Synthesis of dendritic gadolinium complexes with enhanced relaxivities

This thesis deals with the synthesis of dendritic gadolinium complexes based on DOTA, with a view to obtaining enhanced relaxivities. Li addition to the inherently long electronic relaxation time and high paramagnetic moment of the gadolinium (III) ion, the speed of rotation of its complexes in solution is a decisive parameter in the determination of the relaxivity. This parameter is dependent on the molecular mass of the complex. Initially, the enantioselective synthesis of novel a-substituted analogues of DOTA was attempted but was not successful due to difficulties encountered in attaining the tetraalkylation of cyclen and the purification of the products obtained. Therefore, further studies were carried out based on the known [Gd(gDOTA)]" system. The synthesis of three medium M(_W) dendrons, each with a focal primary amino group was carried out. Their structures may be described as dendrimeric analogues of poly(ethylene glycol). Two of these structures were successfully coupled to the gadolinium (III) chelate, [Gd.gDOTA]. The acid-catalysed epimerisation of the statistical distribution of stereoisomers yielded solely the (RRRR)/(SSSS) isomeric pair. This system had previously been shown to undergo fast water exchange. The coupling and deprotection procedure yielded paramagnetic dendritic complexes with molecular weights of 2013 and 3535.Relaxivity measurements were carried out on these systems and the results showed significantly higher relaxivities of 18 and 21 mM(^-1) s(^-1) respectively, compared with a value of 7.8 mM(^-1) s(^-1) for the parent compound. Examination of NMRD profiles for the larger system showed a decrease in the rotational correlation time to 310 ps at 298 K, as expected. However, this was accompanied by an increase in the inner-sphere water exchange lifetime to 570 ns at 298 K. Therefore, although an improvement in relaxivity was obtained through a coupling to the slower rotation of the system in solution, this enhancement was limited by the accompanying decrease in the rate of water exchange. The best fitting procedure of the NMRD profiling procedure revealed the presence of 8 second-sphere water molecules at an average distance of 4Å. The second sphere contribution was shown to be the dominant contributor to the overall relaxivity. This accounted for >50% of the increased relaxivity

Safety Engineering with COTS components

Safety-critical systems are becoming more widespread, complex and reliant on software. Increasingly they are engineered through Commercial Off The Shelf (COTS) (Commercial Off The Shelf) components to alleviate the spiralling costs and development time, often in the context of complex supply chains. A parallel increased concern for safety has resulted in a variety of safety standards, with a growing consensus that a safety life cycle is needed which is fully integrated with the design and development life cycle, to ensure that safety has appropriate influence on the design decisions as system development progresses. In this article we explore the application of an integrated approach to safety engineering in which assurance drives the engineering process. The paper re- ports on the outcome of a case study on a live industrial project with a view to evaluate: its suitability for application in a real-world safety engineering setting; its benefits and limitations in counteracting some of the difficulties of safety en- gineering with COTS components across supply chains; and, its effectiveness in generating evidence which can contribute directly to the construction of safety cases

Hen Harrier Circus cyaneus population trends in relation to wind farms

Capsule: The data presented here demonstrate a considerable spatial overlap between wind farms and the breeding distribution of Hen Harriers in Ireland, but evidence for a negative impact of wind farms on their population is weak. Aims: To assess the extent of the overlap between wind farms and breeding Hen Harriers and to investigate their potential impact on Hen Harrier population trends. Methods: Data on Hen Harrier breeding distribution in 10 km × 10 km survey squares from national surveys were used in conjunction with information on the location of wind farms to examine whether, and to what extent, changes in Hen Harrier distribution and abundance between 2000 and 2010 were related to wind energy development. Results: Of the 69 survey squares holding Hen Harriers during the 2010 breeding season, 28% also overlapped with one or more wind farms. Data from 36 of the squares with breeding Hen Harriers during the 2000 survey revealed a marginally non-significant negative relationship between wind farm presence and change in the number of breeding pairs between 2000 and 2010. Conclusions: A considerable overlap exists between Hen Harrier breeding distribution and the location of wind farms in Ireland, particularly in areas between 200 and 400 m above sea level. The presence of wind farms is negatively related to Hen Harrier population trends in squares surveyed in 2000 and 2010, but this relationship is not statistically significant, and may not be causal. This is the first study to assess the influence of wind energy development on Hen Harriers at such a large geographic and population scale

