Twisted molecular magnets

Journal article (post-print)The use of derivatised salicylaldoximes in manganese chemistry has led to the synthesis of a family of approximately fifty hexanuclear ([MnIII6]) and thirty trinuclear ([MnIII3]) Single-Molecule Magnets (SMMs). Deliberate, targeted structural distortion of the metallic core afforded family members with increasingly puckered configurations, leading to a switch in the pairwise magnetic exchange from antiferromagnetic to ferromagnetic. Examination of both the structural and magnetic data revealed a semi-quantitative magneto-structural correlation, from which the factors governing the magnetic properties could be extracted and used for predicting the properties of new family members and even more complicated structures containing analogous building blocks. Herein we describe an overview of this extensive body of work and discuss its potential impact on similar systems.IRCSETpeer-reviewe

The Rise and Fall of Cooperative Resource Management: A Case Study of Mussel Farming in Killary Harbour

Natural resources have become a critical focus for rural development programmes. In the past many families in rural areas relied upon small scale agriculture as the primary source of income for the household. These households would typically depend on social welfare payments and seasonal work as a secondary source of employment. However with the rising cost of production and a declining price for agriculture products, small scale agriculture was no longer a reliable source of income. This created structural weaknesses for many peripheral rural areas. As a result there has been much focus placed upon diversifying rural economies with a high priority placed on natural resources. This is typified by the Axis 3 programme under the National Development Plan 2007-2013, which cites natural resources as a valuable means to diversify local economies and compensate for the fall off in agriculture. The model of development within this plan has focused upon maximising community participation in natural resource based industries. Such a model immediately introduces the issue of management as many of these resources are finite and subject to depletion. It is imperative that they are managed sustainably as the future needs of rural communities rely upon their continued survival. The most obvious solution would be for the state to take control of management. However questions have been raised over this, mainly due to enforcement difficulties and the fact that the state can often prioritise goals of economic growth over resource sustainability. Consequently much attention has been placed upon decentralised management where the resource users take control of management and devise cooperative strategies to safeguard the resource in the long run. Mckean (1992) has outlined a number of important institutional factors which can improve the likely success of local self-governance. The important features in Mckean's model include restricting access to members of the local community, developing and enforcing rules and establishing local leaders to give the project energy and a focus. She also cites the importance of support from the state where local institutions are given financial assistance and provided with real property rights over the resource. In spite of this, in-depth empirical accounts of local self-governance are absent in the literature on Ireland¿s resource management. Given the high priority now placed on natural resources, this issue should be considered of significant importance. This thesis examines the scope of local self-governance through a case study of mussel farming in Killary harbour, one of Ireland¿s largest aquacultural sites. Killary harbour is an interesting area to conduct this study as it is located in North West Connemara, an underdeveloped region in the west of Ireland, where natural resource have been trumpeted as a means to address local peripherality and decline. Furthermore there was a local co-operative that effectively managed the mussel stocks in Killary for a 20 year period, only for it to subsequently weaken. Consequently it can reveal a considerable amount on the likely dynamics that produce both a success and a decline in cooperative resource management. The findings presented in this study raise much optimism around local self governance given the co-operative's 20 year period of success. The success of the co-operative confirms Mckean's model as many of her factors were found to be present. Based on these findings we should expect local self-governance to be successful in Ireland if Mckean¿s factors can be incorporated into local institutions. A second important contribution made by this study is that Mckean's factors are still relevant despite the emergence of the market. Some commentators have questioned the validity of Mckean¿s model suggesting that it is outdated as it is based upon evidence from the 16th and 17th century. Certain viewpoints have argued that applying the evidence from this to a contemporary market society is suspect as resource users face declining prices at the market. This may cause users to extract more from the resource in order to survive, threatening local rules and institutions. While the market played a small role in the weakening of the co-operative in Killary, it was not the overriding variable. Changing local economic values coupled with a shifting policy direction forced co-operative mussel farming to decline in the area. Critically the co-operative was not provided with real property rights over the resource. When local economic values began to change, a number of 'free riders' emerged, who could not be disciplined as they lacked the necessary statutory instruments to do so. These variables were discussed by Mckean who argues that the state must give local institutions real property rights to deal with emerging 'free riders'. Consequently her model still holds as the lack of state support undermined the co-operative, while the market variable only had a small impac

