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Siloxanes and synthetic musk compounds (SMCs) have been widely used as additives in household and personal care products. Humans are easily exposed to siloxanes and SMCs originating from these products through ingestion and dermal absorption of indoor dust. In the present study, indoor dust samples were analyzed for 19 siloxanes (cyclic and linear) and 12 SMCs (polycyclic, macrocyclic, and nitro musks) to assess their occurrence, time trends over time, source, and health risks. A total of 18 siloxanes and 10 SMCs were detected in all indoor dust samples obtained from 2011â¯2021, indicating widespread and long-term contamination. Higher detection frequencies and concentrations were associated with siloxanes and SMCs with higher use and strong resistance against degradation processes. Indoor dust samples were dominated by linear siloxanes (L11-L13), 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-(g)-2-benzopyran (HHCB), musk ketone (MK), and 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetrahydronaphthalene (AHTN). The frequent use of household and personal care products is likely an important source of siloxane and SMC contamination in indoor environments. The concentrations of siloxanes and SMCs in indoor dust increased from 2011 to 2021, particularly, those of linear siloxanes, reflecting the impact of regulatory actions addressing cyclic siloxanes. The profiles of siloxanes remained stable throughout the study period, whereas those of SMCs shifted from nitro to polycyclic musks. The estimated daily intakes (EDIs) of siloxanes and SMCs arising from ingestion were greater than from dermal absorption of indoor dust. The EDIs of siloxanes and SMCs associated with indoor dust indicated that children are exposed to these pollutants.
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Cosméticos , Siloxanas , Criança , Humanos , Siloxanas/análise , Poeira/análise , República da CoreiaRESUMO
The prevalence of atopic dermatitis (AD), a disease characterized by severe pruritus, immune imbalance, and skin barrier dysfunction, is rapidly increasing worldwide. Deacetylasperulosidic acid (DAA) has anti-atopic activity in the three main cell types associated with AD: keratinocytes, mast cells, and eosinophils. Our study investigated the anti-atopic activity of DAA in 2,4-dinitrochlorobenzene-induced NC/Nga mice. DAA alleviated the symptoms of AD, including infiltration of inflammatory cells (mast cells and eosinophils), epidermal thickness, ear thickness, and scratching behavior. Furthermore, DAA reduced serum IgE, histamine, and IgG1/IgG2a ratio and modulated the levels of AD-related cytokines and chemokines, namely interleukin (IL)-1ß, IL-4, IL-6, IL-9, IL-10, IL-12, tumor necrosis factor-α, interferon-γ, thymic stromal lymphopoietin, thymus and activation-regulated chemokine, macrophage-derived chemokine, and regulated on activation the normal T cell expressed and secreted in the serum. DAA restored immune balance by regulating gene expression and secretion of Th1-, Th2-, Th9-, Th17-, and Th22-mediated inflammatory factors in the dorsal skin and splenocytes and restored skin barrier function by increasing the expression of the pro-filaggrin gene and barrier-related proteins filaggrin, involucrin, and loricrin. These results suggest DAA as a potential therapeutic agent that can alleviate the symptoms of AD by reducing pruritus, modulating immune imbalance, and restoring skin barrier function.
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Dermatite Atópica/induzido quimicamente , Dermatite Atópica/tratamento farmacológico , Dinitroclorobenzeno/efeitos adversos , Imunidade/efeitos dos fármacos , Extratos Vegetais/farmacologia , Prurido/tratamento farmacológico , Pele/efeitos dos fármacos , Animais , Anti-Inflamatórios/farmacologia , Quimiocinas/metabolismo , Dermatite Atópica/metabolismo , Proteínas Filagrinas/metabolismo , Inflamação/tratamento farmacológico , Inflamação/metabolismo , Queratinócitos/efeitos dos fármacos , Queratinócitos/metabolismo , Masculino , Mastócitos/efeitos dos fármacos , Proteínas de Membrana/farmacologia , Camundongos , Precursores de Proteínas/farmacologia , Prurido/metabolismo , Pele/metabolismo , Linfócitos T/efeitos dos fármacos , Linfócitos T/metabolismoRESUMO
The medicinal plant noni (Morinda citrifolia) is widely dispersed throughout Southeast Asia, the Caribbean, and Australia. We previously reported that fermented Noni could alleviate atopic dermatitis (AD) by recovering Th1/Th2 immune balance and enhancing skin barrier function induced by 2,4-dinitrochlorobenzene. Noni has a high deacetylasperulosidic acid (DAA) content, whose concentration further increased in fermented noni as an iridoid constituent. This study aimed to determine the anti-AD effects and mechanisms of DAA on HaCaT, HMC-1, and EOL-1 cells. DAA inhibited the gene expression and secretion of AD-related cytokines and chemokines including interleukin (IL)-1ß, IL-4, IL-6, IL-8, IL-25, IL-33, thymic stromal lymphopoietin, tumor necrosis factor-alpha, monocyte chemoattractant protein-1, thymus and activation-regulated chemokine, macrophage-derived chemokine, and regulated upon activation, normal T cell expressed and secreted, in all cells, and inhibited histamine release in HMC-1 cells. DAA controlled mitogen-activated protein kinase phosphorylation levels and the translocation of nuclear factor-kappa light chain enhancer of activated B cells into the nucleus by inhibiting IκBα decomposition in all the cells. Furthermore, DAA increased the expression of proteins involved in skin barrier functions such as filaggrin and involucrin in HaCaT cells. These results confirmed that DAA could relieve AD by controlling immune balance and recovering skin barrier function.
