Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

Cells, surfaces and adhesion

This thesis concerns cell adhesion to polymer surfaces with an experimental emphasis on hydrogels. The thesis begins with a review of the literature and a synthesis of recent evidence to describe the process of cell adhesion in a given situation. The importance of understanding integrin-adhesion protein interactions and adhesion protein-surface interactions is emphasised. The experimental chapters describe three areas of investigation. Firstly, in vitro cell culture techniques are used to explore a variety of surfaces including polyethylene glycol methacrylate (PEGMA) substituted hydrogels, sequence distribution modified hydrogels and worn contact lenses. Cell adhesion to PEGMA substituted gels is found to decrease with increases in polyethylene oxide chain length and correlations are made between sequence distribution and adhesion. Worn contact lenses are investigated for their cell adhesion properties in the presence of antibodies to specific adhesion proteins, demonstrating the presence of vitronectin and fibronectin on the lenses. The second experimental chapter addresses divalent cation regulation of integrin mediated cell adhesion. Several cell types and various cations are used. Zinc, previously not regarded as an important cation in the process, is found to inhibit 3T3 cell adhesion to vitronectin that is promoted by other divalent cations. The final experimental chapter concerns cell adhesion and growth on macroporous hydrogels. A variety of freeze-thaw formed porous gels are investiated and found generally to promote cell growth rate.Interpenetrating networkbased gels (IPN) are made porous by elution of dextrin particles of varying size and loading density. These materials provide the basis for synthetic cartilage. Cartilage cells (chondrocytes) plated onto the surface of the porous IPN materials maintain a rounded shape and hence phenotypic function when a critical pore size and density is achieved. In this way, a prospective implant, made porous at the perpendicular edges contacting natural cartilage can be both mechanically stabilised and encourage the maintenance of normal matrix production at the tissue interface.

Alzheimer’s disease and the eye

Dementia, including Alzheimer’s disease (AD), is a major disorder causing visual problems in the elderly population. The pathology of AD includes the deposition in the brain of abnormal aggregates of ß-amyloid (Aß) in the form of senile plaques (SP) and abnormally phosphorylated tau in the form of neurofibrillary tangles (NFT). A variety of visual problems have been reported in patients with AD including loss of visual acuity (VA), colour vision and visual fields; changes in pupillary response to mydriatics, defects in fixation and in smooth and saccadic eye movements; changes in contrast sensitivity and in visual evoked potentials (VEP); and disturbances of complex visual functions such as reading, visuospatial function, and in the naming and identification of objects. Many of these changes are controversial with conflicting data in the literature and no ocular or visual feature can be regarded as particularly diagnostic of AD. In addition, some pathological changes have been observed to affect the eye, visual pathway, and visual cortex in AD. The optometrist has a role in helping a patient with AD, if it is believed that signs and symptoms of the disease are present, so as to optimize visual function and improve the quality of life. (J Optom 2009;2:103-111 ©2009 Spanish Council of Optometry)

The design and engineering of a reactor test facility for thermal processing of biomass

This thesis describes the design and engineering of a pressurised biomass gasification test facility. A detailed examination of the major elements within the plant has been undertaken in relation to specification of equipment, evaluation of options and final construction. The retrospective project assessment was developed from consideration of relevant literature and theoretical principles. The literature review includes a discussion on legislation and applicable design codes. From this analysis, each of the necessary equipment units was reviewed and important design decisions and procedures highlighted and explored. Particular emphasis was placed on examination of the stringent demands of the ASME VIII design codes. The inter-relationship of functional units was investigated and areas of deficiency, such as biomass feeders and gas cleaning, have been commented upon. Finally, plant costing was summarized in relation to the plant design and proposed experimental programme. The main conclusion drawn from the study is that pressurised gasification of biomass is far more difficult and expensive to support than atmospheric gasification. A number of recommendations have been made regarding future work in this area.

