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INTRODUCTION: Normothermic regional perfusion (NRP) represents an innovative technology that improves the outcomes for liver and kidney recipients of donation after circulatory determination of death (DCD) organs but protocols for abdominal-only NRP (A-NRP) DCD are lacking in the US. METHODS: We describe the implementation and expansion strategies of a transplant-center-based A-NRP DCD program that has grown in volume, geographical reach, and donor acceptance parameters, presented as four eras. RESULTS: In the implementation era, two donors were attempted, and one liver graft was transplanted. In the local expansion era, 33% of attempted donors resulted in transplantation and 42% of liver grafts from donors who died within the functional warm ischemic time (fWIT) limit were transplanted. In the Regional Expansion era, 25% of attempted donors resulted in transplantation and 50% of liver grafts from donors who died within the fWIT limit were transplanted. In the Donor Acceptance Expansion era, 46% of attempted donors resulted in transplantation and 72% of liver grafts from donors who died within the fWIT limit were transplanted. Eight discarded grafts demonstrated a potential opportunity for utilization. CONCLUSION: The stepwise approach to building an A-NRP program described here can serve as a model for other transplant centers.
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Preservação de Órgãos , Obtenção de Tecidos e Órgãos , Humanos , Preservação de Órgãos/métodos , Perfusão/métodos , Doadores de Tecidos , Morte , Sobrevivência de EnxertoRESUMO
BACKGROUND: In 2018, a set of entrustable professional activities (EPAs) and procedural skills assessments were developed for anesthesiology training, but they did not assess all the Accreditation Council for Graduate Medical Education (ACGME) milestones. The aims of this study were to (1) remap the 2018 EPA and procedural skills assessments to the revised ACGME Anesthesiology Milestones 2.0, (2) develop new assessments that combined with the original assessments to create a system of assessment that addresses all level 1 to 4 milestones, and (3) provide evidence for the validity of the assessments. METHODS: Using a modified Delphi process, a panel of anesthesiology education experts remapped the original assessments developed in 2018 to the Anesthesiology Milestones 2.0 and developed new assessments to create a system that assessed all level 1 through 4 milestones. Following a 24-month pilot at 7 institutions, the number of EPA and procedural skill assessments and mean scores were computed at the end of the academic year. Milestone achievement and subcompetency data for assessments from a single institution were compared to scores assigned by the institution's clinical competency committee (CCC). RESULTS: New assessment development, 2 months of testing and feedback, and revisions resulted in 5 new EPAs, 11 nontechnical skills assessments (NTSAs), and 6 objective structured clinical examinations (OSCEs). Combined with the original 20 EPAs and procedural skills assessments, the new system of assessment addresses 99% of level 1 to 4 Anesthesiology Milestones 2.0. During the 24-month pilot, aggregate mean EPA and procedural skill scores significantly increased with year in training. System subcompetency scores correlated significantly with 15 of 23 (65.2%) corresponding CCC scores at a single institution, but 8 correlations (36.4%) were <30.0, illustrating poor correlation. CONCLUSIONS: A panel of experts developed a set of EPAs, procedural skill assessment, NTSAs, and OSCEs to form a programmatic system of assessment for anesthesiology residency training in the United States. The method used to develop and pilot test the assessments, the progression of assessment scores with time in training, and the correlation of assessment scores with CCC scoring of milestone achievement provide evidence for the validity of the assessments.