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Dermatite Atópica/tratamento farmacológico , Glicosídeos/farmacologia , Linhagem Celular , Quimiocinas/imunologia , Quimiocinas/metabolismo , Citocinas/imunologia , Citocinas/metabolismo , Dermatite Atópica/patologia , Eczema/tratamento farmacológico , Eczema/patologia , Proteínas Filagrinas , Glicosídeos/metabolismo , Humanos , Queratinócitos/efeitos dos fármacos , Morinda/metabolismo , Extratos Vegetais/farmacologia , Pele/metabolismo , Equilíbrio Th1-Th2/efeitos dos fármacosRESUMO
Di(2-ethylhexyl) terephthalate (DEHTP) is an alternative plasticizer widely used in numerous consumer products, replacing di(2-ethylhexyl) phthalate (DEHP). Hence, DEHTP has been frequently detected in the environment and humans. As a structural isomer and functional analog of DEHP, DEHTP is a suspected endocrine disruptor. Here, we evaluated thyroid-disrupting effects of DEHTP using embryo-larval and adult male zebrafish. We also investigated its sex hormone disruption potential in the adult zebrafish. After 5- and 7-days of exposure to DEHTP, significant increases in whole-body thyroid hormonal levels were observed in the larval fish. Down-regulation of several thyroid-regulating genes, including trh, tshß, nis, and dio2, was observed, but only after 5-day exposure. Following a 21-day exposure, the adult male zebrafish exhibited a significant decrease in total triiodothyronine and an increase in thyroid-stimulating hormones. Potential changes in the deiodination of thyroid hormones, supported by the up-regulation of two deiodinases, dio1 and dio3a, along with the down-regulation of dio2, could explain the thyroid hormone changes in the adult zebrafish. Moreover, significant trends of decrease in estradiol and 11-ketotestosterone, along with increase of testosterone (T), were observed in the adult zebrafish. Up-regulation of several steroidogenic genes may explain elevated T, while exact mechanisms of action warrant further investigation. Our results demonstrate that DEHTP can cause disruptions of thyroid and sex hormones at different life stages in zebrafish.
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Disruptores Endócrinos , Glândula Tireoide , Hormônios Tireóideos , Peixe-Zebra , Animais , Masculino , Disruptores Endócrinos/toxicidade , Glândula Tireoide/efeitos dos fármacos , Glândula Tireoide/metabolismo , Hormônios Tireóideos/metabolismo , Hormônios Esteroides Gonadais/metabolismo , Plastificantes/toxicidade , Larva/efeitos dos fármacos , Poluentes Químicos da Água/toxicidade , Ácidos Ftálicos/toxicidade , Tri-Iodotironina , Dietilexilftalato/toxicidade , Dietilexilftalato/análogos & derivadosRESUMO
Diisononyl phthalate (DiNP) has been used to replace bis(2-ethylhexyl) phthalate (DEHP) and is frequently found in the environment and humans. DiNP is reported for its anti-androgenic activity; however, little is known about its effects on thyroid function and neurodevelopment. In the present study, the thyroid disruption and neurobehavioral alteration potential of DiNP and its major metabolites were assessed in a rat pituitary carcinoma cell line (GH3) and embryo-larval zebrafish (Danio rerio). In GH3 cells, exposure to DiNP and its metabolites not only increased proliferation but also induced transcriptional changes in several target genes, which were different from those observed with DEHP exposure. In larval fish, a 5-day exposure to DiNP caused significant increases in thyroid hormone levels, following a similar pattern to that reported for DEHP exposure. Following exposure to DiNP, the activity of the larval fish decreased, and neurodevelopment-related genes, such as c-fos, elavl3, and mbp, were down-regulated. These changes are generally similar to those observed for DEHP. Up-regulation of gap43 and down-regulation of elavl3 gene, which are important for both thyroid hormone production and neurodevelopment, respectively, support the potential for both thyroid and behavioral disruption of DiNP. Overall, these results emphasize the need to consider the adverse thyroid and neurodevelopmental effects in developing regulations for DEHP-replacing phthalates.
