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A large number of oocytes in the perinatal ovary in rodents get lost for unknown reasons. The granulosa cell-oocyte mutual communication is pivotal for directing formation of the primordial follicle, however little is known if paracrine factors participate in modulating programmed oocyte death perinatally. We report here that pre-granulosa cell-derived fibroblast growth factor 23 (FGF23) functioned in preventing oocyte apoptosis in the perinatal mouse ovary. Our results showed that FGF23 was exclusively expressed in pre-granulosa cells while fibroblast growth factor receptors (FGFRs) were specifically expressed in the oocytes in perinatal ovaries. FGFR1 was one of the representative receptors in mediating FGF23 signaling during the formation of the primordial follicle. In cultured ovaries, the number of alive oocytes declines significantly, accompanied by the activation of the p38 MAPK signaling pathway, under the condition of FGFR1 disruption by specific inhibitors of FGFR1 or silencing of Fgf23. As a result, oocyte apoptosis increased and eventually led to a decrease in the number of germ cells in perinatal ovaries following the treatments. In the perinatal mouse ovary, pre-granulosa cell-derived FGF23 binds to FGFR1 and activates at least, the p38 MAPK signaling pathway, thereby regulating the level of apoptosis during primordial follicle formation. This study re-emphasizes the importance of granulosa cell - oocyte mutual communication in modulating primordial follicle formation and supporting oocyte survival under physiological conditions.
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We investigated the optimal number of independent parameters required to accurately represent spectral remote sensing reflectances (R rs) by performing principal component analysis on quality controlled in situ and synthetic R rs data. We found that retrieval algorithms should be able to retrieve no more than four free parameters from R rs spectra for most ocean waters. In addition, we evaluated the performance of five different bio-optical models with different numbers of free parameters for the direct inversion of in-water inherent optical properties (IOPs) from in situ and synthetic R rs data. The multi-parameter models showed similar performances regardless of the number of parameters. Considering the computational cost associated with larger parameter spaces, we recommend bio-optical models with three free parameters for the use of IOP or joint retrieval algorithms.
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Nonexponential relaxations are universal characteristics for glassy materials. There is a well-known hypothesis that nonexponential relaxation peaks are composed of a series of exponential events, which have not been verified. In this Letter, we discover the exponential relaxation events during the recovery process using a high-precision nanocalorimetry, which are universal for metallic glasses and organic glasses. The relaxation peaks can be well fitted by the exponential Debye function with a single activation energy. The activation energy covers a broad range from α relaxation to ß relaxation and even the fast γ/ß' relaxation. We obtain the complete spectrum of the exponential relaxation peaks over a wide temperature range from 0.63Tg to 1.03Tg, which provides solid evidence that nonexponential relaxation peaks can be decomposed into exponential relaxation units. Furthermore, the contribution of different relaxation modes in the nonequilibrium enthalpy space is measured. These results open a door for developing the thermodynamics of nonequilibrium physics and for precisely modulating the properties of glasses by controlling the relaxation modes.
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Ethylhexyl salicylate (EHS) is an organic UV filter commonly used in sunscreens to protect people from the UV radiation. The widespread use of EHS will enter the aquatic environment along with human activities. EHS readily accumulates in adipose tissue as a lipophilic compound, but its toxic effects on lipid metabolism and cardiovascular system of aquatic organisms have not been studied. This study investigated the effects of EHS on lipid metabolism and cardiovascular development during zebrafish embryogenesis. The results showed that EHS caused defects such as pericardial edema, cardiovascular dysplasia, lipid deposition, ischemia, and apoptosis in zebrafish embryos. In addition, qPCR and whole-mount in situ hybridization (WISH) results indicated that EHS treatment significantly altered the expression of genes related to cardiovascular development, lipid metabolism, erythropoiesis, and apoptosis. The hypolipidemic drug rosiglitazone was able to alleviate the cardiovascular defects caused by EHS, indicating that EHS affected cardiovascular development by disrupting lipid metabolism. In addition, severe ischemia caused by cardiovascular abnormalities and apoptosis were observed in the EHS-treated embryos, which was likely to be the main cause of embryonic mortality. In conclusion, this study shows that EHS has toxic effects on lipid metabolism and cardiovascular formation. Our findings provide new evidence for assessing UV filter EHS toxicity and contribute to raising awareness of the safety risks of EHS.
