Synthesis, functionalisation and characterisation of germanium nanocrystals & their applications

In the last two decades, semiconductor nanocrystals have been the focus of intense research due to their size dependant optical and electrical properties. Much is now known about how to control their size, shape, composition and surface chemistry, allowing fine control of their photophysical and electronic properties. However, genuine concerns have been raised regarding the heavy metal content of these materials, which is toxic even at relatively low concentrations and may limit their wide scale use. These concerns have driven the development of heavy metal free alternatives. In recent years, germanium nanocrystals (Ge NCs) have emerged as environmentally friendlier alternatives to II-VI and IV-VI semiconductor materials as they are nontoxic, biocompatible and electrochemically stable. This thesis reports the synthesis and characterisation of Ge NCs and their application as fluorescence probes for the detection of metal ions. A room-temperature method for the synthesis of size monodisperse Ge NCs within inverse micelles is reported, with well-defined core diameters that may be tuned from 3.5 to 4.5 nm. The Ge NCs are chemically passivated with amine ligands, minimising surface oxidation while rendering the NCs dispersible in a range of polar solvents. Regulation of the Ge NCs size is achieved by variation of the ammonium salts used to form the micelles. A maximum quantum yield of 20% is shown for the nanocrystals, and a transition from primarily blue to green emission is observed as the NC diameter increases from 3.5 to 4.5 nm. A polydisperse sample with a mixed emission profile is prepared and separated by centrifugation into individual sized NCs which each showed blue and green emission only, with total suppression of other emission colours. A new, efficient one step synthesis of Ge NCs with in situ passivation and straightforward purification steps is also reported. Ge NCs are formed by co-reduction of a mixture of GeCl4 and n-butyltrichlorogermane; the latter is used both as a capping ligand and a germanium source. The surface-bound layer of butyl chains both chemically passivates and stabilises the Ge NCs. Optical spectroscopy confirmed that these NCs are in the strong quantum confinement regime, with significant involvement of surface species in exciton recombination processes. The PL QY is determined to be 37 %, one of the highest values reported for organically terminated Ge NCs. A synthetic method is developed to produce size monodisperse Ge NCs with modified surface chemistries bearing carboxylic acid, acetate, amine and epoxy functional groups. The effect of these different surface terminations on the optical properties of the NCs is also studied. Comparison of the emission properties of these Ge NCs showed that the wavelength position of the PL maxima could be moved from the UV to the blue/green by choice of the appropriate surface group. We also report the application of water-soluble Ge NCs as a fluorescent sensing platform for the fast, highly selective and sensitive detection of Fe3+ ions. The luminescence quenching mechanism is confirmed by lifetime and absorbance spectroscopies, while the applicability of this assay for detection of Fe3+ in real water samples is investigated and found to satisfy the US Environmental Protection Agency requirements for Fe3+ levels in drinkable water supplies.

The Celtic dragon slayer - a literary analysis of Tochmarc Emire in connection with Tristan et Iseut

As Celtic scholars have long noted, the medieval Irish tale Tochmarc Emire “The Courtship of Emer” is heavily indebted to other medieval Irish texts. In this tale of courtship and otherworldly quests, the Irish hero Cú Chulainn must prove himself worthy of the hand of the noblewoman Emer. Among his overseas adventures, Cú Chulainn rescues a princess from three attackers of the Fomoire. This episode may represent the only medieval Irish example of AT300 “The Dragon Slayer”, a story pattern known from classical models such as the stories of Perseus and Andromeda; and Hercules and Hesione. Moreover, in the company of Cú Chulainn we find a character otherwise unknown to Irish tradition by the name of Drust mac Seirb. This has led scholars to argue that Tochmarc Emire may preserve a Celtic precursor of the Continental Tristan legend, seeing in Drust the Pictish origin of the character Tristan, himself a famous dragon slayer. In this interdisciplinary dissertation, a number of questions are addressed. If the redactor of Tochmarc Emire drew on material from outside Irish tradition, what does this tell us about medieval Irish concepts of literature and genre? Further, what evidence do we have for tracing the origin of the Continental Tristan legend back to Pictland, and what explanation might we offer for a putative Pictish prince featuring in an Irish Dragon Slayer story? Finally, what place does the Dragon Slayer episode occupy within Tochmarc Emire and can we find other narratives, Celtic or classical or other, fitting the pattern of AT300, which may strengthen the link between Tochmarc Emire and Tristan?

