Structural studies in tellurium chemistry

The primary theme of this research was the characterisation of new and novel organo-tellurium complexes, using the technique of single crystal X-ray analysis to establish more firmly the various coordination modes of tellurium. In each study the unit cell dimensions and intensity data were collected using an Enraf-Nonius CAD-4, four circle diffractometer. The raw data collected in turn was transferred to the Birmingham University Honeywell Multics System and processed using the appropriate computer packages for the determination of crystal structures. The molecular and crystal structures of: bis[2-(2-pyridyl)phenyl]tritelluride, bis[2-(N-hydroxy)iminophenyl] ditelluride, 2-(2-pyridyl)phenyltellurium(IV) tribromide, (2-N,N-dimethylbenzylamine-C,N')tellurium(IV)tribromide, 2-dichloro(butyl)tellurobenzaldehyde, 2-dichlorobutotelluro-N-dimethylbenzyl ammonium chloride, dimethyldithiocarbamato[2-(2-pyridyl)phenyl]tellurium(II), dimethyldithiocarbamato[2-(2-quinolinyl)phenyl]tellurium(II) and para-ethoxypheny[2-(2-pyridyl)phenyl]telluride are described. In each structure, the Lewis acidity of tellurium appears to be satisfied by autocomplex formation, through short-range intramolecular secondary bonds between tellurium and an electron denoting species, (generally nitrogen in these structures) with long range weak inter molecular contacts forming in the majority of the tellurium(IV) structures. The order of Lewis acidity in each structure can be considered to be reflected by the length of the short range intramolecular secondary bond, identified, that is, when tellurium has a low Lewis acidity this interaction is long. Interestingly, no primary bonds are found trans to a Te-C covalent bond in any of the above structures, highlighting the strong trans effect of aromatic and aryl groups in tellurium complexes.

Sociolinguistic variability in oral narrative.

This thesis begins with a sociolinguistic correlational study of three phonetic variables - (h), (t) and (ing) - as used by four occupational groups - nurses, chefs, hairdressers and taxi-drivers. The groups were selected to incorporate three independent variables: sex (male-dominated versus female-dominated occupations); training (length and specialisation - nurses and chefs being more specialised than hairdressers and taxi-drivers) and location (the populations were selected from two cities - Liverpool and Birmingham). Although the correlational work demonstrates intra-sex and occupation consistency in speakers' choice of linguistic variants (females (particularly nurses) being significantly closer to the prestige norm), it is essentially non-explanatory and cannot accout for narrative dynamics and style shift. Therefore, an in-depth qualitative examination of the data (which draws mainly on Narrative and Discourse Analysis) forms the major part of the analysis. The study first analyses features common to all the narratives, direct speech, expressive phonology and linguistic ambiguity emerging as characteristic of all humorous storytelling. Secondly, three major sources of inter-personal variation are invetigated: narrator perspective, sex and occuptational role. Perspective is found to vary with topic and personality, greater narrator involvement coinciding with a higher proportion of internal evaluation devices. Sex differences include topic choice and bonding in the storytelling sessions. Sex differences are also evident in style shifting, where the narrator mimics the voice of a character in the narrative (aodpting segmental and/or prosodic tokens to signal a change of persona). The research finds that female narrators rarely employ segmental accommodation downwards on the social scale (whereas men do), but are on the other hand adept at using prosodic effects for mimicry. Taxi-drivers emerge as the group with the most distinctive narrative flair, a fact which is related to their occupation. The conclusion stresses a need for both quantitative and qualitative approaches to data; the importance of occupational role, as opposed to sex role per se in determining narrative conventions; the view of narrative as a negotiable entity, which is the product of relationships among participants; and the importance of considering the totality of the communicative act.

