Synthetic and stereochemical aspects of intramolecular reactions of α-diazoketones catalysed by rhodium(II) carboxylates

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.

An evaluation of orogenic kinematic evolution utilizing crystalline and magnetic anisotropy in granitoids

The Silurian-Devonian Galway Granite Complex (GGC ~425-380Ma) is defined here as a suite of granitoid plutons that comprise the Main Galway Granite Batholith and the Earlier Plutons. The Main Batholith is a composite of the Carna Pluton in the west and the Kilkieran Pluton in the east and extends from Galway City ~130km to the west. The Earlier Plutons are spatially, temporally and structurally distinct, situated northwest of the Main Batholith and include the Roundstone, Omey, Inis and Letterfrack Plutons. The majority of isotopic and structural data currently available pertain to the Kilkieran Pluton, several tectonic models have already been devised for this part of the complex. These relate emplacement of the Kilkieran Pluton to extension across a large east-west Caledonian lineament, i.e. the Skird Rocks Fault, during late Caledonian transtension. No chronological data have been published that directly and accurately date the emplacement of the Carna Pluton or any of the Earlier Plutons. There is also a lack of data pertaining to the internal structure of these intrusions. Accordingly, no previous study has established the mechanisms of emplacement for the Earlier Plutons and only limited work is available for the Carna Pluton. As a consequense of this, constituents of the GGC have not previously been placed in a context relative to each other or to regional scale Silurio-Devonian kinematics. The current work focuses on the Omey, Roundstone and Carna Plutons. Here, results of detailed field and Anisotropy of Magnetic Susceptibiliy (AMS) fabric studies are presented. This work is complemented by geological mapping that focuses on fault dynamics and contact relationships. Interpretation of AMS data is aided by rock magnetic experiment data and petrographic microstructural evaluations of representative samples. A new geological map of the the Omey Pluton demonstrates that this intrusion has a defined roof and base which are gently inclined parallel to the fold hinge of the Connemara Antiform. AMS and petrographic data show the intrusion is cross cut by NNW-SSE shear zones that extend into the country rock. These pre-date and were active during magma emplacement. It is proposed that the Omey pluton was emplaced as a discordant phacolith. Pre-existing subvertical D5 faults in the host rock were reactived during emplacement, due to regional sinistral transpression, and served as centralised ascent conduits. A central portion of the Roundstone Pluton was mapped in detail for the first time. Two facies are identified, G1 forms the majority of the pluton and coeval G2 sheets cross cut G1 at the core of the pluton. NNW-SSE D5 faults mapped in the country rock extend across the pluton. These share a geometrical relationship with the distribution of submagmatic strain in the pluton and parallel the majoity of mapped subvertical G2 dykes. These data indicate that magma ascent was controlled by NNW-SSE conduits that are inherently related to those identifed in the Omey Pluton. It is proposed that the Roundstone Pluton is a punched laccolith, the symmetry and structure of which was controlled by pre-exising host rock structures and regional sinistral transpressive stress which presided during emplacement. Field relationships show the long axis of the Carna Pluton lies parallel to mulitple NNW-SSE shear zones. These are represented on a regional scale by the Clifden-Mace Fault which cross cuts the core of this intrusion. AMS and petrographic data show concentric emplacement fabrics were tectonically overprinted as magma cooled from the magmatic state due to this faulting. It is proposed that the Clifden-Mace Fault system was active during ascent and emplacement of the magma and that pluton inflation only terminated as this controlling structure went into compression due to the onset of regional transtension. U-Pb zircon laser ablation inductively coupled mass spectrometry (LA-ICP-MS) data has been compiled from four sample sites. New geochronological data from the Roundstone Pluton (RD1 = ± 3.2Ma) represent the oldest age determination obtained from any member of the GGC and demonstrates that this pluton predates the Carna Pluton by ~10Ma and probably intruded synchronously with the Omey Pluton (~422.5 ± 1.7Ma). Chronological data from the Carna Pluton (CN2 = 412.9 ± 2.5Ma; CN3 = 409.8 ± 7.2Ma; CN4 = 409.6 ± 3.6Ma) represent the first precise magma crystallisation age for this intrusion. This work shows this pluton is 10Ma older than the Kilkieran Pluton and that the supply of magma into the Carna Pluton had terminated by ~409Ma. Chronological, magnetic and field data have been utilised to evaluate the kinematic evolution of the Caledonides of western Ireland throughout the construction of the GGC. It is proposed that the GGC was constructed during four distinct episodes. The style of emplacement and the conduits used for magma transport to the site of emplacement was dependent on the orientation of local structures relative to the regional ambiant stress field. This philosophy is used to critically evaluate and progress existing hypotheses on the transition from regional transpression to regional transtension at the end of the Caledonian Orogeny.

