Mechanistic Understanding and Development of Catalytic Carbon Dioxide Utilisation Reactions

To enable the rational development of CO2 utilisation processes, it is vital to understand the mechanisms of involved reactions. This thesis reports studies to improve the mechanistic understanding of two catalytic CO2 utilisation reactions and work towards the development of a novel CO2 utilisation process. In Chapter 2, the role of guanidines in the reaction of propargylamines and CO2 to give cyclic carbonates is discussed. Guanidines have multiple potential mechanisms of catalytic activity. Through correlating the catalytic activity and solvent effects with observed guanidine-CO2 complexation, the origin of catalytic activity was determined. Chapters 3-5 report results of a mechanistic investigation into the guanidine catalysed reductive functionalisation of CO2 with amines and hydrosilanes to yield formylamides, methylamines and aminal products. Through monitoring the reaction using GC, 1H & 13C NMR, in situ FT-IR and mass spectrometry, a number of competitive intertwined reaction pathways and intermediates were identified. At low temperatures formylamides are produced via transformylation of a formoxysilane intermediate with an amine. However, at higher temperatures a competing pathway enables further reduction of the formoxysilane to a bis(silyl)acetal, its subsequent reaction with amines yields aminal intermediates which can be further reduced under reaction conditions to yield methylamines and formylamides. A catalyst deactivation pathway was identified whereby formylation of the catalyst itself occurs. By using alkylated guanidines, the deactivation pathway was prevented and the alkylated catalysts could be used at 0.1 mol% loadings and achieved TON of 805 and TOF of 33.5 h-1. In Chapter 6, efforts towards the development of a novel CO2 utilisation reaction are discussed. α-Ketocarboxylic acids were targeted from the insertion of CO2 into an aldehyde C-H bond, inspired by analogous hydroacylation chemistry. A range of reaction conditions, rhodium catalysts and substrates were investigated; however, although a number of products were identified, no incorporation of CO2 was observed

Pleasant emotions widen thought-action repertoires, develop long-term resources, and improve reaction time performance: A multi-study examination of the Broaden-and-Build theory among athletes

The authors investigated relationships between emotions, coping, and resilience across two studies. In Study 1a, 319 athletes completed dispositional questionnaires relating to the aforementioned constructs. In Study 1b, 126 athletes from Study 1a repeated the same questionnaires 6months later. In Study 2, 21 athletes were randomly allocated to an emotional (e.g., pleasant or unpleasant emotions) or control group and undertook a laboratory-based reaction-time task across three time points. Questionnaires and salivary cortisol samples were collected before and after each performance with imagery-based emotional manipulations engendered during the second testing session. Partial longitudinal evidence of the broaden-and-build effects of pleasant emotions was found. Pleasant emotions may undo lingering cognitive resource losses incurred from previous unpleasant emotional experiences. In Study 2, pleasant and unpleasant emotions had an immediate and sustained psychophysiological and performance impact. Taken together, this research supports the application of broaden-and-build theory in framing emotional interventions for athletes

Stress appraisals influence athletic performance and psychophysiological response during 16.1 km cycling time trials

Objectives: We examined how stress appraisals were associated with emotions, coping behaviours, as well as subjective and objective measures of performance.Design: Prospective field- and laboratory-based studies.Methods: In Study 1, 192 athletes completed process-oriented psychometrics pertaining to the aforementioned constructs throughout a sporting competition. Study 2 utilised an experimental design to assess the causal influence of stress appraisals on performance, cortisol, and psychological variables. Thirty gender-matched athletes were randomly assigned to either a stress appraisal (e.g., challenge, threat, benefit, or harm/loss) or the control group. Participants completed three 16.1km cycling time trials (TT) on a cycle ergometer, with their appropriate stress appraisal engendered via falsified performance feedback throughout the final TT. Salivary cortisol samples and psychometrics (e.g., appraisals, emotions, and coping) were collected before and after each TT.Results: The results of Study 1 revealed a sequential link between challenge stress appraisals and perceived goal attainment via pleasant emotions and task-oriented coping behaviours. Threat stress appraisals inversely related to goal attainment via unpleasant emotions and both distraction- and disengagement-oriented coping. In Study 2, no significant psychophysiological or performance differences were found across genders. The temporal orientation of stress appraisals influenced objective cycling TT performance. Benefit and harm/loss stress appraisals significantly facilitated or inhibited performance, respectively. Cortisol spikes were observed in the stress appraisal group’s threat, challenge, and benefit, with a decline detected within the harm/loss group. Whilst the process of winning is physiologically stressful, the fear of defeat may be more stressful than losing itself. Conclusion: Stress appraisals influence subjective and objective performance, as well as neuroendocrine and psychological responses to stress. Stress Appraisals Influence Athletic Performance and Psych

