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Simultaneous elimination of As(III) and Pb(II) from wastewater is still a great challenge. In this work, an iron-sulfur codoped biochar (Fe/S-BC) was successfully fabricated in a simplified way and was applied to the remediate the co-pollution of As(III) and Pb(II). The positive enthalpy indicated that the adsorption in As-Pb co-pollution was an endothermic reaction. The mechanism of As(III) removal could be illustrated by surface complexation, oxidation and precipitation. In addition to precipitation and complexation, the elimination mechanism of Pb(II) also contained ion exchange and electrostatic interactions. Competitive and synergistic effects existed simultaneously in the co-contamination system. The suppression of As(III) was ascribed to competitive complexation of the two metals on Fe/S-BC, while the synergy of Pb(II) was attributed to the formation of the PbFe2(AsO4)2(OH)2. Batch experiments revealed that Fe/S-BC had outstanding ability to remove As(III) and Pb(II), regardless of pH dependency and interference by various coexisting ions. The maximum adsorption capacities of the Fe/S-BC for As(III) and Pb(II) were 91.2 mg/g and 631.7 mg/g, respectively. Fe/S-BC could be treated as a novel candidate for the elimination of As(III)-Pb(II) combined pollution.
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Ferro , Poluentes Químicos da Água , Adsorção , Chumbo , Carvão Vegetal , Enxofre , CinéticaRESUMO
This study investigated the application of a specific soil washing method to remove Cu and Pb from contaminated agricultural soil. To develop an efficient leaching agent of heavy metal compounds for use in farmland soil, a mixed chelator (MC) was prepared using potassium fulvic acid (PFA, 3.2%) and citric acid (CIT, 0.16 M) in a volume ratio of 4:1 (PFA:CIT = 4:1); the optimal solid-liquid ratio (S/L = 1:20), initial pH value (4.51) and contact time (360 min) were also explored. Under optimal conditions, the removal efficiencies of MC for Cu and Pb were 42.92% and 50.46%, respectively, both of which performed better than PFA (27.86% of Cu and 17.91% of Pb) and CIT (42.04% of Cu and 41.46% of Pb). The effective states, bioavailability and relative mobilities of Cu and Pb in soil were also efficiently reduced by MC, which also increased the stability of these elements, thereby lowering the risk to soil health. More importantly, MC not only had little effect on the soil physicochemical properties (e.g., pH, organic matter (OM), cation exchange capacity (CEC), ammonium nitrogen (AN), available phosphorus (AP) and rapidly available potassium (AK)), but also improved the restored soil. Furthermore, soil structure, surface elements and the enzyme activity did not exhibit significantly loss. Therefore, MC has great potential for remediating agricultural soil.
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Cobre/análise , Recuperação e Remediação Ambiental/métodos , Chumbo/análise , Poluentes do Solo/análise , Benzopiranos/química , Disponibilidade Biológica , Quelantes/química , Ácido Cítrico/química , Poluição Ambiental , Metais Pesados/análise , Fósforo , Potássio , Solo/químicaRESUMO
We proposed the deprotection-induced block copolymer self-assembly (DISA); that is, the deprotection of hydroxyl groups resulted in in situ self-assembly of glycopolymers. In the previous studies, block copolymers soluble in common organic solvents were employed as the starting material. In this paper, by using the protected glyco-block containing preassembled glycovesicles in water as the starting material, we moved forward and made two exceeding achievements. First, we have observed a deprotection-induced morphology transition triggered by alkali in water. The carbohydrate-carbohydrate interactions were considered to contribute to such a morphology transition during deprotection. Second, lipase was found to be an efficient enzymatic trigger in the sugar deprotection, which motivates the immune-application of this morphology transition process. When lipase and a model antigen, ovalbumin (OVA), were encapsulated inside the glycovesicles, the deprotection of sugars by lipase induced the transition of vesicles to micelles and the lipase and OVA were released accordingly. When glycovesicles were internalized by dentritic cells (DCs), the lipase from lysosomes efficiently induced the release of OVA and presentation of antigen to T cells. During the process, lysosomal lipase performed as a trigger on the deprotection of sugars and the release of protein without any other reagents. The significance of this design is that as a delivery vehicle, the protected glycovesicles not only avoided unnecessary immune activation but also worked with the released OVA together; that is, the glycovehicle successfully activated DCs and improved the presentation efficiency of T cells remarkably.