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Metal aerogels (MAs) are emerging porous materials displaying unprecedented potential in catalysis, sensing, plasmonic technologies, etc. However, the lack of efficient regulation of their nano-building blocks (NBBs) remains a big hurdle that hampers the in-depth investigation and performance enhancement. Here, by harmonizing composition and ligand effects, Pt- and Bi-based single- and bimetallic aerogels bearing NBBs of controlled dimensions and shapes are obtained by facilely tuning the metal precursors and the applied ligands. Particularly, by further modulating the electronic and optic properties of the aerogels via adjusting the content of the catalytically active Pt component and the semiconducting Bi component, both the electrocatalytic and photoelectrocatalytic performance of the Pt-Bi aerogels can be manipulated. In this light, an impressive catalytic performance for electro-oxidation of methanol is acquired, marking a mass activity of 6.4-fold higher under UV irradiation than that for commercial Pt/C. This study not only sheds light on in situ manipulating NBBs of MAs, but also puts forward guidelines for crafting high-performance MAs-based electrocatalysts and photoelectrocatalysts toward energy-related electrochemical processes.
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Biofilm formation is a major threat to industry, the environment and human health. While killing of embedded microbes in biofilms may inevitably lead to the evolution of antimicrobial resistance (AMR), catalytic quenching of bacterial communications by lactonase is a promising antifouling approach. Given the shortcomings of protein enzymes, it is attractive to engineer synthetic materials to mimic the activity of lactonase. Herein, an efficient lactonase-like Zn-Nx -C nanomaterial was synthesized by tuning the coordination environment around zinc atoms to mimic the active domain of lactonase for catalytical interception of bacterial communications in biofilm formation. The Zn-Nx -C material could selectively catalyze 77.5 % hydrolysis of N-acylated-L-homoserine lactone (AHL), a critical bacterial quorum sensing (QS) signal in biofilm construction. Consequently, AHL degradation downregulated the expression of QS-related genes in antibiotic resistant bacteria and significantly prevented biofilm formation. As a proof of concept, Zn-Nx -C-coated iron plates prevented 80.3 % biofouling after a month exposure in river. Overall, our study provides a nano-enabled contactless antifouling insight to avoid AMR evolution by engineering nanomaterials for mimicking the key bacterial enzymes (e.g., lactonase) functioning in biofilm construction.
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Chromosome rearrangement is one of the main causes of abortion. In individuals with double chromosomal rearrangements, the abortion rate and the risk of producing abnormal chromosomal embryos are increased. In our study, preimplantation genetic testing for structural rearrangement (PGT-SR) was performed for a couple because of recurrent abortion and the karyotype of the male was 45, XY der (14; 15)(q10; q10). The PGT-SR result of the embryo in this in vitro fertilization (IVF) cycle showed microduplication and microdeletion at the terminals of chromosomes 3 and 11, respectively. Therefore, we speculated whether the couple might have a cryptic reciprocal translocation which was not detected by karyotyping. Then, optical genome mapping (OGM) was performed for this couple, and cryptic balanced chromosomal rearrangements were detected in the male. The OGM data were consistent with our hypothesis according to previous PGT results. Subsequently, this result was verified by fluorescence in situ hybridization (FISH) in metaphase. In conclusion, the male's karyotype was 45, XY, t(3; 11)(q28; p15.4), der(14; 15)(q10; q10). Compared with traditional karyotyping, chromosomal microarray, CNV-seq and FISH, OGM has significant advantages in detecting cryptic and balanced chromosomal rearrangements.
