Nanostructured ferroelectric materials

Nanostructured materials are central to the evolution of future electronics and information technologies. Ferroelectrics have already been established as a dominant branch in the electronics sector because of their diverse application range such as ferroelectric memories, ferroelectric tunnel junctions, etc. The on-going dimensional downscaling of materials to allow packing of increased numbers of components onto integrated circuits provides the momentum for the evolution of nanostructured ferroelectric materials and devices. Nanoscaling of ferroelectric materials can result in a modification of their functionality, such as phase transition temperature or Curie temperature (TC), domain dynamics, dielectric constant, coercive field, spontaneous polarisation and piezoelectric response. Furthermore, nanoscaling can be used to form high density arrays of monodomain ferroelectric nanostructures, which is desirable for the miniaturisation of memory devices. This thesis details the use of various types of nanostructuring approaches to fabricate arrays of ferroelectric nanostructures, particularly non-oxide based systems. The introductory chapter reviews some exemplary research breakthroughs in the synthesis, characterisation and applications of nanoscale ferroelectric materials over the last decade, with priority given to novel synthetic strategies. Chapter 2 provides an overview of the experimental methods and characterisation tools used to produce and probe the properties of nanostructured antimony sulphide (Sb2S3), antimony sulpho iodide (SbSI) and lead titanate zirconate (PZT). In particular, Chapter 2 details the general principles of piezoresponse microscopy (PFM). Chapter 3 highlights the fabrication of arrays of Sb2S3 nanowires with variable diameters using newly developed solventless template-based approach. A detailed account of domain imaging and polarisation switching of these nanowire arrays is also provided. Chapter 4 details the preparation of vertically aligned arrays of SbSI nanorods and nanowires using a surface-roughness assisted vapour-phase deposition method. The qualitative and quantitative nanoscale ferroelectric properties of these nanostructures are also discussed. Chapter 5 highlights the fabrication of highly ordered arrays of PZT nanodots using block copolymer self-assembled templates and their ferroelectric characterisation using PFM. Chapter 6 summarises the conclusions drawn from the results reported in chapters 3, 4 and 5 and the future work.

Optimisation of chemoenzymatic processes in asymmetric synthesis

This thesis describes the optimisation of chemoenzymatic methods in asymmetric synthesis. Modern synthetic organic chemistry has experienced an enormous growth in biocatalytic methodologies; enzymatic transformations and whole cell bioconversions have become generally accepted synthetic tools for asymmetric synthesis. Biocatalysts are exceptional catalysts, combining broad substrate scope with high regio-, enantio- and chemoselectivities enabling the resolution of organic substrates with superb efficiency and selectivity. In this study three biocatalytic applications in enantioselective synthesis were explored and perhaps the most significant outcome of this work is the excellent enantioselectivity achieved through optimisation of reaction conditions improving the synthetic utility of the biotransformations. In the first chapter a summary of literature discussing the stereochemical control of baker’s yeast (Saccharomyces Cerevisae) mediated reduction of ketones by the introduction of sulfur moieties is presented, and sets the work of Chapter 2 in context. The focus of the second chapter was the synthesis and biocatalytic resolution of (±)-trans-2-benzenesulfonyl-3-n-butylcyclopentanone. For the first time the practical limitations of this resolution have been addressed providing synthetically useful quantities of enantiopure synthons for application in the total synthesis of both enantiomers of 4-methyloctanoic acid, the aggregation pheromone of the rhinoceros beetles of the genus Oryctes. The unique aspect of this enantioselective synthesis was the overall regio- and enantioselective introduction of the methyl group to the octanoic acid chain. This work is part of an ongoing research programme in our group focussed on baker’s yeast mediated kinetic resolution of 2-keto sulfones. The third chapter describes hydrolase-catalysed kinetic resolutions leading to a series of 3-aryl alkanoic acids. Hydrolysis of the ethyl esters with a series of hydrolases was undertaken to identify biocatalysts that yield the corresponding acids in highly enantioenriched form. Contrary to literature reports where a complete disappearance of efficiency and, accordingly enantioselection, was described upon kinetic resolution of sterically demanding 3-arylalkanoic acids, the highest reported enantiopurities of these acids was achieved (up to >98% ee) in this study through optimisation of reaction conditions. Steric and electronic effects on the efficiency and enantioselectivity of the biocatalytic transformation were also explored. Furthermore, a novel approach to determine the absolute stereochemistry of the enantiopure 3-aryl alkanoic acids was investigated through combination of co-crystallisation and X-ray diffraction linked with chiral HPLC analysis. The fourth chapter was focused on the development of a biocatalytic protocol for the asymmetric Henry reaction. Efficient kinetic resolution in hydrolase-mediated transesterification of cis- and trans- β-nitrocyclohexanol derivatives was achieved. Combination of a base-catalysed intramolecular Henry reaction coupled with the hydrolase-mediated kinetic resolution with the view to selective acetylation of a single stereoisomer was investigated. While dynamic kinetic resolution in the intramolecular Henry was not achieved, significant progress in each of the individual elements was made and significantly the feasibility of this process has been demonstrated. The final chapter contains the full experimental details, including spectroscopic and analytical data of all compounds synthesised in this project, while details of chiral HPLC analysis are included in the appendix. The data for the crystal structures are contained in the attached CD.

