Next Generation Access in a Rural Community Context: An Innovation Analysis

This thesis explores how to resolve the digital divide in Wales. This is important because access to advanced broadband is considered an essential requirement, particularly post-COVID19. UK Government is advocating next generation access (NGA) to capitalise on Industry 4.0. However, the financial costs and complexities of connecting the final few rural areas is a persisting problem area. Hence, this thesis explores new innovative approaches to provide NGA (product) to a final few (market). Studies revealed superfast broadband in remote rural communities has four-fold human, social, environmental and financial capital benefits. Analysis resulted in a new conceptual framework which combines neo-endogenous theories alongside a four-fold capital model to characterise the complex ecosystem. Previous literature focused on either supply or demand, but few studies had investigated both together at the local level. Human & social capital were identified as critical success factors in community-led initiatives, thus providing a theoretical underpinning for this thesis. This study employed a novel mutual business approach utilising the Hybrid Value System (HVS) as an ecosystem connecting the core assets of several stakeholders. Furthermore, the World Bank Social Capital Assessment Tool was modified to investigate social capital fertility to enhance investment. Henceforth, a qualitative multi-method and in-depth intrinsic case study was used to explore the ecosystem. The contribution to knowledge is how to engage multi-stakeholder and multi-capital analysis to resolve the problem area. The results identified human capital productivity, social capital collective action, and shared financial capital are required at the local level to reach the final few. The mutual business paradigm challenges all stakeholders to value non-financial capital alongside financial capital for problem area resolution. This thesis concludes that HVS methodology coupled with complex ecosystem-network visualisation techniques, provide academics, management and government policy makers with practical tools to value four-fold capital resources and bridge the digital divide

The Role of the Leaving Group in the Photo-Favorskii Rearrangement of p-Hydroxyphenacyl

The p-hydroxyphenacyl group has several features that make it an attractive photoremovable protecting group. Literature examples support this statement and the benzoate, formate, and sulfonate derivatives are not exceptions. The synthesis of these targets is straight forward involving few synthetic steps that produce the desired product in good to excellent yield. The purification of these targets is simplified by the fact that these derivatives are all solids. Their solubility and stability in polar organic solvents and in water at low concentrations, the formate solubility in water is the exception, make them ideal for use in organic synthesis and in biological applications. The bulk of the photochemical reactions on these derivatives were performed using a low intensity commercially available Southern New England Photoreactor fitted with RPR 3000 Å lamps in order to excite the chromophore in the region where reasonable absorptivity is displayed, at or above 300 nm. Departure of the substrate or leaving group from the p-hydroxyphenacyl chromophore occurs by the heterolytic rupture of the covalent bond connecting the two and is a primary photochemical process. The reaction results in the formation of two major photoproducts, the released substrate and a product resulting from the rearrangement of chromophore. Their lack of photochemical or chemical reactivity with other reagents, solvent, or other products established the stability of these two products. Finally, the photochemical release is fast (108 s-1) and efficient (Φdis = 0.20 - 1.00). p-Hydroxyphenacyl (pHP) caged compounds release substrates through a novel photo-Favorskii rearrangement. In an effort to systematically explore the effects of the leaving group on the efficacy of photorelease, a series of pHP substituted phenol, benzoate, formate, phosphate, and sulfonate esters have been examined. The quantum yields (Φ), Stern-Volmer quenching rates (kq), and release rates (kr) were determined. When this data was combined with the data from laser flash photolysis data, a correlation between the release rate and the pKa of the leaving group was observed. The βLG for this correlation was calculated to be roughly -0.24 showing that photorelease of the substrate is less sensitive to the structure and pKa of the leaving group than is the reference deprotonation reaction of water. The modest value of βLG suggests a small amount of bond cleavage to leaving group in the transition state. The mechanism of photorelease in aqueous or mixed aqueous solvents follows an ionic pathway with the substrate and a proton release occurring from the triplet ester forming a triplet biradical. This biradical then decays forming a spirodienedione intermediate which can either react with water as part of a Favorskii-like rearrangement yielding p-hydroxyphenylacetic acid, or it can undergo decarbonylation to form p-quinone methide. Subsequent reaction of p-quinone methide with water results in the formation of p-hydroxybenzyl alcohol. This mechanism is supported by the results of the quenching of the reaction of the benzoates by a triplet quencher (piperylene), the formation of only photoproducts when pHP formate, mesylate, and tosylate were photolyzed in the presence of a triplet sensitizer (acetone), the absorption bands for the triplet biradical and p-quinone methide that were observed using laser flash photolysis, and the appearance and decay of singlet and triplet species in the time resolved spectra of pHP benzoate and tosylate. A Brønsted correlation relating the rate constant for photorelease to the pKa of the substrate leaving group for several pHP derivatives, including the benzoate, formate, and sulfonate esters, which indicated there is a moderate degree of bond cleavage in the transition state for the adiabatic triplet fragmentation step. These results have added further insight into the mechanism for the photo-Favorskii rearrangements of p-hydroxyphenacyl derivatives

