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This PhD research investigates the types, implications and origins of constraint within the contexts of various music composition projects. It then presents the practical value of this deeper understanding as a contemporary music composer. To explore the topic of constraint, the doctorate contains a portfolio of original music compositions and a reflective commentary on those compositions. The music spans a wide range of purposes, including works for concert hall, film and videogame. This breadth, across 33 musical works for 17 different projects of both collaborative and independent types, facilitates the extension of our understanding of constraint and its role in the process of music-making. The commentary, focussing on each composition individually or in small groups, extrapolates how constraint emerges within different circumstances. Analysing the music, in tandem with an account of their contextual backgrounds, demonstrates how different constraints influence music composition. The result of this research is that one can start to generalise the creative challenges a contemporary composer faces in the form of constraint. The research does this by proposing a series of labels: intrinsic, extrinsic, functional and aesthetic. These categories emerged through the creative practices of the portfolio, delineating and searching for constraint as a means of grounding creative decisions. The commentary and portfolio, taken together, will offer insights into the four proposed categories of constraint while explicating my compositional practice.

This thesis describes the synthesis of diphenolate and dithiophenolate complexes of ZnII, NiII and CuII that derive inspiration from the natures of the active sites of the nickel-containing superoxide dismutase (NiSOD) and the copper-containing galactose oxidase (GO). Chapter One introduces the roles of transition metals in biology. The structures of the active sites of NiSOD and GO are described, together with a discussion of the proposed mechanisms of their action. A brief review of the coordination chemistry relevant to the chemistry of the actives sites of NiSOD and GO is presented and the aims of the research described in this thesis are set out. Chapter Two describes the syntheses and structural characterisations of a series of pentacoordinate ZnII, NiII and CuII diphenolate complexes MRLoNMe (M= Zn, Ni, Cu; R = Cl, Br, Nap, Ph, PhMe, PhOMe, tBu/Br, tBu/Ph, tBu/PhMe, tBu/PhOMe; page xiii) that differ in the natures of the substituents at the 3- and 5-positions of the phenolate rings within the ligand backbone. X-ray crystallographic studies on the ZnII, NiII and CuII complexes, and room temperature and frozen solution EPR spectroscopic experiments on the CuII complexes provide insight into the influence of the 3- and 5- substitution on the coordination geometries. The changes in substitution at the 3 position of the phenolate rings in MRLoNMe (M= Zn, Ni, Cu; R = tBu/Ph, tBu/PhMe, tBu/PhOMe) have significantly less influence on the geometry about the metal centre when compared to complexes that have substitutions that vary at the 3 and 5 positions in MRLoNMe (M= Zn, Ni, Cu; R = Ph, PhMe, PhOMe). DFT calculations provide a qualitative description of the electronic structures of these complexes, suggesting an increase in the metal character within the HOMOs for the NiII complexes relative to those of their ZnII and CuII counterparts. Chapter Three describes the electrochemical characterisations of the complexes synthesised in Chapter Two [MRLoNMe (M= Zn, Ni, Cu; R = Cl, Br, Nap, Ph, PhMe, PhOMe, tBu/Br, tBu/Ph, tBu/PhMe, tBu/PhOMe)]. Cyclic voltammetry demonstrates that MRLoNMe (M= Zn, Cu; R = Cl, Br, Nap, tBu/Br) possess oxidation processes that are not reversible. MRLoNMe (M= Ni; R = Cl, Br, Nap, tBu/Br) possess a reversible oxidation process assigned to the NiIII/NiII redox couple. MRLoNMe (M= Zn, Ni, Cu; R = Ph, PhMe, PhOMe, tBu/Ph, tBu/PhMe, tBu/PhOMe) display multiple oxidation processes, some of which demonstrate electrochemical reversibility, particularly when M = Ni or Cu. UV/Vis and EPR spectroscopic