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Preparações de Ação Retardada/química , Lipase/administração & dosagem , Ovalbumina/administração & dosagem , Polietilenoglicóis/química , Poliestirenos/química , Açúcares/química , Animais , Apresentação de Antígeno , Linhagem Celular , Células Dendríticas/imunologia , Lipase/química , Camundongos , Micelas , Modelos Moleculares , Ovalbumina/química , Ovalbumina/imunologia , Triticum/enzimologiaRESUMO
Immune checkpoint blockade by anti-PD-L1 monoclonal antibody (αPD-L1) has achieved unprecedented clinical benefits in certain cancers, whereas the therapeutic efficacy is often hindered by immunosuppressive tumor microenvironment mediated by tumor-associated macrophages (TAMs), which leads to innate resistance to this approach. To improve checkpoint blockade efficacy, the amphiphilic diblock copolymers poly(mannopyranoside/galactopyranoside methacrylate)- block-polystyrene are prepared by RAFT polymerization, which are sequentially self-assembled into glycocalyx-mimicking nanoparticles (GNPs) to neutralize TAMs. It is shown that GNPs can be specifically internalized by TAMs via lectin receptors, which results in upregulation of immunostimulatory IL-12 and downregulation of immunosuppressive IL-10, arginase 1, and CCL22, indicating functional reversion of protumor TAMs toward antitumor phenotype. The reversion of TAMs is proved to be mainly controlled by suppressing STAT6 and activating NF-κB phosphorylation. In vivo therapeutic studies have demonstrated that GNPs significantly enhance the therapeutic efficacy of αPD-L1 cancer therapy by reduction of tumor burden. Moreover, combination therapies with GNPs and αPD-L1 greatly improve immunosuppressive tumor microenvironment by reciprocal modulation of tumor-infiltrating effector and regulatory T cells. Notably, for the first time, our results demonstrate the reversion of TAMs and improvement of αPD-L1 cancer therapy by synthetic carbohydrate-containing nanomaterials. This research highlights a promising strategy for optimizing immune checkpoint blockade in cancer immunotherapy.
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Antígeno B7-H1/antagonistas & inibidores , Glicocálix/química , Imunoterapia/métodos , Macrófagos/efeitos dos fármacos , Nanopartículas/química , Animais , Antineoplásicos Imunológicos/química , Antineoplásicos Imunológicos/farmacocinética , Antígeno B7-H1/imunologia , Regulação Neoplásica da Expressão Gênica/efeitos dos fármacos , Humanos , Ativação Linfocitária/efeitos dos fármacos , Macrófagos/metabolismo , Macrófagos/patologia , Camundongos Endogâmicos C57BL , Mimetismo Molecular , NF-kappa B/metabolismo , Nanopartículas/administração & dosagem , Nanopartículas/uso terapêutico , Polimerização , Polímeros/química , Polímeros/farmacologia , Ensaios Antitumorais Modelo de XenoenxertoRESUMO
We measured total mercury (Hg) and selenium (Se) concentrations as well as stable nitrogen (N) isotopic composition in flyingfish and squid muscle tissues from the eastern Indian Ocean and western South China Sea. The results showed that the mean Hg concentration in squid muscle from the western South China Sea was lower than that in the eastern Indian Ocean. The Hg concentrations in flyingfish and squid muscle samples were positively correlated with organism size (length and weight) and δ15N in all the study areas. Furthermore, we found a negative correlation between Se and Hg in molar content of flyingfish and squid muscle from the western South China Sea. The Se:Hg molar ratio was significantly negative correlated with fish weight and δ15N, suggesting that the Se:Hg molar ratio decreases with the increase of fish size and trophic level in the food web.
