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It is a great demand to develop high-performance electrodes for metal-air batteries to boost cathodic oxygen reduction/evolution dynamics and avoid anodic dendrites. The optimization of catalysis at electrode can be conducted by increasing effective surface exposure, active site density, and unsaturated coordination, via using metal clusters or atomic catalysts, along with conductive or defective supports. Herein, the polarized and synergistic cooperation between dual single atom sites (Fe-N4/Co-N4) are developed through electrolytical exfoliation of defect-enriched π-conjugated macrocyclic polyphthalocyanines to expose more active sites on hollow carbonized shells (HCS). Such FeCo-N4/HCS exhibits outstanding performance in oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), to achieve high-performance in an aqueous zinc battery (AZB) with a high discharge capacity (763.6 mAhg-1) after 750 cycles at 10 mA cm-2, showing stable discharge voltage and excellent durability. It also possesses high performance in a lithium-O2 battery owing to abundant defects, synergistic Fe-N4/Co-N4 active sites, reduced energy barriers, and boosted charge and mass transfer and reaction kinetics. This study provides novel perspectives to expand dual single-metal catalysts on macrocycles in the exploration of efficient, durable, and eco-friendly energy devices.
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In order to study the integration of reticuloendotheliosis virus (REV) in pigeonpox virus (PPV), we collected suspected pigeonpox disease material, amplified the 4b core protein gene of PPV, the gp90 gene of REV, and the integrated sequence fragments from the end of the ORF201 segment of PPV to the beginning of the LTR of REV, and sequenced these genes. The results showed that a 4b core protein fragment of 332 bp was amplified and identified as pigeonpox virus, which was named SX/TY/LTR 01/2023. Sequence analysis showed that the pigeonpox virus isolate belonged to genotype A2, which was the closest to the domestic CVL strain, with a identity of 99.4%. A band of 1191 bp was amplified from the gp90 gene of REV, named SX/TY/PPV-REV01/2023, and sequence analysis indicated that REV belonged to genotype III. The sequence analysis showed that REV belonged to genotype III, and belonged to the same large branch as the domestic isolates JSRD0701 and LNR0801, with 99.3% identity. The integrated sequence fragment was amplified to a band of 637 bp, which determined that the REV sequence was integrated in the PPV rather than a mixed infection of the two viruses. This indicates that REV was integrated in this isolation of PPV, suggesting that pigeon farms need to prevent reticuloendotheliosis at the same time when preventing pigeonpox.
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Two new three-dimensional organic-inorganic hybrid crystalline materials, [(Ade)2 CdCl4] (1) and [(Ade)2 CdBr4] (2), were obtained by the slow evaporation of adenine (Ade) and cadmium chloride in aqueous solution at room temperature with hydrochloric acid and hydrobromic acid used as halogen sources. The structural, thermal, optical, and electrical properties were characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, variable-temperature-variable-frequency dielectric constant analysis, and electrochemical tests. With increasing the substitution of Cl by Br, the composition of the material changed and the space group shifted from P-1 to P21/m, with a significant blue-shift in the fluorescence emission. Changing the temperature induced the deformation of the three-dimensional framework structure formed by hydrogen bonding interactions, leading to dielectric anomalies. Cyclic voltammetry tests showed the good reversibility of the electrolysis process. The structural diversity of the complexes was realized by modulating the halogen composition, and a new method for designing novel organic-inorganic hybrids with controllable photoelectric functionality was proposed.
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Graphene quantum dots (GQDs) possess the photosensitive absorption for photoelectrochemical hydrogen evolution owing to special band structures, whereas they usually confront with photo-corrosion or undesired charge recombination during photoelectrochemical reactions. Hence, we establish the heterojunction between GQDs and MoSe2 sheets via a hydrothermal process for improved stability and performance. Photoanodic water splitting with hydrogen evolution boosted by the heteroatom doped N,S-GQDs/MoSe2 heterojunction has been attained due to the abundant active sites, promoted charge separation and transfer kinetics with reduced energy barriers. Diphasic 1T and 2H MoSe2 sheet-hybridized quantum dots contribute to the Schottky heterojunction, which can play a key role in expedited carrier transport to inhibit accumulative photo-corrosion and increase photocurrent. Heteroatom dopants lead to favored energy band matching, bandgap narrowing, stronger light absorption and high photocurrent density. The external quantum efficiency of the doped heterojunction has been elevated twofold over that of the non-doped pristine heterojunction. Modification of the graphene quantum dots and MoSe2 heterojunction demonstrate a viable and adaptable platform toward photoelectrochemical hydrogen evolution processes.
