607 research outputs found

    Solution phase, solid state, and theoretical investigations on the MacMillan imidazolidinone

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    A combination of soln. phase NMR, X-ray crystallog. studies, and DFT calcns. provide a consistent structural conformation for iminium ions derived from the MacMillan imidazolidinone

    Aryldiazonium tetrafluoroborate salts as green and efficient coupling partners for the Suzuki-Miyaura reaction : from optimisation to mole scale

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    The use of aryldiazonium tetrafluoroborate salts as coupling partners in the Suzuki-Miyaura reaction was investigated from a process chemistry perspective including safety evaluation, solvent and catalyst screening and multi-variate factor optimization. Optimised conditions were applied to a range of substrates to evaluate the scope and limitations of the reaction and one example was carried out on mole-scale to demonstrate the practicality and scalability of the proces

    The alpha-effect in cyclic secondary amines: new scaffolds for iminium ion accelerated transformations

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    Five-membered secondary amine heterocycles containing an α-heteroatom were prepared and shown to be ineffective as catalysts for the iminium ion catalysed Diels–Alder reaction between cinnamaldehyde and cyclopentadiene. Their six-membered counterparts proved to be highly active catalysts. In stark contrast, the catalytic activity observed when comparing the non α-heteroatom cyclic amines proline methyl ester and methyl pipecolinate showed the five-membered ring amine was significantly more active. Concurrent density functional theoretical calculations suggest a rationale for the observed trends in reactivity, highlighting that LUMO activation through an iminium ion intermediate plays a key role in catalytic activity

    Relationships between digit ratio (2D:4D) and basketball performance in Australian men

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    Objective To investigate relationships between the digit ratio (2D:4D) and competitive basketball performance in Australian men. Methods Using an observational cross‐sectional design a total of 221 Australian basketball players who competed in the Olympic Games, International Basketball Federation World Championships/Cup, Australian National Basketball League, Central Australian Basketball League or socially had their 2D:4Ds measured. Analysis of variance was used to assess differences in mean 2D:4Ds between men playing at different competitive standards, with relationships between 2D:4Ds and basketball game‐related statistics assessed using Pearson\u27s product moment correlations in men playing at a single competitive standard. Results There were significant differences between competitive standards for the left 2D:4D following Bonferroni correction, but not for the right 2D:4D, with basketballers who achieved higher competitive standards tending to have lower left 2D:4Ds. No important correlations between 2D:4D and basketball game‐related statistics were found, with correlations typically negligible. Conclusions This study indicated that the 2D:4D can discriminate between basketballers competing at different standards, but not between basketballers within a single competitive standard using objective game‐related statistics

    C–H arylation of heterocyclic N oxides through in-situ diazotisation of anilines without added promoters : a green and selective coupling process

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    A green and selective method for the generation of bi-aryl compounds through C—H arylation of heterocyclic N-oxides is presented in which the addition of ascorbic acid as a promoter is not required for either the generation of an aryldiazonium species or the subsequent arylation. Reaction conditions were optimized through Multivariate Data Analysis, including Orthogonal Projections to Latent Structures (OPLS) and Design of Experiments (DoE) methodologies resulting in further sustainability improvements, and were then applied to a range of substrates to establish the scope and limitations of the process. The reaction was studied using in-situ infra-red spectroscopy and a mechanism is presented that accounts for the available data from this and previous studies. The reaction was also per-formed on a multigram scale, with calorimetry studies to support further scale-up of this promoter-free transformation

    Does ratification of human-rights treaties have effects on population health?