Leisure at work in Britain, West Germany, France and Japan : a cross-cultural comparative study

The aim of this thesis was to investigate the impact of changing values and attitudes toward work and the workplace in Britain, West Germany, France and Japan. A cross-national approach was adopted in order to gain a better understanding of differences and similarities in behaviour and to identify aspects specific to each society. Although the relationship between work and leisure has been thoroughly examined and there is a growing body of literature on changes in the values associated with these two phenomena, little research has been carried out into leisure at work. Studies of work time have tended to consider it as a homogeneous block, whereas recent research suggests that more attention should be devoted to unravelling the multiple uses of time at the workplace. The present study sought to review and analyse this new approach to the study of work time, and special attention is devoted to an examination of definitions of leisure, recreation, free time and work within the context of the workplace. The cross-cultural comparative approach gave rise to several problems due to the number of countries involved and the unusual combination of factors being investigated. The main difficulties were differences in the amount and quality of literature available, the non-comparability of existing data, definitions of concepts and socio-linguistic terms, and problems over access to organizations for fieldwork. Much of the literature generalizes about patterns of behaviour and few authors isolate factors specific to particular societies. In this thesis new empirical work is therefore used to ascertain the extent to which generalizations can be made from the literature and characteristics peculiar to each of the four countries identified. White-collar employees in large, broadly comparable companies were studied using identical questionnaires in the appropriate language. Respondents selected were men and women, aged between 20-65 years and either managers or non-managers. Patterns of leisure at work were found to be broadly similar in the national contexts, but with the Japanese and the West Germans experiencing the least leisure at work, and the British and the French perceiving the most. The general trend seems to be toward convergence of attitudes regarding leisure at work in the four countries. Explanations for variations in practice were sought within the wider societal contexts of each country.

An investigation of the relationships between service quality, customer satisfaction, perceived value and behavioural intentions

Customer satisfaction and service quality are two important concepts in the marketing literature. However, there has been some confusion about the conceptualisation and measurement of these two concepts and the nature of the relationship between them. The primary objective of this research was to develop a more thorough understanding of these concepts, and a model that could help to explain the links between them and their relationships with post-purchase behaviour. A preliminary theoretical model was developed, based on an exhaustive review of the literature. Following exploratory research, the model was revised by incorporating "Perceived Value" and "Perceived Sacrifice" to help explain customer's post-purchase behaviour. A longitudinal survey was conducted in the context of the restaurant industry, and the data were analysed using structural equation modelling. The results provided evidence to support the main research hypotheses. However, the effect of "Normative Expectations" on "Encounter Quality" was insignificant, and "Perceived Value" had a direct effect on "Behavioural Intentions" despite expectations that such an effect would be mediated through "Customer Satisfaction". It was also found that "Normative Expectations" were relatively more stable than "Predictive Expectations". It is argued that the present research significantly contributes to the marketing literature, and in particular the role of perceived value in the formation of customers' post-purchase behaviour. Further research efforts in this area are warranted.

Stakeholder accounting : the case of the electricity industry in England and Wales

This thesis proposes to explore the potential for stakeholder based accounting as a means to explain the social performance of organisations. It argues that organisations have a contract with society and as a consequence they must be accountable to that society for their actions. Further, it is suggested that as part of this accountability there is a broader need in the public interest for social accounting. Due to the pluralistic nature of modern societies it is argued that a stakeholder framework is one way in which this accountability can be achieved. In order to consider the nature of such social accounting a case study of the electricity industry in England and Wales is undertaken. This industry is very important to modern society, has significant environment implications and has a recent history of remarkable change. These factors make it an interesting and unique case within which to consider accountability. From the performance measurement and accounting literature and a series of interviews with both stakeholders and privatised companies a model of stakeholder performance is developed. This is then used to analyse the electricity industry in England and Wales since privatisation. The objective is to demonstrate how certain stakeholders have fared, whether they have won or lost. Further, institutional and resource dependency theories are used to consider what factors determine the relative success or failure of the different stakeholder groups. Finally the possible implications of recent developments in Social Accounting Standards, such as the Global Reporting Initiative (GRI), AccountAbility 1000 (AA1000) and Social Accountability 8000 (SA8000), and the potential for Internet reporting are considered.

