Structural studies of peri-interactions and bond formation between electron-rich atomic centres and N-phenylcarboxamides or nitroalkenyl groups

Structural studies of peri-interactions with dimethylamino groups in naphthalene systems indicate that the N-phenylcarboxamide group has a through-space electron attracting power closer to that of a carboxylic ester than a N,N-dialkylcarboxamide, while 2-nitroalkenyl groups have a lower through-space electron attracting power. However, addition of a benzoyl group to the 2-position of the nitroethenyl group leads to cyclisation to give a zwitterion, in which the carbanion is stabilised by full conjugation with the nitro group and partial conjugation with the carbonyl group. An interesting case where a steric interaction overrides an electrophile/nucleophile attraction is also described. The limitations to the interpretation of short contact distances from crystallographic measurements are discussed

Modernised Policy Making? Investigating the Development of the 2009 Migration Impact Fund

This thesis investigates the nature and effectiveness of the New Labour government’s attempt to modernise policy making in Britain. This government had developed and sought to implement a new concept of modernised policymaking, claiming that it represented a significant advance on previous efforts to transform policymaking. The principles, logic and ambition of this new form of modernised policymaking were set out clearly in a number of government publications (Cabinet Office, 1999a; Cabinet Office, 1999b). The objectives of this study are, firstly, to explore and assess the nature of this new concept of policy making, contextualising its claims by reference to the long history of debates about policy-making and modernisation in Britain. Secondly, it will investigate the use of this new form of policy making through a case study. The data collected will be subjected to a detailed analysis to assess the extent to which the development of the 2009 Migration Impact Fund constituted an example of modernised policy making, as conceived by the New Labour government. The ideas contained in the Asymmetrical Power model advanced by Marsh (2003) are used to inform the understanding of the policy setting in which the case occurred. To construct the case study, multiple methods of data collection are used to form a thick narrative that covers a five-year period. This narrative begins with the policy making that took place in anticipation of new migration in the lead up to the enactment of the 2003 Treaty of Accession and culminates in an explanation of how the 2009 Migration Impact Fund was designed and implemented. The case study is then subjected to a detailed analysis designed to generate precise data about the extent to which the nine features of modernised policy making are present; how modernised policy making presents at different points in the case; the extent to which the features of modernised policy making operated synergistically; and the different explanations for the policy making that was observed in the case study. These are used to then come to a statement as to whether policy making in this case was completely modernised; significantly modernised; not particularly modernised; or not modernised. The investigation found that policy making in this case was not particularly modernised. This was so because although all elements of modernised policy making was observed to be consistently present throughout the case, directive and bargaining based policy making were predominant at all crucial points rather than modernised policy making. The investigation showed that policy making operated, for better or worse, in a traditional way with core government’s commitment to increased labour mobility around Europe shaping the response of policy makers. As well, the investigation raised questions about how we may research and come to understand the impact of modernisation reforms when looking at policy making with a high level of detail. This is because the modernised policy making observed was not identified to be a direct result of the Modernising Government reforms, something that calls for further research to better ascertain the basis of choices made by policy makers. Overall, the case study findings confirm the predominant conclusions about New Labour’s efforts to modernise policy making (see for example Massey & Pyper, 2005; Newman, 2005). This is that there was a distinct gap between the rhetoric and practice of policymaking in this period which fundamentally served to continue the advance of business orientated approaches to public administration within the traditional political context of British policy making

The re-emergence of the B1 cell compartment : is this a pre-lymphoma stage?

