Development of low-cost sensing and separation devices based on macro, micro and nano technology for health applications

The work presented in this thesis described the development of low-cost sensing and separation devices with electrochemical detections for health applications. This research employs macro, micro and nano technology. The first sensing device developed was a tonerbased micro-device. The initial development of microfluidic devices was based on glass or quartz devices that are often expensive to fabricate; however, the introduction of new types of materials, such as plastics, offered a new way for fast prototyping and the development of disposable devices. One such microfluidic device is based on the lamination of laser-printed polyester films using a computer, printer and laminator. The resulting toner-based microchips demonstrated a potential viability for chemical assays, coupled with several detection methods, particularly Chip-Electrophoresis-Chemiluminescence (CE-CL) detection which has never been reported in the literature. Following on from the toner-based microchip, a three-electrode micro-configuration was developed on acetate substrate. This is the first time that a micro-electrode configuration made from gold; silver and platinum have been fabricated onto acetate by means of patterning and deposition techniques using the central fabrication facilities in Tyndall National Institute. These electrodes have been designed to facilitate the integration of a 3- electrode configuration as part of the fabrication process. Since the electrodes are on acetate the dicing step can automatically be eliminated. The stability of these sensors has been investigated using electrochemical techniques with excellent outcomes. Following on from the generalised testing of the electrodes these sensors were then coupled with capillary electrophoresis. The final sensing devices were on a macro scale and involved the modifications of screenprinted electrodes. Screen-printed electrodes (SPE) are generally seen to be far less sensitive than the more expensive electrodes including the gold, boron-doped diamond and glassy carbon electrodes. To enhance the sensitivity of these electrodes they were treated with metal nano-particles, gold and palladium. Following on from this, another modification was introduced. The carbonaceous material carbon monolith was drop-cast onto the SPE and then the metal nano-particles were electrodeposited onto the monolith material

Synthesis of 4-substituted-3(2H)-furanones with novel luminescence properties

The objective of this project was to prepare a range of 4-substituted 3-(2H)-furanones, and to investigate the relationship between their molecular structures and photoluminescence properties. The effects of substituents and conjugated linker unit were also investigated. After generation of the key 3(2H)-furanone heterocycle, extension of the conjugated framework at the C-4 position was achieved through Pd(0)-catalysed coupling reactions. Chapter one of the thesis comprises a review of the relavent literature and is split into three sections. These include information about the prevalence of 3-(2H)-furanones as natural products and synthetic routes to 3-(2H)-furanones in general. The synthetic routes are divided according to the synthetic precursor employed. The final section of chapter one outlines the fundamental principles and application of photoluminescence to organic compounds in general. Chapter two contains the results of the research achieved in the course of this work and a discussion of the findings. Two routes were successfully employed to generate 4-unsubstituted 3-(2H)-furanone moieties: (i) base induced cyclisation of hydroxyenones and (ii) isoxazole chemistry. A number of methods which proved ineffective in the production of furanones with the desired substitution pattern are also detailed. The majority of this study was focused on the introduction of substituents at the C-4 position of the 3-(2H)-furanone ring. This was achieved through the use of Sonogashira and Suzuki cross coupling protocols for Pd(0) catalysed C-C bond formation. The further functionalisation of some compounds was performed using transfer hydrogenation and “click chemistry” methodologies. Finally, the photophysical properties of 3-(2H)-furanones prepared in this project are discussed and the effect of substitution patterns in a complementary “push push” and “push pull” manner have also been investigated. All the experimental data and details of the synthetic methods employed, for the compounds prepared during the course of this research is contained in chapter three together with the spectroscopic and analytical properties of the compounds prepared.

A health status survey of clams, Mya arenaria and Ensis siliqua, in the Irish Sea

The soft shell clam, Mya arenaria, and the razor clam, Ensis siliqua, are widely distributed in Irish waters. Though the reproductive biology and other aspects of the physiology of these species has been previously investigated, little or no data are currently available on their health status. As this knowledge is essential for correct management of a species, M. arenaria and E. siliqua were examined to assess their current health status using histological and molecular methods, over a period of sixteen months. No pathogens or disease were observed in M. arenaria, and low incidences of Prokaryote inclusions, trematode parasites, Nematopsis spp. and eosinophilic bodies were recorded in razor clams for the first time in Northern European waters.

