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Cytokines are powerful immune modulators that initiate signaling through receptor dimerization, but natural cytokines have structural limitations as therapeutics. We present a strategy to discover cytokine surrogate agonists by using modular ligands that exploit induced proximity and receptor dimer geometry as pharmacological metrics amenable to high-throughput screening. Using VHH and scFv to human interleukin-2/15, type-I interferon, and interleukin-10 receptors, we generated combinatorial matrices of single-chain bispecific ligands that exhibited diverse spectrums of functional activities, including potent inhibition of SARS-CoV-2 by surrogate interferons. Crystal structures of IL-2R:VHH complexes revealed that variation in receptor dimer geometries resulted in functionally diverse signaling outputs. This modular platform enabled engineering of surrogate ligands that compelled assembly of an IL-2R/IL-10R heterodimer, which does not naturally exist, that signaled through pSTAT5 on T and natural killer (NK) cells. This "cytokine med-chem" approach, rooted in principles of induced proximity, is generalizable for discovery of diversified agonists for many ligand-receptor systems.
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COVID-19 , Citocinas , Humanos , Interleucina-2/farmacologia , Células Matadoras Naturais , Ligantes , Receptores de Interleucina-10 , SARS-CoV-2RESUMO
BACKGROUND AIMS: Human genetic variation is thought to guide the outcome of HCV infection, but model systems within which to dissect these host genetic mechanisms are limited. Norway rat hepacivirus, closely related to HCV, causes chronic liver infection in rats but causes acute self-limiting hepatitis in typical strains of laboratory mice, which resolves in 2 weeks. The Collaborative Cross (CC) is a robust mouse genetics resource comprised of a panel of recombinant inbred strains, which model the complexity of the human genome and provide a system within which to understand diseases driven by complex allelic variation. APPROACH RESULTS: We infected a panel of CC strains with Norway rat hepacivirus and identified several that failed to clear the virus after 4 weeks. Strains displayed an array of virologic phenotypes ranging from delayed clearance (CC046) to chronicity (CC071, CC080) with viremia for at least 10 months. Body weight loss, hepatocyte infection frequency, viral evolution, T-cell recruitment to the liver, liver inflammation, and the capacity to develop liver fibrosis varied among infected CC strains. CONCLUSIONS: These models recapitulate many aspects of HCV infection in humans and demonstrate that host genetic variation affects a multitude of viruses and host phenotypes. These models can be used to better understand the molecular mechanisms that drive hepacivirus clearance and chronicity, the virus and host interactions that promote chronic disease manifestations like liver fibrosis, therapeutic and vaccine performance, and how these factors are affected by host genetic variation.
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Hepacivirus , Hepatite C , Camundongos , Humanos , Ratos , Animais , Hepacivirus/genética , Cirrose Hepática/genética , Doença Aguda , Variação GenéticaRESUMO
The centrosome is a cytoplasmic organelle with roles in microtubule organization that has also been proposed to act as a hub for cellular signaling. Some centrosomal components are required for full activation of the DNA damage response. However, whether the centrosome regulates specific DNA repair pathways is not known. Here, we show that centrosome presence is required to fully activate recombination, specifically to completely license its initial step, the so-called DNA end resection. Furthermore, we identify a centriolar structure, the subdistal appendages, and a specific factor, CEP170, as the critical centrosomal component involved in the regulation of recombination and resection. Cells lacking centrosomes or depleted for CEP170 are, consequently, hypersensitive to DNA damaging agents. Moreover, low levels of CEP170 in multiple cancer types correlate with an increase of the mutation burden associated with specific mutational signatures and a better prognosis, suggesting that changes in CEP170 can act as a mutation driver but could also be targeted to improve current oncological treatments.