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Anestesiologia , Internato e Residência , Estados Unidos , Anestesiologia/educação , Educação de Pós-Graduação em Medicina , Avaliação Educacional/métodos , Competência Clínica , AcreditaçãoRESUMO
INTRODUCTION: The limited prior research examining the association between academic performance and cardiovascular disease (CVD) risk factors in youth did not explore the reciprocal association between these constructs, and analyzed CVD risk factors individually. Thus, the aim of the present study was to explore the bidirectional longitudinal association between clustered CVD risk score and academic performance in adolescents over a 24-month interval. METHODS: A total of 237 adolescents (45.6% girls), aged 13.9 ± 0.3 years old at baseline, from DADOS (Deporte, ADOlescencia y Salud) study were included in this study. A clustered CVD risk score was created by calculating the mean age- and gender-standardized z-scores of waist circumference, systolic blood pressure, total cholesterol to high-density lipoprotein cholesterol ratio, triglycerides, homeostatic model assessment of insulin resistance, and cardiorespiratory fitness (inversed). Academic performance was assessed through the final academic grades and the test of educational abilities. RESULTS: Our results showed that the clustered CVD risk score at baseline was not associated with academic performance 24 months later (all p > .05). Nevertheless, except for physical education, academic grades at baseline were inversely associated with clustered CVD risk score at follow-up in adolescents (ß ranged from -0.140 to -0.102; all p < .05). No associations were found between academic abilities at baseline and clustered CVD risk score at follow-up (all p > .05). CONCLUSION: Academic grades could help predict CVD risk 24 months later during adolescence. Education professionals should foster adolescents' academic performance not only to improve academic results but also to maximize future cardiovascular health benefits.
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Desempenho Acadêmico , Doenças Cardiovasculares , Fatores de Risco de Doenças Cardíacas , Humanos , Adolescente , Feminino , Masculino , Doenças Cardiovasculares/epidemiologia , Doenças Cardiovasculares/etiologia , Desempenho Acadêmico/estatística & dados numéricos , Estudos Longitudinais , Fatores de Risco , México/epidemiologiaRESUMO
There is some, albeit inconsistent, evidence supporting sex differences in preschoolers' motor competence (MC), with these observations not uniform when analyzed by age, and cultural groups. Thus, this study examined sex differences across ages in 3- to 5-year-old children's MC. A cross-country pooled sample of 6241 children aged 3-5 years (49.6% girls) was assessed for MC using the Test of Gross Motor Development-2nd/3rd edition, and children were categorized into groups of age in months. Multiple linear regression models and predictive margins were calculated to explore how sex and age in months affect scores of MC (i.e., locomotor and ball skills), with adjustments for country and BMI. The Chow's Test was used to test for the presence of a structural break in the data. Significant differences in favor of girls were seen at 57-59 and 66-68 months of age for locomotor skills; boys performed better in ball skills in all age periods, except for 42-44 and 45-47 months of age. The higher marginal effects were observed for the period between 45-47 and 48-50 months for locomotor skills (F = 30.21; and F = 25.90 for girls and boys, respectively), and ball skills (F = 19.01; and F = 42.11 for girls and boys, respectively). A significantly positive break point was seen at 45-47 months, highlighting the age interval where children's MC drastically improved. The identification of this breakpoint provides an evidence-based metric for when we might expect MC to rapidly increase, and an indicator of early delay when change does not occur at that age.
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Destreza Motora , Humanos , Destreza Motora/fisiologia , Feminino , Masculino , Pré-Escolar , Estudos Transversais , Fatores Sexuais , Fatores Etários , Desenvolvimento Infantil/fisiologia , Modelos LinearesRESUMO
PURPOSE: The use of strength and conditioning training in childhood is a hot topic surrounded by myths and misconceptions. Despite scientific evidence supporting the safety and benefits of this training for children, the lack of representation of their voices poses a challenge in designing training programs that meet their specific needs and requirements. METHODS: Children's views, experiences, and perceptions of strength and conditioning training were explored by Write, Draw, Show and Tell techniques. Sixteen grassroots soccer players aged 11-12 years took part in one of 3 focus groups exploring the topic. Data were analyzed following an inductive approach enabling themes to be explored and later deductive analyses using the Youth Physical Activity Promotion model to create pen profile diagrams. RESULTS: Strength and conditioning were frequently associated with muscle growth, coordination, endurance, and rest. Enabling factors included autonomy, resilience, physical development, and training opportunities. Reinforcing factors included social support, social interference, coaches' communication, role models, and the ways of implementation. CONCLUSIONS: Participants favor integrating strength and conditioning into their soccer training rather than conducting it as a separate session, which is reflected in their enjoyment. Nonetheless, children remain apprehensive about the potential effects of this type of training on their growth.