Radioimmunoassay of insulin and glucagon with studies on the obese hyperglycaemic syndrome in mice

Sensitive and precise radioimmunoassays for insulin and glucagon have been established. Although it was possible to employ similar precepts to the development of both hormone assays, the establishment of a reliable glucagon radioimmunoassay was complicated by the poor immunogenicity and instability of the peptide. Thus, unlike insulin antisera which were prepared by monthly injection of guinea pigs with crystalline insulin emulsified in adjuvant, the successful production of glucagon antisera was accomplished by immunisation of rabbits and guinea pigs with glucagon covalently linked to bovine plasma albumin. The conventional chloramine-T iodination with purification by gel chromatography was only suitable for the production of labelled insulin. Quality tracer for use in the glucagon radioimmunoassay was prepared by trace iodination, with subsequent purification of monoiodinated glucagon by anion exchange chromatography. Separation of free and antibody bound moieties by coated charcoal was applicable to both hormone assays, and a computerised data processing system, relying on logit-log transformation, was used to analyse all assay results. The assays were employed to evaluate the regulation of endocrine pancreatic function and the role of insulin and glucagon in the pathogenesis of the obese hyperglycaemic syndrome in mice. In the homozygous (ob/ob) condition, mice of the Birmingham strain were characterised by numerous abnormalities of glucose homeostasis, several of which were detected in heterozygous (ob/+) mice. Obese mice exhibited pancreatic alpha cell dysfunction and hyperglucagonaemia. Investigation of this defect revealed a marked insensitivity of an insulin dependent glucose sensing mechanism that inhibited glucagon secretion. Although circulating glucagon was of minor importance in the maintenance of hyperinsulinaemia, lack of suppression of alpha cell function by glucose and insulin contributed significantly to both the insulin insensitivity and the hyperglycaemia of obese mice.

Elastic and inelastic scattering of fast neutrons in fusion reactor materials

In this work, the angular distributions for elastic and. inelastic scattering of fast neutrons in fusion .reactor materials have been studied. Lithium and lead material are likely to be common components of fusion reactor wall configuration design. The measurements were performed using an associated particle time-of- flight technique. The 14 and 14.44 Mev neutrons were produced by the T(d,n} 4He reaction with deuterons being accelerated in a 150kev SAMES type J accelerator at ASTON and in.the 3. Mev DYNAMITRON at the Joint Radiation Centre, Birmingham respectively. The associated alpha-particles and fast. neutrons were detected.by means of a plastic scintillator mounted on a fast focused photomultiplier tube. The samples used were extended flat plates of thicknesses up to 0.9 mean-free-path for Lithium and 1.562 mean-free-path for Lead. The differential elastic scattering cross-sections were measured for 14 Mev neutrons for various thicknesses of Lithium and Lead in the angular range from zero to; 90º. In addition, the angular distributions of elastically scattered 14,.44 Mev .neutrons from Lithium samples were studied in the same angular range. Inelastic scattering to the 4.63 Mev state in 7Li and the 2.6 Mev state, and 4.1 Mev state in 208Pb have:been :measured.The results are compared to ENDF/B-IV data files and to previous measurements. For the Lead samples the differential neutron scattering:cross-sections for discrete 3 Mev ranges and the angular distributions were measured. The increase in effective cross-section due to multiple scattering effects,as the sample thickness increased:was found to be predicted by the empirical .relation ....... A good fit to the exoerimental data was obtained using the universal constant............ The differential elastic scattering cross-section data for thin samples of Lithium and Lead were analyzed in terms of optical model calculations using the. computer code. RAROMP. Parameter search procedures produced good fits to the·cross-sections. For the case of thick samples of Lithium and Lead, the measured angular distributions of :the scattered neutrons were compared to the predictions of the continuous slowing down model.