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We used an animal model of salt-sensitive hypertension (SSH) in which ovariectomized (oVx) rats developed hypertension with high salt (HS) intake. Hypertension is accompanied by changes in the percentage of CD4+ T lymphocytes, immune CD45+ cell infiltration into renal tissue, and changes in Na+, K+- ATPase (NKA) expression in both renal tissue and peripheral blood mononuclear cells (PBMCs). To determine whether the observed changes resulted from HS intake, high blood pressure, or both, hydralazine (HDZ) was used to lower blood pressure. The oVx HS rats received two HDZ schedules either to prevent or to treat hypertension. NKA was overexpressed in the kidneys of all oVx groups and in PBMCs of oVx HS rats. This pattern was not altered with HDZ treatment. Changes in CD4+ T lymphocytes and renal infiltration of CD45+ cells were not reversed either. High salt, but not high blood pressure, induces immune cell activation and renal infiltration. Overexpressed NKA is the primary event, and HS is the perturbation to the system in this model of SSH, which resembles the postmenopausal state.
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Hipertensão , Rim , Ovariectomia , Ratos Wistar , Animais , Feminino , Ratos , Rim/patologia , Rim/metabolismo , Rim/imunologia , Hipertensão/imunologia , Hipertensão/patologia , Hipertensão/metabolismo , ATPase Trocadora de Sódio-Potássio/metabolismo , Cloreto de Sódio na Dieta/efeitos adversos , Pressão Sanguínea/efeitos dos fármacos , Linfócitos T CD4-Positivos/imunologia , Linfócitos T CD4-Positivos/metabolismo , Hidralazina/farmacologiaRESUMO
IMPORTANCE: Giant viruses are noteworthy not only due to their enormous particles but also because of their gigantic genomes. In this context, a fundamental question has persisted: how did these genomes evolve? Here we present the discovery of cedratvirus pambiensis, featuring the largest genome ever described for a cedratvirus. Our data suggest that the larger size of the genome can be attributed to an unprecedented number of duplicated genes. Further investigation of this phenomenon in other viruses has illuminated gene duplication as a key evolutionary mechanism driving genome expansion in diverse giant viruses. Although gene duplication has been described as a recurrent event in cellular organisms, our data highlights its potential as a pivotal event in the evolution of gigantic viral genomes.
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Evolução Molecular , Duplicação Gênica , Vírus Gigantes , Genoma Viral , Vírus Gigantes/genética , FilogeniaRESUMO
Disturbances can produce a spectrum of short- and long-term ecological consequences that depend on complex interactions of the characteristics of the event, antecedent environmental conditions, and the intrinsic properties of resistance and resilience of the affected biological system. We used Hurricane Harvey's impact on coastal rivers of Texas to examine the roles of storm-related changes in hydrology and long-term precipitation regime on the response of stream invertebrate communities to hurricane disturbance. We detected declines in richness, diversity and total abundance following the storm, but responses were strongly tied to direct and indirect effects of long-term aridity and short-term changes in stream hydrology. The amount of rainfall a site received drove both flood duration and flood magnitude across sites, but lower annual rainfall amounts (i.e. aridity) increased flood magnitude and decreased flood duration. Across all sites, flood duration was positively related to the time it took for invertebrate communities to return to a long-term baseline and flood magnitude drove larger invertebrate community responses (i.e. changes in diversity and total abundance). However, invertebrate response per unit flood magnitude was lower in sub-humid sites, potentially because of differences in refuge availability or ecological-evolutionary interactions. Interestingly, sub-humid streams had temporary large peaks in invertebrate total abundance and diversity following recovery period that may be indicative of the larger organic matter pulses expected in these systems because of their comparatively well-developed riparian vegetation. Our findings show that hydrology and long-term precipitation regime predictably affected invertebrate community responses and, thus, our work underscores the important influence of local climate to ecosystem sensitivity to disturbances.