Monitoring behaviours and experiences before, during and after pregnancy in Ireland

Background: On-going surveillance of behaviours during pregnancy is an important but overlooked population health activity that is particularly lacking in Ireland. Few, if any, nationally representative estimates of most maternal behaviours and experiences are available. While on-going surveillance of maternal behaviours has not been a priority thus far in European countries including Ireland, on-going surveillance was identified as a key priority in the United States (US) during the 1980’s when the Pregnancy Risk Assessment Monitoring System (PRAMS), was established. Today, PRAMS is the only surveillance programme of maternal behaviours and experiences world-wide. Although on-going prevalence estimates are required in Ireland, studies which examine the offspring health effects of maternal behaviours are also required, since various questions regarding maternal exposures and their offspring health effects remain unanswered. Gestational alcohol consumption is one such important maternal exposure which is common in pregnancy, though its offspring health effects are unclear, particularly at lower or moderate levels. Thus, guidelines internationally have not reached consensus on safe alcohol recommendations for pregnant women. The aims of this thesis are to implement the PRAMS in Ireland (PRAMS Ireland), to describe the prevalence of health behaviours around the time of pregnancy in Ireland and to examine the effect of health behaviours on pregnancy and child outcomes (specifically the relationship between alcohol use during pregnancy and infant and child growth). Structure: In Chapter 1, a brief background and rationale for the work, as well as the thesis aims and objective is provided. A detailed description of the design and implementation of PRAMS Ireland is described in Chapter 2. Chapter 3 and Chapter 4 describe the methodological results of the implementation of the PRAMS Ireland pilot study and PRAMS Ireland main study. In Chapter 5, a comparison of alcohol prevalence in two Irish studies (PRAMS Ireland and Growing up in Ireland (GUI)) and one multi-centre prospective cohort study, Screening for Pregnancy Endpoints (SCOPE) Study is detailed. Chapter 6 describes findings on adherence to National Clinical Guidelines on health behaviours and nutrition around the time of pregnancy in PRAMS Ireland. Findings on exposure to alcohol use in pregnancy and infant growth outcomes are described in Chapter 7 and Chapter 8. The results of analysis conducted to examine the impact of gestational alcohol use on offspring growth trajectories to age ten are described in Chapter 9. Finally, a discussion of the findings, strengths and limitations of the thesis, direction for future research, policy, practice and public health implications are discussed in Chapter 10.Results: Implementation of PRAMS: PRAMS may be an effective system for the surveillance of health behaviours around the time of pregnancy in the Irish context. PRAMS Ireland had high response rates (67% and 61% response rates in the pilot and main study respectively), high item completion rates and valid prevalence estimates for many health behaviours. Examining prevalence of health behaviours: We found high levels of alcohol consumption before and during pregnancy, poor adherence to healthy diets and high levels of smoking before and during pregnancy among women in Ireland. Socially disadvantaged women had higher rates of deleterious health behaviours before pregnancy, although women with the most deleterious behaviour profiles before pregnancy appeared to experience the greatest gain in protective health behaviours during pregnancy. The impact of alcohol use on infant and offspring growth: We found that low and moderate levels of alcohol use did not impact on birth outcomes or offspring growth whereas heavy alcohol consumption resulted in reduced birth length and birth weight; however, this finding was not consistently observed across all studies. Selection, reporting and confounding biases which are common in observational research could be masking harmful effects. Conclusion: PRAMS is a valid and feasible method of surveillance of health behaviours around the time of pregnancy in Ireland. A surveillance program of maternal behaviours and experiences is immediately warranted due to high levels of deleterious health behaviours around the time of pregnancy in Ireland. Although our results do not indicate any evidence of harm, given the quality of evidence available, abstinence and advice of abstinence from alcohol may be the most prudent choice for patients and healthcare professionals respectively. Further studies of the effects of gestational alcohol use are required; particularly those which can reduce selection bias, reporting bias and confounding.

