Synthesis and evaluation of novel ligands for quantum dot stabilisation and polymerisation studies

This thesis describes the design and synthesis of a variety of functionalised phosphine oxides and sulfides, based on the structure of trioctylphosphine oxide, synthesised for the purpose of surface modification of quantum dots. The ability of the ligands to modify the surface chemistry via displacement of the original hexadecylamine capping layer of quantum dots was evaluated. Finally the surface modified quantum dots were investigated for enhancement in their inherent properties and improved compatibility with the various applications for which they were initially designed. Upon the commencement of research involving quantum dots it became apparent that more information on their behaviour and interaction with the environment was required. The limits of the inherent stability of hexadecylamine capped quantum dots were investigated by exposure to a number of different environments. The effect upon the stability of the quantum dots was monitored by changes in the photoluminescence ability of their cores. Subtle differences between different batches of quantum dots were observed and the necessity to account for these in future applications noted. Lastly the displacement of the original hexadecylamine coating with the "designer" functionalised ligands was evaluated to produce a set of conditions that would result in the best possible surface modification. A general procedure was elucidated however it was discovered that each displacement still required slight adjustment by consideration of the other factors such as the difference in ligand structure and the individuality of the various batches of quantum dots. This thesis also describes a procedure for the addition of a protective layer to the surface of quantum dots by cross-linking the functionalised ligands bound to the surface via an acyclic diene metathesis polymerisation. A detailed description of the problems encountered in the analysis of these materials combined with the use of novel techniques such as diffusion ordered spectroscopy is provided as a means to overcome the limitations encountered. Finally a demonstration of the superior stability, upon exposure to a range of aggressive environments of these protected materials compared with those before cross-linking provided physical proof of the cross-linking process and the advantages of the cross-linking modification. Finally this thesis includes the presentation of initial work into the production of luminescent nanocrystal encoded resin beads for the specific use in solid phase combinatorial chemistry. Demonstration of the successful covalent incorporation of quantum dots into the polymeric matrices of non-functionalised and functionalised resin beads is described. Finally by preliminary work to address and overcome the possible limitations that may be encountered in the production and general employment of these materials in combinatorial techniques is given.

Studies on the generalisation of Gaussian processes and Bayesian neural networks

The assessment of the reliability of systems which learn from data is a key issue to investigate thoroughly before the actual application of information processing techniques to real-world problems. Over the recent years Gaussian processes and Bayesian neural networks have come to the fore and in this thesis their generalisation capabilities are analysed from theoretical and empirical perspectives. Upper and lower bounds on the learning curve of Gaussian processes are investigated in order to estimate the amount of data required to guarantee a certain level of generalisation performance. In this thesis we analyse the effects on the bounds and the learning curve induced by the smoothness of stochastic processes described by four different covariance functions. We also explain the early, linearly-decreasing behaviour of the curves and we investigate the asymptotic behaviour of the upper bounds. The effect of the noise and the characteristic lengthscale of the stochastic process on the tightness of the bounds are also discussed. The analysis is supported by several numerical simulations. The generalisation error of a Gaussian process is affected by the dimension of the input vector and may be decreased by input-variable reduction techniques. In conventional approaches to Gaussian process regression, the positive definite matrix estimating the distance between input points is often taken diagonal. In this thesis we show that a general distance matrix is able to estimate the effective dimensionality of the regression problem as well as to discover the linear transformation from the manifest variables to the hidden-feature space, with a significant reduction of the input dimension. Numerical simulations confirm the significant superiority of the general distance matrix with respect to the diagonal one.In the thesis we also present an empirical investigation of the generalisation errors of neural networks trained by two Bayesian algorithms, the Markov Chain Monte Carlo method and the evidence framework; the neural networks have been trained on the task of labelling segmented outdoor images.

