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The high oxidation activity of coinage metals (Cu, Ag and Au) has been widely applied in various important reactions, such as oxidation of carbon monoxide, alkenes or alcohols. The catalytic behavior of those inert metals has mostly been attributable to their size effect, the physical effect. In the present study, the chemical effects on their high oxidation activity have been investigated. We mechanistically examine the direct and oxidative dehydrogenation (partial oxidation) reactions of ethanol to acetaldehyde on a series of transition metals (groups 9, 10 and 11) with identical physical characteristics and varied chemical origins using density functional theory (DFT) calculations and electronic structure analyses at the GGA-PW91 level. The energetic results show that coinage metals have much lower activation energies and higher exothermicities for the oxidative dehydrogenation steps although they have higher energy for the direct dehydrogenation reaction. In the electronic structure analyses, coinage metals with saturated d bands can efficiently donate electrons to O* and OH*, or other electronegative adspecies, and better promote their p bands to higher energy levels. The negatively charged O* and OH* with high-lying p bands are responsible for lowering the energies in oxidative steps. The mechanistic understanding well explains the better oxidation activity of coinage metals and provides valuable information on their utilization in other useful applications, for example, the dehydrogenation process.
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The spring-loaded inverted pendulum (SLIP) model is an effective model to capture the essential dynamics during human walking and/or running. However, most of the existing three-dimensional (3D) SLIP model does not explicitly account for human movement speed and frequency. To address this knowledge gap, this paper develops a new SLIP model, which includes a roller foot, massless spring, and concentrated mass. The governing equations-of-motion for the SLIP model during its double support phase are derived. It is noted that in the current formulation, the motion of the roller foot is prescribed; therefore, only the equations for the concentrated mass need to be solved. To yield model parameters leading to a periodic walking gait, a constrained optimization problem is formulated and solved using a gradient-based approach with a global search strategy. The optimization results show that when the attack angle ranges from 68° to 74°, the 3D SLIP model can yield a periodic walking gait with walking speeds varying from 0.5 to 2.0 m s-1. The predicted human walking data are also compared with published experimental data, showing reasonable accuracy.
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Simulação por Computador , Marcha , Modelos Biológicos , Caminhada , Humanos , Caminhada/fisiologia , Marcha/fisiologia , Velocidade de Caminhada/fisiologia , Biomimética/métodos , Pé/fisiologiaRESUMO
Migraine is a highly prevalent disease worldwide, imposing enormous clinical and economic burdens on individuals and societies. Current treatments exhibit limited efficacy and acceptability, highlighting the need for more effective and safety prophylactic approaches, including the use of nutraceuticals for migraine treatment. Migraine involves interactions within the central and peripheral nervous systems, with significant activation and sensitization of the trigeminovascular system (TVS) in pain generation and transmission. The condition is influenced by genetic predispositions and environmental factors, leading to altered sensory processing. The neuroinflammatory response is increasingly recognized as a key event underpinning the pathophysiology of migraine, involving a complex neuro-glio-vascular interplay. This interplay is partially mediated by neuropeptides such as calcitonin gene receptor peptide (CGRP), pituitary adenylate cyclase activating polypeptide (PACAP) and/or cortical spreading depression (CSD) and involves oxidative stress, mitochondrial dysfunction, nucleotide-binding domain-like receptor family pyrin domain containing-3 (NLRP3) inflammasome formation, activated microglia, and reactive astrocytes. Omega-3 polyunsaturated fatty acids (PUFAs), particularly eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), crucial for the nervous system, mediate various physiological functions. Omega-3 PUFAs offer cardiovascular, neurological, and psychiatric benefits due to their potent anti-inflammatory, anti-nociceptive, antioxidant, and neuromodulatory properties, which modulate neuroinflammation, neurogenic inflammation, pain transmission, enhance mitochondrial stability, and mood regulation. Moreover, specialized pro-resolving mediators (SPMs), a class of PUFA-derived lipid mediators, regulate pro-inflammatory and resolution pathways, playing significant anti-inflammatory and neurological roles, which in turn may be beneficial in alleviating the symptomatology of migraine. Omega-3 PUFAs impact various neurobiological pathways and have demonstrated a lack of major adverse events, underscoring their multifaceted approach and safety in migraine management. Although not all omega-3 PUFAs trials have shown beneficial in reducing the symptomatology of migraine, further research is needed to fully establish their clinical efficacy and understand the precise molecular mechanisms underlying the effects of omega-3 PUFAs and PUFA-derived lipid mediators, SPMs on migraine pathophysiology and progression. This review highlights their potential in modulating brain functions, such as neuroimmunological effects, and suggests their promise as candidates for effective migraine prophylaxis.
