10 resultados para Rondonia State development
em CORA - Cork Open Research Archive - University College Cork - Ireland
Resumo:
The student bullying of teachers (SBT) is a distinct and complex form of bullying with a multiplicity of diverse, changeable and intersecting causes which is experienced by and affects teachers in a variety of ways. SBT is both a national and an international phenomenon which is under-recognised in academic, societal and political spheres, resulting in limited conceptual understanding and awareness of the issue. This study explores teachers’ experiences of SBT behaviours in Irish second level schools as well as teachers’ perceptions regarding training, policies and supports in Ireland to address the issue. Specifically, the study seeks to explore the influence of historical low State intervention in education on contemporary policies and supports to deal with SBT in Ireland. A mixed methods approach involving a survey of 531 second level school teachers and 17 semi-structured interviews with teachers, Year Heads and representatives from teacher trade unions and school management bodies was employed to collect and analyse data. Findings indicate that SBT behaviours are prevalent in many forms in Irish second level schools. The hidden nature of the phenomenon has simultaneously contributed to and is reinforced by limited understanding of the issue as well as teachers’ reluctance to disclose their experiences. Findings reveal that teachers perceive the contemporary policies, training and support structures in Ireland to be inadequate in equipping them to effectively deal with SBT. State intervention in addressing SBT behaviours to date, has been limited, therefore many teachers are forced to respond to the issue based on their own initiatives and assumptions rather than from an informed critically reflective approach, supported by national guidelines and sufficient State investment. This has resulted in a piecemeal, un-coordinated and ad-hoc approach to SBT in Irish schools both in terms of teachers’ management of SBT behaviours and with respect to the supports extended to staff. The potential negative consequences of SBT behaviours on teachers’ wellbeing and professional performance and thus, on the education system itself, underlines the need for a strategic, evidence-based, resourced and integrated approach which includes, as a pivotal component, consultation with teachers, whose contribution to the process is crucial.
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:
Design, synthesis and structural characterization of a series of diphenylacetylene derivatives bearing organosulfur, amide and amine moieties has been achieved in which the molecular conformation is controlled through variation of the hydrogen bond properties on alteration of the oxidisation level of sulfur.
Resumo:
Given the economic and social importance of agriculture in the early years of the Irish Free State, it is surprising that the development of organisations representing farmers has not received the attention it deserves from historians. While the issues of government agricultural policy and the land question have been extensively studied in the historiography, the autonomous response by farmers to agricultural policies and the detailed study of the farmers’ organisations has simply been ignored in spite of the existence of a range of relevant primary sources. Farmers’ organisations have only received cursory treatment in these studies; they have been presented as passive spectators, responding in a Pavlovian manner to outside events. The existing historiography has only studied farmers’ organisations during periods when they impinged on national politics, epecially during the War of Independence and the Economic War. Therefore chronological gaps exist which has led to much misinterpretation of farmers’ activities. This thesis will redress this imbalance by studying the formation and continuous development of farmers’ organisations within the twenty-six county area and the reaction of farmers to changing government agricultural policies, over the period 1919 to 1936. The period under review entailed many attempts by farmers to form representative organisations and encompassed differing policy regimes. The thesis will open in 1919, when the first national organisation representing farmers, the Irish Farmers’ Union, was formed. In 1922, the union established the Farmers’ Party. By the mid- 1920’s, a number of protectionist agricultural associations had been formed. While the Farmers’ Party was eventually absorbed by Cumann na nGaedheal, local associations of independent farmers occupied the resultant vacuum and contested the 1932 election. These organisations formed the nucleus of a new national organisation; the National Farmers’ and Ratepayers’ League. The agricultural crisis caused by both the Great Depression and the Economic War facilitated the expansion of the league. The league formed a political party, the Centre Party, to contest the 1933 election. While the Centre Party was absorbed by the newly-formed Fine Gael, activists from the former farmer organisations led the campaign against the payment of annuities and rates. Many of them continued this campaign after 1934, when the Fine Gael leadership opposed the violent resistance to the collection of annuities. New farmer organisations were formed to co-ordinate this campaign which continued until 1936, the closing point of the thesis.
