Raman microscopic and computational studies of artists' pigments and molecular inorganic compounds

This thesis is principally concerned with spectroscopic and computational studies of artists' pigments. Manuscripts, art and archaeological artefacts were examined by Raman microscopy, identifying the pigments and drawing conclusions for historical and conservation purposes. Studies of Anglo Saxon and later manuscripts have shown the Insular palette triumvirate, assumed to be orpiment, red lead and verdigris, to contain red ochre and vergaut, but no verdigris. This remains unchanged until the introduction of lazurite in C.920 AD and vermilion in the 12th century. Lazurite has been erroneously identified on the Lindisfarne Gospels, by the technique of Roosen-Runge. Raman microscopy shows the blue pigments to be exclusively indigo, casting doubt on analyses performed using Roosen-Runge's technique. The Islamic manuscript palette was found to be remarkably consistent across a substantial geographical area over an extended period. It is also very similar to that of early Western manuscripts. Comparison of these results with existing literary sources has shown the latter to be highly inaccurate. The palette of William Blake was examined and compared to results of analysis by False Colour Infrared Photography (FC-IP). The FC-IP technique was determined to be inappropriate for pigment identification. Two significant artefacts were shown to be modern forgeries: a rare Assyrian fresco contains a modern green pigment, and the world famous Vinland map was found to have significant quantities of anatase in the yellow lines. Density Functional Theory methods were applied to the mechanism of decay isomerisation of AS4S4, which was partially clarified, and to the geometries of R2SeX2 (R = CF3, CF2H, CFH2, CH3, CH2CH3, CH(CH3)2, t-Butyl, X = F, Cl, Br, I, At). The most stable geometry was found to be determined by the polarity of the Se-X bonds and the steric and electron-withdrawal effects of the R-group on the C-Se bond strength

Using the qubus for quantum computing

In this thesis I explore using the qubus for quantum computing. The qubus is an architecture of quantum computing, where a continuous variable ancilla is used to generate operations between matter qubits. I concentrate on using the qubus for two purposes - quantum simulation, and generating cluster states. Quantum simulation is the idea of using a quantum computer to simulate a quantum system. I focus on conducting a simulation of the BCS Hamiltonian. I demonstrate how to perform the necessary two qubit operations in a controlled fashion using the qubus. In particular I demonstrate an O(N3) saving over an implementation on an NMR computer, and a factor of 2 saving over a naıve technique. I also discuss how to perform the quantum Fourier transform on the qubus quantum computer. I show that it is possible to perform the quantum Fourier transform using just, 24⌊N/2⌋ + 7N − 6, this is an O(N) saving over a naıve method. In the second part of the thesis, I move on, and consider generating cluster states using the qubus. A cluster state, is a universal resource for one-way or measurement-based computation. In one-way computation, the pre-generated, entangled resource is used to perform calculations, which only require local corrections and measurement. I demonstrate that the qubus can generate cluster states deterministically, and in a relatively short time. I discuss several techniques of cluster state generation, one of which is optimal, given the physical architecture we are using. This can generate an n × m cluster in only 3nm − 2n − 2m + 4 operations. The alternative techniques look at generating a cluster using layers or columns, allowing it to be built dynamically, while the cluster is used to perform calculations. I then move on, and discuss problems with error accumulation in the generation process

An Intervention to Increase Condom Use Among Users of Sexually Transmitted Infection Self-sampling Websites (Wrapped) : Protocol for a Randomized Controlled Feasibility Trial