Resonance studies of artificial earth satellites

Orbit determination from artificial satellite observations is a key process in obtaining information about the Earth and its environment. A study of the perturbations experienced by these satellites enables knowledge to be gained of the upper atmosphere, the gravity field, ocean tides, solid-Earth tides and solar radiation. The gravity field is expressed as a double infinite series of associated Legendre functions (tesseral harmonics). In contemporary global gravity field models the overall geoid is well determined. An independent check on these gravity field harmonics of a particular order may be made by analysis of satellites that pass through resonance of that order. For such satellites the perturbations of the orbital elements close to resonance are analysed to derive lumped harmonic coefficients. The orbital parameters of 1984-106A have been determined at 43 epochs, during which time the satellite was close to 14th order resonance. Analysis of the inclination and eccentricity yielded 6 lumped harmonic coefficients of order 14 whilst analysis of the mean motion yielded additional pairs of lumped harmonics of orders 14, 28 and 42, with the 14th order harmonics superseding those obtained from analysis of the inclination. This thesis concentrates in detail on the theoretical changes of a near-circular satellite orbit perturbed by the Earth's gravity field under the influence of minimal air-drag whilst in resonance with the Earth. The satellite 1984-106A experienced the interesting property of being temporarily trapped with respect to a secondary resonance parameter due to the low air-drag in 1987. This prompted the theoretical investigation of such a phenomenon. Expressions obtained for the resonance parameter led to the determination of 8 lumped harmonic coefficients, coincidental to those already obtained. All the derived lumped harmonic values arc used to test the accuracy of contemporary gravity field models and the underlying theory in this thesis.

The evaluation of information systems in the organisational context of the National Health Service. Available in 2 volumes.

This thesis describes a project which has investigated the evaluation of information systems. The work took place in, and is related to, a specific organisational context, that of the National Health Service (NHS). It aims to increase understanding of the evaluation which takes place in the service and the way in which this is affected by the NHS environment. It also investigates the issues which surround some important types of evaluation and their use in this context. The first stage of the project was a postal survey in which respondents were asked to describe the evaluation which took place in their authorities and to give their opinions about it. This was used to give an overview of the practice of IS evaluation in the NHS and to identify its uses and the problems experienced. Three important types of evaluation were then examined in more detail by means of action research studies. One of these dealt with the selection and purchase of a large hospital information system. The study took the form of an evaluation of the procurement process, and examined the methods used and the influence of organisational factors. The other studies are concerned with post-implementation evaluation, and examine the choice of an evaluation approach as well as its application. One was an evaluation of a community health system which had been operational for some time but was of doubtful value, and suffered from a number of problems. The situation was explored by means of a study of the costs and benefits of the system. The remaining study was the initial review of a system which was used in the administration of a Breast Screening Service. The service itself was also newly operational and the relationship between the service and the system was of interest.

Strategic information systems at the Colombian President's Office (1990-1992) : a managerial cybernetic approach

This research studies the issue of using strategic information technology for improving organisational effectiveness. It analyses different academic approaches explaining the nature of information systems and the need organisations feel of developing strategic information systems planning processes, to improve organisational effectiveness. It chooses Managerial Cybernetics as the theoretical foundation supporting development of a "Strategic Information Systems Planning" Framework, and uses it for supporting the analysis of a documented story about the process lived by the Colombian President's Office, in 1990-1992. It argues that by analysing the situation through this new analysis framework we may enlighten some previously unclear situations lived, and not yet properly explained through other approaches to strategic information systems planning. The documented history explains the organisational context and strategic postures of the Colombian President's Office and the Colombian Public Sector, at that time, as well as some of the strategic information systems defined and developed. In particular it analyses a system developed jointly by the President's Office and the National Planning Department, for measuring results of the main national development programmes. Then, it reviews these situations, in the light of the new framework and presents the main findings of the exercise. Finally, it analyses the whole research exercise, the perceived usefulness of the chosen frameworks and tools to enlighten the real situations analysed that were not clear enough, and some open research paths to follow for future researchers interested in the issue.

Understanding accountants' participation in accounting information systems implementation : Malaysian evidence

The study is a two-part study starting with a nationwide survey in the private sector. The hypotheses derived from the Western literature were not significantly supported when the results were analyzed. It seems that the existing literature related to the phenomenon under investigation is mainly Anglo-Saxon culture oriented which is different from the Malaysian culture where the study was conducted. However, access barriers to private sector organizations shifted the focus of the research to the second part of the study that examined the issues in detail in four public sector organizations currently implementing accounting information systems – two hospitals and two universities. In the second part of the main study, the researcher developed formal and substantive propositions from the qualitative interviews which were substantiated using a cross-case analysis; as a result, a model for accountants’ participation in AIS implementation is proposed. The research shows that the process of influencing accountants to participate in AIS implementation is more complex than the literature suggests. There were many issues that surfaced during the case studies, such as conflict and empowerment which set a foundation for further research about how participation can be secured to help make the implementation of AIS part of an organizational agenda success.