Pupil resistance to their schooling experience

The thesis explores the nature of pupil resistance; it investigates what constitutes it and how it can be explained. Various ethnic and national group, male and female working-class resistance if analysed in two secondary schools in Birmingham (England) and one school in Sydney (Australia). It focuses on the pupils’ experience of school. ‘Compressed ethnographies’ (Walford and Miller, 1991) were conducted in each school to examine pupil resistance. The research found that structural societal state factors, regional, community and formal, informal and physical characteristics of each school, together with the teachers and pupils characteristics and background all influence resistance. The class, gender, ethnic and national identity of each pupil shapes resistance. In all three schools that were involved with the research, girls were more likely to exhibit overt, collective forms of resistance, whereas lads were more likely to operate alone. Islander pupils in Sydney and African-Caribbean kids in Birmingham were more likely to display engaged forms of resistance. Girls tended to show more engaged forms compared to their male counterparts across all ethnic and national cultures. Resistance is complex and dynamic, the definition alters depending upon context. Dimensions of resistance are developed; including overt, covert; individual, collective; intentional, unintentional; engaged and detached forms. Resistance operates within a structure and agency framework, the pupils can shape their own schooling experience mediated within the structures of their school, community and society. Some pupils manage their resources and the structures better than others; how the pupil manages and operates within the structures influences their resistance response. Resistance is contradictory and can reinforce the status quo. To fully understand resistance, it must be contextualised.

How SME owners’ characteristics influences external advice and access to finance

This paper aims to investigate the linkage between the use of external advice and access to finance for small and medium-sized enterprises (SMEs) in the UK, with particular consideration of differences in personal characteristics: gender, ethnicity and education. The approach adopted for the research is a telephone survey conducted by the Barclays small business research team in late 2005 on behalf of the authors. These data are quantitative in nature and involve a large sample of 400 SMEs with specific questions analysed by gender, ethnicity and education level. The approach adopted is robust and empirically sound and is a long established research methodology. We find that there appears to be a correlation between the provision of external advice and the ability to raise bank finance. Furthermore, there are clear gender, ethnic and educational differentials in the use of particular sources of advice, for example: Gender • men and women are equally likely to use accountants as sources of advice. • men are more likely to use family and friends and solicitors. • women, however, are around twice as likely to access external advice from Business Link and Enterprise Agencies. Ethnicity • family and friends is predominant amongst Asians or black respondents and the other ethnic group, which is also slightly true of accountants and solicitors. • ethnic minority respondents were considerably less likely to use Business Link/ Enterprise Agencies. Education • graduates are most likely to use solicitors and accountants, whilst they are very low users of advice from family and friends and Business Links/Enterprise Agencies. • O level and A level educated respondents predominate in family and friends and Business Link/ Enterprise Agencies.

A study of potential serum markers for a diagnosis of gram-positive and gram-negative bacterial sepsis

Sepsis continues to be a major cause of morbidity and mortality as it can readily lead tosevere sepsis, septic shock, multiple organ failure and death. The onset can be rapid and difficult to define clinically. Despite the numerous candidate markers proposed in the literature, to date a serum marker for sepsis has not been found. The aim of this study was to assay the serum of clinically diagnosed patients with eithera Gram-negative or Gram- positive bacterial sepsis for elevated levels of nine potentialmarkers of sepsis, using commercially produced enzyme linked immunosorbent assays(ELISA). The purpose was to find a test marker for sepsis that would be helpful toclinicians in cases of uncertain sepsis and consequently expose false positive BC'scaused by skin or environmental contaminants. Nine test markers were assayed including IL-6, IL-I 0, ILI2, TNF-α, lipopolysaccharide binding protein, procalcitonin, sE-selectin, sICAM -1 and a potential differential marker for Gram-positive sepsis- anti-lipid S antibody. A total of 445 patients were enrolled into this study from the Queen Elizabeth Hospital and Selly Oak Hospital (Birmingham). The results showed that all the markers were elevated in patients with sepsis and that patients with a Gram-negative sepsis consistently produced higher median/range serum levels than those with a Gram-positive sepsis. No single marker was able to identify all the septic patients. Combining two markers caused the sensitivities and specificities for a diagnosis of sepsis to increase to within a 90% to 100% range. By a process of elimination the markers that survived into the last phase were IL-6 with sICAM -1, and anti-lipid S IgG assays Defining cut-off levels for a diagnosis of sepsis became problematic and a semi-blind trial was devised to test the markers in the absence of both clinical details and positive blood cultures. Patients with pyrexia of unknown origin and negative BC were included in this phase (4). The results showed that IL-6 with sICAM-l are authentic markers of sepsis. There was 82% agreement between the test marker diagnosis and the clinical diagnosis for sepsis in patients with a Gram-positive BC and 78% agreement in cases of Gram-negative Be. In the PUO group the test markers identified 12 cases of sepsis and the clinical diagnosis 15. The markers were shown to differentiate between early sepsis and sepsis, inflammatory responses and infection. Anti-lipid S with IL-6 proved be a sensitive marker for Gram-positive infections/sepsis.