The influence of utilising government initiatives, servicing foreign MNCs and internationalisation on strategic planning process of local companies in Singapore

This research focuses on two groups of local companies; namely, high-growth local companies and other local companies, to examine and compare the influence of utilising governmental initiatives, servicing foreign MNCs and internationalisation on their strategic planning process. The theme of this thesis argues that the approach of an organisation towards strategic planning is not only determined by the internal influences; namely, its firm size and the planning behaviour and attitude of an entrepreneur, as revealed in the literature, but it can also be affected by external influences. The theoretical contribution of this research determines this unique situation in Singapore, and tests the robustness of the conventional models of planning in smaller companies. As a result of the external influences, this study reveals that local companies are more likely to undertake a much more formal strategic planning than the conventional Western literature and models would indicate. High-growth local companies, in comparison, however, had undertaken a more formal and rigorous strategic planning process than other local companies.

Leadership and the negotiation of order in small groups

This thesis is focussed on the role differentiationhypothesis as it relates to small groups (Bales, 1958). The hypothesis is systematically examined, both conceptually and empirically, in the light of the Equilibrium Hypothesis (Bales, 1953) and the Negotiated Order Theory of leadership (e.g. Hosking, 1988). Chapter 1 sketches in a context for the research,which was stimulated by attempts during the 60s and 70s to organise small groups without leaders (the leaderless group, based on isocratic principles). Chapter 2 gives a conceptual and developmental overview of Bales' work, concentrating on the Equilibrium Hypothesis. It is argued that Bales' conceptual approach, if developed, can potentially integrate the disparate small groups and leadership literatures. Chapters 3 and 4 examine the concepts `group', `leader' and `leadership' in terms of the Negotiated Order perspective. In chapter 3 it is argued that two aspects of the concept group need to be taken separately into account; physical attributes and social psychological aspects (the metaphysical glue). It is further argued that a collection of people becomes a group only when they begin to establish a shared sense of social order. In chapter 4 it is argued that leadership is best viewed as a process of negotiation between those who influence and those who are influenced, in the context of shared values about means and ends. It is further argued that leadership is the process by which a shared sense of social order is established and maintained, thus linking the concepts `leadership' and `group' in a single formulation. The correspondences with Bales' approach are discussed at the end of the chapter. Chapters 5 to 8 present a detailed critical description and evaluation of the empirical work which claims to show role differentiation or test the hypothesis, both Bales original work and subsequent studies. It is argued here, that the measurement and analytical procedures adopted by Bales and others, in particular the use of simple means as summaries of group structures, are fundamentally flawed, and that role differentiation in relation to particular identifiable groups has not been demonstrated clearly anywhere in the literature. Chapters 9 to 13 present the empirical work conducted for the thesis. 18 small groups are examined systematically for evidence of role differentiation using an approach based on early sociometry (Moreno, 1934). The results suggest that role differentiation, as described by Bales, does not occur as often as is implied in the literature, and not equivocally in any case. In particular structures derived from Liking are typically distributed or weak. This suggests that one of Bales' principal findings, that Liking varies independently of his other main dimensions, is the product of statistical artifact. Chapter 14 presents a general summary of results and presents some considerations about future research.

Teenage mothers' experiences of stigma and formal support services

This research has two focal points: experiences of stigma and experiences of formal support services among teenage mothers. Twenty teenage mothers were interviewed in depth, ten from a one-to-one support service, and ten from a group based support service. Contributions to knowledge consisted of the following. First, regarding experiences of stigma, this research integrated concepts from the social psychology literature and established the effects of stigma which are experienced by teenage mothers, offering reasons for the same. Additionally, further coping mechanisms in response to being stigmatized were discovered and grouped into two new headings: active and passive coping mechanisms. It is acknowledged that for a minority of participants, stigma does have negative effects, however, the majority experiences no such serious negative effects. Secondly, regarding experiences of support services, this research was able to directly compare one-to-one with group based support for teenage mothers. Knowledge was unearthed as to influential factors in the selection of a mode of support and the functions of each of the modes of support, which were categorised under headings for ease of comparison. It was established that there is indeed a link between these two research foci in that both the one-to-one and group based support services fulfil a stigma management function, in which teenage mothers discuss the phenomenon, share experiences and offer advice to others. However, it was also established that this function is of minor importance compared to the other functions fulfilled by the support services.