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Beloniformes/metabolismo , Decapodiformes/metabolismo , Monitoramento Ambiental/métodos , Mercúrio/análise , Selênio/análise , Poluentes Químicos da Água/análise , Animais , China , Cadeia Alimentar , Oceano Índico , Mercúrio/metabolismo , Músculos/química , Alimentos Marinhos/análise , Selênio/metabolismo , Poluentes Químicos da Água/metabolismoRESUMO
Glyconanoparticles made by self-assembled glycopolymers currently are practical and efficient mimics of the glycocalyx on cell surfaces. Considering the complexity of the glycocalyx, glyconanoparticles with different sugars on their coronas, i.e., mixed-shell glycomicelles, could be more valuable compared to homoshell micelles. In this paper, we explore the architectural effect of the glyconanoparticle corona on glyconanoparticle macrophage endocytosis and lectin-binding ability. A series of glyconanoparticles composed of a biodegradable polyester backbone functionalized with galactoside or mannoside pendants were designed and prepared. The different architectures explored were single-component (galactoside or mannoside) coronas, homogeneously mixed coronas (MG) made by galactoside-mannoside copolymer chains, and blend-mixed coronas (M/G) constructed from two homoglycopolymers. Nanoparticles with a mixed shell showed a higher efficiency in cellular uptake and lectin-binding than those with a single sugar component. Meanwhile, unexpectedly, MG presented a significantly higher efficiency than M/G, although they had the same particle size and ratio of mannoside to galactoside. We attributed this apparent architectural effect to the difference in the phase behavior between MG and M/G; i.e., the former having a homogeneous corona allowed more sugar-receptor interactions in the contact region, while the latter having phase separation limited the simultaneous interaction of the two kinds of sugar units with the cell receptors.
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Glicocálix/metabolismo , Macrófagos/metabolismo , Nanopartículas/metabolismo , Poliésteres/metabolismo , Animais , Endocitose , Ativação de Macrófagos , Camundongos , Lectinas de Plantas/metabolismo , Células RAW 264.7RESUMO
The role of agricultural versus vehicle emissions in urban atmospheric ammonia (NH3) remains unclear. The lockdown due to the outbreak of COVID-19 provided an opportunity to assess the role of source emissions on urban NH3. Concentrations and δ15N of aerosol ammonium (NH4+) were measured before (autumn in 2017) and during the lockdown (summer, autumn, and winter in 2020), and source contributions were quantified using SIAR. Despite the insignificant decrease in NH4+ concentrations, significantly lower δ15N-NH4+ was found in 2020 (0.6 ± 1.0 in PM2.5 and 1.4 ± 2.1 in PM10) than in 2017 (15.2 ± 6.7 in PM2.5), which indicates the NH3 from vehicle emissions has decreased byâ¼50% during the lockdown while other source emissions are less affected. Moreover, a reversed seasonal pattern of δ15N-NH4+ during the lockdown in Changsha has been revealed compared to previous urban studies, which can be explained by the dominant effect of non-fossil fuel emissions due to the reductions of vehicle emissions during the lockdown period. Our results highlight the effects of lockdown on aerosol δ15N-NH4+ and the importance of vehicle emissions to urban atmospheric NH3, providing conclusive evidence that reducing vehicle NH3 emissions could be an effective strategy to reduce PM2.5 in Chinese megacities.
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Poluentes Atmosféricos , Compostos de Amônio , Compostos de Amônio/análise , Isótopos de Nitrogênio/análise , Emissões de Veículos , Poluentes Atmosféricos/análise , Monitoramento Ambiental , Aerossóis e Gotículas Respiratórios , Amônia/análise , Material Particulado/análise , ChinaRESUMO
The last decades have witnessed a rapid development of noninvasive plant phenotyping, capable of detecting plant stress scale levels from the subcellular to the whole population scale. However, even with such a broad range, most phenotyping objects are often just concerned with leaves. This review offers a unique perspective of noninvasive plant stress phenotyping from a multi-organ view. First, plant sensing and responding to abiotic stress from the diverse vegetative organs (leaves, stems, and roots) and the interplays between these vital components are analyzed. Then, the corresponding noninvasive optical phenotyping techniques are also provided, which can prompt the practical implementation of appropriate noninvasive phenotyping techniques for each organ. Furthermore, we explore methods for analyzing compound stress situations, as field conditions frequently encompass multiple abiotic stressors. Thus, our work goes beyond the conventional approach of focusing solely on individual plant organs. The novel insights of the multi-organ, noninvasive phenotyping study provide a reference for testing hypotheses concerning the intricate dynamics of plant stress responses, as well as the potential interactive effects among various stressors.
