Greener methodology for the synthesis of alpha-diazocarbonyl compounds and a novel approach to dioxinone derivatives

This thesis outlines a more environmentally benign approach to diazo transfer, and the investigation of the reactivity of -diazocarbonyl compounds when subjected to transition metal and lanthanide catalysis. Extensive studies were carried out to find the optimum conditions for a greener diazo transfer methodology, and this was also applied to a continuous process for the synthesis of -diazo--ketoesters. The first chapter includes a literature review of the synthesis and subsequent reactivity of -diazocarbonyl compounds. An overview of the applications of flow chemistry for the synthesis of hazardous intermediates is also included. The applications of lanthanide catalysts in organic synthesis is also discussed. The second chapter outlines the extensive studies undertaken to determine the optimum conditions for a greener diazo transfer methodology, including base and solvent studies. Use of water as a viable solvent for diazo transfer was successfully investigated. Diazo transfer to a range of -diazo--ketoesters was achieved using 5 mol% triethylamine or DMAP in water with high conversions. Polystyrene-supported benzenesulfonyl azide as an alternative diazo transfer reagent was also explored, as well as investigations into cheaper generation of this safer reagent. This polymer-supported benzenesulfonyl azide was used with 25 mol% of base in water to achieve successful diazo transfer to a range of -diazo--ketoesters. The third chapter describes the application of the new methodology developed in Chapter 2 to a continuous processing approach. Various excellent conditions were identified for both batch and flow reactions. A series of -diazo--ketoesters were synthesised with excellent conversions using 25 mol% triethylamine in 90:10 acetone water using flow chemistry. Successful diazo transfer was also achieved using a polymer-supported benzenesulfonyl azide in water under flow conditions. The fourth chapter discusses the reactivity of -diazo--ketoesters under transition metal and lanthanide catalysis. This chapter describes the synthesis of a range of -ketoesters via transesterification, which were used to synthesise a range of novel -diazo--ketoesters that were used in subsequent decomposition reactions. A novel route to dioxinones via rhodium(II) catalysis is reported. Attempted OH and SH insertion reactions in the presence of various lanthanide(II) catalysts are outlined, leading to some unexpected and interesting rearrangement products. The experimental details, including spectroscopic and analytical data for all compounds prepared, are reported at the end of each chapter.

Physicochemical characterisation of protein ingredients prepared from milk by ultrafiltration or microfiltration for application in formulated nutritional products

Formulated food systems are becoming more sophisticated as demand grows for the design of structural and nutritional profiles targeted at increasingly specific demographics. Milk protein is an important bio- and techno-functional component of such formulations, which include infant formula, sports supplements, clinical beverages and elderly nutrition products. This thesis outlines research into ingredients that are key to the development of these products, namely milk protein concentrate (MPC), milk protein isolate (MPI), micellar casein concentrate (MCC), β-casein concentrate (BCC) and serum protein concentrate (SPC). MPC powders ranging from 37 to 90% protein (solids basis) were studied for properties of relevance to handling and storage of powders, powder solubilisation and thermal processing of reconstituted MPCs. MPC powders with ≥80% protein were found to have very poor flowability and high compressibility; in addition, these high-protein MPCs exhibited poor wetting and dispersion characteristics during rehydration in water. Heat stability studies on unconcentrated (3.5%, 140°C) and concentrated (8.5%, 120°C) MPC suspensions, showed that suspensions prepared from high-protein MPCs coagulated much more rapidly than lower protein MPCs. β-casein ingredients were developed using membrane processing. Enrichment of β-casein from skim milk was performed at laboratory-scale using ‘cold’ microfiltration (MF) at <4°C with either 1000 kDa molecular weight cut-off or 0.1 µm pore-size membranes. At pilot-scale, a second ‘warm’ MF step at 26°C was incorporated for selective purification of micellised β-casein from whey proteins; using this approach, BCCs with β-casein purity of up to 80% (protein basis) were prepared, with the whey protein purity of the SPC co-product reaching ~90%. The BCC ingredient could prevent supersaturated solutions of calcium phosphate (CaP) from precipitating, although the amorphous CaP formed created large micelles that were less thermo-reversible than those in CaP-free systems. Another co-product of BCC manufacture, MCC powder, was shown to have superior rehydration characteristics compared to traditional MCCs. The findings presented in this thesis constitute a significant advance in the research of milk protein ingredients, in terms of optimising their preparation by membrane filtration, preventing their destabilisation during processing and facilitating their effective incorporation into nutritional formulations designed for consumers of a specific age, lifestyle or health status

Inhomogeneous cloud coverage through the Coulomb explosion of dust in substellar atmospheres