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Larva , Ácidos Ftálicos , Glândula Tireoide , Hormônios Tireóideos , Peixe-Zebra , Animais , Larva/efeitos dos fármacos , Glândula Tireoide/efeitos dos fármacos , Hormônios Tireóideos/metabolismo , Ratos , Ácidos Ftálicos/toxicidade , Poluentes Químicos da Água/toxicidade , Linhagem Celular Tumoral , Dietilexilftalato/toxicidade , Comportamento Animal/efeitos dos fármacos , Disruptores Endócrinos/toxicidadeRESUMO
Improving the qubit's lifetime (T1) is crucial for fault-tolerant quantum computing. Recent advancements have shown that replacing niobium (Nb) with tantalum (Ta) as the base metal significantly increases T1, likely due to a less lossy native surface oxide. However, understanding the formation mechanism and nature of both surface oxides is still limited. Using aberration-corrected transmission electron microscopy and electron energy loss spectroscopy, we found that Ta surface oxide has fewer suboxides than Nb oxide. We observed an abrupt oxidation state transition from Ta2O5 to Ta, as opposed to the gradual shift from Nb2O5, NbO2, and NbO to Nb, consistent with thermodynamic modeling. Additionally, amorphous Ta2O5 exhibits a closer-to-crystalline bonding nature than Nb2O5, potentially hindering H atomic diffusion toward the oxide/metal interface. Finally, we propose a loss mechanism arising from the transition between two states within the distorted octahedron in an amorphous structure, potentially causing two-level system loss. Our findings offer a deeper understanding of the differences between native amorphous Ta and Nb oxides, providing valuable insights for advancing superconducting qubits through surface oxide engineering.
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Using a monochromator in transmission electron microscopy, a low-energy-loss spectrum can provide inter- and intra-band transition information for nanoscale devices with high energy and spatial resolutions. However, some losses, such as Cherenkov radiation, phonon scattering, and surface plasmon resonance superimposed at zero-loss peak, make it asymmetric. These pose limitations to the direct interpretation of optical properties, such as complex dielectric function and bandgap onset in the raw electron energy-loss spectra. This study demonstrates measuring the dielectric function of germanium telluride using an off-axis electron energy-loss spectroscopy method. The interband transition from the measured complex dielectric function agrees with the calculated band structure of germanium telluride. In addition, we compare the zero-loss subtraction models and propose a reliable routine for bandgap measurement from raw valence electron energy-loss spectra. Using the proposed method, the direct bandgap of germanium telluride thin film was measured from the low-energy-loss spectrum in transmission electron microscopy. The result is in good agreement with the bandgap energy measured using an optical method.
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Reversible conversion over multimillion times in bond types between metavalent and covalent bonds becomes one of the most promising bases for universal memory. As the conversions have been found in metastable states, an extended category of crystal structures from stable states via redistribution of vacancies, research on kinetic behavior of the vacancies is highly in demand. However, it remains lacking due to difficulties with experimental analysis. Herein, the direct observation of the evolution of chemical states of vacancies clarifies the behavior by combining analysis on charge density distribution, electrical conductivity, and crystal structures. Site-switching of vacancies of Sb2Te3 gradually occurs with diverged energy barriers owing to their own activation code: the accumulation of vacancies triggers spontaneous gliding along atomic planes to relieve electrostatic repulsion. Studies on the behavior can be further applied to multiphase superlattices composed of Sb2Te3 (2D) and GeTe (3D) sublayers, which represent superior memory performances, but their operating mechanisms were still under debate due to their complexity. The site-switching is favorable (suppressed) when Te-Te bonds are formed as physisorption (chemisorption) over the interface between Sb2Te3 (2D) and GeTe (3D) sublayers driven by configurational entropic gain (electrostatic enthalpic loss). Depending on the type of interfaces between sublayers, phases of the superlattices are classified into metastable and stable states, where the conversion could only be achieved in the metastable state. From this comprehensive understanding on the operating mechanism via kinetic behaviors of vacancies and the metastability, further studies toward vacancy engineering are expected in versatile materials.
