VAMP - a vision based sensor network for health care hygiene

Adequate hand-washing has been shown to be a critical activity in preventing the transmission of infections such as MRSA in health-care environments. Hand-washing guidelines published by various health-care related institutions recommend a technique incorporating six hand-washing poses that ensure all areas of the hands are thoroughly cleaned. In this paper, an embedded wireless vision system (VAMP) capable of accurately monitoring hand-washing quality is presented. The VAMP system hardware consists of a low resolution CMOS image sensor and FPGA processor which are integrated with a microcontroller and ZigBee standard wireless transceiver to create a wireless sensor network (WSN) based vision system that can be retargeted at a variety of health care applications. The device captures and processes images locally in real-time, determines if hand-washing procedures have been correctly undertaken and then passes the resulting high-level data over a low-bandwidth wireless link. The paper outlines the hardware and software mechanisms of the VAMP system and illustrates that it offers an easy to integrate sensor solution to adequately monitor and improve hand hygiene quality. Future work to develop a miniaturized, low cost system capable of being integrated into everyday products is also discussed.

Becoming a CEO: an exploration of the theory and practice of effective organisational leadership

This Thesis is an exploration of potential enhancement in effectiveness, personally, professionally and organisationally through the use of Theory as an Apparatus of Thought. Enhanced effectiveness was sought by the practitioner (Subject), while in transition to becoming Chief Executive of his organization. The introduction outlines the content and the structure of the University College Cork DBA. Essay One outlines what Theory is, what Adult Mental Development is and an exploration of Theories held in the Authors past professional practice. Immunity to change is also reflected on. Essay Two looks at the construct of the key Theories used in the Thesis. Prof. Robert Kegan’s Theory of Adult Mental Development was used to aid the generation of insight. The other key Theories used were The Theory of The Business, Theory of the Co‐operative and a Theory of Organisational Leadership. Essay Three explores the application of the key Theories in a professional setting. The findings of the Thesis were that the subject was capable of dealing with increased environmental complexity and uncertainty by using Theory as an Apparatus of Thought, which in turn enhanced personal, professional and organisational effectiveness. This was achieved by becoming more aware of the Theories held by the practitioner, the experiences from the application of those Theories, which then led to greater insight. The author also found that a detailed understanding of the Theory of the Business and a Theory of Leadership would support any new CEO in the challenging early part of their tenure.

序破急 Jo-Ha-Kyu: enticement - crux - consolidation. From study to learning: Process drama projects in the Japanese English language university classroom

This dissertation investigates how social issues can be explored through process drama projects in the Japanese university English as a Foreign Language classroom context. The trajectory of this dissertation moves along a traditional Noh three part macro-continuum, called Jo-Ha-Kyu, interpreted as enticement, crux and consolidation. Within these three parts, there are six further divisions. Part I consists of three sections: Section I, the introduction, sets the backdrop for the entire dissertation, that of Japan, and aims to draw the reader into its culturally unique and specific world. This section outlines the rationale for placing the ethnographer at the centre of the research, and presents Japan through the eyes of the writer. Section II outlines relevant Japanese cultural norms, mores and values, the English educational landscape of Japan and an overview of theatre in Japan and its possible influences on the Japanese university student today. Section III provides three literature reviews: second language acquisition, drama in education to process drama, and Content Language Integrated Learning. In Part 2, Sections IV and V respectively consist of the research methodology and the action research at the core of this dissertation. Section IV describes the case of Kwansei Gakuin University, then explains the design of the process drama curricula. Section V details the three-process drama projects based around the three social issues at the centre of this dissertation. There is also a description of an extra project that of the guest lecturer project. The ultimate goals of all four projects were to change motivation through English in a CLIL context, to develop linguistic spontaneity and to deepen emotional engagement with the themes. Part 3 serves to reflect upon the viability of using process drama in the Japanese university curriculum, and to critically self-reflect on the project as a whole.

