7 resultados para Estoppel by record
em CORA - Cork Open Research Archive - University College Cork - Ireland
Resumo:
The past two decades have witnessed concerted efforts by theorists and policy-makers to place civil society at the centre of social, economic and environmental development processes. To this end, policies grounded in a Third Way approach have sought to forge stronger linkages between the state and voluntary community-based organisations. Concepts such as active citizenship, social capital, partnership and sustainability have underpinned this political philosophy, which reflects a movement in development theory and political science away from notions of state-led development and unfettered neo-liberalism. In the Irish context, a series of initiatives have given expression to this new policy agenda, the foremost amongst them the publication of a White Paper in 2000. New local governance structures and development schemes have multiplied since the early 1990s, while the physical planning system has also been modified. All this has taken place against the backdrop of unprecedented economic development and social change precipitated by the ‘Celtic Tiger’.This thesis examines the interaction between community organisations, state institutions and other actors in development processes in East Cork. It focuses upon place-based community organisations, who seek to represent the interests of their particular localities. A case study approach is employed to explore the realpolitik of local development and to gauge the extent to which grassroots community organisations wield influence in determining the development of their communities. The study concludes that the transfer of decision-making power to community organisations has been more illusory than real and that, in practical terms, such groups remain marginal in the circuits of power. However, the situation of community organisations operating in different geographical locales cannot be reduced to an overarching theoretical logic. The case studies show that the modus operandi of community groups varies considerably and can be influenced by specific local geographies, events and personalities.
Resumo:
This study has considered the optimisation of granola breakfast cereal manufacturing processes by wet granulation and pneumatic conveying. Granola is an aggregated food product used as a breakfast cereal and in cereal bars. Processing of granola involves mixing the dry ingredients (typically oats, nuts, etc.) followed by the addition of a binder which can contain honey, water and/or oil. In this work, the design and operation of two parallel wet granulation processes to produce aggregate granola products were incorporated: a) a high shear mixing granulation process followed by drying/toasting in an oven. b) a continuous fluidised bed followed by drying/toasting in an oven. In high shear granulation the influence of process parameters on key granule aggregate quality attributes such as granule size distribution and textural properties of granola were investigated. The experimental results show that the impeller rotational speed is the single most important process parameter which influences granola physical and textural properties. After that binder addition rate and wet massing time also show significant impacts on granule properties. Increasing the impeller speed and wet massing time increases the median granule size while also presenting a positive correlation with density. The combination of high impeller speed and low binder addition rate resulted in granules with the highest levels of hardness and crispness. In the fluidised bed granulation process the effect of nozzle air pressure and binder spray rate on key aggregate quality attributes were studied. The experimental results show that a decrease in nozzle air pressure leads to larger in mean granule size. The combination of lowest nozzle air pressure and lowest binder spray rate results in granules with the highest levels of hardness and crispness. Overall, the high shear granulation process led to larger, denser, less porous and stronger (less likely to break) aggregates than the fluidised bed process. The study also examined the particle breakage of granola during pneumatic conveying produced by both the high shear granulation and the fluidised bed granulation process. Products were pneumatically conveyed in a purpose built conveying rig designed to mimic product conveying and packaging. Three different conveying rig configurations were employed; a straight pipe, a rig consisting two 45° bends and one with 90° bend. Particle breakage increases with applied pressure drop, and a 90° bend pipe results in more attrition for all conveying velocities relative to other pipe geometry. Additionally for the granules produced in the high shear granulator; those produced at the highest impeller speed, while being the largest also have the lowest levels of proportional breakage while smaller granules produced at the lowest impeller speed have the highest levels of breakage. This effect clearly shows the importance of shear history (during granule production) on breakage during subsequent processing. In terms of the fluidised bed granulation, there was no single operating parameter that was deemed to have a significant effect on breakage during subsequent conveying. Finally, a simple power law breakage model based on process input parameters was developed for both manufacturing processes. It was found suitable for predicting the breakage of granola breakfast cereal at various applied air velocities using a number of pipe configurations, taking into account shear histories.
Resumo:
Oxysterols are products of cholesterol oxidation, which may be produced endogenously or may be absorbed from the diet where they are commonly found in foods of animal origin. Oxysterols are known to be cyctotoxic to cells in culture and mode of toxicity has been identified as apoptosis in certain cell lines. The cytotoxicity of the oxysterols 25-hydroxycholesterol (25-OH) and 7β-hydroxycholesterol (7β-OH) was examined in two human cell lines, HepG2, a hepatoma cell line, and U937, a monocytic cell line. Both 25-OH and 7β-OH were cytotoxic to the HepG2 cell line but apoptotic cells were not detected and it was concluded that cells underwent necrosis. 25-OH was not cytotoxic to the U937 cell line but it was found to have a cytostatic effect. 7β-OH was shown to induce apoptosis in the U937 line. The mechanism of oxysterol-induced apoptosis has not yet been fully elucidated, however the generation of an oxidative stress and the depletion of glutathione have been associated with the initial stages of the apoptotic process. The concentration of cellular antioxidant enzyme, superoxide dismutase (SOD) was increased in association with 7β-OH induced apoptosis in the U937 cell line. There was no change in the glutathione concentration or the SOD activity of HepG2 cells, which underwent necrosis in the presence of 7β-OH. Many apoptotic pathways center on the activation of caspase-3, which is the key executioner protease of apoptosis. Caspase-3 activity was also shown to increase in association with 7β-OH-induced apoptosis in U937 cells but there was no significant increase in caspase-3 activity in HepG2 cells. DNA fragmentation is regarded as the biochemical hallmark of apoptosis, therefore the comet assay as a measure of DNA fragmentation was assessed as a measure of apoptosis. The level of DNA fragmentation induced by 7β-OH, as measured using the comet assay, was similar for both cell lines. Therefore, it was concluded that the comet assay could not be used to distinguish between 7β-OH-induced apoptosis in U937 cells and 7β-OH-induced necrosis in HepG2 cells. The cytotoxicity and apoptotic potency of oxysterols 25-OH, 7β-OH, cholesterol- 5a,6a-epoxide (a-epoxide), cholesterol-5β,6β-epoxide (β-epoxide), 19-hydroxy-cholesterol (19-OH), and 7-ketocholesterol (7-keto) was compared in the U937 cell line. 7 β-OH, β-epoxide and 7-keto were found to induce apoptosis in U937 cells. 7β-OH-induced apoptosis was associated with a decrease in the cellular glutathione concentration and an increase in SOD activity, 7-keto and β-epoxide did not affect the glutathione concentration or the SOD activity of the cells.a-Epoxide, 19-OH and 25-OH were not cytotoxic to the U937 cell line.