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Tempestades Ciclônicas , Invertebrados , Rios , Animais , Invertebrados/fisiologia , Texas , Biodiversidade , Chuva , Clima , Inundações , Hidrologia , EcossistemaRESUMO
The red-leg syndrome in amphibians is a condition commonly associated with the bacteria Aeromonas hydrophila and has led to population declines. However, there is little information concerning the inflammatory assemblage in infected anurans. We evaluated immune and endocrine alterations induced by stimulation with heat-killed A. hydrophila injected in Rhinella diptycha toads. Control animals were not manipulated, while the others were separated into groups that received intraperitoneal injection of 300 µl of saline or heat-killed bacteria: groups A1 (3 × 107 cells), A2 (3 × 108 cells), and A3 (3 × 109 cells). Animals were bled and euthanized six hours post-injection. We evaluated neutrophil: lymphocyte ratio (NLR), plasma bacterial killing ability (BKA), testosterone (T), melatonin (MEL), and corticosterone (CORT) plasma levels. Heat-killed A. hydrophila increased CORT and NLR, and decreased MEL, especially at higher concentrations. There was no effect of treatment on T and BKA. We then selected the saline and A3 groups to conduct mRNA expression of several genes including glucocorticoid receptor (GR), toll-like receptor-4 (TLR-4), interferon-γ (IFN-γ), interleukin (IL)-1ß, IL-6, and IL-10. We found higher expression of IL-6, IL-1ß, IL-10, and IFN-γ in group A3 compared to the saline group. These results indicate the beginning of an inflammatory assemblage, notably at the two highest concentrations of bacteria, and give a better understanding of how anurans respond to an infection within an integrated perspective, evaluating different physiological aspects. Future studies should investigate later phases of the immune response to elucidate more about the inflammation in amphibians challenged with A. hydrophila.
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Doenças dos Peixes , Interleucina-10 , Animais , Aeromonas hydrophila , Temperatura Alta , Interleucina-6 , Bufonidae , Anuros , Doenças dos Peixes/genéticaRESUMO
The production of ethylene glycol (EG) from cellulose has garnered significant attention in recent years as an attractive alternative to fossil fuels due to the potential of cellulose as a renewable and sustainable feedstock. In this work, to the best of our knowledge, a series of low-cost Ni-W bimetallic catalysts supported on glucose/carbon nanotube hybrid carbons were synthesised for the first time and employed to transform cellulose into EG. Two different strategies were combined for the preparation of the carbons: the activation and addition of carbon nanotubes (CNTs) to obtain a hybrid material (AG-CNT). The catalytic conversion process proceeded through cellulose hydrolysis to glucose, followed by glucose retro-aldol condensation to glycolaldehyde and its subsequent hydrogenation to EG. Through the optimisation of the catalyst's properties, particularly the metals' content, a good synergistic effect of C-C bond cleavage and hydrogenation capabilities was assured, resulting in the highly selective production of EG. The balance between Ni and W active sites was confirmed to be a crucial parameter. Thus, total cellulose conversion (100%) was achieved with EG yields of 60-62%, which are amongst the best yields ever reported for the catalytic conversion of cellulose into EG via carbon-supported catalysts.
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The catalytic properties of three copper complexes, [Cu(en)2](ClO4)2 (1), [Cu(amp)2](ClO4)2, (2) and [Cu(bpy)2](ClO4)2 (3) (where en = ethylenediamine, amp = 2-aminomethylpyridine and bpy = 2,2'-bipyridine), were explored upon the oxidation of benzyl alcohol (BnOH). Maximized conversions of the substrates to their respective products were obtained using a multivariate analysis approach, a powerful tool that allowed multiple variables to be optimized simultaneously, thus creating a more economical, fast and effective technique. Considering the studies in a fluid solution (homogeneous), all complexes strongly depended on the amount of the oxidizing agent (H2O2), followed by the catalyst load. In contrast, time seemed to be statistically less relevant for complexes 1 and 3 and not relevant for 2. All complexes showed high selectivity in their optimized conditions, and only benzaldehyde (BA) was obtained as a viable product. Quantitatively, the catalytic activity observed was 3 > 2 > 1, which is related to the π-acceptor character of the ligands employed in the study. Density functional theory (DFT) studies could corroborate this feature by correlating the geometric index for square pyramid Cu(II)-OOH species, which should be generated in the solution during the catalytic process. Complex 3 was successfully immobilized in silica-coated magnetic nanoparticles (Fe3O4@SiO2), and its oxidative activity was evaluated through heterogenous catalysis assays. Substrate conversion promoted by 3-Fe3O4@SiO2 generated only BA as a viable product, and the supported catalyst's recyclability was proven. Reduced catalytic conversions in the presence of the radical scavenger (2,2,6,6-tetrametil-piperidi-1-nil)oxil (TEMPO) indicate that radical and non-radical mechanisms are involved.