© 2023 Katie Newby, Rik Crutzen, Katherine Brown, Julia Bailey, John Saunders, Ala Szczepura, Jonny Hunt, Tim Alston, S Tariq Sadiq, Satyajit Das. Originally published in JMIR Formative Research (http://formative.jmir.org). This is an open-access article distributed under the terms of the Creative Commons Attribution License (https://creativecommons.org/licenses/by/4.0/).BACKGROUND: Reducing the rates of sexually transmitted infections (STIs) among young people is a public health priority. The best way to avoid STIs from penetrative sex is to use a condom, but young people report inconsistent use. A missed opportunity to intervene to increase condom use is when young people access self-sampling kits for STIs through the internet. The potential of this opportunity is enhanced by the increasing numbers of young people being tested through this route every year in England. Hence, in a cocreation by young people, stakeholders, and researchers, Wrapped was developed--a fully automated, multicomponent, and interactive digital behavior change intervention developed for users of STI self-sampling websites, who are aged 16-24 years. OBJECTIVE: This paper is a protocol for a feasibility randomized controlled trial (fRCT). The fRCT seeks to establish whether it is feasible to run a randomized controlled trial to test the effectiveness and cost-effectiveness of Wrapped. Wrapped aims to reduce the incidence of STIs through increasing correct and consistent use of condoms among users of STI self-sampling websites, who are aged 16-24 years. METHODS: A 2-arm parallel-group randomized fRCT of Wrapped plus usual care, compared to usual care only (basic information on STIs and condom use), with a nested qualitative study. A minimum of 230 participants (aged 16-24 years) are recruited from an existing chlamydia self-sampling website. Participants are randomized into 1 of 2 parallel groups (1:1 allocation). Primary outcomes are the percentage of users recruited to the fRCT and the percentage of randomized participants who return a chlamydia self-sampling kit at month 12. Additionally, besides chlamydia positivity based on biological samples, surveys at baseline, month 3, month 6, and month 12, are used to assess condom use attitude, behavioral capability, self-efficacy, and intention, along with details of any partnered sexual activity and condom use, and health economic data. Nested qualitative interviews with trial participants are used to gain insight into the factors affecting recruitment and attrition. RESULTS: Recruitment to the fRCT began in March 2021 and was completed in October 2021. Data collection was completed in December 2022. CONCLUSIONS: This feasibility study will provide data to inform the design of a future-definitive trial. This work is timely given a rapid rise in the use of internet testing for STIs and the sustained high levels of STIs among young people. TRIAL REGISTRATION: ISRCTN Registry ISRCTN17478654; http://www.isrctn.com/ISRCTN17478654. INTERNATIONAL REGISTERED REPORT IDENTIFIER (IRRID): DERR1-10.2196/43645.Peer reviewe

Tailored digital behaviour change intervention with e-referral system to increase attendance at NHS Stop Smoking Services (The MyWay Project):study protocol for a randomised controlled feasibility trial.

Introduction: In the UK, smokers who use Stop Smoking Services (SSS) are four times more likely to stop smoking than smokers who do not. Attendance has declined, warranting the development of interventions to address this. StopAppTM is a novel, brief online behaviour change intervention designed to address common barriers to SSS attendance. It links to widely commissioned service management software which enables instant appointment booking at a user’s location and time of choice.Methods and analysis: A two-arm parallel group individual participant randomised feasibility RCT of StopAppTM (intervention) compared with standard promotion of and referral to SSSs (control). The study includes a nested qualitative process evaluation to assess the acceptability of the research processes, with a sub-sample of participants. Smokers aged over 16 years will be recruited via three routes: GP practices, community settings and online. After consenting and the collection of baseline data, participants will be randomised to control or intervention groups. Participants in the intervention group receive a link to StopAppTM and those in the control group receive standard web-based information about the SSS. All participants are told they can book a SSS appointment but are under no obligation to do so. Online follow-up 2 months post randomisation includes data on SSS use and carbon monoxide verified 4 week quit rates. The study aims to recruit 162 smokers. Ethics and dissemination: Ethics approval has been granted by the West Midlands - Edgbaston NHS Research Ethics Committee. The findings will be reported in conferences and peer-reviewed publications; and will be used to design the parameters necessary for a definitive trial to ascertain the effectiveness of StopAppTM at increasing booking and attendance at SSSs compared with existing methods for encouraging uptake.Trial Registration: Research Registry: 3995. Trial Registered 18th April 2018

Multi-disciplinary Evaluation of Sexual Assault Referral Centres (SARCs) for better Health (MESARCH): protocol for a 1-year cohort study examining health, well-being and cost outcomes in adult survivors of sexual assault attending SARCs in England