Chronic Lymphocytic Leukemia (CLL) are in some cases stereotyped for immunoglobulin variants in different populations, suggesting emergence of B cell subsets following presentation of the same antigen. CLL cells may originate from CD5+ naïve cells and from CD5 memory cells. Gene expression studies characterized a common cell of origin of the two clinical categories of CLL; the unmutated aggressive type and the mutated indolent type. The aim of this study was to investigate the presence of CD5 positive B cells in the elderly and their potential stimulation with exosomes derived from tumor cells. The findings from this study is aimed to create a model to identify instigating carcinomatous factors that may stimulate B1 cells to transform into a CLL-like model. In this study we show that CD19\textsuperscript+ cells (B cells) in cord blood have a high expression of CD5. CD19/CD5 staining of blood samples from senior citizens showed the presence of B cells which also express the CD5 marker, though at a lower expression when compared to CLL cells (CD19+/CD5 dim B cells). Measurement of clonality using λ/Κ flow cytometry staining show a monoclonal origin of the human CD19+/CD5 dim B cells. Monoclonal B cell Lymphocytosis in the elderly is a potential cell compartment that represents the origin of B cell proliferative disorders. The origin of the B cell proliferative disease requires antigen stimulation. A preliminary experiment showed that sorted lymphocytes can be stimulated by exosomes isolated from 2 cancer cells lines, A549 (lung epithelial) and PC3 (prostate cell line). In comparison with phytohaemagglutinin (PHA) and phorbolmyristate acetate (PMA), known lymphocyte stimulators, the exosomes stimulated the proliferation of monocytic-like cells. Further characterization is required to know the origin of these cells. The result shows that one can speculate that exosomes present cancer-derived antigens and stimulate cell proliferation. Further studies are required to evaluate the potential transformation capacity of cancer-derived exosomes. In addition, various cytokines were measured in the sera of senior citizens to investigate a differential release of cytokines in the presence or absence of the CD19+/CD5 dim B cells. Cytokines examined were not significantly different between the 2 groups and further evaluation of cytokine levels is required.peer-reviewe

About optimal location of sensors and actuators for the control of flexible structures

This work deals with the problem of efficient location of sensors and actuators encountered in the domain of active control of flexible structure. It appears that the optimal solution depends upon the type ofcontrol scheme that is used as well as the kinds of sensors and actuators that are implemented, and on the criterion that is considered. This paper recalls and discusses some approaches that are presented in the literature and presents some results that are obtained with a mock-up equipped with piezoelectric sensors and actuators

Life Cycle Assessment of Alkali Activated Cement compared to Ordinary Portland Cement

Approximately 8% of the global emissions of CO2 are originated by the cement industry, which consumes on average between 4 to 6 GJ per ton of cement. Ordinary Portland Cement (OPC) is the most used cement for construction purposes. Every year, around 4 billion tonnes (Gt) of OPC are manufactured. For each kg of OPC produced, 0.81 kg of CO2 is generated. Therefore, seeking cements with more environmentally friendly manufacturing process, economically viable, and socially relevant is necessary. One of the most promising materials are the Alkali-Activated Cements (AAC), where its components are an aluminosilicate precursor and alkaline activators. The precursor used in this study is Weathered Bottom Ash (WBA), a waste obtained from the Municipal Solid Waste Incineration (MSWI). On the other hand, the alkaline activators are sodium hydroxide (NaOH) and sodium silicate (Na2SiO3). The name of the AAC developed is Sustainable-AAC (Sust-AAC). This project is focused on searching for new materials that could reduce the use of OPC as a building material. To be able to assess the associated environmental impacts, a comparison between AAC and OPC (CEM I) through a Life Cycle Assessment (LCA) following the standards ISO 14040:2006 and ISO 14044:2006 is performed. The LCA methodology allows identification and quantification of relevant inputs and outputs of the system, thus, evaluating the potential environmental impacts associated. The system boundary of this project is cradle-to-gate and the functional unit of the assessment is 1 ton of commercial cement. The OPC inventory is carried out through the values obtained in GaBi Software and the Sust-AAC inventory is made from the previous studies performed in the DIOPMA research group, on a laboratory scale. The results show that the OPC has higher impact on global warming, energy consumption, water consumption, and mineral extraction categories compared to Sust-AAC. In OPC manufacturing, the kiln stage is the most energy intensive stage (by the chemical reaction and by the fossil fuel requirement) and therefore, has the most significant environmental impact in terms of CO2 emissions and energy consumption. In contrast, the highest environmental impacts on the Sust-AAC are due to the production of Na2SiO3. The main reason for the energysaving is because Sust-AAC production does not need a kiln with high temperatures. In addition, the use of waste as raw material promotes a circular economy and, at the same time, reduces the extraction of natural resources. Then, the environmental performance in the Sust-AAC is promising compared to OPC. Sust-AAC is suitable to be used as lightweight material and as insulation material for thermal insulating applications. This application can contribute to realising operational energy savings and performance benefits