Resumo:
The use of optical sensor technology for non-invasive determination of key quality pack parameters improved package/product quality. This technology can be used for optimization of packaging processes, improvement of product shelf-life and maintenance of quality. In recent years, there has been a major focus on O2 and CO2 sensor development as these are key gases used in modified atmosphere packaging (MAP) of food. The first and second experimental chapters (chapter 2 and 3) describe the development of O2, pH and CO2 solid state sensors and its (potential) use for food packaging applications. A dual-analyte sensor for dissolved O2 and pH with one bi-functional reporter dye (meso-substituted Pd- or Ptporphyrin) embedded in plasticized PVC membrane was developed in chapter 2. The developed CO2 sensor in chapter 3 was comprised of a phosphorescent reporter dye Pt(II)- tetrakis(pentafluorophenyl) porphyrin (PtTFPP) and a colourimetric pH indicator α-naphtholphthalein (NP) incorporated in a plastic matrix together with a phase transfer agent tetraoctyl- or cetyltrimethylammonium hydroxide (TOA-OH or CTA-OH). The third experimental chapter, chapter 4, described the development of liquid O2 sensors for rapid microbiological determination which are important for improvement and assurance of food safety systems. This automated screening assay produced characteristic profiles with a sharp increase in fluorescence above the baseline level at a certain threshold time (TT) which can be correlated with their initial microbial load and was applied to various raw fish and horticultural samples. Chapter 5, the fourth experimental chapter, reported upon the successful application of developed O2 and CO2 sensors for quality assessment of MAP mushrooms during storage for 7 days at 4°C.
Resumo:
This thesis is focused on the design and synthesis of a diverse range of novel organosulfur compounds (sulfides, sulfoxides and sulfones), with the objective of studying their solid state properties and thereby developing an understanding of how the molecular structure of the compounds impacts upon their solid state crystalline structure. In particular, robust intermolecular interactions which determine the overall structure were investigated. These synthons were then exploited in the development of a molecular switch. Chapter One provides a brief overview of crystal engineering, the key hydrogen bonding interactions utilized in this work and also a general insight into “molecular machines” reported in the literature of relevance to this work. Chapter Two outlines the design and synthetic strategies for the development of two scaffolds suitable for incorporation of terminal alkynes, organosulfur and ether functionalities, in order to investigate the robustness and predictability of the S=O•••H-C≡C- and S=O•••H-C(α) supramolecular synthons. Crystal structures and a detailed analysis of the hydrogen bond interactions observed in these compounds are included in this chapter. Also the biological activities of four novel tertiary amines are discussed. Chapter Three focuses on the design and synthesis of diphenylacetylene compounds bearing amide and sulfur functionalities, and the exploitation of the N-H•••O=S interactions to develop a “molecular switch”. The crystal structures, hydrogen bonding patterns observed, NMR variable temperature studies and computer modelling studies are discussed in detail. Chapter Four provides the overall conclusions from chapter two and chapter three and also gives an indication of how the results of this work may be developed in the future. Chapter Five contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of the NCI (National Cancer Institute) biological test results are included in the appendix.
Resumo:
PTEN‐induced kinase 1 (PINK1) was identified initially in cancer cells as a gene up‐regulated by overexpression of the central tumour suppressor, PTEN. Loss‐of‐function mutations in PINK1 were discovered subsequently to cause autosomal recessive Parkinsonʹs disease (ARPD). Despite much research focusing on the proposed mechanism(s) through which loss of PINKI function causes neurodegeneration, few studies have focused on a direct role for this serine/threonine kinase in cancer biology. The focus of this thesis was to examine a direct role for PINK1 function in tumourigenesis. Initial studies showed that loss of PINK1 reduces tumour‐associated phenotypes including cell growth, colony formation and invasiveness, in several cell types in vitro, indicating a pro‐tumourigenic role for PINK1 in cancer. Furthermore, results revealed for the first time that PINK1 deletion, examined in mouse embryonic fibroblasts (MEFS) from PINK1 knock‐out animals, causes cell cycle defects, whereby cells arrest at in cytokinesis, giving rise to a highly significant increase in the number of multinucleated cells. This results in several key changes in the expression profile of cell cycle associated protein. In addition, PINK1‐deficient MEFs were found to resist cell cycle exit, with a proportion of cells remaining in proliferative phases upon removal of serum. The ability of cells to progress through mitosis conferred by PINK1 expression was independent of its kinase activity, while the cell cycle exit following serum withdrawal was kinase dependent. Investigations into the mechanism through which loss of PINK1 function gives rise to cell cycle defects revealed that dynamin related protein 1 (Drp1)‐mediated mitochondrial fission is enhanced in PINK1‐ deficient MEFs, and that increased expression of Drp1 on mitochondria and activation of Drp1 is highly significant in PINK1‐deficient multinucleated cells. Deregulated and increased levels and activation of mitochondrial fission via Drp1 was shown to be a major feature of cell cycle defects caused by PINK1 deletion, both during