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Redox-Mediated Electrocatalytic Ammonia Synthesis On Metalloporphyrin Metal-Organic Frameworks
No full textAmmonia is a critical commodity for fertilisers and chemical industry but is currently synthesised by the carbon-intensive Haber-Bosch process. Ammonia electrosynthesis in aqueous conditions could allow low-emission ammonia to be generated using abundant starting materials and renewable energy. As such, both the electrocatalytic nitrogen reduction reaction (eNRR) and electrocatalytic nitrate reduction reaction (eNO3RR) are active areas of research. Unfortunately, most reported electrocatalysts for these reactions fail to achieve industrially relevant current densities (≥ 300 mA/cm^2). Metalloporphyrin metal-organic frameworks (MOFs) are nanoporous, 3D arrays which host a high density of metalloporphyrin active sites. Such materials could yield high ammonia production current densities, making them ideal electrocatalyst candidates. However, such MOFs generally exhibit poor electrical conductivity, limiting their activity.This thesis investigates the activity and viability of the metalloporphyrin MOF PCN-222(M) for eNRR and eNO3RR, as well as the use of a molecular redox mediator to bypass the insulating framework. By using a redox mediator, electrons from the cathode can be shuttled to the metalloporphyrin active sites, potentially boosting the ammonia current density. After successfully exploring post-synthetic metalation techniques to synthesise PCN-222(M), the MOFs were investigated for both eNRR and eNO3RR. The latter proved successful, with PCN-222(Cu)-coated electrodes achieving an ammonia yield rate of up to 350 ± 40 μg/h/cm^2 and faradaic efficiency of up to 18.5 ± 0.6% in a membrane-free cell. Lastly, the interaction between the redox mediator methyl viologen and an iron(III) porphyrin was investigated.</p
Two Gaps in Studying High‐Fidelity Imitation Across Diverse Childhood Ecologies
No full textABSTRACTRecent empirical investigations have concentrated primarily on studying imitation as a social tool that satisfies social motivations, while other potential reasons for and forms of imitation have attracted less attention. These investigations have also focused on studying the role of pedagogy in imitative learning and set up most experiments in a pedagogical framework. In this article, we present two gaps in studying high‐fidelity imitation. First, social motivation may not be the only motivation, especially in less socially stratified communities. Second, imitative learning in observational contexts is understudied. We discuss these gaps by providing examples of alternative imitative learning scenarios and aspects that may have been overlooked and thus underexplored. Moving forward, cross‐cultural investigations targeting other aspects and forms of imitative learning can provide insights into how observational and pedagogical learning together foster effective learning across diverse childhood ecologies
Experiences of early childhood teachers with refugee children and their families in New Zealand.
No full textThis qualitative narrative inquiry examined the teaching and learning experiences of six early childhood teachers working with refugee children and their families in an urban district of New Zealand. Using (a) filmed observations, (b) semi-structured interviews with teachers, and (c) stimulated recall interviews I collected narratives about the teachers’ encounters, and the relationships they developed, with refugee- background families and their children in their centres. Research journals kept by the teachers and myself as the researcher recorded further reflections on the data and supplemented the oral narratives. This study also investigated the sources of knowledge teachers relied upon when working with families and children who were refugees; and how their professional training prepared them for teaching refugee children.My analysis used theoretical constructs from Dewey’s notions of experience (Dewey, 1938), culture and culturally responsive practices (Gay, 2000; Ladson-Billings, 1995), and ethics of care (Noddings, 1995), to understand teachers’ experiences of working with refugee children and their families.Data were transcribed and analysed using a constant comparative analysis within the framework of sociocultural theory (Rogoff, 1995 and Vygotsky, 1978). Through a detailed examination of the teachers’ narratives and stories, I found that teachers created a culture that demonstrated an ethic of care to support refugee children during enrolment and settling phases, and celebrated the diverse cultures refugee children brought into the centres. The study also found that teachers’ experiences with refugee parents were characterised by language and cultural barriers. The parents had contrasting educational perceptions to those held by teachers which made communication between teachers and refugee families a challenge. Teachers in this study attempted to promote refugee families' participation and reported moments of deep satisfaction in connecting refugee families with the community.The findings of this study indicate that teachers did not experience adequate opportunities in their initial teacher training to learn about how to address the needs of refugee children. They noted that they lacked training in understanding children with refugee experiences, parent communication, and culturally diverse practices. The need for continual professional development in working with refugees from culturally diverse backgrounds was highlighted by the teachers. Implications for teacher preparation and practices are discussed in light of existing research literature.</p
Investigating immunomodulation and promotion of remyelination by regulatory T cells, in response to nalfurafine treatment.
