Chelating carbene ligands and their metal complexes

This thesis describes the synthesis of a number of functionalised imidazolium salts as precursors to N- heterocyclic carbenes and their subsequent coordination to Ag and Pd. Further a number of the Pd complexes were tested in the Heck reaction and their activities compared to complexes with similar structural features currently within the literature. A range of imidazolium salts have been synthesised which include quinoline and octahydroacridine moieties and have been characterised by a number of methods including X-ray crystallography. A bis imidazolium salt has also been prepared as a DIOP analogue. The imidazolium salts were successfully reacted with Ag20 to form the NHCAg(I) complexes. The quinoline and octahydroacridine based NHCs were transmetallated to Pd as chelating ligands, the quinoline based systems appearing as planar, strained complexes in the X-ray structure. The activities of the quinoline and octahydroacridine based NHCPd(II) complexes in the Heck coupling of 4-bromoacetophenone and 4-chlorobenzaldehyde with n-butyl acrylate were assessed and found to be comparable to similar systems with low to satisfactory conversions.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Performance comparison between signal digitizers and low-cost digital oscilloscopes: spectroscopic, pulse shape discrimination and timing capabilities for nuclear detectors

Signal digitizers revolutionized the approach to the electronics readout of radiation detectors in Nuclear Physics. These highly specialized pieces of equipment are designed to acquire the signals that are characteristic of the detectors in nuclear physics experiments. The functions of the several modules that were once needed for signal acquisition, can now be substituted by a single digitizer. As suggested by the name, with such readout modules, signals are first digitized (i.e. the signal waveform is sampled and converted to a digital representation) and then either stored or analyzed on-the-fly. The performances can be comparable or better than the traditional analog counterparts, in terms of energy, time resolution, and acquisition rate. In this work, we investigate the use of general-purpose digital oscilloscopes as signal digitizers for nuclear detectors. In order to have a proper comparison, we employ a distributed data acquisition system (DAQ), that standardizes the interface between the hardware and the on-line data analysis. The signals, from a set of typical radiation detectors, are digitized and analyzed with the very same algorithms in order to avoid biases due to different software analysis. We compare two traditional signal digitizers (CAEN DT5725 and CAEN DT5751) to two low-cost digital oscilloscopes (Digilent Analog Discovery 2, and Red Pitaya STEMLab 125-14), in terms of their capabilities for spectroscopy (energy resolution), time resolution, pulse shape discrimination, and maximum acquisition rate.Comment: 17 pages, 8 figures, 4 tables, Prepared for submission to JINS

Expression of tumour necrosis factors during chick lens development

During development of the lens, epithelial cells at the lens equator begin a differentiation process to become secondary fibre cells. The differentiating cells elongate and migrate towards the centre of the lens where they envelop the older, central fibre cells. Differentiation into fibre cells is accompanied by the breakdown of all organelles, such as the mitochondria. All organelle degradation is completed and denucleation occurs at the border of the organelle free zone (OFZ) which contains the central, terminally differentiated, fibre cells. The differentiation pathway is not well characterised, though it is believed to have similarities to an attenuated form of apoptosis supported by the identification of apoptosis related genes, such as TNF, in the lens. This study continues the search for and characterisation of apoptosis related genes expressed during lens development, focusing on TNFs and their extended family. Reverse Transcriptase-(RT-) PCR was carried out, identifying a number of TNF and extended family member genes in the chick lens, expression studies established novel, statistically significant differential expression for TRAF2 and TRAF3. TRAF2 protein expression from western blotting, similar to RT-PCR expression was found to decline as the lens developed. TRAF2 localisation studies showed limited expression in the equatorial region but there was extensive signalling found in the developing iris, a region in the corneal-scleral boundary and some staining was also detected in the ciliary body. TRAF3 protein and RT-PCR expression were similar, with increasing expression as the lens developed. Western blotting identified two bands and subcellular fractionation confirmed different localisation for the two isoforms. Immunofluorescence identified increasing TRAF3 staining in the cortical fibre cells, this staining was found to be similar to proteins that were reported to be involved in lens fibre cell remodelling and maintenance, suggesting a possibly similar role for TRAF3. Following interest in TRAIL as a gene therapy for Posterior Capsule Opacification (PCO) its expression was examined using RT-PCR and Western blotting which showed low, similar levels of expression throughout the stages of lens development studied. Peroxidase staining showed interesting staining in the equatorial epithelial cells and those just beginning to differentiate at the transition zone. Novel nuclear staining was identified at all time points in both epithelial and fibre cells containing nuclei. Characterisation of whole lens culture was undertaken to discover the optimum culture system for the whole chick lens. Of the published research using whole chick lens culture none stated the basic morphology of the developing lens in organ culture, though each lab had their preferred methodology. The characterisation resulted in the preference of E10 chick lenses being grown with vitreous attached in medium containing glucose. Understanding the morphology of lenses in culture will be invaluable when undertaking the functional studies required to clarify the roles in the lens of the newly identified genes, specifically TRAF2 and TRAF3.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Capital and culture : an investigation into New Labour cultural policy and the European Capital of Culture 2008