studies on the oxidised species [MRLoNMe]+ (M= Zn, Ni, Cu; R = Ph, PhMe, PhOMe, tBu/Ph, tBu/PhMe, tBu/PhOMe), supported by DFT calculations, suggest that the first oxidation process is significantly more metal based when M = Ni than for M = Cu or Zn and for the generation of [NiRLoNMe]+ is associated with the formation of formal NiIII species. The UV/vis and EPR spectroscopic results also suggest that [NiPhOMeLoNMe]+ exhibits temperature-dependent NiIII-phenolate  NiII-phenoxyl redox tautomerism. The variation of the aromatic substituents systematically decreases the redox potential in the order R = Ph > PhMe > PhOMe, consistent with the relative electron donor properties of each group. Chapter Four examines complexes that incorporate an aromatic, N-donor group pendant to the ligand background. These complexes serve as analogues of the active site of NiSOD. The dithiophenolate and diphenolate complexes NitBuLSPy, NitBuLSPyOMe, NitBuLOPy, NitBuLOPyOMe, and NitBuLOPh are prepared and characterised to examine the effect of different N-donor groups as potential axial donors to the metal centre on the redox properties of each complex. Advanced pulsed ESSEM and HYSCORE EPR spectroscopic studies probe the weak superhyperfine couplings involving the 14N imine donors in [NitBuLSPy]+, and benchmark the spin densities associated with these donors calculated by DFT. These spectroscopically validated DFT calculations show how the distribution of spin density varies between complexes incorporating an N-donor pendant to the ligand backbone and those that do not. Thus, those incorporating an additional N-donor possess spin density that is considerably more localised at the formal NiIII centre than those that do not. Chapter Five discusses the key conclusions of the research described in this thesis and compares and contrasts the chemistry exhibited by ZnII, NiII and CuII diphenolate and dithiophenolate complexes. The structural and electrochemical differences observed upon the introduction of alternative diphenolate substituents in MRLoNMe (M= Zn, Ni, Cu; R = Cl, Br, Nap, Ph, PhMe, PhOMe, tBu/Br, tBu/Ph, tBu/PhMe, tBu/PhOMe) are summarised, together with the importance of the geometric structure of NitBuLSPy in controlling the redox chemistry of this centre. Finally, implications for the chemistry of the active sites of GO and NiSOD are discussed.

This thesis describes a search for transient phenomena using data from the Wide Angle Search for Planets (WASP) observatories. With images taken of the same region of sky every 15 minutes and a field-of-view of 974 degrees squared, the WASP survey is ideal for identifying both short and long duration transients to a limiting magnitude of 16 in V. A high cadence wide-field survey of this type has not been carried out before so provides a different method of sampling variable populations and has the potential to identify previously unknown phenomena. An algorithm to carry out a full untargeted search of the database was developed, tested and run on data from 2004, 2006, 2007 and 2008. False positives were rejected based on their proximity to similar magnitude stars, the tightness of the clustering of detections in sky coordinates, the focus of the images and the number of corroborating detections. Overall, 44 cataclysmic variable candidates, 144 extreme flare candidates, 63 variable star candidates and 57 transients of unknown type were identified. The cataclysmic variable candidates showed similarities to the currently known population although some selection effects were uncovered. Of particular note were two new WZ Sge systems, an eclipsing system with a period of 540 minutes and an object with an M-star spectrum and broad Balmer lines but no visible white dwarf. The flares are some of the largest ever observed on M-type stars. The largest of these released ~1035erg in the V-band alone. A candidate flare was also identified on a G-type star releasing 1.6×1037erg in the V-band. Alternatively, it may be unrelated to the G-star and could be a gamma ray burst or similar transient without a persistent counterpart. A known supernova and two known novae were also identified.