The investigation of vegetation change using remote sensing to detect and monitor migration of landfill gas

Decomposition of domestic wastes in an anaerobic environment results in the production of landfill gas. Public concern about landfill disposal and particularly the production of landfill gas has been heightened over the past decade. This has been due in large to the increased quantities of gas being generated as a result of modern disposal techniques, and also to their increasing effect on modern urban developments. In order to avert diasters, effective means of preventing gas migration are required. This, in turn requires accurate detection and monitoring of gas in the subsurface. Point sampling techniques have many drawbacks, and accurate measurement of gas is difficult. Some of the disadvantages of these techniques could be overcome by assessing the impact of gas on biological systems. This research explores the effects of landfill gas on plants, and hence on the spectral response of vegetation canopies. Examination of the landfill gas/vegetation relationship is covered, both by review of the literature and statistical analysis of field data. The work showed that, although vegetation health was related to landfill gas, it was not possible to define a simple correlation. In the landfill environment, contribution from other variables, such as soil characteristics, frequently confused the relationship. Two sites are investigated in detail, the sites contrasting in terms of the data available, site conditions, and the degree of damage to vegetation. Gas migration at the Panshanger site was dominantly upwards, affecting crops being grown on the landfill cap. The injury was expressed as an overall decline in plant health. Discriminant analysis was used to account for the variations in plant health, and hence the differences in spectral response of the crop canopy, using a combination of soil and gas variables. Damage to both woodland and crops at the Ware site was severe, and could be easily related to the presence of gas. Air photographs, aerial video, and airborne thematic mapper data were used to identify damage to vegetation, and relate this to soil type. The utility of different sensors for this type of application is assessed, and possible improvements that could lead to more widespread use are identified. The situations in which remote sensing data could be combined with ground survey are identified. In addition, a possible methodology for integrating the two approaches is suggested.

Pre-conception care : current practice and methods of provision

This thesis examines the present provisions for pre-conception care and the views of the providers of services. Pre-conception care is seen by some clinicians and health educators as a means of making any necessary changes in life style, corrections to imbalances in the nutritional status of the prospective mother (and father) and the assessment of any medical problems, thus maximizing the likelihood of the normal development of the baby. Pre-conception care may be described as a service to bridge the gap between the family planning clinic and the first ante-natal booking appointment. There were three separate foci for the empirical research - the Foresight organisation (a charity which has pioneered pre-conception care in Britain); the pre-conception care clinic at the West London Hospital, Hammersmith; and the West Midlands Regional Health Authority. The six main sources of data were: twenty five clinicians operating Foresight pre-conception clinics, couples attending pre-conception clinics, committee members of the Foresight organisation, staff of the West London Hospital pre-conception clinic, Hammersmith, District Health Education Officers working in the West Midlands Regional Health Authority and the members of the Ante-Natal Care Action Group, a sub-group of the Regional Health Advisory Group on Health Promotion and Preventive Medicine. A range of research methods were adopted. These were as follows: questionnaires and report forms used in co-operation with the Foresight clinicians, interviews, participant observation discussions and informal meetings and, finally, literature and official documentation. The research findings illustrated that pre-conception care services provided at the predominantly private Foresight clinics were of a rather `ad hoc' nature. The type of provision varied considerably and clearly reflected the views held by its providers. The protocol which had been developed to assist in the standardization of results was not followed by the clinicians. The pre-conception service provided at the West London Hospital shared some similarities in its approach with the Foresight provision; a major difference was that it did not advocate the use of routine hair trace metal analysis. Interviews with District Health Education Officers and with members of the Ante Natal Care Action Group revealed a tentative and cautious approach to pre-conception care generally and to the Foresight approach in particular. The thesis concludes with a consideration of the future of pre-conception care and the prospects for the establishment of a comprehensive pre-conception care service.