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Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is the causative agent of the coronavirus disease 2019 (COVID-19). COVID-19 is now recognized as a multiorgan disease with a broad spectrum of manifestations. A substantial proportion of individuals who have recovered from COVID-19 are experiencing persistent, prolonged, and often incapacitating sequelae, collectively referred to as long COVID. To date, definitive diagnostic criteria for long COVID diagnosis remain elusive. An emerging public health threat is neuropsychiatric long COVID, encompassing a broad range of manifestations, such as sleep disturbance, anxiety, depression, brain fog, and fatigue. Although the precise mechanisms underlying the neuropsychiatric complications of long COVID are presently not fully elucidated, neural cytolytic effects, neuroinflammation, cerebral microvascular compromise, breakdown of the blood-brain barrier (BBB), thrombosis, hypoxia, neurotransmitter dysregulation, and provoked neurodegeneration are pathophysiologically linked to long-term neuropsychiatric consequences, in addition to systemic hyperinflammation and maladaptation of the renin-angiotensin-aldosterone system. Vitamin D, a fat-soluble secosteroid, is a potent immunomodulatory hormone with potential beneficial effects on anti-inflammatory responses, neuroprotection, monoamine neurotransmission, BBB integrity, vasculometabolic functions, gut microbiota, and telomere stability in different phases of SARS-CoV-2 infection, acting through both genomic and nongenomic pathways. Here, we provide an up-to-date review of the potential mechanisms and pathophysiology of neuropsychiatric long COVID syndrome and the plausible neurological contributions of vitamin D in mitigating the effects of long COVID.
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COVID-19 , Vitamina D , Humanos , Síndrome de COVID-19 Pós-Aguda , COVID-19/complicações , SARS-CoV-2 , VitaminasRESUMO
To understand the present status of the heavy metal (Cr, Cu, Zn, Cd, Pb and Hg) pollution of the sediments in water supply reservoirs in Huizhou, sediment cores were sampled from three representative reservoirs. The heavy metal concentrations were analyzed by ICP-MS, and the pollution status was assessed by geo-accumulation index (Igeo) and potential ecological risk index (RI). In the meantime, the possible sources of the heavy metals were analyzed by the principal component analysis (PCA). In the sediments of the three reservoirs, the test heavy metals had different vertical distribution, some had less change, the others decreased or increased with depth, and the distribution patterns differed with the reservoirs. According to the Igeo, the sediments in the reservoirs were seriously polluted by Zn and Pb (Zn: 49.98-640.29 mg x kg(-1); Pb: 21.94-300.66 mg x kg(-1)), reaching slight to high pollution, and the middle or bottom part of the sediments was slightly polluted by Cu (16.85-45.46 mg x kg(-1)). On the whole, the sediments were not polluted by Cr, Cd and Hg. According to the RI and the potential ecological risk coefficient [Er(i)], the sediments in the three reservoirs were under low potential ecological risk. Based on the PCA and relevant information, the human activities such as mining and smelting, urbanization, and agriculture and forestry had great contribution to the heavy metal pollution. The Zn and Pb pollution mainly originated from mining and smelting, Pb pollution also came from motor vehicle exhaust emission and domestic wastes, and Cu pollution mainly derived from agriculture and forestry.
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Monitoramento Ambiental/métodos , Sedimentos Geológicos/química , Metais Pesados/análise , Poluentes Químicos da Água/análise , Abastecimento de Água/análise , ChinaRESUMO
Core sediments were collected from the riverine, transition and lacustrine zones of Hedi Reservoir in southern China to investigate the spatial distributions of nutrients and heavy metals and assess the potential ecological risk of heavy metals. The total nitrogen (TN) contents of the sediments at three sampling sites are between 2.314-2.427 mg x g(-1), while total phosphorus (TP) contents range from 0.591 mg x g(-1) to 0.760 mg x g(-1), TN contents of the surface sediments increase from the riverine zone to the lacustrine zone, but the TP content in the transition zone is higher than that in the other two sites (riverine zone and lacustrine zone). The mean contents of heavy metals are: 31.094, 46.85, 75.615, 385.739, 0.624 and 0.171 mg x kg(-1) respectively, except Cr, the contents of heavy metals in sediment of lacustrine zone are higher than the sediment of transition zone. In all core sediments, the contents of nutrients and heavy metals decrease from the surface to the bottom of core sediments. Inorganic phosphorus (IP) is the dominant fraction of phosphorus in the sediment and the NaOH-P is the main forms of inorganic phosphorus. The potential ecological risk assessed by using of the highest environmental background values before industrialization as the reference indicates that each single heavy metal only causes slightly pollution, but two heavy metals (Cd and Hg) cause heavy pollution based on the soil environmental background values of Guangdong province. In spite of the slight difference between two kinds of risk assessment, all demonstrated that Cd and Hg resulted in more serious pollution than the other metals and these two metals contributed most to the RI values.