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Synthesis of a terminal Ce(iv) oxo complex by photolysis of a Ce(iii) nitrate complex.
Reaction of [Ce(NR2)3] (R = SiMe3) with LiNO3 in THF, in the presence of 2,2,2-cryptand, results in the formation of the Ce(iii) "ate" complex, [Li(2,2,2-cryptand)][Ce(κ2-O2NO)(NR2)3] (1) in 38% yield. Photolysis of 1 at 380 nm affords [Li(2,2,2-cryptand)][Ce(O)(NR2)3] (2), in 33% isolated yield after reaction work-up. Complex 2 is the first reported example of a Ce(iv) oxo complex where the oxo ligand is not supported by hydrogen bonding or alkali metal coordination. Also formed during photolysis are [Li(2,2,2-cryptand)]2[(μ3-O){Ce(μ-O)(NR2)2}3] (3) and [Li(2,2,2-cryptand)][Ce(OSiMe3)(NR2)3] (4). Their identities were confirmed by X-ray crystallography. Complex 4 can also be prepared via reaction of [Ce(NR2)3] with LiOSiMe3 in THF, in the presence of 2,2,2-cryptand. When synthesized in this fashion, 4 can be isolated in 47% yield. To rationalize the presence of 2, 3, and 4 in the reaction mixture, we propose that photolysis of 1 first generates 2 and NO2, via homolytic cleavage of the N-O bond in its nitrate co-ligand. Complex 2 then undergoes decomposition via two separate routes: (1) ligand scrambling and oligomerization to form 3; and, (2) abstraction of a trimethylsilyl cation to form a transient Ce(iv) silyloxide, [CeIV(OSiMe3)(NR2)3], followed by 1e- reduction to form 4. Alternatively, complex 4 could form directly via ·SiMe3 abstraction by 2
Let's Get It On: Dressing Skill Development in Children With Vision Impairment and Children With Down Syndrome
Dressing is a fundamental independent living skill often haphazardly acquired via visual observation. For children with vision impairment and children with Down Syndrome (where vision impairment is a component), dressing skill acquisition can be delayed due to a reduced/absent visual modality. Independent living skills is an aspect of habilitation practice and training, designed to maximise independence in children and young people with vision impairment and prepare them for adulthood. This paper, presented in two parts, first details a systematic (UK based) survey exploring fastening use across a clothing sample of birth-adult clothing (N = 12,967). Study 1 presents a frequency distribution exploring types of fastenings used on clothing items from birth-adulthood. The data are fundamental in exploring the likelihood of fastening exposure across developmental phases. Further, Study 1 details the process behind developing a novel dressing skill intervention. Informed by Study 1, Study 2 qualitatively explored the effectiveness of an original resource/group-based intervention over a 10-week period. Eighteen children were recruited for the study, namely children with vision impairment (n = 9) and children with Down Syndrome (n = 9) aged 5–11 years. Collective and illustrative case studies are presented based on emergent themes from intervention observations. The findings reveal areas for consideration by Habilitation Specialists and the multidisciplinary team surrounding children with vision impairment and/or Down Syndrome as this may inform Habilitation Plans, and Educational Health Care Plan reports. The implications of this study extend beyond dressing skill development in children with vision impairment and/or Down Syndrome and inform resource development and subsequent practice when working with children with special educational needs and disabilities
The Major Histocompatibility Complex–related Fc Receptor for IgG (FcRn) Binds Albumin and Prolongs Its Lifespan
The inverse relationship between serum albumin concentration and its half-life suggested to early workers that albumin would be protected from a catabolic fate by a receptor-mediated mechanism much like that proposed for IgG. We show here that albumin binds FcRn in a pH dependent fashion, that the lifespan of albumin is shortened in FcRn-deficient mice, and that the plasma albumin concentration of FcRn-deficient mice is less than half that of wild-type mice. These results affirm the hypothesis that the major histocompatibility complex–related Fc receptor protects albumin from degradation just as it does IgG, prolonging the half-lives of both
Crossing the chasm:The role of co-investment funds in strengthening the regional business angel ecosystem
Development of a scale to measure stigma related to podoconiosis in Southern Ethiopia
Background:
Health-related stigma adds to the physical and economic burdens experienced by people suffering from neglected tropical diseases (NTDs). Previous research into the NTD podoconiosis showed significant stigma towards those with the disease, yet no formal instrument exists by which to assess stigma or interventions to reduce stigma. We aimed to develop, pilot and validate scales to measure the extent of stigma towards podoconiosis among patients and in podoconiosis-endemic communities.
Methods:
Indicators of stigma were drawn from existing qualitative podoconiosis research and a literature review on measuring leprosy stigma. These were then formulated into items for questioning and evaluated through a Delphi process in which irrelevant items were discounted. The final items formed four scales measuring two distinct forms of stigma (felt stigma and enacted stigma) for those with podoconiosis and those without the disease. The scales were formatted as two questionnaires, one for podoconiosis patients and one for unaffected community members. 150 podoconiosis patients and 500 unaffected community members from Wolaita zone, Southern Ethiopia were selected through multistage random sampling to complete the questionnaires which were interview-administered. The scales were evaluated through reliability assessment, content and construct validity analysis of
the items, factor analysis and internal consistency analysis.
Results:
All scales had Cronbach’s alpha over 0.7, indicating good consistency. The content and construct validity of the scales were satisfactory with modest correlation between items. There was significant correlation between the felt and enacted stigma scales among patients (Spearman’s r = 0.892; p < 0.001) and within the community (Spearman’s r = 0.794; p < 0.001).
Conclusion:
We report the development and testing of the first standardised measures of podoconiosis stigma. Although further research is needed to validate the scales in other contexts, we anticipate they will be useful in situational analysis and in designing, monitoring and evaluating interventions. The scales will enable an evidencebased approach to mitigating stigma which will enable implementation of more effective disease control and help
break the cycle of poverty and NTDs
The presentation, diagnosis and management of non-traumatic wrist pain: an evaluation of current practice in secondary care in the UK NHS
Promoting students’ interest through culturally sensitive curricula in higher education
Previous studies have emphasized culturally sensitive curricula in the context of enhancing minoritized students’ education. We examined the relationship between second-year higher education students’ perceptions of the cultural sensitivity of their curriculum and both majoritized and minoritized students’ interest in their course. A total of 286 (228 F) students rated the cultural sensitivity of their curriculum on six scales using a revised version of the Culturally Sensitive Curricula Scales (CSCS-R), the perceived quality of their relationships with teachers, and their interest. The CSCS-R widened the construct with two new scales and showed better reliability. Ethnic minority students (n = 99) perceived their curriculum as less culturally sensitive than White students (n = 182), corroborating previous findings. Black students perceived their curriculum as less culturally sensitive than Asian students. There were no significant differences between ethnic minority and White students on interest or perceived quality of relationships with teachers. Five dimensions of cultural sensitivity (Diversity Represented, Positive Depictions, Challenge Power, Inclusive Classroom Interactions, Culturally Sensitive Assessments) and perceived quality of relationships with teachers predicted interest. Ethnicity did not. Ensuring curricula and assessments represent diversity positively, challenge power and are inclusive may support students’ interest while reflecting an increasingly diverse society
Mapping the Spread of Malaria Drug Resistance
Tim Anderson discusses a new study of molecular variation in alleles at the dihydropteroate synthase locus, which underlies resistance to sulfadoxine, in over 5,000 parasites from 50 locations
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