THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

The Third Campaign: Extracts

Why do public art commissions spark such controversy? The stories behind radical proposals for public sculptures in London – some realised, others thwarted – are drawn from the Henry Moore Institute’s rich collection of sculptors’ papers. Laurence Bradshaw’s (1899–1978) iconic Karl Marx memorial (1956) became an ideological site prompting both pilgrimage and attack. Jacob Epstein’s (1880–1959) explicit nudes for the British Medical Association became a battleground for Modernism and are the subject of a new work by Neal White. Other featured artists include Rose Finn-Kelcey, Alfred Frank Hardiman, Paul Neagu and Oscar Nemon whose drawings and documents reveal sculpture’s passage into public life. Curated by Yiakoumaki, N (Whitechapel Gallery) & La Fevre, L (Henry Moore Institute).

Patterns of Behaviour, Group Structure and Reproductive Status Predict Levels of Glucocorticoid Metabolites in Zoo-Housed Ring-Tailed Lemurs, Lemur catta

In ring-tailed lemurs, Lemur catta, the factors modulating hypothalamic-pituitaryadrenal (HPA) activity differ between wild and semi-free-ranging populations. Here we assess factors modulating HPA activity in ring-tailed lemurs housed in a third environment: the zoo. First we validate an enzyme immunoassay to quantify levels of glucocorticoid (GC) metabolites in the faeces of L. catta . We determine the nature of the femalefemale dominance hierarchies within each group by computing David's scores and examining these in relation to faecal GC (fGC). Relationships between female age and fGC are assessed to evaluate potential age-related confounds. The associations between fGC, numbers of males in a group and reproductive status are explored. Finally, we investigate the value of 7 behaviours in predicting levels of fGC. The study revealed stable linear dominance hierarchies in females within each group. The number of males in a social group together with reproductive status, but not age, influenced fGC. The 7 behavioural variables accounted for 68% of the variance in fGC. The amounts of time an animal spent locomoting and in the inside enclosure were both negative predictors of fGC. The study highlights the flexibility and adaptability of the HPA system in ring-tailed lemurs.

A realist synthesis of educational interventions to improve nutrition care competencies and delivery by doctors and other healthcare professionals

Objective: To determine what, how, for whom, why, and in what circumstances educational interventions to improve the delivery of nutrition care by doctors and other healthcare professionals work?

Design: Realist synthesis following a published protocol and reported following Realist and Meta-narrative Evidence Synthesis: Evolving Standards (RAMESES) guidelines. A multidisciplinary team searched Medline, CINAHL, ERIC, EMBASE, PsyINFO, Sociological Abstracts, Web of Science, Google Scholar, and Science Direct for published and unpublished (grey) literature. The team identified studies with varied designs; appraised their ability to answer the review question; identified relationships between contexts, mechanisms, and outcomes (CMOs); and entered them into a spreadsheet configured for the purpose. The final synthesis identified commonalities across CMO configurations.

Results: Over half of the 46 studies from which we extracted data originated from the US. Interventions that improved the delivery of nutrition care improved skills and attitudes rather than just knowledge; provided opportunities for superiors to model nutrition care; removed barriers to nutrition care in health systems; provided participants with local, practically relevant tools and messages; and incorporated non-traditional, innovative teaching strategies. Operating in contexts where student and qualified healthcare professionals provided nutrition care in both developed and developing countries, these interventions yielded health outcomes by triggering a range of mechanisms, which included: feeling competent; feeling confident and comfortable; having greater self-efficacy; being less inhibited by barriers in healthcare systems; and feeling that nutrition care was accepted and recognised.

Conclusion: These findings show how important it is to move education for nutrition care beyond the simple acquisition of knowledge. They show how educational interventions embedded within systems of healthcare can improve patients’ health by helping health students and professionals to appreciate the importance of delivering nutrition care and feel competent to deliver it.

