Embedding at electrode surfaces

Electronic structure calculations are performed on metal surfaces using an embedding method. Firstly, Cu and Ni surfaces with adsorbates are studied. The O/Cu(00T) reconstruction is investigated, and it is found that atomic displacements increase bonding symmetry and is most likely the cause of reconstruction. The interaction between a single graphitic layer and the Ni(III) substrate is also studied, and it is found that interacting states are formed at Ni band gaps. The remainder of the thesis deals with steps on metal surfaces. First, the jellium model is used to calculate the work function dependence on step density. In the low step density limit, the work function varies linearly with step density. Further calculations are performed on realistic Pd and Pt surfaces. When electric fields are applied, the screening charge of stepped surfaces is mostly located at the step edge. This is explained by the increased fields associated with the edge. Field emission from Pd and Pt surfaces is also studied. It is found that Pd is a better emitter than Pt, owing to work function effects. Transmission is dependent on the surface parallel wavevector and decreases with increasing wavevector. The reduced work function also plays a role at stepped surfaces, although the major influence stems from the reduced local work function at the step site. The low effective potential at the step provides a locally reduced barrier to electron removal. In addition, an increase in transmission is seen from non-zero wavevectors for stepped surfaces. The result is that stepped Pd and Pt surfaces, with a step density of one step in every three (001) unit cells, show field emission increased by a factor of four compared with the flat (001) surfaces.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Embedding at electrode surfaces

Electronic structure calculations are performed on metal surfaces using an embedding method. Firstly, Cu and Ni surfaces with adsorbates are studied. The O/Cu(00T) reconstruction is investigated, and it is found that atomic displacements increase bonding symmetry and is most likely the cause of reconstruction. The interaction between a single graphitic layer and the Ni(III) substrate is also studied, and it is found that interacting states are formed at Ni band gaps. The remainder of the thesis deals with steps on metal surfaces. First, the jellium model is used to calculate the work function dependence on step density. In the low step density limit, the work function varies linearly with step density. Further calculations are performed on realistic Pd and Pt surfaces. When electric fields are applied, the screening charge of stepped surfaces is mostly located at the step edge. This is explained by the increased fields associated with the edge. Field emission from Pd and Pt surfaces is also studied. It is found that Pd is a better emitter than Pt, owing to work function effects. Transmission is dependent on the surface parallel wavevector and decreases with increasing wavevector. The reduced work function also plays a role at stepped surfaces, although the major influence stems from the reduced local work function at the step site. The low effective potential at the step provides a locally reduced barrier to electron removal. In addition, an increase in transmission is seen from non-zero wavevectors for stepped surfaces. The result is that stepped Pd and Pt surfaces, with a step density of one step in every three (001) unit cells, show field emission increased by a factor of four compared with the flat (001) surfaces

Electron field emission from surfaces with steps

First-principles electron field emission calculations have been performed on flat and stepped Pt and Pd surfaces. An increase in electron transmission is seen for well-defined stepped surfaces. This stems from the reduction in the work function caused by Smoluchowski electron-smoothing and an increased tunneling contribution from surface parallel wave vectors at the stepped surface. A reduced effective potential at the step site may also contribute to increased electron transmission

Understanding the relationship between the perceived characteristics of clinical practice guidelines and their uptake: protocol for a realist review

<p>Abstract</p> <p>Background</p> <p>Clinical practice guidelines have the potential to facilitate the implementation of evidence into practice, support clinical decision making, specify beneficial therapeutic approaches, and influence public policy. However, these potential benefits have not been consistently achieved. The limited impact of guidelines can be attributed to organisational constraints, the complexity of the guidelines, and the lack of usability testing or end-user involvement in their development. Implementability has been referred to as the perceived characteristics of guidelines that predict the relative ease of their implementation at the clinical level, but this concept is as yet poorly defined. The objective of our study is to identify guideline attributes that affect uptake in practice by considering evidence from four disciplines (medicine, psychology, management, human factors engineering) to determine the relationship between the perceived characteristics of recommendations and their uptake and to develop a framework of implementability.</p> <p>Methods</p> <p>A realist-review approach to knowledge synthesis will be used to understand attributes of guidelines (<it>e.g</it>., its text and content) and how changing these elements might impact clinical practice and clinical decision making. It also allows for the exploration of 'what works for whom, in what circumstances, and in what respects'. The realist review will be structured according to Pawson's five practical steps in realist reviews: (1) clarifying the scope of the review, (2) determining the search strategy, (3) ensuring proper article selection and study quality assessment, (4) extracting and organising data, and (5) synthesising the evidence and drawing conclusions. Data will be synthesised according to a two-stage analysis: (1) we will extract and define all relevant guideline attributes from the different disciplines, then create a shortlist of unique attributes and investigate their relationships with uptake, and (2) we will compare and contrast the attributes and guideline uptake within each and between the four disciplines to create a robust framework of implementability.</p> <p>Discussion</p> <p>Creating guidelines that are designed to maximise uptake may be a potentially effective and inexpensive way of increasing their impact. However, this is best achieved by a comprehensive framework to inform the design of guidelines drawing on a range of disciplines that study behaviour change. This study will use a customised realist-review approach to synthesising the literature to better understand and operationalise a complex and under-theorised concept.</p