Poverty, demographic change and inequality in Nigeria: a microsimulation analysis

The primary aim of this thesis is to develop and uses demographic dynamic microsimulation model to examine the various forces that impact on the distribution of household income. The model is capable of examining a wide range of policy issues such as demographic change resulting from HIV/AIDS, the distribution of income associated with the labour market, the impact of tax policy change on household disposable income and the distributional impact of HIV/AIDS on income inequality and poverty.. when focusing on the impact of HIV/AIDS mortality on household structure in Nigeria. it was observed that the impact of AIDS death on the population structure of Nigeria is considerable. it was estimated at approximately 2 percent reduction.2016-08-1

Detention without trial in the United Kingdom: From empire to the 'War on Terror'

This thesis analyses detention without trial in the United Kingdom by applying a socio-legal lens to several instances where these extra-judicial powers have been adopted. What will emerge from this examination is twofold. Firstly, detention without trial in the state of emergency, as seen through five case studies, is inherently violent. The architecture of the camp lends itself to physical violence, but moreover, a space is created which demands detainee submission to camp authorities as proxy agents of the state. Slavoj Zizek developed a model of violence as a triumvirate, in which subjective violence, that is, 'directly visible' violence performed by a clearly identifiable agent,¿ forms the most obvious portion, but it is also sustained by two types of 'objective violence.' The manifest violence that occurs in sites of detention is analysed, but the thesis also probes the more profound silent violence; what Zizek terms 'symbolic violence,' which is 'embodied in language and its forms.' On one level, symbolic violence can be connected with hate speech and incitement to hatred, but it also pertains to the 'imposition of a certain universe of meaning.' Secondly, the thesis examines the 'universe of meaning' surrounding detention which is disseminated within the 'liberal state' that denies its own violence and hides the 'systemic violence' of the state. 'Systemic violence', the other form of objective 'invisible' violence, is, the often catastrophic consequences of the smooth functioning of our economic and political systems.' In this study, systemic violence is the result of the smooth functioning of emergency legal systems created by politico-executive decisionism. Whereas detention without trial challenges some of the foundational precepts of the democratic state, law gives the institution and its techniques a mantle of legitimacy, and the violence becomes invisible. Periodic outbursts or acts of aggression that occur in detention are generally portrayed as aberrant against this invisible violence. Therefore, to appreciate the violence of the camp in its totality, it is necessary to deconstruct the symbolic violence of language and law, and highlight the quiet systemic violence that accompanies the architecture of detention. These extrajudicial structures outside common law jurisdiction are underpinned by discourse that imposes an interpretative framework of detainee difference, emphasising their 'essential' violent tendencies, claiming that this threat is such that rule of law standards must be abrogated. Departing from Zizek, the thesis further argues that the violent framework of detention is sustained by an underlying culture of impunity; detention without trial makes individuals more vulnerable to manifest and 'symbolic violence' but abuses and violations that occur in these sites have proven extremely difficult to prosecute, because of structural obstacles, and the 'consequences of the smooth functioning' of emergency law regulatory frameworks.2018-05-3