Spatial and energetic mode dynamics of cold atomic systems

In this thesis we relate the formal description of various cold atomic systems in the energy eigenbasis, to the observable spatial mode dynamics. Herein the `spatial mode dynamics' refers to the direction of photon emission following the spontaneous emission of an excited fermion in the presence of a same species and spin ideal anisotropic Fermi sea in its internal ground state. Due to the Pauli principle, the presence of the ground state Fermi sea renders the phase space, anisotropic and only partially accessible, thereby a ecting the direction of photon emission following spontaneous emission. The spatial and energetic mode dynamics also refers to the quantum `tunneling' interaction between localised spatial modes, synonymous with double well type potentials. Here we relate the dynamics of the wavefunction in both the energetic and spatial representations. Using this approach we approximate the relationship between the spatial and energetic representations of a wavefunction spanning three spatial and energetic modes. This is extended to a process known as Spatial Adiabatic Passage, which is a technique to transport matter waves between localised spatial modes. This approach allows us to interpret the transport of matter waves as a signature of a geometric phase acquired by the one of the internal energy eigenstates of the system during the cyclical evolution. We further show that this geometric phase may be used to create spatial mode qubit and qutrit states.

Quantum behavior in mesoscopic systems

In this thesis I present the work done during my PhD. The Thesis is divided into two parts; in the first one I present the study of mesoscopic quantum systems whereas in the second one I address the problem of the definition of Markov regime for quantum system dynamics. The first work presented is the study of vortex patterns in (quasi) two dimensional rotating Bose Einstein condensates (BECs). I consider the case of an anisotropy trapping potential and I shall show that the ground state of the system hosts vortex patterns that are unstable. In a second work I designed an experimental scheme to transfer entanglement from two entangled photons to two BECs. This work is meant to propose a feasible experimental set up to bring entanglement from microscopic to macroscopic systems for both the study of fundamental questions (quantum to classical transition) and technological applications. In the last work of the first part another experimental scheme is presented in order to detect coherences of a mechanical oscillator which is assumed to have been previously cooled down to the quantum regime. In this regime in fact the system can rapidly undergo decoherence so that new techniques have to be employed in order to detect and manipulate their states. In the scheme I propose a micro-mechanical oscillator is coupled to a BEC and the detection is performed by monitoring the BEC with a negligible back-action on the cantilever. In the second part of the thesis I give a definition of Markov regime for open quantum dynamics. The importance of such definition comes from both the mathematical description of the system dynamics and from the understanding of the role played by the environment in the evolution of an open system. In the Markov regime the mathematical description can be simplified and the role of the environment is a passive one.

Tropospheric aerosol detection over Southern Ireland using a backscatter Raman lidar