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BACKGROUND/OBJECTIVES: Engagement in sport offers the potential for improved physical and psychological well-being and has been shown to be beneficial for promoting healthy aging. Opportunities for older adults to (re)engage with sport are limited by a paucity of age-appropriate introductory sports intervention programs. As such, the study evaluated the efficacy of a newly designed 8-week badminton training program (Shuttle Time for Seniors) on markers of healthy aging and the lived experiences of participation. METHODS: Forty-three older adults assigned to a control (N = 20) or intervention group (N = 23) completed pre-post assessment of physical and cognitive function, self-efficacy for exercise, and well-being. Focus groups were conducted for program evaluation and to understand barriers and enablers to sustained participation. RESULTS: Those in the intervention group increased upper body strength, aerobic fitness, coincidence anticipation time, and self-efficacy for exercise. Objectively improved physical and cognitive functions were corroborated by perceived benefits indicated in thematic analysis. Shuttle Time for Seniors was perceived as appropriate for the population, where the age-appropriate opportunity to participate with likeminded people of similar ability was a primary motivator to engagement. Despite willingness to continue playing, lack of badminton infrastructure was a primary barrier to continued engagement. CONCLUSION: Shuttle Time for Seniors offered an important opportunity for older adults to (re)engage with badminton, where the physical and psychosocial benefits of group-based badminton improved facets important to healthy aging. Significance/Implications: Age-appropriate introductory intervention programs provide opportunity for older adults to (re)engage with sport. However, important barriers to long-term engagement need to be addressed from a whole systems perspective.
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Understanding the associations and possible mechanisms between Cardiorespiratory Fitness (CRF) and residential location is an important focus of public health research. This is a cross-sectional study carried out with 2250 students (6-17 years), from southern Brazil. In addition to age, sex, and body size measurements, we also recorded hemoglobin and platelet count measurements using venous blood samples (10 ml). The CRF was measured using the 6-minute run/walk test, with predictors explored via allometry. Results identified a novel and independent association between the hemoglobin-to-platelet count ratio and children's CRF, after controlling for confounders. We also provide evidence of a possible mechanism for this association, having identified reduced measures of hemoglobin and increased platelet counts observed in children living in urban (vs rural) areas. These results suggest the need for more effective public health practices and policies addressing the built enviroment´s health effects in Brazil and potentially other congested ciries.
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Tunable laser photodissociation spectroscopy in the 700-400 nm region and photofragment imaging experiments are employed to investigate the Fe+(acetylene) ion-molecule complex. At energies above a threshold at 679 nm, continuous dissociation is detected throughout the visible wavelength region, with regions of broad structure. Comparison to the spectrum predicted by time-dependent density functional theory (TD-DFT) indicates that the complex has a quartet ground state. The dissociation threshold for Fe+(acetylene) at 679 nm provides the dissociation energy on the quartet potential energy surface. Correction for the atomic quartet-sextet spin state energy difference provides an adiabatic dissociation energy of 36.8 ± 0.2 kcal/mol. Photofragment imaging of the Fe+ photoproduct produced at 603.5 nm produces significant kinetic energy release (KER). The photon energy and the maximum value of the KER provide an upper limit on the dissociation energy of D0 ≤ 34.6 ± 3.2 kcal/mol. The dissociation energies determined from the spectroscopy and photofragment imaging experiments agree nicely with the value determined previously by collision-induced dissociation (38.0 ± 2.6 kcal/mol). However, both values are significantly lower than those produced by computational chemistry at the DFT level using different functionals recommended for transition-metal chemistry.
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Tunable laser photodissociation spectroscopy measurements and photofragment imaging experiments are employed to investigate the dissociation energy of the Fe+(benzene) ion-molecule complex. Additional spectroscopy measurements determine the dissociation energy of Fe+(benzene)2. The dissociation energies for Fe+(benzene) determined from the threshold for the appearance of the Fe+ fragment (48.4 ± 0.2 kcal/mol) and photofragment imaging (≤49.3 ± 3.2 kcal/mol) agree nicely with each other and with the value determined previously by collision-induced dissociation (49.5 ± 2.9 kcal/mol), but they are lower than the values produced by computational chemistry at the density functional theory level using different functionals recommended for transition-metal chemistry. The threshold measurement for Fe+(benzene)2 (43.0 ± 0.2 kcal/mol) likewise agrees with the value (44.7 ± 3.8 kcal/mol) from previous collision-induced dissociation measurements.
