Volunteering for the Commonwealth Games: what can realist synthesis contribute to health policy making?

The aim of this thesis was to investigate, using the real-time test case of the 2014 Commonwealth Games, whether the realist synthesis methodology could contribute to the making of health policy in a meaningful way. This was done by looking at two distinct research questions: first, whether realist synthesis could contribute new insights to the health policymaking process, and second, whether the 2014 Commonwealth Games volunteer programme was likely to have any significant, measurable, impact on health inequalities experienced by large sections of the host population. The 2014 Commonwealth Games legacy laid out ambitious plans for the event, in which it was anticipated that it would provide explicit opportunities to impact positively on health inequalities. By using realist synthesis to unpick the theories underpinning the volunteer programme, the review identifies the population subgroups for whom the programme was likely to be successful, how this could be achieved and in what contexts. In answer to the first research question, the review found that while realist methods were able to provide a more nuanced exposition of the impacts of the Games volunteer programme on health inequalities than previous traditional reviews had been able to provide, there were several drawbacks to using the method. It was found to be resource-intensive and complex, encouraging the exploration of a much wider set of literatures at the expense of an in-depth grasp of the complexities of those literatures. In answer to the second research question, the review found that the Games were, if anything, likely to exacerbate health inequalities because the programme was designed in such a way that individuals recruited to it were most likely to be those in least need of the additional mental and physical health benefits that Games volunteering was designed to provide. The following thesis details the approach taken to investigate both the realist approach to evidence synthesis and the likelihood that the 2014 Games volunteer programme would yield the expected results.

Towards participatory political theology: democratic consolidation in Southeastern Europe and the role of Eastern Christianity in the process

This thesis defends the position that the Eastern Orthodoxy has the potential to develop, on the basis of its core concepts and doctrines, a new political theology that is participatory, personalist and universalist. This participatory political theology, as I name it, endorses modern democracy and the values of civic engagement. It enhances the process of democracy-building and consolidation in the SEE countries through cultivating the ethos of participation and concern with the common good among and the recognition of the dignity and freedom of the person. This political-theological model is developed while analyzing critically the traditional models of church-state relations (the symphonia model corresponding to the medieval empire and the Christian nation model corresponding to the nation-state) as being instrumentalized to serve the political goals of non-democratic regimes. The participatory political-theological model is seen as corresponding to the conditions of the constitutional democratic state. The research is justified by the fact the Eastern Orthodoxy has been a dominant religiouscultural force in the European South East for centuries, thus playing a significant role in the process of creation of the medieval and modern statehood of the SEE countries. The analysis employs comparative constitutional perspectives on democratic transition and consolidation in the SEE region with the theoretical approaches of political theology and Eastern Orthodox theology. The conceptual basis for the political-theological synthesis is found in the concept and doctrines of the Eastern Orthodoxy (theosis and synergy, ecclesia and Eucharist, conciliarity and catholicity, economy and eschatology) which emphasize the participatory, personalist and communal dimensions of the Orthodox faith and practice. The paradigms of revealing the political-theological potential of these concepts are the Eucharistic ecclesiology and the concept of divine-human communion as defining the body of Orthodox theology. The thesis argues that with its ethos of openness and engagement the participatory political theology presupposes political systems that are democratic, inclusive, and participatory, respecting the rights and the dignity of the person. The political theology developed here calls for a transformation and change of democratic systems towards better realization of their personalist and participatory commitments. In the context of the SEE countries the participatory political theology addresses the challenges posed by alternative authoritarian political theologies practiced in neighboring regions.

Trapping phosphorus (III) into polyoxometalates: synthesis, characterisation and electronic behaviour study

