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Virtually all living cells are encased in glycans. They perform key cellular functions such as immunomodulation and cell-cell recognition. Yet, how their composition and configuration affect their functions remains enigmatic. Here, we constructed isogenic capsule-switch mutants harboring 84 types of capsular polysaccharides (CPSs) in Streptococcus pneumoniae. This collection enables us to systematically measure the affinity of structurally related CPSs to primary human nasal and bronchial epithelial cells. Contrary to the paradigm, the surface charge does not appreciably affect epithelial cell binding. Factors that affect adhesion to respiratory cells include the number of rhamnose residues and the presence of human-like glycomotifs in CPS. Besides, pneumococcal colonization stimulated the production of interleukin 6 (IL-6), granulocyte-macrophage colony-stimulating factor (GM-CSF), and monocyte chemoattractantprotein-1 (MCP-1) in nasal epithelial cells, which also appears to be dependent on the serotype. Together, our results reveal glycomotifs of surface polysaccharides that are likely to be important for colonization and survival in the human airway.
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Células Epiteliais , Streptococcus pneumoniae , Humanos , Streptococcus pneumoniae/genética , Streptococcus pneumoniae/metabolismo , Sistema Respiratório , Polissacarídeos/metabolismo , NarizRESUMO
Controllable ring-opening of polycyclic aromatic hydrocarbons plays a crucial role in various chemical and biological processes. However, breaking down aromatic covalent C-C bonds is exceptionally challenging due to their high stability and strong aromaticity. This study presents a seminal report on the precise and highly selective on-surface ring-opening of the seven-membered ring within the aromatic azulene moieties under mild conditions. The chemical structures of the resulting products were identified using bond-resolved scanning probe microscopy. Furthermore, through density functional theory calculations, we uncovered the mechanism behind the ring-opening process and elucidated its chemical driving force. The key to achieving this ring-opening process lies in manipulating the local aromaticity of the aromatic azulene moiety through strain-induced internal ring rearrangement and cyclodehydrogenation. By precisely controlling these factors, we successfully triggered the desired ring-opening reaction. Our findings not only provide valuable insights into the ring-opening process of polycyclic aromatic hydrocarbons but also open up new possibilities for the manipulation and reconstruction of these important chemical structures.
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BACKGROUND & AIMS: Discerning whether laryngeal symptoms result from gastroesophageal reflux is clinically challenging and a reliable tool to stratify patients is needed. We aimed to develop and validate a model to predict the likelihood of gastroesophageal reflux disease (GERD) among patients with chronic laryngeal symptoms. METHODS: This multicenter international study collected data from adults with chronic laryngeal symptoms who underwent objective testing (upper gastrointestinal endoscopy and/or ambulatory reflux monitoring) between March 2018 and May 2023. The training phase identified a model with optimal receiver operating characteristic curves, and ß coefficients informed a weighted model. The validation phase assessed performance characteristics of the weighted model. RESULTS: A total of 856 adults, 304 in the training cohort and 552 in the validation cohort, were included. In the training phase, the optimal predictive model (area under the curve, 0.68; 95% CI, 0.62-0.74), was the Cough, Overweight/obesity, Globus, Hiatal Hernia, Regurgitation, and male seX (COuGH RefluX) score, with a lower threshold of 2.5 and an upper threshold of 5.0 to predict proven GERD. In the validation phase, the COuGH RefluX score had an area under the curve of 0.67 (95% CI, 0.62-0.71), with 79% sensitivity and 81% specificity for proven GERD. CONCLUSIONS: The externally validated COuGH RefluX score is a clinically practical model to predict the likelihood of proven GERD. The score classifies most patients with chronic laryngeal symptoms as low/high likelihood of proven GERD, with only 38% remaining as indeterminate. Thus, the COuGH RefluX score can guide diagnostic strategies and reduce inappropriate proton pump inhibitor use or testing for patients referred for evaluation of chronic laryngeal symptoms.