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Brown carbon (BrC), the light-absorbing component of organic aerosols, plays a significant role in climate change and atmospheric photochemistry. However, the water-insoluble fractions of BrC have not been extensively studied, limiting the assessment of the overall climate effects of BrC. In this study, water-soluble and -insoluble organic carbon (i.e., WSOC and WIOC) in wintertime aerosols in Hefei were subsequently fractionated, and their fluorescence properties were comparatively investigated with the excitation-emission matrix method. WIOC contributing 57.1 % was the major component of organic carbon. WSOC with the largest contribution from humic-like regions exhibited a redshift compared to WIOC. Three humic-like substances (HULIS) with different oxidation degrees and one protein-like substances (PRLIS) were identified as the major fluorescent components by the parallel factor analysis. WSOC had more highly oxygenated HULIS, whereas low-oxygenated HULIS dominated WIOC. Nighttime WIOC contained more less-oxygenated species. The positive matrix factorization analysis suggested that biomass burning (43 %) was the largest source of both fluorescent WSOC and WIOC. Coal combustion contributed much more to fluorescent WIOC (40 %), whereas secondary formation contributed more to fluorescent WSOC (12 %). During aerosol pollution episodes, the increase in fluorescence efficiency was much greater for WIOC (25 %) than for WSOC (12 %), and WSOC and WIOC experienced a redshift and blueshift in emission wavelength, respectively. WSOC had more highly oxygenated HULIS, while WIOC had more less-oxygenated HULIS in aerosol episodes than the non-episodic periods. In addition, aerosol pollution was accompanied by the increased contributions of biomass burning and coal combustion to both fluorescent WSOC and WIOC, while the decreased relative contribution of secondary formation to fluorescent WSOC. Our findings highlighted the different fluorescence properties, compositions and sources of fluorescent WSOC and WIOC, providing a comprehensive view of BrC aerosols.
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Aerosol ammonium (NH4+), mainly produced from the reactions of ammonia (NH3) with acids in the atmosphere, has significant impacts on air pollution, radiative forcing, and human health. Understanding the source and formation mechanism of NH4+ can provide scientific insights into air quality improvements. However, the sources of NH3 in urban areas are not well understood, and few studies focus on NH3/NH4+ at different heights within the atmospheric boundary layer, which hinders a comprehensive understanding of aerosol NH4+. In this study, we perform both field observation and modeling studies (the Community Multiscale Air Quality, CMAQ) to investigate regional NH3 emission sources and vertically resolved NH4+ formation mechanisms during the winter in Beijing. Both stable nitrogen isotope analyses and CMAQ model suggest that combustion-related NH3 emissions, including fossil fuel sources, NH3 slip, and biomass burning, are important sources of aerosol NH4+ with more than 60% contribution occurring on heavily polluted days. In contrast, volatilization-related NH3 sources (livestock breeding, N-fertilizer application, and human waste) are dominant on clean days. Combustion-related NH3 is mostly local from Beijing, and biomass burning is likely an important NH3 source (â¼15%-20%) that was previously overlooked. More effective control strategies such as the two-product (e.g., reducing both SO2 and NH3) control policy should be considered to improve air quality.
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Non-destructive plant stress phenotyping begins with traditional one-dimensional (1D) spectroscopy, followed by two-dimensional (2D) imaging, three-dimensional (3D) or even temporal-three-dimensional (T-3D), spectral-three-dimensional (S-3D), and temporal-spectral-three-dimensional (TS-3D) phenotyping, all of which are aimed at observing subtle changes in plants under stress. However, a comprehensive review that covers all these dimensional types of phenotyping, ordered in a spatial arrangement from 1D to 3D, as well as temporal and spectral dimensions, is lacking. In this review, we look back to the development of data-acquiring techniques for various dimensions of plant stress phenotyping (1D spectroscopy, 2D imaging, 3D phenotyping), as well as their corresponding data-analyzing pipelines (mathematical analysis, machine learning, or deep learning), and look forward to the trends and challenges of high-performance multi-dimension (integrated spatial, temporal, and spectral) phenotyping demands. We hope this article can serve as a reference for implementing various dimensions of non-destructive plant stress phenotyping.