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The incidence of atopic dermatitis (AD), a disease characterized by an abnormal immune balance and skin barrier function, has increased rapidly in developed countries. This study investigated the anti-atopic effect of Lithospermum erythrorhizon (LE) using NC/Nga mice induced by 2,4-dinitrochlorobenzene. LE reduced AD clinical symptoms, including inflammatory cell infiltration, epidermal thickness, ear thickness, and scratching behavior, in the mice. Additionally, LE reduced serum IgE and histamine levels, and restored the T helper (Th) 1/Th2 immune balance through regulation of the IgG1/IgG2a ratio. LE also reduced the levels of AD-related cytokines and chemokines, including interleukin (IL)-1ß, IL-4, IL-6, tumor necrosis factor-α (TNF-α), thymic stromal lymphopoietin, thymus and activation-regulated chemokine, macrophage-derived chemokine, regulated on activation, normal T cell expressed and secreted, and monocyte chemoattractant protein-1 in the serum. Moreover, LE modulated AD-related cytokines and chemokines expressed and secreted by Th1, Th2, Th17, and Th22 cells in the dorsal skin and splenocytes. Furthermore, LE restored skin barrier function by increasing pro-filaggrin gene expression and levels of skin barrier-related proteins filaggrin, involucrin, loricrin, occludin, and zonula occludens-1. These results suggest that LE is a potential therapeutic agent that can alleviate AD by modulating Th1/Th2 immune balance and restoring skin barrier function.
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Dermatite Atópica/tratamento farmacológico , Lithospermum/química , Extratos Vegetais/farmacologia , Pele/efeitos dos fármacos , Pele/patologia , Animais , Benzofuranos/química , Benzofuranos/farmacologia , Citocinas/genética , Citocinas/metabolismo , Depsídeos/química , Depsídeos/farmacologia , Regulação da Expressão Gênica/efeitos dos fármacos , Imunoglobulina G/sangue , Imunoglobulina G/metabolismo , Masculino , Camundongos , Camundongos Endogâmicos , Extratos Vegetais/química , Pele/imunologia , Baço/citologia , Equilíbrio Th1-Th2/efeitos dos fármacosRESUMO
The size of the advanced Cu interconnects has been significantly reduced, reaching the current 7.0 nm node technology and below. With the relentless scaling-down of microelectronic devices, the advanced Cu interconnects thus requires an ultrathin and reliable diffusion barrier layer to prevent Cu diffusion into the surrounding dielectric. In this paper, amorphous carbon (a-C) layers of 0.75-2.5 nm thickness have been studied for use as copper diffusion barriers. The barrier performance and thermal stability of the a-C layers were evaluated by annealing Cu/SiO2/Si metal-oxide-semiconductor (MOS) samples with and without an a-C diffusion barrier at 400 °C for 10 h. Microstructure and elemental analysis performed by transmission electron microscopy (TEM) and secondary ion mass spectroscopy showed that no Cu diffusion into the SiO2 layer occurred in the presence of the a-C barrier layer. However, current density-electric field and capacitance-voltage measurements showed that 0.75 and 2.5 nm thick a-C barriers behave differently because of different microstructures being formed in each thickness after annealing. The presence of the 0.75 nm thick a-C barrier layer considerably improved the reliability of the fabricated MOS samples. In contrast, the reliability of MOS samples with a 2.5 nm thick a-C barrier was degraded by sp2 clustering and microstructural change from amorphous phase to nanocrystalline state during annealing. These results were confirmed by Raman spectroscopy, X-ray photoelectron spectroscopy and TEM analysis. This study provides evidence that an 0.75 nm thick a-C layer is a reliable diffusion barrier.
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Study on recrystallization of deformed metal is important for practical industrial applications. Most of studies about recrystallization behavior focused on the migration of the high-angle grain boundaries, resulting in lack of information of the kinetics of the low angle grain boundary migration. In this study, we focused on the migration of the low angle grain boundaries during recrystallization process. Pure nickel deformed by shot peening which induced plastic deformation at the surface was investigated. The surface of the specimen was prepared by mechanical polishing using diamond slurry and colloidal silica down to 0.02 µm. Sequential heat treatment under a moderate annealing temperature facilitates to observe the migration of low angle grain boundaries. The threshold energy for low angle boundary migration during recrystallization as a function of misorientation angle was evaluated using scanning electron microscopy techniques. A combination of electron channeling contrast imaging and electron backscatter diffraction was used to measure the average dislocation density and a quantitative estimation of the stored energy near the boundary. It was observed that the migration of the low angle grain boundaries during recrystallization was strongly affected by both the stored energy of the deformed matrix and the misorientation angle of the boundary. Through the combination of electron channeling contrast imaging and electron backscatter diffraction, the threshold stored energy for the migration of the low angle grain boundaries was estimated as a function of the boundary misorientation.
