The impacts of past land-use on the ecology of an ancient woodland in south-west Ireland

A multi-disciplinary study was conducted to compare stands of ancient and secondary origin within a single wood, the Gearagh woodland, County Cork. These sites were compared with adjacent areas of grassland, which provided a reference for the former land-use (pasture) of the secondary woodland. A historical study confirmed that while the core of the Gearagh has been subject to minimal human interference, other sections have been cleared in the past for agricultural purposes. Investigations into soil structure and composition showed that soil properties in these secondary woodland areas were significantly altered by this past woodland clearance and conversion to agriculture, while the soil of the ancient woodland showed little signs of disturbance. The vegetation community also differed between the two woodland areas, partly due to altered environmental conditions. Many of the ancient woodland plant species were unable to form a persistent seed bank, while there was increased representation of species associated with more open-habitat conditions in the seed bank of the secondary woodland. While germination of woodland species was low in all sites, overall, seeds tended to germinate more successfully in the ancient woodland. The ancient woodland also provided a suitable habitat for many soil and ground detritivores, most notably enchytraeids, although earthworms were not abundant. Past agricultural use, however, changed the decomposer community considerably, with increased representation of earthworm species and a decline in the abundance of enchytraeids in the secondary stands. In conclusion, the legacies of historical agricultural activities can continue to significantly affect the structure and composition of present-day woodlands so that they may differ considerably from undisturbed ancient woodland stands, even within the same woodland. A greater understanding of the origin, development and ecological functioning of ancient woodlands should aid in determining future conservation and management requirements.

Irish state infrastructural investment: an analysis of past patterns, and an outline of a future integrated systems of systems evaluation methodology

The literature clearly links the quality and capacity of a country’s infrastructure to its economic growth and competitiveness. This thesis analyses the historic national and spatial distribution of investment by the Irish state in its physical networks (water, wastewater and roads) across the 34 local authorities and examines how Ireland is perceived internationally relative to its economic counterparts. An appraisal of the current status and shortcomings of Ireland’s infrastructure is undertaken using key stakeholders from foreign direct investment companies and national policymakers to identify Ireland's infrastructural gaps, along with current challenges in how the country is delivering infrastructure. The output of these interviews identified many issues with how infrastructure decision-making is currently undertaken. This led to an evaluation of how other countries are informing decision-making, and thus this thesis presents a framework of how and why Ireland should embrace a Systems of Systems (SoS) methodology approach to infrastructure decision-making going forward. In undertaking this study a number of other infrastructure challenges were identified: significant political interference in infrastructure decision-making and delivery the need for a national agency to remove the existing ‘silo’ type of mentality to infrastructure delivery how tax incentives can interfere with the market; and their significance. The two key infrastructure gaps identified during the interview process were: the need for government intervention in the rollout of sufficient communication capacity and at a competitive cost outside of Dublin; and the urgent need to address water quality and capacity with approximately 25% of the population currently being served by water of unacceptable quality. Despite considerable investment in its national infrastructure, Ireland’s infrastructure performance continues to trail behind its economic partners in the Eurozone and OECD. Ireland is projected to have the highest growth rate in the euro zone region in 2015 and 2016, albeit that it required a bailout in 2010, and, at the time of writing, is beginning to invest in its infrastructure networks again. This thesis proposes the development and implementation of a SoS approach for infrastructure decision-making which would be based on: existing spatial and capacity data of each of the constituent infrastructure networks; and scenario computation and analysis of alternative drivers eg. Demographic change, economic variability and demand/capacity constraints. The output from such an analysis would provide valuable evidence upon which policy makers and decision makers alike could rely, which has been lacking in historic investment decisions.