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Regulatory T (Treg) cell dysfunction is involved in the pathogenesis of autoimmune premature ovarian insufficiency (POI). Adoptive transfer of Treg cells has been shown to be effective in the treatment of autoimmune POI in mice. However, the therapeutic effect of Treg cell therapy is limited because the phenotype and function of Treg cells is not properly maintained when they are reinfused in an inflammatory environment. Therefore, enhancing the function of Treg cells using genetic engineering is of great significance for improving the efficacy of Treg cells in the treatment of immune diseases. In this study, we investigated the role of the E3 ubiquitinated ligase Pellino 1 (Peli1) in the proliferation and immunosuppressive function of Treg cells and the therapeutic effect of Treg cells overexpressing Peli1 on autoimmune POI. The results showed that the overexpression of Peli1 promoted cell proliferation and enhanced the immunosuppressive function of Treg cells in vitro. After the adoptive transfer of Treg cells overexpressing Peli1 in autoimmune POI mice, the apoptosis rate of ovarian granulosa cells declined. The levels of the inflammatory inhibitors interleukin 10 and transforming growth factor-ß as well as the ovarian hormone estradiol were elevated. The number of primordial, primary, secondary, and mature follicles was restored to a certain extent compared with those in control subjects. These results revealed that the adoptive transfer of Treg cells overexpressing Peli1 promoted its efficacy against zona pellucida protein 3 peptide-induced POI, which provides new insights into the treatment of autoimmune POI.
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Proteínas Nucleares , Insuficiência Ovariana Primária , Linfócitos T Reguladores , Ubiquitina-Proteína Ligases , Animais , Feminino , Humanos , Camundongos , Estradiol , Proteínas Nucleares/genética , Insuficiência Ovariana Primária/terapia , Fator de Crescimento Transformador beta , Ubiquitina-Proteína Ligases/genéticaRESUMO
Fine particulates (FPs) are a major class of airborne pollutants. In mammals, FPs may reach the alveoli through the respiratory system, cross the air-blood barrier, spread into other organs, and induce hazardous effects. Although birds have much higher respiratory risks to FPs than mammals, the biological fate of inhaled FPs in birds has rarely been explored. Herein, we attempted to disclose the key properties that dictate the lung penetration of nanoparticles (NPs) by visualizing a library of 27 fluorescent nanoparticles (FNPs) in chicken embryos. The FNP library was prepared by combinational chemistry to tune their compositions, morphologies, sizes, and surface charges. These NPs were injected into the lungs of chicken embryos for dynamic imaging of their distributions by IVIS Spectrum. FNPs with diameters <16 nm could cross the air-blood barrier in 20 min, spread into the blood, and accumulate in the yolk sac. In contrast, large FNPs (>30 nm) were mainly retained in the lungs and rarely detected in other tissues/organs. In addition to size, surface charge was the secondary determinant for NPs to cross the air-blood barrier. Compared to cationic and anionic particles, neutrally charged FNPs showed the fastest lung penetration. A predictive model was therefore developed to rank the lung penetration capability of FNPs by in silico analysis. The in silico predictions could be well validated in chicks by oropharyngeal exposure to six FNPs. Overall, our study discovered the key properties of NPs that are responsible for their lung penetration and established a predictive model that will greatly facilitate respiratory risk assessments of nanoproducts.