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Tosse , Refluxo Gastroesofágico , Humanos , Masculino , Feminino , Refluxo Gastroesofágico/diagnóstico , Refluxo Gastroesofágico/complicações , Pessoa de Meia-Idade , Tosse/etiologia , Adulto , Doença Crônica , Idoso , Curva ROC , Doenças da Laringe/diagnóstico , Doenças da Laringe/complicaçõesRESUMO
INTRODUCTION: Among patients with chronic laryngeal symptoms, ambulatory reflux monitoring off acid suppression is recommended to evaluate for laryngopharyngeal reflux (LPR). However, reflux monitoring systems are diverse in configuration and monitoring capabilities, which present a challenge in creating a diagnostic reference standard in these patients. This study aimed to compare diagnostic yield and performance between reflux monitoring systems in patients with chronic laryngeal symptoms. METHODS: This multicenter, international study of adult patients referred for evaluation of LPR over a 5-year period (March 2018-May 2023) assessed and compared diagnostic yield of pathologic gastroesophageal reflux (GER+) on ambulatory reflux monitoring off acid suppression. RESULTS: Of 813 patients, 296 (36%) underwent prolonged wireless pH, 532 (65%) underwent 24-hour pH-impedance monitoring, and 15 (2%) underwent both tests. Overall diagnostic yield for GER+ was 36% and greater for prolonged wireless pH compared with that for 24-hour pH-impedance monitoring (50% vs 27%; P < 0.01). Among 15 patients who underwent both prolonged wireless pH and 24-h pH-impedance monitoring, concordance between systems for GER+ was 40%. The most common source of discordance was strong evidence of GER+ across multiple days on prolonged wireless pH compared with no evidence of GER+ on pH-impedance. DISCUSSION: In this multicenter international study of patients with chronic laryngeal symptoms referred for LPR evaluation, diagnostic yield of ambulatory reflux monitoring off acid suppression was 36% and rose to 50% when using wireless pH monitoring. In patients referred for chronic laryngeal symptoms, 24-hour pH-impedance monitoring may risk a low negative predictive value in patients with unproven GER+ disease.
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Esofagite Péptica , Refluxo Laringofaríngeo , Adulto , Humanos , Refluxo Laringofaríngeo/diagnóstico , Monitorização Ambulatorial , Impedância Elétrica , Monitoramento do pH Esofágico , Concentração de Íons de HidrogênioRESUMO
Tropical small island developing states (SIDS), with their geographical isolation and limited resources, heavily rely on the fisheries industry for food and revenue. The presence of marine lipophilic phycotoxins (MLPs) poses risks to their economy and human health. To understand the contamination status and potential risks, the Republic of Kiribati was selected as the representative tropical SIDS and 55 species of 256 coral reef fish encompassing multiple trophic levels and feeding strategies were collected to analyze 17 typical MLPs. Our results showed that the potential risks of ciguatoxins were the highest and approximately 62% of fish species may pose risks for consumers. Biomagnification of ciguatoxins was observed in the food web with a trophic magnification factor of 2.90. Brevetoxin-3, okadaic acid, and dinophysistoxin-1 and -2 were first reported, but the risks posed by okadaic acid and dinophysistoxins were found to be negligible. The correlation analysis revealed that fish body size and trophic position are unreliable metrics to indicate the associated risks and prevent the consumption of contaminated fish. The potential risks of MLPs in Kiribati are of concern, and our findings can serve as valuable inputs for developing food safety policies and fisheries management strategies specific to tropical SIDS contexts.
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Peixes , Toxinas Marinhas , Animais , Cadeia Alimentar , Ilhas , Humanos , Medição de Risco , Clima Tropical , Ciguatoxinas/toxicidadeRESUMO
Considering the challenges in reactivity, potential contamination, and substrate selectivity, the ammonolysis of traditional halosilanes in silicon nitride (SiN) thin film processing motivates the exploration of alternative precursors. In this pioneering study, we employed density functional theory calculations at the M06-2X/6-311++G(3df,2p) level to comprehensively screen potential pseudo-halide substituents on silane compounds as substitutes for conventional halosilanes. Initially, we investigated the ammonolysis mechanism of halosilanes, exploring factors influencing activation barriers, with the aid of frontier molecular orbital and charge density analyses. Subsequently, a systematic screening of silane substituents from group 14 to group 16 was conducted to identify pseudo-halides with low reaction barriers. Additionally, we examined the inductive effects on pseudohalide substituents. Using cluster models to represent the silicon surface validates the realistic prediction of ammonolysis barriers with a simplified model. Our findings indicate that pseudo-halide substituents from group 16, particularly those with electron-withdrawing groups, present as practical alternatives to traditional halosilanes in SiN thin film processing, including applications such as low-temperature atomic layer deposition (ALD) techniques.