No full textMultiple sclerosis (MS) is a chronic inflammatory condition characterised by the targeted destruction of the protective myelin sheath surrounding nerve cells in the central nervous system (i.e. demyelination). In demyelinating diseases, the process of remyelination is either impaired or the rate of myelin production fails to compensate for its depletion. This prolonged demyelination with inadequate remyelination results in symptoms of MS including visual disturbances, cognitive impairment, fatigue, and paralysis. The current treatment options are limited to immunomodulatory agents and generalised symptom management, which do not directly support remyelination. Our research is focused on developing therapeutics to promote remyelination and recovery in MS.The kappa opioid receptor (KOR) agonist, nalfurafine, has been shown to promote functional recovery and remyelination in experimental autoimmune encephalomyelitis (EAE), an animal model of demyelination. Previous work conducted by the La Flamme research group indicated that nalfurafine-mediated benefit in control of EAE disease may be regulatory T cell (Treg)-dependent. Tregs play a regulatory role in the immune system by suppressing T cell responses and promoting immune resolution. Research has shown that Treg abundance and/or function is impaired in several chronic inflammatory conditions including MS. More recently, studies have identified that Tregs are involved in the remyelination process by contributing to both inflammatory resolution and promoting the differentiation of the cells which provide the myelin sheaths (i.e., oligodendrocyte precursor cells).The in vitro assessment of nalfurafine on Treg function demonstrated an enhancement in Treg expansion and proliferation. Furthermore, we revealed that nalfurafine may also augment the suppressive capacity of Tregs, both in vitro and in vivo. We have demonstrated that in vivo neutralisation of regulatory T cell function with anti-CD25 antibody treatment abolished nalfurafine-mediated recovery from disease and hindered spinal cord remyelination. Through the selective genetic deletion of the kappa opioid receptor on regulatory T cells, we have shown that FoxP3+ regulatory T cells are crucial for nalfurafine-mediated remyelination and recovery from EAE, and that this protective effect is mediated through the kappa opioid receptor on regulatory T cells specifically. We subsequently utilised human PBMCs in vitro to assess the immune-related changes occurring as a result of nalfurafine treatment. We observed similar immune profiles in these human PBMCs, following nalfurafine treatment, as we do in murine splenocytes. Most notably, an increase in regulatory T cells was observed. Given the essential role of Tregs in nalfurafine-mediated remyelination and recovery from animal models of MS, these results suggest that nalfurafine may provide additional benefit by supporting the protective functions of Tregs in MS.This study was pivotal in assessing the potential of using nalfurafine in the treatment of MS, and provides a promising rationale for its translation to the clinic. Moreover, this research contributes to the understanding and development of therapeutics targeted at promoting remyelination within the central nervous system, which would directly address the cause of disability in MS – demyelination.</p
An Entangled Language of Music and Nature: Exploring Musical Ecopoiesis
No full textWhat does it mean for an ocean to be played like a drum? Could a dawn chorus be considered a form of orchestral music? How does one use sound to ‘paint an image’ of a mountain valley? An Entangled Language of Music and Nature: Exploring Musical Ecopoiesis will address questions such as these. I have devised the term musical ecopoiesis to refer to any creative process in music or sonic art that is informed, engendered, or otherwise inspired by the natural world. In musical practices that incorporate this approach, the poietic—or compositional—effort can be attributed to both human and more-than-human entities. Although the practice of musical ecopoiesis spans innumerable cultures and time periods, no generalised research framework exists that can disentangle its fundamental mechanisms. This dissertation and its accompanying portfolio of work seeks to address this, introducing a new practice-centric framework dedicated towards developing a holistic understanding of both the past and possible future of musical ecopoiesis.</p
Japanese children's experiences in Aotearoa New Zealand early childhood education and care settings
No full textAotearoa New Zealand is now regarded as a superdiverse country. Early childhood education and care (ECEC) settings in Aotearoa New Zealand reflect this diversity presenting challenges and complex situations for children and adults to navigate. However, there is a paucity of research in this area, along with understanding the experiences of children from ethnic minorities, including Japanese. This study investigated Japanese children’s experiences in New Zealand ECEC contexts and explored how these children responded to and negotiated situations that are culturally challenging in their ECEC settings.Using a qualitative multiple-case study approach, I focused on five Japanese children in separate ECEC settings across New Zealand. Data was gathered through observing each child, interviewing their parents and teachers/educators, and analysing national and international frameworks that are part of the broader context in which ECEC settings are located. Rogoff’s three foci of analysis (2003) were used to analyse the children’s experiences from multiple perspectives including personal, interpersonal, and cultural-institutional. I also drew on concepts from critical multicultural perspectives as a way of interrogating the position of children in a minority group – i.e., Japanese – in a predominantly Western and bicultural education system.The findings suggest that Japanese children experienced complex cultural situations that created challenges and influenced their choice of cultural identities while negotiating their sense of belonging in their ECEC communities. Furthermore, the findings suggest that there are multiple ways of being Japanese. The children’s identities were largely fluid and changed in response to the current situation and the opportunities and challenges it afforded. I argue that the Japanese concept of Ibasho – referring to the place where people can be themselves – was crucial to understanding shifts in the children’s sense of belonging and in their expressions of identity.My study contributes to understanding the diversity of Japanese children’s experiences in New Zealand ECEC centres. It signals the importance of avoiding overgeneralizations of ethnic identities and the need for teachers to be supported in their work in superdiverse settings.</p
Show Me the Common Space: How Can the Design of Shared Space Facilitate Economic and Social Value in High-Density Housing?