Modelling the EB-PVD thermal barrier coating process: Component clusters and shadow masks

Electron beam-physical vapour deposition (EB-PVD) is a commonly employed process for the production of thermal barrier coatings (TBCs), used in high performance applications such as gas turbines high-pressure aerofoil blades for the aerospace industry. Computer modelling can contribute to improved control of the coating process, important to support a continuous drive for increased efficiency. This paper considers two aspects associated with the EB-PVD coating of TBCs for commercial application: firstly, that clusters of blades are coated simultaneously in commercial coaters and, secondly, that these parts possess a complex geometry, such that shadow masks need to be taken into account. In this context, a computer model that calculates coating thickness distribution along the surface of different engine components, based on the analysis of the vapour deposition flux around complex geometries, is presented. To validate the predictive capability of the computer model two deposition trials were performed. Firstly, a cluster of components was simulated using three rotating cylinders, as a simple representation of coating multiple blades. Secondly, the effect of shadow masks was studied with an arrangement in which flat plates were welded, in the form of a U-shaped component, but with one side shorter than the other. The predicted results generated by the computer model compare favourably with those measured in the experimental runs presented. For the cluster of three cylinders, an error of 4% was obtained whilst the divergence was around 20% for the simulated shadow mask due to the fact that overall coating thickness was significantly reduced. In spite of this, the results obtained from the model were promising with respect to the degree of fit of the inverse square law. It is thought that a virtual source may be responsible for measurements being generally higher than those predicted by the model

Crystal structure of poly[[mu]-acetato-bis­[[mu]-2-oxo-2-(quinolin-8-yl)ethano­ato]tris­odium]

The title compound [Na3(C11H6NO3)2(C2H3O2)]n, crystallized through diffusion of diethyl ether into methanol as needles. There are three crystallographically independent Na+ cations present, each exhib­it­ing a distorted octa­hedral coordination geometry, two through coordination by five O atoms and one N atom, and one through coordination by six O atoms. A series of inter­molecular O...Na and N...Na contacts leads to the formation of chains along the a-axis direction

Factors influencing public health engagement in alcohol licensing in England and Scotland including legal and structural differences:comparative interview analysis