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Toy production has been increasing over the last few decades to meet the growing demands for toys across the globe, which has inevitably worsened the problem of toy waste. Given the lack of modern waste disposal facilities, rural villagers in many developing countries often discard and incinerate toy waste in backyards or riverbanks, which may release the pollutants from toys (e.g., heavy metals), contaminate the surrounding areas, and eventually threaten the health of residents. As such, this study examined the impact of improper toy waste handling on the nearby aquaculture site by measuring the contamination level of heavy metals (As, Cd, Cu, Pb, and Zn) in the sediment and seafood (crabs, shrimps, and fish). The health risk of heavy metals via seafood consumption was assessed in different groups of people (males, females, teenagers, and seniors). Results showed that the sediment and seafood at the aquaculture site were generally not contaminated with heavy metals (contamination factor and bioaccumulation factor <1). However, consuming the seafood cultured at this site, especially for crabs, could pose a health risk to humans due to As and Cd (hazard quotient > 1), irrespective of their age and gender. This risk could not be lowered by cooking, except As by boiling. Overall, we revealed that improper toy waste handling did not cause severe heavy metal pollution in the surrounding environment, but the consumption of contaminated seafood could still threaten human health. To safeguard public health, we propose that toy waste should be appropriately treated by the authorities concerned. In addition, consuming seafood with long culture periods (e.g., crabs) should be reduced to minimize the dietary intake of heavy metals and their associated health risk.
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Anthropogenic activities are leaving lots of chemical footprints on the soil. It alters the physiochemical characteristics of the soil thereby modifying the natural soil microbiome. The prevalence of antimicrobial-resistance microbes in polluted soil has gained attention due to its obvious public health risks. This study focused on assessing the prevalence and distribution of antibiotic-resistance genes in polluted soil ecosystems impacted by industrial enterprises in southern Russia. Metagenomic analysis was conducted on soil samples collected from polluted sites using various approaches, and the prevalence of antibiotic-resistance genes was investigated. The results revealed that efflux-encoding pump sequences were the most widely represented group of genes, while genes whose products replaced antibiotic targets were less represented. The level of soil contamination increased, and there was an increase in the total number of antibiotic-resistance genes in proteobacteria, but a decrease in actinobacteria. The study proposed an optimal mechanism for processing metagenomic data in polluted soil ecosystems, which involves mapping raw reads by the KMA method, followed by a detailed study of specific genes. The study's conclusions provide valuable insights into the prevalence and distribution of antibiotic-resistance genes in polluted soils and have been illustrated in heat maps.
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Metais Pesados , Hidrocarbonetos Policíclicos Aromáticos , Microbiologia do Solo , Poluentes do Solo , Poluentes do Solo/análise , Poluentes do Solo/toxicidade , Metais Pesados/análise , Metais Pesados/toxicidade , Hidrocarbonetos Policíclicos Aromáticos/análise , Resistência Microbiana a Medicamentos/genética , Federação Russa , Metagenômica , Genes Bacterianos , Farmacorresistência Bacteriana/genética , Monitoramento AmbientalRESUMO
Present study included technological methods that made it possible to synthesize CdO nanoparticles and carry out their qualitative and quantitative diagnostics, confirming the as-prepared CdO nanoparticles (NPs) were spherical and had a size of 25 nm. Then, under the conditions of the model experiment the effect of CdO in macro and nanosized particles on absorption, transformation, and structural and functional changes occurring in cells and tissues of Hordeum vulgare L. (spring barley) during its ontogenesis was analyzed. Different analytical techniques were used to detect the transformation of CdO forms: Fourier-transform infrared spectroscopy (FTIR), Dynamic light scattering (DLS), X-ray fluorescence analysis (XRF), Scanning electron microscopy (SEM-EDXMA and TEM), X-ray diffraction (XRD), and X-ray absorption fine structure, consists of XANES - X-ray absorption near edge structure, and EXAFS - Extended X-ray absorption fine structure. Quantitative differences in the elemental chemical composition of barley root and leaf samples were observed. The predominant root uptake of Cd was revealed. CdO-NPs were found to penetrate deeply into barley plant tissues, where they accumulated and formed new mineral phases such as Cd5(PO4)3Cl and CdSO4 according to XRD analysis. The molecular-structural state of the local Cd environment in plant samples corresponding to Cd-O and Cd-Cd. The toxicity of CdO-NPs was found to significantly affect the morphology of intracellular structures are the main organelles of photosynthesis therefore, destructive changes in them obviously reduce the level of metabolic processes ensuring the growth of plants. This study is an attempt to show results how it is possible to combine some instrumental techniques to characterize and behavior of NPs in complex matrices of living organisms.
