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Investigation of pain sensitivity in individuals with shoulder pain
No full textBackground: Shoulder pain is a common musculoskeletal (MSK) complaint associated with a significant impact on health and socioeconomic outcomes. Currently, there is a poor and conflicting evidence on the mechanisms driving shoulder pain experience. Review of the literature highlighted several methodological issues among previous cross-sectional studies, which investigated the contribution of peripheral and central sensitization in patients with shoulder pain. Particularly, the confounding role of psychological, social, and lifestyle factors (sleep, and physical activity) on the measures of sensitization were not taken into account. Therefore, research improving the knowledge about the mechanisms behind variability in shoulder pain experience would help to plan better management strategies for improving clinical outcomes.
Aim: The overall aim of the thesis was to establish the role of peripheral and central sensitization in explaining shoulder pain experience. This thesis involves a systematic review and three original investigations: a parallel-group cross-sectional study, a prospective study, and a methodological investigation.
Methods: The systematic review established the level of evidence of the relationships between psychological, social, physical activity, and sleep measures and measures of sensitization in individuals with MSK pain. Study-1: A parallel-group cross-sectional study investigated the presence of sensitization in patients with shoulder pain. Study-2 investigated the cross-sectional and prospective predictive relationships of measures of sensitization on shoulder pain outcomes. Study-3 investigated the concurrent validity of sensitivity to movement-evoked pain (SMEP) procedure, a novel, functional form of pain sensitivity testing against other measures of sensitization (i.e. quantitative sensory testing).
Results: The systematic review identified a moderate level of evidence supporting the negative relationships between depression and pain catastrophizing and quantitative sensory testing (QST) measures among individuals with musculoskeletal pain. Particularly in shoulder pain, depression and pain catastrophizing have significant (small to fair) associations with QST measures with level of evidence ranged from ‘very low’ to ‘low’. Study-1 demonstrated mechanical allodynia, greater symptomology related to central sensitization, and greater SMEP when compared to healthy controls. Study-2 identified measures of sensitization were independently associated with worse shoulder pain outcomes at both baseline and follow-up. Sub-study: SMEP has demonstrated significant associations with measures of sensitization (i.e. QST).
Conclusion: The thesis established that sensitization explains shoulder pain experience; however, it is confounded by psychological factors. This thesis also established the validity of SMEP, as a valid way of evaluating pain sensitivity in individuals with chronic shoulder pain.
What's a Judge to Do? Allegations of Police Torture in China as Evidence in an English Court
Get PDFThe author considers the UKSC case Shagang Shipping Co Ltd (in liq) v HNA Group Co Ltd, in which the Supreme Court had to determine the admissibility go unproven but credible allegations of torture by Chinese police. The Court made the perhaps politically charged decision to overturn the Court of Appeal’s ruling and admit the allegations in the assessment of other evidence’s reliability and weight. Ultimately, torture is illegal in China and remains its government’s responsibility to investigate and prevent
Paying with dignity: Neoliberalisation and the human cost of food charity
Get PDFThis project explores how domestic hunger is understood and addressed in Aotearoa New Zealand, and the development and institutionalisation of food charity. A charitable solution is at odds with a state’s legal obligations to realise the human right to adequate food of all its citizens, as outlined to in numerous United Nations treaties. It is therefore inconsistent that Aotearoa New Zealand is a signatory to multiple treaties of this kind, yet the dominant model for responding to food hunger is charity. Using a critical qualitative approach and human dignity as a research lens, I explore both the macro-socio-economic context in which food charity exists in the country, and the micro-level lived experiences of those who depend on it.
I start my investigation by exploring the dominant economic model of neoliberalism, including its influences on human dignity—its definition and how it is experienced—before moving onto examining the place food charity has in mitigating, reproducing, and contesting this ideology, and the impacts this has had on the dignity of those it is attempting to assist. I use this as a foundation from which to explore the socio-economic context of Aotearoa New Zealand, beginning with an examination of the country’s historical context, with a focus on the colonisation of Aotearoa and the establishment of capitalism, and the introduction of neoliberal policies. I then evaluate the existence of domestic hunger today and delve into the state’s understanding of food security and the policies it has enacted that both follow and reinforce this understanding. Within this overall framework, I then hone in on the historical development of food charity in the country, concentrating particularly on attitudes towards food charity as well as those who depend on it.
