Mapping professional lives: the study of the professionalisation of actors and dancers

This thesis explores the under-theorised and under-mapped area of labour supply within the field of artistic production. It agrees with cultural economists that the neoclassical economic theoretical models used to analyse the behaviour of artistic labour supply are inadequate - hampered by a lack of differentiated understanding of the employment modes, transactional roles and internal market relationships of artistic production. This thesis argues that generating a more powerful dynamic model for artistic labour behaviour depends on factoring in variables associated with work mode and functional role. There is evidence to suggest that artists and in particular, actors and dancers who are the subject of this study, mix a variety of functional roles in a mixed portfolio of entrepreneurial and employed work and the "mix" may change at different points in the career. Moreover, artists make apparently "irrational" work choices which cannot be explained by neo-classical economic theory. The thesis uses an empirical study of the working lives of eight performing artists to investigate the ways in which they act and inter-act within the artistic labour market. It finds that rational work choices are made which balance opportunities for accumulating reputation, investing in expertise, creative engagement and the minimising of financial risk

Transition State Theory: Thermodynamics and Kinetics of Ammonia Production via DFT Functional

The thermodynamics and kinetics of a proposed mechanism for ammonia production from nitrogen and hydrogen gas were analyzed by utilizing transition state theory (TST) and density functional theory (DFT). The enthalpy and entropy for the overall reaction were computed via DFT functionals, PBE0 and B3LYP, and were compared to literature values for the thermodynamics of ammonia production. PBE0 produced an enthalpy and entropy for the overall reaction of -81.32 kJ/mol and -197.75 kJ/mol K with percent errors of -11.5 % and -0.18 %, respectively. In comparison, B3LYP produced an enthalpy and entropy for the overall reaction of -1923.02 kJ/mol and -244.25 kJ/mol K with percent errors of 1990 % and 24 %, respectively. Therefore, the PBE0 functional provided a better approximation to the thermodynamics of ammonia production due to the limitations of B3LYP’s empirical approximations. The approximations of B3LYP considers experimental values for specific systems and geometries; however, if the experimental values do not reflect the proposed geometries in the mechanism, it will not be as accurate. Thus, the forward and reverse rate constants of ammonia production were predicted for each step utilizing the DFT functional PBE0

Towards a dance technique for the secondary school

In recent years the approach to dance in education has undergone considerable change, generating a need to reappraise the role of technique within the educational context. In this thesis it is argued: (1) that when dance is taught as an art form, with a contribution to make to aesthetic education, greater attention must be paid to the technical aspect of performance; (2) that such technical aspects are best taught through the vehicle of an Educational Dance Technique rather than a professional training technique. It is further argued that an educational dance technique would act: (1) as a practical basis for the teaching of performance skills; (2) as a conceptual basis for the comparison of the style characteristics of theatre dance techniques. A core of basic performance skills is identified and proposals are made for teaching strategies appropriate to the eleven to fourteen age range and the fourteen to eighteen age range. Selected techniques, relevant to the major Western Theatre Dance Genres, are examined in order to elicit their style characteristics in terms of action vocabulary and spatial and dynamic qualities. These characteristics are then summarised and appropriate teaching strategies are proposed

Study to determine the rate of kill of anti-leishmanial drugs using a novel bioluminescence-based assay

Leishmaniasis is a neglected tropical disease associated with poverty, deprived socio-economic settings and population displacement, primarily due to conflict. The causative agent are species of Leishmania parasites that are transmitted by sand flies. It is a disease that affects millions every year and manifests into three primary forms; cutaneous, mucocutaneous and visceral leishmaniasis. Each of these forms are extremely debilitating to the everyday life of those living with leishmaniasis. The current drugs used are re-purposed treatments that are far from ideal. Emerging reports of resistance, poor patient cooperation as a result of long treatment regimens and highly toxic side effects are indicative of essential improvements needed.This thesis focuses on using a transgenic Leishmania cell line in a novel bioluminescence-based assay to determine the rate of kill of four current anti-leishmanial drugs: amphotericin B, miltefosine, pentamidine and potassium antimonyl tartrate. This axenic in vitro assay is studied to address the pharmacodynamic gap in the early drug discovery process and to evaluate the use of a novel technique and its potential in the development of more dynamic and predictive assays. At 3-fold the EC50 concentration, amphotericin B had completely eliminated all viable parasites within 4 hours, demonstrating that it is a fast-acting drug. Miltefosine on the other hand, failed to reduce total parasite viability after 72-hour exposure and we therefore characterised miltefosine as slow-acting. Pentamidine and potassium antimonyl tartrate exhibited an intermediate rate of kill, reaching maximal effect on parasite growth within 72 hours at 9 x the EC50. The bioluminescence-based assay provides a dynamic reporter for parasite viability and exciting potential for fast, sensitive results in early drug screening as shown by the ability to quickly discriminate between fast- and slow- acting compounds. Addressing and identifying this research gap can aid with treatment regimens and dosage improvements of current and novel drug treatments for leishmaniasis

Acetylene hydrochlorination using Au / Carbon: a journey towards single site catalysis