The characterisation and optimisation of modified herbaceous grasses for identifying pyrolisis-oil quality traits

The primary objective of this work is to relate the biomass fuel quality to fast pyrolysis-oil quality in order to identify key biomass traits which affect pyrolysis-oil stability. During storage the pyrolysis-oil becomes more viscous due to chemical and physical changes, as reactions and volatile losses occur due to aging. The reason for oil instability begins within the pyrolysis reactor during pyrolysis in which the biomass is rapidly heated in the absence of oxygen, producing free radical volatiles which are then quickly condensed to form the oil. The products formed do not reach thermodynamic equilibrium and in tum the products react with each other to try to achieve product stability. The first aim of this research was to develop and validate a rapid screening method for determining biomass lignin content in comparison to traditional, time consuming and hence costly wet chemical methods such as Klason. Lolium and Festuca grasses were selected to validate the screening method, as these grass genotypes exhibit a low range of Klason /Acid Digestible Fibre lignin contents. The screening methodology was based on the relationship between the lignin derived products from pyrolysis and the lignin content as determined by wet chemistry. The second aim of the research was to determine whether metals have an affect on fast pyrolysis products, and if any clear relationships can be deduced to aid research in feedstock selection for fast pyrolysis processing. It was found that alkali metals, particularly Na and K influence the rate and yield of degradation as well the char content. Pre-washing biomass with water can remove 70% of the total metals, and improve the pyrolysis product characteristics by increasing the organic yield, the temperature in which maximum liquid yield occurs and the proportion of higher molecular weight compounds within the pyrolysis-oil. The third aim identified these feedstock traits and relates them to the pyrolysis-oil quality and stability. It was found that the mineral matter was a key determinant on pyrolysis-oil yield compared to the proportion of lignin. However the higher molecular weight compounds present in the pyrolysis-oil are due to the lignin, and can cause instability within the pyrolysis-oil. The final aim was to investigate if energy crops can be enhanced by agronomical practices to produce a biomass quality which is attractive to the biomass conversion community, as well as giving a good yield to the farmers. It was found that the nitrogen/potassium chloride fertiliser treatments enhances Miscanthus qualities, by producing low ash, high volatiles yields with acceptable yields for farmers. The progress of senescence was measured in terms of biomass characteristics and fast pyrolysis product characteristics. The results obtained from this research are in strong agreement with published literature, and provides new information on quality traits for biomass which affects pyrolysis and pyrolysis-oils.

Examining green production and its role within the competitve strategy of manufacturers

Purpose: This paper reviews current literature and contributes a set of findings that capture the current state-of-the-art of the topic of green production. Design/methodology/approach: A literature review to capture, classify and summarize the main body of knowledge on green production and, translate this into a form that is readily accessible to researchers and practitioners in the more mainstream operations management community. Findings: The existing knowledge base is somewhat fragmented. This is a relatively unexplored topic within mainstream operations management research and one which could provide rich opportunities for further exploration. Originality/value: This paper sets out to review current literature, from a more conventional production operations perspective, and contributes a set of findings that capture the current state-of-the-art of this topic.

State-of-the-art of ‘Lean’ in the aviation maintenance, repair, and overhaul industry

The increasing need for maintenance, repair, and overhaul (MRO) organizations to meet customers' demands in quality and reduced lead times is key to its survival within the aviation industry. Furthermore, with the unpredictability in the global market and difficulties with forecasting characteristic of the MRO industry there is an increased need for the reevaluation of the operation models of organizations within this sector. However, severe economic turmoil and ever-increasing global competition introduce the opportunity for the adoption of a resilient, tried, and tested business operation model such as 'Lean'. In order to understand this concept, its long-term viability, and its application within the aerospace MRO sector fully, this paper presents the state-of-the-art in terms of the adoption of Lean within the MRO industry by carrying out a systematic review of the literature. This paper establishes the common perception of Lean by the MRO industry and the measurable progress that has been made on the subject. Some issues and challenges are also highlighted including the misconceptions that arise from the direct transference of the perception of Lean from other industrial sectors into the aerospace MRO industry. The 'enablers and inhibitors' of Lean within the aviation industry are also discussed. This paper exposes the scarcity of the literature and the general lagging behind of the industry to the adoption of the Lean paradigm and thus highlights areas where further research is required. © 2011 Authors.