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Cardiopulmonary bypass (CPB), though indispensable in many cardiac surgery procedures, has several undesirable consequences. The aim of this study was to identify potential genes that may reduce the inflammatory response and complications after CPB. The GSE132176 dataset was selected from the Gene Expression Omnibus (GEO) database and included 10 patients with tetralogy of Fallot and 10 patients with an atrial septal defect who underwent CPB surgery. TSV files were downloaded after GEO2R processing. Protein-protein interaction analysis of common differentially expressed genes (DEGs) was performed using the Search Tool for the Retrieval of Interacting Genes. Gene modules and hub genes were visualized in the protein-protein interaction network using Cytoscape. Enrichment analysis was performed for all important DEGs, modular genes, and hub genes. A total of 72 DEGs were screened, including two functional and one hub gene module. FOS modular genes were primarily enriched in NGF-stimulated transcription, spinal cord injury, and PID AP1 pathway. The ATF3 modular gene was mainly enriched in cytomegalovirus infection and transcriptional misregulation in cancer. Hub gene modules were primarily enriched in the PID AP1 pathway, positive regulation of pri-miRNA transcription by RNA polymerase II, and the PID ATF2 pathway. FOS, JUN, ATF3, and EGR1 were the four most important hub genes; the top three hub genes were involved in the formation of AP-1 and enriched in the AP-1 pathway. Finally, we measured the expression levels of these four genes in patients undergoing CPB via qRT-PCR, and the results were consistent with those obtained in bioinformatic analysis. FOS, JUN, ATF3, and EGR1 and the AP-1 pathway may play key roles in inflammation and complications caused by CPB.
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Biologia Computacional , Perfilação da Expressão Gênica , Ponte Cardiopulmonar/efeitos adversos , Biologia Computacional/métodos , Perfilação da Expressão Gênica/métodos , Humanos , Inflamação/genética , Inflamação/prevenção & controle , Fator de Transcrição AP-1RESUMO
An electromembrane microextraction (EME)-assisted fluorescent molecularly imprinted polymer (MIP) sensing method is presented for detecting the total cathinone drugs in urine samples. In this detection system, the clean-up ability of EME eliminated the matrix effects on both target binding with MIPs and the luminescence of the fluorophore in the sensor. Moreover, by optimizing the extraction conditions of EME, different cathinone drugs with a same concentration show a same response on the single aggregation induced emission (AIE) based MIP (AIE-MIP) sensor (λex = 360 nm, λem = 467 nm). The recoveries were 57.9% for cathinone (CAT) and 78.2% for methcathinone (MCAT). The EME-assisted "light-up" AIE-MIP sensing method displayed excellent performance with a linear range of 2.0-12.0 µmol L-1 and a linear determination coefficient (R2) of 0.99. The limit of detection (LOD) value for EME-assisted "light-up" AIE-MIP sensing method was 0.3 µmol L-1. The relative standard deviation (RSD) values for the detection were found to be within the range 2.0-12.0%. To the best of our knowledge, this is the first time that determination of total illicit drugs with a single fluorescent MIP sensor was achieved and also the first utilization of sample preparation to tune the sensing signal of the sensor to be reported. We believe that this versatile combination of fluorescent MIP sensor and sample preparation can be used as a common protocol for sensing the total amount of a group of analytes in various fields.
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Alcaloides , Impressão Molecular , Corantes , Limite de Detecção , Impressão Molecular/métodos , PolímerosRESUMO
Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO2 reduction reaction (CRR). A heterojunction prototype on Co3 S4 @Co3 O4 core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co3 O4 core and n-type Co3 S4 shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO2 into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations.