Party rules, party resources and the politics of parliamentary democracies How parties organize in the 21st century

This article introduces the first findings of the Political Party Database Project, a major survey of party organizations in parliamentary and semi-presidential democracies. The project’s first round of data covers 122 parties in 19 countries. In this article, we describe the scope of the database, then investigate what it tells us about contemporary party organization in these countries, focusing on parties’ resources, structures and internal decision-making. We examine organizational patterns by country and party family, and where possible we make temporal comparisons with older data sets. Our analyses suggest a remarkable coexistence of uniformity and diversity. In terms of the major organizational resources on which parties can draw, such as members, staff and finance, the new evidence largely confirms the continuation of trends identified in previous research: that is, declining membership, but enhanced financial resources and more paid staff. We also find remarkable uniformity regarding the core architecture of party organizations. At the same time, however, we find substantial variation between countries and party families in terms of their internal processes, with particular regard to how internally democratic they are, and the forms that this democratization takes.

A two-step approach for the analysis of hybrids in comparative social policy analysis: a nuanced typology of childcare policies

Typologies have represented an important tool for the development of comparative social policy research and continue to be widely used in spite of growing criticism of their ability to capture the complexity of welfare states and their internal heterogeneity. In particular, debates have focused on the presence of hybrid cases and the existence of distinct cross-national pattern of variation across areas of social policy. There is growing awareness around these issues, but empirical research often still relies on methodologies aimed at classifying countries in a limited number of unambiguous types. This article proposes a two-step approach based on fuzzy-set-ideal-type analysis for the systematic analysis of hybrids at the level of both policies (step 1) and policy configurations or combinations of policies (step 2). This approach is demonstrated by using the case of childcare policies in European economies. In the first step, parental leave policies are analysed using three methods – direct, indirect, and combinatory – to identify and describe specific hybrid forms at the level of policy analysis. In the second step, the analysis focus on the relationship between parental leave and childcare services in order to develop an overall typology of childcare policies, which clearly shows that many countries display characteristics normally associated with different types (hybrids and. Therefore, this two-step approach enhances our ability to account and make sense of hybrid welfare forms produced from tensions and contradictions within and between policies.

Combustion Noise

Combustion noise is becoming increasingly important as a major noise source in aeroengines and ground based gas turbines. This is partially because advances in design have reduced the other noise sources, and partially because next generation combustion modes burn more unsteadily, resulting in increased external noise from the combustion. This review reports recent progress made in understanding combustion noise by theoretical, numerical and experimental investigations. We first discuss the fundamentals of the sound emission from a combustion region. Then the noise of open turbulent flames is summarized. We subsequently address the effects of confinement on combustion noise. In this case not only is the sound generated by the combustion influenced by its transmission through the boundaries of the combustion chamber, there is also the possibility of a significant additional source, the so-called ‘indirect’ combustion noise. This involves hot spots (entropy fluctuations) or vorticity perturbations produced by temporal variations in combustion, which generate pressure waves (sound) as they accelerate through any restriction at the exit of the combustor. We describe the general characteristics of direct and indirect noise. To gain further insight into the physical phenomena of direct and indirect sound, we investigate a simple configuration consisting of a cylindrical or annular combustor with a low Mach number flow in which a flame zone burns unsteadily. Using a low Mach number approximation, algebraic exact solutions are developed so that the parameters controlling the generation of acoustic, entropic and vortical waves can be investigated. The validity of the low Mach number approximation is then verified by solving the linearized Euler equations numerically for a wide range of inlet Mach numbers, stagnation temperature ratios, frequency and mode number of heat release fluctuations. The effects of these parameters on the magnitude of the waves produced by the unsteady combustion are investigated. In particular the magnitude of the indirect and direct noise generated in a model combustor with a choked outlet is analyzed for a wide range of frequencies, inlet Mach numbers and stagnation temperature ratios. Finally, we summarize some of the unsolved questions that need to be the focus of future research

Fast and sensitive aflatoxin B1 and total aflatoxins ELISAs for analysis of peanuts, maize and feed ingredients