In-situ removal and characterisation of uranium-containing particles from sediments surrounding the Fukushima Daiichi Nuclear Power Plant

AbstractTraditional methods to locate and subsequently study radioactive fallout particles have focused heavily on autoradiography coupled with in-situ analytical techniques. Presented here is the application of a Variable Pressure Scanning Electron Microscope with both backscattered electron and energy dispersive spectroscopy detectors, along with a micromanipulator setup and electron-hardening adhesive to isolate and remove individual particles before synchrotron radiation analysis. This system allows for a greater range of new and existing analytical techniques, at increased detail and speed, to be applied to the material. Using this method, it was possible to erform detailed energy dispersive spectroscopy and synchrotron radiation characterisation of material likely ejected from the Fukushima Daiichi Nuclear Power Plant found within a sediment sample collected from the edge of the 30km exclusion zone. Particulate material sub-micron in maximum dimension examined during this work via energy dispersive spectroscopy was observed to contain uranium at levels between 19.68 and 28.35 weight percent, with the application of synchrotron radiation spectroscopy confirming its presence as a major constituent.With great effort and cost being devoted to the remediation of significant areas of eastern Japan affected by the incident, it is crucial to gain the greatest possible understanding of the nature of this contamination in order to inform the most appropriate clean-up response

Looking inside the black box : a theory-based process evaluation alongside a randomised controlled trial of printed educational materials (the Ontario printed educational message, OPEM) to improve referral and prescribing practices in primary care in Ontario, Canada

Background: Randomised controlled trials of implementation strategies tell us whether (or not) an intervention results in changes in professional behaviour but little about the causal mechanisms that produce any change. Theory-based process evaluations collect data on theoretical constructs alongside randomised trials to explore possible causal mechanisms and effect modifiers. This is similar to measuring intermediate endpoints in clinical trials to further understand the biological basis of any observed effects (for example, measuring lipid profiles alongside trials of lipid lowering drugs where the primary endpoint could be reduction in vascular related deaths). This study protocol describes a theory-based process evaluation alongside the Ontario Printed Educational Message (OPEM) trial. We hypothesize that the OPEM interventions are most likely to operate through changes in physicians' behavioural intentions due to improved attitudes or subjective norms with little or no change in perceived behavioural control. We will test this hypothesis using a well-validated social cognition model, the theory of planned behaviour (TPB) that incorporates these constructs. Methods/design: We will develop theory-based surveys using standard methods based upon the TPB for the second and third replications, and survey a subsample of Ontario family physicians from each arm of the trial two months before and six months after the dissemination of the index edition of informed, the evidence based newsletter used for the interventions. In the third replication, our study will converge with the "TRY-ME" protocol (a second study conducted alongside the OPEM trial), in which the content of educational messages was constructed using both standard methods and methods informed by psychological theory. We will modify Dillman's total design method to maximise response rates. Preliminary analyses will initially assess the internal reliability of the measures and use regression to explore the relationships between predictor and dependent variable (intention to advise diabetic patients to have annual retinopathy screening and to prescribe thiazide diuretics for first line treatment of uncomplicated hypertension). We will then compare groups using methods appropriate for comparing independent samples to determine whether there have been changes in the predicted constructs (attitudes, subjective norms, or intentions) across the study groups as hypothesised, and will assess the convergence between the process evaluation results and the main trial results.The OPEM trial and OPEM process evaluation are funded by the Canadian Institute of Health Research (CIHR). The OPEM process evaluation study was developed as part of the CIHR funded interdisciplinary capacity enhancement team KT-ICEBeRG. Gaston Godin, Jeremy Grimshaw and France Légaré hold Canada Research Chairs. Louise Lemyre holds an R.S. McLaughlin Research Chair

Groundwater Laws and Regulations: Survey of Sixteen U.S. States

This report is the second volume in a continuing project designed to explore and articulate the groundwater laws and regulations of all fifty U.S. states. This particular report presents surveys for sixteen states throughout the country. The first volume featured thirteen state surveys and can be found at: http://www.law.tamu.edu/usgroundwaterlaws. The purpose of the project is to compile and present the groundwater laws and regulations of every state in the United States that could then be used in a series of comparisons of groundwater governance principles, strategies, issues, and challenges. Professor Gabriel Eckstein at Texas A&M University School of Law and Professor Amy Hardberger at Texas Tech University School of Law developed a matrix to ascertain chief components and characteristics of the groundwater legal regime of each state. Student researchers then used the matrix to respond to a standardized set of questions about the groundwater laws and regulations of a selection of states. In the near future, additional volumes with surveys of the remaining twenty-one U.S. states will be issued

