Synthesis of f-block complexes in a polypyrrolic macrocyclic environment

In this thesis, the chemistry of lanthanide and actinide complexes of Schiff-base, polypyrrolic macrocyclic ligands has been evaluated. Chapter one introduces some general chemistry of uranium before focussing on uranium(III) and (IV) coordination complexes of nitrogen donor ligands. The surface chemistry of uranium metal is also briefly discussed along with the synthesis of uranium borohydride, hydride and alkyl complexes. Chapter two describes the synthesis and characterisation of the monometallic complexes [M(L)] or [M(HL)], where M = Y, Ce, and U, of the octadentate Schiffbase pyrrole macrocycle H4L. In particular, these complexes display a new binding mode of the macrocycle which leads to the formation of the unique trinuclear supramolecular complexes [M(HL)]3, (M = Ce, Y). Reactions of these materials towards hydrolysis, oxygen sources and other metal reagents are also exemplified. Chapter three details the synthesis and characterisation of the bimetallic complexes, [(MX)2(L)], where M = Ce, U, and Np and X = I or Cl, and [(MX2)2(L)], where M = U, and the attempts to transform these complexes into metal hydrides via their borohydrides. The solid state variable temperature magnetism of the binuclear U(III) and Np(III) complexes was recorded and was found to be consistent with the formation of iodide-bridged, polymeric structures. Chapter four explores the synthesis and reactions of adducts between UI3 and neutral macrocyclic ligands that incorporate either oxygen or nitrogen donors such as crown ethers and cyclam, respectively. The new synthesis of the key starting material, unsolvated UI3 is also outlined, along with the full characterisation of UI4(OEt)2

Using the Theory of Emotional Stakeholders to Experimentally Test the Influence of Proxy Communicators about Organizational Crises in Digital News Reports

The emergence of new and social media has transformed the way that stakeholders and organizations interact between and amongst each other. Online news consumers are now able to directly respond to crisis news reports by offering their own interpretation, thus expanding the diversity of viewpoints audiences are exposed to (Carpenter, 2010; Springer, 2014). Using the Theory of Emotional Stakeholders framework our study aims (1) to understand how positive and negative user-generated comments in response to online news reports of crisis events impacts audience perceptions of organizational blame; (2) to examine the persuasive effects of user comments when expert or official organizational responses are provided; and, (3) to measure the affective response to online news reports including user comments. Using experimental procedures our findings show that user comments from organizations, faith-holders, and hate-holders contribute to audience evaluations of crisis responsibility, both causal and treatment. Results found that user comments from faith-holders reduced causal responsibility in the intentional cluster compared to the control condition; however, when organizations were facing preventable crises, user comments from faith-holders amplified perceived treatment responsibility. A detailed description of the findings, discussion, limitations and future directions are provided

Changing Attitudes About Being a Bystander to Violence: Translating an In-Person Sexual Violence Prevention Program to a New Campus

Bystander approaches to reducing sexual violence train community members in prosocial roles to interrupt situations with risk of sexual violence and be supportive community allies after an assault. This study employs a true experimental design to evaluate the effectiveness of Bringing in the Bystander™ through 1-year post-implementation with first-year students from two universities (one rural, primarily residential; one urban, heavily commuter). We found significant change in bystander attitudes for male and female student program participants compared with the control group on both campuses, although the pattern of change depended on the combination of gender and campus

Changing Attitudes About Being a Bystander to Violence: Translating an In-Person Sexual Violence Prevention Program to a New Campus

Bystander approaches to reducing sexual violence train community members in prosocial roles to interrupt situations with risk of sexual violence and be supportive community allies after an assault. This study employs a true experimental design to evaluate the effectiveness of Bringing in the Bystander™ through 1-year post-implementation with first-year students from two universities (one rural, primarily residential; one urban, heavily commuter). We found significant change in bystander attitudes for male and female student program participants compared with the control group on both campuses, although the pattern of change depended on the combination of gender and campus

Increased diastolic blood pressure is associated with MRI biomarkers of dementia-related brain pathology in normative ageing