Variable impedance bearings for large rotating machinery

This thesis describes an investigation which was carried out under the Interdisciplinary Higher Degres (IHD) Scheme of The University of Aston in Birmingham. The investigation, which involved joint collaboration between the IHD scheme, the Department of Mechanical Engineering, and G.E.C. Turbine Generators Limited, was concerned with hydrostatic bearing characteristics and of how hydrostatic bearings could be used to enable turbine generator rotor support impedances to be controlled to give an improved rotor dynamic response. Turbine generator rotor critical speeds are determined not only by the mass and flexibility of the rotor itself, which are relatively easily predicted, but also by the dynamic characteristics of the bearing oil film, pedestal, and foundations. It is because of the difficulty in accurately predicting the rotor support characteristics that the designer has a problem in ensuring that a rotor's normal running speed is not close to one of its critical speeds. The consequence of this situation is that some rotors do have critical speeds close to their normal running speed and the resulting high levels of vibration cause noise, high rotor stresses, and a shortening of bearing life. A combined theoretical and experimental investigation of the effects of mounting the normal rotor journal bearing in a hydrostatic bearing was carried out. The purpose of the work was to show that by changing the oil flow resistance offered by capillaries connecting accumulators to the hydrostatic bearing, the overall rotor support characteristics could be tuned to enable rotor critical speeds to be moved at will. Testing of a combined journal and hydrostatic bearing has confirmed the theory of its operation and a theoretical study of a full size machine showed that its critical speed could be moved by over 350 rpm and that its rotor vibration at running speed could be reduced by 80%.

Heat transfer from molten materials to liquids

An apparatus was designed and constructed which enabled material to be melted and heated to a maximum temperature of 1000C and then flooded with a pre-heated liquid. A series of experiments to investigate the thermal interaction between molten metals (aluminium, lead and tin) and sub-cooled water were conducted. The cooling rates of the molten materials under conditions of flooding were measured with a high speed-thermocouple and recorded with a transient recorder. A simplified model for calculating heat fluxes and metal surface temperatures was developed and used. Experimental results yielded boiling heat transfer in the transition film and stable film regions of the classic boiling curve. Maximum and minimum heat fluxes were observed at nucleate boiling crisis and the Leidenfrost point respectively. Results indicate that heat transfer from molten metals to sub-cooled water is a function of temperature and coolant depth and not a direct function of the physical properties of the metals. Heat transfer in the unstable transition film boiling region suggests that boiling dynamics in this region where a stationary molten metal is under pool boiling conditions at atmospheric pressure would not initiate a fuel-coolant interaction. Low heat fluxes around the Leidenfrost point would provide efficient fuel-coolant decoupling by a stable vapour blanket to enable coarse mixing of the fuel and coolant to occur without appreciable loss of thermal energy from the fuel. The research was conducted by Gareph Boxley and was submitted for the degree of PhD at the University of Aston in Birmingham in 1980.