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Salt stress is considered one of the primary threats to cotton production. Although cotton is found to have reasonable salt tolerance, it is sensitive to salt stress during the seedling stage. This research aimed to propose an effective method for rapidly detecting salt stress of cotton seedlings using multicolor fluorescence-multispectral reflectance imaging coupled with deep learning. A prototyping platform that can obtain multicolor fluorescence and multispectral reflectance images synchronously was developed to get different characteristics of each cotton seedling. The experiments revealed that salt stress harmed cotton seedlings with an increase in malondialdehyde and a decrease in chlorophyll content, superoxide dismutase, and catalase after 17 days of salt stress. The Relief algorithm and principal component analysis were introduced to reduce data dimension with the first 9 principal component images (PC1 to PC9) accounting for 95.2% of the original variations. An optimized EfficientNet-B2 (EfficientNet-OB2), purposely used for a fixed resource budget, was established to detect salt stress by optimizing a proportional number of convolution kernels assigned to the first convolution according to the corresponding contributions of PC1 to PC9 images. EfficientNet-OB2 achieved an accuracy of 84.80%, 91.18%, and 95.10% for 5, 10, and 17 days of salt stress, respectively, which outperformed EfficientNet-B2 and EfficientNet-OB4 with higher training speed and fewer parameters. The results demonstrate the potential of combining multicolor fluorescence-multispectral reflectance imaging with the deep learning model EfficientNet-OB2 for salt stress detection of cotton at the seedling stage, which can be further deployed in mobile platforms for high-throughput screening in the field.
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The planting of salt-tolerant plants is regarded as the one of important measurements to improve the saline-alkali lands. The outstanding biological properties of JUNCAOs have made them candidates to improve and utilize saline-alkali lands. At present, little attention has been paid to developing a non-destructive and high throughput approach to evaluate the salt tolerance of JUNCAO. To close the gaps, three typical JUNCAOs (A.donax. No.1, A.donax. No.5 and A.donax. No.10) were evaluated by combining prompt chlorophyll a fluorescence (ChlF) with hyperspectral spectroscopy (HS). The results showed that salt stress reduced relative stem growth, water content, and total chlorophyll content but enhanced the malondialdehyde (MDA) content. It caused a significant change in chlorophyll a fluorescence kinetics with an appearance of L-, K- and J-band, implying damaging energetic connectivity between PSII units, uncoupling of the oxygen evolving complex (OEC) and inhibition of the QA-reoxidation. The negative impact of salt stress on JUNCAOs increased with the increasing level of salt concentration. Effect on spectral reflectance in the in the visible region with shifts on red edge position (REP) and blue edge position (BEP) to shorter wavelength was also found in salt stress plants. Combining principal component analysis (PCA) with the membership function method based on spectral indices and JIP-test parameters could well screen JUNCAOs salt tolerant ability with the highest for A.donax. NO.10 but lowest for A.donax. NO.1, which was the same as that of using conventional approach. The results demonstrate that prompt ChlF coupling with HS could provide potentials for non-invasively and high-throughput phenotyping salt tolerance in JUNCAOs.
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Clorofila , Tolerância ao Sal , Clorofila A , Fluorescência , Clorofila/análise , Estresse Salino , Análise EspectralRESUMO
Forest soils cover about 30 % of the Earth's land surface and play a fundamental role in the global cycle of organic matter. Dissolved organic matter (DOM), the largest active pool of terrestrial carbon, is essential for soil development, microbial metabolism and nutrient cycling. However, forest soil DOM is a highly complex mixture of tens of thousands of individual compounds, which is largely composed of organic matter from primary producers, residues from microbial process and the corresponding chemical reactions. Therefore, we need a detailed picture of molecular composition in forest soil, especially the pattern of large-scale spatial distribution, which can help us understand the role of DOM in the carbon cycle. To explore the spatial and molecular variations of DOM in forest soil, we choose six major forest reserves located in different latitudes ranging in China, which were investigated by Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR MS). Results show that aromatic-like molecules are preferentially enriched in DOM at high latitude forest soils, while aliphatic/peptide-like, carbohydrate-like, and unsaturated hydrocarbon molecules are preferentially enriched in DOM at low latitude forest soils, besides, lignin-like compounds account for the highest proportion in all forest soil DOM. High latitude forest soils have higher aromatic equivalents and aromatic indices than low latitude forest soils, which suggest that organic matter at higher latitude forest soils preferentially contain plant-derived ingredients and are refractory to degradation while microbially derived carbon is dominant in organic matter at low latitudes. Besides, we found that CHO and CHON compounds make up the majority in all forest soil samples. Finally, we visualized the complexity and diversity of soil organic matter molecules through network analysis. Our study provides a molecular-level understanding of forest soil organic matter at large scales, which may contribute to the conservation and utilization of forest resources.