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Compostos de Cádmio , Hordeum , Nanopartículas Metálicas , Nanopartículas , Hordeum/metabolismo , Cádmio , Óxidos/química , Nanopartículas/toxicidade , Nanopartículas/química , Espectroscopia de Infravermelho com Transformada de Fourier , Difração de Raios X , Antibacterianos/farmacologia , Nanopartículas Metálicas/toxicidade , Nanopartículas Metálicas/químicaRESUMO
The study explored the impact of water management on rice cultivation in mercury-contaminated paddy soil. The objective was to analyze the characteristics of mercury translocation by converting flooded soils to dry farming (non-flooded) to alleviate mercury accumulation in rice grains. The experiment was conducted over three consecutive rice-growing seasons, employing two distinct water management models: a continuously flooded rice cultivation mode and a flooded rice planting mode in the first season, followed by a non-flooded rice farming mode in the second and third seasons. The results showed that the change from flooded to non-flooded rice cultivation patterns presented extremely excellent environmental potential for inhibiting the uptake of both methylmercury and total mercury in rice. When transitioning from flooded cultivation to dry farming, the concentration of methylmercury and total mercury in the grains of non-flooded rice decreased by 87.15â¯% and 9.57â¯%, respectively, compared to that in the grains of flooded rice. In the third season, the methylmercury and total mercury in the grains of non-flooded rice decreased further by 95.03â¯% and 69.45â¯%, respectively. This study verified that the conversion of rice cultivation from flooded to non-flooded is an efficient strategy for suppressing the accumulation of methylmercury in rice grains, and it might offer a promising solution for managing soil mercury risks and ensuring the safety of rice for human consumption.
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To understand the mechanism of dark abiotic mercury (Hg) methylation by algae-derived dissolved organic matter (DOM) and effectively manage the environmental risks of mercury methylation in aquaculture areas, we investigated the influence of subfractions of DOM released from algae (Ulothrix sp.) decomposition on mercury methylation. The results showed that the hydrophobic basic component (HOB) in DOM exhibited the most substantial promotion effect on Hg methylation. The methylmercury (MeHg) production in the HOB treatment increased significantly, while the production rate of MeHg (%MeHg represented the concentration ratio of MeHg to THg) in the six subfractions treated solutions decreased significantly with the increase of Hg concentration. The change of the %MeHg was more evident at low Hg concentration, indicating the limited number of binding sites and methyl donors on DOM. As a consequence, Hg(â ¡) in the solution could not be converted into MeHg in equal proportion. Furthermore, the production of MeHg in solution was significantly reduced by the decomposed algae DOM, and its concentration was in the range of 0.017-0.085 ng·L-1 (significantly lower than undecomposed algal). The difference between the decomposed and the non-decomposed algae DOM reached a significant level (P < 0.05). When the DOM decayed for 20 and 30 days, the Hg methylation ability of DOM was weakened most obviously. During the decomposition process, considerable variations were observed among the subfractions, with HOB consistently playing a dominant role in Hg methylation. At the same time, the hydrophilic acid component exhibited a significant inhibitory effect on Hg methylation. Generally, the main components (e.g. HOB and HIA (hydrophilic acid component)) of DOM affecting mercury methylation were found in our study, which provided a better understanding of algae-derived DOM subfractions on the Hg methylation, in an attempt to prevent and control water pollution in aquaculture areas.
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Mercúrio , Compostos de Metilmercúrio , Poluentes Químicos da Água , Mercúrio/análise , Matéria Orgânica Dissolvida , Compostos de Metilmercúrio/metabolismo , Metilação , Poluentes Químicos da Água/análiseRESUMO
Prior studies have demonstrated that perceived stigma is robustly associated with risky and life-threatening behaviors, including non-suicidal self-injury (NSSI), among men who have sex with men (MSM). However, studies regarding the relationship between perceived stigma and NSSI are limited. The present study aimed to investigate the network structure of perceived stigma and NSSI functions, along with bridge nodes, to elucidate how they co-exist. A sample of 2610 Chinese MSM (mean age = 23.99, age range: 18-68 years) was recruited from an online survey platform. All participants completed a web-based survey with measures of perceived stigma and NSSI functions. Results indicated that 'negative attitudes towards homosexuality' and 'disappointment in gay son' were identified as the most central nodes in the perceived stigma network, whereas 'seeking attention' and 'influencing others to change' ranked highest on centrality in the NSSI network. Two bridge connections were exhibited within the combined perceived stigma and NSSI network model: 'unwelcoming in public' and 'avoiding unpleasant tasks' from perceived stigma and NSSI communities, respectively. This is among the first studies investigating the co-occurrence between perceived stigma and NSSI from the network approach. Our findings provide an empirically-based perspective on the importance of family- and community-based interventions, with potential clinical implications for reducing NSSI among sexual and gender minority groups.
