RESUMO
Glass metal-organic framework (MOF) films can be fabricated from their crystalline counterparts through a melt-quenching process and are prospective candidates for gas separation because of the elimination of the grain boundaries in crystalline MOF films. However, current techniques are limited to producing glass MOF films with a thickness of tens of micrometers, which leads to ultralow gas permeances. Here, we report a novel cathodic deposition-assisted synthesis of glass ZIF-62 films with a thickness as low as ~1â µm. Electrochemical analyses and deposition experiments suggest that the cathodic deposition can lead to pure crystalline ZIF-62 films with a controllable thickness of ~2â µm to ~15â µm. Accordingly, glass ZIF-62 films with a thickness of ~1â µm to ~10â µm can be obtained after a thermal treatment. The fabricated defect-free glass ZIF-62 film measuring 2â µm in thickness shows a remarkable CO2/N2 and CO2/CH4 selectivity of 31.4 and 33.4, respectively, with a CO2 permeance which is over 30 times higher than the best-performing glass ZIF-62 films in literature.
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The deposition of metal-organic framework (MOF) films with defined exposed facets is important to enhance the performance of these films for, for example, catalysis or separations. In this work, MOF films with specific exposed facets are electrodeposited anodically on various substrates (e. g. on copper-sputtered Si wafers, copper meshes, copper foams, and polypropylene membranes). The influence of the deposition parameters, including the pH of the solution, current density, concentration of linker, and solvent, on the exposed facets of the deposited MOFs was investigated. The results suggest that precise control over the supersaturation during anodic deposition is a possible strategy for synthesizing MOF crystals with well-defined exposed facets. This approach provides a powerful toolbox for various applications requiring crystal facet control of MOF films.
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Dioxins and the emerging dioxin-like compounds (DLCs) have recruited increasing concerns about their environmental contamination, toxicity, health impacts, and mechanisms. Based on the structural similarity of dioxins and many DLCs, their toxicity was predominantly mediated by the dioxin receptor (aryl hydrocarbon receptor, AHR) in animals (including human), which can be different in expression and function among species and then possibly produce the species-specific risk or toxicity. To date, characterizing the AHR of additional species other than human and rodents can increase the accuracy of toxicity/risk evaluation and increase knowledge about AHR biology. As a key model, the medaka AHR has not been clearly characterized. Through genome survey and phylogenetic analysis, we identified four AHRs (olaAHR1a, olaAHR1b, olaAHR2a, and olaAHR2b) and two ARNTs (olaARNT1 and olaARNT2). The medaka AHR pathway was conserved in expression in nine tested tissues, of which olaAHR2a represented the predominant subform with greater abundance. Medaka AHRs and ARNTs were functional and could be efficiently transactivated by the classical dioxin congener 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), although olaAHR1a did not seem to cooperate with olaARNT2. In terms of function/sensitivity, the EC50 values of medaka olaAHR1a (9.01 ± 1.43 nM), olaAHR1b (4.00 ± 1.10 nM), olaAHR2a (8.75 ± 3.34 nM), and olaAHR2b (3.06 ± 0.81 nM) showed slight differences; however, they were all at the nM level. The sensitivity of four medaka AHRs to TCDD was similar to that of zebrafish dreAHR2 (the dominant form, EC50 = 3.14 ± 4.19 nM), but these medaka AHRs were more sensitive than zebrafish dreAHR1b (EC50 = 27.05 ± 18.51 nM). The additional comparison also indicated that the EC50 values in various species were usually within the nM range, but AHRs of certain subforms/species can vary by one or two orders of magnitude. In summary, the present study will enhance the understanding of AHR and help improve research on the ecotoxicity of dioxins/DLCs.
Assuntos
Dioxinas , Oryzias , Receptores de Hidrocarboneto Arílico , Poluentes Químicos da Água , Peixe-Zebra , Animais , Receptores de Hidrocarboneto Arílico/metabolismo , Receptores de Hidrocarboneto Arílico/genética , Dioxinas/toxicidade , Poluentes Químicos da Água/toxicidade , Filogenia , Especificidade da EspécieRESUMO
For wearable electronics, radial scalability is one of the key research areas for fibrous energy storage devices to be commercialized, but this field has been shelved for years due to the lack of effective methods and configuration arrangements. Here, the team presents a generalizable strategy to realize radial scalability by applying a synchronous-twisting method (STM) for synthesizing a coaxial-extensible configuration (CEC). As examples, aqueous fiber-shaped Zn-MnO2 batteries and MoS2-MnO2 supercapacitors with a diameter of ~500 µm and a length of 100 cm were made. Because of the radial scalability, uniform current distribution, and stable binding force in CEC, the devices not only have high energy densities (~316 Wh liter-1 for Zn-MnO2 batteries and ~107 Wh liter-1 for MoS2-MnO2 supercapacitors) but also maintain a stable operational state in textiles when external bending and tensile forces were applied. The fabricating method together with the radial scalability of the devices provides a reference for future fiber-shaped energy storage devices.