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The quantity of the crystalline phases present in a nanomaterial is an important parameter that governs the correlation between its properties and microstructure. However, quantification of crystallinity in nanoscale-level applications by conventional methods (Raman spectroscopy and X-ray diffraction) is difficult because of the spatial limitations of sampling. Therefore, we propose a technique that involves using energy-filtered electron diffraction in transmission electron microscopy which offers improved spatial resolution. The degree of crystallinity (DOC) was calculated by separating the crystalline and amorphous intensities from the total intensity histogram acquired by the azimuthal averaging of the zero-loss filtered signals from electron diffraction. In order to validate the method, it was demonstrated that the DOC calculated by zero-loss filtered electron diffraction was consistent with the DOC measured by the area ratio using an amorphous silicon on crystalline silicon standard sample. In addition, the results obtained from zero-loss filtered and conventional electron diffractions were compared. The zero-loss filtered electron diffraction successfully provided the reliable results of the crystallinity quantification. In contrast, the DOC measured using conventional electron diffraction yielded extremely variable results. Therefore, our results provide a crystallinity quantification technique that can extract quantitative information about crystallinity of nanoscale devices by using zero-loss filtered electron diffraction with better reliability than conventional electron diffraction. RESEARCH HIGHLIGHTS: The degree of crystallinity can be measured by separating the crystalline and amorphous intensities from the total intensity histogram acquired by the azimuthal averaging of the zero-loss filtered signals from selected area electron diffraction.
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An amorphous TaxMnyOz layer with 1.0 nm thickness was studied as an alternative Cu diffusion barrier for advanced interconnect. The thermal and electrical stabilities of the 1.0-nm-thick TaxMnyOz barrier were evaluated by transmission electron microscopy (TEM) and current density-electric field (J-E) and capacitance-voltage (C-V) measurements after annealing at 400 °C for 10 h. X-ray photoelectron spectroscopy revealed the chemical characteristics of the TaxMnyOz layer, and a tape peeling test showed that the TaxMnyOz barrier between the Cu and SiO2 layers provided better adhesion compared to the sample without the barrier. TEM observation and line profiling measurements in energy-dispersive X-ray spectroscopy after thermal annealing revealed that Cu diffusion was prevented by the TaxMnyOz barrier. Also, the J-E and C-V measurements of the fabricated metal-oxide-semiconductor sample showed that the TaxMnyOz barrier significantly improved the electrical stability of the Cu interconnect. Our results indicate that the 1.0-nm-thick TaxMnyOz barrier efficiently prevented Cu diffusion into the SiO2 layer and enhanced the thermal and electrical stability of the Cu interconnect. The improved performance of the TaxMnyOz barrier can be attributed to the microstructural stability achieved by forming ternary Ta-Mn-O film with controlled Ta/Mn atomic ratio. The chemical composition can affect the atomic configuration and density of the Ta-Mn-O film, which are closely related to the diffusion behavior. Therefore, the 1.0-nm-thick amorphous TaxMnyOz barrier is a promising Cu diffusion barrier for advanced interconnect technology.
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Focused ion beam method, which has excellent capabilities such as local deposition and selective etching, is widely used for micro-electromechanical system (MEMS)-based in situ transmission electron microscopy (TEM) sample fabrication. Among the MEMS chips in which one can apply various external stimuli, the electrical MEMS chips require connection between the TEM sample and the electrodes in MEMS chip, and a connected deposition material with low electrical resistance is required to apply the electrical signal. Therefore, in this study, we introduce an optimized condition by comparing the electrical resistance for C-, Pt-, and W- ion beam induced deposition (IBID) at 30 kV and electron beam induced deposition (EBID) at 1 and 5 kV. The W-IBID at 30 kV with the lowest electrical resistance of about 30 Ω shows better electrical properties than C- and Pt-IBID electrodes. The W-EBID at 1 kV has lower electrical resistance than that at 5 kV; thus, confirming its potential as an electrode. Therefore, for the materials that are susceptible to ion beam damage, it is recommended to fabricate electrical connections using W-EBID at 1 kV.