Dynamic Properties of Materials: Phonons from Neutron Scattering

Related article - "FORTRAN routines for the new SQW and PDF modules of GULP and TOBYFIT" at http://www.dspace.cam.ac.uk/handle/1810/225173 in the Data sets - Mineral Science CollectionA detailed understanding of fundamental material properties can be obtained through the study of atomic vibrations, performed experimentally with neutron scattering techniques and coupled with the two powerful new computational methodologies I have developed. The first approach involves phonon-based simulations of the pair distribution function -- a histogram of localised atomic positions generated experimentally from total scattering data. This is used to reveal ordering behaviour, to validate interatomic models and localised structure, and to give insights into how far dynamic behaviour can be studied using total scattering techniques. Most importantly, the long-standing controversy over dynamic disorder in $\beta$-cristobalite is resolved using this technique. Inelastic neutron spectroscopy (INS) allows \emph{direct} study of vibrational modes through their interaction with the neutron beam, and is the experimental basis for the second strand of the new methodology. I have developed new simulation and refinement tools based on the next generation of spectrometers currently being commissioned at the ISIS pulsed neutron source. This allows a detailed powder spectroscopy study of cristobalite and vitreous silica demonstrating that the Bose peak and so-called `fast sound' features can be derived from standard lattice dynamics in both the crystal and the amorphous counterpart, and allowing discussion of their origins. Given the controversy in the literature, this is a key result. The new methodology also encompasses refinement of interatomic models against powder INS data, with aluminium providing a successful test-case. A more complex example is seen in calcite, with experimental data collected during the commissioning of the new MERLIN spectrometer. Simulated one-phonon coherent INS spectra for the single crystal and powder (the latter including approximations to multi-phonon and multiple scatter) are fully convolved with experimental resolution functions. These are used in the analysis of the experimental data, yielding previously unpublished dispersion curves and soft mode information, as well as allowing the effectiveness of powder refinement of more complex materials to be assessed. Finally, I present further applications with technologically important materials -- relaxor ferroelectrics and high temperature pnictide superconductors. The conclusions draw together the different strands of the work, discussing the importance of these new advances together with future developments and scientific applications.This work was supported by a NERC studentship and CASE funding from STF

Remedial discourses : men, madness and mental management in fin-de-siècle literature

The period between 1880 and 1913, commonly known as the fin de siècle, was a time of great social, political and industrial change, an era in which the Victorian man saw his position within his society, his workplace and his family home undergo a radical transformation. It was also a period of evolution within the realm of mental medicine, which saw the development of radical new treatments across Europe and America. The methods, discourses and ideologies that underpinned these novel practices played a key role in the conception of mental illness, as well as the reconfiguration of the curative practices employed in its management. This thesis seeks to explore the depiction both of mental illness and of these new remedial discourses within the popular fiction of the period. Focusing specifically on the presentation of male madness, it seeks to extend the growing number of studies on masculinity and insanity in the nineteenth century, by considering its position at this late point of the period. It also breaks new ground by studying the depiction in fin de siècle literature not of illness, but of treatments for disorder, an area that has been considerably neglected critically. Divided into chapters based on genre, this thesis examines the portrayal of various types of madness in middle class male literary characters, arguing for a distinctive link between social anxieties and mental breakdown. It also explores how the fictional text engages with the scientific advancements of the period in treating mental illness, the key role played by narrative in both the creation of the story and the creation of the cure, and the clear interrelation and reciprocal influence between psychology and fiction at the end of the nineteenth century