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Brønsted acidic ionic liquids (BAILs) can play a dual role, as a solvent and as a catalyst, in many reactions. However, molecular details of the catalytic mechanism are poorly understood. We present here a density functional theory (DFT) study for the catalytic mechanism of the transesterification of methyl ester (ME) with trimethylolpropane (TMP), in the presence of three representative BAILs, namely, N-methylimidazole-IL, pyridinium-IL, and triethylamine-IL. The deprotonation of the BAIL cation and the transesterification step are investigated. Key inter- and intra-molecular hydrogen bonds (HBs) that govern the catalytic performance of BAILs were identified and analyzed using natural bond orbital (NBO) and atoms in molecule (AIM) methods. For the deprotonation of BAILs, it was found that the intermolecular O-HO HB between the hydroxyl group of TMP and the oxygen of the sulfonic group of BAIL was indispensable for proton transfer. DFT computed free energy barriers for the transesterification step are in excellent agreement with the experimental results only after taking into account the BAIL cation-anion interaction in terms of HBs in which the O-HO between the hydroxyl group of the anion and the oxygen of the sulfonic group of the cation was the strongest HB, suggesting the role of the anion in governing the catalytic activity of BAILs. The existence of the HBs suggested by DFT calculations was further validated using in situ FTIR experiments/ATR-FTIR.
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Basilar fractures are one of the consequences of craniocerebral injury, which is serious enough to cause death. Legal examiners often pay attention to basilar fractures at autopsy and analyze the relationship between them and death. It is noteworthy whether the fracture is premortem or postmortem. Here, we describe a rarely reported case of basilar fracture due to freezing. In this case, a 30-year-old man was frozen (-18°C) for 6 months after death. At autopsy, external examination showed no trauma. However, on internal examination, there was a basilar fracture which caused controversy but turned out to be a postmortem injury. We provide the case description and discussion on antemortem or postmortem basilar fractures as a differential for these cases.
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Criopreservação , Fratura da Base do Crânio/etiologia , Adulto , Humanos , Masculino , Mudanças Depois da Morte , Fratura da Base do Crânio/patologiaRESUMO
Carbon nanotubes are promising materials for various applications. In recent years, progress in manufacturing and functionalizing carbon nanotubes has been made to achieve the control of bulk and surface properties including the wettability, acid-base properties, adsorption, electric conductivity and capacitance. In order to gain the optimal benefit of carbon nanotubes, comprehensive understanding on manufacturing and functionalizing carbon nanotubes ought to be systematically developed. This review summarizes methodologies of manufacturing carbon nanotubes via arc discharge, laser ablation and chemical vapor deposition and functionalizing carbon nanotubes through surface oxidation and activation, doping of heteroatoms, halogenation, sulfonation, grafting, polymer coating, noncovalent functionalization and nanoparticle attachment. The characterization techniques detecting the bulk nature and surface properties as well as the effects of various functionalization approaches on modifying the surface properties for specific applications in catalysis including heterogeneous catalysis, photocatalysis, photoelectrocatalysis and electrocatalysis are highlighted.
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Soil potentially toxic elements (PTEs) pollution of contaminated sites has become a global environmental issue. However, given that previous studies mostly focused on pollution assessment in surface soils, the current status and environmental risks of potentially toxic elements in deeper soils remain unclear. The present study aims to cognize distribution characteristics and spatial autocorrelation, pollution levels, and risk assessment in a stereoscopic environment for soil PTEs through 3D visualization techniques. Pollution levels were assessed in an integrated manner by combining the geoaccumulation index (Igeo), the integrated influence index of soil quality (IICQs), and potential ecological hazard index. Results showed that soil environment at the site was seriously threatened by PTEs, and Cu and Cd were ubiquitous and the predominant pollutants in the study area. The stratigraphic models and pollution plume simulation revealed that pollutants show a decreasing trend with the deepening of the soil layer. The ranking of contamination soil volume is as follows: Cu > Cd > Zn > As > Pb > Cr > Ni. According to the IICQs evaluation, this region was subject to multiple PTE contamination, with more than 60% of the area becoming seriously and highly polluted. In addition, the ecological hazard model revealed the existence of substantial ecological hazards in the soils of the site. The integrated potential ecological risk index (RI) indicated that 45.7%, 10.13%, and 4.15% of the stereoscopic areas were in considerable, high, and very high risks, respectively. The findings could be used as a theoretical reference for applying multiple methods to integrate evaluation through 3D visualization analysis in the assessment and remediation of PTE-contaminated soils.