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Platinum cation complexes with multiple acetylene molecules are studied with mass spectrometry and infrared laser spectroscopy. Complexes of the form Pt+(C2H2)n are produced in a molecular beam by laser vaporization, analyzed with a time-of-flight mass spectrometer, and selected by mass for studies of their vibrational spectroscopy. Photodissociation action spectra in the C-H stretching region are compared to the spectra predicted for different structural isomers using density functional theory. The comparison between experiment and theory demonstrates that platinum forms cation-π complexes with up to three acetylene molecules, producing an unanticipated asymmetric structure for the three-ligand complex. Additional acetylenes form solvation structures around this three-ligand core. Reacted structures that couple acetylene molecules (e.g., to form benzene) are found by theory to be energetically favorable, but their formation is inhibited under the conditions of these experiments by large activation barriers.
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Gas-phase ion-molecule complexes of silver cation with benzene or toluene are produced via laser vaporization in a pulsed supersonic expansion. These ions are mass-selected and photodissociated with tunable UV-visible lasers. In both cases, photodissociation produces the organic cation as the only fragment via a metal-to-ligand charge-transfer process. The wavelength dependence of the photodissociation produces electronic spectra of the charge-transfer process. Broad structureless spectra result from excitation to the repulsive wall of the charge-transfer excited states. Additional transitions are detected correlating to the forbidden 1S â 1D silver cation-based atomic resonance and to the HOMO-LUMO excitation on the benzene or toluene ligand. Transitions to these states produce the same molecular cation photofragments produced in the charge-transfer transitions, indicating an unanticipated excited-state curve-crossing mechanism. Spectra measured for these ions are compared to those for ions tagged with argon atoms. The presence of argon causes a significant shift on the energetic positions of these electronic transitions for both Ag+(benzene) and Ag+(toluene).
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BACKGROUND: There has been a decline in children's physical fitness in recent decades. Such concerns are largely based on evidence from North America, Europe, and Asia. The current study describes the secular trend and variation (spread) in the physical fitness scores of young Brazilians from 2005 to 2022. METHODS: This study is a repeated, cross-sectional surveillance study (1999-2022). Children and adolescents (n = 65 139; boys = 36 539) participated between 2005 and 2022. In each cohort six physical fitness tests were conducted: (1) 20-m sprint speed (m s-1 ), (2) cardio-respiratory 6-min run test (m min-1 ), (3) abdominal strength test (sit-ups per min), (4) horizontal jump test (cm), (5) the agility test (m s-1 ), and (6) the medicine ball throw test (cm). Means and distributional characteristics of the population were assessed using ANOVA, ANCOVA adopting BMI as the body-size covariate, Levene's test of equality-of-error variances, and Box and whisker plots. RESULTS: ANOVAs and ANCOVA's identified significant declines in physical fitness over time/year in 5 of the 6 physical fitness variables (e.g., 20-m sprint speed slope B = -0.018 (m s-1 y-1 ); 95% CI -0.019 to -0.017; p < 0.001), the only exception being the medicine ball throw test (cm). The Levene's test of equality-of-error variances also identified a systematic increase in the variances/standard deviations over time/years. CONCLUSIONS: Results provide powerful evidence that children and adolescents' physical fitness is declining, a trend that is also diverging asymmetrically, becoming more extreme in more recent years. The "fit" appear to be getting fitter, but the fitness of the "less-fit" appears to be declining further. These results have important implications for sports medicine and government policy makers.