Context. Recent observations of brown dwarf spectroscopic variability in the infrared infer the presence of patchy cloud cover. Aims. This paper proposes a mechanism for producing inhomogeneous cloud coverage due to the depletion of cloud particles through the Coulomb explosion of dust in atmospheric plasma regions. Charged dust grains Coulomb-explode when the electrostatic stress of the grain exceeds its mechanical tensile stress, which results in grains below a critical radius a < a Coul crit being broken up. Methods. This work outlines the criteria required for the Coulomb explosion of dust clouds in substellar atmospheres, the effect on the dust particle size distribution function, and the resulting radiative properties of the atmospheric regions. Results. Our results show that for an atmospheric plasma region with an electron temperature of Te = 10 eV (≈105 K), the critical grain radius varies from 10−7 to 10−4 cm, depending on the grains’ tensile strength. Higher critical radii up to 10−3 cm are attainable for higher electron temperatures. We find that the process produces a bimodal particle size distribution composed of stable nanoscale seed particles and dust particles with a ≥ a Coul crit , with the intervening particle sizes defining a region devoid of dust. As a result, the dust population is depleted, and the clouds become optically thin in the wavelength range 0.1–10 μm, with a characteristic peak that shifts to higher wavelengths as more sub-micrometer particles are destroyed. Conclusions. In an atmosphere populated with a distribution of plasma volumes, this will yield regions of contrasting radiative properties, thereby giving a source of inhomogeneous cloud coverage. The results presented here may also be relevant for dust in supernova remnants and protoplanetary disks.

A Most Serviceable Drudge: the papermills of the Water of Leith.

This article outlines the twentieth century history of papermaking on the Water of Leith using interviews conducted with a variety of former mill employees as part of the SAPPHIRE initiative. Until the mid-twentieth century, the Water of Leith was an important industrial centre for Edinburgh, particularly in papermaking.

Development of a real time Image analysis system for traffic monitoring applications.

Image processing offers unparalleled potential for traffic monitoring and control. For many years engineers have attempted to perfect the art of automatic data abstraction from sequences of video images. This paper outlines a research project undertaken at Napier University by the authors in the field of image processing for automatic traffic analysis. A software based system implementing TRIP algorithms to count cars and measure vehicle speed has been developed by members of the Transport Engineering Research Unit (TERU) at the University. The TRIP algorithm has been ported and evaluated on an IBM PC platform with a view to hardware implementation of the pre-processing routines required for vehicle detection. Results show that a software based traffic counting system is realisable for single window processing. Due to the high volume of data required to be processed for full frames or multiple lanes, system operations in real time are limited. Therefore specific hardware is required to be designed. The paper outlines a hardware design for implementation of inter-frame and background differencing, background updating and shadow removal techniques. Preliminary results showing the processing time and counting accuracy for the routines implemented in software are presented and a real time hardware pre-processing architecture is described.

From policy development to effectiveness and alignment: An analysis of the UK’s Higher Education Open Access policy landscape

The number of Open Access (OA) policies that have been adopted by universities, research institutes and research funders has been increasing at a fast pace. The Registry of Open Access Repository Mandates and Policies (ROARMAP) records the existence of 724 OA policies across the world, of which 512 have been adopted by universities and research institutions. The UK is one of the leading countries in terms of OA policy development and implementation with a total of 85 institutional1 and an estimated 35 funder2 OA policies. In order to understand and contextualise how OA policies are developed and how they can be effectively implemented and aligned, this brief looks at two areas. The first section provides an overview on the processes evolving around policy making, policy effectiveness and policy alignment. In particular, it summarises the criteria and elements generally specified in OA policies, it points out some of the relevant steps informing the development, monitoring and revision of OA policies, it outlines what OA policy elements contribute to policy effectiveness, and highlights the benefits in aligning OA policies. The second section revisits the issues previously discussed within the context of the UK institutional (universities) OA policy landscape.

Using technology to overcome the tyranny of space: information provision and wayfinding.

Urban wayfinding technology offers many possibilities by which older people and mobility-impaired users can overcome the barriers encountered on every-day journeys in the built environment. Previous work has highlighted the extent to which personal mobility and independence are significant determinants of the quality of life amongst both elderly and visually impaired groups. The paper outlines the development of the auditory location finder (ALF), which is a beacon-based local information system designed to enhance the wayfinding activities of these, and potentially other, user-groups in the community. The proposed system provides the user with an audio message, which is obtained on request via a small portable hand unit. The messages inform the user of their whereabouts and give information about the area that they are currently in. The development of the device involves issues such as message content and structure, route choice, orientation, landmarks, clues and the extent of user reliance on technology. Preliminary trials have been carried out in a UK city and have obtained initial user feedback to help underpin the technological development of the device and its potential application. The paper concludes by outlining the importance of new urban technology and the way in which such local information systems can potentially contribute to overcoming particular patterns of exclusion experienced by mobility-impaired groups, such as the visually impaired

