Palladium(II)-catalyzed allylic acetoxylation has been the focus of extensive development and investigation. Methods that use molecular oxygen (O2) as the terminal oxidant typically benefit from the ...use of benzoquinone (BQ) and a transition-metal (TM) cocatalyst, such as Co(salophen), to support oxidation of Pd0 during catalytic turnover. We previously showed that Pd(OAc)2 and 4,5-diazafluoren-9-one (DAF) as an ancillary ligand catalyze allylic oxidation with O2 in the absence of cocatalysts. Herein, we show that BQ enhances DAF/Pd(OAc)2 catalytic activity, nearly matching the performance of reactions that include both BQ and Co(salophen). These observations are complemented by mechanistic studies of DAF/Pd(OAc)2 catalyst systems under three different oxidation conditions: (1) O2 alone, (2) O2 with cocatalytic BQ, and (3) O2 with cocatalytic BQ and Co(salophen). The beneficial effect of BQ in the absence of Co(salophen) is traced to the synergistic roles of O2 and BQ, both of which are capable of oxidizing Pd0 to PdII. The reaction of O2 generates H2O2 as a byproduct, which can oxidize hydroquinone to quinone in the presence of PdII. NMR spectroscopic studies, however, show that hydroquinone is the predominant redox state of the quinone cocatalyst in the absence of Co(salophen), while inclusion of Co(salophen) maintains oxidized quinone throughout the reaction, resulting in better reaction performance.
Abstract Objectives: To compare the cumulative costs of public services used through to adulthood by individuals with three levels of antisocial behaviour in childhood. Design: Costs applied to data ...of 10 year old children from the inner London longitudinal study selectively followed up to adulthood. Setting: Inner London borough. Participants: 142 individuals divided into three groups in childhood: no problems, conduct problems, and conduct disorder. Main outcome measures: Costs in 1998 prices for public services (excluding private, voluntary agency, indirect, and personal costs) used over and above basic universal provision. Results: By age 28, costs for individuals with conduct disorder were 10.0 times higher than for those with no problems (95% confidence interval of bootstrap ratio 3.6 to 20.9) and 3.5 times higher than for those with conduct problems (1.7 to 6.2). Mean individual total costs were £70 019 for the conduct disorder group (bootstrap mean difference from no problem group £62 898; £22 692 to £117 896) and £24 324 (£16 707; £6594 to £28 149) for the conduct problem group, compared with £7423 for the no problem group. In all groups crime incurred the greatest cost, followed by extra educational provision, foster and residential care, and state benefits; health costs were smaller. Parental social class had a relatively small effect on antisocial behaviour, and although substantial independent contributions came from being male, having a low reading age, and attending more than two primary schools, conduct disorder still predicted the greatest cost. Conclusions: Antisocial behaviour in childhood is a major predictor of how much an individual will cost society. The cost is large and falls on many agencies, yet few agencies contribute to prevention, which could be cost effective. What is already known on this topic Children who show substantial antisocial behaviour have poor social functioning as adults and are at high risk of social exclusion Costs are available for particular items of public service such as receiving remedial education or appearing in court What this study adds Costs of antisocial behaviour incurred by individuals from childhood to adulthood were 10 times greater for those who were seriously antisocial in childhood than for those who were not The costs fell on a wide range of agencies Reduction of antisocial behaviour in childhood could result in large cost savings
Iridium complexes containing CCC-pincer m-phenylene-bridged N-heterocyclic carbene ligands were examined as catalysts for alkene isomerization. Complexes containing either mesityl or adamantyl side ...groups were found to catalyze the isomerization of a number of alkenes to the internal isomers, including 1-octene, vinylcyclohexane, and allylbenzene. Mechanistic studies indicate a surprising dichotomy, apparently caused by ligand steric effects. For the mesityl-substituted catalyst, several lines of evidence provide strong support for isomerization via an iridium allyl hydride intermediate: (1) H–D crossover experiments indicate that 1,3-hydrogen migration is exclusively intramolecular, (2) the catalyst resting state, a π-allyl hydride species, was isolated and serves as a kinetically competent catalyst, (3) NMR experiments indicate that the π-allyl hydride resting state undergoes reversible C–H reductive elimination that is rapid relative to catalytic turnover, and (4) kinetic studies indicate that the isomerization reaction is first order in substrate and catalyst, consistent with turnover-limiting ligand substitution. H–D crossover experiments for alkene isomerization catalyzed by the adamantyl-substituted complex show selectivity for a 1,3-deuterium shift, as well as the intermolecular transfer of hydrogen. These results are consistent with an insertion/elimination mechanism proceeding selectively through a secondary metal–alkyl or with a π-allyl-type mechanism with an unknown pathway for intermolecular hydrogen crossover.