INTRODUCTION Sexual violence is commonplace and has serious adverse consequences for physical and mental health. Sexual Assault Referral Centres (SARCs) are viewed as a best practice response. Little is known about their effectiveness and cost-effectiveness. Long-term data on the health and well-being of those who have experienced rape and sexual assault are also lacking. METHODS AND ANALYSIS This is a mixed-methods protocol for a 1-year cohort study aiming to examine the health and well-being in survivors of sexual violence after attending a SARC in England. Quantitative measures are being taken at baseline, 6 and 12 months. Post-traumatic stress (PTS) is the primary outcome (target N=270 at 12-month follow-up). Secondary measures include anxiety, depression, substance use and sexual health and well-being. Using mixed-effects regression, our main analysis will examine whether variation in SARC service delivery and subsequent mental healthcare is associated with improvement in trauma symptoms after 12 months. An economic analysis will compare costs and outcomes associated with different organisational aspects of SARC service delivery and levels of satisfaction with care. A nested qualitative study will employ narrative analysis of transcribed interviews with 30 cohort participants and 20 survivors who have not experienced SARC services. ETHICS AND DISSEMINATION The research is supported by an independent study steering committee, data monitoring and ethics committee and patient and public involvement (PPI) group. A central guiding principle of the research is that being involved should feel diametrically opposed to being a victim of sexual violence, and be experienced as empowering and supportive. Our PPI representatives are instrumental in this, and our wider stakeholders encourage us to consider the health and well-being of all involved. We will disseminate widely through peer-reviewed articles and non-academic channels to maximise the impact of findings on commissioning of services and support for survivors. TRIAL REGISTRATION NUMBER ISRCTN30846825

People with Type 2 Diabetes Mellitus (T2DM) Self-Reported Views on Their Own Condition Management Reveal a High Level of Insight into the Challenges Faced

From SAGE Publishing via Jisc Publications RouterHistory: epub 2021-05-17Publication status: Publishe

Big hearts, small hands:A focus group study exploring parental food portion behaviours

© The Author(s). 2017. This article is distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated.Background: The development of healthy food portion sizes among families is deemed critical to childhood weight management; yet little is known about the interacting factors influencing parents' portion control behaviours. This study aimed to use two synergistic theoretical models of behaviour: the COM-B model (Capability, Opportunity, Motivation - Behaviour) and Theoretical Domains Framework (TDF) to identify a broad spectrum of theoretically derived influences on parents' portion control behaviours including examination of affective and habitual influences often excluded from prevailing theories of behaviour change. Methods: Six focus groups exploring family weight management comprised of one with caseworkers (n = 4), four with parents of overweight children (n = 14) and one with parents of healthy weight children (n = 8). A thematic analysis was performed across the dataset where the TDF/COM-B were used as coding frameworks. Results: To achieve the target behaviour, the behavioural analysis revealed the need for eliciting change in all three COM-B domains and nine associated TDF domains. Findings suggest parents' internal processes such as their emotional responses, habits and beliefs, along with social influences from partners and grandparents, and environmental influences relating to items such as household objects, interact to influence portion size behaviours within the home environment. Conclusion: This is the first study underpinned by COM-B/TDF frameworks applied to childhood weight management and provides new targets for intervention development and the opportunity for future research to explore the mediating and moderating effects of these variables on one another.Peer reviewedFinal Published versio

A digital behaviour change intervention to increase booking and attendance at Stop Smoking Services: the MyWay feasibility RCT

© Queen’s Printer and Controller of HMSO 2021. This work was produced by Fulton et al. under the terms of a commissioning contract issued by the Secretary of State for Health and Social Care. The final published version can be accessed here: https://dx.doi.org/10.3310/phr09050Background: Smoking remains a leading cause of illness and preventable death. NHS Stop Smoking Services increase quitting, but, as access is in decline, cost-effective interventions are needed that promote these services. StopApp™ (Coventry University, Coventry, UK) is designed to increase booking and attendance at Stop Smoking Services. Design: A two-arm feasibility randomised controlled trial of StopApp (intervention) compared with standard promotion and referral to Stop Smoking Services (control) was conducted to assess recruitment, attrition and health equity of the design, alongside health economic and qualitative process evaluations. Setting: Smokers recruited via general practitioners, community settings and social media. Participants: Smokers aged ≥ 16 years were recruited in one local authority. Participants had to live or work within the local authority area, and there was a recruitment target of 120 participants. Interventions: StopApp to increase booking and attendance at Stop Smoking Services. Main outcome measures: Participants completed baseline measures and follow-up at 2 months post randomisation entirely online. Objective data on the use of Stop Smoking Services were collected from participating Stop Smoking Services, and age groups, sex, ethnicity and socioeconomic status in baseline recruits and follow-up completers/non-completers were assessed for equity. Results: Eligible participants (n = 123) were recruited over 116 days, with good representation of lower socioeconomic status groups; black, Asian and minority ethnic groups; and all age groups. Demographic profiles of follow-up completers and non-completers were broadly similar. The attrition rate was 51.2%Peer reviewe