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Monitoramento Ambiental , Metais Pesados , Mineração , Poluentes do Solo , Solo , Poluentes do Solo/análise , Monitoramento Ambiental/métodos , Solo/química , Medição de Risco/métodos , Metais Pesados/análise , Poluição Ambiental/análise , CidadesRESUMO
Objective.Automated segmentation of targets in ultrasound (US) images during US-guided liver surgery holds the potential to assist physicians in fast locating critical areas such as blood vessels and lesions. However, this remains a challenging task primarily due to the image quality issues associated with US, including blurred edges and low contrast. In addition, studies specifically targeting liver segmentation are relatively scarce possibly since studying deep abdominal organs under US is difficult. In this paper, we proposed a network named BAG-Net to address these challenges and achieve accurate segmentation of liver targets with varying morphologies, including lesions and blood vessels.Approach.The BAG-Net was designed with a boundary detection module together with a position module to locate the target, and multiple attention-guided modules combined with the depth supervision strategy to enhance detailed segmentation of the target area.Main Results.Our method was compared to other approaches and demonstrated superior performance on two liver US datasets. Specifically, the method achieved 93.9% precision, 91.2% recall, 92.4% Dice coefficient, and 86.2% IoU to segment the liver tumor. Additionally, we evaluated the capability of our network to segment tumors on the breast US dataset (BUSI), where it also achieved excellent results.Significance.Our proposed method was validated to effectively segment liver targets with diverse morphologies, providing suspicious areas for clinicians to identify lesions or other characteristics. In the clinic, the method is anticipated to improve surgical efficiency during US-guided surgery.
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Fígado , Ultrassonografia Mamária , Feminino , Humanos , Cintilografia , Ultrassonografia , Fígado/diagnóstico por imagem , Fígado/cirurgia , Ultrassonografia de Intervenção , Processamento de Imagem Assistida por ComputadorRESUMO
Styrene-maleic acid (SMA) copolymer has received much attention for its excellent solubilization characteristics. In this work, SMA copolymer brush-based chromatographic stationary phases were exploited and developed for the first time. First, SMA copolymer brush was in situ grown on the surface of spherical silica via living/controlled reversible addition-fragmentation chain transfer (RAFT) polymerization method. Subsequently, as a proof-of-concept demonstration, the copolymer was esterified by diethylene glycol mono-2-ethylhexyl ether (DGME) and 2-(2-ethylhexyloxy) ethanol (EHOE), respectively. The obtained Sil-SMA-DGME and Sil-SMA-EHOE copolymer-brush chromatographic stationary phases were characterized by transmission electron microscopy, Fourier transform infrared spectrometer, X-ray photoelectron spectroscopy, and thermogravimetric analysis, respectively. The chromatographic retention mechanism indicated that both the two packed columns exhibited hydrophilic/reverse mixed-mode retention modes. The maximum column efficiency was up to 71,000 N/m. The chromatographic separation performance evaluation indicated that the novel kind of stationary phases had excellent separation capabilities for hydrophilic, hydrophobic compounds and phospholipid standards. In addition, by combination with mass spectrometry identification, the Sil-SMA-DGME column was further exploited for separation and identification of phospholipids in human lung cancer cells. Totally, 9 classes including 186 phospholipid species were successfully identified. The results demonstrated the promising application prospects of the novel kind of SMA copolymer-brush chromatographic stationary phases.