Aflatoxins are a group of carcinogenic compounds produced by Aspergillus fungi that can grow on different agricultural crops. Both acute and chronic exposure to these mycotoxins can cause serious illness. Due to the high occurrence of aflatoxins in crops worldwide fast and cost-effective analytical methods are required for the identification of contaminated agricultural commodities before they are processed into final products and placed on the market. In order to provide new tools for aflatoxin screening two prototype fast ELISA methods: one for the detection of aflatoxin B₁ and the other for total aflatoxins were developed. Seven monoclonal antibodies with unique high sensitivity and at the same time good cross-reactivity profiles were produced. The monoclonal antibodies were characterized and two antibodies showing IC₅₀ of 0.037 ng/mL and 0.031 ng/mL for aflatoxin B₁ were applied in simple and fast direct competitive ELISA tests. The methods were validated for peanut matrix as this crop is one of the most affected by aflatoxin contamination. The detection capabilities of aflatoxin B₁ and total aflatoxins ELISAs were 0.4 μg/kg and 0.3 μg/kg for aflatoxin B₁, respectively, which are one of the lowest reported values. Total aflatoxins ELISA was also validated for the detection of aflatoxins B₂, G₁ and G₂. The application of the developed tests was demonstrated by screening 32 peanut samples collected from the UK retailers. Total aflatoxins ELISA was further applied to analyse naturally contaminated maize porridge and distiller's dried grain with solubles samples and the results were correlated with these obtained by UHPLC-MS/MS method.

The economic impact of sports mega-events : The case study of the FIS Nordic World Ski Championship Falun 2015

Since the second half of 1990s, the economic impact of sports mega-events concerned the researchers, the public and the professionals. The investment of public funds and the effects on several sectors of the economy motivate the economic impact studies. The economic impact of the FIS Nordic World Ski Championship Falun 2015 to the region of Dalarna is the topic of this thesis. This requires the calculation of direct, indirect and induced economic impact. Within the analysis, data from a questionnaire survey conducted on seven different days during the event are used. The final sample of the analysis contains 893 observations. The segmentation approach was applied for the calculations and the visitors were classified regarding their choice of accommodation. The regional economic impact is calculated at 321 M SEK and the employment effect on the tourism sector is estimated. However, the lack of information limits the study. The analysis could be extended with an accurate investigation of certain issues. Further, the impact of the event should be estimated from all the perspectives. The organization of sports mega-events creates tangible and intangible effects to the host-city. The thesis reviews literature on the economic impact studies of sports mega-events. The results of the study can be used for a comprehensive analysis of the case study. Further, the professionals of the tourism and the event could be benefited.

Occupied childhoods: discourses and politics of childhood and their place in Palestinian and Pan-­Arab screen content for children

This thesis explores changing discourses of childhood and the ways in which power relations intersect with socio-cultural norms to shape screen-based media for Palestinian children. Situated within the interdisciplinary study of childhood, the research is an institutional and textual analysis that includes discursive and micro-level analysis of the socio-political circumstances within which children consume media in present-day Palestine. The thesis takes a social constructionist view, arguing that ‘childhood’ is not a fixed universal concept and that discourses of childhood are produced at specific historical moments as an effect of power. The study has a three-part research agenda. The first section uses secondary literature to explore theories and philosophies relating to definitions of childhood in Arab societies. The second employs participant observation and semi-structured interviews to understand the history and politics of children’s media in the West Bank. The final part of the research activity focuses on the impact that definitions of childhood and the politics of children’s media have on broadcasting outcomes through an analysis of (a) discourses on children’s media that circulate in Palestinian society, and (b) local and pan-Arab cultural texts consumed by Palestinian children. The analysis demonstrates that complex ideological and political factors are at play, which has led to the marginalisation, politicisation and internationalisation of local production for children. Due to the lack of alternatives, local producers often rely on international funding, and are hence forced to negotiate competing definitions of childhood, which while fitting with an international agenda of normalising the Israeli occupation, conflict culturally and politically with local conceptions of childhood and hopes for the Palestinian nation. While the Palestinian community appreciates the positive potential of local production, discourses and strategies around children’s media show that Palestinian children are constructed as vulnerable, incomplete and in constant need of guidance. Pan-Arab content presents a slightly less didactic approach and in certain cases presents childhood as a dynamic space of empowerment. However, by constructing children as ‘consumercitizens’, it alienates Arab (and Palestinian) children from disadvantaged backgrounds,as the preferred audience is middle-class children living in oil-rich countries of the Gulf.