The impact of first pregnancy and delivery on pelvic floor dysfunction

Background: The first childbirth has the greatest impact on a woman’s pelvic floor when major changes occur. The aim of this study was to comprehensively describe pelvic floor dysfunction (PFD) in young nulliparous women, and its correlation with postnatal pathology. Methods: A prospective study was performed at Cork University Maternity Hospital, Ireland. Initially 1484 nulliparous women completed the validated Australian Pelvic Floor Questionnaire at 15 weeks’ gestation and repeatedly at one year postnatally (N=872). In the second phase, at least one year postnatally, 202 participants without subsequent pregnancies attended the clinical follow up which included: pelvic organ prolapse quantification, a 3D-Transperineal ultrasound scan and collagen level assessment. Results: A high pre-pregnancy prevalence of various types of PFD was detected, which in the majority of cases persisted postnatally and included multiple types of PFD. The first birth had a negative impact on severity of pre-pregnancy symptoms in <15% of cases. Apart from prolapse, vaginal delivery, including instrumental delivery did not increase the risk of PFD symptoms, where as Caesarean section was protective for all types of PFD. The first birth had a bigger impact on pre-existing symptoms of overactive bladder compared to stress urinary incontinence. Pelvic organ prolapse is extremely prevalent in young primiparous women, however usually it is low grade and asymptomatic. Congenital factors and high collagen type III levels play an important role in the aetiology of pelvic organs prolapse. Levator ani trauma is present in one in three women after the first pregnancy and delivery. Conclusion: The main damage to the pelvic floor most likely occurs due to an undiagnosed congenital intrinsic weakness of the pelvic floor structures. PFD is highly associated with first childbirth, however it seems that pregnancy and delivery are contributing factors only which unmask the congenital intrinsic weakness of the pelvic floor support.

Optimised crystal morphologies for active pharmaceutical ingredients and related studies

The majority of active pharmaceutical ingredients (APIs) are crystalline solids in their pure forms. Crystalline solids have definable morphologies, i.e. shape and size. Crystal morphology is determined by both the internal structure of the crystals and external factors during growth from solution. The morphology of a crystal batch can affect key processes during manufacturing. Companies generally accept whatever morphology the manufacturing process provides and deal with any subsequent problems by costly trouble‒shooting. Rational design of optimised morphologies for crystalline pharmaceutical solids would be a very significant technical and commercial advance. Chapter one introduces the concept of crystal nucleation and growth. The phenomenon of polymorphism alongside the causes and impact is discussed. A summary of the scope of instrumentation used in the investigation of crystal polymorphism and morphology, including crystal size distribution (CSD), is also included. Chapter two examines the research carried out during an exploration of the optimum crystallisation parameters of phenacetin. Following a morphological study, the impact this induces on particle density and flow properties is examined. The impact of impurities on the crystallisation properties of phenacetin is investigated. Significantly, the location of impurities within individual crystals is also studied. The third chapter describes an industrial collaboration looking at the resolution and polymorphic study of trometamol and lysine salts of ketoprofen and 2‒phenylpropionic acid (2‒PPA). Chapter four incorporates a solid state study on three separate compounds: 2‒chloro‒4‒nitroaniline, 4‒hydroxy‒N‒phenylbenzenesulfonamide and N‒acetyl‒D‒glucosamine‒6‒O‒sulfate. 2‒Chloro‒4‒nitroaniline and 4‒hydroxy‒N‒phenylbenzenesulfonamide both produced interesting, extreme morphologies which warranted further investigation as part of a collaborative study. Following a summarisation of results in chapter five, chapter six contains the full experimental details, incorporating spectral and other analytical data for all compounds synthesised during the course of the research.

Public evaluations of novel food technologies: a qualitative citizen-scientist deliberative discourse approach