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Galinhas , Nanopartículas , Embrião de Galinha , Animais , Barreira Alveolocapilar , Nanopartículas/química , Pulmão , Corantes , Tamanho da Partícula , MamíferosRESUMO
Inflammatory markers have a wide range of predictive values in the prognosis of non-small lung cancer (NSCLC). Poor nutritional status usually means a poor prognosis in patients with NSCLC, which is widely recognized by oncologists and nutritionists. Serum albumin has a certain value in evaluating the prognosis of patients. Several inflammatory albumin-related markers have been proposed, but they have not been widely used in predicting the prognosis of NSCLC in clinical practice. We aim to systematically review the published clinical evidence of albumin-related inflammatory markers in predicting the prognosis of NSCLC and to describe their progress and value. The results showed that the markers included in the review could be prognostic indicators in patients with NSCLC. However, we found that the cut-off value of albumin-related inflammatory markers with quantitative nature was very chaotic and needed to be defined by recognized standards. We summarized and compared the advantages and disadvantages of these markers, but a prospective cohort study with long-term follow-up after adjustment for important confounders is still necessary. Whether the results and conclusions could be directly applied in clinical practice needs to be identified and evaluated. There is an urgent need to classify and standardize the albumin-related inflammatory markers that play an important role in the prognosis of NSCLC, which is the key to ensuring the transformation from clinical study to clinical application.
Albumin-related inflammatory markers could be prognostic indicators in non-small cell lung cancer.The classification and standardization of albumin-related inflammatory markers guarantee the transformation from clinical study to clinical application.Future prospective studies of albumin-related inflammatory markers excluding confounding factors are very necessary.
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Carcinoma Pulmonar de Células não Pequenas , Neoplasias Pulmonares , Humanos , Carcinoma Pulmonar de Células não Pequenas/diagnóstico , Neoplasias Pulmonares/diagnóstico , Estudos Prospectivos , Estudos Retrospectivos , Prognóstico , Biomarcadores , Albumina SéricaRESUMO
Monopolar spindle kinase 1 (Mps1) is a key element of the mitotic checkpoint and clinically evaluated as a target in the treatment of aggressive tumors. With this aim, a set of pyrazolo[3,4-b]pyridine-based compounds as new Mps1 inhibitors was investigated through a multidisciplinary approach, based on virtual screening, chemical synthesis and biological evaluation. One of the representative compounds, 31, exhibited strong kinase inhibitory potency against Mps1 with an IC50 value of 2.596 nM and significantly inhibited proliferation of cancer cells, especially MDA-MB-468 and MV4-11 cells. Compound 31 also displayed reasonable kinome selectivity against a panel of 606 wild-type kinases at 1 µM. Moreover, compound 31 exhibited suitable preclinical pharmacokinetic parameters and a promising pharmacodynamic profile. Further, compound 31 showed good antitumor efficacy in MDA-MB-468 xenograft model with no obvious toxicity. Overall, compound 31 was identified as a potential Mps1 inhibitor for cancer therapy and deserve further research.
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Antineoplásicos , Neoplasias , Humanos , Proteínas Serina-Treonina Quinases , Proteínas de Ciclo Celular , Proteínas Tirosina Quinases , Neoplasias/tratamento farmacológico , Piridinas/farmacologia , Antineoplásicos/farmacologia , Antineoplásicos/química , Inibidores de Proteínas Quinases/química , Linhagem Celular Tumoral , Proliferação de CélulasRESUMO
BACKGROUND: Self-sampling HPV test and thermal ablation are effective tools to increase screening coverage and treatment compliance for accelerating cervical cancer elimination. We assessed the cost-effectiveness of their combined strategies to inform accessible, affordable, and acceptable cervical cancer prevention strategies. METHODS: We developed a hybrid model to evaluate costs, health outcomes, and incremental cost-effectiveness ratios (ICER) of six screen-and-treat strategies combining HPV testing (self-sampling or physician-sampling), triage modalities (HPV genotyping, colposcopy or none) and thermal ablation, from a societal perspective. A designated initial cohort of 100,000 females born in 2015 was considered. Strategies with an ICER less than the Chinese gross domestic product (GDP) per capita ($10,350) were considered highly cost-effective. RESULTS: Compared with current strategies in China (physician-HPV with genotype or cytology triage), all screen-and-treat strategies are cost-effective and self-HPV without triage is optimal with the most incremental quality-adjusted life-years (QALYs) gained (220 to 440) in rural and urban China. Each screen-and-treat strategy based on self-collected samples is cost-saving compared with current strategies (-$818,430 to -$3540) whereas more costs are incurred using physician-collected samples compared with current physician-HPV with genotype triage (+$20,840 to +$182,840). For screen-and-treat strategies without triage, more costs (+$9404 to +$380,217) would be invested in the screening and treatment of precancerous lesions rather than the cancer treatment compared with the current screening strategies. Notably, however, more than 81.6% of HPV-positive women would be overtreated. If triaged with HPV 7 types or HPV16/18 genotypes, 79.1% or 67.2% (respectively) of HPV-positive women would be overtreated with fewer cancer cases avoided (19 cases or 69 cases). CONCLUSIONS: Screen-and-treat strategy using self-sampling HPV test linked to thermal ablation could be the most cost-effective for cervical cancer prevention in China. Additional triage with quality-assured performance could reduce overtreatment and remains highly cost-effective compared with current strategies.