To develop and validate a psychometrically rigorous measure of health-related quality of life (HRQoL) for people with dementia: DEMQOL.
Literature review. Expert opinion. Interviews and ...questionnaires.
Gold standard psychometric techniques were used to develop DEMQOL and DEMQOL-Proxy. A conceptual framework was generated from a review of the literature, qualitative interviews with people with dementia and their carers, expert opinion and team discussion. Items for each component of the conceptual framework were drafted and piloted to produce questionnaires for the person with dementia (DEMQOL) and carer (DEMQOL-Proxy). An extensive two-stage field-testing was then undertaken of both measures in large samples of people with dementia (n = 130) and their carers (n = 126) representing a range of severity and care arrangements. In the first field test, items with poor psychometric performance were eliminated separately for DEMQOL and DEMQOL-Proxy to produce two shorter, more scientifically robust instruments. In the second field test, the item-reduced questionnaires were evaluated along with other validating measures (n = 101 people with dementia, n = 99 carers) to assess acceptability, reliability and validity.
Rigorous evaluation in two-stage field testing with 241 people with dementia and 225 carers demonstrated that in psychometric terms: (1) DEMQOL is comparable to the best available dementia-specific HRQoL measures in mild to moderate dementia, but is not appropriate for use in severe dementia Mini Mental State Examination (MMSE) <10; and (2) DEMQOL-Proxy is comparable to the best available proxy measure in mild to moderate dementia, and shows promise in severe dementia. In addition, the DEMQOL system has been validated in the UK in a large sample of people with dementia and their carers, and it provides separate measures for self-report and proxy report, which allows outcomes assessment across a wide range of severity in dementia.
The 28-item DEMQOL and 31-item DEMQOL-Proxy provide a method for evaluating HRQoL in dementia. The new measures show comparable psychometric properties to the best available dementia-specific measures, provide both self- and proxy-report versions for people with dementia and their carers, are appropriate for use in mild/moderate dementia (MMSE >/= 10) and are suitable for use in the UK. DEMQOL-Proxy also shows promise in severe dementia. As DEMQOL and DEMQOL-Proxy give different but complementary perspectives on quality of life in dementia, the use of both measures together is recommended. In severe dementia, only DEMQOL-Proxy should be used. Further research with DEMQOL is needed to confirm these findings in an independent sample, evaluate responsiveness, investigate the feasibility of use in specific subgroups and in economic evaluation, and develop population norms. Additional research is needed to address the psychometric challenges of self-report in dementia and validating new dementia-specific HRQoL measures.
Imaging patients with obesity Alqahtani, Saeed J; Knapp, Karen M
Journal of medical radiation sciences,
March 2022, Volume:
69, Issue:
1
Journal Article
Peer reviewed
Open access
Obesity is a major global health issue, which directly impacts on health and is associated with multiple comorbidities. This editorial explores the challenges and clinical decision making relating to ...imaging patients with obesity.
To produce a robust measure of social inclusion Social and Community Opportunities Profile (SCOPE) that is multidimensional and captures multiple life domains; incorporates objective and subjective ...indicators of inclusion; has sound psychometric properties including responsiveness; facilitates benchmark comparisons with normative general population and mental health samples including common mental disorder (CMD) and severe mental illness groups; can be used with people with mental health problems receiving support from mental health services or not; and can be used across a range of community service settings.
Phase I: conceptual framework developed from a review of the literature and concept mapping. Phase II: questionnaire developed including UK national population surveys and other normative data. Pre-testing using cognitive appraisal and evaluation then pilot testing in a small convenience sample. Preliminary testing (following modification) in community (n = 252) and mental health service users (MHSUs) samples (n = 43). Data reduction including factor analysis and Mokken scaling for polytomous item response analysis then psychometric evaluation, including internal consistency and discriminant and construct validity. Test-retest reliability assessed in a convenience sample of students (n = 119). Final testing in clinical services including psychometric evaluation and responsiveness testing.
The community sample was set in participants' households across the UK. The MHSU sample was set in a south Wales resource centre. The student sample was set in a university.
The community sample was randomly selected from the postal address file in five areas in England and Wales. Forty people in this sample were subgrouped as having a CMD based on their responses to the Mental Health Index five items. Two MHSU samples were obtained from existing services.
