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Two-dimensional transition metal carbides/nitrides (MXenes) have shown great promise in various applications. However, mass production of MXenes suffers from the excessive use of toxic fluorine-containing reagents. Herein, a new method was validated for synthesizing MXenes from five MAX ceramics. The method features a minimized (stoichiometric) dosage of F-containing reagent (NaBF4) and polyols (glycerol, erythritol, and xylitol) as the reaction solvent. Due to the sweetness of polyols and the low environmental impact, we refer to this method as a "sweet" synthesis of MXenes. An in-depth molecular dynamics simulation study, combined with experimental kinetic parameters, further revealed that the diffusion of F- in the confined interplanar space is rate-determining for the etching reaction. The expansion of interlayer spacing by polyols effectively reduces the diffusion activation energy of F- and accelerates the etching reaction.
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INTRODUCTION: Since the outbreak of COVID-19, microplastics (MPs) and triclosan in pharmaceuticals and personal care products (PPCPs) are markedly rising. MPs and triclosan are co-present in the environment, but their interactions and subsequent implications on the fate of triclosan in plants are not well understood. OBJECTIVE: This study aimed to investigate effects of charged polystyrene microplastics (PS-MPs) on the fate of triclosan in cabbage plants under a hydroponic system. METHODS: 14C-labeling method and liquid chromatography coupled with quadrupole/time-of-flight mass spectrometry (LC-QTOF-MS) analysis were applied to clarify the bioaccumulation, distribution, and metabolism of triclosan in hydroponics-cabbage system. The distribution of differentially charged PS-MPs in cabbage was investigated by confocal laser scanning microscopy and scanning electron microscopy. RESULTS: The results showed that MPs had a significant impact on bioaccumulation and metabolism of triclosan in hydroponics-cabbage system. PS-COO-, PS, and PS-NH3+ MPs decreased the bioaccumulation of triclosan in cabbage by 69.1 %, 81.5 %, and 87.7 %, respectively, in comparison with the non-MP treatment (control). PS-MPs also reduced the translocation of triclosan from the roots to the shoots in cabbage, with a reduction rate of 15.6 %, 28.3 %, and 65.8 % for PS-COO-, PS, and PS-NH3+, respectively. In addition, PS-NH3+ profoundly inhibited the triclosan metabolism pathways such as sulfonation, nitration, and nitrosation in the hydroponics-cabbage system. The above findings might be linked to strong adsorption between PS-NH3+ and triclosan, and PS-NH3+ may also potentially inhibit the growth of cabbage. Specially, the amount of triclosan adsorbed on PS-NH3+ was significantly greater than that on PS and PS-COO-. The cabbage biomass was reduced by 76.9 % in PS-NH3+ groups, in comparison with the control. CONCLUSION: The uptake and transformation of triclosan in hydroponics-cabbage system were significantly inhibited by charged PS-MPs, especially PS-NH3+. This provides new insights into the fate of triclosan and other PPCPs coexisted with microplastics for potential risk assessments.
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Metal-organic frameworks (MOFs), characterized by tunable porosity, high surface area, and diverse chemical compositions, offer unique prospects for applications in optoelectronic devices. However, the prevailing research on thin-film devices utilizing MOFs has predominantly focused on aspects such as information storage and photosensitivity, often neglecting the integration of the advantages inherent in both photonics and electronics to enhance optical memory. This work demonstrates a light-mediated resistive memory device based on a highly oriented porphyrin-based MOFs film, in which the resistance state of the memristor is modulated by light, realizing the integration of the perception and storage of optical information. The memristor shows excellent performance with a wide light range of 405-785 nm and a persistent photoconductivity phenomenon up to 8.3 × 103 s. Further mechanistic studies have revealed that the resistive switching effect in the memristor is primarily associated with the reversible formation and annihilation of Ag conductive filaments.