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Infecções por Papillomavirus , Displasia do Colo do Útero , Neoplasias do Colo do Útero , Feminino , Humanos , Criança , Neoplasias do Colo do Útero/diagnóstico , Neoplasias do Colo do Útero/patologia , Displasia do Colo do Útero/diagnóstico , Análise Custo-Benefício , Papillomavirus Humano 16/genética , Infecções por Papillomavirus/diagnóstico , Papillomavirus Humano 18/genética , Programas de Rastreamento , Detecção Precoce de CâncerRESUMO
Didymella arachidicola is one of the most important fungal pathogens, causing foliar disease and leading to severe yield losses of peanuts (Arachis hypogaea L.) in China. Two main lesion phenotypes of peanut web blotch have been identified as reticulation type (R type) and blotch type (B type). As no satisfactory reference genome is available, the genomic variations and pathogenicity factors of D. arachidicola remain to be revealed. In the present study, we collected 41 D. arachidicola isolates from 26 geographic locations across China (33 for R type and 8 for B type). The chromosome-scale genome of the most virulent isolate (YY187) was assembled as a reference using PacBio and Hi-C technologies. In addition, we re-sequenced 40 isolates from different sampling sites. Genome-wide alignments showed high similarity among the genomic sequences from the 40 isolates, with an average mapping rate of 97.38%. An average of 3242 SNPs and 315 InDels were identified in the genomic variation analysis, which revealed an intraspecific polymorphism in D. arachidicola. The comparative analysis of the most and least virulent isolates generated an integrated gene set containing 512 differential genes. Moreover, 225 genes individually or simultaneously harbored hits in CAZy-base, PHI-base, DFVF, etc. Compared with the R type reference, the differential gene sets from all B type isolates identified 13 shared genes potentially related to lesion phenotype. Our results reveal the intraspecific genomic variation of D. arachidicola isolates and pathogenicity factors potentially related to different lesion phenotypes. This work sets a genomic foundation for understanding the mechanisms behind genomic diversity driving different pathogenic phenotypes of D. arachidicola.
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Correlation of lattice vibrational properties with local atomic configurations in materials is essential for elucidating functionalities that involve phonon transport in solids. Recent developments in vibrational spectroscopy in a scanning transmission electron microscope have enabled direct measurements of local phonon modes at defects and interfaces by combining high spatial and energy resolution. However, pushing the ultimate limit of vibrational spectroscopy in a scanning transmission electron microscope to reveal the impact of chemical bonding on local phonon modes requires extreme sensitivity of the experiment at the chemical-bond level. Here we demonstrate that, with improved instrument stability and sensitivity, the specific vibrational signals of the same substitutional impurity and the neighbouring carbon atoms in monolayer graphene with different chemical-bonding configurations are clearly resolved, complementary with density functional theory calculations. The present work opens the door to the direct observation of local phonon modes with chemical-bonding sensitivity, and provides more insights into the defect-induced physics in graphene.