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Organic nitrogen (ON) is an important participant in the Earth's N cycle. Previous studies have shown that penguin feces add an abundance of nutrients including N to the soil, significantly changing the eco-environment in ice-free areas in Antarctica. To explore the molecular transformation of ON in penguin guano-affected soil, we collected guano-free weathered soil, modern guano-affected soil from penguin colonies, ancient guano-affected soil from abandoned penguin colonies, and penguin feces from the Ross Sea region, Antarctica, and Fourier transform ion cyclotron mass spectrometry (FT-ICR MS) was used to investigate the chemical composition of water-extractable ON. By comparing the molecular compositions of ON among different samples, we found that the number of ON compounds (>4,000) in weathered soil is minimal, while carboxylic-rich alicyclic-like molecules (CRAM-like) are dominant. Penguin feces adds ON into the soil with > 10,000 CHON, CHONS and CHN compounds, including CRAM-like, lipid-like, aliphatic/ peptide-like molecules and amines in the guano-affected soil. After the input of penguin feces, macromolecules continue to degrade, and other ON compounds tend to be oxidized into relatively stable CRAM-like molecules, this is an important transformation process of ON in guano-affected soils. We conclude the roles of various forms of ON in the N cycle are complex and diverse. Combined with previous studies, ON eventually turns into inorganic N and is lost from the soil. The lost N ultimately returns to the ocean and the food web, thus completing the N cycle. Our study preliminarily reveals the molecular transformation of ON in penguin guano-affected soil and is important for understanding the N cycle in Antarctica.
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Spheniscidae , Humanos , Animais , Nitrogênio , Regiões Antárticas , Solo/química , AminasRESUMO
Professor CHU Hao-ran believes that the clinical diagnosis and treatment of diarrhea-predominant irritable bowel syndrome with acupuncture and moxibustion should concentrate on the integration of disease and syndrome differentiation. According to the evolution of pathogenesis, this disease is divided into 4 stages, i.e. invasion of exogenous pathogens, liver stagnation and spleen deficiency, spleen and kidney yang deficiency and interaction of cold and heat. Hence, the treatment should be provided by stages. Focusing on regulating the spleen and stomach, a specific acupuncture-moxibustion prescription is proposed, including Tianshu (ST 25), Zhongwan (CV 12), Zusanli (ST 36) and Shangjuxu (ST 37). Additionally, the combination of distal and nearby acupoints is considered and an unique needling manipulation, named the fight between dragon and tiger, is exerted. On the base of syndrome and meridian differentiation, the modern medicine is combined, stressing on the mind regulation and the mutual application of acupuncture and moxibustion in treatment. Eventually, a distinctive treatment system with acupuncture and moxibustion is formed for "regulating the spleen and stomach and differentiating meridians".
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Terapia por Acupuntura , Acupuntura , Síndrome do Intestino Irritável , Meridianos , Moxibustão , Pontos de Acupuntura , Diarreia/etiologia , Diarreia/terapia , Humanos , Síndrome do Intestino Irritável/terapiaRESUMO
Tumor-associated carbohydrate antigen (TACA)-based cancer vaccines achieved promising results, whereas missing the T cell-mediated cellular immune response is still a crucial problem to be solved. Here, we have developed Tn antigen (GalNAc)-modified liposome-encapsulated TLR9 agonist CpG ODN adjuvant as a cancer vaccine. The glyco-liposome vaccines exhibit strong binding ability with an anti-Tn specific antibody and enhance antigen presentation of both bone marrow-derived dendritic cells (BMDCs) and spleen B cells. In vivo immunogenicity studies have demonstrated that the glyco-liposome vaccines can significantly enhance the generation of high anti-Tn antigen antibody titers and further induce a Th1-dependent cellular immune response, evidenced by IFN-γ secretion in an immune coculture of immunized T cells with Tn-expression 4T1 cancer cells. Collectively, our results highlight a liposome-based carbohydrate vaccine as a promising platform, which can simultaneously elicit both humoral and cellular antitumor immunity.