This thesis is an investigation into the relationship between culture in New Labour policy and within the competition for the European Capital of Culture 2008. The study interrogates a policy paradigm which it identifies as a 'creative city/urban planning' approach to urban regeneration. It locates this approach within a wider New Labour 'Third Way' politics, in that it attempts to reconcile economic instrumentalism with a rhetorical commitment to a politics of the social. Based on elite interviews and documentary analysis, this thesis argues that this approach to urban regeneration draws on a misappropriation of the work of cultural theorist Raymond Williams. It demonstrates how this misappropriation results in an unbounded anthropological definition, whereby culture colonises all areas of economic and social life. Within this template, culture becomes a surrogate economic and social policy. This is illustrated in the case-study of Liverpool's bidding for, winning of and plans for Capital of Culture 2008. This analysis shows how culture without parameters is usurped within both a neo-liberal economic agenda, and a policy template which recasts social inequality as a personal cultural deficit. Within Liverpool's urban strategy, culture is conceived as a social and economic panacea. However, when culture comes to mean everything, it invariably means nothing. This thesis attempts to put Raymond Williams' 'vague and baggy monster' back in its theoretical cage.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

a distributed data acquisition system for nuclear detectors

Nowadays, many examples of data acquisition (DAQ) software for experimental nuclear physics are monolithic processes that run on a computer attached to the DAQ hardware. In this article we present a distributed DAQ system developed for the C-BORD project. With our system, we propose a novel approach, in which each task related to the different DAQ parts (acquisition, pre-process, analysis, etc.) runs in a separate process. In particular, the system is composed of a set of servers that exchange information through dedicated communication sockets. Therefore, with this architecture, an important advantage is the possibility to run the processes on different computers to distribute the computational load. The initial tests of the system have been giving excellent results, both in terms of performance (i.e., maximum acquisition rates) and stability. The project entitled "Effective container inspection at BORDer control points" (C-BORD) is funded by the European H2020 programme. Its aim is to develop a comprehensive set of technologies for the generalized non-intrusive inspection (NII) of containers and large-volume freight at the European Union border

Study of nuclear targets of phosphatidylinositol-3 kinase in lymphocytes

Pathways regulated by Phosphotidylinositide-3-kinase (PI3K) have emerged as important mediators of cell proliferation and survival. When altered, several components of this pathway have been identified to contribute towards a wide range of human malignancies. PI3K has been implicated in the development of several EBV-associated malignancies of both lymphoid and epithelial origin. These include Burkitt's lymphoma, Hodgkin's disease and nasopharyngeal carcinoma. Although progress has been made in dissecting the pathways regulated by PI3K, the key components contributing to lymphocyte transformation have not been fully characterised. This study sought to investigate downstream targets of PI3K in lymphocytes in order to further our understanding of the contribution of PI3K signalling to lymphocyte proliferation and survival, particularly within the context of EBV-associated B-cell lymphomas. Initial work in this study revealed that a component of the mammalian ribosome, S6-ribosomal protein, is a major target for PI3K activation in transformed lymphocytes. In order to study PI3K and EBV regulated proteins on a larger scale, the technology of two-dimensional electrophoresis (2DE) was employed. The use of 2DE in combination with a PI3K inhibitor did not allow the identification of PI3K regulated proteins. However, three EBV regulated proteins were detected in the B-lymphocyte nucleus using this technology. The technology was further developed to study the post-translational modifications of DNA bound transcription factors. This detected multiple isoforms of the cAMP-response element binding protein (CREB), signal transducers and activators of transcription 1 (STAT1) and forkhead box O (FOXO) transcription factors in the nuclei of EBV immortalized lymphocytes. More detailed analysis of the PI3K regulated pro-apoptotic transcription factor, FOXOl, revealed that this protein is downregulated in EBV positive cells at both the transcriptional and translational levels. This downregulation was shown to directly correlate with the protein expression of a known target gene activated by FOXOl, Bcl-6, and to inversely correlate with protein levels of Cyclin D2, a target transcriptionally repressed by FOXOl. Further investigations into the mechanisms by which EBV downregulates FOXOl implicated a role for two EBV encoded proteins, Latent membrane protein-1 (LMP1) and LMP2A in the downregulation of both FOXOl, and its target gene, Bcl-6. In conclusion, this work has explored the use of antibody detection and proteomic techniques for the identification and analysis of nuclear proteins and transcription factors regulated by PI3K and EBV. Together, these investigations have deepened our understanding of the molecular changes that occur in lymphocytes in response to EBV infection, and how EBV may influence malignancy.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

A dual-omics approach for profiling plant responses to biostimulant applications under controlled and field conditions

A comprehensive approach using phenomics and global transcriptomics for dissecting plant response to biostimulants is illustrated with tomato (Solanum lycopersicum cv. Micro-Tom and Rio Grande) plants cultivated in the laboratory, greenhouse, and open field conditions. Biostimulant treatment based on an Ascophyllum nodosum extract (ANE) was applied as a foliar spray with two doses (1 or 2 l ha-1) at three different phenological stages (BBCH51, BBCH61, and BBCH65) during the flowering phase. Both ANE doses resulted in greater net photosynthesis rate, stomatal conductance, and fruit yield across all culture conditions. A global transcriptomic analysis of leaves from plants grown in the climate chamber, revealed a greater number of differentially expressed genes (DEGs) with the low ANE dose compared to the greater one. The second and third applications induced broader transcriptome changes compared to the first one, indicating a cumulative treatment effect. The functional enrichment analysis of DEGs highlighted pathways related to stimulus-response and photosynthesis, consistent with the morpho-physiological observations. This study is the first comprehensive dual-omics approach for profiling plant responses to biostimulants across three different culture conditions