The economic and societal impact of University College Cork

Read before the Society on 16th December 2021 at the Symposium: ‘Societal Impact of our Universities’Located in the heart of Cork city, University College Cork has been the comprehensive university of the south of Ireland since 1845. Today, UCC is a globally-oriented, research-led university with more than 22,000 students and more than 3,000 staff (Anon, 2021). It is the greenest university in Ireland, currently ranked 8th in the world and 1st in Ireland for its success in delivering on sustainability goals. Reaching into the community, both locally and globally, there are many educational, financial, developmental, medical, societal and cultural benefits to having a leading-edge, world-class university in the region. In the same way that UCC’s role in society and the community has developed over the past 176 years (Galvin et al., 2017), the University has also become engrained economically in Ireland and the Southwest

Farming the Iveragh uplands: A tale of humans and nature

The rugged beauty of the Iveragh peninsula has fascinated many a passing visitor and never fails to make some of us linger or stay for good. For those who need proof of the area’s uniqueness, a variety of national and European designations provide ample attestation of the splendour of Iveragh’s scenery, the diversity of its landscape and its heritage. Being surrounded on three sides by the Atlantic, Iveragh is the largest and most geographically isolated peninsula in Ireland whose western extremity, the Great Skellig, forms the westernmost point of Europe. Despite its maritime location, Iveragh’s character is fundamentally determined by the mountains, valleys and streams that form the peninsula’s interior—the bequest of a landscape sculpted by ice thousands of years ago (Crowley and Sheehan, 2009). Distinctive mountain scene in the Bridia Valley, Glencar Perhaps most distinctive, however, are the extensive blanket bogs and upland heather moorlands that cover most of the peninsula and captivate the imagination with the wild and austere appeal of an area where life did not change much for man and beast until relatively recently. Having come into existence in the wake of woodland clearances, the cutting of vegetation for fuel and the harvesting of crops for food and fiber by Neolithic farmers in the first and second millennium BC, this unique cultural landscape continues to be managed by traditional farmers and their animals to the present day. The value of areas such as Iveragh as repositories of a unique flora and fauna has long been recognized, but they have entered a period of major transformation as the agricultural economy that lay behind them no longer exists (Webb, 1998). The single largest danger is that farming communities may not survive the present discussion of how competitive European agriculture should be, as under present market conditions they are unable to compete without fundamentally changing their way of farming (Luick, 1998). The last 10 years have seen a growing debate over the future of areas like the Iveragh peninsula that may be ‘marginal’ in agricultural terms, but that are quite essential to life in Europe as we know and cherish it. Upland farmed landscapes provide clean water, maintain a rich plant and animal life and help to keep families in regions that offer few alternative employment opportunities – at the same time as attracting millions of tourists each year. The Caragh in Glencar—one of Europe’s cleanest rivers. Such areas, also termed high nature value farmland, cover about 25% of all agricultural land in Ireland and include, besides Iveragh, other parts of Kerry, Connemara, Mayo, Donegal, the Comeraghs, Wicklow, the Burren and the offshore Islands. The farming systems of these areas are characterised by extensive mixed livestock grazing and little agro-chemical inputs combined with labour-intensive management practices. Without dedicated farmers and their families, the character of these areas would change completely leading to the disappearance of unique cultural landscapes with effects such as rural depopulation and the loss of local communities. Already farming systems have changed substantially with livestock being concentrated on better quality land while marginal areas are being abandoned. Along with this, there are changes in the animals being farmed. The traditional Scotch Blackface sheep are increasingly crossed with or replaced by lowland breeds to satisfy market demands for heavy lamb. This has led to a softening in sheep and the fear among farmers that the traditional grazers of the uplands may be extinct in years to come. Going, too, is the use of the native rustic Kerry cow that grazed the rough Farming the Iveragh Uplands grasses, bracken, gorse and soft rushes in the winter - growth that sheep cannot control. Unsurprisingly, this disruption over a relatively short time, in what was formerly a sustainable relationship between farming and nature, will have implications for the area’s flora and fauna. Some of the repercussions are obvious; others need to be researched in more depth if appropriate solutions are to be formulated. It is now a stated objective of EU environment and rural development policy to maintain and conserve traditional farming systems like the one practised on Iveragh. Beyond acknowledging the importance of traditional farming for nature conservation and local livelihoods, it is necessary to understand how such farming systems function and to determine how the inevitable process of change can be redirected to provide a way of life that is socially and economically rewarding for farm families while preserving the farming practices necessary for Iveragh’s unique landscape to persist into the future. In this light, University College Cork (UCC) in conjunction with the Environmental Research Institute (ERI) and funded by Science Foundation Ireland (SFI) initiated BioUp, a 3 year research programme to investigate the upland farming system and rich biodiversity associated with it. Managing rural change in the uplands calls for the active involvement of many stakeholders, including farmers and agricultural advisory groups, land owners, conservation groups, forestry, tourism, and local authorities. In the BioUp project, researchers and stakeholders worked closely together. It is hoped that this will help to obtain a better understanding of the social, economic and environmental challenges facing Iveragh and promote greater public appreciation of the indispensable contributions made by farm families to maintaining our unique heritage - a service that has gone unappreciated too long