No full textUrban intensive housing is predominantly developer-led in Aotearoa New Zealand resulting in an absence of quality shared space that limits opportunity for residents to build community. Collective housing addresses issues of isolation and loneliness associated with individualised housing, which is mostly seen in intentional communities with formal social structures. This research investigates social and economic benefits of shared spaces in urban collective housing. It focuses on fostering neighbourhood social ties through informal social exchanges. The methodology follows a comparative analysis of a proposed developer-led housing project in Christchurch identifying the extent and spatial distribution of public, common and private space. 26 Aroha demonstrates the economic value of shared space in collective housing with 27% common space. Its above market rentals and waiting list highlight the need for more community-centric urban intensive housing in Aotearoa New Zealand. Design-led research emphasises the importance of semi-private design elements and buffer zones in establishing boundaries between walkways and private space. The functional qualities of common rooms and their connection to walkways are important for enhancing the potential for chance interactions. There is a link between social capital and self-management demonstrated in cohousing. A suggested maximum of 25 households is identified, resulting in a series of micro-communities distributed throughout a large-scale housing complex. Cluster apartments is another significant model presented in the final concept. The final design concept findings demonstrate 28% common space, 60% private space and 12% public space as the sweet spot to efficiently facilitate community activity for residents who otherwise would not have the chance to connect.</p
Making moral selves through comparison: Narratives of moral decline and the modern virtuous self among middle‐class older adults in Nepal
No full textAbstractDuring fieldwork among older adults in middle‐class families in the city of Bhaktapur (2018–2019), I recurrently came across comparative narratives of moral decline, depicting a stark contrast between the present time and a mythical past where ageing parents were treated “as gods.” In this paper, I analyze how, through acts of comparisons involving the weighing of opportunities between the past and the present and between difficulties facing parents and children, older people define their “moralities of expectation,” through which intimate politics of giving and taking are weighed against perceptions of hardship in the context of precarious middle‐class livelihoods. I suggest that comparison functions as a social practice with epistemological and affective connotations and that by comparing with real and imagined others, older people validate themselves as virtuous by anchoring to fluid and ever‐changing social systems. Ultimately, these findings shed light on how moral selfhoods are shaped through comparison with models of the past and the present, revealing how it is in this careful and purposeful evaluation of one's own behavior and that of others that social change is negotiated and the broader ethos revised
Whare Tapere: A House of Storytelling in the Space of Lost Time
No full textWritten by female, award-winning Māori author Whiti Hereaka, the 2021 novel Kurangaituku reimagines the traditional pūrākau (oral narrative) of Hatupatu and the ‘terrible bird-woman’, Kurangaituku. The novel has two front covers that allow the reader’s journey to begin from either end of the codex: the light cover or the dark cover. This unique structure reflects a deeply-held Māori worldview, where time and space are fluid, ever-shifting, and interconnected. The narrative traverses the dual realms of te ao Mārama (the realm above) in one direction and Rarohenga (the realm below) in the other. Threads from te ao Mārama and Rarohenga are skilfully raranga (woven) together to shape Kurangaituku’s story; weaving is an important allegorical storytelling device in the novel and as such will be re-presented as an allegorical device in this architectural investigation.At the beginning of both the light and dark covers, a Whare Tapere—House of Storytelling—is described; however, it is only in the middle, the ‘In-between’ layer of the book where the two tales overlap, that the Whare Tapere can be fully understood. This ‘In-between’ layer where the two stories overlap is referred to as a ‘Space of Lost Time’. Here, the Whare Tapere cycles continually from beginning to middle and end, rather than existing at a fixed point in time or space; here, time slows itself, blurring the boundaries between the seen and unseen, the known and the forgotten.Hereaka’s work of literature uses the allegory of a House of Storytelling sited within a Space of Lost Time to challenge fixed Western notions of time and space. She uses three principal literary devices—Dualities and Oppositions, Liminality, and Temporality—to represent a cyclical temporal sequence that allows a reader to engage with the story from any direction, thereby reinforcing the te ao Māori idea of time and space as fluid, ever-shifting, and interconnected. This thesis proposes to architecturally represent this notion of fluid time and space, by exploring how an allegorical architectural project might re-present the te ao Māori concept of a House of Storytelling in the Space of Lost Time.This design-led research investigation asks: How can the principal literary devices used by New Zealand Māori author Whiti Hereaka in her novel Kurangaituku to represent a House of Storytelling in the Space of Lost Time, be applied to a design-led research proposition and re-presented as an allegorical architectural outcome?</p
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