This qualitative research expands understanding of how information about a range of Novel Food Technologies (NFTs) is used and assimilated, and the implications of this on the evolution of attitudes and acceptance. This work enhances theoretical and applied understanding of citizens’ evaluative processes around these technologies. The approach applied involved observations of interactive exchanges between citizens and information providers (i.e. food scientists), during which they discussed a specific technology. This flexible, yet structured, approach revealed how individuals construct meaning around information about specific NFTs. A rich dataset of 42 ‘deliberate discourse’ and 42 postdiscourse transcripts was collected. Data analysis encompassed three stages: an initial descriptive account of the complete dataset based on the top-down bottom-up (TDBU) model of attitude formation, followed by inductive and deductive thematic analysis across the selected technology groups. The hybrid thematic analysis undertaken identified a Conceptual Model, which represents a holistic perspective on the influences and associated features directing ‘sense-making’ and ultimate evaluations around the technology clusters. How individuals make sense of these technologies is shaped by: their beliefs, values and personal characteristics; their perceptions of power and control over the application of the technology; and, the assumed relevance of the technology and its applications within different contexts. These influences form the frame for the creation of sense-making around the technologies. Internal negotiations between these influences are evident and evaluations are based on the relative importance of each influence to the individual, which tend to contribute to attitude ambivalence and instability. The findings indicate the processes of forming and changing attitudes towards these technologies are: complex; dependent on characteristics of the individual, technology, application and product; and, impacted by the nature and forms of information provided. Challenges are faced in engaging with the public about these technologies, as levels of knowledge, understanding and interest vary.

Nietzsche and Montaigne: cheerful naturalism

The influence of the Essays of Michel de Montaigne on the thought of Friedrich Nietzsche has, hitherto, received scant scholarly attention. The aim of this thesis is to address this lacuna in the literature by making evident the importance of the Essays to the development of Nietzsche’s philosophy. I argue that, in order to fully appreciate Nietzsche’s thought, it must be recognized that, from the beginning to the end of his philosophical life, Montaigne was for him a thinker of the deepest personal and philosophical significance. Against the received scholarly opinion, which would see Montaigne as influential only for Nietzsche’s middle works, I contend that the Essays continue to be a key inspiration for Nietzsche even into his late and final works. Montaigne, with his cheerful affirmation of life, his experimental mode of philosophizing, and his resolutely naturalized perspective, was an exemplar for Nietzsche as a philosopher, psychologist, sceptic and naturalist. The Essays not only stimulated Nietzsche’s thinking on questions to do with morality, epistemology and the nature of the soul but also informed his conception of the ideal philosophical life. Moreover, to explore the Essays from a Nietzschean viewpoint, allows the drawing out of the more radical aspects of Montaigne’s thought, while to probe Montaigne’s impact on Nietzsche, provides insight into the trajectory of Nietzsche’s philosophy as he broke free from romantic pessimism and embraced the naturalism that would guide his works from Human, All Too Human onward.

Chamber investigations of atmospheric mercury oxidation chemistry

Mercury is a potent neurotoxin even at low concentrations. The unoxidised metal has a high vapour pressure and can circulate through the atmosphere, but when oxidised can deposit and be accumulated through the food chain. This work aims to investigate the oxidation processes of atmospheric Hg0(g). The first part describes efforts to make a portable Hg sensor based on Cavity Enhanced Absorption Spectroscopy (CEAS). The detection limit achieved was 66 ngm−3 for a 10 second averaging time. The second part of this work describes experiments carried out in a temperature controlled atmospheric simulation chamber in the Desert Research Institute, Reno, Nevada, USA. The chamber was built around an existing Hg CRDS system that could measure Hg concentrations in the chamber of<100 ngm−3 at 1 Hz enabling reactions to be followed. The main oxidant studied was bromine, which was quantified with a LED based CEAS system across the chamber. Hg oxidation in the chamber was found to be mostly too slow for current models to explain. A seven reaction model was developed and tested to find which parameters were capable of explaining the deviation. The model was overdetermined and no unique solution could be found. The most likely possibility was that the first oxidation step Hg + Br →HgBr was slower than the preferred literature value by a factor of two. However, if the more uncertain data at low [Br2] was included then the only parameter that could explain the experiments was a fast, temperature independent dissociation of HgBr some hundreds of times faster than predicted thermolysis or photolysis rates. Overall this work concluded that to quantitatively understand the reaction of Hg with Br2, the intermediates HgBr and Br must be measured. This conclusion will help to guide the planning of future studies of atmospheric Hg chemistry.