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Increasing use and release of graphene nanomaterials and pharmaceutical and personal care products (PPCPs) in soil environment have polluted the environment and posed high ecological risks. However, little is understood about the interactive effects and mechanism of graphene on the behaviors of PPCPs in soil. In the present study, the effects of reduced graphene oxide nanomaterials (RGO) on the fate of triclosan in two typical soils (S1: silty loam; S2: silty clay loam) were investigated with 14C-triclosan, high-resolution mass spectrometry, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), density functional theory (DFT) calculations, and microbial community structure analysis. The results showed that RGO prolonged the half-life of triclosan by 23.6-51.3 %, but delayed the formation of transformed products such as methyl triclosan and dechlorinated dimer of triclosan in the two typical soils. Mineralization of triclosan to 14CO2 was inhibited by 48.2-79.3 % in 500 mg kg-1 RGO in comparison with that in the control, whereas the bound residue was 54.2-56.4 % greater than the control. RGO also reduced the relative abundances of triclosan-degrading bacteria (Pseudomonas and Sphingomonas) in soils. Compared to silty loam, RGO more effectively inhibited triclosan degradation in silty clay loam. Furthermore, the DFT calculations suggested a strong association of the adsorption of triclosan on RGO with the van der Waals forces and π-π interactions. These results revealed that RGO inhibited the transformation of 14C-triclosan in soil through strong adsorption and triclosan-degrading bacteria inhibition in soils. Therefore, the presence of RGO may potentially enhance persistence of triclosan in soil. Overall, our study provides valuable insights into the risk assessment of triclosan in the presence of GNs in soil environment.
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Grafite , Nanoestruturas , Poluentes do Solo , Solo , Triclosan , Grafite/química , Solo/química , Microbiologia do Solo , Radioisótopos de CarbonoRESUMO
The aim of this study was to explore the formation of volatile lipid oxidation products by the lipoxygenase (LOX)-hydroperoxide lyase (HPL)-mediated pathway in oat, barley and soy bean. LOX activity was found only in barley and soy bean samples, but the lipase and HPL activity was detected in all samples. HPL showed particularly high activity with 13-hydroperoxides, while the activity was quite low when using 9-hydroperoxides, especially in the oat and barley. The optimum pH for HPL in different samples was similar, i.e., pH 6-7. In this condition, the volatile compounds formed dramatically with aldehydes and furans as the dominant products. Furthermore, a remarkable enzymatic degradation of lipids occurred during the preparation of food models with highly refined rapeseed oil (RO) and rapeseed oil fatty acid (ROFA) emulsions, where the ROFAs were more prone to oxidation than RO. This study shows the significance of lipid-degrading enzymes in plant-food flavour formation.
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Nanoconfined catalysts enhance stabilization of reaction intermediates, facilitate electron transfer, and safeguard active centers, leading to superior electrocatalytic activity, particularly in CO2 reduction reactions (CO2RR). Despite their effectiveness, crafting nanoconfined catalysts is challenging due to unclear formation mechanisms. In this study, we introduce an electrochemical method to grow Pd clusters within the interlayers of two-dimensional black phosphorus, creating Pd cluster-intercalated black phosphorus (Pd-i-BP) as an electrocatalyst. Using in situ electrochemical liquid phase transmission electron microscopy (EC-TEM), we revealed the synthesis mechanism of Pd-i-BP, involving electrochemically driven Pd ion intercalation followed by reduction within the BP layers. The Pd-i-BP electrocatalyst exhibits exemplary CO2-to-formate conversion, achieving 90% Faradaic efficiency for formate production, owing to its distinct nanoconfined structure that stabilizes intermediates and enhances electron transfer. Density functional theory (DFT) calculations underscore the structural benefits for enhancing intermediate adsorption and catalyzing the reaction. Our insights deepen understanding of nanoconfined material synthesis, promising advanced, high-efficiency catalysts.
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Adsorption and activation of C-H bonds by photocatalysts are crucial for the efficient conversion of C-H bonds to produce high-value chemicals. Nevertheless, the delivery of surface-active oxygen species for C-H bond oxygenation inevitably needs to overcome obstacles due to the separated active centers, which suppresses the catalytic efficiency. Herein, Ni dopants are introduced into a monolayer Bi2WO6 to create cascaded active units consisting of unsaturated W atoms and Bi/O frustrated Lewis pairs. Experimental characterizations and density functional theory calculations reveal that these special sites can establish an efficient and controllable C-H bond oxidation process. The activated oxygen species on unsaturated W are readily transferred to the Bi/O sites for C-H bond oxygenation. The catalyst with a Ni mass fraction of 1.8% exhibits excellent toluene conversion rates and high selectivity towards benzaldehyde. This study presents a fascinating strategy for toluene oxidation through the design of efficient cascaded active units.