Synthesis of tumour cell migration inhibitors

Chapter one and two of this thesis describe the synthesis of novel migrastatin derivatives. Migrastatin is a fourteen-membered macrocycle isolated by Japanese researchers from the Streptomyces platensis. It has been shown to inhibit tumour cell migration. The total synthesis of migrastatin and a number of analogues have previously been described. However it has been found that analogues of the migrastatin core are up to one thousand times more active than migrastatin itself. As a result, current work focuses on the synthesis of new analogues of the migrastatin core. Much of the previous research has focused on closed macrocycles. However recent work suggests that the acyclic ring-closing metathesis pre-cursors also display activity. In this thesis, the synthesis of acyclic ester analogues of migrastatin will be described. Previous efforts have focused on relatively flexible structures. However in this study, the analogues synthesised incorporate aromatic rings such as 2, and sugars such as 3, and can be considered to be more rigid structures. Efforts towards the ring-closing metathesis of these acyclic compounds are also described. Chapter three seeks to investigate the conformations of a number of migrastatin analogues. It focuses on trying to rationalise on difficulties in obtaining ring closed products from more constrained substrates. This chapter also includes a study as to whether the structures of the macrolactone core of migrastatin, obtained from modelling using Macromodel¿, are supported experimentally by examining NMR data for the macrolactone. It seeks to investigate how well the modelling can predict the structure of the macrocycle. Chapter four describes the synthesis of a number of dimeric compounds. These are dimers of allylated aromatic compounds prepared by cross metathesis reactions. A vast number of stilbenoid natural products exist within the literature. However di-aryl compounds with a four-carbon inter-aryl bridge incorporating an alkene such as 4 and 5 are much less investigated. Chapter four contains a description of research on the synthesis of such dimers. Previously synthesised compounds appear to show that the two aryl rings must be in close proximity to one another for activity and as a result trans stilbenoids have shown little activity. It appears that it is the proximity of the aromatic rings to one another rather than the stereochemistry of bridging atoms which is of most importance for biological activity. It is hoped that, although the inter-aryl bridge is longer, that the increased flexibility this affords will allow both the cis and trans compounds to show activity.2017-12-0

Development Studies

Book chapterThis contribution identifies development as an emergent and contested key concept in the social and environmental sciences. Development studies describes a field that includes multi-, inter-, and transdisciplinary approaches to economic growth, basic needs, inequality, human development, rights, resources, livelihoods, and sustainability, focusing mainly, but not exclusively, on developing countries. The scope and content of development studies is described and the main schools of thought, theoretical debates, concepts, and indicators are discussed in historical context, ranging from the colonial appropriation of natural resources to modernization and its critiques, to current agendas for sustainable and rights-based human development.Peer reviewe

A theatre of truth? Negotiating place, politics and policy in the Dublin Fringe Festival

[No abstract available]Peer reviewe

A preliminary design methodology for fatigue life prediction of polymer composites for tidal turbine blades

Journal articleTidal turbine blades experience significant fatigue cycles during operation and it is expected that fatigue strength will be a major consideration in their design. Glass fibre reinforced polymers are a candidate low-cost material for this application. This article presents a methodology for preliminary fatigue design of glass fibre reinforced polymer tidal turbine blades. The methodology combines: (a) a hydrodynamic model for calculation of local distributions of fluid-blade forces; (b) a finite element structural model for prediction of blade strain distributions; (c) a fatigue damage accumulation model, which incorporates mean stress effects; and (d) uniaxial fatigue testing of two candidate glass fibre reinforced polymer materials (for illustrative purposes). The methodology is applied here for the preliminary design of a three-bladed tidal turbine concept, including tower shadow effects, and comparative assessment of pitch-and stall-regulated control with respect to fatigue performance.peer-reviewe

International players fiddle while Syria burns

The UN Human Rights office estimated that more than 60,000 people have died in Syria's bloody civil war, surpassing the Syrian opposition's estimates by one-third. UN High Commissioner for Human Rights Navi Pillay faulted the entire international community, including the UN, for having 'fiddled around the edges while Syria burns.' As the violence threatens to engulf the region, the question remains what can be done to halt the slaughter of innocent civilians.non-peer-reviewe

Sharing the pain, striving for gain

Ireland is experiencing a particularly severe and sudden economic downturn. Spending on higher education is under the microscope, with implications for university libraries. The impact of this new environment at National University of Ireland, Galway, in particular, is discussed and a range of challenges, opportunities and coping strategies explored in the context of staffing, information resources and operations. The national dimension is also covered, notably implications for the IReL (Irish Research eLibrary) service. Overall, a combination of pain and gain is identified, with resource losses balanced against opportunities for new thinking and models.non-peer-reviewe