Multi-parametric metabolic assessment of cells under stress conditions

Glycolysis, glutaminolysis, the Krebs cycle and oxidative phosphorylation are the main metabolic pathways. Exposing cells to key metabolic substrates (glucose, glutamine and pyruvate); investigation of the contribution of substrates in stress conditions such as uncoupling and hypoxia was conducted. Glycolysis, O2 consumption, O2 and ATP levels and hypoxia inducible factor (HIF) signalling in PC12 cells were investigated. Upon uncoupling with FCCP mitochondria were depolarised similarly in all cases, but a strong increase in respiration was only seen in the cells fed on glutamine with either glucose or pyruvate. Inhibition of glutaminolysis reversed the glutamine dependant effect. Differential regulation of the respiratory response to FCCP by metabolic environment suggests mitochondrial uncoupling has a potential for substrate-specific inhibition of cell function. At reduced O2 availability (4 % and 0 % O2), cell bioenergetics and local oxygenation varied depending on the substrate composition. Results indicate that both supply and utilisation of key metabolic substrates can affect the pattern of HIF-1/2α accumulation by differentially regulating iO2¬, ATP levels and Akt/Erk/AMPK pathways. Inhibition of key metabolic pathways can modulate HIF regulatory pathways, metabolic responses and survival of cancer cells in hypoxia. Hypoxia leads to transcriptional activation, by HIF, of pyruvate dehydrogenase (PDH) kinase which phosphorylates and inhibits PDH, a mitochondrial enzyme that converts pyruvate into acetyl-CoA. The levels of PDH (total and phosphorylated), PDH kinase and HIF-1α were analysed in HCT116 and HCT116 SCO2-/- (deficient in complex IV of the respiratory chain) grown under 20.9 % and 3 % O2. Data indicate that regulation of PDH can occur in a manner independent of the HIF-1/PDH kinase 1 axis, mitochondrial respiration and the demand for acetyl-CoA. Collectively these results can be applied to many diseases; reduced nutrient supply and O2 during ischemia/stroke, hypoglycaemia in diabetes mellitus and cancer associated changes in uncoupling protein expression levels.

Citizenship education in Irish secondary schools: the influence of curriculum content, school culture and stakeholder perspectives

This research interrogates the status of citizenship education in Irish secondary schools. The following questions are examined: How does school culture impact on citizenship education? What value is accorded to the subjects, Civic, Social and Political Education (CSPE) and Social, Personal and Health Education (SPHE)? To what extent are the subjects of both the cognitive and non-cognitive curricula affirmed? The importance of these factors in supporting the social, ethical, personal, political and emotional development of students is explored. The concept of citizenship is dynamic and constantly evolving in response to societal change. Society is increasingly concerned with issues such as: globalisation; cosmopolitanism; the threat of global risk; environment sustainability; socio-economic inequality; and recognition/misrecognition of new identities and group rights. The pedagogical philosophy of Paulo Freire which seeks to educate for the conscientisation and humanisation of the student is central to this research. Using a mixed methods approach, data on the insights of students, parents, teachers and school Principals was collected. In relation to Irish secondary school education, the study reached three main conclusions. (1) The educational stakeholders rate the subjects of the non-cognitive curriculum poorly. (2) The subjects Civic, Social and Political education (CSPE), and Social, Personal and Health Education (SPHE) command a low status in the secondary school setting. (3) The day-to-day school climate is influenced by an educational philosophy that is instrumentalist in character. Elements of school culture such as: the ethic of care; the informal curriculum; education for life after school; and affirmation of teachers, are not sufficiently prioritised in supporting education for citizenship. The research concludes that the approach to education for citizenship needs to be more robust within the overall curriculum, and culture and ethos of the Irish education system.

Subterfuge-safe trust management for delegation of permissions in open environments

Open environments involve distributed entities interacting with each other in an open manner. Many distributed entities are unknown to each other but need to collaborate and share resources in a secure fashion. Usually resource owners alone decide who is trusted to access their resources. Since resource owners in open environments do not have a complete picture of all trusted entities, trust management frameworks are used to ensure that only authorized entities will access requested resources. Every trust management system has limitations, and the limitations can be exploited by malicious entities. One vulnerability is due to the lack of globally unique interpretation for permission specifications. This limitation means that a malicious entity which receives a permission in one domain may misuse the permission in another domain via some deceptive but apparently authorized route; this malicious behaviour is called subterfuge. This thesis develops a secure approach, Subterfuge Safe Trust Management (SSTM), that prevents subterfuge by malicious entities. SSTM employs the Subterfuge Safe Authorization Language (SSAL) which uses the idea of a local permission with a globally unique interpretation (localPermission) to resolve the misinterpretation of permissions. We model and implement SSAL with an ontology-based approach, SSALO, which provides a generic representation for knowledge related to the SSAL-based security policy. SSALO enables integration of heterogeneous security policies which is useful for secure cooperation among principals in open environments where each principal may have a different security policy with different implementation. The other advantage of an ontology-based approach is the Open World Assumption, whereby reasoning over an existing security policy is easily extended to include further security policies that might be discovered in an open distributed environment. We add two extra SSAL rules to support dynamic coalition formation and secure cooperation among coalitions. Secure federation of cloud computing platforms and secure federation of XMPP servers are presented as case studies of SSTM. The results show that SSTM provides robust accountability for the use of permissions in federation. It is also shown that SSAL is a suitable policy language to express the subterfuge-safe policy statements due to its well-defined semantics, ease of use, and integrability.