Background hypertension is a risk for brain ageing, but the mechanisms underlying this effect remain unclear. Magnetic resonance imaging (MRI) detected biomarkers of brain ageing include white matter hyperintensities (WMHs), a marker of cerebrovascular disease, and hippocampal volume, a marker of Alzheimer’s disease pathology. Objective to examine relationships between blood pressure (BP) components and brain pathology in older adults. Subjects two hundred and twenty-seven members of the Aberdeen 1936 Birth Cohort between ages 64 and 68 years. Methods BP was assessed biennially between 64 and 68 years and brain MRI performed at 68 years. The risk factors of interest were diastolic and systolic BP and their visit-to-visit variability. Outcomes were WMH abundance and hippocampal volume. Regression models, controlling for confounding factors, examined their relationships. Results higher diastolic BP predicted increased WMH (β = 0.13, P = 0.044) and smaller hippocampi (β = −0.25, P = 0.006). In contrast, increased systolic BP predicted larger hippocampi (β = 0.22, P = 0.013). Variability of diastolic BP predicted lower hippocampal volume (β = −0.15, P = 0.033). These relationships were independent of confounding life-course risk factors. Anti-hypertensive medication did not modify these relationships, but was independently associated with increased WMH (β = 0.17, P = 0.011). Conclusion increased diastolic BP is associated with biomarkers of both cerebrovascular and Alzheimer’s diseases, whereas the role of systolic BP is less clear, with evidence for a protective effect on hippocampal volume. These differing relationships emphasise the importance of considering individual BP components with regard to brain ageing and pathology. Interventions targeting diastolic hypertension and its chronic variability may provide new strategies able to slow the accumulation of these harmful pathologies

In-vitro dissolution of vitreous silicate fibres according to EURIMA test guideline - Results of two Round Robins

The EURIMA (The European Insulation Manufacturers Association) test guideline "In-vitro acellular dissolution of man-made vitreous silicate fibres" provides a state-of-the-art method for measuring in-vitro dissolution rates relevant for evaluating the biopersistence of insulation wool fibres and other vitreous silicate fibres. Based on this guideline two Round Robins were conducted as well as specific investigations on the influence of selected test parameters. Nine and six laboratories, respectively, participated in the two Round Robins. The standard deviation between Kdis results obtained by different laboratories was slightly lower in the second Round Robin ranging from 24 to 61 % (highest for the low-soluble fibres). The relatively high inter-laboratory variation suggests that the equipment, setup and procedures should be specified in much more detail in a future test method. Key parameters to be kept constant are flow rate/surface area and liquid composition, and care should be taken to maintain constant conditions and eliminate outlier measurements. Α laboratory may use the method described in the guideline for quality assurance of maintained biosolubility and for development of alternative fibre modifications as the method is well suited for ranking different fibres with respect to dissolution coefficients within one laboratory. However, caution should be exercised when comparing values obtained by one laboratory to values obtained by another

Increasing the Impact: Building on the Library Impact Data Project

The third phase of LIDP (LIDP3), is an internal project at Huddersfield that commenced in 2014. LIDP3 will focus on making use of the data and insights generated from phases 1 and 2 to increase library usage among the groups identified as having the lowest use. It is clear from the results from phases 1 and 2 that a ‘one-size-fits-all’, generic approach to information literacy is inadequate. Therefore, the Academic Services Team’s in-depth knowledge of each subject and student cohort has been used to identify the most appropriate interventions for each group - this is a logical progression from the data-driven approach of the first two phases. If targeted successfully it is anticipated that LIDP3 could lead to a rise in use of library resources, which in turn could be a contributing factor to better student attainment and retention

Augmenting Hand and Arm Function for Persons with Hemiparesis

Background. Hand and arm dysfunction due to neural disorders significantly influences quality of life. Activity-based training has been found to improve function. These improvements could be augmented with transcutaneous spinal cord stimulation (tSCS) due to the modulatory effect it has on spinal and supraspinal networks. Objective. The primary aim is to determine if a 4-week training program will improve hand and arm function. The secondary aim is to determine if the addition of tSCS to a second 4-week training session will further improve function. Design. This is a pre-posttest, controlled trial for persons 10-75 years of age, \u3e6 months post stroke or with unilateral cerebral palsy.Methods. Participants will engage in two 4-week training periods, 3x/week for 2 hours/day. The 1st period will include unimanual and bimanual training alone. The 2nd period will be augmented with low frequency tSCS to the C5-T1 spinal region. Stimulation intensity will be based on individual muscle activation during 3 tasks: 1) grip dynamometry; 2) grip-lift; and 3) target pointing. Outcome measures taken before, midway, and after training are: Canadian Occupational Performance Measure (COPM), dexterity, daylong arm use, grip/pinch strength, sensibility, questionnaires, bilateral hand/arm surface electromyography, and Upper Extremity Fugl-Meyer (UEFM). Results: Nine participants have completed the 1st 4-week training period without tSCS. Individual data reveals improvements in the COPM, Grip strength, dexterity, and the UEFM. Findings for other measures after the 1st period are mixed or in process. Conclusion: Preliminary findings from this ongoing study reveal that participants made improvements in most measures. The next phase of the study will determine if the addition of tSCS to training further augments hand and arm function