MergeMaid: R Tools for Merging and Cross-Study Validation of Gene Expression Data

Cross-study validation of gene expression investigations is critical in genomic analysis. We developed an R package and associated object definitions to merge and visualize multiple gene expression datasets. Our merging functions use arbitrary character IDs and generate objects that can efficiently support a variety of joint analyses. Visualization tools support exploration and cross-study validation of the data, without requiring normalization across platforms. Tools include “integrative correlation” plots that is, scatterplots of all pairwise correlations in one study against the corresponding pairwise correlations of another, both for individual genes and all genes combined. Gene-specific plots can be used to identify genes whose changes are reliably measured across studies. Visualizations also include scatterplots of gene-specific statistics quantifying relationships between expression and phenotypes of interest, using linear, logistic and Cox regression. Availability: Free open source from url http://www.bioconductor.org. Contact: Xiaogang Zhong [email protected] Supplementary information: Documentation available with the package

Cross-study Validation and Combined Analysis of Gene Expression Microarray Data

Investigations of transcript levels on a genomic scale using hybridization-based arrays led to formidable advances in our understanding of the biology of many human illnesses. At the same time, these investigations have generated controversy, because of the probabilistic nature of the conclusions, and the surfacing of noticeable discrepancies between the results of studies addressing the same biological question. In this article we present simple and effective data analysis and visualization tools for gauging the degree to which the finding of one study are reproduced by others, and for integrating multiple studies in a single analysis. We describe these approaches in the context of studies of breast cancer, and illustrate that it is possible to identify a substantial, biologically relevant subset of the human genome within which hybridization results are reproducible. The subset generally varies with the platforms used, the tissues studied, and the populations being sampled. Despite important differences, it is also possible to develop simple expression measures that allow comparison across platforms, studies, labs and populations. Important biological signal is often preserved or enhanced. Cross-study validation and combination of microarray results requires careful, but not overly complex, statistical thinking, and can become a routine component of genomic analysis

Nurse Discharge Planning in the Emergency Department: A Toowoomba, Australia, Study

Aim. This study aimed to ascertain whether a model of risk screening carried out by an experienced community nurse was effective in decreasing re-presentations and readmissions and the length of stay of older people presenting to an Australian emergency department. Objectives. The objectives of the study were to (i) identify all older people who presented to the emergency department of an Australian regional hospital; (ii) identify the proportion of re-presentations and readmissions within this cohort of patients; and (iii) risk-screen all older patients and provide referrals when necessary to community services. Design. The study involved the application of a risk screening tool to 2139 men and women over 70 years of age from October 2002 to June 2003. Of these, 1102 (51.5%) were admitted and 246 (11.5%) were re-presentations with the same illness. Patients presenting from Monday to Friday from 08:00 to 16:00 hours were risk-screened face to face in the emergency department. Outside of these hours, but within 72 hours of presentation, risk screening was carried out by telephone if the patient was discharged or within the ward if the patient had been admitted. Results. There was a 16% decrease in the re-presentation rate of people over 70 years of age to the emergency department. Additionally during this time there was a 5.5% decrease in the readmission rate (this decrease did not reach significance). There was a decrease in the average length of stay in hospital from 6.17 days per patient in October 2002 to 5.37 days per patient in June 2003. An unexpected finding was the decrease in re-presentations in people who represented to the emergency department three or more times per month (known as 'frequent flyers'). Conclusions. Risk screening of older people in the emergency department by a specialist community nurse resulted in a decrease of re-presentations to the emergency department. There was some evidence of a decreased length of stay. It is suggested that the decrease in re-presentations was the result of increased referral and use of community services. It appears that the use of a specialist community nurse to undertake risk screening rather than the triage nurse may impact on service utilization. Relevance to clinical practice. It is apparent that older people presenting to the emergency department have complex care needs. Undertaking risk screening using an experienced community nurse to ascertain the correct level of community assistance required and ensuring speedy referral to appropriate community services has positive outcomes for both the hospital and the patient

Comment on "Local accumulation times for source, diffusion, and degradation models in two and three dimensions" [J. Chem. Phys. 138, 104121 (2013)]