Novel insights into the expression and function of p38δ MAPK in oesophageal squamous cell carcinoma

Oesophageal cancer is an aggressive malignancy which is resistant to conventional therapy and has a poor prognosis. A greater understanding of the underlying molecular biology of oesophageal cancer and the identification of novel targets is necessary for the future treatment of this disease. This thesis focuses specifically on the ill-defined and understudied p38δ mitogen-activated protein kinase (MAPK) and its function(s) in oesophageal squamous cell carcinoma (OESCC). In contrast to the three other p38 isoforms (p38α, -β and –γ which have to-date been relatively well-studied), p38δ MAPK signalling is poorly understood. Thus, this research elucidates some of the role(s) played by p38δ MAPK in cancer progression. This work outlines how loss of p38δ MAPK expression confers greater tumourigenicity in oesophageal cancer. Restoration of p38δ MAPK expression, however, has anti-proliferative and anti-migratory effects and decreases OESCC capacity for anchorageindependent growth. Using a novel application of an enzyme-substrate fusion approach, the effect of phosphorylated p38δ (p-p38δ) MAPK expression is also considered. The work goes onto describe the effect(s) of p38δ MAPK status on the chemosensitivity of OESCC to conventional cisplatin and 5-fluorouracil (CF) versus the effectiveness of doxorubicin, cisplatin and 5-fluorouracil (ACF). ACF treatment of p38δ MAPK-negative OESCC results in decreased proliferation, migration and recovery, and increased apoptosis when compared with CF treatment. This thesis examines the potential mechanisms by which p38δ MAPK expression is lost in OESCC and identifies epigenetic regulation as the probable cause of differential p38δ MAPK expression. Also analysed is the role p38δ MAPK and p-p38δ MAPK play in the cell cycle. In summary, this research identifies p38δ MAPK as a possible molecular target and a potential predictor of response to chemotherapy in OESCC patients.

Stair na Gaeilge i gContae Thiobraid Árann 1700-1901

Stair na Gaeilge i gCo. Thiobraid Árann i rith na tréimhse 1700-1901 atá á ríomhadh sa tráchtas seo. Tar éis a cúlra agus a comhthéacs a shuíomh i gCaibidil a hAon, déantar scríobhaithe an cheantair a áireamh, fara tráchtaireacht orthu, i gCaibidil a Dó. I gCaibidlí a Trí agus a Ceathair, féachtar ar thionchar na hEaglaisí Caitlicí agus Eaglais na hÉireann (i measc eaglaisí Protastúnacha eile) ar an dteangain. I gCaibidil a Cúig, faightear spléachadh ar ghnéithe éagsúla de shaíocht an chontae, ag tabhairt léargais ar tháirgí na scríobhaithe, ar leabhair a clóbhualadh sa réigiún, agus ar fhilí móra na háite, leithéidí Liam Daill Uí Ifearnáin, ag sonrú limistéir faoi leith, an t-oirdheisceart, mar shampla. Léirítear éifeacht na gcumann Gaelach agus na ndíograiseoirí iomadúla a bhain leo. Ábhar suime, leis, feidhm na Gaeilge sna cúirteanna dlí. Tugtar faisnéis i gCaibidil a Sé ar fhianaise cuairteoirí ar an Ghaeilge mar urlabhra i dTiobraid Árann. Is anseo chomh maith a deintear anailís ar Dhaonáirimh na mblianta 1861-1901, le mórchuid adhmaid á baint as ceann 1901 go háirithe. Breactar as ainmneacha sagart agus múinteoirí le Gaeilge, agus tráchtar ar aicmí suntasacha eile, na póilíní agus na saighdiúirí a raibh an teanga sin ina mbéal acu. Tugtar le chéile dá réir na snáithíní difriúla eolais ar an dúiche ar bhealach nár tharla cheana don gcontae casta fairsing seo le haghaidh na tréimhse atá idir lámha ag an saothar.