Targeting aberrant kinase activity in myeloid leukaemias

Acute myeloid leukaemia (AML) is the most common form of acute leukaemia in adults. Its treatment has remained largely unchanged for the past 30 years. Chronic myeloid leukaemia (CML) represents a tremendous success story in the era of targeted therapy but significant challenges remain including the development of drug resistance and disease persistence due to presence of CML stem cells. The Aurora family of kinases is essential for cell cycle regulation and their aberrant expression in cancer prompted the development of small molecules that selectively inhibit their activity. Chapter 2 of this thesis outlines the efficacy and mechanism of action of alisertib, a novel inhibitor of Aurora A kinase, in preclinical models of CML. Alisertib possessed equipotent activity against CML cells expressing unmutated and mutated forms of BCR-ABL. Notably, this agent retained high activity against the T315I and E255K BCR-ABL mutations, which confer the greatest degree of resistance to standard CML therapy. Chapter 3 explores the activity of alisertib in preclinical models of AML. Alisertib disrupted cell viability, diminished clonogenic survival, induced expression of the forkhead box O3 (FOXO3a) targets p27 and BCL-2 interacting mediator (BIM), and triggered apoptosis. A link between Aurora A expression and sensitivity to ara-C was established. Chapter 4 outlines the role of the proto-oncogene serine/threonine-protein (PIM) kinases in resistance to ara-C in AML. We report that the novel small molecule PIM kinase inhibitor SGI-1776 disrupted cell viability and induced apoptosis in AML. We establish a link between ara-C resistance and PIM over-expression. Finally, chapter 5 explores how the preclinical work outlined in this thesis may be translated into clinical studies that may lead to novel therapeutic approaches for patients with refractory myeloid leukaemia.

Crystal engineering: exploiting variation of sulfur oxidation for the control of the solid state structure of organosulfur compounds

This thesis is focused on the design and synthesis of a diverse range of novel organosulfur compounds (sulfides, sulfoxides and sulfones), with the objective of studying their solid state properties and thereby developing an understanding of how the molecular structure of the compounds impacts upon their solid state crystalline structure. In particular, robust intermolecular interactions which determine the overall structure were investigated. These synthons were then exploited in the development of a molecular switch. Chapter One provides a brief overview of crystal engineering, the key hydrogen bonding interactions utilized in this work and also a general insight into “molecular machines” reported in the literature of relevance to this work. Chapter Two outlines the design and synthetic strategies for the development of two scaffolds suitable for incorporation of terminal alkynes, organosulfur and ether functionalities, in order to investigate the robustness and predictability of the S=O•••H-C≡C- and S=O•••H-C(α) supramolecular synthons. Crystal structures and a detailed analysis of the hydrogen bond interactions observed in these compounds are included in this chapter. Also the biological activities of four novel tertiary amines are discussed. Chapter Three focuses on the design and synthesis of diphenylacetylene compounds bearing amide and sulfur functionalities, and the exploitation of the N-H•••O=S interactions to develop a “molecular switch”. The crystal structures, hydrogen bonding patterns observed, NMR variable temperature studies and computer modelling studies are discussed in detail. Chapter Four provides the overall conclusions from chapter two and chapter three and also gives an indication of how the results of this work may be developed in the future. Chapter Five contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of the NCI (National Cancer Institute) biological test results are included in the appendix.

Synthesis & characterisation of group IV semiconducting nanowires

Semiconductor nanowires, particularly group 14 semiconductor nanowires, have been the subject of intensive research in the recent past. They have been demonstrated to provide an effective, versatile route towards the continued miniaturisation and improvement of microelectronics. This thesis aims to highlight some novel ways of fabricating and controlling various aspects of the growth of Si and Ge nanowires. Chapter 1 highlights the primary technique used for the growth of nanowires in this study, namely, supercritical fluid (SCF) growth reactions. The advantages (and disadvantages) of this technique for the growth of Si and Ge nanowires are highlighted, citing numerous examples from the past ten years. The many variables involved in this technique are discussed along with the resultant characteristics of nanowires produced (diameter, doping, orientation etc.). Chapter 2 outlines the experimental methodologies used in this thesis. The analytical techniques used for the structural characterisation of nanowires produced are also described as well as the techniques used for the chemical analysis of various surface terminations. Chapter 3 describes the controlled self-seeded growth of highly crystalline Ge nanowires, in the absence of conventional metal seed catalysts, using a variety of oligosilylgermane precursors and mixtures of germane and silane compounds. A model is presented which describes the main stages of self-seeded Ge nanowire growth (nucleation, coalescence and Ostwald ripening) from the oligosilylgermane precursors and in conjunction with TEM analysis, a mechanism of growth is proposed. Chapter 4 introduces the metal assisted etching (MAE) of Si substrates to produce Si nanowires. A single step metal-assisted etch (MAE) process, utilising metal ion-containing HF solutions in the absence of an external oxidant, was developed to generate heterostructured Si nanowires with controllable porous (isotropically etched) and non-porous (anisotropically etched) segments. In Chapter 5 the bottom-up growth of Ge nanowires, similar to that described in Chapter 3, and the top down etching of Si, described in Chapter 4, are combined. The introduction of a MAE processing step in order to “sink” the Ag seeds into the growth substrate, prior to nanowire growth, is shown to dramatically decrease the mean nanowire diameters and to narrow the diameter distributions. Finally, in Chapter 6, the biotin – streptavidin interaction was explored for the purposes of developing a novel Si junctionless nanowire transistor (JNT) sensor.

