Ab initio molecular dynamics study of manganese porphine hydration and interaction with nitric oxide

The authors use ab initio molecular dynamics and the density functional theory+U (DFT+U) method to compute the hydration environment of the manganese ion in manganese (II) and manganese (III) porphines (MnP) dispersed in liquid water. These are intended as simple models for more complex water soluble porphyrins, which have important physiological and electrochemical applications. The manganese ion in Mn(II)P exhibits significant out-of-porphine plane displacement and binds strongly to a single H2O molecule in liquid water. The Mn in Mn(III)P is on average coplanar with the porphine plane and forms a stable complex with two H2O molecules. The residence times of these water molecules exceed 15 ps. The DFT+U method correctly predicts that water displaces NO from Mn(III)P-NO, but yields an ambiguous spin state for the MnP(II)-NO complex.Comment: 10 pages, 6 figure

Cobalt-Porphyrin Catalyzed Electrochemical Reduction of Carbon Dioxide in Water II: Mechanism from First Principles

We apply first principles computational techniques to analyze the two-electron, multi-step, electrochemical reduction of CO2 to CO in water using cobalt porphyrin as a catalyst. Density Functional Theory calculations with hybrid functionals and dielectric continuum solvation are used to determine the steps at which electrons are added. This information is corroborated with ab initio molecular dynamics simulations in an explicit aqueous environment which reveal the critical role of water in stabilizing a key intermediate formed by CO2 bound to cobalt. Using potential of mean force calculations, the intermediate is found to spontaneously accept a proton to form a carboxylate acid group at pH<9.0, and the subsequent cleavage of a C-OH bond to form CO is exothermic and associated with a small free energy barrier. These predictions suggest that the proposed reaction mechanism is viable if electron transfer to the catalyst is sufficiently fast. The variation in cobalt ion charge and spin states during bond breaking, DFT+U treatment of cobalt 3d orbitals, and the need for computing electrochemical potentials are emphasized.Comment: 33 pages, 7 figure

Real People, Real Lives: a small scale pilot project exploring case studies of the transition experiences of young people with long term conditions and disabilities who have recently moved from children's to adult serrvices in Cheshire and Merseyside

Aims The aim of this pilot project was to carry out Case Studies which will explore the different transition pathways and experiences of young people representing the following groups: • Young people who have common long – term conditions such as Diabetes and Epilepsy which are predominantly self-managed at home, with oversight from centres with specialist expertise. • Young People who have long term conditions which require intermittent or regular hospital-based intensive support such as those who are technology dependant or require frequent admissions for acute or specialist care. • Young people who have disabilities and complex needs. • Young people who are receiving support from Child and Adolescent Mental Health Services. The intended outcomes were to provide the local Strategic Clinical Network Special Interest Group with insight into how strategies to improve the experience of transition could be informed by the lived experiences of: • Young Service Users who had recently undergone transition from children’s to adult services • The viewpoints of their parents and carers • The perspectives of lead professionals involved in planning, coordinating and supporting the transition process. Methods Six Case Studies were constructed following face-to-face semi-structured interviews with young people, parents and carers representing the above groups. The young people involved had experienced the transition from children’s to adult services during the previous six months to three years. Where it was possible to identify and access a lead professional who was involved in planning and co-ordinating the transition their perspective was also sought through separate face to face and telephone interviews before inclusion within the appropriate case study. Results The Case Studies demonstrate that parents have a good understanding of what Transition means, and have endeavoured to explain this to their children. Some parents and carers were aware of policy guidance and expectations, for example the recommendation that planning should start during the early teenage years. This is not necessarily what they have experienced themselves. There were some examples of good practice and transitions support where knowledgeable and experienced practitioners were able to plan holistically to work across boundaries and overcome barriers to assure the best possible outcomes for young people. Other young people and their parents were not able to identify someone who had taken lead responsibility for co-ordinating their transition to adult services. Emerging themes included : • Variable Transition Plans and experiences • Young people still “getting lost” in transition • Variable involvement of young people and families in decision-making • The influence of different traditions, levels of practitioner confidence and models of service provision • Training needs and developing expertise and best practice in transition support • Fearful young people and “battle-weary” parents • The positive and negative impact of transition experiences • Loss of services • Key messages from families • Communication, planning and process • Improving services and support Conclusions 1. Transition services across the region include some areas of good or developing practice as well as some examples of inadequate transition planning and services to meet the needs of young people who have long term conditions, special educational needs or disabilities. 2. It is not currently possible to conclude that all transition experiences in the region universally meet sector standards and best practice guidance. 3. Families would like those in charge of commissioning services and making financial decisions to hear their stories and understand the challenges they face. 4. The Strategic Clinical Network is in a privileged position to make some transformational changes to benefit young people, parents and carers – to achieve this they may need to be courageous in re-thinking delivery models and the relationship between services designed to meet the needs of children and adults. This is likely to involve working in partnership with other Strategic Clinical Networks and Clinical Commissioning Groups. 5. There are some good examples of effective practice, but transition planning often starts late and may be vague and fragmented, have gaps or fail to adequately involve young people parents and carers in decisions. 6. Transition outcomes for young people and families can be positive, however the researchers found several examples of diminished service provision to the detriment of service users. 7. Where transition planning has worked well this has been because there has been a dedicated Key Worker, named lead professional or Transition Team who have developed expertise; are able to coordinate regular meetings and bring together multi-disciplinary/ multi-agency teams; effectively involve service providers and users and develop creative solutions to overcome barriers in order to meet the individual needs of young people and their families. 8. The planning process needs an approach which bridges divisions between children’s and adult services; health, social care and education; hospital and community settings; geographical boundaries - service provision needs to develop to match this approach. 9. Training, resources, and pathways need to be developed for both practitioners and families involved in developing and implementing Transition Plans. 10. New models of care provision and new ways of working will be essential to success; new technologies could contribute to solutions