progression through G2/M and cell cycle exit following serum removal. Altered PINK1 localisation was also observed during progression of mitosis, and upon serum deprivation. Thus, PINK1 dissociated from the mitochondria during the mitotic phases and localised to mitochondria upon serum withdrawal. During serum withdrawal deletion of PINK1 disabled the ability of MEFs to increase mitochondrial membrane potential (ΔΨm), and increase autophagy. This was co‐incident with increased mitochondrial fission, and increased localisation of Drp1 to mitochondria following serum deprivation. Together, this indicates an inability of PINK1‐negative cells to respond protectively to this stress‐induced state, primarily via impaired mitochondrial function. In contrast, PINK1 overexpression was found to protect cells from DNA damage following treatment with oxidants. In addition, deletion of PINK1 blocked the ability of cells to re‐enter the cell cycle in response to insulin‐like growth factor‐1 (IGF‐1), a major cancer promoting agonistwhich acts primarily via PI3‐kinase/Akt activation. Furthermore, PINK1 mRNA expression was significantly increased following serum deprivation of MCF‐7 cells, and this was rendered more significant upon additional inhibition of PI3‐kinase. Conversely, IGF‐1 activation of PI3‐kinase/Akt causes a time‐dependent and significant reduction of PINK1 mRNA expression that was PI3‐kinase dependent. Together these results indicate that PINK1 expression is necessary for IGF‐1 signalling and is regulated reciprocally in the absence and presence of IGF‐1, via PI3‐kinase/Akt, a signalling system which has major tumour‐promoting capacity in cancer cell biology. The results of this thesis indicate PINK1 is a candidate tumour-promoting gene which has a significant function in the regulation of the cell cycle, and growth factor responses, at key cell cycle checkpoints, namely, during progression through G2/M and during exit of the cell cycle following removal of serum. Furthermore, the results reveal that the regulation of mitochondrial fission and Drp1 function is mechanistically important in the regulation of cell cycle control by PINK1. As deregulation of the cell cycle is linked to both tumourigenesis and neurodegeneration, the findings of this thesis are of importance not just for understanding cancer biology, but also in the context of PINK1‐associated neurodegeneration.
Resumo:
Defects in commercial cheese result in a downgrading of the final cheese and a consequential economic loss to the cheese producer. Developments of defects in cheese are often not fully understood and therefore not controllable by the producer. This research investigated the underlying factors in the development of split and secondary fermentation defect and of pinking defects in commercial Irish cheeses. Split defect in Swiss-type cheese is a common defect associated with eye formation and manifests as slits and cracks visible in the cut cheese loaf (Reinbold, 1972; Daly et al., 2010). No consensus exists as to the definitive causes of the defect and possible factors which may contribute to the defect were reviewed. Models were derived to describe the relationship between moisture, pH, and salt levels and the distance from sample location to the closest external block surface during cheese ripening. Significant gradients within the cheese blocks were observed for all measured parameters in cheeses at 7 day post/after manufacture. No significant pH gradient was found within the blocks on exit from hot-room ripening and at three months post exit from the hot-room. Moisture content reached equilibrium within the blocks between exit from hot-room and 3 months after exit from hot-room while salt and salt-to-moisture levels had not reached equilibrium within the cheese blocks even at three months after exit from hot-room ripening. A characterisation of Swiss-type cheeses produced from a seasonal milk supply was undertaken. Cheeses were sampled on two days per month of the production year, at three different times during the manufacturing day, at internal and external regions of the cheese block and at four ripening time points (7 days post manufacture, post hot-room, 14 days post hot-room and 3 months in a cold room after exit from hot-room). Compositional, biochemical and microbial indices were determined, and the results were analysed as a splitplot with a factorial arrangement of treatments (season, time of day, area) on the main plot and ripening time on the sub-plot. Season (and interactions) had a significant effect on pH and salt-in-moisture levels (SM), mean viable counts of L. helveticus, propionic acid and non-starter lactic acid bacteria, levels of primary and secondary proteolysis and cheese firmness. Levels of proteolysis increased significantly during hot-room ripening but also during cold room storage, signifying continued development of cheese ripening during cold storage (> 8°C). Rheological parameters (e.g. springiness and cohesiveness) were significantly affected by interactions between ripening and location within cheese blocks. Time of day of manufacture significantly affected mean cheese calcium levels at 7 days post manufacture and mean levels of arginine and mean viable counts of NSLAB. Cheeses produced during the middle of the production day had the best grading scores and were more consistent compared to cheeses produced early or late during day of manufacture. Cheeses with low levels of S/M and low values of resilience were associated with poor grades at 7 days post manufacture. Chesses which had high elastic index values and low values of springiness in the external areas after exit from hot-room ripening also obtained good commercial grades. Development of a pink colour defect is an intermittent defect in ripened cheese which may or may not contain an added