The replacement of mercuric chloride in the production of vinyl chloride monomer, a precursor to PVC, would greatly reduce the environmental impact of this large scale industrial process. The validation of single Au cations supported on carbon as the best catalyst for this reaction at an industrial scale has resulted from nearly 35 years of research. In this feature article we review the development of this catalyst system and address the limitations of a range of characterisation techniques used previously which may induce damage to the fresh catalyst. Following our latest findings using X-ray absorption spectroscopy, we show that under operating conditions the catalyst is atomically dispersed and can be classed as a single site catalyst, we give a perspective on future directions in single atom catalysis

Investigations into the direct synthesis of hydrogen peroxide and CO oxidation using precious metal catalysts

The direct synthesis of hydrogen peroxide from molecular hydrogen and oxygen represents an attractive atom efficient alternative to the current industrial auto-oxidation process which relies on the sequential oxidation and reduction of an anthraquinone. The first and most widely studied catalysts for this reaction were palladium based however over-hydrogenation of the synthesised hydrogen peroxide is a problem. Recent advances demonstrate that the addition of gold to the catalyst has been shown to significantly improve the productivity of the catalysts by suppressing the hydrogenation and decomposition activity. The work in this thesis shows that tin can be used as a catalyst additive as a direct replacement for gold by a simple impregnation method. By tuning the heat treatments of these bimetallic tin-palladium catalysts it was possible to switch off the competing hydrogenation and decomposition reactions. The construction of a small scale flow system has allowed the independent study of reaction variables and the determination of global kinetics and rate constants for the synthesis and subsequent reactions. It was shown that in a flow system it was the decomposition reaction that had a greater limiting effect on the production of hydrogen peroxide than the hydrogenation reaction. A study was also carried out into CO oxidation using gold / iron oxide catalyst prepared in Cardiff and by Prof. Haruta’s group in Tokyo. These catalysts underwent extensive tests to try and identify the active species of the catalyst. Detailed testing and STEM characterisation of the samples identified the possibility of different mechanisms operating at different temperatures and no correlation between the nanoparticle population and activity at sub ambient temperature could be made which challenges the hypothesis that nanoparticles are the most active species and that sub nanometer clusters may be the active species at low temperatures

Direct synthesis of hydrogen peroxide in water at ambient temperature

The direct synthesis of hydrogen peroxide (H2O2) from hydrogen and oxygen has been studied using an Au–Pd/TiO2 catalyst. The aim of this study is to understand the balance of synthesis and sequential degradation reactions using an aqueous, stabilizer-free solvent at ambient temperature. The effects of the reaction conditions on the productivity of H2O2 formation and the undesirable hydrogenation and decomposition reactions are investigated. Reaction temperature, solvent composition and reaction time have been studied and indicate that when using water as the solvent the H2O2 decomposition reaction is the predominant degradation pathway, which provides new challenges for catalyst design, which has previously focused on minimizing the subsequent hydrogenation reaction. This is of importance for the application of this catalytic approach for water purification

The effect of polymer addition on base catalysed glycerol oxidation using gold and gold-palladium bimetallic catalysts

The oxidation of glycerol represents both a viable route to catalytic upgrading of biomass and has become a model reaction for catalytic polyol oxidation. Gold and gold–palladium nanoparticle catalysts prepared by colloidal methods involving polymer additives have been extensively studied. However, the effect of residual polymer at the catalyst surface on reaction pathways has not been decoupled from particle size effects. We show that when using catalysts prepared without polymer stabilisers the addition of either polyvinyl alcohol or polyvinylpyrrolidone to the reaction changes the reaction rate and results in a change in reaction selectivity. We conclude that the polymer additive has a significant effect on the reaction pathway and that these systems should be considered as a metal surface–polymer interface catalytic systems and properties should not be rationalised solely based on nanoparticle size

Plasmonic oxidation of glycerol using AuPd/TiO₂ catalysts

AuPd nanoparticles supported on P25 TiO2 (AuPd/TiO2) were prepared by a facile sol-immobilisation method and investigated for surface plasmon-assisted glycerol oxidation under base-free conditions. The AuPd/TiO2 samples were characterized by UV-vis spectroscopy and transmission electron microscopy. The sol-immobilisation method readily permitted the Au : Pd molar ratio to be changed over a wide range whilst keeping the mean particle size of the AuPd nanoparticles at 3 nm. Visible light irradiation during the reaction has a beneficial effect on the conversion of glycerol with the most marked effect being observed with gold-rich catalysts and the increase of conversion on light irradiation increases linearly with the gold content of the nanoparticles. The reaction selectivity is also affected by the plasmon-assisted oxidation and glycolic acid, not observed during the dark reactions, was observed for all illuminated reactions due to the enhanced activity of these catalysts

Gas-Phase Deposition of Gold Nanoclusters to Produce Heterogeneous Glycerol Oxidation Catalysts

Gold nanoparticles prepared by colloidal methods are effective catalysts for selective glycerol oxidation under basic conditions. Large-scale synthesis of catalysts by wet chemical methods leads to large amounts of waste and can result in polymer or salt residues remaining on the catalyst. In contrast, gas-phase cluster deposition (cluster beam deposition) offers a solvent-free method to synthesize controlled nanoparticles/clusters. We show that the deposition of bare gas-phase gold clusters onto carbon powder leads to a catalyst comparable to that prepared by colloidal methods. This shows the feasibility of the synthesis method to produce oxidation catalysts with reduced waste