HER2-HER3 heterodimer quantification by FRET-FILM and patient subclass analysis of the COIN colorectal trial

BACKGROUND: The phase 3 MRC COIN trial showed no statistically significant benefit from adding the EGFR-target cetuximab to oxaliplatin-based chemotherapy in first-line treatment of advanced colorectal cancer. This study exploits additional information on HER2-HER3 dimerization to achieve patient stratification and reveal previously hidden subgroups of patients who had differing disease progression and treatment response. METHODS: HER2-HER3 dimerization was quantified by 'FLIM Histology' in primary tumor samples from 550 COIN trial patients receiving oxaliplatin and fluoropyrimidine chemotherapy +/-cetuximab. Bayesian latent class analysis (LCA) and covariate reduction was performed to analyze the effects of HER2-HER3 dimer, RAS mutation and cetuximab on progression-free survival (PFS) and overall survival (OS). All statistical tests were two-sided. RESULTS: LCA on a cohort of 398 patients revealed two patient subclasses with differing prognoses (median OS: 1624 days [95%CI=1466-1816] vs 461 [95%CI=431-504]): Class 1 (15.6%) showed a benefit from cetuximab in OS (HR = 0.43 [95%CI=0.25-0.76]; p = 0.004). Class 2 showed an association of increased HER2-HER3 with better OS (HR = 0.64 [95%CI=0.44-0.94]; p = 0.02). A class prediction signature was formed and tested on an independent validation cohort (N = 152) validating the prognostic utility of the dimer assay. Similar subclasses were also discovered in full trial dataset (N = 1,630) based on 10 baseline clinicopathological and genetic covariates. CONCLUSIONS: Our work suggests that the combined use of HER dimer imaging and conventional mutation analyses will be able to identify a small subclass of patients (>10%) who will have better prognosis following chemotherapy. A larger prospective cohort will be required to confirm its utility in predicting the outcome of anti-EGFR treatment

The experience of blood glucose monitoring in people with type 2 diabetes mellitus (T2DM)

Background: Finger prick blood glucose (BG) monitoring remains a mainstay of management in people with type 2 diabetes (T2DM) who take sulphonylurea (SU) drugs or insulin. We recently examined patient experience of BG monitoring in people with type 1 diabetes (T1DM). There has not been any recent comprehensive assessment of the performance of BG monitoring strips or the patient experience of BG strips in people with T2DM in the UK. Methods: An online self‐reported questionnaire containing 44 questions, prepared following consultation with clinicians and patients, was circulated to people with T2DM. 186 responders provided completed responses (25.5% return rate). Fixed responses were coded numerically (eg not confident = 0 fairly confident = 1). Results: Of responders, 84% were treated with insulin in addition to other agents. 75% reported having had an HbA1c check in the previous 6 months. For those with reported HbA1c ≥ 65 mmol/mol, a majority of people (70%) were concerned or really concerned about the shorter term consequences of running a high HbA1c This contrasted with those who did not know their recent HbA1c, of whom only 33% were concerned/really concerned and those with HbA1c <65 mmol/mol of whom 35% were concerned. Regarding BG monitoring/insulin adjustment, only 25% of responders reported having sufficient information with 13% believing that the accuracy and precision of their BG metre was being independently checked. Only 9% recalled discussing BG metre accuracy when their latest metre was provided and only 7% were aware of the International Standardisation Organisation (ISO) standards for BG metres. 77% did not recall discussing BG metre performance with a healthcare professional. Conclusion: The group surveyed comprised engaged people with T2DM but even within this group there was significant variation in (a) awareness of shorter term risks, (b) confidence in their ability to implement appropriate insulin dosage (c) awareness of the limitations of BG monitoring technology. There is clearly an area where changes in education/support would benefit many