Using this as a contextual backdrop, I introduce the personal experiences of food charity of 55 residents of Ōtepoti-Dunedin, a city in the South Island of Aotearoa New Zealand. Using a critical hermeneutic phenomenology and inductive thematic analysis, I organise the stories they shared into three main themes that consider the indignities of: living in poverty; the systems in place to address domestic hunger—food charity and social welfare; and food charity interactions.
Reflecting on both my macro and micro-level analyses, I concentrate on the significance of human dignity in people’s lives, particularly as it relates to how neoliberal tenets have shaped and capitalised on narrow understandings of dignity. I then investigate how food charity has inadvertently amplified neoliberal narratives, focusing on those of social (un)acceptability, (in)dependency, and (un)deservingness, and how the denial of choice, rights, and power relations within food charity spaces has been detrimental to food parcel recipients’ sense of dignity. Finally, I consider how, despite the indignities associated with and experienced within food charities, dignity is also present in the relational components. I then end by reflecting on the place of the human right to adequate food within Aotearoa New Zealand and how it is both advantageous, yet currently unattainable
NOx electroreduction: reaction mechanisms and catalyst structure
Get PDFReactive nitrogen is becoming a prevalent and threatening pollutant in the biosphere, with the rate of pollution continuing to increase. Thus, an efficient method for denitrification is essential. One promising method is the use of electrocatalysis to remove nitrate, a common form of reactive nitrogen, from water. CuPd nanoparticles (clusters) have shown great promise as a catalyst for selective nitrate electroreduction to dinitrogen (N2), a benign form of nitrogen. In order to enable the use of CuPd catalysts as a denitrification method, their catalytic ability must be improved. For this to happen, we must understand more about two key factors: the mechanisms of nitrate reduction toward different products, and the structure of the CuPd cluster catalysts. These are the two broad aims of the research presented in this thesis.
First, using density functional theory, we determine the mechanisms by which NO electroreduction products are formed, on planar and stepped transition metal surfaces, as the reduction of NO is key to determining the product selectivity of the overall nitrate reduction reaction. There are a number of possible reduction products in addition to N2, with the common products on most transition metals being ammonia (NH4+), hydroxylamine (H3NOH+), and nitrous oxide (N2O), which are the products considered here. In addition, the theoretical onset potentials for each product on the different metals are calculated, and scaling relations and a limiting potential volcano are constructed to investigate the trends across the range of metals.
On the planar metal surfaces, it was found that the mechanism toward ammonia on the majority of metals goes via an NOH intermediate, while for hydroxylamine both NOH and HNO are key intermediates. In addition, it was found that the onset potential for NO reduction is not strongly influenced by the energy of N binding, and thus is relatively invariant across the range of metals. For nitrous oxide formation, two mechanisms are considered: an Eley-Rideal mechanism is found to be possible on all of the metals studied, while a Langmuir-Hinshelwood mechanism was only found to be possible on Ag, Au and Cu. The influence of the choice of solvation correction, surface NO coverage, and exchange-correlation functional were also investigated, and were found to have minimal influence on the overall results and trends.
Following on from the planar surfaces, stepped metal surfaces were investigated in order to determine the impact of surface morphology on the reaction mechanisms and onset potentials. The steps represent a more complex surface geometry, and have been shown to have higher catalytic activity than planar surfaces, and are potentially present on clusters. The largest impact of the surface morphology was on the mechanisms by which the products are formed; for ammonia and hydroxylamine, reaction pathways via both HNO and NOH intermediates are competitive, whereas for planar surfaces, NOH was more favoured. For nitrous oxide formation, it was found that both the Langmuir-Hinshelwood and Eley-Rideal mechanisms are plausible for most metals, which is a distinct difference from the planar surfaces, where the Eley-Rideal mechanism was the only plausible mechanism on most metals. The onset potentials and scaling relations were found to be relatively insensitive to the surface morphology, and were found to be similar to the planar surfaces.
