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Exploration of the chemistry of f-element complexes of a polydentate iminopyrrolide ligand
Get PDFThe work described in this thesis concerns the design and synthesis of a tripodal
pyrrole-imine ligand and its coordination to f-elements. The reduction chemistry and potential applications in small molecule activation chemistry of these complexes is evaluated.
Chapter one discusses important advances in organo-lanthanide and -actinide chemistry, emphasising the applications of polypyrrolic Schiff-base ligands in the reduction chemistry of the uranyl dication, the reduction of the redox-inert rare-earth elements, and redox activity of ligands in f-element complexes. A discussion of low oxidation state actinide coordination chemistry is presented.
Chapter two presents the synthesis and characterisation of the tripodal pyrrole-imine
ligand, in addition to a number of attempted syntheses for tripodal secondary- and tertiaryamide ligands. The synthesis and characterisation of the uranyl(VI) complex formed with this ligand is discussed along with its reduction to a hetero-bimetallic uranyl(V) dimer.
Transmetalation of this complex is explored with transition metal and lanthanide halides to form a variety of heterometallic uranyl(V) complexes. The further reduction of an yttrium-uranyl complex to a uranium(IV) multimetallic complex is reported.
Chapter three reports the synthesis and characterisation of mono- and binuclear rareearth metal complexes of this tripodal ligand. The reduction chemistry of these complexes is explored with subsequent metal-based and ligand-based reductions evident. In the case of the ytterbium bimetallic complex, the properties of a mixed-valence singly reduced complex is investigated by X-ray crystallography, electronic absorption spectroscopy, magnetic susceptibility measurements and computational modelling.
Chapter four describes the synthesis of a range of low oxidation state uranium and
thorium complexes. The coordination chemistry and potential applications in small molecule activation is discussed. The solid-state structures of these compounds are reported and reduction of these complexes is attempted.
Chapter five provides a summary of the work presented along with a future outlook.
Chapter six contains detailed experimental methods used in this research and any
analytical data for the compounds synthesised in this thesis
Intercultural language education in China: a comparison of intercultural communication courses in two universities
No full textIn recent decades, China has risen to prominence in the global economy and international politics. This has resulted in an urgent need to develop language learners’ intercultural communicative competence (ICC) in order to achieve more efficient intercultural interaction in the globalised world. This study investigates intercultural language education (ILE) in the Chinese higher education context and how intercultural education policies in China are implemented in intercultural communication courses for English and Business English majors in two universities. Specifically, it focuses on teaching practices, learning processes, teachers, students and programme directors’ perceptions of ICC.
This longitudinal qualitative study was conducted in Northeast China for a period of seven months and consisted of two case studies. Each case focused on a specific university, looking at one higher-ranking university and one lower-ranking university. The study used semi-structured interviews with programme directors, teachers and students, and classroom observation of intercultural communication courses and the analysis of relevant policy documents.
The findings revealed that outdated essentialist theories like Hofstede’s (1991) cultural dimension theories and Hall’s (1976) context theory, as well as cultural knowledge such as eating habits, arts and taboos, were still prevalent within intercultural communication courses and were taught using a teacher-centred approach. University teachers tended to present an essentialist view by equating culture with nation. Guided by an essentialist conceptualisation, classroom activities – such as group discussion, presentations, analysis of critical incidents in groups, as well as watching and analysing films – tend to be dominated by a superficial focus on cultural differences.
The critical discourse analysis of policy documents reveals that ILE serves the government’s aims of promoting China’s growth in a globalised world, and ICC development is seen as being connected to the country’s global engagements, economic ambitions and political concerns. The Chinese government has called for the construction of cultural confidence with the aim of engaging in globalisation without harming national unity or the dominant position of socialism. These political concerns have strengthened a monolithic culture and identity, which now poses a challenge to ICC development in the Chinese context
The non-canonical role of the outer kinetochore protein KNL-1 in axonal development
No full textThe nervous system is composed of specialized cells; glia and neurons, that form an
interconnected network to relay information. Proper transmission of information relies
on the two main compartments within neurons, dendrites, that receive information, and
axons, that relay the information through specialized domains called synapses. Axon
development is a multi-step process that involves, axon outgrowth, guidance,
termination and synaptogenesis. In every step of axonal development rearrangements
in the microtubule and actin cytoskeleton are essential to mediate the morphological
changes that the axon undergoes. The molecular mechanism governing cytoskeletal
regulation during axon development is still not fully characterized.