Racist harassment in the white hinterlands: minority ethnic children and parents' experiences in schools in Northern Ireland

This article explores the nature and extent of racist harassment in predominantly white areas. It is based upon a case study of Northern Ireland and draws upon data from indepth interviews with a total of 32 children and 43 parents drawn from the four largest minority ethnic groups in the region: Chinese, Irish Travellers, South Asians and Black Africans. The article demonstrates that racist harassment is a significant problem in schools in Northern Ireland and highlights the varied forms that it can take from overt acts of physical and verbal abuse to more covert and subtle forms of teasing and 'friendly' banter. Following a consideration of the differing responses that schools have made to racist incidents reported to them by children and/or parents, the article concludes by considering the implications of the findings and re-affirming the argument that anti-racist strategies are as relevant and necessary for schools in predominantly white regions as they are in multi-ethnic areas.

Sheriffs and outlaws: in pursuit of effective enforcement

Compliance has emerged as a key component of regulatory control, but has been subject to limited research. This paper examines compliance in relation to planning control in the jurisdiction of Northern Ireland. It draws upon a review of practice and procedure used to deal with planning enforcement cases and interviews conducted with professional planners. Many of the options considered emerge from the Review of Planning Enforcement System in England published by the Office of the Deputy Prime Minister (2002). The findings are incorporated with theoretical perspectives of regulatory compliance and provide a platform for more effective control of development.

Northern Ireland:Democratizing for Development

This introductory article does three things. First, it indicates the general purpose of this special edition an d outlines the structure an d intention of the four main articles that follow. Secondly, it elaborates the arguments and theoretical discourse underpinning the articles, and thirdly, it locates these concerns and development initiatives not only in the specifiŽc regional context of Northern Ireland, but also in the wider framework of a new global econom y.

'Ancient Enmities' and Modern Conflict: History and Politics in Northern Ireland

This article investigates the role of history and historical consciousness in deeply divided societies. It looks at the case of Northern Ireland. It argues that, while the conflict here is caused by contemporary divisions, perceptions of the past have had considerable influence. Recent years have seen efforts to change historical attitudes and this has aided political accommodation. An important lesson from the conflict in Northern Ireland points to the need to challenge such historical perceptions.

Northern Ireland:The Development Context

This article provides a contextual framework for the new agenda for development, represented in the economic strategy known as Strategy 2010, and the regional spatial plan known as Shaping Our Future. These are considered in the following two articles. This article begins by setting a perspective on the political economy of Northern Ireland and follows with an outline of the spatial planning process. In conclusion, it raises the key challenges facing attempts to renew the region.

No War, No Peace: Northern Ireland after the Agreement

In 1998 a historic agreement, commonly known as the Belfast or Good Friday Agreement, formed the basis of a negotiated settlement for the future of Northern Ireland. Since that time the level of violence in Northern Ireland has reduced but many problematic issues related to governance, sectarianism, and community relations remain on the political agenda and have destabilized the post-peace accord environment. Many of these issues can be viewed as either causes or consequences of the protracted conflict in Northern Ireland. This special issue examines some of these issues from a political psychology perspective. Economic, political, social, and psychological factors that have supported and hindered progress towards peace and stability are considered. While the paramilitary ceasefires have remained intact and certain aspects of life in Northern Ireland have been transformed, the road to peace has been hindered by both political and psychological intransigence. This paper offers an opportunity to reevaluate conceptualisations of conflict and its management in chronic situations, where divisions are deeply embedded within societal structures and relationships, and consider factors that may act as barriers to the development of a lasting peace.

Between the devil and the deep blue sea: Nationality, power and symbolic trade-offs among evangelical Protestants in contemporary Northern Ireland

National identity is symbolically complex configuration, with shifts of emphasis and reprioritisations of content negotiated in contexts of power. This paper shows how they occur in one post-conflict situation - Northern Ireland - among some of the most extreme of national actors - evangelical Protestants. In-depth interviews reveal quite radical shifts in the content of their British identity and in their understanding of and relation to the Irish state, with implications for their future politics. The implications for understanding ethno-religious nationalism, nationality shifts and the future of Northern Ireland are drawn out.

