2 resultados para cellulose solution in ionic liquids

em Glasgow Theses Service


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Background: Community participation has become an integral part of many areas of public policy over the last two decades. For a variety of reasons, ranging from concerns about social cohesion and unrest to perceived failings in public services, governments in the UK and elsewhere have turned to communities as both a site of intervention and a potential solution. In contemporary policy, the shift to community is exemplified by the UK Government’s Big Society/Localism agenda and the Scottish Government’s emphasis on Community Empowerment. Through such policies, communities have been increasingly encouraged to help themselves in various ways, to work with public agencies in reshaping services, and to become more engaged in the democratic process. These developments have led some theorists to argue that responsibilities are being shifted from the state onto communities, representing a new form of 'government through community' (Rose, 1996; Imrie and Raco, 2003). Despite this policy development, there is surprisingly little evidence which demonstrates the outcomes of the different forms of community participation. This study attempts to address this gap in two ways. Firstly, it explores the ways in which community participation policy in Scotland and England are playing out in practice. And secondly, it assesses the outcomes of different forms of community participation taking place within these broad policy contexts. Methodology: The study employs an innovative combination of the two main theory-based evaluation methodologies, Theories of Change (ToC) and Realist Evaluation (RE), building on ideas generated by earlier applications of each approach (Blamey and Mackenzie, 2007). ToC methodology is used to analyse the national policy frameworks and the general approach of community organisations in six case studies, three in Scotland and three in England. The local evidence from the community organisations’ theories of change is then used to analyse and critique the assumptions which underlie the Localism and Community Empowerment policies. Alongside this, across the six case studies, a RE approach is utilised to examine the specific mechanisms which operate to deliver outcomes from community participation processes, and to explore the contextual factors which influence their operation. Given the innovative methodological approach, the study also engages in some focused reflection on the practicality and usefulness of combining ToC and RE approaches. Findings: The case studies provide significant evidence of the outcomes that community organisations can deliver through directly providing services or facilities, and through influencing public services. Important contextual factors in both countries include particular strengths within communities and positive relationships with at least part of the local state, although this often exists in parallel with elements of conflict. Notably this evidence suggests that the idea of responsibilisation needs to be examined in a more nuanced fashion, incorporating issues of risk and power, as well the active agency of communities and the local state. Thus communities may sometimes willingly take on responsibility in return for power, although this may also engender significant risk, with the balance between these three elements being significantly mediated by local government. The evidence also highlights the impacts of austerity on community participation, with cuts to local government budgets in particular increasing the degree of risk and responsibility for communities and reducing opportunities for power. Furthermore, the case studies demonstrate the importance of inequalities within and between communities, operating through a socio-economic gradient in community capacity. This has the potential to make community participation policy regressive as more affluent communities are more able to take advantage of additional powers and local authorities have less resource to support the capacity of more disadvantaged communities. For Localism in particular, the findings suggest that some of the ‘new community rights’ may provide opportunities for communities to gain power and generate positive social outcomes. However, the English case studies also highlight the substantial risks involved and the extent to which such opportunities are being undermined by austerity. The case studies suggest that cuts to local government budgets have the potential to undermine some aspects of Localism almost entirely, and that the very limited interest in inequalities means that Localism may be both ‘empowering the powerful’ (Hastings and Matthews, 2014) and further disempowering the powerless. For Community Empowerment, the study demonstrates the ways in which community organisations can gain power and deliver positive social outcomes within the broad policy framework. However, whilst Community Empowerment is ostensibly less regressive, there are still significant challenges to be addressed. In particular, the case studies highlight significant constraints on the notion that communities can ‘choose their own level of empowerment’, and the assumption of partnership working between communities and the local state needs to take into account the evidence of very mixed relationships in practice. Most importantly, whilst austerity has had more limited impacts on local government in Scotland so far, the projected cuts in this area may leave Community Empowerment vulnerable to the dangers of regressive impact highlighted for Localism. Methodologically, the study shows that ToC and RE can be practically applied together and that there may be significant benefits of the combination. ToC offers a productive framework for policy analysis and combining this with data derived from local ToCs provides a powerful lens through which to examine and critique the aims and assumptions of national policy. ToC models also provide a useful framework within which to identify specific causal mechanisms, using RE methodology and, again, the data from local ToC work can enable significant learning about ‘what works for whom in what circumstances’ (Pawson and Tilley, 1997).