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Theta and gamma oscillations in the hippocampus have been hypothesized to play a role in the encoding and retrieval of memories. Recently, it was shown that an intrinsic fast gamma mechanism in medial entorhinal cortex can be recruited by optogenetic stimulation at theta frequencies, which can persist with fast excitatory synaptic transmission blocked, suggesting a contribution of interneuronal network gamma (ING). We calibrated the passive and active properties of a 100-neuron model network to capture the range of passive properties and frequency/current relationships of experimentally recorded PV+ neurons in the medial entorhinal cortex (mEC). The strength and probabilities of chemical and electrical synapses were also calibrated using paired recordings, as were the kinetics and short-term depression (STD) of the chemical synapses. Gap junctions that contribute a noticeable fraction of the input resistance were required for synchrony with hyperpolarizing inhibition; these networks exhibited theta-nested high frequency oscillations similar to the putative ING observed experimentally in the optogenetically-driven PV-ChR2 mice. With STD included in the model, the network desynchronized at frequencies above ~200 Hz, so for sufficiently strong drive, fast oscillations were only observed before the peak of the theta. Because hyperpolarizing synapses provide a synchronizing drive that contributes to robustness in the presence of heterogeneity, synchronization decreases as the hyperpolarizing inhibition becomes weaker. In contrast, networks with shunting inhibition required non-physiological levels of gap junctions to synchronize using conduction delays within the measured range.
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Depressão , Infecções Sexualmente Transmissíveis , Camundongos , Animais , Interneurônios/fisiologia , Transmissão Sináptica/fisiologia , Junções Comunicantes/fisiologia , Hipocampo/fisiologiaRESUMO
Global demand for crops will continue increasing over the next few decades to cover both food and biofuel needs. This demand will put further pressure to expand arable land and replace natural habitats. However, we are only beginning to understand the combined effects of agrochemicals and land-use change on tropical freshwater biodiversity. In this study, we analyzed how pond-dwelling anuran larvae responded to pond characteristics, landscape composition, and agrochemical contamination in a sugarcane-dominated agroecosystem in Brazil. Then we used an information theoretical approach with generalized linear models to relate species richness and abundance to predictor variables. The variation in tadpole abundance was associated with both agrochemical concentration (e.g., ametryn, diuron, and malathion) and landscape variables (e.g., percentage of forest, percentage of agriculture, and distance to closest forest). The relationship between species abundance and agrochemicals was species-specific. For example, the abundances of Scinax fuscovarius and Physalaemus nattereri were negatively associated with ametryn, and Dendropsophus nanus was negatively associated with tebuthiuron, whereas that of Leptodactylus fuscus was positively associated with malathion. Conversely, species richness was associated with distance to forest fragments and aquatic vegetation heterogeneity, but not agrochemicals. Although we were unable to assign a specific mechanism to the variation in tadpole abundance based on field observations, the lower abundance of three species in ponds with high concentrations of agrochemicals suggest they negatively impact some frog species inhabiting agroecosystems. We recommend conserving ponds near forest fragments, with abundant stratified vegetation, and far from agrochemical runoffs to safeguard more sensitive pond-breeding species.
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Saccharum , Animais , Malation , Melhoramento Vegetal , Ecossistema , Anuros , Biodiversidade , LarvaRESUMO
PURPOSEOF REVIEW: Female sex hormones have systemic effects unrelated to their reproductive function. We describe experiences of different research groups and our own, on aspects related to the importance of female sex hormones on blood pressure (BP) regulation and salt-sensitivity-mediated BP response and salt sensitivity without alterations in BP, as well as renal sodium handling and interactions with the immune system. RECENT FINDINGS: Changes in sodium intake in normotensive premenopausal women cause more BP variations than in men. After menopause, women often develop arterial hypertension (HT) with a profile of sodium sensitivity. Besides, experimental results have shown that in adult rat models resembling the postmenopausal hormonal state induced by ovariectomy, controlling BP is not enough to avoid renal and other tissue infiltration with immune cells, which does not occur when sodium intake is low or normal. Therefore, excess sodium promotes an inflammatory state with the involvement of immune cells. The evidence of activation of adaptive immunity, besides changes in T cell subpopulations, includes changes in sodium transporters and receptors. More studies are needed to evaluate the particular sodium sensitivity of women and its meaning. Changes in lifestyle and sodium intake reduction are the main therapeutic steps. However, to face the actual burden of salt-sensitive HT in postmenopausal women and its associated inflammatory/immune changes, it seems reasonable to work on immune cell activity by considering the peripheral blood mononuclear cell phenotypes of molecules and transport proteins related to sodium handle, both to screen for and treat cell activation.