BACKGROUND: Greater availability of alcohol is associated with higher consumption and harms. The legal systems, by which premises are licensed to sell alcohol in England and Scotland, differ in several ways. The 'Exploring the impact of alcohol licensing in England and Scotland' study measured public health team activity regarding alcohol licensing from 2012 to 2019 and identified seven differences between England and Scotland in the timing and type of activities undertaken.OBJECTIVES: To qualitatively describe the seven previously identified differences between Scotland and England in public health approaches to alcohol licensing, and to examine, from the perspective of public health professionals, what factors may explain these differences.METHODS: Ninety-four interviews were conducted with 52 professionals from 14 English and 6 Scottish public health teams selected for diversity who had been actively engaging with alcohol licensing. Interviews focused primarily on the nature of their engagement (n = 66) and their rationale for the approaches taken (n = 28). Interview data were analysed thematically using NVivo. Findings were constructed by discussion across the research team, to describe and explain the differences in practice found.FINDINGS: Diverse legal, practical and other factors appeared to explain the seven differences. (1) Earlier engagement in licensing by Scottish public health teams in 2012-3 may have arisen from differences in the timing of legislative changes giving public health a statutory role and support from Alcohol Focus Scotland. (2) Public Health England provided significant support from 2014 in England, contributing to an increase in activity from that point. (3) Renewals of statements of licensing policy were required more frequently in Scotland and at the same time for all Licensing Boards, probably explaining greater focus on policy in Scotland. (4) Organisational structures in Scotland, with public health stakeholders spread across several organisations, likely explained greater involvement of senior leaders there. (5) Without a public health objective for licensing, English public health teams felt less confident about making objections to licence applications without other stakeholders such as the police, and instead commonly negotiated conditions on licences with applicants. In contrast, Scottish public health teams felt any direct contact with applicants was inappropriate due to conflicts of interest. (6) With the public health objective in Scotland, public health teams there were more active in making independent objections to licence applications. Further in Scotland, licensing committee meetings are held to consider all new applications regardless of whether objections have been submitted; unlike in England where there was a greater incentive to resolve objections, because then a meeting was not required. (7) Finally, Scottish public health teams involved the public more in licensing process, partly because of statutory licensing forums there.CONCLUSIONS: The alcohol premises licensing systems in England and Scotland differ in important ways including and beyond the lack of a public health objective for licensing in England. These and other differences, including support of national and local bodies, have shaped opportunities for, and the nature of, public health engagement. Further research could examine the relative success of the approaches taken by public health teams and how temporary increases in availability are handled in the two licensing systems.FUNDING: This article presents independent research funded by the National Institute for Health and Care Research (NIHR) Public Health Reseacrh programme as award number 15/129/11.</p

Factors influencing public health engagement in alcohol licensing in England and Scotland including legal and structural differences:Comparative interview analysis

BACKGROUND: Greater availability of alcohol is associated with higher consumption and harms. The legal systems, by which premises are licensed to sell alcohol in England and Scotland, differ in several ways. The 'Exploring the impact of alcohol licensing in England and Scotland' study measured public health team activity regarding alcohol licensing from 2012 to 2019 and identified seven differences between England and Scotland in the timing and type of activities undertaken.OBJECTIVES: To qualitatively describe the seven previously identified differences between Scotland and England in public health approaches to alcohol licensing, and to examine, from the perspective of public health professionals, what factors may explain these differences.METHODS: Ninety-four interviews were conducted with 52 professionals from 14 English and 6 Scottish public health teams selected for diversity who had been actively engaging with alcohol licensing. Interviews focused primarily on the nature of their engagement (n = 66) and their rationale for the approaches taken (n = 28). Interview data were analysed thematically using NVivo. Findings were constructed by discussion across the research team, to describe and explain the differences in practice found.FINDINGS: Diverse legal, practical and other factors appeared to explain the seven differences. (1) Earlier engagement in licensing by Scottish public health teams in 2012-3 may have arisen from differences in the timing of legislative changes giving public health a statutory role and support from Alcohol Focus Scotland. (2) Public Health England provided significant support from 2014 in England, contributing to an increase in activity from that point. (3) Renewals of statements of licensing policy were required more frequently in Scotland and at the same time for all Licensing Boards, probably explaining greater focus on policy in Scotland. (4) Organisational structures in Scotland, with public health stakeholders spread across several organisations, likely explained greater involvement of senior leaders there. (5) Without a public health objective for licensing, English public health teams felt less confident about making objections to licence applications without other stakeholders such as the police, and instead commonly negotiated conditions on licences with applicants. In contrast, Scottish public health teams felt any direct contact with applicants was inappropriate due to conflicts of interest. (6) With the public health objective in Scotland, public health teams there were more active in making independent objections to licence applications. Further in Scotland, licensing committee meetings are held to consider all new applications regardless of whether objections have been submitted; unlike in England where there was a greater incentive to resolve objections, because then a meeting was not required. (7) Finally, Scottish public health teams involved the public more in licensing process, partly because of statutory licensing forums there.CONCLUSIONS: The alcohol premises licensing systems in England and Scotland differ in important ways including and beyond the lack of a public health objective for licensing in England. These and other differences, including support of national and local bodies, have shaped opportunities for, and the nature of, public health engagement. Further research could examine the relative success of the approaches taken by public health teams and how temporary increases in availability are handled in the two licensing systems.FUNDING: This article presents independent research funded by the National Institute for Health and Care Research (NIHR) Public Health Reseacrh programme as award number 15/129/11.</p

