and related aspects of police in Ireland. Broadly speaking the thesis contains three major interrelated components. The first is concerned with the concept of police in Ireland and the legal, constitutional and political context in which it operates. This reveals that although the Garda Siochana is established as a national force the legal prescriptions concerning its role and governance are very vague. Although a similar legislative format in Britain, and elsewhere, have been interpreted as conferring operational autonomy on the police it has not stopped successive Irish governments from exercising close control over the police. The second component analyses the structure and operation of the traditional police accountability mechanisms in Ireland; namely the law and the democratic process. It concludes that some basic aspects of the peculiar legal, constitutional and political structures of policing seriously undermine their capacity to deliver effective police accountability. In the case of the law, for example, the status of, and the broad discretion vested in, each individual member of the force ensure that the traditional legal actions cannot always provide redress where individuals or collective groups feel victimised. In the case of the democratic process the integration of the police into the excessively centralised system of executive government, coupled with the refusal of the Minister for Justice to accept responsibility for operational matters, project a barrier between the police and their accountability to the public. The third component details proposals on how the current structures of police accountability in Ireland can be strengthened without interfering with the fundamentals of the law, the democratic process or the legal and constitutional status of the police. The key elements in these proposals are the establishment of an independent administrative procedure for handling citizen complaints against the police and the establishment of a network of local police-community liaison councils throughout the country coupled with a centralised parliamentary committee on the police. While these proposals are analysed from the perspective of maximising the degree of police accountability to the public they also take into account the need to ensure that the police capacity to deliver an effective police service is not unduly impaired as a result.

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This work examines the origins and early history of the Queen's College, Cork. Designedly there is as much stress on the origins as on the early history, for it is the contention of the work that the College was something more than a legislative mushroom. It was very much in the tradition of the civic universities which added an exciting new dimension to academic life in these islands in the nineteenth century. The first chapter surveys university practice and thinking at the opening of the century, relying exclusively on published sources. The second chapter is devoted specifically to the state of learning in Cork during the period, and makes extensive use of hitherto unpublished manuscript material in relation to the Royal Cork Institution. The third chapter deals with the highly significant evidence on education embodied in the Report of the Select Committee on Irish Education of 1838. This material has not previously been published. In chapter four an extended study is made of relevant letters in the manuscript correspondence of Sir Robert Peel - even the most recent authoritative biography has ignored this material. The remaining three chapters are devoted more specifically to the College, both in the formulation or policy and in its practical working. In chapter six there is an extended survey of early College life based exclusively on hitherto unpublished manuscript material in the College Archives. All of these sources, together with incidental published material, are set out at the end of each chapter.

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Bioluminescence is the production of light by living organisms as a result of a number of enzyme catalysed reactions caused by enzymes termed luciferases. The lux genes responsible for the emission of light can be cloned from one bioluminescent microorganism into one that is not bioluminescent. The light emitted can be monitored and quantified and will provide information on the metabolic activity, quantity and location of cells in a particular environment, in real-time. The primary aim of this thesis was to investigate and identify several food industry related applications of lux-tagged microorganisms. The first aim was to monitor a lux-tagged Cronobacter sakazakii in reconstituted infant milk formula, in realtime. The second aim was to investigate a bioluminescent-based early warning system for starter culture disruption by bacteriophages and antibiotic residues. The third of this thesis was to examine the use of a bioluminescent-based assay to test the activity of bioengineered Nisin derivatives M21V and S29A against foodborne pathogens in laboratory media and selected foods.