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Exercício Físico , Aptidão Física , Masculino , Criança , Humanos , Adolescente , Estudos Transversais , Brasil , Teste de EsforçoRESUMO
BACKGROUND: The cut-off date in the education system causes a relative age difference, with developmental advantages for children who are born on the "early side" of the cut-off date and disadvantages for those born later, which is known as the relative age effect (RAE). Very few studies have examined whether there is a RAE on the development of fundamental movement skills (FMSs) in preschool children, and no studies have been conducted in China. The purpose of this study is to identify whether a RAE exists on FMS in Chinese preschool children, comparing RAEs according to gender and age. METHODS: From a total of 378 invited preschool children regularly registered at one Chinese kindergarten, a total of 288 healthy and typically developing preschoolers (4.33 ± 0.84 years-old; 56.6% boys) were included in this study. All children were required to take part in anthropometry and FMS assessments. Analysis of covariance (ANCOVA) was applied to examine the difference in each of the FMS items across quarter categories, year and gender groups, controlling for body mass index (BMI). RESULTS: For the overall sample, the data show the significant main effects on the quarter of birth factor in locomotor skills (LC; F (3, 265) = 2.811, p = 0.04, ηp2 = 0.031), object control skills (OB; F (3, 265) = 6.319, p = 0.04, ηp2 = 0.031), and total test score (TTS; F (3, 265) = 5.988, p = 0.001, ηp2 = 0.063). There were also significant differences in the age effect on all the domains of FMS (FLC (2, 265) = 100.654, p < 0.001, ηp2 = 0.432; FOB (2, 265) = 108.430, p < 0.001, ηp2 = 0.450; FTTS (2, 265) = 147.234, p < 0.001, ηp2 = 0.526) but a gender effect only in LC (F (1, 265) = 20.858; p < 0.001; ηp2 = 0.073). For gender and quarter of birth groups, RAEs in LC only exists in girls. Moreover, regarding age and quarter of birth factors, RAEs are only found at younger ages. CONCLUSIONS: This study suggests the existence of RAEs in the FMS of Chinese preschool children. Teachers need to be aware of the effect of RAEs on the FMS when approaching development, evaluation, and teaching approaches in preschools.
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População do Leste Asiático , Destreza Motora , Masculino , Feminino , Pré-Escolar , Humanos , Índice de Massa Corporal , Antropometria , MovimentoRESUMO
The attainment of laboratory-based skills is essential for the development of all students who study the Life Sciences. When the COVID-19 pandemic hit and Universities worldwide closed campuses, there was great uncertainty around how long people would have to work from home, leading to a real risk that students could miss out on obtaining laboratory practice for one or perhaps 2 years. It, therefore, became critical that processes were put in place that would allow students the opportunity to gain insight into what the laboratory environment is like, and to also gain experience in data collection, interpretation, and analysis. The adoption of Lt systems (a cloud-based learning platform for the Life Sciences) to create laboratory-based teaching allowed for these issues to be addressed. Detailed planning, teamwork and production of online lab sessions allowed for the creation of bespoke lessons that replicated as best as possible the 'face-to-face' experience. This was achieved by taking aspects of pre-existing labs, filming new material and utilising interactive data analysis tools in order to create online Lt labs that gave students a feel of what it would be like to be in a laboratory on campus. Lt systems also doubled as a revision tool to enhance student learning and ultimately allowed intended learning outcomes to be successfully met. The labs were well received by students and the online material meant that they could access content at a time convenient to them. This 'online anytime' possibility was crucial for such a large class (n = 378) who were working from home in many different countries worldwide during a pandemic. Going forward, the online lessons built during the pandemic can be integrated with future face-to-face sessions to create a more enhanced learning experience for the student.
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COVID-19 , Pandemias , Humanos , COVID-19/epidemiologia , Aprendizagem , Universidades , EstudantesRESUMO
Growing anterior cruciate ligament (ACL) injury incidence is reported in countries across Europe, North America and in Australia for 5-14-year-olds, yet research on injury risk reduction predominantly focuses on populations aged > 13 years. For injury risk reduction, it is crucial to understand (i) which modifiable risk factors are associated with ACL injury in children (6-13 years) and (ii) how these risk factors are assessed. Articles were grouped according to sex/gender and/or maturational/age differences and examined modifiable risk factors during different physical screening tasks. The included articles (n = 40) predominantly examined intrinsic risk factors in girls aged 10-13 years. Factors mechanically linked to increased ACL loading at this age included increased peak knee adductor moments, knee valgus angles, hip and knee extension, and ground reaction forces. Assessment focused on laboratory-based assessments (e.g., motion capture, force plates). This review concluded that modifiable risk factors are present in children aged 6-13 years and that injury risk reduction strategies should be implemented as early as possible regardless of sex/gender. Further, screening strategies need updating to be childhood specific and feasible for the wide community. Additional research on extrinsic risk factors, norm values and children aged 6-9 years could allow for more targeted risk reduction strategies.