Public health engagement in alcohol licensing in England and Scotland:the ExILEnS mixed-method, natural experiment evaluation

BACKGROUND: International systematic reviews suggest an association between alcohol availability and increased alcohol-related harms. Alcohol availability is regulated through separate locally administered licensing systems in England and Scotland, in which local public health teams have a statutory role. The system in Scotland includes a public health objective for licensing. Public health teams engage to varying degrees in licensing matters but no previous study has sought to objectively characterise and measure their activity, examine their effectiveness, or compare practices between Scotland and England.AIM: To critically assess the impact and mechanisms of impact of public health team engagement in alcohol premises licensing on alcohol-related harms in England and Scotland.METHODS: We recruited 39 diverse public health teams in England (n = 27) and Scotland (n = 12). Public health teams more active in licensing were recruited first and then matched to lower-activity public health teams. Using structured interviews (n = 66), documentation analysis, and expert consultation, we developed and applied the Public Health Engagement In Alcohol Licensing (PHIAL) measure to quantify six-monthly activity levels from 2012 to 2019. Time series of PHIAL scores, and health and crime outcomes for each area, were analysed using multivariable negative binomial mixed-effects models to assess correlations between outcome and exposure, with 18-month average PHIAL score as the primary exposure metric. In-depth interviews (n = 53) and a workshop (n = 10) explored public health team approaches and potential mechanisms of impact of alcohol availability interventions with public health team members and licensing stakeholders (local authority licensing officers, managers and lawyers/clerks, police staff with a licensing remit, local elected representatives).FINDINGS: Nineteen public health team activity types were assessed in six categories: (1) staffing; (2) reviewing and (3) responding to licence applications; (4) data usage; (5) influencing licensing stakeholders/policy; and (6) public involvement. Usage and intensity of activities and overall approaches varied within and between areas over time, including between Scotland and England. The latter variation could be explained by legal, structural and philosophical differences, including Scotland's public health objective. This objective was felt to legitimise public health considerations and the use of public health data within licensing. Quantitative analysis showed no clear evidence of association between level of public health team activity and the health or crime outcomes examined, using the primary exposure or other metrics (neither change in, nor cumulative, PHIAL scores). Qualitative data suggested that public health team input was valued by many licensing stakeholders, and that alcohol availability may lead to harms by affecting the accessibility, visibility and norms of alcohol consumption, but that the licensing systems have limited power to act in the interests of public health.CONCLUSIONS: This study provides no evidence that public health team engagement in local licensing matters was associated with measurable downstream reductions in crime or health harms, in the short term, or over a 7-year follow-up period. The extensive qualitative data suggest that public health team engagement is valued and appears to be slowly reorienting the licensing system to better address health (and other) harms, especially in Scotland, but this will take time. A rise in home drinking, alcohol deliveries, and the inherent inability of the licensing system to reduce - or in the case of online sales, to contain - availability, may explain the null findings and will continue to limit the potential of these licensing systems to address alcohol-related harms.FUTURE WORK: Further analysis could consider the relative success of different public health team approaches in terms of changing alcohol availability and retailing. A key gap relates to the nature and impact of online availability on alcohol consumption, harms and inequalities, alongside development and study of relevant policy options. A national approach to licensing data and oversight would greatly facilitate future studies and public health input to licensing.LIMITATIONS: Our interview data and therefore PHIAL scores may be limited by recall bias where documentary evidence of public health activity was not available, and by possible variability in grading of such activity, though steps were taken to minimise both. The analyses would have benefited from additional data on licensing policies and environmental changes that might have affected availability or harms in the study areas.STUDY REGISTRATION: The study was registered with the Research Registry (researchregistry6162) on 26 October 2020. The study protocol was published in BMC Medical Research Methodology on 6 November 2018.FUNDING: This synopsis presents independent research funded by the National Institute for Health and Care Research (NIHR) Public Health Research programme as award number 15/129/11.</p