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Steroid hormones (e.g. androgens [AN] and corticosterone [CORT]) modulate complex physiological functions such as reproduction, energy mobilization, metabolism, and immunity. The effects of these steroids on immunocompetence and its metabolic costs can also be affected by fluctuations in environmental resource availability and other factors such as parasitism. To understand these possible interactions, we studied AN and CORT, immune response [swelling response to phytohemagglutinin (PHA) injection and bacterial killing ability (BKA)], parasite load, resting metabolic rate (RMR) and post-immune challenge (PHA injection) oxygen consumption rates during two different phases of the annual cycle of Rhinella jimi toads from the Brazilian semi-arid region (Caatinga), where environmental conditions are highly seasonal. We observed an increase in O2 consumption rates after both PHA and saline (control) injections, indicating a metabolic response to adverse stimuli rather than the immune challenge. Toads showing higher RMR and VO2 after the adverse stimuli (PHA/saline injections) had lower field AN and CORT plasma levels, suggesting these hormones might mediate a metabolic energy conservation strategy both at baseline levels and after adverse stimuli. Parasite load appear to constrain the metabolic response to PHA and saline injections. Additionally, individuals with a higher swelling response to PHA had higher field CORT plasma levels (particularly when males are breeding), which opposes the idea of a possible trade-off between reproductive activity and other physiological traits, indicating the immunoenhancing effects of elevated CORT at physiological levels. BKA did not show a seasonal variation or correlation with body condition or hormone levels, indicating that the immune surveillance mediated by the complement remains constant despite ecological and physiological changes.
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Androgênios , Bufonidae , Humanos , Masculino , Animais , Estações do Ano , Esteroides , Imunidade , CorticosteronaRESUMO
Lymphomas are malignant neoplasms of the hematopoietic system arising from lymphocytes with highly variable biologic behavior. B-cell small lymphocytic lymphoma (B-SLL) is a non-Hodgkin lymphoma infrequently described in domestic and wild animals. The present study describes a case of B-SLL in a free-ranging adult male Arctocephalus australis in Brazil. The main necropsy findings included poor body condition, generalized lymphadenomegaly, severe and diffuse splenomegaly, and multiple, white to yellow nodules in the kidneys and small intestine. Histologically, these organs were partially or totally effaced by neoplastic small lymphocytes arranged in sheets, with moderate anisocytosis and anisokaryosis and a low mitotic count. These cells diffusely immunolabeled for CD79α and CD20, and were negative for CD3. A diagnosis of multicentric B-SLL was established and to the authors' knowledge, it has not been previously described in this genus.
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Otárias , Leucemia Linfocítica Crônica de Células B , Masculino , Animais , Leucemia Linfocítica Crônica de Células B/veterinária , Leucemia Linfocítica Crônica de Células B/patologia , Animais Selvagens , Brasil/epidemiologiaRESUMO
This work presents a multi-parameter optical fiber monitoring solution applied to an underground power distribution network. The monitoring system demonstrated herein uses Fiber Bragg Grating (FBG) sensors to measure multiple parameters, such as the distributed temperature of the power cable, external temperature and current of the transformers, liquid level, and intrusion in the underground manholes. To monitor partial discharges of cable connections, we used sensors that detect radio frequency signals. The system was characterized in the laboratory and tested in underground distribution networks. We present here the technical details of the laboratory characterization, system installation, and the results of 6 months of network monitoring. The data obtained for temperature sensors in the field tests show a thermal behavior depending on the day/night cycle and the season. The temperature levels measured on the conductors indicated that in high-temperature periods, the maximum current specified for the conductor must be reduced, according to the applied Brazilian standards. The other sensors detected other important events in the distribution network. All the sensors demonstrated their functionality and robustness in the distribution network, and the monitored data will allow the electric power system to have a safe operation, with optimized capacity and operating within tolerated electrical and thermal limits.