Performance assessment of a vertical axis turbine in a marine current flume tank and CFD modelling

As advances in numerical modelling techniques support the increased confidence in predictions from computer simulations, the need remains to have experimental verification built into the design process. This paper outlines the experimental investigation carried out on a shielded vertical axis turbine in a marine environment. The experiments consist of performance measurements and the use of particle image velocimetry on a small scale device in a marine current flume. The results demonstrate that the performance of the device can be modelled numerically; in particular, the results show that the numerical model used can correctly predict the increase in performance with Reynolds number.

A longitudinal qualitative exploration of healthcare and informal support needs among survivors of critical illness: the RELINQUISH protocol.

Introduction and background: Survival following critical illness is associated with a significant burden of physical, emotional and psychosocial morbidity. Recovery can be protracted and incomplete, with important and sustained effects upon everyday life, including family life, social participation and return to work. In stark contrast with other critically ill patient groups (eg, those following cardiothoracic surgery), there are comparatively few interventional studies of rehabilitation among the general intensive care unit patient population. This paper outlines the protocol for a sub study of the RECOVER study: a randomised controlled trial evaluating a complex intervention of enhanced ward-based rehabilitation for patients following discharge from intensive care. Methods and analysis: The RELINQUISH study is a nested longitudinal, qualitative study of family support and perceived healthcare needs among RECOVER participants at key stages of the recovery process and at up to 1 year following hospital discharge. Its central premise is that recovery is a dynamic process wherein patients’ needs evolve over time. RELINQUISH is novel in that we will incorporate two parallel strategies into our data analysis: (1) a pragmatic health services-oriented approach, using an a priori analytical construct, the ‘Timing it Right’ framework and (2) a constructivist grounded theory approach which allows the emergence of new themes and theoretical understandings from the data. We will subsequently use Qualitative Health Needs Assessment methodology to inform the development of timely and responsive healthcare interventions throughout the recovery process. Ethics and dissemination: The protocol has been approved by the Lothian Research Ethics Committee (protocol number HSRU011). The study has been added to the UK Clinical Research Network Database (study ID. 9986). The authors will disseminate the findings in peer reviewed publications and to relevant critical care stakeholder groups.

Functional surface chemistry of carbon-based nanostructures

The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and assessing their selectivity in separating metallic and semiconducting SWNTs. Chapter 4 describes how optical phonon population extinction lifetime is affected by covalent functionalization and doping and includes discussions on static Raman linewidths. Increasing defect concentration is shown to decrease G-band phonon population lifetime and increase G-band linewidth. Doping only increases G-band linewidth, leaving non-equilibrium population decay rate unaffected. Phonon mediated electron scattering is especially strong in nanotubes making optical phonon decay of interest for device applications. Optical phonon decay also has implications on device thermal management. Chapter 5 treats doping of graphene showing ambient air can lead to inadvertent Fermi level shifts which exemplifies the sensitivity that sp2-bonded carbon nanostructures have to chemical doping through sidewall adsorption. Removal of this doping allows for an investigation of electron-phonon coupling dependence on temperature, also of interest for devices operating above room temperature. Finally, in Chapter 6, utilizing the information obtained in previous chapters, single carbon nanotube diodes are fabricated and characterized. Electrical performance shows these diodes are nearly ideal and photovoltaic response yields 1.4 nA and 205 mV of short circuit current and open circuit voltage from a single nanotube device. A summary and discussion of future directions in Chapter 7 concludes my work.

Blood donor motivation and recruitment : a comparative study in West of Scotland and the Sudan

In modern society, blood donor motivation and recruitment is a fundamental part of health care delivery. Well defined and documented programmes exist throughout the world but new ideas are always welcome. The situation in the Sudan is different and much remains to be done by way of comparison with elsewhere. This thesis outlines the objectives of a study, how it was supported, sponsored and achieved. It describes briefly the geography of the Sudan, the source of Sudanese economy, climate, culture and historical backgrounds. The problems of existing services in the Sudan are reviewed and a brief account of the demographic characteristics of the Sudanese population is given. Two surveys done in West of Scotland and in the Sudan are described in detail. This work discloses and compares the positive motives that enhances giving of blood and the negative motives that hinders its donation. The comparison is between an Eastern Society with a voluntary motivation not fully activated because of lack of understanding and awareness of the need to give blood voluntarily for strangers and Western Society with a well established voluntary system of donation. An addition to this research was the investigation into the immunity to tetanus and hepatitis in the Sudanese population. An estimate of the percentage of individuals with detectable levels of hepatitis A and B antibodies and tetanus antibodies is included since there is a need to establish a plasmapheresis programme as part of a good Blood Transfusion Service for the procurement of specific immunoglobulin's. This work has revealed major differences between the West of Scotland and the Sudan and suggestions are made for their resolution. The main conclusion and comparison are summarised in Chapter 7. It is hoped that many of the suggestions in this thesis can be introduced in the Sudan at an early date.