Studies of solar radiation and its measurement

A mathematical model has been developed for predicting the spectral distribution of solar radiation incident on a horizontal surface. The solar spectrum in the wavelength range 0.29 to 4.0 micrometers has been divided in 144 intervals. Two variables in the model are the atmospheric water vapour content and atmospheric turbidity. After allowing for absorption and scattering in the atmosphere, the spectral intensity of direct and diffuse components of radiation are computed. When the predicted radiation levels are compared with the measured values for the total radiation and the values with glass filters RG715, RG630 and OG530, a close agreement (± 5%) has been achieved under clear sky conditions. A solar radiation measuring facility, close to the centre of Birmingham, has been set up utilising a microcomputer based data logging system. A suite of computer programs in the BASIC programming language has been developed and extensively tested for solar radiation data, logging, analysis and plotting. Two commonly used instruments, the Eppley PSP pyranometer and the Kipp and Zonen CM5 pyranometer, have been compared under different experimental conditions. Three models for computing the inclined plane irradiation, using total and diffuse radiation on a horizontal surface, have been tested for Birmingham. The anisotropic-alI-sky model, proposed by Klucher, provides a good agreement between the measured and the predicted radiation levels. Measurements of solar spectral distribution, using glass filters, are also reported for a number of inclines facing South.

Gamma rays associated with neutron scattering in fusion reactor materials

The gamma-rays produced by the inelastic scattering of 14 MeV neutrons. in fusion reactor materials have been studied using a gamma-ray spectrometer employing a sodium iodide scintillation detector. The source neutrons are produced by the T(d,n)4He reaction using the SAMES accelerator at the University of Aston in Birmingham. In order to eliminate the large gamma-ray background and neutron signal due to the sensitivity of the sodium iodide detector to neutrons, the gamma-ray detector is heavily shielded and is used together with a particle time of flight discrimination system based on the associated particle time of flight method. The instant of production of a source neutron is determined by detecting the associated alpha-particle enabling discrimination between the neutrons and gamma-rays by their different time of flight times. The electronic system used for measuring the time of flight of the neutrons and gamrna-rays over the fixed flight path is described. The materials studied in this work were Lithium and Lead because of their importance as fuel breeding and shielding materials in conceptual fusion reactor designs. Several sample thicknesses were studied to determine the multiple scattering effects. The observed gamma-ray spectra from each sample at several scattering angles in the angular range Oº - 90° enabled absolute differential gamma-ray production cross-sections and angular distributions of the resolved gamma-rays from Lithium to be measured and compared with published data. For the Lead sample, the absolute differential gamma-ray production cross-sections for discrete 1 MeV ranges and the angular distributions were measured. The measured angular distributions of the present work and those on Iron from previous work are compared to the predictions of the Monte Carlo programme M.O.R.S.E. Good agreement was obtained between the experimental results and the theoretical predictions. In addition an empirical relation has been constructed which describes the multiple scattering effects by a single parameter and is capable of predicting the gamma-ray production cross-sections for the materials to an accuracy of ± 25%.

Cost models for engineering services

This thesis describes the procedure and results from four years research undertaken through the IHD (Interdisciplinary Higher Degrees) Scheme at Aston University in Birmingham, sponsored by the SERC (Science and Engineering Research Council) and Monk Dunstone Associates, Chartered Quantity Surveyors. A stochastic networking technique VERT (Venture Evaluation and Review Technique) was used to model the pre-tender costs of public health, heating ventilating, air-conditioning, fire protection, lifts and electrical installations within office developments. The model enabled the quantity surveyor to analyse, manipulate and explore complex scenarios which previously had defied ready mathematical analysis. The process involved the examination of historical material costs, labour factors and design performance data. Components and installation types were defined and formatted. Data was updated and adjusted using mechanical and electrical pre-tender cost indices and location, selection of contractor, contract sum, height and site condition factors. Ranges of cost, time and performance data were represented by probability density functions and defined by constant, uniform, normal and beta distributions. These variables and a network of the interrelationships between services components provided the framework for analysis. The VERT program, in this particular study, relied upon Monte Carlo simulation to model the uncertainties associated with pre-tender estimates of all possible installations. The computer generated output in the form of relative and cumulative frequency distributions of current element and total services costs, critical path analyses and details of statistical parameters. From this data alternative design solutions were compared, the degree of risk associated with estimates was determined, heuristics were tested and redeveloped, and cost significant items were isolated for closer examination. The resultant models successfully combined cost, time and performance factors and provided the quantity surveyor with an appreciation of the cost ranges associated with the various engineering services design options.