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As an endogenous gas signalling molecule, hydrogen sulfide (H2S) is frequently present in a variety of mammals and plays a significant role in the cardiovascular and nervous systems. Reactive oxygen species (ROS) are produced in large quantities as a result of cerebral ischaemia-reperfusion, which is a very serious class of cerebrovascular diseases. ROS cause oxidative stress and induce specific gene expression that results in apoptosis. H2S reduces cerebral ischaemia-reperfusion-induced secondary injury via anti-oxidative stress injury, suppression of the inflammatory response, inhibition of apoptosis, attenuation of cerebrovascular endothelial cell injury, modulation of autophagy, and antagonism of P2X7 receptors, and it plays an important biological role in other cerebral ischaemic injury events. Despite the many limitations of the hydrogen sulfide therapy delivery strategy and the difficulty in controlling the ideal concentration, relevant experimental evidence demonstrating that H2S plays an excellent neuroprotective role in cerebral ischaemia-reperfusion injury (CIRI). This paper examines the synthesis and metabolism of the gas molecule H2S in the brain as well as the molecular mechanisms of H2S donors in cerebral ischaemia-reperfusion injury and possibly other unknown biological functions. With the active development in this field, it is expected that this review will assist researchers in their search for the potential value of hydrogen sulfide and provide new ideas for preclinical trials of exogenous H2S.
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Lesões Encefálicas , Isquemia Encefálica , Sulfeto de Hidrogênio , Traumatismo por Reperfusão , Animais , Sulfeto de Hidrogênio/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Traumatismo por Reperfusão/tratamento farmacológico , Traumatismo por Reperfusão/metabolismo , Estresse Oxidativo , Infarto Cerebral/tratamento farmacológico , Isquemia Encefálica/tratamento farmacológico , Lesões Encefálicas/tratamento farmacológico , MamíferosRESUMO
Sulfur dioxide (SO2) gas, which can effectively prohibit the growth of pathogenic microorganisms, has been internationally used in commercial food packaging to maintain high-quality food and reduce the incidence of foodborne illnesses. However, the current mainstream methods for SO2 detection are either large and expensive instruments or synthesized chemical-based labels, which are not suitable for large-scale gas detection in food packaging. Recently, we discovered that petunia dye (PD), which is extracted from natural petunia flowers, demonstrates a highly sensitive colorimetric response to SO2 gas with its total color difference (ΔE) modulation reaching up to 74.8 and detection limit down to 1.52 ppm. To apply the extracted petunia dye in smart packaging for real-time gas sensing and food-quality prediction, a flexible and freestanding PD-based SO2 detection label is prepared by incorporating PD in biopolymers and assembling the films through a layer-by-layer approach. The developed label is utilized to predict grapes' quality and safety by monitoring the embedded SO2 gas concentration. The developed colorimetric SO2 detection label could potentially be used as an intelligent gas sensor for food status prediction in daily life, food storage, and supply chains.
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Colorimetria , Dióxido de Enxofre , Colorimetria/métodos , Biomassa , Embalagem de AlimentosRESUMO
Extreme event-based synchronicity is a specific measure of similarity of extreme event-like time series. It is capable to capture the nonlinear interactions between climatic extreme events. In this study, we proposed a modified extreme event-based synchronicity measure that incorporates two types of extreme events (positive and negative) simultaneously in climate anomalies to characterize the synchronization and time delays. Statistical significance of the modified extreme event synchronization measure is tested by Monte-Carlo simulations. The applications of the modified extreme event-based synchronicity measure on synthetic time series verified that it was superior to the traditional event synchronicity measure. Both synchronous and antisynchronous features between climate time series could be captured by the modified measure. It is potentially applied in investigating the interrelationship between climate extremes and climate index or constructing complex networks of climate variables. In addition, this modified extreme event-based synchronicity measure could be easily applied to other types of time series just by identifying the extreme events properly.