Lidar is an optical remote sensing instrument that can measure atmospheric parameters. A Raman lidar instrument (UCLID) was established at University College Cork to contribute to the European lidar network, EARLINET. System performance tests were carried out to ensure strict data quality assurance for submission to the EARLINET database. Procedures include: overlap correction, telecover test, Rayleigh test and zero bin test. Raman backscatter coefficients, extinction coefficients and lidar ratio were measured from April 2010 to May 2011 and February 2012 to June 2012. Statistical analysis of the profiles over these periods provided new information about the typical atmospheric scenarios over Southern Ireland in terms of aerosol load in the lower troposphere, the planetary boundary layer (PBL) height, aerosol optical density (AOD) at 532 nm and lidar ratio values. The arithmetic average of the PBL height was found to be 608 ± 138 m with a median of 615 m, while average AOD at 532 nm for clean marine air masses was 0.119 ± 0.023 and for polluted air masses was 0.170 ± 0.036. The lidar ratio showed a seasonal dependence with lower values found in winter and autumn (20 ± 5 sr) and higher during spring and winter (30 ± 12 sr). Detection of volcanic particles from the eruption of the volcano Eyjafjallajökull in Iceland was measured between 21 April and 7 May 2010. The backscatter coefficient of the ash layer varied between 2.5 Mm-1sr-1 and 3.5 Mm-1sr-1, and estimation of the AOD at 532 nm was found to be between 0.090 and 0.215. Several aerosol loads due to Saharan dust particles were detected in Spring 2011 and 2012. Lidar ratio of the dust layers were determine to be between 45 and 77 sr and AOD at 532 nm during the dust events range between 0.84 to 0.494.

Investigation of growth and stress tolerance characteristics of Cronobacter spp.

Cronobacter spp. are opportunistic pathogens which can be isolated from a wide variety of foods and environments. They are Gram negative, motile, non-spore forming, peritrichous rods of the Enterobacteriaceae family. This food-borne pathogen is associated with the ingestion of contaminated infant milk formula (IMF), causing necrotizing enterocolitis, sepsis and meningitis in neonatal infants. The work presented in this thesis involved the investigation and characterisation of a bank of Cronobacter strains for their ability to tolerate physiologically relevant stress conditions that are commonly encountered in the gastrointestinal tract. While all strains were able to endure the suboptimal conditions tested, noteworthy variations were observed between strains. A collection of these strains were Lux-tagged to determine if their growth could be tracked in IMF by measuring bioluminescence. The resulting strains could be easily and reproducibly monitored in real time by measuring light emission. Following this a transposon mutagenesis library was created in one of the Lux-tagged strains of Cronobacter sakazakii. This library was screened for mutants with affected growth in milk. The majority of mutants identified were associated with amino acid metabolism. The final section of this thesis identified genes involved in the tolerance of C. sakazakii to the milk derived antimicrobial peptide, Lactoferricin B (Lfcin B). This was achieved by creating a transposon mutagenesis library in C. sakazakii and screening for mutants with increased susceptibility to Lfcin B. Overall this thesis demonstrates the variation between Cronobacter strains. It also identifies genes required for growth of the bacteria in milk, as well as genes needed for antimicrobial peptide tolerance.

The corporate social responsibility movement and law's empire: Is there a conflict?

At the heart of corporate governance and social responsibility discourse is recognition of the fact that the modern corporation is primarily governed by the profit maximisation imperative coupled with moral and ethical concerns that such a limited imperative drives the actions of large and wealthy corporations which have the ability to act in influential and significant ways, shaping how our social world is experienced. The actions of the corporation and its management will have a wide sphere of impact over all of its stakeholders whether these are employees, shareholders, consumers or the community in which the corporation is located. As globalisation has become central to the way we think it is also clear that ‘community’ has an ever expanding meaning which may include workers and communities living very far away from Corporate HQ. In recent years academic commentators have become increasingly concerned about the emphasis on what can be called short-term profit maximisation and the perception that this extremist interpretation of the profit imperative results in morally and ethically unacceptable outcomes.1 Hence demands for more corporate social responsibility. Following Cadbury’s2 classification of corporate social responsibility into three distinct areas, this paper will argue that once the legally regulated tier is left aside corporate responsibility can become so nebulous as to be relatively meaningless. The argument is not that corporations should not be required to act in socially responsible ways but that unless supported by regulation, which either demands high standards, or at the very least incentivises the attainment of such standards such initiatives are doomed to failure. The paper will illustrate by reference to various chosen cases that law’s discourse has already signposted ways to consider and resolve corporate governance problems in the broader social responsibility context.3 It will also illustrate how corporate responsibility can and must be supported by legal measures. Secondly, this paper will consider the potential conflict between an emphasis on corporate social responsibility and the regulatory approach.4 Finally, this paper will place the current interest in corporate social responsibility within the broader debate on the relationship between law and non-legally enforceable norms and will present some reflections on the norm debate arising from this consideration of the CSR movement.