The reproductive biology of the exploited razor clam, Ensis siliqua, in the Irish Sea

Knowledge of the reproductive cycle of a species is a prerequisite for sustainable management of a fishery. The infaunal marine bivalve, Ensis siliqua, is a commercially important species in Europe, and is exploited in many countries, including Ireland, where it is sold by wet weight. Seasonal variations in the reproductive cycle of subtidal razor clams from the Skerries region of the Irish Sea, an important fisheries area, were examined between June 2010 and September 2011 while monitoring weight. Histological examination revealed that the E. siliqua sex-ratio was not different from parity, and no hermaphrodites were observed in the samples collected. In the summer months of 2010 all female clams were either spent or in early development, with just a small percentage of males still spawning. The gonads of both sexes developed over the autumn and winter months of 2010, with the first spawning individuals recorded in January 2011. Spawning peaked in March 2011, but unlike in 2010, spawning continued through June and July with all animals spent in August 2011. The earlier and longer spawning period found in this species in 2011 compared to 2010 may have been due to the colder than normal temperature observed during the winter of 2010 plus the relatively warmer temperatures of Spring 2011, which could have affected the gametogenic development of E. siliqua in the Irish Sea. It was noted that wet weight dropped in the summer months of both years, immediately after the spawning period which may impact on the practicality of fishing for this species during this period. Timing of development and spawning is compared with other sites in the Irish Sea and elsewhere in Europe, including the Iberian Peninsula.

Psychosocial well-being of African migrant children in Ireland: a cultural orientation

This thesis explores the psychosocial wellbeing of sub-Saharan African migrant children in Ireland. A sociocultural ecological (Psychosocial Working Group, 2003) and resilience lens (Masten & Obradovic, 2008; Ungar, 2011) is used to analyse the experiences of African migrant children in Ireland. The research strategy employs a mixed-methods design, combining both an etic and emic perspective. Grounded theory inquiry (Strauss and Corbin, 1994) explores the experiences of African migrant children in Ireland by drawing on multi-sited observations over a period of six months in 2009, and on interviews and focus group discussions conducted with African children (aged 13-18), mothers and fathers. An emically derived ‘African Migrant Child Psychosocial Well-being’ scale was developed by drawing on data gathered through rapid ethnographic (RAE) free listing exercises carried out in Cork, Dublin and Dundalk with sixty-one participants (N=21 adults, N=28 15-18-year-olds, N=12 12-14-year-olds) and three African community key informants to elicit local understandings of psychosocial well-being. This newly developed scale was used alongside standardised measures of well-being to quantitatively measure the psychosocial adjustment of 233 African migrant children in Cork, Dublin and Dundalk aged 11-18. Findings indicate that the psychosocial wellbeing of the study population is satisfactory when benchmarked against the psychosocial health profile of Irish youth (Dooley & Fitzgerald, 2012). These findings are similar to trends reported in international literature in this field (Georgiades et al., 2006; Gonneke, Stevens, Vollebergh, 2008; Sampson et al., 2005). Study findings have implications for advancing psychosocial research methods with non-Western populations and on informing the practice of Irish professionals, mainly in the areas of teaching, psychology and community work.