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How can we control the experimental conditions towards the isolation of specific structures? Why do particular architectures form? These are some challenging questions that synthetic chemists try to answer, specifically within polyoxometalate (POM) chemistry, where there is still much unknown regarding the synthesis of novel molecular structures in a controlled and predictive manner. This work covers a wide range of POM chemistry, exploring the redox self-assembly of polyoxometalate clusters, using both “one-pot”, flow and hydrothermal conditions. For this purpose, different vanadium, molybdenum and tungsten reagents, heteroatoms, inorganic salts and reducing agents have been used. The template effect of lone-pair containing pyramidal heteroatoms has been investigated. Efforts to synthesize new POM clusters displaying pyramidal heteroanions (XO32-, where X= S, Se, Te, P) are reported. The reaction of molybdenum with vanadium in the presence of XO32- heteroatoms is explored, showing how via the cation and experimental control it is possible to direct the self-assembly process and to isolate isostructural compounds. A series of four isostructural (two new, namely {Mo11V7P} and {Mo11V7Te} and two already known, namely {Mo11V7Se} and {Mo11V7S} disordered egg-shaped Polyoxometalates have been reported. The compounds were characterized by X-ray structural analysis, TGA, UV-Vis, FT-IR, Elemental and Flame Atomic Absorption Spectroscopy (FAAS) analysis and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Cyclic Voltammetry measurements have been carried out in all four compounds showing the effect of the ionic density of the heteroatom on the potential. High-Resolution ESI-MS studies have revealed that the structures retain their integrity in solution. Efforts to synthesize new mixed-metal compounds led to isolation, structural, and electronic characterization of the theoretically predicted, but experimentally elusive δ-isomer of the Keggin polyoxometalate cluster anion, {H2W4V9O33(C6H13NO3)}, by the reaction of tungstate(VI) and vanadium(V) with triethanolammonium ions (TEAH), acting as a tripodal ligand grafted to the surface of the cluster. Control experiments (in the absence of the organic compound) have proven that the tripodal ligand plays crucial role on the formation of the isomer. The six vanadium metal centres, which consist the upper part of the cluster, are bonded to the “capping” TEA tripodal ligand. This metal-ligand bonding directs and stabilises the formation of the final product. The δ-Keggin species was characterized by single-crystal X-ray diffraction, FT-IR, UV-vis, NMR and ESI-MS spectrometry. Electronic structure and structure-stability correlations were evaluated by means of DFT calculations. The compounds exhibited photochromic properties by undergoing single-crystal-to-single-crystal (SC-SC) transformations and changing colour under light. Non-conventional synthetic approaches are also used for the synthesis of the POM clusters comparing the classical “one-pot” reaction conditions and exploring the synthetic parameters of the synthesis of POM compounds. Reactions under hydrothermal and flow conditions, where single crystals that depend on the solubility of the minerals under hot water and high pressure can be synthesized, resulted in the isolation of two isostructural compounds, namely, {Mo12V3Te5}. The compound isolated from a continuous processing method, crystallizes in a hexagonal crystal system, forming a 2D porous plane net, while the compound isolated using hard experimental conditions (high temperature and pressure) crystallizes in monoclinic system, resulting in a different packing configuration. Utilizing these alternative synthetic approaches, the most kinetically and thermodynamically compounds would possibly be isolated. These compounds were characterised by single-crystal X-ray diffraction, FT-IR and UV-vis spectroscopy. Finally, the redox-controlled driven oscillatory template exchange between phosphate (P) and vanadate (V) anions enclosed in an {M18O54(XO4)2} cluster is further investigated using UV-vis spectroscopy as a function of reaction time, showed that more than six complete oscillations interconverting the capsule species present in solution from {P2M18} to {V2M18} were possible, provided that a sufficient concentration of the TEA reducing agent was present in solution. In an effort to investigate the periodicity of the exchange of the phosphate and vanadate anions, time dependent Uv-vis measurements were performed for a period at a range of 170-550 hours. Different experimental conditions were also applied in order to investigate the role of the reducing agent, as well as the effect of other experimental variables on the oscillatory system.