Advanced Islandora Workshop

Workshop at Open Repositories 2014, Helsinki, Finland, June 9-13, 2014Workshops and TutorialsIslandora is a digital asset management system that provides out-of-the-box repository solutions (Solution Packs) for a wide range of digital collections and research domains. Islandora combines the Drupal CMS and Fedora Commons repository software, together with additional open source applications (including Solr), to deliver a wide range of functionality. The proposed workshop will give participants a chance to explore some of the advanced features of Islandora, including the Solr client and the XML Form Builder. Learning outcomes include: - Users understand the basic Solr and XML Form Builder technologies as they relate to Islandora, and sources for support and additional documentation. - Users can configure a basic Solr installation (using Islandora) and conduct searches of repository content. - Users are introduced to some of the ways Solr can be customized to suit the needs of their own collections. - Users can clone and edit a metadata form using XML Form Builder.Tripp (O'Halloran), Erin (discoverygarden inc (dgi), Canada)MacKenzie, Mitch (discoverygarden inc (dgi), Canada)Leggott, Mark (Islandora Foundation

Evidencia en video de fratricidio y canibalismo, movimiento de polluelos e interacciones con depredadores en nidos de Circus cyaneus

During a nest-camera study of Hen Harriers (Circus cyaneus), we recorded siblicide, cannibalism, movement of nestlings by adult birds, and interactions with predators. We deployed cameras at 13 nests across three study areas in Ireland between 2008 and 2010. At a nest with two well-developed nestlings (approximately 25–30 d old), the older nestling killed its sibling and fed on it. This was the first documented case of siblicide in this species, to our knowledge. Recordings also revealed three other events of cannibalism in which one of the nestlings in a brood died from unknown causes and was then eaten by its siblings (n = 1), by the adult male (n = 1), or was used by the adult female to feed the remaining nestlings (n = 1). At two nests, recordings showed the adult female picking up and moving nestlings that were outside the nest cup. In addition, cameras recorded two instances of full brood predation by red fox (Vulpes vulpes) and an attack on a nest by a female Eurasian Kestrel (Falco tinnunculus) that had no apparent consequences for the nestlings or the female Hen Harrier. The behaviors reported here, which are difficult to observe directly, may have important consequences for our understanding of productivity and population dynamics of Hen Harriers.Durante un estudio sobre patrones de actividad de individuos reproductores de Circus cyaneus realizado con cámaras para monitoreo de nidos, registramos comportamientos de fratricidio, canibalismo, movimientos de polluelos e interacciones con depredadores. Colocamos cámaras en 13 nidos distribuidos en tres áreas de estudio en Irlanda entre 2008 y 2010. En un nido con dos polluelos en un estado de desarrollo avanzado (c. 25-30 días), el polluelo de mayor edad mató al otro y se alimentó de él. Este es el primer caso documentado de fratricidio en esta especie. Obtuvimos imágenes de otros tres casos de canibalismo en que uno o más polluelos fallecieron por causas desconocidas y sus cadáveres fueron usados como alimento por los otros polluelos (n = 1), por el macho adulto (n = 1) o por la hembra adulta para alimentar a los otros polluelos (n = 1). En dos nidos, las imágenes muestran a la hembra adulta repetidamente recogiendo polluelos que se alejan del nido para intentar llevarlos al nido. Por último, las cámaras captaron dos eventos de depredación de polluelos por parte de Vulpes vulpes y un enfrentamiento entre la hembra adulta de C. cyaneus y una hembra de Falco tinnunculus sin consecuencias para los polluelos o la hembra adulta. Estos comportamientos, difíciles de detectar mediante metodologías de monitoreo tradicionales, pueden tener consecuencias para el éxito reproductivo y la dinámica poblacional de esta especie