Becoming a father of a child with an intellectual disability- a narrative inquiry of Irish fathers’ stories

Background: This thesis explored men’s experiences of becoming a father of a child with an intellectual disability in the early years. In Ireland, it is estimated that there are almost 97% (n= 9,914) children with intellectual disabilities living at home in the care of parents, siblings, relatives or foster parents. While mothers and fathers are the primary caregivers, mothers’ experiences are well documented in comparison to the dearth of reports on fathers’ experiences. This descriptive narrative study aims to redress this gap in knowledge and understanding of men’s experiences of becoming a father of a child with an intellectual disability in the early years. Method: Narrative inquiry was employed for this study as it allows stories told by fathers to be collected as a means of exploring men’s transition to becoming a father of a child with an intellectual disability. A sample of 10 fathers of children with intellectual disabilities aged between thirteen months and five years of age were recruited from a large intellectual disability Health Service Provider (HSP) in the South of Ireland. Data were collected through semi-structured interviews which were audio-recorded, transcribed, and analysed using a narrative thematic approach. Findings: Findings are presented in four themes: i) ‘becoming a father’, ii) ‘something wrong with my child’, iii) ‘entering the world of disability’ and iv) ‘living a different life’. For all 10 fathers the time of being told that their child had an intellectual disability was laden with negative emotional responses irrespective of whether the diagnosis was at birth or more gradual over the child’s early developmental period. When fathers found out that ‘something was wrong’ they spoke of ‘moving on’ and entering the world of disability. In their narratives, becoming the father of a child with an intellectual disability had changed their lives and would inevitably change their futures. Fathers’ positivity was clearly evident with many fathers identifying that the diagnosis of their child with an intellectual disability was not a life ending event but rather a life changing event. Conclusions: Healthcare professionals have a critical role in supporting fathers during the transition to becoming a father of a child with an intellectual disability. Factors which require consideration include recognising that each father’s experience is unique; that fathers require support; and that fathers achieve personal growth because of their experiences of their transition to becoming a father of a child with an intellectual disability in the early years.

The effects of copayment policies on adherence to prescription medicines in publicly insured populations

Introduction: Copayments for prescriptions are associated with decreased adherence to medicines resulting in increased health service utilisation, morbidity and mortality. In October 2010 a 50c copayment per prescription item was introduced on the General Medical Services (GMS) scheme in Ireland, the national public health insurance programme for low-income and older people. The copayment was increased to €1.50 per prescription item in January 2013. To date, the impact of these copayments on adherence to prescription medicines on the GMS scheme has not been assessed. Given that the GMS population comprises more than 40% of the Irish population, this presents an important public health problem. The aim of this thesis was to assess the impact of two prescription copayments, 50c and €1.50, on adherence to medicines.Methods: In Chapter 2 the published literature was systematically reviewed with meta-analysis to a) develop evidence on cost-sharing for prescriptions and adherence to medicines and b) develop evidence for an alternative policy option; removal of copayments. The core research question of this thesis was addressed by a large before and after longitudinal study, with comparator group, using the national pharmacy claims database. New users of essential and less-essential medicines were included in the study with sample sizes ranging from 7,007 to 136,111 individuals in different medication groups. Segmented regression was used with generalised estimating equations to allow for correlations between repeated monthly measurements of adherence. A qualitative study involving 24 individuals was conducted to assess patient attitudes towards the 50c copayment policy. The qualitative and quantitative findings were integrated in the discussion chapter of the thesis. The vast majority of the literature on this topic area is generated in North America, therefore a test of generalisability was carried out in Chapter 5 by comparing the impact of two similar copayment interventions on adherence, one in the U.S. and one in Ireland. The method used to measure adherence in Chapters 3 and 5 was validated in Chapter 6. Results: The systematic review with meta-analysis demonstrated an 11% (95% CI 1.09 to 1.14) increased odds of non-adherence when publicly insured populations were exposed to copayments. The second systematic review found moderate but variable improvements in adherence after removal/reduction of copayments in a general population. The core paper of this thesis found that both the 50c and €1.50 copayments on the GMS scheme were associated with larger reductions in adherence to less-essential medicines than essential medicines directly after the implementation of policies. An important exception to this pattern was observed; adherence to anti-depressant medications declined by a larger extent than adherence to other essential medicines after both copayments. The cross country comparison indicated that North American evidence on cost-sharing for prescriptions is not automatically generalisable to the Irish setting. Irish patients had greater immediate decreases of -5.3% (95% CI -6.9 to -3.7) and -2.8% (95% CI -4.9 to -0.7) in adherence to anti-hypertensives and anti-hyperlipidaemic medicines, respectively, directly after the policy changes, relative to their U.S. counterparts. In the long term, however, the U.S. and Irish populations had similar behaviours. The concordance study highlighted the possibility of a measurement bias occurring for the measurement of adherence to non-steroidal anti-inflammatory drugs in Chapter 3. Conclusions: This thesis has presented two reviews of international cost-sharing policies, an assessment of the generalisability of international evidence and both qualitative and quantitative examinations of cost-sharing policies for prescription medicines on the GMS scheme in Ireland. It was found that the introduction of a 50c copayment and its subsequent increase to €1.50 on the GMS scheme had a larger impact on adherence to less-essential medicines relative to essential medicines, with the exception of anti-depressant medications. This is in line with policy objectives to reduce moral hazard and is therefore demonstrative of the value of such policies. There are however some caveats. The copayment now stands at €2.50 per prescription item. The impact of this increase in copayment has yet to be assessed which is an obvious point for future research. Careful monitoring for adverse effects in socio-economically disadvantaged groups within the GMS population is also warranted. International evidence can be applied to the Irish setting to aid in future decision making in this area, but not without placing it in the local context first. Patients accepted the introduction of the 50c charge, however did voice concerns over a rising price. The challenge for policymakers is to find the ‘optimal copayment’ – whereby moral hazard is decreased, but access to essential chronic disease medicines that provide advantages at the population level is not deterred. This evidence presented in this thesis will be utilisable for future policy-making in Ireland.