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Forkhead box O3 is a protein encoded by the FOXO3 gene expressed throughout the body. FOXO3 could play a crucial role in longevity and many other pathologies, such as Alzheimer's disease, glioblastoma, and stroke. This study is a comprehensive review of the expression of FOXO3 under ischemia and reperfusion (IR) and the molecular mechanisms of its regulation and function. We found that the expression level of FOXO3 under ischemia and IR is tissue-specific. Specifically, the expression level of FOXO3 is increased in the lung and intestinal epithelial cells after IR. However, FOXO3 is downregulated in the kidney after IR and in the skeletal muscles following ischemia. Interestingly, both increased and decreased FOXO3 expression have been reported in the brain, liver, and heart following IR. Nevertheless, these contribute to stimulating ischemia and reperfusion injury via the induction of inflammatory response, apoptosis, autophagy, mitophagy, pyroptosis, and oxidative damage. These results suggest that FOXO3 could play protective effects in some organs and detrimental effects in others against IR injury. Most importantly, these findings indicate that controlling FOXO3 expression, genetically or pharmacologically, could contribute to preventing or treating ischemia and reperfusion damage.
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Traumatismo por Reperfusão , Humanos , Proteína Forkhead Box O3/genética , Proteína Forkhead Box O3/metabolismo , Traumatismo por Reperfusão/genética , Traumatismo por Reperfusão/metabolismo , Apoptose/genética , Estresse Oxidativo , IsquemiaRESUMO
CeO2 has attracted much attention in the field of selective catalytic reduction of NO with NH3 (NH3-SCR). However, poor low-temperature activity and a narrow operation window restrict the industrial application of Ce-based oxide catalysts. Herein, the low-temperature NH3-SCR activity of Ce-based oxide catalysts was dramatically improved by Mn doping, and the mechanism was elucidated at the atomic level by experimental measurements and density functional theory calculations. We found that the addition of Mn significantly promoted the formation of surface oxygen vacancies. The oxygen vacancies easily captured O2 in air and formed active oxygen species (superoxide and peroxide) on the surface. The surface active oxygen species efficiently oxidized NO into NO2 and then facilitated the "fast SCR" reaction. This study provides atomic-level insights into the promotion of the NH3-SCR activity over Mn-Ce composite oxides and is beneficial for the development of low-temperature Ce-based catalysts.
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Amônia , Óxidos , Temperatura , Oxirredução , Espécies Reativas de Oxigênio , Teoria da Densidade Funcional , Catálise , OxigênioRESUMO
A large-scale survey was conducted by measuring five organophosphite antioxidants (OPAs) and three novel organophosphate esters (NOPEs) in 139 dust samples across China. The median summed concentrations of OPAs and NOPEs in outdoor dust were 33.8 ng/g (range: 0.12-53,400 ng/g) and 7990 ng/g (2390-27,600 ng/g), respectively. The dust concentrations of OPAs associated with the increasing economic development and population density from western to eastern China, whereas the NOPE concentration in Northeast China (median, 11,900 ng/g; range, 4360-16,400 ng/g) was the highest. Geographically, the distribution of NOPEs was significantly associated with annual sunshine duration and precipitation at each sampling site. Results of laboratory experiments further revealed that the simulated sunlight irradiation promoted the heterogeneous phototransformation of OPAs in dust, and this process was accelerated with the existence of reactive oxygen species and enhanced relative humidity. Importantly, during this phototransformation, the hydroxylated, hydrolyzed, dealkylated, and methylated products, e.g., bis(2,4-di-tert-butylphenyl) methyl phosphate, were identified by nontargeted analysis, part of which were estimated to be more toxic than their parent compounds. The heterogeneous phototransformation pathway of OPAs was suggested accordingly. For the first time, the large-scale distribution of OPAs and NOPEs and the phototransformation of these "new chemicals" in dust were revealed.