Managers today are faced with a bewildering choice of Management Standards that are being promoted to improve personal and organisational performance by a wide range of Standards-setting bodies. Standards-based management is a well-researched field, but all the research concentrates on individual Standards such as ISO 9000 and 14000 without identifying the influences of other Management Standards. This research seeks to extend the debate about Standards-based management and to encourage other researchers to consider it as both an entity and a phenomenon and to note its divergence from other management theories. A taxonomy of Management Standards is presented to enable the principal Standards to be categorised and a definition of a Management Standard is proposed to enable the distillation of the considerable body of literature into more manageable proportions. A chronology of Management Standards development is tabled and compared with the evolution of Quality Management and Total Quality Management (TQM) and the possible future development of Management Standards is examined. The literature research confirmed that Standards-based management approaches had increased very significantly, despite a lack of empirical research to show that this method of management yielded uniform improvements. It identified a trend for integrating Management Standards and creating a “super” Management Standard that would incorporate all the functions of management within an organisation. The Scottish Quality Management System (SQMS) is an integrated Management Standard that incorporates many of the key functions of management within an audited Management Standards framework that its architects claim is based on the principles of TQM. While originally developed for the Scottish training provider network in 1993, it has spread internationally and is currently in use by circa 600 organisations in several countries. It is the only example of a Management Standard of this kind, and despite its longevity, extensive coverage and significant public investment, it has not attracted any previous research interest. The SQMS project was ambitious, seeking to impose a major new Standard on a diverse and predominately unsophisticated population of organisations within a tight time frame. The field research surveyed the entire SQMS registered organisation population using a questionnaire that was based upon the principles of ISO 9004: 1994 and some preliminary research. The questionnaire was designed to examine attitudes and motivation, as well as gauging the effectiveness of the SQMS Standard as determined by an analysis of the improvements that could be directly associated with its implementation. The survey achieved over 70% response rate and the resulting data set was comprehensive and the analysis robust. An additional element of the research compared the results of the questionnaire response analysis with the perceptions of the SQMS Auditors who had audited a majority of the respondent organisations. The field research showed that the SQMS population was very experienced and had been working with SQMS for well over three years. This is a period that the literature research indicated was the minimum time required for the benefits of quality improvement initiatives to become measurable. In the absence of any clear published objectives for the implementation of SQMS, a number of likely objectives were postulated and these objectives were measured against the results of the research. The results of the research suggest an attitude of compliance, rather than improvement as the underlying mind-set of the SQMS organisations and an absence of quality improvement planning or measurement of key performance indicators. This attitude was no different among organisations that had also adopted ISO 9000 and IiP. SQMS accreditation had not shown to provide any marketing or promotional benefit in the same way as ISO 9000 and it had not led to increased market share or profitability. Few of the possible benefits of applying a Standard of this nature had been realised by the majority of organisations and there was little evidence of tangible organisational improvement. The Standard could not be deemed to have met its proposed objectives and a comparison with an accepted model of TQM did not find sufficient compatibility to designate SQMS as a tool for TQM implementation. The interviews with SQMS Auditors identified major discrepancies between their perceptions and the views of the organisations that they audited. The admission by over half of the respondent organisations that they produced evidence purely to satisfy audits raised questions about the effectiveness of the Standard and its audits and the competence of auditors to audit “super” Standards. The novelty of the research is examined and suggestions for future research proposed.

The purpose of the present study was to document the fine structural distribution of collagen types I-VI and laminin in various human ocular tissues (cornea, trabecular meshwork, iris, ciliary body, lens capsule and retinal vessels) and relate their distribution to the functional requirements of each tissue. Twenty-three human eyes (aged 43-82) were suitably prepared for immunocytochemistry. The distribution of the extracellular matrix components studied was determined using the immunogold technique on ultrathin frozen and LR white sections. Two different preparative techniques were employed to consolidate results. Perhaps the most surprising finding among the many features of great interest, was the presence of type I collagen in all of the vascular basement membranes studied. Other interesting features included the interfibrillar location of type VI collagen in cornea, meshwork and retinal vasculature, the presence of collagens V and VI in corneal keratocyte bodies, and the association of collagen VI and laminin with the corneal basement membrane complex. the identification of collagen IV and laminin in extracellular matrix deposits in the cribriform layer was also of interest as was the association of laminin with linear deposits in the lens capsule and increased labelling of types I and IV collagen associated with pericytes in retinal capillaries. The presence of the components studied could be related to the functional demands of each tissue.