Studies of recognition and selectivity by fluorescent polymers imprinted with N1-benzylidene pyridine-2-carboxamidrazones

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

The application of monolayer studies in the understanding of liposomal formulations

The study of surfactant monolayers is certainly not a new technique, but the application of monolayer studies to elucidate controlling factors in liposome design remains an underutilised resource. Using a Langmuir-Blodgett trough, pure and mixed lipid monolayers can be investigated, both for their interactions within the monolayer, and for interfacial interactions with drugs in the aqueous sub-phase. Despite these monolayers effectively being only half a bilayer, with a flat rather than curved structure, information from these studies can be effectively translated into liposomal systems. Here we outline the background, general protocols and application of Langmuir studies with a focus on their application in liposomal systems. A range of case studies are discussed which show how the system can be used to support its application in the development of liposome drug delivery. Examples include investigations into the effect of cholesterol within the liposome bilayer, understanding effective lipid packaging within the bilayer to promote water soluble and poorly soluble drug retention, the effect of alkyl chain length on lipid packaging, and drug-monolayer electrostatic interactions that promote bilayer repackaging.

Surface studies in ultra high vacuum

An ultra high vacuum system capable of attaining pressures of 10-12 mm Hg was used for thermal desorption experiments. The metal chosen for these experiments was tantalum because of its suitability for thermal desorption experiments and because relatively little work has been done using this metal. The gases investigated were carbon monoxide, hydrogen and ethylene. The kinetic and thermodynamic parameters relating to the desorption reaction were calculated and the values obtained related to the reaction on the surface. The thermal desorption reaction was not capable of supplying all the information necessary to form a complete picture of the desorption reaction. Further information was obtained by using a quadrupole mass spectrometer to analyse the desorbed species. The identification of the desorbed species combined with the value of the desorption parameters meant that possible adatom structures could be postulated. A combination of these two techniques proved to be a very powerful tool when investigating gas-metal surface reactions and gave realistic values for the measured parameters such as the surface coverage, order of reaction, the activation energy and pre-exponential function for desorption. Electron microscopy and X-ray diffraction were also used to investigate the effect of the gases on the metal surface.

Studies in the handling and absorption of biopterin derivatives in man

DUE TO COPYRIGHT RESTRICTIONS ONLY AVAILABLE FOR CONSULTATION AT ASTON UNIVERSITY LIBRARY AND INFORMATION SERVICES WITH PRIOR ARRANGEMENT

Surface coating deterioration studies

This project is concerned with the deterioration of surface coatings as a result of weathering and exposure to a pollutant gas (in this case nitric oxide). Poly(vinyl chloride) (PVC) plastisol surface coatings have been exposed to natural and artificial weathering and a comparison of the effects of these two types of weathering has been made by use of various analytical techniques. These techniques have each been assessed as to their value in providing information regarding changes taking place in the coatings during ageing, and include, goniophotometry, micro-penetrometry, surface energy measurements, weight loss measurements, thermal analysis and scanning electron microscopy. The results of each of these studies have then been combined to show the changes undergone by PVC plastisol surface coatings during ageing and to show the effects which additives to the coatings have on their behaviour and in particular the effects of plasticiser, pigment and uv and thermal stabilisers. Finally a preliminary study of the interaction between five commercial polymers and nitric oxide has been carried out, the polymers being polypropylene, cellulose acetate butyrate, polystyrene, polyethylene terephthalate and polycarbonate. Each of the samples was examined using infra-red spectroscopy in the transmission mode.

Studies of molecular interactions using physical techniques

The investigations described in this thesis concern the molecular interactions between polar solute molecules and various aromatic compounds in solution. Three different physical methods were employed. Nuclear magnetic resonance (n.m.r.) spectroscopy was used to determine the nature and strength of the interactions and the geometry of the transient complexes formed. Cryoscopic studies were used to provide information on the stoichiometry of the complexes. Dielectric constant studies were conducted in an attempt to confirm and supplement the spectroscopic investigations. The systems studied were those between nitromethane, chloroform, acetonitrile (solutes) and various methyl substituted benzenes. In the n.m.r. work the dependence of the solute chemical shift upon the compositions of the solutions was determined. From this the equilibrium quotients (K) for the formation of each complex and the shift induced in the solute proton by the aromatic in the complex were evaluated. The thermodynamic parameters for the interactions were obtained from the determination of K at several temperatures. The stoichiometries of the complexes obtained from cryoscopic studies were found to agree with those deduced from spectroscopic investigations. For most systems it is suggested that only one type of complex, of 1:1 stiochiometry, predominates except that for the acetonitrile-benzene system a 1:2 complex is formed. Two sets of dielectric studies were conducted, the first to show that the nature of the interaction is dipole-induced dipole and the second to calculate K. The equilibrium quotients obtained from spectroscopic and dielectric studies are compared. Time-averaged geometries of the complexes are proposed. The orientation of solute, with respect to the aromatic for the 1:1 complexes, appears to be the one in which the solute lies symmetrically about the aromatic six-fold axis whereas for the 1:2 complex, a sandwich structure is proposed. It is suggested that the complexes are formed through a dipole-induced dipole interaction and steric factors play some part in the complex formation.