Recent findings have highlighted a novel, non-canonical role for the outer
kinetochore protein network, KMN (Knl-1, Mis12, Ndc80), in neuronal development.
KMN, primarily recognized for its role in tethering chromosomes to spindle
microtubules during chromosome segregation in cell division, has emerged as a
potential key cytoskeletal regulator in neurons. This work investigates the noncanonical
neuronal role of the outer kinetochore signalling and scaffolding protein
KNL-1, in brain organization and axon development. In my thesis I show that KNL-1 is
essential for axon organization and termination in the nervous system of C. elegans.
In the first part I show that KNL-1 is required for the organization of the C.
elegans nerve ring axons and ganglia organization in the brain. Specifically, loss of
KNL-1 affects the correct placement and fasciculation of the axons within the nerve.
Structure-function analysis of KNL-1 showed that this function requires both the
signalling and microtubule binding domains of KNL-1.
The second part of my work reveals an essential role for KNL-1 in axon
termination, a process whereby the axonal growth cone is destabilized and stops its
growth upon reaching its target. The effect of KNL-1 in axon termination, requires
reorganization of F-actin at the axonal tip and is regulated by microtubule dynamics.
In the final part, I have used Correlative Light-Electron Microscopy and a GFPTrap
of KNL-1 in C. elegans embryonic neurons to identify the neuronal structures and
proteins that KNL-1 associates within the axon. KNL-1 associates with endo-lysosomal
structures in the cell body and synaptic vesicles in the axon. Mass spectrometry
analysis revealed a synaptic protein as a potential interactor-candidate of KNL-1. This
work showed a new potential link of KNL-1’s neuronal activity with synaptic
organization and function.
Overall, this study provides insights into the mechanism by which the outer
kinetochore component KNL-1 functions in brain development, identifies a novel role
for this protein in axon termination and reveals neuronal interactors of KNL-1
highlighting a potential role of the protein in synapses
Obfuscated Konkat: a concatenative audio-visual composition system for game engines
Get PDFCreating audio-visual art using a game engine presents a unique set of challenges and
opportunities for artists and developers. As computation continues to advance, the
possibilities for real-time systems not only expand artistic expression but also redefine
the role of the creator and the relationship between the artwork and the audience. This
project represents a series of extensive experiments in creating an interactive audio-visual
composition system within the Unity game engine. The primary results are presented
in the form of video documentation of performances and compositions. The final work,
titled ‘Obfuscated Konkat’ (OK), is a fully interactive, game-like virtual world that
aims to create a new multimedia experience by combining video games, cinema, and
contemporary audio-visual art. Due to the complexity of designing and developing a
dynamic real-time system on this scale, OK is still experimental software. While many
aspects of game development go beyond the scope of this project, substantial efforts
have been made to document and demonstrate its capabilities
Rough analysis meets 2D Yang–Mills theory
No full textWe study probabilistic two-dimensional Yang–Mills theory with tools from rough analysis across three different projects. The first project develops tools for the Yang–Mills–Higgs measure: we define a Polish state space that carries Wilson loop observables for the gauge fields and string observables for the Higgs fields. We also provide conditions under which a separable Banach space with a continuous action of a topological group admits a Polish quotient space—conditions that find application in both the first and third projects.