Development of germanium/silicon integration for near infrared detection

Silicon (Si) is the base material for electronic technologies and is emerging as a very attractive platform for photonic integrated circuits (PICs). PICs allow optical systems to be made more compact with higher performance than discrete optical components. Applications for PICs are in the area of fibre-optic communication, biomedical devices, photovoltaics and imaging. Germanium (Ge), due to its suitable bandgap for telecommunications and its compatibility with Si technology is preferred over III-V compounds as an integrated on-chip detector at near infrared wavelengths. There are two main approaches for Ge/Si integration: through epitaxial growth and through direct wafer bonding. The lattice mismatch of ~4.2% between Ge and Si is the main problem of the former technique which leads to a high density of dislocations while the bond strength and conductivity of the interface are the main challenges of the latter. Both result in trap states which are expected to play a critical role. Understanding the physics of the interface is a key contribution of this thesis. This thesis investigates Ge/Si diodes using these two methods. The effects of interface traps on the static and dynamic performance of Ge/Si avalanche photodetectors have been modelled for the first time. The thesis outlines the original process development and characterization of mesa diodes which were fabricated by transferring a ~700 nm thick layer of p-type Ge onto n-type Si using direct wafer bonding and layer exfoliation. The effects of low temperature annealing on the device performance and on the conductivity of the interface have been investigated. It is shown that the diode ideality factor and the series resistance of the device are reduced after annealing. The carrier transport mechanism is shown to be dominated by generation–recombination before annealing and by direct tunnelling in forward bias and band-to-band tunnelling in reverse bias after annealing. The thesis presents a novel technique to realise photodetectors where one of the substrates is thinned by chemical mechanical polishing (CMP) after bonding the Si-Ge wafers. Based on this technique, Ge/Si detectors with remarkably high responsivities, in excess of 3.5 A/W at 1.55 μm at −2 V, under surface normal illumination have been measured. By performing electrical and optical measurements at various temperatures, the carrier transport through the hetero-interface is analysed by monitoring the Ge band bending from which a detailed band structure of the Ge/Si interface is proposed for the first time. The above unity responsivity of the detectors was explained by light induced potential barrier lowering at the interface. To our knowledge this is the first report of light-gated responsivity for vertically illuminated Ge/Si photodiodes. The wafer bonding approach followed by layer exfoliation or by CMP is a low temperature wafer scale process. In principle, the technique could be extended to other materials such as Ge on GaAs, or Ge on SOI. The unique results reported here are compatible with surface normal illumination and are capable of being integrated with CMOS electronics and readout units in the form of 2D arrays of detectors. One potential future application is a low-cost Si process-compatible near infrared camera.

An Irish apostle: articulating and actualising apostolicity in the early Irish church