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    Human-rights treaties indicate a country's commitment to human rights. Here, we assess whether ratification of human-rights treaties is associated with improved health and social indicators. Data for health (including HIV prevalence, and maternal, infant, and child [<5 years] mortalities) and social indicators (child labour, human development index, sex gap, and corruption index), gathered from 170 countries, showed no consistent associations between ratification of human-rights treaties and health or social outcomes. Established market economy states had consistently improved health compared with less wealthy settings, but this was not associated with treaty ratification. The status of treaty ratification alone is not a good indicator of the realisation of the right to health. We suggest the need for stringent requirements for ratification of treaties, improved accountability mechanisms to monitor compliance of states with treaty obligations, and financial assistance to support the realisation of the right to health

    The 20-m shuttle run: Assessment and interpretation of data in relation to youth aerobic fitness and health

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    Cardiorespiratory fitness (CRF) is a good summative measure of the body’s ability to perform continuous, rhythmic, dynamic, large-muscle group physical activity, and exercise. In children, CRF is meaningfully associated with health, independent of physical activity levels, and it is an important determinant of sports and athletic performance. Although gas-analyzed peak oxygen uptake is the criterion physiological measure of children’s CRF, it is not practical for population-based testing. Field testing offers a simple, cheap, practical alternative to gas analysis. The 20-m shuttle run test (20mSRT)—a progressive aerobic exercise test involving continuous running between 2 lines 20 m apart in time to audio signals—is probably the most widely used field test of CRF. This review aims to clarify the international utility of the 20mSRT by synthesizing the evidence describing measurement variability, validity, reliability, feasibility, and the interpretation of results, as well as to provide future directions for international surveillance. The authors show that the 20mSRT is an acceptable, feasible, and scalable measure of CRF and functional/exercise capacity, and that it has moderate criterion validity and high to very high reliability. The assessment is pragmatic, easily interpreted, and results are transferable to meaningful and understandable situations. The authors recommend that CRF, assessed by the 20mSRT, be considered as an international population health surveillance measure to provide additional insight into pediatric population health

    Criterion-referenced mCAFT cut-points to identify metabolically healthy cardiorespiratory fitness among adults aged 18–69 years: An analysis of the Canadian Health Measures Survey

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    Objective: This study aimed to develop and validate health-related criterion-referenced cutpoints for the modified Canadian Aerobic Fitness Test (mCAFT), a field-based measure to predict cardiorespiratory fitness (CRF) among adults (18–69 years). Methods: Criterionreferenced mCAFT cut-points were developed using nationally representative data from cycles 1 (2007–09) and 2 (2009–11) of the Canadian Health Measures Survey (CHMS). Receiver operating characteristic curves were used to identify age- and sex-specific cut-points for measured waist circumference, blood pressure, and high-density lipoprotein. Cut-points were validated against metabolic syndrome using a fasted sub-sample (n=1,093) from cycle 5 (2016– 17). Results: 4,967 participants (50% women) were retained for the main analyses. The mCAFT cut-points ranged from 28 to 43 mL‱kg–1‱min–1 (AUC: 0.60-0.87) among men, and 23 to 37 mL‱kg–1‱min–1 (AUC: 0.61-0.86) among women. The likelihood of meeting the new mCAFT cut-points decreased with an increase in the presence of metabolic risk factors. In total, 54% (95%CI: 42 to 67%) of Canadian adults met the new mCAFT cut-points in 2016–17. Conclusion: This study developed and validated the first health-related criterion-referenced mCAFT cutpoints for metabolic health among Canadian adults aged 18–69 years. These mCAFT cut-points may be useful in health surveillance, clinical, and public health settings. Novelty bullets We developed and validated new criterion-referenced cut-points for the modified Canadian Aerobic Fitness Test to help identify adults at potential risk of poor metabolic health. These new cut-points could help support national health surveillance efforts

    Perception of threat and intent to harm from vocal and facial cues

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    What constitutes a “threatening tone of voice”? There is currently little research exploring how listeners infer threat, or the intention to cause harm, from speakers’ voices. Here, we investigated the influence of key linguistic variables on these evaluations (Study 1). Results showed a trend for voices perceived to be lower in pitch, particularly those of male speakers, to be evaluated as sounding more threatening and conveying greater intent to harm. We next investigated the evaluation of multimodal stimuli comprising voices and faces varying in perceived dominance (Study 2). Visual information about the speaker’s face had a significant effect on threat and intent ratings. In both experiments, we observed a relatively low level of agreement among individual listeners’ evaluations, emphasising idiosyncrasy in the ways in which threat and intent-to-harm are perceived. This research provides a basis for the perceptual experience of a “threatening tone of voice,” along with an exploration of vocal and facial cue integration in social evaluation
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