Effects of development of wind energy and associated changes in land use on bird densities in upland areas

Wind energy development is the most recent of many pressures on upland bird communities and their habitats. Studies of birds in relation to wind energy development have focused on effects of direct mortality, but the importance of indirect effects (e.g., displacement, habitat loss) on avian community diversity and stability is increasingly being recognized. We used a control‐impact study in combination with a gradient design to assess the effects of wind farms on upland bird densities and on bird species grouped by habitat association (forest and open‐habitat species). We conducted 506 point count surveys at 12 wind‐farm and 12 control sites in Ireland during 2 breeding seasons (2012 and 2013). Total bird densities were lower at wind farms than at control sites, and the greatest differences occurred close to turbines. Densities of forest species were significantly lower within 100 m of turbines than at greater distances, and this difference was mediated by habitat modifications associated with wind‐farm development. In particular, reductions in forest cover adjacent to turbines was linked to the observed decrease in densities of forest species. Open‐habitat species’ densities were lower at wind farms but were not related to distance from turbines and were negatively related to size of the wind farm. This suggests that, for these species, wind‐farm effects may occur at a landscape scale. Our findings indicate that the scale and intensity of the displacement effects of wind farms on upland birds depends on bird species’ habitat associations and that the observed effects are mediated by changes in land use associated with wind‐farm construction. This highlights the importance of construction effects and siting of turbines, tracks, and other infrastructure in understanding the impacts of wind farms on biodiversity

Innovative approaches for research led education: UCC’s Green Campus Living Laboratory Programme

Ireland’s National Strategy on Education for Sustainable Development (2014-2020), highlights the need to equip students with “the relevant knowledge (the ‘what’), the key dispositions and skills (the ‘how’) and the values (the ‘why’)” to contribute to a more sustainable future (Department of Education and Skills, 2014). Delivering on this challenge requires embedding sustainability within both the formal and informal learning that occurs on campus (Hopkinson et al. 2008), while also integrating sustainability both within and across disciplines (Byrne et al., 2018). UCC is a global leader in sustainability in higher education, being the first University in the world to be awarded a Green Flag from the Foundation for Environmental Education (Reidy et al, 2015). Sustainability at UCC is “student-led, research-informed, and practice-focused” that is, the programme takes an integrated approach and aims to utilise the collective student agency and research capability to deliver real and lasting change on the ground (Pelenc et al. 2015). UCC’s Academic Strategy, with sustainability and interdisciplinarity as key components of the new “Connected Curriculum”, aims to “facilitate students to develop values, skills and aptitudes that promote civic participation, social inclusion, sustainability, digital fluency and impactful, global citizenship” (UCC, 2018). A key aim of delivering its Sustainability Strategy is that UCC would become a “Living Laboratory”, where students, academics and practitioners work together, using the campus itself as a testbed for solutions to today’s major societal challenges (UCC, 2016). A Living Laboratory project should aim to: • Solve a real-life problem • Be based on a partnership among key stakeholders, often crossing disciplinary and/or sectoral boundaries • Trial and test ideas in real life settings • Share data and findings generated openly (EAUC, 2017)