This thesis examines the earliest extant Latin Lives of Brigit and Patrick; Cogitosus’s Vita Brigidae and Muirchú’s Vita Patricii as evidence for a seventh-century debate on Irish apostolicity. While often dismissed as mere propaganda, this thesis shows they are highly sophisticated demonstrations of the continuing connection that Kildare and Armagh had to their patron saints and their authority. It examines the importance of this connection for concepts of ecclesiastical organisation, teaching authority and episcopal succession against the backdrop of the seventh-century Easter question in the Insular Church. This will show that apostolicity was considered to be intrinsically linked with orthodoxy and universality. A textual focus brings forth general patristic themes and ideas that Irish hagiographers evoked through specific words and phrases. The thesis contextualises hagiographical material using evidence from Hiberno-Latin and early Insular exegetical commentaries, referring to major patristic exegetes such as Origen, Jerome, Augustine, and Gregory the Great as support. The introduction discusses the importance of apostolic ideology for the seventh-century Irish Church, and outlines a methodology for examining such abstract themes. The first chapter looks at how developments in apostolic ideology led to ideas of apostolic primacy seen in the Insular material. Chapters two, three, and four examine metaphors of food and feeding, the fountain and the stream, and the head and the body, as significant articulations of apostolicity. Chapter five examines how corporeal relics were understood as the visible proof of this continuity and preserved a saint’s authority for their episcopal heirs. Chapter six looks at how Muirchú engaged with Patrick’s connection to the universal Church and his self-professed lack of disciplina to reconcile his apostolicity with seventh-century norms. Chapter seven places the issues considered thus far in a thoroughly Insular context by examining how the earliest English sources present the Irish legacy in Northumbria after the synod of Whitby. Chapter eight looks at how the text of Patrick’s Confessio in the Book of Armagh relates to a wider seventh-century campaign by Armagh to rehabilitate Patrick’s apostolicity. The conclusion briefly summarizes the thesis, and suggests further avenues for researching this topic in the Insular material

Synthesis of iminophosphine and phosphinoiminol cyclometallated Pt (II) and Pt (IV) chloro complexes and studies into their biological and photophysical properties

This thesis focuses on the synthesis and analysis of novel chloride based platinum complexes derived from iminophosphine and phosphinoamide ligands, along with studies on their reactivity towards substitution and oxidation reactions. Also explored here are the potential applications of these complexes for biological and luminescent purposes. Chapter one provides an extensive overview of platinum coordination chemistry with examples of various mixed donor ligands along with the history of platinum anticancer therapy. It also looks at metals in medicine, both for biological functions as well as for therapeutic purposes and gives a background to some other applications for platinum complexes. Chapter two outlines the design and synthetic strategies employed for the development of novel platinum (II) chloride complexes from iminophosphine and phosphinoamide ligands. Also reported is the cyclometallation of these complexes to form stable tridentate mixed donor platinum (II) compounds. In Chapter three the development of a direct method for displacing a chloride from a platinum metal centre with a desired phosphine is reported. Numerous methods for successful oxidation of the platinum (II) complexes will also be explored, leading to novel platinum (IV) complexes being reported here also. The importance of stabilisation of the displaced anion, chloride, by the solvent system will also be discussed in this chapter. Chapter four investigates the reactivity of the platinum (II) complexes towards two different biomolecules to form novel platinum bio-adducts. The potential application of the platinum (II) cyclometallates as chemotherapeutics will also be explored here using in-vitro cancer cell testing. Finally, luminescence studies are also reported here for the ligands and platinum complexes reported in chapter two and three to investigate potential applications in this field also. Chapter five provides a final conclusion and an overall summary of the entire project as well as identifying key areas for future work.

Rapid separation of biologically important low molecular weight compounds by microchip electrophoresis and ultra-fast performance liquid chromatography

The research work in this thesis reports rapid separation of biologically important low molecular weight compounds by microchip electrophoresis and ultrahigh liquid chromatography. Chapter 1 introduces the theory and principles behind capillary electrophoresis separation. An overview of the history, different modes and detection techniques coupled to CE is provided. The advantages of microchip electrophoresis are highlighted. Some aspects of metal complex analysis by capillary electrophoresis are described. Finally, the theory and different modes of the liquid chromatography technology are presented. Chapter 2 outlines the development of a method for the capillary electrophoresis of (R, S) Naproxen. Variable parameters of the separation were optimized (i.e. buffer concentration and pH, concentration of chiral selector additives, applied voltage and injection condition).The method was validated in terms of linearity, precision, and LOD. The optimized method was then transferred to a microchip electrophoresis system. Two different types of injection i.e. gated and pinched, were investigated. This microchip method represents the fastest reported chiral separation of Naproxen to date. Chapter 3 reports ultra-fast separation of aromatic amino acid by capillary electrophoresis using the short-end technique. Variable parameters of the separation were optimized and validated. The optimized method was then transferred to a microchip electrophoresis system where the separation time was further reduced. Chapter 4 outlines the use of microchip electrophoresis as an efficient tool for analysis of aluminium complexes. A 2.5 cm channel with linear imaging UV detection was used to separate and detect aluminium-dopamine complex and free dopamine. For the first time, a baseline, separation of aluminium dopamine was achieved on a 15 seconds timescale. Chapter 5 investigates a rapid, ultra-sensitive and highly efficient method for quantification of histamine in human psoriatic plaques using microdialysis and ultrahigh performance liquid chromatography with fluorescence detection. The method utilized a sub-two-micron packed C18 stationary phase. A fluorescent reagent, 4-(1-pyrene) butyric acid N-hydroxysuccinimide ester was conjugated to the primary and secondary amino moieties of histamine. The dipyrene-labeled histamine in human urine was also investigated by ultrahigh pressure liquid chromatography using a C18 column with 1.8 μm particle diameter. These methods represent one of the fastest reported separations to date of histamine using fluorescence detection.