A contingency framework for information systems development

This research concerns information systems and information systems development. The thesis describes an approach to information systems development called Multiview. This is a methodology which seeks to combine the strengths of a number of different, existing approaches in a coherent manner. Many of these approaches are radically different in terms of concepts, philosophy, assumptions, methods, techniques and tools. Three case studies are described presenting Multiview 'in action'. The first is used mainly to expose the strengths and weaknesses of an early version of the approach discussed in the thesis. Tools and techniques are described in the thesis which aim to strengthen the approach. Two further case studies are presented to illustrate the use of this second version of Multiview. This is not put forward as an 'ideal methodology' and the case studies expose some of the difficulties and practical problems of information systems work and the use of the methodology. A more contingency based approach to information systems development is advocated using Multiview as a framework rather than a prescriptive tool. Each information systems project and the use of the framework is unique, contingent on the particular problem situation. The skills of different analysts, the backgrounds of users and the situations in which they are constrained to work have always to be taken into account in any project. The realities of the situation will cause departure from the 'ideal methodology' in order to allow for the exigencies of the real world. Multiview can therefore be said to be an approach used to explore the application area in order to develop an information system.

The use of ERS-1 crossovers and TOPEX/Poseidon repeat pass data for global sea surface variability studies

In previous sea-surface variability studies, researchers have failed to utilise the full ERS-1 mission due to the varying orbital characteristics in each mission phase, and most have simply ignored the Ice and Geodetic phases. This project aims to introduce a technique which will allow the straightforward use of all orbital phases, regardless of orbit type. This technique is based upon single satellite crossovers. Unfortunately the ERS-1 orbital height is still poorly resolved (due to higher air drag and stronger gravitational effects) when compared with that of TOPEX/Poseidon (T/P), so to make best use of the ERS-1 crossover data corrections to the ERS-1 orbital heights are calculated by fitting a cubic-spline to dual-crossover residuals with T/P. This correction is validated by comparison of dual satellite crossovers with tide gauge data. The crossover processing technique is validated by comparing the extracted sea-surface variability information with that from T/P repeat pass data. The two data sets are then combined into a single consistent data set for analysis of sea-surface variability patterns. These patterns are simplified by the use of an empirical orthogonal function decomposition which breaks the signals into spatial modes which are then discussed separately. Further studies carried out on these data include an analysis of the characteristics of the annual signal, discussion of evidence for Rossby wave propagation on a global basis, and finally analysis of the evidence for global mean sea level rise.

The geometric correction and registration of airborne line-scanned imagery for temporal thermal studies

This thesis begins by providing a review of techniques for interpreting the thermal response at the earth's surface acquired using remote sensing technology. Historic limitations in the precision with which imagery acquired from airborne platforms can be geometrically corrected and co-registered has meant that relatively little work has been carried out examining the diurnal variation of surface temperature over wide regions. Although emerging remote sensing systems provide the potential to register temporal image data within satisfactory levels of accuracy, this technology is still not widely available and does not address the issue of historic data sets which cannot be rectified using conventional parametric approaches. In overcoming these problems, the second part of this thesis describes the development of an alternative approach for rectifying airborne line-scanned imagery. The underlying assumption that scan lines within the imagery are straight greatly reduces the number of ground control points required to describe the image geometry. Furthermore, the use of pattern matching procedures to identify geometric disparities between raw line-scanned imagery and corresponding aerial photography enables the correction procedure to be almost fully automated. By reconstructing the raw image data on a truly line-by-line basis, it is possible to register the airborne line-scanned imagery to the aerial photography with an average accuracy of better than one pixel. Providing corresponding aerial photography is available, this approach can be applied in the absence of platform altitude information allowing multi-temporal data sets to be corrected and registered.