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Defect engineering has been widely applied in semiconductors to improve photocatalytic properties by altering the surface structures. This study is about the transformation of inactive WO3 nanosheets to a highly effective CO2-to-CH4 conversion photocatalyst by introducing surface-ordered defects in abundance. The nonstoichiometric WO3-x samples were examined by using aberration-corrected electron microscopy. Results unveil abundant surface-ordered terminations derived from the periodic {013} stacking faults with a defect density of 20.2%. The {002} surface-ordered line defects are the active sites for fixation CO2, transforming the inactive WO3 nanosheets into a highly active catalyst (CH4: O2 = 8.2: 16.7 µmol h-1). We believe that the formation of the W-O-C-W-O species is a critical step in the catalytic pathways. This work provides an atomic-level comprehension of the structural defects of catalysts for activating small molecules.
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Little information is known regarding how the lagged pollution of polycyclic aromatic hydrocarbon (PAH) influenced the environment and human health after an e-waste dismantling site was rebuilt. This study investigated the characteristics, sources, and risk assessment of PAHs in a rebuilt e-waste site and its surrounding farmland by analyzing the samples of soil, dust, water, and vegetable. Concentrations of PAHs in soil, vegetable and water in the rebuilt site were relatively higher than in its surrounding farmland. The concentrations in surface soils, soil columns, dust, vegetables, and water varied from 55.4 to 3990 ng g-1, 1.65 to 5060 ng g-1, 2190 to 2420 ng g-1, 2670 to 10,300 ng g-1, and 46.8 to 110 µg L-1 in the e-waste site, respectively. On the farmland, PAH concentrations in surface soils, vegetables, and water ranged from 41.5 to 2760 ng g-1, 506 to 7640 ng g-1, and 56.6 to 89.2 µg L-1, respectively. A higher proportion of high-molecular-weight PAHs (HMW-PAHs) appeared in all multimedia compared with low-molecular-weight PAHs (LMW-PAHs). Diagnostic ratio together with positive matrix factorization (PMF) revealed that vehicle emission was the primary source in this area, and the activity of e-waste disposal was another important source in the rebuilt e-waste site. Based on the deterministic health risks, people working in the reconstructed e-waste site were exposed to low risks, whereas the residents living near the surrounding farmland were exposed to low risk. Sensitivity analyses indicated that exposure frequency and PAH concentrations were the main factors that influenced exposure risk. This study provides valuable insight into the comprehension of the lagging pollution effects of PAH on the environment and human health after the e-waste site was rebuilt.
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Resíduo Eletrônico , Monitoramento Ambiental , Hidrocarbonetos Policíclicos Aromáticos , Poluentes do Solo , Hidrocarbonetos Policíclicos Aromáticos/análise , Medição de Risco , Resíduo Eletrônico/análise , Poluentes do Solo/análise , Humanos , Solo/química , ChinaRESUMO
Materials that can provide reliable electromagnetic interference (EMI) shielding in highly oxidative atmosphere at elevated temperature are indispensable in the fast-developing aerospace field. However, most of conductor-type EMI shielding materials such as metals can hardly withstand the high-temperature oxidation, while the conventional dielectric-type materials cannot offer sufficient shielding efficiency in gigahertz (GHz) frequencies. Here, a highly deficient medium-entropy (ME) perovskite ceramic as an efficient EMI shielding material in harsh environment, is demonstrated. The synergistic effect of entropy stabilization and aliovalent substitution on A-site generate abnormally high concentration of Ti and O vacancies that are stable under high-temperature oxidation. Due to the clustering of vacancies, the highly deficient perovskite ceramic exhibits giant complex permittivity and polarization loss in GHz, leading to the specific EMI shielding effectiveness above 30 dB/mm in X-band even after 100 h of annealing at 1000 °C in air. Along with the low thermal conductivity, the aliovalent ME perovskite can serve as a bifunctional shielding material for applications in aircraft engines and reusable rockets.