A cluster randomised controlled trial to evaluate a policy of making hip protectors available to residents of nursing homes

Objectives: to evaluate the effectiveness of a policy of making hip protectors available to residents of nursing homes. Design: a cluster randomised controlled trial of the policy in nursing and residential homes, with the home as the unit of randomisation. Setting: 127 nursing and residential homes in the greater Belfast area of Northern Ireland. Participants: 40 homes in the intervention group (representing 1,366 occupied beds) and 87 homes in the control group (representing 2,751 occupied beds). Interventions: a policy of making hip protectors available free of charge to residents of nursing homes and supporting the implementation process by employing a nurse facilitator to encourage staff in the homes to promote their use, over a 72-week period. Main outcome measures: the rate of hip fractures in intervention and control homes, and the level of adherence to use of hip protectors. Results: there were 85 hip fractures in the intervention homes and 163 in the control homes. The mean fracture rate per 100 residents was 6.22 in the intervention homes and 5.92 in the control homes, giving an adjusted rate ratio for the intervention group compared to the control group of 1.05 (95% CI 0.77, 1.43, P = 0.76). Initial acceptance of the hip protectors was 37.2% (508/1,366) with adherence falling to 19.9% (272/1,366) at 72 weeks. Conclusions: making hip protectors available to residents of nursing and residential homes did not reduce the rate of hip fracture.

Community Relations in Northern Ireland: a shift in Attitudes?

The paper presents an analysis of Northern Ireland Social Attitudes data available at the time of writing. Its significance lay in emerging disparities in the responses, over time, of Protestants and Catholics to key social issues such as integrated education. The data, made public just one year after the signing of the Belfast/Good Friday Agreement, generated intense media interest. Findings were reported in 400 outlets worldwide (UU media monitoring). Hughes was also interviewed for local and national news programmes (including BBC World Service). The data informed a decision by Government to undertake a major review of community relations policy, and Hughes was invited to advise the Head of the Northern Ireland review team. She was also invited to Chair the Community Relations Panel of the ESRC Devolution

El idiotismo de la sociedad tradicionalista tecnificada de principios de siglo XX en Colombia: La crítica de Luis Vidales a través de "Suenan timbres"

En este artículo tratamos, por medio de Suenan timbres de Luis Vidales, el idiotismo de la sociedad tradicionalista tecnificada de principios de siglo XX en Colombia. Estudio que realizamos desde el concepto de idiotismo de Vidales, en estrecha relación con el de cultura de viñeta de Rafael Gutiérrez Girardot, para plantear la burla del poeta a la sociedad capitalista, que cuestiona la presencia de la Iglesia católica y la política conservadora en todos los estadios de la vida nacional.

'Leaving Nothing to Chance'?: Joint Tenancies, The 'Right' of Survivorship and Unilateral Severance

The joint tenancy with its inherent right of survivorship is the most prevalent form of co-ownership in the common law world today. Most couples will be joint tenants of a family home, while relations (such as siblings) who purchase property together may opt for this arrangement. Inter vivos acquisitions aside, the huge intergenerational transfer of wealth within families on death can result in a joint tenancy, and it may also be a convenient estate planning device. The fact that property automatically vests in the surviving joint tenants on death is the reason why many people choose this form of co-ownership. However, there is one serious disadvantage. A joint tenancy is an inflexible form of landholding where relationships sour or family circumstances change over time, and co-owners want their respective `shares' of the property to pass to someone else on death. Where consensual severance is not possible, one joint tenant can sever unilaterally. The latter mechanism is vital in terms of giving effect to the wishes of the severing joint tenant, especially in situations of discord or a breakdown in relations with their fellow co-owners. However, unilateral severance also has serious implications for the non-severing joint tenant(s) who expected to inherit property through survivorship, and can impact significantly on ownership of the home and other family property. This article looks at unilateral severance as a means of subverting the right of survivorship. The focus is on personal and inter-family relationships, and the various legal issues and policy considerations associated with unilateral severance across the common law jurisdictions of Britain, Ireland, Australia, Canada, and New Zealand. It assesses the various methods of effecting unilateral severance and proposes specific measures, as well as considering novel arguments for preventing unilateral severance based on contractual agreements to the contrary and proprietary estoppel.