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Comportamento Autodestrutivo , Minorias Sexuais e de Gênero , Masculino , Humanos , Adolescente , Adulto Jovem , Adulto , Pessoa de Meia-Idade , Idoso , Homossexualidade Masculina , Comportamento Sexual , EmoçõesRESUMO
The combustion of coal in power plants releases significant amounts of polycyclic aromatic hydrocarbons (PAHs), which are highly toxic and carcinogenic. This study assesses the ecological and human health impacts of PAHs contamination from a coal-fired power plant over 8 years. The monitoring site selection considered the distance from the power plant and the prevailing wind direction in the investigated area. The results reveal that, during the monitoring period, PAH levels increased on average by 43%, 61%, and 37% in the zone of the prevailing wind direction, in the area proximate to the power plant, and the zone distant from it, respectively. The site, which has a radius of 4.5 km in the prevailing wind direction, exhibited the highest ecological and human health impacts. Additionally, a strong correlation was observed between environmental and human health impacts, depending on the distance from the power plant, particularly in areas with the prevailing wind direction. These insights contribute to a comprehensive understanding of the intricate dynamics linking power plant emissions, PAHs contamination, and their far-reaching consequences on the environment and human health.
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Carvão Mineral , Monitoramento Ambiental , Hidrocarbonetos Policíclicos Aromáticos , Centrais Elétricas , Poluentes do Solo , Hidrocarbonetos Policíclicos Aromáticos/análise , Humanos , Monitoramento Ambiental/métodos , Poluentes do Solo/análise , Vento , Avaliação do Impacto na SaúdeRESUMO
To assess the total daily mercury intake and main exposure sources of residents, six food groups, including marine fish, freshwater fish, poultry, livestock, vegetables, and cereals, were collected from five districts of Chengdu, China. The median concentrations of total mercury (THg) and methylmercury (MeHg) were 12.8 and 6.94 µg kg-1 ww, respectively. Cereals (32.2%), vegetables (30.5%), and livestock (16.2%) contributed to a much larger extent to the total consumption for the participants in Chengdu. All food categories that contributed the most of THg (2.16 µg day-1) and MeHg 1.44 (µg day-1) to the daily intake in Chengdu were cereals and marine fish, respectively. The total Hazard Ratios values below 1 in this study indicate that there is no health risk associated with Hg ingestion from the consumption of these foods for the residents in Chengdu.
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Mercúrio , Compostos de Metilmercúrio , Animais , Humanos , Mercúrio/análise , Monitoramento Ambiental , Contaminação de Alimentos/análise , Compostos de Metilmercúrio/análise , Dieta , Medição de Risco , Verduras , Peixes , Grão Comestível/química , ChinaRESUMO
Stress due to drought lowers crop yield and frequently leads to a rise in food scarcity. Plants' intricate metabolic systems enable them to tolerate drought stress, but they are unable to handle it well. Adding some external, environmentally friendly supplements can boost plant growth and productivity when it comes to drought-stressed plants. In order to prevent the detrimental effects of drought in agricultural regions, environmentally friendly practices must be upheld. Plant growth-promoting rhizobacteria (PGPR) can exhibit beneficial phytostimulation, mineralization, and biocontrol activities under drought stress. The significant impact of the PGPR previously reported has not been accepted as an effective treatment to lessen drought stress. Recent studies have successfully shown that manipulating microbes can be a better option to reduce the severity of drought in plants. In this review, we demonstrate how modifying agents such as biochar, PGPR consortia, PGPR, and mycorrhizal fungi can help overcome drought stress responses in crop plants. This article also discusses CRISPR/Cas9-modifiable genes, increase plant's effectiveness in drought conditions, and increase plant resistance to drought stress. With an eco-friendly approach in mind, there is a need for practical management techniques having potential prospects based on an integrated strategy mediated by CRISPR-Cas9 editing, PGPR, which may alleviate the effects of drought stress in crops and aid in achieving the United Nation Sustainable Development Goals (UN-SDGs-2030).