The introduction of electronically-active heteroanions into polyoxometalates (POMs) is one of the emerging topics in this field. The novel clusters have shown unprecedented intramolecular electron-transfer features that can be directly mediated by the incorporated heteroanions. In this thesis, we will focus on the study of phosphite (HPO32-) as new non-traditional heteroanions, discover HPO32- templated nanostructures, investigate their electronic behaviours as well as understand the self-assembly process of HPO32--templated species. The thesis starts with incorporating HPO32- into POM cages. The feasibility of this work was illustrated by the successful trapping of HPO32- into a “Trojan Horse” type {W18O56} nanocage. The reactivity of embedded {HPO3} was fully studied, showing the cluster undergoes a structural rearrangement in solution whereby the {HPO3} moieties dimerise to form a weakly interacting (O3PH···HPO3) moiety. In the crystalline state a temperature-dependent intramolecular redox reaction and structural rearrangement occurs. This rearrangement appears to proceed via an intermediate containing two different templates, a pyramidal {HPO3} and a tetrahedral {PO4} moiety. {HPO3} templated POM cages were then vigorously expanded and led to the isolation of five either fully oxidised or mixed-valence clusters trapped with mono-, di-, or tri- {HPO3}. Interestingly, an intriguing 3D honeycomb-like host-guest structure was also synthesised. The porous framework was self-aggregated by a tri-phopshite anion templated {W21} cluster with a {VO4} templated Wells-Dawson type {W18} acting as a guest species within the hexagonal channels. Based on this work, we further extended the templating anions to two different redox-active heteroanions, and discovered a unique mixed-heteroatom templated system built by pairing redox-active {HPIIIO3} with {TeO3}, {SeO3} or {AsO3}. Two molecular systems were developed, ie. “Trojan Horse” type [W18O56(HPO3)0.8(SeO3)1.2(H2O)2]8- and cross-shaped [H4P4X4W64O224]32-/36-, where X=TeIV, SeIV, AsIII. In the case of {W18(HPO3)0.8(SeO3)1.2}, the compound is found to be a mixture of heteroleptic {W18(HPO3)(SeO3)} and homoleptic {W18(SeO3)2} and {W18(HPO3)2}, identified by single crystal x-ray diffraction, NMR as well as high resolution mass spectrometry. The cluster exhibited similar temperature-dependent electronic features to “Trojan Horse” type {W18(HPO3)2O56}. However, due to the intrinsic reactivity difference between {HPO3} and {SeO3}, the thermal treatment leads to the formation of an unusual species [W18O55(PO4)(SeO3)]5-, in which {HPO3} was fully oxidised to {PO4} within the cage, whereas and lone-pair-containing {SeO3} heteroanions were kept intact inside the shell. This finding is extremely interesting, as it demonstrated that multiple and independent intramolecular electronic performance can be achieved by the coexistence of distinct heteroatoms within a single molecule. On the other hand, the cross-shaped [H4P4X4W64O224]32-/36- were constructed by four {W15(HPO3)(XO3)} building units linked by four {WO6} octahedra. Each building unit traps two different heteroatoms. It is interesting to note that the mixed heteroatom species show self-sorting, with a highly selective positional preference. Smaller ionic sized {HPO3} are self-organised into the uncapped side of {W15} cavity, whereas closed side are occupied by larger heteroatoms, which is surprisingly opposed to steric hindrance. Density functional theory (DFT) calculations are currently underway to have a full understanding of the preference of heteroatom substitutions. This series of clusters is of great interest in terms of achieving single molecule-based heteroatom-dependent multiple levels of electron transfer. It has opened a new way to design and synthesise POMs with higher diversity of electrical states, which may lead to a new type of Q-bits for quantum computing. The third chapter is focused on developing polyoxotungstate building blocks templated by {HPO3}. A series of building blocks, {W15O48(HPO3)2}, {W9O30(HPO3)} {W12O40(HPO3)2} and hexagonal {W6O18(HPO3)} have been obtained. The first four building blocks have been reported with {SeO3} and/or {TeO3} heteroanions. This result demonstrates {HPO3} has a similar reactivity as {SeO3} and {TeO3}, therefore studying the self-assembly of {HPO3}-based building blocks would be helpful to have a general understanding of pyramidal heteroatom-based molecular systems. The hexagonal {W6O18(HPO3)} is observed for the first time in polyoxotungstates, showing some of reactivity difference between {HPO3} and {SeO3} and {TeO3}. Furthermore, inorganic salts and pH values have some directing influence on the formation and transformation of various building blocks, resulting in the discovery of a family of {HPO3}-based clusters with nuclearity ranging from {W29} to {W106}. High resolution mass spectrometry was also carried out to investigate the cluster solution behaviour and also gain information of building block speciation. It is found that some clusters experienced decomposition, which gives rise to potential building blocks accountable for the self-assembly.