Increasing rates of ACL injuries in children aged 5 to 14 years are reported in countries across Europe, North America and in AustraliaResearch on modifiable risk factors focuses on internal risk factors in children aged 10-13 years and neglects external risk factors as well as younger children (6-10 years)Screening strategies to determine risk of ACL injury risk in children are laboratory based as opposed to cost-effective and quicker-to-analyse in-field assessmentResearch is warranted to examine external risk factors and in-field screening strategies in childhood.
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Lesões do Ligamento Cruzado Anterior , Feminino , Humanos , Criança , Lesões do Ligamento Cruzado Anterior/diagnóstico , Lesões do Ligamento Cruzado Anterior/epidemiologia , Lesões do Ligamento Cruzado Anterior/prevenção & controle , Ligamento Cruzado Anterior , Articulação do Joelho , Joelho , Fatores de Risco , Fenômenos BiomecânicosRESUMO
BACKGROUND: Understanding determinants of children's outdoor play is important for improving low physical activity levels, and schools are a key setting for both. Safety concerns shape children's opportunity to play actively outdoors, therefore, this qualitative evidence synthesis aimed to i) examine adult (e.g., parent, teacher, yard supervisor, principal) perspectives on safety and risk in children's active play during recess in elementary and/or middle schools, and ii) identify how safety and risk influence playground supervision and decision making in this setting. METHODS: Six electronic databases were systematically searched in March 2021, with an updated search in June 2022. Records were screened against eligibility criteria using Covidence software, and data extraction and synthesis were performed using predesigned coding forms in Microsoft Excel and NVivo. Framework synthesis methodology was employed, guided by a conceptual framework structured on the socio-ecological model (SEM) and affordance theory. RESULTS: From 10,370 records, 25 studies were included that represented 608 adults across 89 schools from nine countries. The synthesis identified 10 constraining and four affording factors that influenced whether school staff were risk-averse or risk tolerant during recess, and, in turn, the degree to which children's play was managed. Constraining factors stemmed from fears for children's physical safety, and fear of blame and liability in the event of playground injury, which shaped parent, school staff and institutional responses to risk. Interrelated factors across SEM levels combined to drive risk-averse decision making and constraining supervision. Emerging evidence suggests children's active play in schools can be promoted by fostering a risk tolerant and play friendly culture in schools through play facilitation training (e.g., risk-reframing, conflict resolution) and engaging stakeholders in the development of school policies and rules that balance benefits of play against potential risks. CONCLUSIONS: Findings show several socio-cultural factors limited the ability of school staff to genuinely promote active play. Future work should seek to foster risk tolerance in schools, challenge the cultural norms that shape parent attitudes and institutional responses to risk in children's play, and explore novel methods for overcoming policy barriers and fear of liability in schools. TRIAL REGISTRATION: PROSPERO registration: CRD42021238719.
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Jogos e Brinquedos , Instituições Acadêmicas , Criança , Audição , Humanos , Motivação , PaisRESUMO
BACKGROUND: Active play is vital for healthy child development, and schools are a valuable setting to promote this behaviour. Understanding the determinants of children's physical activity behaviour during recess, particularly the role of risk-taking and the influence safety concerns have on active play, is required. This systematic review aimed to 1) synthesise qualitative research with children that explored their perceptions of safety and risk in active play during recess in elementary and/or middle school, and 2) develop a model from the findings to guide efforts in schools to optimise children's active play opportunities during recess. METHODS: Six online databases were systematically searched for articles published between January 2000 and March 2021. Following PRISMA guidelines, records were screened against eligibility criteria using Covidence software, and data extraction and synthesis was conducted using customised forms in Excel and NVivo software. Framework synthesis methodology was employed, conceptually guided by Bronfenbrenner's socio-ecological model and Gibson's affordance theory. RESULTS: Of 9664 records, 31 studies met inclusion criteria, representing 1408 children across 140 schools from 11 countries. An emergent conceptual framework was developed encompassing 23 risk and safety themes and 10 risky play types that children desired in schools. Individual characteristics (age, gender, physical literacy) influenced children's engagement with risk and how they kept themselves safe. Across outer SEM levels, factors interacted to constrain or afford children's active play. Socio-cultural factors (supervision practices, rules, equipment restrictions) constrained active play, which children perceived were driven by adults' concern with physical safety. These factors contributed to a cycle of risk-averse decision making and diminished play affordances, which could inadvertently exacerbate safety issues. A model for risk tolerance in children's active play has been proposed. CONCLUSIONS: The findings show a disparity between the active play children want in schools and what they are able to do. Future work should balance the concerns of adults against the active play children want, involve children in decisions about playground policy, and foster a risk-tolerant culture in schools.