Brief Psychotherapy with Children in a Specialist School: An Exploration of the Underlying Issues for Children and Mainstream Schools

This thesis explores brief psychotherapy with children on placement at a specialist school setting, as part of an on-site, child psychotherapy outreach provision. The study sought to explore two research questions concerning the themes that could emerge in brief work with children and how these themes could be discussed in relation to the understanding formed by their mainstream school teachers. A qualitative research design was used to investigate these questions. The methods used to collect data were case studies, concerning the brief psychotherapy with 4 boys, aged 7 years, and and semi-structured interviews were conducted with the teachers. Thematic analysis was used to explore the data. The themes that were derived from the analysis were described in detail. The research found that brief work has considerable benefit for children and mainstream schools. Through the brief work intervention, the children all made significant progress in all areas of their lives a school. Contributions that the research makes to related fields, the implications that it has for policy and practice and recommendations for future research were all discussed.

Migration and Residence Patterns of Salmonids in Puget Sound, Washington

Thesis (Ph.D.)--University of Washington, 2016-08

Values and Beliefs Held About Parenting and Education by School Staff and Parents of Pupils with Special Educational Needs in the Context of Home- School Collaboration

Effective collaboration between school staff and parents of children identified as having special educational needs is considered to be an essential component of the child’s successful education. Differences in beliefs and perspectives adopted by the school staff and parents play an important role in the process of collaboration. However, little is known about the precise relationship between the beliefs and the process of collaboration. The purpose of this study was to explore the values and beliefs held by the school staff and parents in the areas of parenting and education. The study also explored the link between these beliefs and the process of collaboration within four parent-teacher dyads from mainstream primary schools. Focus groups and semi-structured interviews based on repertory grid technique were used. The findings highlighted an overall similarity in the participants’ views on collaboration and in their important beliefs about parenting and education. At the same time, differences in perspectives adopted by parents and teachers were also identified. The author discusses how these differences in perspectives are manifested in the process of collaboration from the point of Cultural Capital Theory. The factors such as power differentials, trust between parents and teachers, and limited resources and constraints of educational system are highlighted. Implication for practice for teachers and educational psychologists are discussed.

European student mobility and intercultural learning at a portuguese university

The purpose of this study is to understand, impact and evaluate the development of intercultural communicative competencies among European credit-seeking exchange students and other sojourners through purposeful intercultural pedagogy. This pedagogy encompasses intentional intercultural- educational approaches which aim to support and enhance sojourners’ intercultural learning throughout the study abroad cycle (pre-departure, in-country and reentry phases). To test and validate these pedagogies a 20-hour intervention was designed and implemented among two cohorts of 31 sojourners during the in-country phase of their sojourn in Portugal. The process to develop and validate the intercultural intervention was driven by a mixed-methods methodology which combined quantitative and qualitative data to triangulate, complement and expand research results from a pragmatic stance. The mixed methods research design adopted is multi-phased and encompasses a multi-case study and an evaluative component. The multi-case component is embodied by sojourner cohorts: (1) the primary case study involves 19 incoming students at the University of Aveiro (Portugal) as participants in the European exchange program Campus Europae; (2) the second case study comprises three incoming Erasmus students and nine highly skilled immigrants at the same university. All 31 sojourners attended two intermediate Portuguese as Foreign Language classrooms where the intervention was employed. Data collection was extensive and involved collecting, analyzing and mixing quantitative and qualitative strands across four research phases. These phases refer to the: (1) development, (2) implementation and (3) evaluation of the intervention, as well as to (4) a stakeholder analysis of the external value of the intervention and of the Campus Europae program. Data collection instruments included pre and posttest questionnaires and semi-structured interviews. Results confirm the intercultural effectiveness of the intervention and the positive impact upon research participants’ intercultural gains. This impact was, however, greater in case study 2. Among explanatory variables, three stand out: (1) participant meaning-making abilities, (2) host language proficiency and related variables, and (3) type of sojourn or exchange programs. Implications for further research highlight the need to systematize purposeful intercultural pedagogy in sojourner populations in general, and in European credit student mobility in particular. In the latter case, these pedagogies should be part of the design and delivery of credit-bearing exchange programs in pre- departure, in-country and re-entry phases. Implications for practice point to the urge to improve intercultural practices in: macro (higher education institutions), mezzo (exchange programs) and micro (sojourner language classrooms) contexts where this research took place, and wider social scenarios they represent.