An exploratory study on the impact of an early years' preschool intervention programme in the Republic of Ireland

Early years’ education has increasingly been identified as a mechanism to alleviate educational disadvantage in areas of social exclusion. Early years’ intervention programmes are now a common government social policy for addressing social problems (Reynolds, Mann, Miedel, and Smokowski, 1997). In particular, state provided early years’ programmes such as Head Start in the United States and Early Start in Ireland have been established to combat educational disadvantage for children experiencing poverty and socio-economic inequality. The focus of this research is on the long-term outcomes of an early years’ intervention programme in Ireland. It aims to assess whether participation in the programme enhances the life course of children at-risk of educational disadvantage. It involves an in-depth analysis of one Early Start project which was included in the original eight projects established by the Department of Education and Science in 1994. The study utilises a multi-group design to provide a detailed analysis of both the academic and social progress of programme participants. It examines programme outcomes from a number of perspectives by collecting the views of the three main stakeholders involved in the education process; students who participated in Early Start in 1994/5, their parents and their teachers. To contribute to understanding the impact of the programme from a community perspective interviews were also conducted with local community educators and other local early years’ services. In general, Early Start was perceived by all participants in this study as making a positive contribution to parent involvement in education and to strengthening educational capital in the local area. The study found that parents and primary school teachers identified aspects of school readiness as the main benefit of participation in Early Start and parents and teachers were very positive about the role of Early Start in preparing children for the transition to formal school. In addition to this, participation in Early Start appears to have made a positive contribution to academic attainment in Maths and Science at Junior Certificate level. Students who had participated in Early Start were also rated more highly by their second level teachers in terms of goal-setting and future orientation which are important factors in educational attainment. Early Start then can be viewed as providing a positive contribution to the long-term social and academic outcomes for its participants.

Coherent wavelength division multiplexing: a novel transmission format for high spectral density optical communication networks

In this thesis a novel transmission format, named Coherent Wavelength Division Multiplexing (CoWDM) for use in high information spectral density optical communication networks is proposed and studied. In chapter I a historical view of fibre optic communication systems as well as an overview of state of the art technology is presented to provide an introduction to the subject area. We see that, in general the aim of modern optical communication system designers is to provide high bandwidth services while reducing the overall cost per transmitted bit of information. In the remainder of the thesis a range of investigations, both of a theoretical and experimental nature are carried out using the CoWDM transmission format. These investigations are designed to consider features of CoWDM such as its dispersion tolerance, compatibility with forward error correction and suitability for use in currently installed long haul networks amongst others. A high bit rate optical test bed constructed at the Tyndall National Institute facilitated most of the experimental work outlined in this thesis and a collaboration with France Telecom enabled long haul transmission experiments using the CoWDM format to be carried out. An amount of research was also carried out on ancillary topics such as optical comb generation, forward error correction and phase stabilisation techniques. The aim of these investigations is to verify the suitability of CoWDM as a cost effective solution for use in both current and future high bit rate optical communication networks

The differences in the social competence of children who attend integrated junior infant classes and children who attend segregated learning environments

There are a number of reasons why this researcher has decided to undertake this study into the differences in the social competence of children who attend integrated Junior Infant classes and children who attend segregated learning environments. Theses reasons are both personal and professional. My personal reasons stem from having grown up in a family which included both an aunt who presented with Down Syndrome and an uncle who presented with hearing impairment. Both of these relatives' experiences in our education system are interesting. My aunt was considered ineducable while her brother - my uncle - was sent to Dublin (from Cork) at six years of age to be educated by a religious order. My professional reasons, on the other hand, stemmed from my teaching experience. Having taught in both special and integrated classrooms it became evident to me that there was somewhat 'suspicion' attached to integration. Parents of children without disabilities questioned whether this process would have a negative impact on their children's education. While parents of children with disabilities debated whether integrated settings met the specific needs of their children. On the other hand, I always questioned whether integration and inclusiveness meant the same thing. My research has enabled me to find many answers. Increasingly, children with special educational needs (SEN) are attending a variety of integrated and inclusive childcare and education settings. This contemporary practice of educating children who present with disabilities in mainstream classrooms has stimulated vast interest on the impact of such practices on children with identified disabilities. Indeed, children who present with disabilities "fare far better in mainstream education than in special schools" (Buckley, cited in Siggins, 2001,p.25). However, educators and practitioners in the field of early years education and care are concerned with meeting the needs of all children in their learning environments, while also upholding high academic standards (Putman, 1993). Fundamentally, therefore, integrated education must also produce questions about the impact of this practice on children without identified special educational needs. While these questions can be addressed from the various areas of child development (i.e. cognitive, physical, linguistic, emotional, moral, spiritual and creative), this research focused on the social domain. It investigates the development of social competence in junior infant class children without identified disabilities as they experience different educational settings.