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Maleatos , Dióxido de Silício , Maleatos/química , Dióxido de Silício/química , Humanos , Interações Hidrofóbicas e Hidrofílicas , Poliestirenos/química , Esterificação , Cromatografia Líquida de Alta Pressão/métodos , Polímeros/químicaRESUMO
Ultrasound-guided percutaneous interventions have numerous advantages over traditional techniques. Accurate needle placement in the target anatomy is crucial for successful intervention, and reliable visual information is essential to achieve this. However, previous studies have revealed several challenges, such as the variability in needle echogenicity and the common misalignment of the ultrasound beam and the needle. Advanced techniques have been developed to optimize needle visualization, including hardware-based and image-processing-based methods. This paper proposes a novel strategy of integrating ultrasound-based deep learning approaches into an optical navigation system to enhance needle visualization and improve tip positioning accuracy. Both the tracking and detection algorithms are optimized utilizing optical tracking information. The information is introduced into the tracking network to define the search patch update strategy and form a trajectory reference to correct tracking results. In the detection network, the original image is processed according to the needle insertion position and current position given by the optical localization system to locate a coarse region, and the depth-score criterion is adopted to optimize detection results. Extensive experiments demonstrate that our approach achieves promising tip tracking and detection performance with tip localization errors of 1.11 ± 0.59 mm and 1.17 ± 0.70 mm, respectively. Moreover, we establish a paired dataset consisting of ultrasound images and their corresponding spatial tip coordinates acquired from the optical tracking system and conduct real puncture experiments to verify the effectiveness of the proposed methods. Our approach significantly improves needle visualization and provides physicians with visual guidance for posture adjustment.
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Algoritmos , Aprendizado Profundo , Processamento de Imagem Assistida por Computador , Agulhas , Ultrassonografia de Intervenção , Humanos , Ultrassonografia de Intervenção/métodos , Processamento de Imagem Assistida por Computador/métodos , Cirurgia Assistida por Computador/métodosRESUMO
Revealing the spatiotemporal (ST) distribution and changes in regional soil heavy metals is significant to soil pollution control and management. However, most of the ST analysis models in the existing studies ignore the uncertainty of ST changes in soil heavy metals, making their results unreliable. In this study, using soil Pb collected from 2016 to 2019 in a mining city in China as case data, an ST sequential Gaussian simulation (STSGS) is proposed to reveal the ST distribution and variation in heavy metals in regional soils and their uncertainties. Firstly, the ST variogram was analysed and fitted using a theoretical variogram model integrating the experimental variations at the ST scale. Secondly, 500 simulation realisations with random access path were generated by the ST Kriging method. Considering the obtained 500 simulation realisations, a series of ST analysis methods was proposed and employed to reveal the ST distribution and changes with uncertainty assessment of regional soil heavy metals. The main results are as follows. (1) For the whole study region, soil Pb content initially increased and then decreased from 2016 to 2019. The average probability of soil Pb exceeding 90 mg/kg was 0.121, 0.214, 0.312 and 0.291 in 2016, 2017, 2018 and 2019, respectively, whereas the average probability of always exceeding 90 mg/kg in the 4 years was only 0.032. (2) From 2016 to 2019, the area proportions of the increase and decrease of soil Pb content in the study area were 87.2% and 12.8%, respectively. However, according to the standardised statistic, only 0.161% and 8.72% of the total areas were determined to have a significant decrease and increase in soil Pb content from 2016 to 2019. (3) From 2016 to 2019, the areas with a greater than 0.6 probability of soil Pb concentration decreasing by more than 5 mg/kg and increasing by more than 20, 40 and 80 mg/kg accounted for 4.96%, 32.2%, 11.5% and only 1.91% of the total study region, respectively. The incremental high-probability areas were primarily those where Pb pollution was already serious. Finally, the advantages of the proposed STSGS method were summarised.