The second project is the main contribution of the thesis and is concerned with rough Uhlenbeck compactness, which provides a gauge fixing for the Yang–Mills measure. In this project, we introduce the concept of rough additive functions, extending rough paths theory to line integrals of distributional 1-forms. In the context of gauge theory, this allows us to define controlled gauge transformations and holonomies via rough differential equations. The metric for rough additive functions serves as a gauge-invariant quantity used to prove a rough Uhlenbeck compactness result on the unit square. The main ingredient is a singular elliptic stochastic partial differential equation used to obtain a Coulomb gauge, which we solve using regularity structures. Surprisingly, we manage to define the model on the singular terms occurring in the regularity structure deterministically via the given rough additive function. This leads to a phenomenon where the underlying model is determined by a much simpler and geometrically more natural object. Consequently, our result can be seen as the first gauge-fixed representation of the Yang–Mills measure on the unit square using PDE techniques.
In the third and final project we initiate an operator approach to Yang–Mills theory. We study Dirac operators induced by the covariant derivative associated to a connection form. This operator is viewed as an unbounded operator on an Lp-space of differential forms. We characterise the domain via paraproducts, prove resolvent estimates and further analytic properties of this operator. Using spectral theory we define gauge-invariant observables that characterise the underlying forms up to gauge equivalence. This is a new result even in the smooth setting. Finally, we prove closedness of orbits under gauge transformations of a Hölder–Besov space of connection forms of certain regularity using resolvent estimates. This is a crucial step which we use to prove that a certain quotient space is Polish. That space is important as the Yang–Mills measure is supported on such a space under a suitable viewpoint
The Chang'an rhapsody: towards a graphmatology of writing
No full textAs a critical response to Heidegger’s claim in The End of Philosophy and the Task of Thinking (1972) that the end of philosophy signifies Western European thought becoming the foundation of world civilization, philosopher and sinologist François Jullien seeks to re-envision the task of post-European thought. In contrast to Derrida’s project of deconstruction from within, Jullien proposes a “detour” through the Chinese philosophical tradition, offering a form of deconstruction from without. He methodologically contrasts China and Europe as having two distinct philosophical systems, and by attempting to elaborate on these differences, Jullien opens up a new horizon for the emergence of alternative modes of thinking. Beyond suggesting a detour for the West to reflect on its own system through the lens of Chinese thought, Jullien points to the possibility for a non-European mode of thought — one that requires a new language, a new mode of writing, and a new way of articulating objectives and values.
In Writing and Difference (1967), as part of his attempt to overcome the ontology of a phonocentric writing system, Derrida envisions a “graphmetics” inspired by Freud’s psychoanalytic model of a writing machine, using the Chinese script as a metaphor for a writing apparatus yet to come. Taking the Chinese aesthetic and poetic tradition as a starting point, the design research project The Chang’an Rhapsody, aims to develop a “graphmatology” of writing by engaging with Jullien’s critique.
The project challenges contemporary thought on themes such as language, media, environment, technology, and time—areas constrained in this technological epoch by the limitations of existing ontological frameworks.
By reinterpreting the ancient Chinese literary genre of fu (rhapsody, 賦) and extending it beyond its traditional literary confines, The Rhapsody serves as a design-driven, critical speculation within a broader de-ontological framework. It metaphorically reconstructs Chang’an (長安), the ancient Chinese capital, as a writing machine through seven tactical apparatuses. The thesis examines specific rhapsodic moments of creation in China’s history, including: Ban Gu (班固)’s Chang’an Fu (長安賦, 65 AD), the noblewoman Lady Dai (辛追)’s Tomb Banner (168 BC), The Night Baquet of Han Xizai (韓熙載夜宴圖, 10th century AD), Adachi Kiroku’s (足立喜六, 1871-1949) photographic survey of Xi’an, as well as modern literary works like Lu Xun (魯迅)’s Diary of a Madman (狂人日記, 1918) and Gao Xingjian (高行健)’s Between Life and Death (生死界, 1991).