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Single-atom catalysis (SAC) attracts wide interest for zinc-air batteries that require high-performance bifunctional electrocatalysts for oxygen reactions. However, catalyst design is still highly challenging because of the insufficient driving force for promoting multiple-electron transfer kinetics. Herein, we report a superstructure-assisted SAC on tungsten carbides for oxygen evolution and reduction reactions. In addition to the usual single atomic sites, strikingly, we reveal the presence of highly ordered Co superstructures in the interfacial region with tungsten carbides that induce internal strain and promote bifunctional catalysis. Theoretical calculations show that the combined effects from superstructures and single atoms strongly reduce the adsorption energy of intermediates and overpotential of both oxygen reactions. The catalyst therefore presented impressive bifunctional activity with an ultralow potential gap of 0.623 V and delivered a high power density of 188.5 mW cm-2 for assembled zinc-air batteries. This work opens up new opportunities for atomic catalysis.
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Hybridizing two heterocomponents to construct a built-in electric field (BIEF) at the interface represents a significant strategy for facilitating charge separation in carbon dioxide (CO2)-photoreduction. However, the unidirectional nature of BIEFs formed by various low-dimensional materials poses challenges in adequately segregating the photogenerated carriers produced in bulk. In this study, leveraging zinc oxide (ZnO) nanodisks, a sulfurization reaction is employed to fabricate Z-scheme ZnO/zinc sulfide (ZnS) heterojunctions featuring a multiple-order BIEF. These heterojunctions reveal distinctive interfacial structures characterized by two semicoherent phase boundaries. The cathodoluminescence 2D maps and density functional theory calculation results demonstrate that the direction of the multiple-order BIEF spans from ZnS to ZnO. This directional alignment significantly fosters the spatial separation of photogenerated electrons and holes within ZnS nanoparticles and enhances CO2-to-carbon monoxide photoreduction performance (3811.7 µmol h-1 g-1). The findings present a novel pathway for structurally designing BIEFs within heterojunctions, while providing fresh insights into the migratory behavior of photogenerated carriers across interfaces.
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Background: Despite the increasing global prevalence of depression, existing treatment methods have limitations. Acupuncture has been recognized for its potential to alleviate various diseases by regulating inflammatory cytokines. However, a comprehensive systematic analysis of the effects of acupuncture on depression through inflammatory cytokines is currently lacking. This review aims to evaluate the impact of acupuncture on inflammatory cytokines in animal models of depression. Methods: A comprehensive search was conducted in PubMed, EMBASE, MEDLINE, and the Research Information Service System to identify studies that met predefined inclusion and exclusion criteria. The quality of each included study was assessed using a 10-item checklist adapted from the Cochrane Collaboration methods and animal data review. Meta-analysis was performed using STATA 17.0 software for literature that met the inclusion criteria. Results: The meta-analysis included a total of 21 studies involving 376 rodents. The overall quality of the included reports was rated as moderate or higher. The results demonstrated that acupuncture had a significant effect on the reduction of pro-inflammatory cytokines, including: IL-1ß [SMD = 3.36, 95% CI (2.73, 4.00), I2 = 73.3%, p < 0.05], IL-6 [SMD = 3.05, 95% CI (2.45, 3.64), I2 = 68%, p < 0.05], and TNF-α [SMD = 3.30, 95% CI (2.53, 4.06), I2 = 74.5%, p < 0.05]. Conversely, acupuncture was associated with an increased expression of anti-inflammatory cytokines, notably: IL-4 [SMD = -1.64, 95% CI (-2.46, -0.82), I2 = 4.1%, p = 0.307] and IL-10 [SMD = -1.45, 95% CI (-2.24, -0.66), I2 = 0, p = 0.678]. These results suggest that acupuncture modulates cytokine levels in depressed rodents, including reducing the expression of pro-inflammatory cytokines and increasing the expression of anti-inflammatory cytokines, thereby regulating the immune-related antidepressant pathway. Conclusion: While this study is limited by the number of included studies, the results suggest that acupuncture may be a viable option for the treatment of depression, and this effect is achieved through the regulation of various inflammatory cytokines. Systematic review registration: This research endeavor was duly registered with PROSPERO (ID: CRD42023420919, https://www.crd.york.ac.uk/PROSPERO/display_record.php?RecordID=420919).