An investigation of post-primary students' images of mathematics

This research study investigates the image of mathematics held by 5th-year post-primary students in Ireland. For this study, “image of mathematics” is conceptualized as a mental representation or view of mathematics, presumably constructed as a result of past experiences, mediated through school, parents, peers or society. It is also understood to include attitudes, beliefs, emotions, self-concept and motivation in relation to mathematics. This study explores the image of mathematics held by a sample of 356 5th-year students studying ordinary level mathematics. Students were aged between 15 and 18 years. In addition, this study examines the factors influencing students‟ images of mathematics and the possible reasons for students choosing not to study higher level mathematics for the Leaving Certificate. The design for this study is chiefly explorative. A questionnaire survey was created containing both quantitative and qualitative methods to investigate the research interest. The quantitative aspect incorporated eight pre-established scales to examine students‟ attitudes, beliefs, emotions, self-concept and motivation regarding mathematics. The qualitative element explored students‟ past experiences of mathematics, their causal attributions for success or failure in mathematics and their influences in mathematics. The quantitative and qualitative data was analysed for all students and also for students grouped by gender, prior achievement, type of post-primary school attending, co-educational status of the post-primary school and the attendance of a Project Maths pilot school. Students‟ images of mathematics were seen to be strongly indicated by their attitudes (enjoyment and value), beliefs, motivation, self-concept and anxiety, with each of these elements strongly correlated with each other, particularly self-concept and anxiety. Students‟ current images of mathematics were found to be influenced by their past experiences of mathematics, by their mathematics teachers, parents and peers, and by their prior mathematical achievement. Gender differences occur for students in their images of mathematics, with males having more positive images of mathematics than females and this is most noticeable with regards to anxiety about mathematics. Mathematics anxiety was identified as a possible reason for the low number of students continuing with higher level mathematics for the Leaving Certificate. Some students also expressed low mathematical self-concept with regards to higher level mathematics specifically. Students with low prior achievement in mathematics tended to believe that mathematics requires a natural ability which they do not possess. Rote-learning was found to be common among many students in the sample. The most positive image of mathematics held by students was the “problem-solving image”, with resulting implications for the new Project Maths syllabus in post-primary education. Findings from this research study provide important insights into the image of mathematics held by the sample of Irish post-primary students and make an innovative contribution to mathematics education research. In particular, findings contribute to the current national interest in Ireland in post-primary mathematics education, highlighting issues regarding the low uptake of higher level mathematics for the Leaving Certificate and also making a preliminary comparison between students who took part in the piloting of Project Maths and students who were more recently introduced to the new syllabus. This research study also holds implications for mathematics teachers, parents and the mathematics education community in Ireland, with some suggestions made on improving students‟ images of mathematics.

Peanut Allergen Threshold Study (PATS): validation of eliciting doses using a novel single-dose challenge protocol

Background: The eliciting dose (ED) for a peanut allergic reaction in 5% of the peanut allergic population, the ED05, is 1.5 mg of peanut protein. This ED05 was derived from oral food challenges (OFC) that use graded, incremental doses administered at fixed time intervals. Individual patients’ threshold doses were used to generate population dose-distribution curves using probability distributions from which the ED05 was then determined. It is important to clinically validate that this dose is predictive of the allergenic response in a further unselected group of peanut-allergic individuals. Methods/Aims: This is a multi-centre study involving three national level referral and teaching centres. (Cork University Hospital, Ireland, Royal Children’s Hospital Melbourne, Australia and Massachusetts General Hospital, Boston, U.S.A.) The study is now in process and will continue to run until all centres have recruited 125 participates in each respective centre. A total of 375 participants, aged 1–18 years will be recruited during routine Allergy appointments in the centres. The aim is to assess the precision of the predicted ED05 using a single dose (6 mg peanut = 1.5 mg of peanut protein) in the form of a cookie. Validated Food Allergy related Quality of Life Questionnaires-(FAQLQ) will be self-administered prior to OFC and 1 month after challenge to assess the impact of a single dose OFC on FAQL. Serological and cell based in vitro studies will be performed. Conclusion: The validation of the ED05 threshold for allergic reactions in peanut allergic subjects has potential value for public health measures. The single dose OFC, based upon the statistical dose-distribution analysis of past challenge trials, promises an efficient approach to identify the most highly sensitive patients within any given food-allergic population.

A study of the Hobson and Rogers volatility model

We firstly examine the model of Hobson and Rogers for the volatility of a financial asset such as a stock or share. The main feature of this model is the specification of volatility in terms of past price returns. The volatility process and the underlying price process share the same source of randomness and so the model is said to be complete. Complete models are advantageous as they allow a unique, preference independent price for options on the underlying price process. One of the main objectives of the model is to reproduce the `smiles' and `skews' seen in the market implied volatilities and this model produces the desired effect. In the first main piece of work we numerically calibrate the model of Hobson and Rogers for comparison with existing literature. We also develop parameter estimation methods based on the calibration of a GARCH model. We examine alternative specifications of the volatility and show an improvement of model fit to market data based on these specifications. We also show how to process market data in order to take account of inter-day movements in the volatility surface. In the second piece of work, we extend the Hobson and Rogers model in a way that better reflects market structure. We extend the model to take into account both first and second order effects. We derive and numerically solve the pde which describes the price of options under this extended model. We show that this extension allows for a better fit to the market data. Finally, we analyse the parameters of this extended model in order to understand intuitively the role of these parameters in the volatility surface.