Public health engagement in alcohol licensing in England and Scotland:The ExILEnS mixed-method, natural experiment evaluation

BACKGROUND: International systematic reviews suggest an association between alcohol availability and increased alcohol-related harms. Alcohol availability is regulated through separate locally administered licensing systems in England and Scotland, in which local public health teams have a statutory role. The system in Scotland includes a public health objective for licensing. Public health teams engage to varying degrees in licensing matters but no previous study has sought to objectively characterise and measure their activity, examine their effectiveness, or compare practices between Scotland and England.AIM: To critically assess the impact and mechanisms of impact of public health team engagement in alcohol premises licensing on alcohol-related harms in England and Scotland.METHODS: We recruited 39 diverse public health teams in England (n = 27) and Scotland (n = 12). Public health teams more active in licensing were recruited first and then matched to lower-activity public health teams. Using structured interviews (n = 66), documentation analysis, and expert consultation, we developed and applied the Public Health Engagement In Alcohol Licensing (PHIAL) measure to quantify six-monthly activity levels from 2012 to 2019. Time series of PHIAL scores, and health and crime outcomes for each area, were analysed using multivariable negative binomial mixed-effects models to assess correlations between outcome and exposure, with 18-month average PHIAL score as the primary exposure metric. In-depth interviews (n = 53) and a workshop (n = 10) explored public health team approaches and potential mechanisms of impact of alcohol availability interventions with public health team members and licensing stakeholders (local authority licensing officers, managers and lawyers/clerks, police staff with a licensing remit, local elected representatives).FINDINGS: Nineteen public health team activity types were assessed in six categories: (1) staffing; (2) reviewing and (3) responding to licence applications; (4) data usage; (5) influencing licensing stakeholders/policy; and (6) public involvement. Usage and intensity of activities and overall approaches varied within and between areas over time, including between Scotland and England. The latter variation could be explained by legal, structural and philosophical differences, including Scotland's public health objective. This objective was felt to legitimise public health considerations and the use of public health data within licensing. Quantitative analysis showed no clear evidence of association between level of public health team activity and the health or crime outcomes examined, using the primary exposure or other metrics (neither change in, nor cumulative, PHIAL scores). Qualitative data suggested that public health team input was valued by many licensing stakeholders, and that alcohol availability may lead to harms by affecting the accessibility, visibility and norms of alcohol consumption, but that the licensing systems have limited power to act in the interests of public health.CONCLUSIONS: This study provides no evidence that public health team engagement in local licensing matters was associated with measurable downstream reductions in crime or health harms, in the short term, or over a 7-year follow-up period. The extensive qualitative data suggest that public health team engagement is valued and appears to be slowly reorienting the licensing system to better address health (and other) harms, especially in Scotland, but this will take time. A rise in home drinking, alcohol deliveries, and the inherent inability of the licensing system to reduce - or in the case of online sales, to contain - availability, may explain the null findings and will continue to limit the potential of these licensing systems to address alcohol-related harms.FUTURE WORK: Further analysis could consider the relative success of different public health team approaches in terms of changing alcohol availability and retailing. A key gap relates to the nature and impact of online availability on alcohol consumption, harms and inequalities, alongside development and study of relevant policy options. A national approach to licensing data and oversight would greatly facilitate future studies and public health input to licensing.LIMITATIONS: Our interview data and therefore PHIAL scores may be limited by recall bias where documentary evidence of public health activity was not available, and by possible variability in grading of such activity, though steps were taken to minimise both. The analyses would have benefited from additional data on licensing policies and environmental changes that might have affected availability or harms in the study areas.STUDY REGISTRATION: The study was registered with the Research Registry (researchregistry6162) on 26 October 2020. The study protocol was published in BMC Medical Research Methodology on 6 November 2018.FUNDING: This synopsis presents independent research funded by the National Institute for Health and Care Research (NIHR) Public Health Research programme as award number 15/129/11.</p