RESUMO
Tetrabromobisphenol A (TBBPA) is a widely used plastic additive with high bioaccumulation potential and toxicity on both humans and wildlife. Currently, research on its ecotoxicity and the underlying mechanism is limited. Using common carp (Cyprinus carpio), we evaluated the toxicity of TBBPA, especially focusing on its alteration of a key metabolism-related pathway aryl hydrocarbon receptor (AHR), using in vivo/vitro assays and in silico simulation. The 96 h LC50 of TBBPA of common carp was 4.2 mg/L and belonged to the acute toxic level II. The bioaccumulation potential of TBBPA follows the role of liver > gill > brain and varies between 3- and 14-day exposure. On the AHR pathway respect, as expected, the metabolism-related cyp1a1 and cyp1b1 were upregulated in the liver and brain. Ahr2, the receptor, was also upregulated in the brain under TBBPA exposure. The alteration of gene expression was tissue-specific while the difference between 3- or 14-day exposure was minor. AHR inhibition assay indicated the 2, 3, 7, 8-tetrachlorodibenzo-p-dioxin (TCDD)-induced AHR transactivation can be inhibited by TBBPA suggesting it is not a potent agonist but a competitive antagonist. In silico analysis indicated TBBPA can be successfully docked into the binding cavity with similar poses but still have AHR-form-specific interactions. Molecular dynamics simulation proved TBBPA can be more flexible than the coplanar ligand TCDD, especially in ccaAHR1b with greater root-mean-square deviation (RMSD), of which TCDD-induced transactivation seemed not to be blocked by TBBPA. This research increased the understanding of TBBPA toxicity and alteration of the AHR pathway, and pointed out the need to perform additional toxicology evaluation of emerging contaminants, especially on non-model species.
Assuntos
Carpas , Dibenzodioxinas Policloradas , Animais , Humanos , Receptores de Hidrocarboneto Arílico/metabolismo , Carpas/metabolismo , Fígado/metabolismo , Dibenzodioxinas Policloradas/metabolismo , Citocromo P-450 CYP1A1/metabolismoRESUMO
Dioxins are widely known to bioaccumulate in the body and produce a wide spectrum of toxic effects on both humans and wildlife. In addition, some novel sorts of compounds that were similar in structure and effect were gradually identified and termed dioxin-like compounds (DLCs). The toxicity of dioxins as well as DLCs is predominantly mediated by the dioxin receptor (aryl hydrocarbon receptor, AHR) in animals, which is usually differentially expressed and functionally distinct (especially the sensitivity to dioxins) among species, possibly resulting in species-specific variations in the toxicity of dioxins. Therefore, detailed functional exploration of the AHRs of a given species, such as the common carp (which is a vital wild and commercial species with a broad geological distribution) in the current study, will enable a comprehensive ecotoxicity evaluation. Through genome survey and phylogenetic analysis, we identified three AHRs (AHR1a, AHR1b, and AHR2) and two ARNTs (ARNT1 and ARNT2). AHR2 was observed to have greater expression abundance in the gill and brain, and may serve as the predominant subform. Those AHRs and ARNTs are functional, and the AHRs can be efficiently transactivated by the classical dioxin congener 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). We individually determined the EC50 values of AHR1a (0.41 ± 0.24 nM), AHR1b (12.80 ± 3.28 nM), and AHR2 (0.64 ± 0.49 nM), and found that: 1) The AHR sensitivities of common carp and zebrafish (phylogenetically close species) are relatively similar. AHR1a and the predominant form AHR2 have greater sensitivity to TCDD. 2) ARNT1 and ARNT2 do not produce different sensitivities, but with distinct induction fold, of a given AHR transactivation when cooperating as the partner; 3) Distinct AHR subforms of the same or distinct species can have even one or two orders of magnitude differences in sensitivity. In summary, the current study will add to the knowledge of AHR biology and help improve ecotoxicology research on dioxins and DLCs.