Psychometric testing on the field data from the SCOPE long version demonstrated good internal consistency of all scales (alpha ≥ 0.7), good construct validity, with SCOPE scales correlating highly with each other sharing between 40% and 61% of variance and a close but lesser association with community participation and social capital. Chi-squared tests on objective items and analysis of variance between groups on SCOPE scales demonstrated good discriminant validity between different mental health groups (and better than the Mokken scaling results). Acceptability was good, with 77% of the service user sample finding the SCOPE domains relevant. The number of items in SCOPE decreased from 121 to 48 following data reduction. Scales in the short version of SCOPE retained reasonable internal consistency (alpha between 0.60 and 0.75). Test-retest reliability demonstrated reliability over time, with strong associations between all items over a 2-week period. Repeating the discriminant validity tests on the short version demonstrates good discriminant validity between the mental health groups. Acceptability improved, with 90% of the sample describing questions as relevant to them.
The main aim of producing an instrument with good psychometric properties for use in research and clinical settings, namely the SCOPE short version, was achieved. Ongoing data collection will enable responsiveness testing in the future. Further research is needed including larger samples of minority and disadvantaged groups, including those with physical illnesses and disabilities, and specific mental health diagnostic groups.
The National Institute for Health Research Health Technology Assessment programme.
Antithrombin deficiency (ATD) is an autosomal dominant thrombophilia presenting with varying phenotypes. In pediatric patients with ATD, thrombosis typically develops during the neonatal period or ...adolescence. However, to date there are no consistent recommendations on the therapeutic management of children with ATD. Inferior vena cava atresia (IVCA) belongs to a range of congenital or acquired vena cava malformations and is described as an independent risk factor for thrombosis. The present case report explores two cases of combined ATD and IVCA in an adolescent and his mother.
A 14-year-old male presented with extensive deep venous thromboses (DVTs) of both lower extremities as well as an IVCA. The patient had previously been diagnosed with an asymptomatic ATD without therapeutic consequences at that time. His mother was suffering from an ATD and had herself just been diagnosed with IVCA, too. The DVTs in the adolescent were treated by systemic anticoagulation and catheter-directed local thrombolysis causing favourable results. Yet, despite adequate oral anticoagulation the DVTs in both lower extremities reoccurred within 1 week after the patient was discharged from hospital. This time, thrombolysis could not be fully achieved. Surprisingly, probing and stenting of the IVCA was achieved, indicating an acquired IVCA which could have occurred after undetected thrombosis in early childhood. Genetic analyses showed the same mutation causing ATD in both son and mother: heterozygote missense mutation c.248 T > C, p.(Leu83Pro), within the heparin binding domain of antithrombin. This mutation was never reported in mutation databases before.
To our knowledge this is the first case report discussing combined ATD and IVCA in two family members. Since ATDs present with clinical heterogeneity, taking a thorough family history is crucial for the anticipation of possible complications in affected children and decisions on targeted diagnostics and therapeutic interventions. Affected families must be educated on risk factors and clinical signs of thrombosis and need an immediate diagnostic workup in case of clinical symptoms. IVCA in patients with ATD could occur due to thrombotic occlusion at a very early age. Therefore, in case of family members with IVCA and ATD ultrasound screening in newborns should be considered.
Objective:
Poor vascular health is associated with reduced bone strength and increased risk of fragility fracture. However, direct measurement of intraosseous vascular health is difficult due to the ...density and mineral content of bone. We investigated the feasibility of using a commercially available continuous wave near infrared spectroscopy (NIRS) system for the investigation of vascular haemodynamics in human bone
in vivo
.
Approach:
An arterial occlusion (AO) protocol was developed for obtaining haemodynamic measurements of the proximal tibia and lateral calf, including assessment of the protocol’s intra operator reproducibility. For 36 participants, intraosseous haemodynamics derived by NIRS were compared to alternative tests of bone health based on dual x-ray absorptiometry (DXA) testing and MRI.
Main Results:
Near infrared spectroscopy markers of haemodynamics of the proximal tibia demonstrated acceptable reproducibility, comparable with reproducibility assessments of alternative modalities measuring intraosseous haemodynamics, and the use of NIRS for measuring muscle. Novel associations have been demonstrated between haemodynamic markers of bone measured with NIRS and body composition and bone mineral density (BMD) measurements obtained with both DXA and MRI.
Significance:
Near infrared spectroscopy provides inexpensive, non-invasive, safe, and real time data on changes in oxygenated and deoxygenated haemoglobin concentration in bone at the proximal tibia. This study has demonstrated the potential for NIRS to contribute to research investigating the pathophysiological role of vascular dysfunction within bone tissue, but also the limitations and need for further development of NIRS technology.
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