On transition metals, formation of N2 in significant amounts is only observed on Pd. Here we investigate the mechanism of N2 formation on Pd, and the adsorption and reaction of relevant species, in comparison with Pt, a metal that does not form any significant amount of N2, despite its similarity to Pd for many other catalytic applications. It was found that the potential dependent adsorption of hydrogen is a key difference on the metals; on Pt, hydrogen may inhibit the adsorption and formation of key precursors to N2 formation, while on Pd, this inhibition is unlikely to occur.
Understanding the structure of CuPd clusters is essential to understanding their nitrate reduction ability, due to the intrinsic link between a cluster's structure and catalytic ability. Here we use a genetic algorithm, with energies calculated using an empirical potential, to investigate the structure of CuPd clusters at multiple sizes and Cu:Pd ratios. First, we consider 38 atom clusters, and explore the influence of the chosen parameters in the empirical potential. It is found that using multiple parameterisations across multiple genetic algorithm runs improves the search for low energy cluster structures, and increases the chance of success in finding the global minimum energy structure. At the 38 atom size, it is found that for compositions close to either Cu38 or Pd38, a structure similar to the monometallic cluster structure, a truncated octahedron, is favoured. For intermediate compositions (Cu5Pd33 to Cu25Pd13), a "pancake" icosahedron (a type of poly-icosahedron) is most stable, which is a structural motif that is particularly stable for bimetallic clusters, and is potentially interesting for catalytic purposes due to its unique structure, especially compared to the monometallic clusters.
We then consider larger clusters, extending the work from 38 atom clusters to include clusters up to 309 atoms. At these larger sizes, it was found that the overall trends are similar to those seen for 38 atoms; the most stable clusters in the Pd- and Cu-majority compositions are found to have a structure similar to the monometallic cluster structure and in the intermediate composition range are found to adopt poly-icosahedral structures. It was also found that in Pd-majority regions, Cu atoms occupied the core or vertex positions, while in intermediate regions, the segregation was mixed, however in the Cu-majority regions, the Pd atoms occupied the faces of the clusters. Given that similar structures and segregations were seen for CuPd clusters across multiple sizes, the structures found here may be representative of experimental CuPd clusters in this size range, and therefore provide an excellent platform for future catalytic studies
Lightweight Magnesium Metal-Organic Framework
Get PDFMagnesium metal-organic frameworks (Mg-MOFs) are a relatively new field of research. Currently, only a small number of Mg-MOFs exist, and most of them have not been studied very extensively. This work investigates three new magnesium structures made with a pre-existing ligand used for MOF synthesis.
Chapter one of this thesis details information about MOFs generally with specific focus on certain parts of their structures and capabilities. This includes a brief overview of different types of MOFs, including, multiwalled and lightweight MOFs. This is followed by a more in-depth literature review of the synthesis and applications of a number of Mg-MOFs.
Chapter two focuses on the synthesis and characterisation of the pre-existing ligand, 2-(4- carboxy-1, 1’-biphenyl)imidazo(4, 5-f)-1, 10-phenanthroline (L1). This includes the characterisation of L1 by single crystal X-ray crystallography. This was followed by the synthesis and characterisation of a new ligand 2-(3, 5-biscarboxy-1, 1’-biphenyl)imidazo(4, 5-f)-1, 10-phenanthroline (L2). The methylated version of L2 was characterised via single crystalX-ray crystallography due to the low solubility of the non-protected L2. Attempts were made to produce ruthenium-ligand complexes with L1 and L2, but these processes were unsuccessful.
Chapter three focuses on how L1 and L2 were used to create a number of new metal-organic structures. These structures were, three separate magnesium MOFs, a cadmium MOF, and two sodium coordination polymers. L1 was also used to produce a zinc MOF that had recently been published. The three magnesium-L1 MOFs were synthesised, characterised, and compared to determine why and how they were produced. The first Mg-MOF was a simple one-dimensional chain with two sets of L1 bound to each magnesium ion metal node in opposite directions (Mg MOF-1). The second Mg-MOF formed as a two-dimensional layered sheet framework with large 1D pores. The framework was held together by secondary building units (SBUs) with four magnesium ions bound together by formate bridging ions and the carboxylate groups of L1 (Mg-MOF-2). The third Mg-MOF formed was a much more intricate 1D chain, with each chain-link comprising of multiple L1 ions and magnesium ions bound together with formate bridging (Mg-MOF-3). The structure of Mg-MOF-3 indicates that it may have been a partially formed version of Mg-MOF-2.