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Metais Pesados , Poluentes do Solo , Solo , Incerteza , Chumbo/análise , Poluentes do Solo/análise , Monitoramento Ambiental/métodos , Metais Pesados/análise , China , Medição de RiscoRESUMO
As an important component of bike-sharing (BS) users, the travel behavior of college students and office workers is important to the promotion of BS within Chinese cities. To explore the influencing factors for the behavioral intentions of BS, this paper makes a different analysis between the two groups. Based on the theory of planned behavior, and using environmental awareness as an extended variable, a BS travel intention model was developed. A total of 676 valid questionnaires were collected and analyzed from college students and office workers in Zhengzhou. The results indicate that attitude, subjective norms, perceived behavior control, and environmental awareness have a positive impact on the behavioral intentions of BS. However, the influence degree of each variable is different between the two groups. Perceived behavior control, including travel time, travel cost, and cycling difficulty, has the greatest impact on BS behavioral intention for college students. Meanwhile, subjective norms, including policy and media publicity, has the most significant impact on BS behavioral intention for office workers. The impact of environmental awareness on college students' use of BS is higher than that of office workers. We also found that undergraduates use BS more frequently than postgraduates. The findings provide the clear influence factors on behavioral intentions of BS between college students and office workers, that can help policy optimization in terms of bike-sharing systems, giving some suggestion for an approach devoted to deepen the individual-context interactions.
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Microneedles (MNs) have drawn rising attention owing to their merits of convenience, noninvasiveness, flexible applicability, painless microchannels with boosted metabolism, and precisely tailored multifunction control. MNs can be modified to serve as novel transdermal drug delivery, which conventionally confront with the penetration barrier caused by skin stratum corneum. The micrometer-sized needles create channels through stratum corneum, enabling efficient drug delivery to the dermis for gratifying efficacy. Then, incorporating photosensitizer or photothermal agents into MNs can conduct photodynamic or photothermal therapy, respectively. Besides, health monitoring and medical detection by MN sensors can extract information from skin interstitial fluid and other biochemical/electronic signals. Here, this review discloses a novel monitoring, diagnostic, and therapeutic pattern by MNs, with elaborate discussion about the classified formation of MNs together with various applications and inherent mechanism. Hereby, multifunction development and outlook from biomedical/nanotechnology/photoelectric/devices/informatics to multidisciplinary applications are provided. Programmable intelligent MNs enable logic encoding of diverse monitoring and treatment pathways to extract signals, optimize the therapy efficacy, real-time monitoring, remote control, and drug screening, and take instant treatment.
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The development of graphene promotes the research of similar two-dimensional (2D) materials, especially 2D transition metal dichalcogenides (TMDCs) with semiconductor properties. Monolayer or few-layer TMDCs have several advantages, such as direct band gap, weak interlayer van der Waals force, large interlayer spacing, and abundant marginal active sites, which make them widely used in catalysis, optoelectronics, as well as energy conversion and storage devices. In addition, transition metal diselenides (TMDSs) also possess many intriguing characteristics. For instance, transition metal diselenides (e.g., MoSe2) have a more stable 1T phase, larger interlayer spacing, smaller band gap, and more obvious metallic property of Se than TMDCs (e.g., MoS2). Thus, it has become one of the most attractive research topics branching out from TMDCs. Herein, this review unveils the structures, synthesis, properties, modifications, applications, and perspectives for TMDSs.
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People's perceptions and understanding of the built environment can shape and regulate travel intention and behavior. From the perspective of urban design, improving the built urban environment is an important way to encourage green travel. This study determined the impact path from the built environment to subway travel behavior, considering the intermediate effect of psychological factors. The impact path could provide feedback for optimizing the built environment, thereby improving the ratio of subway travel. In this study, the impact path hypothesis of "objective environment-subjective psychological-travel behavior" was first proposed, taking travelers' psychological perceptions as the intermediary variable. Second, questionnaires and geographic information were used to measure the objective environment and subjective psychological perceptions. Third, a structural equation model was constructed to verify the proposed path hypothesis. Finally, multiscale geographically weighted regression was used to analyze the influence of subjective and objective factors on travel behavior and its spatial differences. The empirical case sampled 405 residents of Zhengzhou, China. The results verified the proposed impact path hypothesis and revealed spatial heterogeneity in its impact on travel behavior. The research explains how travel behavior is generated and could support the optimization of the urban built environment.