Drama Grammatik: Dramapädagogische Ansätze für den Grammatikunterricht Deutsch als Fremdsprache

This dissertation introduces and evaluates dramagrammar, a new concept for the teaching and learning of foreign language grammar. Grammar, traditionally taught in a predominantly cognitive, abstract mode, often fails to capture the minds of foreign language learners, who are then unable to integrate this grammatical knowledge into their use of the foreign language in a meaningful way. The consequences of this approach are manifested at university level in German departments in England and Ireland, where the outcomes are unconvincing at best, abysmal at worst. Language teaching research suggests that interaction plays an important role in foreign language acquisition. Recent studies also stress the significance of grammatical knowledge in the learning process. Dramagrammar combines both interactive negotiation of meaning and explicit grammar instruction in a holistic approach, taking up the concept of drama in foreign language education and applying it to the teaching and learning of grammar. Techniques from dramatic art forms allow grammar to be experienced not only cognitively but also in social, emotional, and bodily-kinaesthetic ways. Dramagrammar lessons confront the learner with fictitious situations in which grammar is experienced 'hands-on'. Learners have to use grammatical structures in a variety of contexts, reflect upon their use, and then enlarge and enrich the dramatic situations with their newly acquired or more finely nuanced knowledge. The initial hypothesis of this dissertation is that the drammagrammar approach is beneficial to the acquisition of foreign language grammar. This hypothesis is corroborated by research findings from language teaching pedagogy and drama in education. It is further confirmed by empirical data gained from specifically designed dramagrammar modules that have been put into practice in German departments at the University of Leicester (England), the University Colleges Cork and Dublin (Ireland), the University of Bologna (Italy), as well as the Goethe-Institute Bratislava (Slovenia). The data suggests that drammagrammar has positive effects on both understanding of and attitudes towards grammar.

Biological wastes as plant growth substrate amendments

Globally, agriculture is being intensified with mechanization and increased use of synthetic fertilizers and pesticides. There has been a scaling up of production to satisfy the demands of supermarket distribution. Problems associated with intensification of production, trade globalisation and a larger market demand for greater volumes of fresh produce, include consumers' concern about pesticide residues and leaching of nutrients and pesticides into the environment, as well as increases in the transmission of human food-poisoning pathogens on raw vegetables and in fruit juices. The first part of this research was concerned with the evaluation of a biological control strategy for soil-borne pathogens, these are difficult to eliminate and the chemicals of which the most effective fumigants e.g. methyl bromide, are being withdrawn form use. Chitin-containing crustaceans shellfish waste was investigated as a selective growth substrate amendment in the field, in glasshouse and in storage trials against Sclerotinia disease of Helianthus tuberosus, Phytophthora fragariae disease of Fragaria vesca and Fusarium disease of Dianthus. Results showed that addition to shellfish waste stimulated substrate microbial populations and lytic activity and induced plant defense proteins, namely chitinases and cellulases. Protective effects were seen in all crop models but the results indicate that further trials are required to confirm long-term efficacy. The second part of the research investigated the persistence of enteric bacteria in raw salad vegetables using model food poisoning isolates. In clinical investigations plants are sampled for bacterial contamination but no attempt is made to differentiate between epiphytes and endophytes. Results here indicate that the mode isolates persist endophytically thereby escaping conventional chlorine washes and they may also induce host defenses, which results in their suppression and in negative results in conventional plate count screening. Finally a discussion of criteria that should be considered for a HACCP plan for safe raw salad vegetable production is presented.