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Carvão Vegetal , Secas , Edição de Genes , Agricultura , Produtos AgrícolasRESUMO
The association and overlap between psychotic and dissociative phenomena have been increasingly recognized. Previous studies found that psychotic symptoms are closely associated with post-traumatic and dissociative symptoms and that these trauma-related phenomena may mediate the relationship between trauma and psychotic symptoms. It remained less explored which specific post-traumatic and dissociative symptom clusters are particularly associated with psychotic symptoms. This cross-sectional study used a data-driven approach (network analysis) to explore the associations among different psychotic and post-traumatic/dissociative symptom clusters in an online convenience predominantly female sample (N = 468)(59.2% had ever seen a psychiatrist). Participants completed well-established multidimensional measures that assessed different symptom clusters of psychosis, dissociation, and PTSD. In addition, multiple mediation analysis was conducted to examine which post-traumatic/dissociative symptoms could mediate the relationship between childhood and adulthood trauma and different psychotic symptoms. Our results confirmed previous findings that PTSD and dissociative symptoms are closely associated with psychotic symptoms. More importantly, both data-driven and multiple mediation analysis results indicated that identity dissociation was particularly associated with perceptual anomalies and bizarre experiences, while emotional constriction was particularly associated with negative symptoms. It is important to screen for trauma and dissociation and provide trauma-and dissociation-informed care when working with people at risk of or experiencing psychosis. Further longitudinal studies using more representative samples are needed.
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Transtornos Psicóticos , Transtornos de Estresse Pós-Traumáticos , Humanos , Feminino , Criança , Masculino , Transtornos de Estresse Pós-Traumáticos/psicologia , Estudos Transversais , Síndrome , Transtornos Psicóticos/psicologia , Transtornos Dissociativos/psicologiaRESUMO
Background/objectives: The study aimed to examine the physical fitness and activity levels of kindergarteners in Hong Kong during the coronavirus disease 2019 pandemic. Methods: A total of 2052 kindergarteners (48% girls; 32.9% Grade 1, 34% Grade 2, and 33.1% Grade 3) were recruited from July 2020 to November 2021. Participants completed the physical fitness tests, including body composition, flexibility, lower-limb muscle strength, upper-limb muscle strength, lower-limb muscle endurance, and agility. Children's physical activity and overall well-being were examined using parental proxy reports. Parents also reported their physical activity and parental support to children's physical activity engagement, as well as their perception of children's kindergarten physical activity environment. Fitness differences by age and gender were analyzed using one-way ANOVA and ANCOVA measuring effect size with partial eta-squared. Additionally, correlations assessed the relationship between children's fitness and parents' proxy reports. Results: The results of the physical fitness tests were higher than those in previous studies conducted by the Physical Fitness Association of Hong Kong in 2015-2018. Gender-based differences were observed in most tests for children aged 4 years and older, with boys showing higher scores in the standing long jump, shot put, and balance tests, while girls had higher scores in the sit-and-reach test. Parents' proxy questionnaire answers indicated that children's continuous jump test performances were significantly related to their frequency of physical activity per week (r = 0.19, p < 0.001), and that children's health was significantly and positively correlated with their fitness level (r = 0.179, p < 0.009). Inadequate school physical activity was associated with poor upper-limb strength (r = 0.078, p < 0.005). Moreover, a high level of parental support for their children's participation in physical activity was correlated with a high level of parental participation in vigorous-intensity physical activities (r = 0.167, p < 0.005). Conclusion: The physical fitness of children in Hong Kong was less affected by the epidemic. Parents' healthy behaviors and support were related to children's participation in PA. Efforts to improve children's physical fitness and motor development should include parent education and physical activity involvement.