Beyond simple imaging with energetic beams – nanopatterning, correlative microscopy and statistical analysis of inclusions

Electron microscopy (EM) has advanced in an exponential way since the first transmission electron microscope (TEM) was built in the 1930’s. The urge to ‘see’ things is an essential part of human nature (talk of ‘seeing is believing’) and apart from scanning tunnel microscopes which give information about the surface, EM is the only imaging technology capable of really visualising atomic structures in depth down to single atoms. With the development of nanotechnology the demand to image and analyse small things has become even greater and electron microscopes have found their way from highly delicate and sophisticated research grade instruments to key-turn and even bench-top instruments for everyday use in every materials research lab on the planet. The semiconductor industry is as dependent on the use of EM as life sciences and pharmaceutical industry. With this generalisation of use for imaging, the need to deploy advanced uses of EM has become more and more apparent. The combination of several coinciding beams (electron, ion and even light) to create DualBeam or TripleBeam instruments for instance enhances the usefulness from pure imaging to manipulating on the nanoscale. And when it comes to the analytic power of EM with the many ways the highly energetic electrons and ions interact with the matter in the specimen there is a plethora of niches which evolved during the last two decades, specialising in every kind of analysis that can be thought of and combined with EM. In the course of this study the emphasis was placed on the application of these advanced analytical EM techniques in the context of multiscale and multimodal microscopy – multiscale meaning across length scales from micrometres or larger to nanometres, multimodal meaning numerous techniques applied to the same sample volume in a correlative manner. In order to demonstrate the breadth and potential of the multiscale and multimodal concept an integration of it was attempted in two areas: I) Biocompatible materials using polycrystalline stainless steel and II) Semiconductors using thin multiferroic films. I) The motivation to use stainless steel (316L medical grade) comes from the potential modulation of endothelial cell growth which can have a big impact on the improvement of cardio-vascular stents – which are mainly made of 316L – through nano-texturing of the stent surface by focused ion beam (FIB) lithography. Patterning with FIB has never been reported before in connection with stents and cell growth and in order to gain a better understanding of the beam-substrate interaction during patterning a correlative microscopy approach was used to illuminate the patterning process from many possible angles. Electron backscattering diffraction (EBSD) was used to analyse the crystallographic structure, FIB was used for the patterning and simultaneously visualising the crystal structure as part of the monitoring process, scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed to analyse the topography and the final step being 3D visualisation through serial FIB/SEM sectioning. II) The motivation for the use of thin multiferroic films stems from the ever-growing demand for increased data storage at lesser and lesser energy consumption. The Aurivillius phase material used in this study has a high potential in this area. Yet it is necessary to show clearly that the film is really multiferroic and no second phase inclusions are present even at very low concentrations – ~0.1vol% could already be problematic. Thus, in this study a technique was developed to analyse ultra-low density inclusions in thin multiferroic films down to concentrations of 0.01%. The goal achieved was a complete structural and compositional analysis of the films which required identification of second phase inclusions (through elemental analysis EDX(Energy Dispersive X-ray)), localise them (employing 72 hour EDX mapping in the SEM), isolate them for the TEM (using FIB) and give an upper confidence limit of 99.5% to the influence of the inclusions on the magnetic behaviour of the main phase (statistical analysis).

An investigation into reactivity and selectivity in cycloadditions of 1,3-dipoles with formamidines

The objective of this research was to investigate the synthesis of nitrile oxides and to study their reactivity in 1,3-dipolar cycloadditions with formamidines. Chapter one looks at the literature surrounding the 1,3-dipolar cycloaddition reaction. It explores the generation of 1,3-dipoles (mainly nitrile oxides) and dipolarophiles (predominantly amidines). It discusses the potential synthetic uses of the 1,3-dipolar cycloadducts. It examines both and inter- and intra-molecular cycloaddition reactions. It recognises the use of the 1,3-dipolar cycloadditions as a successful method in building natural products and oxadiazolines. The decomposition of oxadiazolines as a route to nitriles is also outlined in this chapter. Chapter two discusses the results of this research candidate. The preparation of nitrile oxide precursors - hydroximoyl halides - is outlined at first. The generation of nitrile oxides is then demonstrated, followed by the preparation of furoxans. Methods for preparing the reference materials (nitriles and ureas), which result from decomposition of oxadiazolines, then follow. The preparation of series of Δ2-1,2,4- oxadiazolines via the 1,3-dipolar cycloaddition reaction is illustrated in this chapter. The selectivity of the addition of nitrile oxides to dipolarophiles was tested by competition reactions, which are also described in this chapter. NMR techniques were used in the study of the kinetics of the 1,3-dipolar cycloadditions used for the preparation of a series of Δ2-1,2,4-oxadiazolines, which is addressed in this chapter. Chapter three charts the experimental procedures followed to gain results which are discussed in chapter two. It also outlines all analytical data produced during the course of this research.