Resumo:
Stress can be understood in terms of the meaning of stressful experiences for individuals. The meaning of stressful experiences involves threats to self-adequacy, where self-adequacy is considered a basic human need. Appropriate research methods are required to explore this aspect of stress. The present study is a qualitative exploration of the stress experienced by a group of 27 students at the National Institute of Higher Education, Limerick (since renamed the University of Limerick). The study was carried out by the resident student counsellor at the college. A model of student stress was explored, based on student developmental needs. The data consist of a series of interviews recorded with each of the 27 students over a 3 month period. These interviews were transcribed and the resulting transcripts are the subject of detailed analysis. The analysis of the data is an account of the sense-making process by the student counsellor of the students' reported experiences. The aim of the analysis was to reduce the large amounts of data to their most salient aspects in an ordered fashion, so as to examine the application of a developmental model of stress with this group of students. There were two key elements to the analysis. First, the raw data were edited to identify the key statements contained in the interviews. Second, the statements were categorised, as a means of summarising the data. The results of the qualitative dataanalysis were then applied to the developmental model. The analysis of data revealed a number of patterns of stress amongst the sample of students. Patterns of academic over-identification, parental conflict and social inadequacy were particularly noteworthy. These patterns consisted of an integration of academic, family and social stresses within a developmental framework. Gender differences with regard to the need for separateness and belonging are highlighted. Appropriate student stress intervention strategies are discussed. Based on the present results, the relationship between stress and development has been highlighted and is recommended as a firm basis for future studies of stress in general and student stress in particular.
Resumo:
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.
Resumo:
Chapter 1 of this thesis is a brief introduction to the preparation and reactions of α-diazocarbonyl compounds, with particular emphasis on the areas relating to the research undertaken: C-H insertion, addition to aromatics, and oxonium ylide generation and rearrangement. A short summary of catalyst development illustrates the importance of rhodium(II)carboxylates for α-diazocarbonyl decomposition. Chapter 2 describes intramolecular C-H insertion reactions of α-diazo-β-keto sulphones to form substituted cyclopentanones. Rhodium(II) carboxylates derived from homochiral carboxylic acids were used as catalysts in these reactions and enantioselection achieved through their use is discussed. Chapter 3 describes intramolecular Buchner cyclisation of aryl diazoketones with emphasis on the stereochemical aspects of the cyclisation and subsequent reaction of the bicyclo[5.3.0]decatrienones produced. The partial asymmetric synthesis achieved through use of chiral rhodium(II) carboxylates as catalysts is discussed. The application of the intramolecular Buchner reaction to the synthesis of hydroazulene lactones is illustrated. Chapter 4 demonstrates oxonium ylide formation and rearrangement in the decomposition of an α-diazoketone. The consequences of the use of chiral rhodium(II) carboxylates as catalysts are described. Particularly significant was the discovery that rhodium(II) (S)-mandelate acts as a very efficient catalyst for α-diazoketone decompositions, in general. Moderate asymmetric induction was possible in the decomposition of α-diazoketones with chiral rhodium(II) carboxylates, with rhodium(II) (S)-mandelate being one of the more enantioselective catalysts investigated. However, the asymmetric induction obtained was very dependent on the exact structure of the α-diazoketone, the catalyst, and the nature of the reaction. Chapter 5 contains the experimental details, and the spectral and analytical data for all new compounds reported.
Resumo:
This thesis investigated the relationship of explicit (self-report), implicit (IAT) and physiological variables to the placebo effect. The thesis consisted of three main parts. The first collected background data and developed models for two constructs (Optimism and Mindfulness) associated with the placebo effect and implicit attitudes, respectively. The second part of the thesis consisted of the development of an explicit measure of treatment expectancies, and the development of two IATs, one for Optimism and the other for Treatment Credibility. The final portion of the thesis was an experimental study (N=111) which tested these new measures in a sample of healthy volunteers. The primary hypothesis of the thesis, that there would be a relationship between the placebo effect and implicit measures, was not supported. Major findings include an effect of semantic priming on placebo response mediated by condition (Deceptive versus Open Placebo), an unexpected negative relationship between Optimism and self-reported Health, and a physiological relationship between pain ratings and GSR data, which was also mediated by Condition in the experiment. A complete record of the code and data for this thesis can be found at https://github.com/richiemorrisroe/Thesis