Chapter four presents an overview of the future work that can be investigated regarding the structures that have been made with L1 and L2. This includes a more comprehensive investigation into the materials that have been produced such as their gas adsorption and photophysical properties. It also includes the planned production and analysis of isoreticular analogues of the already produced material. Finally, it includes the synthesis of ruthenium-ligand complexes via literature methods and the potential bimetallic MOFs that could be synthesised with those complexes
System.out.println(“Challenging the Human-Machine Divide: The Relevance of Pre-Digital Literary Criticism to Computational Poetics”);
No full textComputational poetry has redrawn the limits that putatively define what poems can and cannot do. Because of the major poetic transformations that the union of poetry and programmable machines has wrought, many critics have assumed that the conventional modes of print-based literary criticism must undergo a similarly profound transformation before we can apply them to computational poems. I argue against this assumption. Although I acknowledge that the criticism of computational texts must reckon with their specifically computational elements, and indeed enact this acknowledgment by performing several readings of code, I show that literary ideas from classical antiquity are surprisingly relevant to contemporary network-based texts. In chapter one, for example, I demonstrate how we can use fragments of classical text as a heuristic to help us interpret a poem (Nick Montfort and Stephanie Strickland’s Sea and Spar Between) that is, on the face of it, quintessentially nonfragmentary because it contains over 225,000,000,000,000 stanzas. In the second chapter, I show how we can use the classical literary-rhetorical mode of imitatio to theorize neural network poetry. Imitatio was a Greco-Roman pedagogical tool whereby students would imitate canonical poets or poetic modes to improve their compositional skill; I argue that the process by which neural networks learn to write poetry is fundamentally similar, and that this similarity allows us to recycle preexisting critical insights from the theory of imitatio into the theory of neural network poetry. Finally, in the third chapter, I firstly interpret the full-FACE poetry generation algorithm through the modern philosophical apparatus of moral luck. Then I look at John Cayley’s The Listeners (an aural computational text narrated by Amazon’s voice-transactive AI, Alexa) through the lens of a classical poetic genre, georgic, that is centrally concerned with agrarian labour. I show how Cayley’s text can be thought of as a post-classical participant in the georgic genre because it too is centrally concerned with harvesting, though of a more abstract variety than usual; The Listeners explores the ‘harvesting’ of language data by semi-intelligent computational actors, and I argue that we can see further into the terrain being explored if we stand on the shoulders of previous georgic scholarship.
This thesis demonstrates that classical literary modes, when used in conjunction with the computational tools that programmable media additionally require, are usefully applicable to computational poetics. In doing so, I demonstrate that the relationship between human and computer-generated poetry is one of collaboration and continuity rather than one of radical separation
Understanding the Mechanics of Natural Ice
Get PDFOne of the most substantial challenges posed to us today is global warming induced by human activity. Some recent studies have shown ice loss from polar ice sheets such as the West Antarctic Ice Sheet (WAIS) is accelerating towards tipping point and will result in ice sheet collapse and destructive sea level rise felt globally. Current ice sheet models are hindered by our lack of knowledge on the mechanical behaviour and response of flowing ice at a continental scale. Ice flow comprises a combination of sliding at the base of the ice sheet and internal deformation. The latter is controlled primarily by englacial temperature, the arrangement of ice grains into a crystallographic preferred orientation (CPO), and the stresses acting on the flowing mass. While many experimental studies in the past have contributed to our understanding of the mechanical behaviour of ice under stress, these are based largely on pure, isotropic samples deformed to low (e <20-30%) strains. Flow laws used in ice sheet modelling are defined by these studies, based specifically on the behaviour of ice before weakening is initiated. Natural ice contains soluble and insoluble impurities, mechanical heterogeneities like layering, fracturing and bubbles, and can flow and deform under different kinematic regimes resulting in changes to CPO and mechanical anisotropy throughout its long strain history.