Medicines non-use in primary care

This study expands the current knowledge base on the nature, causes and fate of unused medicines in primary care. Three methodologies were used and participants for each element were sampled from the population of Eastern Birmingham PCT. A detailed assessment was made of medicines returned to pharmacies and GP surgeries for destruction and a postal questionnaire covering medicines use and disposal was used to patients randomly selected from the electoral roll. The content of this questionnaire was informed by qualitative data from a group interview on the subject. By use of these three methods it was possible to triangulate the data, providing a comprehensive assessment of unused medicines. Unused medicines were found to be ubiquitous in primary care and cardiovascular, diabetic and respiratory medicines are unused in substantial quantities, accounting for a considerable proportion of the total financial value of all unused medicines. Additionally, analgesic and psychoactive medicines were highlighted as being unused in sufficient quantities for concern. Anti-infective medicines also appear to be present and unused in a substantial proportion of patients’ homes. Changes to prescribed therapy and non-compliance were identified as important factors leading to the generation of unused medicines. However, a wide array of other elements influence the quantities and types of medicines that are unused including the concordancy of GP consultations and medication reviews and patient factors such as age, sex or ethnicity. Medicines were appropriately discarded by 1 in 3 patients through return to a medical or pharmaceutical establishment. Inappropriate disposal was by placing in household refuse or through grey and black water with the possibility of hoarding or diversion also being identified. No correlations wre found between the weight of unused medicines and any clinical or financial factor. The study has highlighted unused medicines to be an issue of some concern and one that requires further study.

High-performance liquid chromatography and pharmacokinetics of some antibiotics

The principles of High Performance Liquid Chromatography (HPLC) and pharmacokinetics were applied to the use of several clinically-important drugs at the East Birmingham Hospital. Amongst these was gentamicin, which was investigated over a two-year period by a multi-disciplinary team. It was found that there was considerable intra- and inter-patient variation that had not previously been reported and the causes and consequences of such variation were considered. A detailed evaluation of available pharmacokinetic techniques was undertaken and 1- and 2-compartment models were optimised with regard to sampling procedures, analytical error and model-error. The implications for control of therapy are discussed and an improved sampling regime is proposed for routine usage. Similar techniques were applied to trimethoprim, assayed by HPLC, in patients with normal renal function and investigations were also commenced into the penetration of drug into peritoneal dialysate. Novel assay techniques were also developed for a range of drugs including 4-aminopyridine, chloramphenicol, metronidazole and a series of penicillins and cephalosporins. Stability studies on cysteamine, reaction-rate studies on creatinine-picrate and structure-activity relationships in HPLC of aminopyridines are also reported.

Evaluation of remote sensing for the detection of landfill gas and leachate in an urban environment

The technique of remote sensing provides a unique view of the earth's surface and considerable areas can be surveyed in a short amount of time. The aim of this project was to evaluate whether remote sensing, particularly using the Airborne Thematic Mapper (ATM) with its wide spectral range, was capable of monitoring landfill sites within an urban environment with the aid of image processing and Geographical Information Systems (GIS) methods. The regions under study were in the West Midlands conurbation and consisted of a large area in what is locally known as the Black Country containing heavy industry intermingled with residential areas, and a large single active landfill in north Birmingham. When waste is collected in large volumes it decays and gives off pollutants. These pollutants, landfill gas and leachate (a liquid effluent), are known to be injurious to vegetation and can cause stress and death. Vegetation under stress can exhibit a physiological change, detectable by the remote sensing systems used. The chemical and biological reactions that create the pollutants are exothermic and the gas and leachate, if they leave the waste, can be warmer than their surroundings. Thermal imagery from the ATM (daylight and dawn) and thermal video were obtained and used to find thermal anomalies on the area under study. The results showed that vegetation stress is not a reliable indicator of landfill gas migration, as sites within an urban environment have a cover too complex for the effects to be identified. Gas emissions from two sites were successfully detected by all the thermal imagery with the thermal ATM being the best. Although the results were somewhat disappointing, recent technical advancements in the remote sensing systems used in this project would allow geo-registration of ATM imagery taken on different occasions and the elimination of the effects of solar insolation.