Young people with learning disabilities who sexually harm others: the role of criminal justice within a multi-agency response

This paper outlines the key findings from a recent study of statutory service responses to young people with learning disabilities who show sexually inappropriate or abusive behaviours, with a particular focus on the involvement of criminal justice agencies. The study found that although inappropriate sexual behaviours were commonplace in special schools, and that serious acts of abuse including rape had sometimes occurred, education, welfare and criminal justice agencies struggled to work together effectively. In particular, staff often had difficulty in determining the point at which a sexually inappropriate behaviour warranted intervention. This problem was frequently compounded by a lack of appropriate therapeutic services. In many cases this meant that no intervention was made until the young person committed a sexual offence and the victim reported this to the police. As a consequence, young people with learning disabilities are being registered as sex offenders. The paper concludes by addressing some of the policy and practice implications of the study’s findings, particularly those which relate to criminal justice.

Mapping the uncharted territory of folk drama

Students of mumming and guising plays – the seasonal verse dramas performed for over 200 years throughout much of England, Scotland, and northern Ireland – have suffered from having too much information to work with. The first part of this poster presentation outlines and illustrates the situation. There are thousands of places where the plays are known to have been performed, and hundreds of texts have been collected. Furthermore, the plays show some tantalising similarities while simultaneously exhibiting the wide range of variation one would expect from orally transmitted dialogue. Until recently, scholars openly admitted to not knowing where to start with such a flood of material, to the extent that some dismissed the texts altogether as unimportant and irrelevant, focussing instead on the "actions". Fortunately, the introduction of computers has managed to break the impasse and is aiding the intellectual process. Part two shows a case study for one of the tools on the Master Mummers website - the Folk Play Scripts Explorer – which is based on a large database of digitised texts and a typology for individual lines. This allows researchers to search for lines, explore textual variants, and map their geographical distribution. This is yielding some interesting surprises. Seemingly trivial variations often turn out to have discrete distribution patterns, while it transpires that certain "ubiquitous" lines have restricted geographical ranges. Thus, the Scripts Explorer is providing novel insights into how the plays evolved and spread.

MEN WRITING WOMEN: “THE WOMAN QUESTION” AND MALE DISCOURSE OF IRANIAN MODERNITY"

In this dissertation I explore “The Woman Question” in the discourse of Iranian male authors. A pro-modernity group, they placed women’s issues at the heart of their discourse. This dissertation follows the trajectory of the representation of “The Woman Question” as it is reflected in the male discourse over the course of a century. It discusses the production of a literature that was anchored in the idea of reform and concerned itself with issues pertaining to women. These men challenged lifelong patriarchal notions such as veiling, polygamy, gender segregation, and arranged marriages, as well as traditional roles of women and gender relations. This study is defined under the rubrics of “The Woman Question” and “The New Woman,” which I have borrowed from the Victorian and Edwardian debates of similar issues as they provide clearer delineations. Drawing upon debates on sexuality, and gender, this dissertation illustrates the way these men championed women was both progressive and regressive. This study argues that the desire for women’s liberation was couched in male ideology of gender relations. It further illustrates that the advancement of “The Woman Question,” due to its continuous and yet gradual shifting concurrent with each author’s nuanced perception of women’s issues, went through discernible stages that I refer to as observation, causation, remedy, and confusion. The analytical framework for this project is anchored in the “why” and the “how” of the Iranian male authors’ writings on women in addition to “what” was written. This dissertation examines four narrative texts—two in prose and two in poetry—entitled: “Lankaran’s Vizier,” “The Black Shroud,” “‘Arefnameh,” and “Fetneh” written respectively by Akhundzadeh, ‘Eshqi, Iraj Mirza, and Dashti. Chapter one outlines the historical background, methodology, theoretical framework, and literature review. The following chapters examine, the advocacy for companionate marriage and romantic love, women and nationalistic cause, veiling and unveiling, and the emerging figure of the New Iranian Woman as morally depraved.

[Cadastral map of part of the West End, Washington D.C.].

Cadastral map showing unidentified tinted lots, lot numbers, and block numbers.