Geopolymers based on the valorization of Municipal Solid Waste Incineration residues

he proper management of Municipal Solid Waste (MSW) has become one of the main environmental commitments for developed countries due to the uncontrolled growth of waste caused by the consumption patterns of modern societies. Nowadays, municipal solid waste incineration (MSWI) is one of the most feasible solutions and it is estimated to increase in Europe where the accessibility of landfill is restricted. Bottom ash (BA) is the most significant by-product from MSWI as it accounts for 85-95 % of the solid product resulting from combustion, which is classified as a non-hazardous residue that can be revalorized as a secondary aggregate in road sub-base, bulk lightweight filler in construction. In this way, revalorization of weathered BA (WBA) for the production of geopolymers may be a good alternative to common reuse as secondary aggregate material; however, the chemical process to obtain these materials involves several challenges that could disturb the stability of the material, mainly from the environmental point of view. Accordingly, it is necessary that geopolymers are able to stabilize heavy metals contained in the WBA in order to be classified as non-hazardous materials. In this regard, the SiO2/Al2O3 ratio plays an important role for the encapsulation of heavy metals and other toxic elements. The aim of this research is to formulate geopolymers starting from the 0-2 mm particle size fraction of WBA, as a unique raw material used as aluminumsilicate precursor. Likewise, leaching tests of the geopolymers formulated were performed to assess their environmental impact. The findings show that it is possible to formulate geopolymers using 100 % WBA as precursor, although more investigations are needed to sustain that geopolymer obtained can be considered as non-hazardous materials

Education and older adults at the University of the Third Age

This article reports a critical analysis of older adult education in Malta. In educational gerontology, a critical perspective demands the exposure of how relations of power and inequality, in their myriad forms, combinations, and complexities, are manifest in late-life learning initiatives. Fieldwork conducted at the University of the Third Age (UTA) in Malta uncovered the political nature of elder-learning, especially with respect to three intersecting lines of inequality - namely, positive aging, elitism, and gender. A cautionary note is, therefore, warranted at the dominant positive interpretations of UTAs since late-life learning, as any other education activity, is not politically neutral.peer-reviewe

Aryl hydrocarbon receptor (AHR) is a potential tumour suppressor in pituitary adenomas

Pituitary adenomas (PA) represent the largest group of intracranial neoplasms and yet the molecular mechanisms driving this disease remain largely unknown. The aim of this study was to use a high-throughput screening method to identify molecular pathways that may be playing a significant and consistent role in PA. RNA profiling using microarrays on eight local PAs identified the aryl hydrocarbon receptor (AHR) signalling pathway as a key canonical pathway downregulated in all PA types. This was confirmed by real-time PCR in 31 tumours. The AHR has been shown to regulate cell cycle progression in various cell types; however, its role in pituitary tissue has never been investigated. In order to validate the role of AHR in PA behaviour, further functional studies were undertaken. Over-expression of AHR in GH3 cells revealed a tumour suppressor potential independent of exogenous ligand activation by benzo α-pyrene (BαP). Cell cycle analysis and quantitative PCR of cell cycle regulator genes revealed that both unstimulated and BαP-stimulated AHR reduced E2F-driven transcription and altered expression of cell cycle regulator genes, thus increasing the percentage of cells in G0/G1 phase and slowing the proliferation rate of GH3 cells. Co-immunoprecipitation confirmed the interaction between AHR and retinoblastoma (Rb1) protein supporting this as a functional mechanism for the observed reduction. Endogenous Ahr reduction using silencing RNA confirmed the tumour suppressive function of the Ahr. These data support a mechanistic pathway for the putative tumour suppressive role of AHR specifically in PA, possibly through its role as a cell cycle co-regulator, even in the absence of exogenous ligands.peer-reviewe