Estudo do aerossol (poeira do Sara) na região de Cabo Verde

No âmbito do projeto CV-DUST foi desenvolvida uma campanha de medição do aerossol atmosférico na Cidade da Praia (14° 55’ N, 23°29’ W), de janeiro de 2011 a janeiro de 2012. A concentração do aerossol foi determinada com base no método gravimétrico, com a amostragem feita em termos de PM10 e em frações granulométricas, usando impactores. Complementarmente, foi usado um contador ótico de partículas que permite a monitorização em contínuo e a classificação do número de partículas em 31 frações de tamanho na gama entre 0,25 e 32 μm. A composição química do aerossol foi determinada com incidência nos seguintes componentes: iões inorgânicos solúveis em água (Cl-, NO3-, SO42-, Na+, NH4+, K+, Mg2+ e Ca2+), carbonato total, elementos maioritários da crosta (Si, Na, Al, Fe, Ca, Mg, K, Ti e Mn) e elementos vestigiais (Ba, Zn, Zr, Pb, Cu, Ce, Ni, Cr, V, Co, Sc, As, Sm e Sb), assim como a fração carbonácea (carbono elementar – EC e o carbono orgânico - OC). Durante a campanha, a concentração de PM10 apresentou uma grande variabilidade temporal, com valores médios (à escala diária) situados entre 10 μg/m3 e 507 μg/m3, sendo a concentração média anual estimada em cerca de 59 μg/m3. As concentrações mais elevadas (tipicamente acima dos 100 μg/m3) foram registadas durante os eventos de poeira proveniente do Norte de África, sendo os mais intensos observados nos meses de janeiro, fevereiro e dezembro de 2011. Os registos do contador ótico, feitos em intervalos de 5 min, revelaram que durante os eventos de poeira as concentrações médias horárias das partículas PM10 e PM2.5 podem ultrapassar os 700 μg/m3 e 200 μg/m3, respetivamente. Com base nos resultados do método ótico, as contribuições das frações granulométricas PM1, PM(1-2.5) e PM(2.5-10) para a massa de PM10 foram estimadas em cerca de 11 %, 28 % e 61 %, respetivamente. A composição química do aerossol varia consideravelmente ao longo do ano e revela a predominância das partículas minerais e do sal marinho. Com base em cálculos do balanço mássico das espécies químicas, as contribuições dos dois constituintes maioritários para a massa de PM10 foram estimadas em cerca de 47 % (partículas minerais) e 17 % (sal marinho). O aerossol secundário (NO3-, NH4+ e fração não marinha do SO42) e o aerossol carbonáceo (EC + OC) contribuem cada um com cerca de 4 % e 3 %, respetivamente. A fração mássica restante (cerca de 29 %), corresponde aos constituintes não analisados, podendo a água ser a mais importante neste grupo. A análise química das amostras segregadas por tamanho revela a seguinte composição para as partículas PM1, PM(1-2.5) e PM(2.5-10): 5,2, 11,8 e 20,7 % (constituintes do sal marinho); 8,6, 3,7 e 3,1 % (iões secundários); 8,9, 1,5 e 1,3 % (EC + OC).