Fabrication and characterisation of semiconductor nanowires and metal interconnects

One-dimensional semiconductor nanowires are considered to be promising materials for future nanoelectronic applications. However, before these nanowires can be integrated into such applications, a thorough understanding of their growth behaviour is necessary. In particular, methods that allow the control over nanowire growth are deemed especially important as it is these methods that will enable the control of nanowire dimensions such as length and diameter (high aspect ratios). The production of nanowires with high-aspect ratios is vital in order to take advantage of the unique properties experienced at the nanoscale, thus allowing us to maximise their use in devices. Additionally, the development of low-resistivity interconnects is desirable in order to connect such nanowires in multi-nanowire components. Consequently, this thesis aims to discuss the synthesis and characterisation of germanium (Ge) nanowires and platinum (Pt) interconnects. Particular emphasis is placed on manipulating the nanowire growth kinetics to produce high aspect ratio structures. The discussion of Pt interconnects focuses on the development of low-resistivity devices and the electrical and structural analysis of those devices. Chapter 1 reviews the most critical aspects of Ge nanowire growth which must be understood before they can be integrated into future nanodevices. These features include the synthetic methods employed to grow Ge nanowires, the kinetic and thermodynamic aspects of their growth and nanowire morphology control. Chapter 2 outlines the experimental methods used to synthesise and characterise Ge nanowires as well as the methods used to fabricate and analyse Pt interconnects. Chapter 3 discusses the control of Ge nanowire growth kinetics via the manipulation of the supersaturation of Ge in the Au/Ge binary alloy system. This is accomplished through the use of bi-layer films, which pre-form Au/Ge alloy catalysts before the introduction of the Ge precursor. The growth from these catalysts is then compared with Ge nanowire growth from standard elemental Au seeds. Nanowires grown from pre-formed Au/Ge alloy seeds demonstrate longer lengths and higher growth rates than those grown from standard Au seeds. In-situ TEM heating on the Au/Ge bi-layer films is used to support the growth characteristics observed. Chapter 4 extends the work of chapter 3 by utilising Au/Ag/Ge tri-layer films to enhance the growth rates and lengths of Ge nanowires. These nanowires are grown from Au/Ag/Ge ternary alloy catalysts. Once again, the supersaturation is influenced, only this time it is through the simultaneous manipulation of both the solute concentration and equilibrium concentration of Ge in the Au/Ag/Ge ternary alloy system. The introduction of Ag to the Au/Ge binary alloy lowers the equilibrium concentration, thus increasing the nanowire growth rate and length. Nanowires with uniform diameters were obtained via synthesis from AuxAg1-x alloy nanoparticles. Manifestation of the Gibbs-Thomson effect, resulting from the dependence of the mean nanowire length as a function of diameter, was observed for all of the nanowires grown from the AuxAg1-x nanoparticles. Finally, in-situ TEM heating was used to support the nanowire growth characteristics. Chapter 5 details the fabrication and characterisation of Pt interconnects deposited by electron beam induced deposition of two different precursors. The fabrication is conducted inside a dual beam FIB. The electrical and structural characteristics of interconnects deposited from a standard organometallic precursor and a novel carbon-free precursor are compared. The electrical performance of the carbon-free interconnects is shown to be superior to that of the organometallic devices and this is correlated to the structural composition of both interconnects via in-situ TEM heating and HAADF-STEM analysis. Annealing of the interconnects is carried out under two different atmospheres in order to reduce the electrical resistivity even further. Finally, chapter 6 presents some important conclusions and summarises each of the previous chapters.