A study of the extent to which Irish law, policy and practice allow for Ireland's application of the United Nations Convention on the Rights of the Child, 1989 to pre-natal children

The central research question of this thesis asks the extent to which Irish law, policy and practice allow for the application of the United Nations Convention on the Rights of the Child (CRC) to pre-natal children. First, it is demonstrated that pre-natal children can fall within the definition of ‘child’ under the Convention and so the possibility of applying the Convention to children before birth is opened. Many State Parties to the CRC have interpreted it as applicable to pre-natal children, while others have expressed that it only applies from birth. Ireland has not clarified whether or not it interprets it as being applicable from conception, birth, or some other point. The remainder of the thesis examines the extent to which Ireland interprets the CRC as applicable to the pre-natal child. First, the question of whether Ireland affords to the pre-natal child the right to life under Article 6(1) of the Convention is analysed. Given the importance of the indivisibility of rights under the Convention, the extent to which Ireland applies other CRC rights to pre-natal children is examined. The rights analysed are the right to protection from harm, the right to the provision of health care and the procedural right to representation. It is concluded that Ireland’s laws, policies and practices require urgent clarification on the issue of the extent to which rights such as protection, health care and representation apply to children before birth. In general, there are mixed and ad hoc approaches to these issues in Ireland and there exists a great deal of confusion amongst those working on the frontline with such children, such as health care professionals and social workers. The thesis calls for significant reform in this area in terms of law and policy, which will inform practice.

Caring for the Celtic cubs: Discursive constructions of mothers and mothering in the Irish childcare debate

Drawing on an understanding of the public sphere as a multiplicity of communicative and discursive spaces this paper examines the constructions of mothers, mothering and motherhood which emerged in recent debates about childcare in Ireland. Preliminary analysis of these discursive constructions suggest that they are often based on rhetoric, informed by stereotypical assumptions and rooted in frames of reference which mitigate against the emergence of alternative ways of understanding the issues of mothering and childcare. It will be argued that the reductionist and divisive nature of the childcare debate which ensued prior to the 2005 budget, stymied childcare policy development at a time when its unprecedented prominence on the political agenda and the strength of public finances could have underpinned a shift in policy approach. The paper concludes with an exploration of the ways in which feminist scholarship can challenge the Irish model of childcare policy, which continues to be premised on an understanding of childcare and the reconciliation of work and family life as the privatised responsibility of individual women.