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Vacinas Anticâncer , Lipossomos , Adjuvantes Imunológicos , Carboidratos , Imunidade CelularRESUMO
Glycopeptide supramolecular polymers displaying multivalent carbohydrates are particularly suitable for immune-relevant biomaterials, due to the important functions of carbohydrates in mediating cell-cell communication and modulating immune responses. However, the diversity and complexity of carbohydrates limited the generation of glycopeptide supramolecular monomers. Thereby, a modular platform of presenting various carbohydrates, especially more complex oligosaccharides, is highly desirable but remains underexplored. Here, we first prepared the linear amphiphilic glycopeptides that self-assembled into spherical nanoparticles and worm-like nanoparticles. Furthermore, the dendritic glycopeptides that self-assembled into uniform nanorods were designed to generate modular supramolecular polymers with variable functionality, via redesigning the molecular backbone. With various functional oligosaccharide-modified supramolecular polymers, the in vitro studies further indicated that these polymers were not cytotoxic to macrophages, and significantly modulated the production of proinflammatory cytokines. These findings provide a promising platform to develop supramolecular glycopeptide biomaterials with potential applications in immunomodulation and immunotherapy.
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Sulfamethoxazole (SMX) is highly persistent and difficult to remove, making it urgent to find an efficient method for alleviating the enormous environmental pressure of SMX. In this study, sulfide-modified nanoscale zero-valent iron on carbon nanotubes (S-nZVI@CNTs) was prepared to activate peroxydisulfate (PDS) for the degradation of SMX. The results showed that SMX was completely removed within 40 min (kobs=0.1058 min-1) in the S-nZVI@CNTs/PDS system. By analyzing quenching experiments and electron paramagnetic resonance (EPR), singlet oxygen (1O2) was the main active species of the S-nZVI@CNTs/PDS system. 1O2 might be mediated by the abundant carbonyl groups (CO) on carbon nanotubes through spectroscopic analyses. In addition, sulfur doping transitioned the activation pathway to a nonradical pathway. Spectroscopic analyses and electrochemical experiments confirmed that the formation of CNTs-PDS complexes and S-nZVI could promote electron transfer on the catalyst surface. Furthermore, the main degradation intermediates of SMX were identified, and five possible transformation pathways were proposed. The S-nZVI@CNTs/PDS system possessed advantages including high anti-interference (Cl-, NO3-, HA), a strong applicability, recyclability and a low PDS consumption, offering new insight into the degradation of antibiotic wastewater.
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Nanotubos de Carbono , Poluentes Químicos da Água , Transporte de Elétrons , Ferro , Sulfametoxazol , Sulfetos , Poluentes Químicos da Água/análiseRESUMO
Lipids are important biogenic markers to indicate the sources and chemical process of aerosol particles in the atmosphere. To better understand the influences of biogenic and anthropogenic sources on forest aerosols, total suspended particles (TSP) were collected at Mt. Changbai, Shennongjia, and Xishuangbanna that are located at different climatic zones in northeastern, central and southwestern China. n-Alkanes, fatty acids and n-alcohols were detected in the forest aerosols based on gas chromatography-mass spectrometry. The total concentrations of aliphatic compounds ranged from 15.3 ng m-3 to 566 ng m-3, and fatty acids were the most abundant (44-95%) followed by n-alkanes and n-alcohols. Low molecular weight- (LFAs) and unsaturated fatty acids (UnFAs) showed diurnal variation with higher concentrations during the nighttime in summer, indicating the potential impact from microbial activities on forest aerosols. The differences of oleic acid (C18:1) and linoleic acid (C18:2) concentrations between daytime and nighttime increased at lower latitude, indicating more intense photochemical degradation occurred at lower latitude regions. High levels of n-alkanes during daytime in summer with higher values of carbon preference indexes, combining the strong odd carbon number predominance with a maximum at C27 or C29, implied the high contributions of biogenic sources, e.g., higher plant waxes. In contrast, higher concentrations of low molecular weight n-alkanes were detected in winter forest aerosols. Levoglucosan showed a positive correlation (R2 > 0.57) with high- and low molecular weight aliphatic compounds in Mt. Changbai, but such a correlation was not observed in Shennongjia and Xishuangbanna. These results suggest the significant influence of biomass burning in Mt. Changbai, and fossil fuel combustion might be another important anthropogenic source of forest aerosols. This study adds useful information to the current understanding of forest organic aerosols at different geographical locations in China.