Mediated and curated across both analogue and digital forms, the thesis is driven by a series of design acts, functioning as a means of critical interpretation and creative exploration. It aims to engage with, and contribute to, the established scholarly debate on de-ontology while envisioning its spatial, architectural, and urban implications
Electrodeposition of Cu-based catalysts for the electrochemical conversion of CO₂ to valuable chemicals and renewable fuels
No full textElectrochemical carbon dioxide reduction (CO2R) is a promising technology for sustainably storing renewable energy and producing carbon-based chemicals. To commercialise CO₂R, catalysts must achieve high selectivity and efficiency at low energy costs. However, achieving reproducible gas diffusion electrodes (GDEs) remains a challenge, as small variations in preparation can lead to variations in features such as surface uniformity, morphology and catalyst loading. This research follows a systematic approach to address these challenges by optimising the fabrication of GDEs for CO₂R. Electrodeposition, a widely used and time-efficient technique for synthesising Cu catalysts, plays a central role in this process. Its precise control over surface morphology, crystal orientation, and alloying with other elements enables the production of catalysts with tailored activity and selectivity. By ensuring reproducibility in GDE fabrication, electrodeposition provides a fundamental solution for advancing the commercial viability of CO₂R. The manufacturing of CO₂ catalysts by electrodeposition begins by carefully ’activating’ a commercial carbonaceous gas diffusion layer (GDL) using HNO₃, which makes the surface sufficiently hydrophilic, so that droplets remain on the surface rather than penetrating the GDL bulk for uniform catalyst electrodeposition, while maintaining the bulk hydrophobicity to prevent flooding during electrolysis.
Key electrodeposition parameters, including pH, temperature, current density, and catalyst load, were optimised under galvanostatic conditions, achieving reproducible GDEs with uniform Cu catalyst distribution. Cu GDEs with 5 cm² showed a CO₂R Faradaic efficiency of 70% at 200 mA cm⁻², while material use was reduced by 50% (1 compared with 2 C cm⁻²) and electrodeposition time by 75% (30 vs. 15 mA cm−2 at 1 C cm⁻²).
To enhance product selectivity towards C₂₊ products and suppress the competing hydrogen evolution reaction, Cu was alloyed with Ag to produce bimetallic CuAg catalysts. Citrate was used as a stabilising additive to enable uniform deposition and improve electrolyte stability. CuAg catalysts deposited at 15 mA cm−2 with a catalyst loading of 2 C cm⁻² exhibited the best overall performance, achieving C₂₊ Faradaic efficiency of 73% at 200 mA cm⁻², with high selectivity for ethylene and alcohols while reducing HER to less than 20%. At 200 mA cm⁻², Cu exhibited slightly higher energy efficiency, whereas CuAg favoured C₂₊ products, particularly alcohols, indicating more effective utilisation of CO intermediates.
The combination of morphological control, catalyst integration, and electrochemical evaluation presented in this work provides a scalable and reproducible strategy for GDE fabrication. This approach contributes to the advancement of efficient, cost-effective, and industrially relevant CO₂ electroreduction technologies
Investigating the intrapersonal and interpersonal functions of adolescent self-harm: a research portfolio
Get PDFOBJECTIVE:
This thesis aimed to explore the intrapersonal and interpersonal functions of self-harm for young people. The systematic review aimed to synthesise studies which explored how caregivers understand their young person’s self-harm. The empirical project aimed to examine whether attachment insecurity predicted which functions of self-harm were endorsed and whether this relationship was mediated by difficulties in emotion regulation.
METHODS:
The systematic review searched eight databases to identify eligible studies which included qualitative data on how caregivers understand their young person’s self-harm and thematic synthesis was used to analyse results. The empirical project was a cross-sectional, questionnaire-based study and was analysed using three mediation models.
RESULTS:
The systematic review identified 22 eligible studies and identified four superordinate themes: 1) A Lack of Understanding 2) Searching for a Cause 3) Internal Functions 4) Interpersonal Functions. The empirical project found support that attachment avoidance could predict intrapersonal functions of self-harm and attachment anxiety could predict interpersonal functions of self-harm. There was also support that these relationships were mediated by differences in emotion regulation in three out of four cases.