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The rapid increase in the number of older people under the background of population aging has gradually changed the disease spectrum of society, making aging diseases more prevalent, and increasing the demand for health care services, medical and health services, and health insurance among older people, ultimately leading to increasing household and social spending on old age. This study is conducted to assess the impact of those spending burden on the sustainable development of economy and find out some practical and effective solutions. This paper constructs a theoretical model to illustrate the relationship between the old-age dependency ratio and the marginal product of capital (MPK), and then establishes a two-way fixed effect model based on transnational panel data of 81 countries from 1981 to 2017 to verify this relationship empirically. This paper finds that, after controlling a series of variables, an increased burden of old-age dependency leads to a decline in the MPK, a key macroeconomic variable and also a sustainable development criteria, but in which health care, health security systems, and technological innovation play a key and moderating role. The conclusion is also valid after tackling the problem of endogeneity with different methods, like two-stage least squares (TSLS) and the generalized methods of moments (GMM). Overall, before population aging, countries that are old-but-not-rich should encourage more supply-side investments in public health system or technological innovation, and adjust retirement system, or gradually encourage childbearing to strive for time and space for later sustainable development of public health system and economy.
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Administração Financeira , Desenvolvimento Sustentável , Humanos , Idoso , Dinâmica Populacional , Investimentos em Saúde , Características da FamíliaRESUMO
Inspired by the potential of architected materials for achieving biomimicking functionalities and the advancement of multi-material additive manufacturing to fabricate parts with complex structures and heterogeneous material distributions, this study investigates the feasibility of using a multi-material, flexible chain mail sheet for the design of an additively manufactured artificial spinal disc for reproducing patient-specific anisotropic and nonlinear rotational behaviors. The application of a chain mail-based structure is motivated by its similarities in behaviors compared with a natural disc's fiber network that likewise has negligible bending stiffness and shape-changing ability. The proposed approach for the chain mail sheet design includes an initial characterization of the uniaxial tensile responses of the chain mail unit cell defined as the basic building block of the chain mail sheet, modeling and response calculation, and material optimization. Results show that the additively manufactured chain mail sheet is not only able to exhibit a natural strain-stiffening rotational response but also is able to reproduce natural anisotropy of three natural disc specimens in the six most common rotational scenarios in daily life. This study shows the potential of additively manufactured mechanical-metamaterials-inspired structures for implant design to restore natural mechanics.
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X-ray imaging plays an increasingly crucial role in clinical radiography, industrial inspection, and military applications. However, current X-ray imaging technologies have difficulty in protecting against information leakage caused by brute force attacks via trial-and-error. Here high-confidentiality X-ray imaging encryption by fabricating ultralong radioluminescence memory films composed of lanthanide-activated nanoscintillators (NaLuF4 : Gd3+ or Ce3+ ) with imperceptible purely-ultraviolet (UV) emission is reported. Mechanistic investigations unveil that ultralong X-ray memory is attributed to the long-lived trapping of thermalized charge carriers within Frenkel defect states and subsequent slow release in the form of imperceptible radioluminescence. The encrypted X-ray imaging can be securely stored in the memory film for more than 7 days and optically decoded by perovskite nanocrystal. Importantly, this encryption strategy can protect X-ray imaging information against brute force trial-and-error attacks through the perception of lifetime change in the persistent radioluminescence. It is further demonstrated that the as-fabricated flexible memory film enables achieving of 3D X-ray imaging encryption of curved objects with a high spatial resolution of 20 lp/mm and excellent recyclability. This study provides valuable insights into the fundamental understanding of X-ray-to-UV conversion in nanocrystal lattices and opens up a new avenue toward the development of high-confidential 3D X-ray imaging encryption technologies.