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Líquidos Corporais , Humanos , Brasil , Fontes de Energia Elétrica , Eletricidade , FebreRESUMO
The dolphinfish (Coryphaena hippurus) is a globally distributed marine predator that supports one of the most important coastal fisheries along the Eastern Tropical Pacific (ETP), but its spatial movements in this area are poorly understood. Stable isotope values (δ13 C and δ15 N) of white muscle from dolphinfish (n = 220) captured at different locations across the ETP (i.e., Mexico, Costa Rica, Ecuador, Peru and oceanic areas) were normalized to copepod baseline stable isotope values to estimate dolphinfish trophic position, movements and population dispersal. Movement or residence patterns were inferred from the difference in δ15 N values (Δ15 Ndolphinfish-copepod ) between copepods and dolphinfish muscle. Baseline corrected isotope values (δ13 Cdolphinfish-copepod and δ15 Ndolphinfish-copepod ) of dolphinfish muscle were used to estimate isotopic niche metrics and infer population dispersal across isoscapes. Values of δ13 C and δ15 N differed between juvenile and adult dolphinfish and across the ETP. Trophic position estimates ranged from 3.1 to 6.0 with a mean of 4.6. Adults and juveniles had similar trophic position estimates, whereas isotopic niche areas (SEA 2 ) of adults were greater relative to juveniles in every location. Adult dolphinfish showed "moderate movement by some individuals" in all locations based on Δ15 Ndolphinfish-copepod values, except for Costa Rica where adults were classified with "high degree of movement by some individuals" whereas juveniles showed "limited movement" in all areas except Mexico. Population dispersal based on Δ15 Ndolphinfish-copepod values showed "moderate" and "high" dispersal for adults and "no dispersal" for most juveniles, except for Mexico. This study provides insight into potential dolphinfish spatial mobility across an area of interest for multiple nations, which can help to improve stock assessments and management of the species.
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Copépodes , Perciformes , Animais , Carbono , Isótopos de Nitrogênio , Músculos , Pesqueiros , Isótopos de CarbonoRESUMO
Although a growing body of literature recognises the importance of rarity for biodiversity conservation, it is unclear how the interaction of different forms of rarity, extrinsic causes of extinction, and protection affect species' vulnerability. Here we addressed the extinction vulnerability of 2203 shrub and tree species of the South American savanna (SAS). For this, species were attributed a form of rarity, a synergistic risk index (SRI), and a protection index (PI). The SRI combines three extrinsic causes of extinction (climate hazard, fire frequency, and human footprint). The PI is the ratio between the number of a species occurrences within protected areas and the total number of occurrences in the SAS. By combining the SRI and PI, we classified common and rare species into five vulnerability classes. Some regions of the SAS show high values of climate hazard, fire frequency, human footprint, and SRI. Each extrinsic cause of extinction is differently distributed across the SAS and shows no or low spatial congruence with the SRI. Many species show a low ratio of occurrences within PAs, which in combination with high SRI results in high vulnerability to extinction. Surprisingly, the number of common species in the higher vulnerability classes is higher than of rare species. Common and rare species in different vulnerability classes occur in somewhat different locations across the SAS and mainly constitute spatially incongruent centres with high species richness. Given our results, we propose that strategies for the effective conservation of SAS species are challenging and must be carefully designed.