In a recent paper, Gordon, Muratov, and Shvartsman studied a partial differential equation (PDE) model describing radially symmetric diffusion and degradation in two and three dimensions. They paid particular attention to the local accumulation time (LAT), also known in the literature as the mean action time, which is a spatially dependent timescale that can be used to provide an estimate of the time required for the transient solution to effectively reach steady state. They presented exact results for three-dimensional applications and gave approximate results for the two-dimensional analogue. Here we make two generalizations of Gordon, Muratov, and Shvartsman’s work: (i) we present an exact expression for the LAT in any dimension and (ii) we present an exact expression for the variance of the distribution. The variance provides useful information regarding the spread about the mean that is not captured by the LAT. We conclude by describing further extensions of the model that were not considered by Gordon,Muratov, and Shvartsman. We have found that exact expressions for the LAT can also be derived for these important extensions..

Development and initial validation of the Seated Posture Scale

—Literature shows that some health outcomes (e.g., eating, breathing, and speaking) are directly related to posture. Evidence of outcomes mediated by wheelchair seated posture is limited to interface pressure, physical function, and wheelchair skills and safety. This study’s purpose was to develop and validate a rapid, low-burden, paper-pencil assessment of wheelchair seated posture for research use and to test feasibility of its use with a sample of older adults. We used a prospective design and a convenience sample of older adults who were receiving rehabilitation services in a community living center. Forty-nine older wheelchair users participated. Main measures were the Seated Posture Scale (SPS), Modified Ashworth Scale, Barthel Index, Visual Descriptor Scale, scale-content validity index (S-CVI), Cronbach alpha, and test-retest reliability. Rating by six experts yielded the overall content validity score (S-CVI) of 0.744. Total SPS score correlated positively with physical function (Barthel Index, r = 0.46, p \u3c 0.001) and negatively with muscle tone (Modified Ashworth Scale, r = –0.44, p = 0.001), supporting SPS construct validity. Internal consistency was 0.66 (Cronbach alpha). Test-retest reliability yielded Pearson product-moment correlations of 0.89 to 0.99. We conclude that the SPS has sufficient preliminary validity and reliability to support its use as an evaluation of wheelchair seated posture in outcomes research

OPTIMIZED CROSS-STUDY ANALYSIS OF MICROARRAY-BASED PREDICTORS

Background: Microarray-based gene expression analysis is widely used in cancer research to discover molecular signatures for cancer classification and prediction. In addition to numerous independent profiling projects, a number of investigators have analyzed multiple published data sets for purposes of cross-study validation. However, the diverse microarray platforms and technical approaches make direct comparisons across studies difficult, and without means to identify aberrant data patterns, less than optimal. To address this issue, we previously developed an integrative correlation approach to systematically address agreement of gene expression measurements across studies, providing a basis for cross-study validation analysis. Here we generalize this methodology to provide a metric for evaluating the overall efficacy of preprocessing and cross-referencing, and explore optimal combinations of filtering and cross-referencing strategies. We operate in the context of validating prognostic breast cancer gene expression signatures on data reported by three different groups, each using a different platform. Results: To evaluate overall cross-platform reproducibility in the context of a specific prediction problem, we suggest integrative association, that is the cross-study correlation of gene-specific measure of association with the phenotype predicted. Specifically, in this paper we use the correlation among the Cox proportional hazard coefficients for association of gene expression to relapse free survival (RFS). Gene filtering by integrative correlation to select reproducible genes emerged as the key factor to increase the integrative association, while alternative methods of gene cross-referencing and gene filtering proved only to modestly improve the overall reproducibility. Patient selection was another major factor affecting the validation process. In particular, in one of the studies considered, gene expression association with RFS varied across subsets of patients that differ by their ascertainment criteria. One of the subsets proved to be highly consistent with other studies, while others showed significantly lower consistency. Third, as expected, use of cluster-specific mean expression profiles in the Cox model yielded more generalizable results than expression data from individual genes. Finally, by using our approach we were able to validate the association between the breast cancer molecular classes proposed by Sorlie et al. and RFS. Conclusions: This paper provides a simple, practical and comprehensive technique for measuring consistency of molecular classification results across microarray platforms, without requiring subjective judgments about membership of samples in putative clusters. This methodology will be of value in consistently typing breast and other cancers across different studies and platforms in the future. Although the tumor subtypes considered here have been previously validated by their proponents, this is the first independent validation, and the first to include the Affymetrix platform