colourant, e.g., annatto. Factors associated with the defect were reviewed. Attempts at extraction and identification of the pink discolouration were unsuccessful. The pink colour partitioned with the water insoluble protein fraction. No significant difference was observed between ripened control and defect cheese for oxygen levels and redox potential or for the results of elemental analysis. A possible relationship between starter activity and defect development was established in cheeses with added coulourant, as lower levels of residual galactose and lactose were observed in defective cheese compared to control cheese free of the defect. Swiss-type cheese without added colourant had significantly higher levels of arginine and significantly lower lactate levels. Flow cell cytometry indicated that levels of bacterial cell viability and metabolic state differed between control and defect cheeses (without added colourant). Pyrosequencing analysis of cheese samples with and without the defect detected the previously unreported bacteria in cheese, Deinococcus thermus (a potential carotenoid producer). Defective Swiss-type cheeses had elevated levels of Deinococcus thermus compared to control cheeses, however the direct cause of pink was not linked to this bacterium alone. Overall, research was undertaken on underlying factors associated with the development of specific defects in commercial cheese, but also characterised the dynamic changes in key microbial and physicochemical parameters during cheese ripening and storage. This will enable the development of processing technologies to enable seasonal manipulation of manufacture protocols to minimise compositional and biochemical variability and to reduce and inhibit the occurrence of specific quality defects.
Development of large-scale colloidal crystallisation methods for the production of photonic crystals
Resumo:
Colloidal photonic crystals have potential light manipulation applications including; fabrication of efficient lasers and LEDs, improved optical sensors and interconnects, and improving photovoltaic efficiencies. One road-block of colloidal selfassembly is their inherent defects; however, they can be manufactured cost effectively into large area films compared to micro-fabrication methods. This thesis investigates production of ‘large-area’ colloidal photonic crystals by sonication, under oil co-crystallization and controlled evaporation, with a view to reducing cracking and other defects. A simple monotonic Stöber particle synthesis method was developed producing silica particles in the range of 80 to 600nm in a single step. An analytical method assesses the quality of surface particle ordering in a semiquantitative manner was developed. Using fast Fourier transform (FFT) spot intensities, a grey scale symmetry area method, has been used to quantify the FFT profiles. Adding ultrasonic vibrations during film formation demonstrated large areas could be assembled rapidly, however film ordering suffered as a result. Under oil cocrystallisation results in the particles being bound together during film formation. While having potential to form large areas, it requires further refinement to be established as a production technique. Achieving high quality photonic crystals bonded with low concentrations (<5%) of polymeric adhesives while maintaining refractive index contrast, proved difficult and degraded the film’s uniformity. A controlled evaporation method, using a mixed solvent suspension, represents the most promising method to produce high quality films over large areas, 75mm x 25mm. During this mixed solvent approach, the film is kept in the wet state longer, thus reducing cracks developing during the drying stage. These films are crack-free up to a critical thickness, and show very large domains, which are visible in low magnification SEM images as Moiré fringe patterns. Higher magnification reveals separation between alternate fringe patterns are domain boundaries between individual crystalline growth fronts.
Resumo:
The core of this thesis is the study of NATO’s Comprehensive Approach strategy to state building in Afghanistan between 2006 and 2011. It argues that this strategy sustained operational and tactical practices which were ineffective in responding to the evolved nature of the security problem. The thesis interrogates the Comprehensive Approach along ontological, empirical and epistemological lines and concludes that the failure of the Comprehensive Approach in the specific Afghan case is, in fact, indicative of underlying theoretical and pragmatic flaws which, therefore, generalize the dilemma. The research is pragmatic in nature, employing mixed methods (quantitative and qualitative) concurrently. Qualitative methods include research into primary and secondary literature sources supplemented with the author’s personal experiences in Afghanistan in 2008 and various NATO HQ and Canadian settings. Quantitative research includes an empirical case study focussing on NATO’s Afghan experience and its attempt at state building between 2006 and 2011. This study incorporates a historical review of NATO’s evolutionary involvement in Afghanistan incorporating the subject timeframe; offers an analysis of human development and governance related data mapped to expected outcomes of the Afghan National Development Strategy and NATO’s comprehensive campaign design; and interrogates the Comprehensive Approach strategy by means of an analysis of conceptual, institutional and capability gaps in the context of an integrated investigational framework. The results of the case study leads to an investigation of a series of research questions related to the potential impact of the failure of the Comprehensive Approach for NATO in Afghanistan and the limits of state building as a means of attaining security for the Alliance.