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Conservação dos Recursos Naturais , Árvores , Humanos , Pradaria , Biodiversidade , América do Sul , Ecossistema , Extinção BiológicaRESUMO
Over the past years, there has been an increasing concern about the occurrence of antineoplastic drugs in water bodies. The incomplete removal of these pharmaceuticals from wastewaters has been confirmed by several scientists, making it urgent to find a reliable technique or a combination of techniques capable to produce clean and safe water. In this work, the combination of nanofiltration and ozone (O3)-based processes (NF + O3, NF + O3/H2O2 and NF + O3/H2O2/UVA) was studied aiming to produce clean water from wastewater treatment plant (WWTP) secondary effluents to be safely discharged into water bodies, reused in daily practices such as aquaculture activities or for recharging aquifers used as abstraction sources for drinking water production. Nanofiltration was performed in a pilot-scale unit and O3-based processes in a continuous-flow column. The peroxone process (O3/H2O2) was considered the most promising technology to be coupled to nanofiltration, all the target pharmaceuticals being removed at an extent higher than 98% from WWTP secondary effluents, with a DOC reduction up to 92%. The applicability of the clean water stream for recharging aquifers used as abstraction sources for drinking water production was supported by a risk assessment approach, regarding the final concentrations of the target pharmaceuticals. Moreover, the toxicity of the nanofiltration retentate, a polluted stream generated from the nanofiltration system, was greatly decreased after the application of the peroxone process, which evidences the positive impact on the environment of implementing a NF + O3/H2O2 process.
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Antineoplásicos , Água Potável , Ozônio , Poluentes Químicos da Água , Purificação da Água , Águas Residuárias , Peróxido de Hidrogênio , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Preparações Farmacêuticas , OxirreduçãoRESUMO
Eighteen per-and polyfluoroalkyl substances (PFASs) were investigated in surface waters of four river basins in Portugal (Ave, Leça, Antuã, and Cértima) during the dry and wet seasons. All sampling sites showed contamination in at least one of the seasons. In the dry season, perfluorooctanoate acid (PFOA) and perfluoro-octane sulfonate (PFOS), were the most frequent PFASs, while during the wet season these were PFOA and perfluobutane-sulfonic acid (PFBS). Compounds detected at higher concentrations were PFOS (22.6 ng L-1) and perfluoro-butanoic acid (PFBA) (22.6 ng L-1) in the dry and wet seasons, respectively. Moreover, the prospective environmental risks of PFASs, detected at higher concentrations, were evaluated based on the Risk Quotient (RQ) classification, which comprises acute and chronic toxicity. The results show that the RQ values of eight out of the nine PFASs were below 0.01, indicating low risk to organisms at different trophic levels in the four rivers in both seasons, wet and dry. Nevertheless, in the specific case of perfluoro-tetradecanoic acid (PFTeA), the RQ values calculated exceeded 1 for fish (96 h) and daphnids (48 h), indicating a high risk for these organisms. Furthermore, the RQ values were higher than 0.1, indicating a medium risk for fish, daphnids and green algae (96 h).
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Ácidos Alcanossulfônicos , Fluorocarbonos , Poluentes Químicos da Água , Animais , Rios , Ácidos Alcanossulfônicos/análise , Portugal , Estudos Prospectivos , Poluentes Químicos da Água/análise , Monitoramento Ambiental , Fluorocarbonos/análise , Alcanossulfonatos , PeixesRESUMO
Carbonyl compounds are widely explored in medicinal inorganic chemistry and have drawn attention due to their signaling functions in homeostasis. Carbon-monoxide-releasing molecules (CORMs) were developed with the purpose of keeping the CO inactive until its release in the intracellular environment, considering its biological relevance. However, for therapeutic applications, the mechanisms of photorelease and which electronic and structural variations influence its rates must be fully understood. In this work, four ligands containing a pyridine, a secondary amine, and a phenolic group with different substituents were used to prepare new Mn(I) carbonyl compounds. Structural and physicochemical characterization of these complexes was carried out and confirmed the proposed structures. X-ray diffractometry structures obtained for the four organometallic compounds revealed that the substituents in the phenolic ring promote only negligible distortions in their geometry. Furthermore, UV-Vis and IR kinetics showed the direct dependence of the electron-withdrawing or donating ability of the substituent group, indicating an influence of the phenol ring on the CO release mechanism. These differences in properties were also supported by theoretical studies at the DFT, TD-DFT, and bonding situation analyses (EDA-NOCV). Two methods were used to determine the CO release constants (kCO,old and kCO,new), where Mn-HbpaBr (1) had the greatest kCO by both methods (Kco,old = 2.36 × 10-3 s-1 and kCO,new = 2.37 × 10-3 s-1). Carbon monoxide release was also evaluated using the myoglobin assay, indicating the release of 1.248 to 1.827 carbon monoxides upon light irradiation.