Density functional theory and DFT+U study of transition metal porphines adsorbed on Au(111) surfaces and effects of applied electric fields

We apply Density Functional Theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an eV. The DFT+U technique, parameterized to B3LYP predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP, and ~ 0.1 Angstrom, changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first row transition metal ion complexes in a condensed-matter setting.Comment: 14 pages, 6 figure

Monkey’s Guide to Healthy Living and NHS Services An evaluation of the implementation of resources designed to support the learning of primary school aged children in England

A team of researchers from the Faculty of Education, Health and Community recently carried out a national evaluation project on behalf of the NHS Institute for Innovation and Improvement. Colleagues from across the faculty were involved in evaluating the impact of resources provided to every primary school in England. The resources were designed to enable teachers and health professionals to work together to help children learn about the NHS and the range of services they could access if they required acute of emergency care

"Our Unified Voice to Implement Change and Advance the View of Young Carers and Young Adult Carers." An Appreciative Evaluation of the Impact of a National Young Carer Health Champions Programme

A growing evidence base highlights the challenges and support needs of young carers and young adult carers, however research and policy frequently neglect the voice and experience of young people themselves. A team at NHS England developed the Young Carer Health Champions programme to bring together young carers and young adult carers from across England, establishing a network of peer support, sharing of experiences and improving confidence, health literacy and wellbeing. This commissioned independent evaluation aimed to explore the impact of the programme and inform future delivery. Taking a qualitative case study approach, young participants have a central voice, illuminated through the observations of the researcher during residential activities, and data generated during a focus group and telephone and on-line interviews. Findings demonstrate positive impact on the personal development and lifestyles of the Young Carer Health Champions, and their journey from beneficiary to pro-active shaper of services and policy

Do We Need to Re-Think Transition to Take a More Comprehensive Approach to Supporting Young People to Navigate Complex Journeys to Adulthood?

This discussion paper draws on a range of personal and other published research articles to respond to calls for a re-conceptualization of the concept of Transition. Acknowledging the roots of the concept in developmental and health psychology, the article briefly considers application to fields of practice in formal and informal education, health, social care, counseling, and psychotherapy that underpin approaches to supporting young people to navigate the journey to adulthood. UK service provision is discussed to consider why linear developmental approaches may be problematic, alongside recent calls for a re-conceptualization of what we mean by Transition to successfully understand, support, and enable complex journeys to young adulthood. The paper concludes by proposing a holistic, non-linear bio-ecological systems approach within which it is possible to integrate globally evolving research, pathways, models, and interventions. The approach will be of interest to an international readership because principles can be adapted to respond to shared and country-specific challenges, developments, and models of service provision as we approach the second quarter of the twenty-first century

Challenges, Complexity, and Developments in Transition Services for Young People with Disabilities, Mental Health, and Long-Term Conditions: An Integrative Review

Transition to adulthood for young people is complex and multi-faceted, with additional hurdles for young people who have disabilities, long-term, or life-limiting conditions or mental health problems. The challenges in providing effective transition support are not new; researchers, policymakers, commissioners, and service providers have been grappling with the problem for several decades, with varying degrees of success. The aims of this integrative review were firstly to build on previous research to synthesize and evaluate recently published evidence. Secondly to provide an overview of the effectiveness of interventions (in one or a combination of health, social care, and education transitions) designed to support transition to adulthood in these groups of young people. A search of a range of databases retrieved published literature from January 2015 to January 2021 demonstrating global interest in the topic. Fifty-one articles were included following an appraisal of quality and eligibility. Qualitative, quantitative, mixed methods studies, and evidence synthesis were included. Some studies were clinically orientated whilst others examined the impact of the transition process, or utilized participatory approaches which give young service-users and families a voice. Transition between children's and adult health or care services as well as other life-course trajectories, such as life-skills development, education transitions, social inclusion and employability were evaluated. Thematic analysis and synthesis of articles retrieved in this review highlighted themes identified in previous reviews: timing of, and preparation for transition; perceptions and experience of transition; barriers and facilitators; transition outcomes. Additional themes included special considerations; dealing with complexity; advocacy, participation, autonomy, aspirations, and young people's rights; future work, research, and evaluation. Novel perspectives and diverse data sources contributed to holistic understanding of an ongoing priority for international policy, service development, and research: the complexity of providing effective transition support and achieving positive outcomes for young people with long-term and life-limiting health conditions, disabilities, and mental health difficulties