Embodied sexualities: Exploring accounts of Irish women's sexual knowledge and sexual experiences, 1920-1970

This chapter explores the ways in which sexuality has been understood, embodied and negotiated by a cohort of Irish women through their lives. It is based on qualitative data generated as part of an oral history project on Irish women’s experiences of sexuality and reproduction during the period 1920–1970.1 The interviews, which were conducted with 21 Irish women born between 1914 and 1955, illustrate that social and cultural discourses of sexuality as secretive, dangerous, dutiful and sinful were central to these women’s interpretative repertoires around sexuality and gender. However, the data also contains accounts of behaviours, experiences and feelings that challenged or resisted prevailing scripts of sexuality and gender. Drawing on feminist conceptualisations of sexuality and embodiment (Holland et al., 1994; Jackson and Scott, 2010), this chapter demonstrates that the women’s sexual subjectivities were forged in the tensions that existed between normative sexual scripts and their embodied experiences of sexual desires and sexual and reproductive practices. While recollections of sexual desire and pleasure did feature in the accounts of some of the women, it was the difficulties experienced around sexuality and reproduction that were spoken about in greatest detail. What emerges clearly from the data is the confusion, anxiety and pain occasioned by the negotiation of external demands and internal desires and the contested, unstable nature of both cultural power and female resistance.

Quaternary geology of the German North Sea and Western Irish Sea Mud Belt: revised stratigraphies, geotechnical properties, sedimentology and anthropogenic impacts

The climatic development of the Mid to Late Quaternary (last 400,000 years) is characterised by fluctuation between glacial and interglacial periods leading to the present interglacial, the Holocene. In comparison to preceding periods it was believed the Holocene represented a time of relative climatic stability. However, recent work has shown that the Holocene can be divided into cooler periods such as the Little Ice Age alternating with time intervals where climatic conditions ameliorated i.e. Medieval Warm Period, Holocene Thermal Optimum and the present Modern Optimum. In addition, the Holocene is recognised as a period with increasing anthropogenic influence on the environment. Onshore records recording glacial/interglacial cycles as well as anthropogenic effects are limited. However, sites of sediment accumulation on the shallow continental shelf offer the potential to reconstruct these events. Such sites include tunnel valleys and low energy, depositional settings. In this study we interrogated the sediment stratigraphy at such sites in the North Sea and Irish Sea using traditional techniques, as well as novel applications of geotechnical data, to reconstruct the palaeoenvironmental record. Within the German North Sea sector a combination of core, seismic and in-situ Cone Penetration Testing (CPT) data was used to identify sedimentary units, place them within a morphological context, relate them to glacial or interglacial periods stratigraphically, and correlate them across the German North Sea. Subsequently, we were able to revise the Mid to Late Quaternary stratigraphy for the North Sea using this new and novel data. Similarly, Holocene environmental changes were investigated within the Irish Sea at a depositional site with active anthropogenic influence. The methods used included analyses on grain-size distribution, foraminifera, gamma spectrometry, AMS 14C and physical core logging. The investigation revealed a strong fluctuating climatic signal early in the areas history before anthropogenic influence affects the record through trawling.

Transitions: From novice participation to expertise, pre-school 'matters' in an Irish pre-school community

This in depth, qualitative, participant observer study tracks children's transition experiences from novice to experienced membership of their pre-school community. It also considers adult roles in mediating this process in the context of the recent introduction of a universal free-pre-school year for children growing up in Ireland. Participation and the space to negotiate a participatory identity is understood in this study as a key element of positive experiences of early years transitions, within pre-school and beyond. The underlying theoretical framework is socio-cultural. This approach shifts from a scientific positivist view of thinking and learning as an individual inside the head process and asserts the historical, social, cultural as well as the situated context of learning and meaning making All participants, including myself as researcher, are recognised, explored and valued as embedded in the cultural context studied. In a sense, this approach tilts the worlds being observed through participation in them and reflects them in new light. The aim is to interpret and reflect the multiple realities constructed in this context rather than seek a truth out there waiting to be found. Special efforts are made to be invited in to and acknowledge children's expertise in the cultural worlds they negotiate with peers and adults in pre-school. The aim is to better understand what children may find motivating, interesting or problematic as they interpret reproduce and transform meaning within their play and learning worlds. My aim is for an honest rendering of the voices of stakeholders in pre-school communities from teachers, parents, and policy makers to children themselves. It makes visible constraints; potentials and possibilities within everyday Irish pre-school practices in the situated context studied as well as the broader societal, legislative and macro policy influences it reflects. Casting light on the taken for granted opens the possibility of adaptation or transformation. Transition itself can act as a tool to meet the changing needs of children on their developmental pathways across the life cycle