Issues in the prescribing of psychotropic and psychoactive medication for persons with learning disability: quantitative and qualitative perspectives

The administration of psychotropic and psychoactive medication for persons with learning disability and accompanying mental illness and/or challenging behaviour has undergone much critical review over the past two decades. Assessment and diagnosis of mental illness in this population continues to be psychopharmacological treatment include polypharmacy, irrational prescription procedures and frequent over-prescription. It is clear that all forms of treatment including non-pharmacological interventions need to be driven by accurate and appropriate diagnoses. Where a psychiatric diagnosis has been identified, it greatly aides the selection of appropriate medication, although a specific medication for each diagnosis, as was once hoped, is simply no longer a reality in practice. Part one of the present thesis seeks to address many of the current issues in mental health problems and pharmacological treatment to date. The author undertook a drug prevalence study within both residential and community facilities for persons with learning disability within the Mid-West region of Ireland in order to ascertain the current level of prescribing of psychotropic and psychoactive medications for this population. While many attempts have been made to account for the variation in prescribing, little systematic and empirical research has been undertaken to investigate the factors thought to influence such prescribing. While studies investigating the prescribing behaviours of General Practitioners (GP's) have illustrated the complex nature of the decision making process in the context of general practice, no similar efforts have yet been directed at examining the prescribing behaviours of Consultant Psychiatrists. Using The Critical Incident Technique, the author interviewed Consultant Psychiatrists in the Republic of Ireland to gather information relating not only to their patterns of prescribing for learning disabled populations, but also to examine reasons influencing their prescribing in addition to several related factors. Part two of this thesis presents the findings from this study and a number of issues are raised, not only in relation to attempting to account for the findings from part one of the thesis, but also with respect to implications for improved management and clinical practice.

Synthesis and reactivity of α-diazosulfoxide and α-diazosulfone derivatives

The research described in this thesis involves the synthesis of α-diazo-β-oxo sulfoxides, and exploration of their reactivity. The first chapter includes an introduction to diazocarbonyl chemistry, specifically focusing on the synthesis of diazo compounds, and diazosulfoxide derivatives. The chemistry of sulfines, in particular the generation of α-oxo sulfines and their subsequent trapping as cycloadducts and dimerisation is discussed. The results of this research are discussed in the second and third chapters. The design, synthesis and reactivity of α-diazo-β-oxo sulfoxides is described in chapter 2 where diazo transfer adjacent to sulfoxides to form stable α-diazo-β-oxo sulfoxides has been achieved in cyclic systems. Decomposition of theses α-diazosulfoxides using rhodium carboxylate or carboxamide catalysts is also described. These processes proceed via a Wolff type rearrangement to form α-oxo sulfine intermediates, which were trapped as cycloadducts with dienes. In the absence of a diene trap, dimerisation of the sulfine intermediate was observed. Intramolecular C-H insertion reasctios of α-diazo-α-sulfonyl esters to form substituted sulfolane esters is described in chapter 3. The reactivity of these sulfolane esters is briefly explored. The fourth chapter contains the experimental details and the spectral and analytical data for all new compounds reported.

The impact of new public management on the roles of elected councillors, management and the community sector in Irish local government: a case study of Cork County Council

The fundamental aim of this thesis is to examine the effect of New Public Management (NPM) on the traditional roles of elected representatives, management and community activists in Irish local government. This will be achieved through a case study analysis of one local authority, Cork County Council. NPM promises greater democracy in decision-making. Therefore, one can hypothesise that the roles of the three key groupings identified will become more influenced by principles of participatory decision-making. Thus, a number of related questions will be addressed by this work, such as, have the local elected representatives been empowered by NPM? Has a managerial revolution taken place? Has local democracy been enhanced by more effective community participation? It will be seen in chapter 2 that these questions have not been adequately addressed to date in NPM literature. The three groups identified can be regarded as stakeholders although the researcher is cautious in using this term because of its value-laden nature. Essentially, in terms of Cork County Council, stakeholders can be defined as decision-makers and people within the organization and its environment who are interested in or could be affected directly or indirectly by organizational performance. This is an all-embracing definition and includes all citizens, residents, community groups and client organizations. It is in this context that the term 'stakeholder' should be understood when it is occasionally used in this thesis. In this case, the perceptions of elected councilors, management and community representatives with regard to their changing roles are as significant as the changes themselves. The chapter begins with a brief account of the background to this research. This is followed by an explanation of the methodology which is used and then concludes with short statements about the remaining chapters in the thesis.