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Nitroreductases (NTRs) constitute an important class of oxidoreductase enzymes that have evolved to metabolize nitro-containing compounds. Their unique characteristics have spurred an array of potential uses in medicinal chemistry, chemical biology, and bioengineering toward harnessing nitro caging groups and constructing NTR variants for niche applications. Inspired by how they carry out enzymatic reduction via a cascade of hydride transfer reactions, we sought to develop a synthetic small-molecule NTR system based on transfer hydrogenation mediated by transition metal complexes harnessing native cofactors. We report the first water-stable Ru-arene complex capable of selectively and fully reducing nitroaromatics into anilines in a biocompatible buffered aqueous environment using formate as the hydride source. We further demonstrated its application to activate nitro-caged sulfanilamide prodrug in formate-abundant bacteria, specifically pathogenic methicillin-resistant Staphylococcus aureus. This proof of concept paves the way for a new targeted antibacterial chemotherapeutic approach leveraging on redox-active metal complexes for prodrug activation via bioinspired nitroreduction.
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Complexos de Coordenação , Staphylococcus aureus Resistente à Meticilina , Pró-Fármacos , Pró-Fármacos/farmacologia , Staphylococcus aureus Resistente à Meticilina/metabolismo , Complexos de Coordenação/farmacologia , Bactérias/metabolismo , Nitrocompostos/química , Nitrorredutases/metabolismo , FormiatosRESUMO
INTRODUCTION: Laryngopharyngeal reflux (LPR) is a clinical conundrum without a diagnostic gold standard. The Esophageal Hypervigilance and Anxiety Scale (EHAS) is a questionnaire designed for cognitive-affective evaluation of visceral sensitivity. We hypothesized that esophageal hypervigilance and symptom-specific anxiety have an etiopathological role in generation of LPR symptoms, especially when gastroesophageal reflux disease (GERD) cannot explain these symptoms. METHODS: Consecutive patients with LPR and/or GERD symptoms lasting >3 months were prospectively enrolled and characterized using the Reflux Symptom Index, GERD questionnaire, and EHAS. Eligible patients with negative endoscopy underwent 24-hour impedance-pH monitoring off acid suppression for phenotyping GERD and assessment of reflux burden, using conventional metrics (acid exposure time and number of reflux episodes) and novel metrics (mean nocturnal baseline impedance and postreflux swallow-induced peristaltic wave index). RESULTS: Of 269 enrolled patients (mean age 47.1 years, 21-65 years, 60.6% female), 90 patients were with concomitant GERD and LPR symptoms, 32 patients were with dominant LPR symptoms, 102 patients were with dominant GERD symptoms, and 45 were controls. Patients with concomitant GERD and LPR symptoms had higher EHAS than those with dominant GERD symptoms and controls ( P ≤ 0.001); patients with dominant LPR symptoms had higher EHAS than controls ( P = 0.007). On Pearson correlation, EHAS positively correlated with the Reflux Symptom Index. DISCUSSION: Esophageal hypervigilance and symptom-specific anxiety may be more important than reflux burden in LPR symptom perception.
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Refluxo Laringofaríngeo , Humanos , Feminino , Pessoa de Meia-Idade , Masculino , Refluxo Laringofaríngeo/diagnóstico , Ansiedade , Endoscopia Gastrointestinal , Transtornos de AnsiedadeRESUMO
Rechargeable aqueous Zn/S batteries exhibit high capacity and energy density. However, the long-term battery performance is bottlenecked by the sulfur side reactions and serious Zn anode dendritic growth in the aqueous electrolyte medium. This work addresses the problem of sulfur side reactions and zinc dendrite growth simultaneously by developing a unique hybrid aqueous electrolyte using ethylene glycol as a co-solvent. The designed hybrid electrolyte enables the fabricated Zn/S battery to deliver an unprecedented capacity of 1435 mAh g-1 and an excellent energy density of 730 Wh kg-1 at 0.1 Ag-1 . In addition, the battery exhibits capacity retention of 70% after 250 cycles even at 3 Ag-1 . Moreover, the cathode charge-discharge mechanism studies demonstrate a multi-step conversion reaction. During discharge, the elemental sulfur is sequentially reduced by Zn to S2- ( S 8 â S x 2 - â S 2 2 - + S 2 - ) ${{\rm{S}}_8}{\bm{ \to }}{\rm{S}}_{\rm{x}}^{2{\bm{ - }}}{\bm{ \to }}{\rm{S}}_2^{2{\bm{ - }}}{\bm{ + }}{{\rm{S}}^{2{\bm{ - }}}})$ , forming ZnS. On charging, the ZnS and short-chain polysulfides will oxidize back to elemental sulfur. This electrolyte design strategy and unique multi-step electrochemistry of the Zn/S system provide a new pathway in tackling both key issues of Zn dendritic growth and sulfur side reactions, and also in designing better Zn/S batteries in the future.