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).

A river of memory: landscape, narrative and identity in the Lee Valley, Co. Cork, Ireland

In moments of rapid social changes, as has been witnessed in Ireland in the last decade, the conditions through which people engage with their localities though memory, individually and collectively, remains an important cultural issue with key implications for questions of heritage, preservation and civic identity. In recent decades, cultural geographers have argued that landscape is more than just a view or a static text of something symbolic. The emphasis seems to be on landscape as a dynamic cultural process – an ever-evolving process being constructed and re-constructed. Hence, landscape seems to be a highly complex term that carries many different meanings. Material, form, relationships or actions have different meanings in different settings. Drawing upon recent and continuing scholarly debates in cultural landscapes and collective memory, this thesis sets out to examine the generation of collective memory and how it is employed as a cultural tool in the production of memory in the landscape. More specifically, the research considers the relationships between landscape and memory, investigating the ways in which places are produced, appropriated, experienced, sensed, acknowledged, imagined, yearned for, appropriated, re-appropriated, contested and identified with. A polyvocal-bricoleur approach aims to get below the surface of a cultural landscape, inject historical research and temporal depth into cultural landscape studies and instil a genuine sense of inclusivity of a wide variety of voices (role of monuments and rituals and voices of people) from the past and present. The polyvocal-bricoleur approach inspires a mixed method methodology approach to fieldsites through archival research, fieldwork and filmed interviews. Using a mixture of mini-vignettes of place narratives in the River Lee valley in the south of Ireland, the thesis explores a number of questions on the fluid nature of narrative in representing the story and role of the landscape in memory-making. The case studies in the Lee Valley are harnessed to investigate the role of the above questions/ themes/ debates in the act of memory making at sites ranging from an Irish War of Independence memorial to the River Lee’s hydroelectric scheme to the valley’s key religious pilgrimage site. The thesis investigates the idea that that the process of landscape extends not only across space but also across time – that the concept of historical continuity and the individual and collective human engagement and experience of this continuity are central to the processes of remembering on the landscape. In addition the thesis debates the idea that the production of landscape is conditioned by several social frames of memory – that individuals remember according to several social frames that give emphasis to different aspects of the reality of human experience. The thesis also reflects on how the process of landscape is represented by those who re-produce its narratives in various media.

New phosphorescence based probes and techniques for the analysis of cellular oxygen and respiration

Real time monitoring of oxygenation and respiration is on the cutting edge of bioanalysis, including studies of cell metabolism, bioenergetics, mitochondrial function and drug toxicity. This thesis presents the development and evaluation of new luminescent probes and techniques for intracellular O2 sensing and imaging. A new oxygen consumption rate (OCR) platform based on the commercial microfluidic perfusion channel μ-slides compatible with extra- and intracellular O2 sensitive probes, different cell lines and measurement conditions was developed. The design of semi-closed channels allowed cell treatments, multiplexing with other assays and two-fold higher sensitivity to compare with microtiter plate. We compared three common OCR platforms: hermetically sealed quartz cuvettes for absolute OCRs, partially sealed with mineral oil 96-WPs for relative OCRs, and open 96-WPs for local cell oxygenation. Both 96-WP platforms were calibrated against absolute OCR platform with MEF cell line, phosphorescent O2 probe MitoXpress-Intra and time-resolved fluorescence reader. Found correlations allow tracing of cell respiration over time in a high throughput format with the possibility of cell stimulation and of changing measurement conditions. A new multimodal intracellular O2 probe, based on the phosphorescent reporter dye PtTFPP, fluorescent FRET donor and two-photon antennae PFO and cationic nanoparticles RL-100 was described. This probe, called MM2, possesses high brightness, photo- and chemical stability, low toxicity, efficient cell staining and high-resolution intracellular O2 imaging with 2D and 3D cell cultures in intensity, ratiometric and lifetime-based modalities with luminescence readers and FLIM microscopes. Extended range of O2 sensitive probes was designed and studied in order to optimize their spectral characteristics and intracellular targeting, using different NPs materials, delivery vectors, ratiometric pairs and IR dyes. The presented improvements provide useful tool for high sensitive monitoring and imaging of intracellular O2 in different measurement formats with wide range of physiological applications.