Stakeholder views regarding ethical issues in the design and conduct of pragmatic trials : study protocol

This work is supported by the Canadian Institutes of Health Research through the Project Grant competition (competitive, peer reviewed), award number PJT-153045. Jeremy Grimshaw holds a Canada Research Chair in Health Knowledge Transfer and Uptake and a CIHR Foundation Grant (FDN-143269). Charles Weijer holds a Canada Research Chair in Bioethics. Joanne McKenzie is supported by an Australian National Health and Medical Research Council Career Development Fellowship (1143429). Vipul Jairath hold a personal Endowed Chair at Western University (John and Susan McDonald Endowed Chair). Marion Campbell is based with the Health Services Research Unit which is core-funded by the Chief Scientist Office of the Scottish Government Health and Social Care Directorates. Ian Graham is a CIHR Foundation Grant recipient (FDN# 143237).Peer reviewedPublisher PD

Looking inside the black box: results of a theory-based process evaluation exploring the results of a randomized controlled trial of printed educational messages to increase primary care physicians' diabetic retinopathy referrals [Trial registration number ISRCTN72772651]

Background: Theory-based process evaluations conducted alongside randomized controlled trials provide the opportunity to investigate hypothesized mechanisms of action of interventions, helping to build a cumulative knowledge base and to inform the interpretation of individual trial outcomes. Our objective was to identify the underlying causal mechanisms in a cluster randomized trial of the effectiveness of printed educational materials (PEMs) to increase referral for diabetic retinopathy screening. We hypothesized that the PEMs would increase physicians’ intention to refer patients for retinal screening by strengthening their attitude and subjective norm, but not their perceived behavioral control. Methods: Design: A theory based process evaluation alongside the Ontario Printed Educational Material (OPEM) cluster randomized trial. Postal surveys based on the Theory of Planned Behavior were sent to a random sample of trial participants two months before and six months after they received the intervention. Setting: Family physicians in Ontario, Canada. Participants: 1,512 family physicians (252 per intervention group) from the OPEM trial were invited to participate, and 31.3% (473/1512) responded at time one and time two. The final sample comprised 437 family physicians fully completing questionnaires at both time points. Main outcome measures: Primary: behavioral intention related to referring patient for retinopathy screening; secondary: attitude, subjective norm, perceived behavioral control. Results: At baseline, family physicians reported positive intention, attitude, subjective norm, and perceived behavioral control to advise patients about retinopathy screening suggesting limited opportunities for improvement in these constructs. There were no significant differences on intention, attitude, subjective norm, and perceived behavioral control following the intervention. Respondents also reported additional physician- and patient-related factors perceived to influence whether patients received retinopathy screening. Conclusions: Lack of change in the primary and secondary theory-based outcomes provides an explanation for the lack of observed effect of the main OPEM trial. High baseline levels of intention to advise patients to attend retinopathy screening suggest that post-intentional and other factors may explain gaps in care. Process evaluations based on behavioral theory can provide replicable and generalizable insights to aid interpretation of randomized controlled trials of complex interventions to change health professional behavior

Further investigation of confirmed urinary tract infection (UTI) in children under five years: a systematic review.

Background: Further investigation of confirmed UTI in children aims to prevent renal scarring and future complications. Methods: We conducted a systematic review to determine the most effective approach to the further investigation of confirmed urinary tract infection (UTI) in children under five years of age. Results: 73 studies were included. Many studies had methodological limitations or were poorly reported. Effectiveness of further investigations: One study found that routine imaging did not lead to a reduction in recurrent UTIs or renal scarring. Diagnostic accuracy: The studies do not support the use of less invasive tests such as ultrasound as an alternative to renal scintigraphy, either to rule out infection of the upper urinary tract (LR- = 0.57, 95%CI: 0.47, 0.68) and thus to exclude patients from further investigation or to detect renal scarring (LR+ = 3.5, 95% CI: 2.5, 4.8). None of the tests investigated can accurately predict the development of renal scarring. The available evidence supports the consideration of contrast-enhanced ultrasound techniques for detecting vesico-ureteric reflux (VUR), as an alternative to micturating cystourethrography (MCUG) (LR+ = 14.1, 95% CI: 9.5, 20.8; LR- = 0.20, 95%CI: 0.13, 0.29); these techniques have the advantage of not requiring exposure to ionising radiation. Conclusion: There is no evidence to support the clinical effectiveness of routine investigation of children with confirmed UTI. Primary research on the effectiveness, in terms of improved patient outcome, of testing at all stages in the investigation of confirmed urinary tract infection is urgently required