Public health engagement in alcohol licensing in England and Scotland:the ExILEnS mixedmethod, natural experiment evaluation

Background: International systematic reviews suggest an association between alcohol availability and increased alcohol-related harms. Alcohol availability is regulated through separate locally-administered licensing systems in England and Scotland, in which local public health teams (PHTs) have a statutory role. The system in Scotland includes a public health objective for licensing. PHTs engage to varying degrees in licensing matters but no previous study has sought to objectively characterise and measure their activity, examined its effectiveness, or compared practices between Scotland and England. Aim: To critically assess the impact and mechanisms of impact of PHT engagement in alcohol premises licensing on alcohol-related harms in England and Scotland.Methods: We recruited 39 diverse PHTs in England (n=27) and Scotland (n=12). PHTs more active in licensing were recruited first and then matched to lower activity PHTs. Using structured interviews (n=66), documentation analysis, and expert consultation, we developed and applied the Public Health engagement In Alcohol Licensing (PHIAL) measure to quantify six-monthly activity levels from 2012 to 2019. Time series of PHIAL scores, and health and crime outcomes for each area, were analysed using multivariable negative binomial mixed-effects models to assess correlations between outcome and exposure, with 18-month average PHIAL score as the primary exposure metric. In-depth interviews (n=53) and a workshop (n=10) explored PHT approaches and potential mechanisms of impact of alcohol availability interventions with PHT members and licensing stakeholders (local authority licensing officers, managers and lawyers/clerks, police staff with a licensing remit, local elected representatives).Findings: 19 PHT activity types were assessed in six categories: (1) staffing; (2) reviewing and (3) responding to licence applications; (4) data usage; (5) influencing licensing stakeholders/policy; and (6) public involvement. Usage and intensity of activities and overall approaches varied within and between areas over time, including between Scotland and England. The latter variation could be explained by legal, structural and philosophical differences, including Scotland’s public health objective. This objective was felt to legitimise PH considerations and the use of PH data within licensing. Quantitative analysis showed no clear evidence of association between level of PHT activity and the health or crime outcomes examined, using the primary exposure or other metrics (neither change in, nor cumulative, PHIAL scores). Qualitative data suggested that PHT input was valued by many licensing stakeholders, and that alcohol availability may lead to harms by affecting the accessibility, visibility and norms of alcohol consumption, but that the licensing systems have limited power to act in the interests of public health.Conclusions: This study provides no evidence that PHT engagement in local licensing matters was associated with measurable downstream reductions in crime or health harms, in the short term, or over a 7-year follow-up period. The extensive qualitative data suggest that PHT engagement is valued and appears to be slowly reorienting the licensing system to better address health (and other) harms, especially in Scotland, but this will take time. A rise in home drinking, alcohol deliveries, and the inherent inability of the licensing system to reduce, or in the case of online sales, to contain availability, may explain the null findings, and will continue to limit the potential of these licensing systems to address alcohol-related harms. Future work: Further analysis could consider the relative success of different PHT approaches in terms of changing alcohol availability and retailing. A key gap relates to the nature and impact of online availability on alcohol consumption, harms and inequalities, alongside development and study of relevant policy options. A national approach to licensing data and oversight would greatly facilitate future studies and public health input to licensing. Limitations: Our interview data and therefore PHIAL scores may be limited by recall bias where documentary evidence of public health activity was not available, and by possible variability in grading of such activity, though steps were taken to minimise both. The analyses would have benefited from additional data on licensing policies and environmental changes that might have affected availability or harms in the study areas. Funding details:This study was funded by the NIHR Public Health Research programme (15/129/11). The views expressed are those of the authors and not necessarily those of the NHS, the NIHR or the Department of Health. Frank de Vocht is partly funded by National Institute for Health Research Applied Research Collaboration West (NIHR ARC West) at University Hospitals Bristol NHS Foundation Trust. Study registration:The study was registered with the Research Registry (researchregistry6162) on 26th October 2020. The study protocol was published in BMC Medical Research Methodology on 6th November 2018.<br/