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This study investigated the effect of electron beam irradiation (EBI) on the lipid stability of oat and barley during long-term storage. Results showed that the initial free fatty acid content in oat was higher than that in barley. This may mean that lipid hydrolysis started under the function of lipase when oat and barley were milled into flours. Both storage and EBI factors influenced lipid-degrading enzyme activity and promoted lipid oxidation in oat and barley. However, it seemed that storage had higher impacts because the DPPH scavenging activity decreased greatly, and the contents of both malondialdehyde and volatile lipid oxidation products increased in all samples. Thus, the antioxidant capacity and level of lipid oxidation after EBI treatment should be considered when producing oat and barley foods. Overall, this study shows the high potential of EBI for use as a non-thermal technique in stabilising the storage quality of oat and barley.
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Bisphenol S (BPS), being structurally similar to bisphenol A (BPA), has been widely used as an alternative to BPA in industrial applications. However, in-depth studies on the environmental behavior and fate of BPS in various soils have been rarely reported. Here, 14C-labeled BPS was used to investigate its mineralization, bound residues (BRs) formation and extractable residues (ERs) in three soils for 64 days. Significant differences were found in the dissipation rates of BPS in three soils with different pH values. The dissipation of BPS followed pseudo first-order kinetics with half-lives (T1/2) of 15.2 ± 0.1 d, 27.0 ± 0.2 d, 180.4 ± 5.3 d, and 280.5 ± 3.3 d in the alkaline soil (fluvo-aquic soil, FS), the neutral soil (cinnamon soil, CS), the acidic soil (red soil, RS), and sterilized cinnamon soil (CS-S), respectively. The mineralization and BRs formation contributed the most to the dissipation of BPS in soil. BPS was persistent in acidic soil, and may pose a significant threat to plants grown in acidic soils. Additionally, soil microorganisms played a key role in BPS degradation, and the organic matter content might be a major factor that promotes the adsorption and degradation of BPS in soils. Two transformed products, P-hydroxybenzenesulfonic acid and methylated BPS were identified in soils. This study provides new insights into the fate of BPS in various soils, which will be useful for risk assessments of BPS in soil.
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The integration of hydrogen-bonded organic frameworks (HOFs) into electronic devices holds great promise due to their high crystallinity, intrinsic porosity, and easy regeneration. However, despite their potential, the utilization of HOFs in electronic devices remains largely unexplored, primarily due to the challenges associated with fabricating high-quality films. Herein, a controlled synthesis of HOF nanofilms with smooth surface, good crystallinity, and high orientation is achieved using a solution-processed approach. The memristors exhibit outstanding bipolar switching performance with a low set voltage of 0.86 V, excellent retention of 1.64 × 104 s, and operational endurance of 60 cycles. Additionally, these robust memristors display remarkable thermal stability, maintaining their performance even at elevated temperatures of up to 200 °C. More strikingly, scratched HOF films can be readily regenerated through a simple solvent rinsing process, enabling their reuse for the fabrication of new memristors, which is difficult to achieve with traditional resistive switching materials. Additionally, a switching mechanism based on the reversible formation and annihilation of conductive filaments is revealed. This work provides novel and invaluable insights that have a significant impact on advancing the widespread adoption of HOFs as active layers in electronic devices.
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The safety of railway transportation is crucial to social and economic development. Therefore, real-time monitoring of the rail is particularly necessary. The current track circuit structure is complex and costly, posing challenges to monitoring broken tracks using alternative methods. As a non-contact detection technology with a lower environmental impact, electromagnetic ultrasonic transducers (EMATs) have become a concern. However, traditional EMATs have problems such as low conversion efficiency and complex modes, which can limit their effectiveness for long-distance monitoring. Therefore, this study introduces a novel dual-magnet phase-stacked EMAT (DMPS-EMAT) design comprising two magnets and a dual-layer winding coil arrangement. The magnets are positioned at a distance equal to the wavelength of the A0 wave from each other, while the center distance between the two sets of coils beneath the transducer is also equal to the wavelength. After analyzing the dispersion curves of the rail waist, it was determined that the optimal frequency for long-distance rail monitoring is 35 kHz. At this frequency, adjusting the relative positions of the two magnets and the coil directly underneath to be one A0 wavelength can effectively excite a constructive interference A0 wave in the rail waist. The simulation and experimental results show that DMPS-EMAT excited a single-mode A0 wave, resulting in a 1.35-times increase in amplitude.