DISCUSSION:
The systematic review identified that caregivers often feel that they lack understanding of their young person’s self-harm, and access to good psychoeducational materials and support is important to relieve their feelings of guilt and allow them to better support their young person. The findings of the empirical project suggest that promoting greater attachment security, improving emotion regulation skills, and identifying alternative means of meeting specific functions of self-harm can be important targets for intervention
Regenerating well-being: exploring the impact of the urban environment on the well-being of young people in Glasgow, UK
Get PDFThis doctoral thesis explores the effect of urban liveability on the well-being of young people in Glasgow. My interest in this topic came from my experiences living and working in Drumchapel, Glasgow in 2019-2020. It was here that I began to observe aspects that made living in this community difficult: poor transportation, fewer job opportunities, abandoned physical spaces, lack of healthy food choices, and a lack of green space. These are arguably key features of what makes a community liveable, and their absence affects every part of one's life, including health and well-being (Badland and Pearce, 2019). These experiences, the interest in young people's participation and in what has been coined ‘the Glasgow Effect’ phenomenon, led me to develop the research question: How do young people's interaction with environments, (economic, physical, social) shape their wellbeing in Drumchapel, Glasgow, UK?
The field of youth development and wellbeing in the UK emphasizes a participatory approach to achieving change (Hagen, 2021). There are parts of cities globally that, because of their geographical position in the city, have different stressors impacting the population (Maantay and Maroko, 2015). This project seeks to understand if this is true for the young people living in Drumchapel. While Glasgow has some entrenched social and economic problems, it is a good case study to understand the interrelated problems involving wellbeing and environment in other urban areas.
To explore these issues, I conducted a yearlong ethnography alongside participatory activities and interviews. The methodological approach included collaborative data analysis with the participants throughout the ethnography. The young people (ages 1219) were recruited through G15 Youth Project in Drumchapel. My research and the inclusion of a reflexive thematic analysis was informed by my position as a middleclass American-origin researcher, living outside of a working-class Scottish community (Carlson, 2017). This positionality and my concern to provide a platform for the opinions and vision of the young people, made it important that young people were involved as much as possible.
Throughout the collaborative data analysis three themes emerged to help understand how young people are impacted by their environment. The first theme was the discrimination they experienced and its impact on their identity which includes self-esteem issues and internalised oppression from negative stereotypes. The second was experiencing a lack of environmental justice in the quality and quantity of resources they have access to. The third theme showed the impact identity and environmental injustice have on their social capital and social mobility which can impede their overall wellbeing.
Overall, my analysis demonstrates that in this study, the young people’s well-being is negatively impacted by the lack of material resources and negative stereotypes held about their neighbourhood. The young people in this study reject the path set out by them and call for changes if they are to have equal opportunities. Some of the calls for change the research recommends include material changes in the community like improving streetlights, streets, and access to transportation and others reflect a wider societal change including improved social and educational resources and a change of attitude towards policing. This research shows that these changes can only be achieved by implementing a wider cultural change into the priorities of local and national authorities
TikTok mental health and the impact of adolescent self-diagnosis exploration in the counselling room: a reflexive thematic analysis of therapeutic practice
Get PDFThis thesis explores how therapists perceive and work with adolescent clients who are
exploring self-diagnosis of mental health conditions after viewing social media content.
Using semi-structured interviews and reflexive thematic analysis, the thesis examines the
experiences of six qualified therapists working with young people in Scotland. Two research
questions guide this investigation: "What are therapists' perceptions of what a self-diagnosis
means for adolescent clients?" and "How are therapists working with adolescent clients
exploring a self-diagnosis from social media?" The analysis reveals that therapists perceive
social media self-diagnosis as serving multiple functions for adolescents, including identity
formation, seeking certainty during a developmental period of ambiguity, and communicating
needs. While therapists expressed concerns about algorithmic influence and misinformation,
they maintained primarily humanistic approaches in their practice, prioritizing the therapeutic
alliance and exploring the meaning of self-diagnosis for each client. The study found that
therapists often navigate this phenomenon without specific training, leading to an expansion
of their professional roles to include viewing social media content in sessions, providing
psychoeducation, and explaining formal diagnostic processes. This research contributes
original insights to an emerging field, highlighting implications for therapeutic practice,
supervision, and training, while identifying the need for additional resources to support
therapists working with this growing presentation in the post-pandemic digital landscap
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