Comparative genomics of Bifidobacteria

Chapter 2 of this thesis describes the sequence analysis of 14 bifidobacterial genomes from various species of the genus Bifidobacterium, and the determination of their open pan-genome trend. This analysis first determined the total number of genes to be considered as the reservoir of functions available to representatives of this genus. Many identified genes are still uncharacterized, but may be involved in the adaptation to the gut environment. This comparative genomic analysis also determined a pool of ortholog functions used to infer their phylogenetic relationship, thereby providing a more robust approach compared to that based solely on the16S rRNA-encoding gene. The genome sequence of an isolate from the insect hindgut Bifidobacterium asteroides PRL2011 was fully characterized in Chapter 3, surprisingly revealing a putative respiratory metabolism, which was also found to be present in other insect isolates, suggesting that respiration was an ancient feature of this genus, but also an adaptative trait to different atmosferic oxygen levels. Chapter 4 of this thesis outlines a comparative study which focused on the analysis of representatives of the Bifidobacterium breve species, revealing that the genetic variability among members of this species principally consists of genes with a role in adaptation to host environment and gut colonization. Finally, Chapter 5 describes the analysis of the genome sequence of Bifidobacterium animalis subsp. lactis BLC1, a probiotic bacterium widely used in food industries as an ingredient of functional foods, providing information that will allow future investigations of this species.

Leadership, fairness and gender: a practitioner's perspective

This Portfolio of Exploration outlines the course of learning by a practitioner on a personal leadership journey. It constructs a functional examination of ideas around leadership. It explores the belief system which underpins leadership practice and it also explores to what extent the increased participation of women can lead to a qualitatively different type of leadership. Different models of leadership are explored to find the model which can best fit with the author’s perception of leadership. The Women’s Intercultural Leadership Model is discussed. This model conceptualises leadership as the envisioning of oneself and others as potential leaders. It seeks to promote that recognition whilst at the same time encouraging personal transformation. The promotion of a values based leadership is examined. The value of fairness is examined as an element of functional leadership. The extent to which increasing the number of women in leadership can lead to a qualitatively different type of leadership is explored. Drucker’s assertion that every practice rests on theory is used to unearth the underlying assumptions of this reflective practitioner doctorate. Kegan’s Theory of Adult Mental Development and Subject-Object separation is used to explicitly examine knowledge construction. Myers Briggs Type Indicator (MBTI) and Assumption/Commitment/Behaviour/Outcome (ACBO) template are used to promote practice change.

Magnetic materials and soft-switched topologies for high-current DC-DC converters

The thesis is focused on the magnetic materials comparison and selection for high-power non-isolated dc-dc converters for industrial applications or electric, hybrid and fuel cell vehicles. The application of high-frequency bi-directional soft-switched dc-dc converters is also investigated. The thesis initially outlines the motivation for an energy-efficient transportation system with minimum environmental impact and reduced dependence on exhaustible resources. This is followed by a general overview of the power system architectures for electric, hybrid and fuel cell vehicles. The vehicle power sources and general dc-dc converter topologies are discussed. The dc-dc converter components are discussed with emphasis on recent semiconductor advances. A novel bi-directional soft-switched dc-dc converter with an auxiliary cell is introduced in this thesis. The soft-switching cell allows for the MOSFET's intrinsic body diode to operate in a half-bridge without reduced efficiency. The converter's mode-by-mode operation is analysed and closed-form expressions are presented for the average current gain of the converter. The design issues are presented and circuit limitations are discussed. Magnetic materials for the main dc-dc converter inductor are compared and contrasted. Novel magnetic material comparisons are introduced, which include the material dc bias capability and thermal conductivity. An inductor design algorithm is developed and used to compare the various magnetic materials for the application. The area-product analysis is presented for the minimum inductor size and highlights the optimum magnetic materials. Finally, the high-flux magnetic materials are experimentally compared. The practical effects of frequency, dc-bias, and converters duty-cycle effect for arbitrary shapes of flux density, air gap effects on core and winding, the winding shielding effect, and thermal configuration are investigated. The thesis results have been documented at IEEE EPE conference in 2007 and 2008, IEEE APEC in 2009 and 2010, and IEEE VPPC in 2010. A 2011 journal has been approved by IEEE Transactions on Power Electronics.

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.