Response to the review of the white paper on Irish aid. The urbanisation of poverty: drawing on the skills and techniques of spatial planning to support the aid programme

Submission on behalf of UCC to the Government Consultation on the White paper on Irish Aid

'Muchos Méxicos': widening the lens in Rulfo's cinematic texts

It is difficult to overstate the importance of Juan Rulfo’s two major pieces of fictional narrative work—his haunting, enigmatic novel Pedro Páramo (1955) and his unrelenting depictions of the failures of post-revolutionary Mexico in his short story collection El Llano en llamas (1953). In her foreword to the Margaret Sayers Peden English translation, Susan Sontag hails Pedro Páramo as ‘not only one of the masterpieces of 20th Century world literature, but one of the most influential of the century’s books’. García Márquez has compared the influence of Rulfo on 20th Century world literature to that of Sophocles: ‘No son más de 300 páginas, pero son casi tantas y creo tan perdurables como las que conocemos de Sófocles’ and, completing this oftrepeated triumvirate of recommendations, Jorge Luis Borges has referred to Pedro Páramo as: ‘una de las mejores novelas de las literaturas de lengua hispánica, y aun de la literatura.’ Despite the praise heaped upon Rulfo’s two most famous books, when his third book of fiction, El gallo de oro y otros textos para cine, was finally published in 1980, just six years before his death, it was greeted with almost critical silence. It is precisely this publication that provides the focus of this investigation. The collection contains three texts—El despojo, La fórmula secreta and El gallo de oro. Constituting a third of the fictional work he published in his lifetime, expanding upon themes present in El Llano en llamas and Pedro Páramo while, at the same time, examining new ground, no thematic discussion of Rulfo’s written output is complete without including these texts. Yet they are frequently dismissed. In this way this investigation attempts to go some way towards filling this critical gap in the work of one of the most influential writers of the twentieth century

The role of structure in the electrochemical performance of nanostructured metal oxides for lithium ion battery anodes

The Li-ion battery has for a number of years been a key factor that has enabled an ever increasing number of modern consumer devices, while in recent years has also been sought to power a range of emerging electric and hybrid electric vehicles. Due to their importance and popularity, a number of characteristics of Li-ion batteries have been subjected to intense work aimed at radical improvement. Although electrode material selection intrinsically defines characteristics like maximum capacity or voltage, engineering of the electrode structure may yield significant improvements to the lifetime performance of the battery, which would not be available if the material was used in its bulk form. The body of work presented in this thesis describes the relationship between the structure of electrochemically active materials and the course of the electrochemical processes occurring within the electrode. Chapter one describes the motivation behind the research presented herein. Chapter two serves to highlight a number of key advancements which have been made and detailed in the literature over recent years, pertaining to the use of nanostructured materials in Li-ion technology. Chapter three details methods and techniques applied in developing the body of work presented in this thesis. Chapter four details structural, molecular and electrochemical characteristics of tin oxide nanoparticle based electrodes, with particular emphasis on the relationship between the size distribution and the electrode performance. Chapter five presents findings of structural, electrochemical and optical study of indium oxide nanoparticles grown on silicon by molecular beam epitaxy. In chapter 6, tin oxide inverted opal electrodes are investigated for the conduct of the electrochemical performance of the electrodes under varying rate of change of potential. Chapter 7 presents the overall conclusions drawn from the results presented in this thesis, coupled with an indication of potential future work which may be explored further.