This study combines experimental data and observations from a shallow ice core to contribute to the understanding of the mechanical behaviour of natural ice. Ices with a natural chemical composition and initial isotropic fabric have been deformed under uniaxial compression at varying strain rates (10-4, 10-5, 5x10-6 s-1) and temperatures (-10 and -30°C). Mechanical data demonstrates an increase in ionic concentrations strengthens ice only at warm temperatures, becoming more prominent at slow strain rates. Microstructural analysis shows impure ices with microstructures typically indicative of weakening. It is proposed that solid solution strengthening and grain boundary strengthening, processes typically seen in metals, may be strengthening the impure ices. This could have significant implications for marginal and basal regions of ice sheets, ice streams and glaciers, suggesting models could be overestimating weakening during ductile flow in these high temperature, relatively slow flowing regions.
A microstructural record of the near surface (<33 m) Priestley Glacier shear margin has been compiled and the seismic and dielectric anisotropy of the core has been constrained. The area is dominated by simple shear kinematics and is south of the glacier’s grounding line, so the glacier is floating, and basal traction does not need to be accounted for. The core samples have a very strong c-axis cluster CPO, which rotates generally from sub-perpendicular to 50° antithetic to the shear plane from the surface to 33 m depth. Microstructural and misorientation analysis indicates the shear margin is deforming by a combination of basal and nonbasal slip, with basal slip becoming more prominent below 5-10 m. Subgrain rotation is an active recovery mechanism, and grain boundary migration recrystallisation is active most effectively in shallow, seasonally perturbed (air temperature-controlled) ice and below 25 m, likely due to an increase in strain energy driving migration. Seismic and dielectric anisotropy strongly correlates with CPO strength and orientation with depth. The P-wave velocity patterns in core samples and observed horizontal velocities are geometrically similar, but the CPO rotation seen in the core is not present at depth. It is proposed that rigid body rotation is causing these rotations, which do not extend beyond 100 m. This highlights the usefulness of seismic datasets in attaining deep ice fabrics, but the difference in mechanical behaviour of ice at the near surface and ice at depth should be acknowledged in future ice sheet models
Help and Hindrances to Completion of Psychiatric Advance Directives
Get PDFPsychiatric advance directives (ADs) allow service users to participate in their mental health care, but few are completed. This paper reports on factors that help and hinder AD completion. Perceived barriers included resource limitations, procedural issues, access and storage problems, and mistrust between clinicians and service users regarding their implementation. What seems to help includes having management and nursing “champions”, and organising outreach meetings for all interested parties. Targeted education and training promotes creation and use of ADs, addresses negative attitudes, and assists service users to create ADs. Information technology support is vital to having ADs uploaded and accessed.
Dr X has a research contract with Douglas Pharmaceuticals to develop novel formulations of ketamine. No other authors report competing interests.
Funding for this project was a grant from the James Hume Foundation
New Zealand votes on end of life choice and cannabis legalisation
Get PDFAlongside New Zealand’s general parliamentary election on October 17, voters also were tasked with answering two referendum questions of significant medico-legal importance. The first asked whether the End of Life Choice Act 2019, permitting medically assisted dying for terminally ill persons, second was whether Parliament ought to enact into law the draft Cannabis Legalisation and Control Bill
Computational tools for improving recombinant protein production
Get PDFRecombinant protein production is a cornerstone of modern biotechnology and has been utilised to produce many proteins of scientific and commercial interest. The optimality of result is dependent on the balances among the involved intricate stochastic processes. In particular, two of the critical processes are protein expression and solubility. Collectively, the failures at these two steps drop down the success rate of protein production to around 25%. Furthermore, toxicity of recombinant proteins may also significantly reduce the amount of protein produced. Therefore, prediction and optimisation of expression, solubility and an early detection of these toxic proteins could save resources and assist in better planning of the experiment.
In this work, we show that mRNA accessibility, measured through the opening energy, and protein structural flexibility, measured by using the normalised B-factors, can describe protein expression and solubility respectively with a higher accuracy than other features. We also develop a new and more accurate protein solubility predicting metric called the Solubility-Weighted Index (SWI). Using these findings, we develop a gene expression prediction and optimisation tool: Translation Initiation coding region designer (TIsigner), available at https://tisigner.com/tisigner and protein solubility prediction and optimisation tool: Soluble Domain of Protein Expression (SoDoPE), available at https://tisigner.com/sodope. We also developed a third tool, Razor https://tisigner.com/razor, for the detection of toxins. To assist in maximising protein production, we also develop a pipeline for optimising protein expression, solubility and toxin detection by integrating these three tools