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Jogos e Brinquedos , Instituições Acadêmicas , Criança , Audição , Humanos , Atividade Motora , Pesquisa QualitativaRESUMO
Ion-molecule complexes of uranium or thorium singly-charged positive ions bound to cyclooctatetraene (COT), i.e., M+(COT)1,2, are produced by laser ablation and studied with UV laser photodissociation. The ions are selected by mass and excited at 355 or 532 nm, and the ionized dissociation products are detected using a reflectron time-of-flight mass spectrometer. The abundant fragments M+(C6H6), M+(C4H4), and M+(C2H2) occur for complexes of both metals, whereas the M+(C4H2), M+(C3H3), and M+(C5H5) fragments are prominent for uranium complexes but not for thorium. Additional experiments investigate the dissociation of M+(benzene)1,2 ions which may be intermediates in the fragmentation of the COT ions. The experiments are complemented by computational quantum chemistry to investigate the structures and energetics of fragment ions. Various cation-π and metallacycle structures are indicated for different fragment ions. The metal ion-ligand bond energies for corresponding complex ions are systematically greater for the thorium species. The computed thermochemistry makes it possible to explain the mechanistic details of the photochemical fragmentation processes and to reveal new actinide organometallic structures.
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Laser photochemistry of pressed-pellet samples of polycyclic aromatic hydrocarbons (PAHs) produces covalently bonded dimers and some higher polymers. This chemistry was discovered initially via laser desorption time-of-flight mass spectrometry experiments, which produced masses (m/z) of 2M-2 and 2M-4 (where M is the monomer parent mass). Dimers are believed to be formed from photochemical dehydrogenation and radical polymerization chemistry in the desorption plume. Replication of these ablation conditions at higher throughput allowed PAH dimers of pyrene, perylene, and coronene to be produced and collected in milligram quantities. Differential sublimation provided purification of the dimers and elimination of residual monomers. The purified dimers were investigated with UV-visible, IR, and Raman spectroscopy, complemented by computational studies using density functional theory at the CAM-B3LYP/def2-TZV level. Calculations and predicted spectra were calibrated by comparison with the corresponding monomers and used to determine the lowest energy dimer structures. Infrared and Raman spectroscopy provided few distinctive signatures, but UV-visible spectra detected new transitions for each dimer. The comparison of simulated and experimental spectra allows determination of the most prevalent structures for the PAH dimers. The work presented here provides interesting insights into the spectroscopy of extended aromatic systems and a new strategy for the photochemical synthesis of large PAH dimers.
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Fe+(acetylene)n ion-molecule complexes are produced in a supersonic molecular beam with pulsed laser vaporization. These ions are mass selected and studied with infrared photodissociation spectroscopy in the C-H stretching region, complemented by computational chemistry calculations. All C-H stretch vibrations are shifted to frequencies lower than the vibrations of isolated acetylene because of the charge transfer that occurs between the metal ion and the molecules. Complexes in the size range of n = 1-4 are found to have structures with individual acetylene molecules bound to the core metal ion via cation-π interactions. The coordination is completed with four ligands in a structure close to a distorted tetrahedron. Larger complexes in the range of n = 5-8 have external acetylene molecules solvating this n = 4 core ion via CH-π bonding to inner-shell ligands. DFT computations predict that quartet spin states are more stable for all complex sizes, but infrared spectra for quartet and doublet spin states are quite similar, precluding definitive determination of the spin states. There is no evidence for any of these complexes having acetylenes coupled into reacted structures. This is consistent with computed thermochemistry, which finds significant activation barriers to such reactions.