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Herein, a variety of 2,6-diaminopyridine (DAP) derived nitrogen-doped hierarchically porous carbon (DAP-NHPC-T) prepared from carbonization-induced structure transformation of DAP-Zn-SiO2-P123 nanocomposites are reported, which are facilely prepared from solvent-free co-assembly of block copolymer templates P123 with pyridine-rich monomer of DAP, Zn(NO3)2 and tetramethoxysilane. In the pyrolysis process, P123 and SiO2 templates promote the formation of mesoporous and supermicroporous structures in the DAP-NHPC-T, while high-temperature volatilization of Zn contributed to generation of micropores. The DAP-NHPC-T possess large BET surface areas (≈956-1126 m2 g-1), hierarchical porosity with micro-supermicro-mesoporous feature and high nitrogen contents (≈10.44-5.99 at%) with tunable density of pyridine-based nitrogen sites (≈5.99-3.32 at%), exhibiting good accessibility and reinforced interaction with SO2. Consequently, the DAP-NHPC-T show high SO2 capacity (14.7 mmol g-1, 25 °C and 1.0 bar) and SO2/CO2/N2 IAST selectivities, extraordinary dynamic breakthrough separation efficiency and cycling stability, far beyond any other reported nitrogen-doped metal-free carbon. As verified by in situ spectroscopy and theoretical calculations, the pyridine-based nitrogen sites of the DAP-NHPC-T boost SO2 adsorption via the unique charge transfer, the adsorption mechanism and reaction model have been finally clarified.
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Global climate change and rapid urbanization have resulted in more frequent and intense rainfall events in urban areas, raising concerns about the effectiveness of stormwater bioretention systems. In this study, we optimized the design by constructing a multi-layer filler structure, including plant layer, biochar layer, and pyrite layer, and evaluated its performance in nitrogen (N) and phosphorus (P) removal under different temperatures (5-18 °C and 24-43 °C), rainfall intensity (47.06 mm rainfall depth), and frequency (1-5 days rainfall intervals) conditions. The findings indicate that over 775 days, the plant system consistently removed 62.3% of total nitrogen (TN) and 97.0% of total phosphorus (TP) from 103 intense rainfall events. Temperature fluctuations had minimal impact on nitrate nitrogen (NO3--N) and TP removal, with differences in removal rates of only 1.0% and 0.6%, respectively, among plant groups. Across the multi-layer structure, plant roots mitigated the impact of temperature differences on NO3--N removal, while high-frequency rainfall fluctuated the stability of NO3--N removal. Dense plant roots reinforced N and P removal by facilitating denitrification in the vadose zone (biochar) and strengthening denitrification processes. Biochar and pyrite contributed to stable microenvironments and diverse ecological functions, enhancing NO3--N and PO43- removal. In summary, the synergistic effects of the multi-layer filler structure improved and stabilized N and P removal, providing valuable insights for addressing runoff pollution in bioretention systems amidst rapid urbanization and climate change challenges.
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Selective removal of carbonyl sulfide (COS) and hydrogen sulfide (H2S) is the key step for natural gas desulfurization due to the highly toxic and corrosive features of these gaseous sulfides, and efficient and stable desulfurizers are urgently needed in the industry. Herein, we report a class of nitrogen-functionalized, hierarchically lamellar carbon frameworks (N-HLCF-xs), which are obtained from the structural transformation of Zn zeolitic imidazolate frameworks via controllable carbonization. The N-HLCF-xs possess the desirable characteristics of large Brunauer-Emmett-Teller surface areas (645-923 m2/g), combined primary three-dimensional microporosity and secondary two-dimensional lamellar microstructure, and high density of nitrogen base sites with enhanced pyridine ratio (17.52 wt %, 59.91%). The anchored nitrogen base sites in N-HLCF-xs show improved accessibility, which boosts their interaction with acidic COS and H2S. As expected, N-HLCF-xs can be employed as multifunctional and efficient desulfurizers for selective removal of COS and H2S from natural gas. COS was first transformed into H2S via catalytic hydrolysis, and the produced H2S was then captured and separated and catalyzed oxidation into elemental sulfur. The above continuous processes can be achieved with solo N-HLCF-xs, giving extremely high efficiencies and reusability. Their integrated desulfurization performance was better than many desulfurizers used in the area, such as activated carbon, ß zeolite, MIL-101(Fe), K2CO3/γ-Al2O3, and FeOx/TiO2.
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Efficient catalytic elimination of hydrogen sulfide (H2 S) with high activity and durability in nature gas and blast-furnace gas is very critical for both fundamental catalytic research and applied environmental chemistry. Herein, atomically dispersed Co atom catalysts with Co-N4 sites that can transform H2 S into S with conversion rate of ≈100% are designed and prepared. The representative 4Co-N/NC achieves a sulfur yield of nearly 100% and TOF(Co) of 869 h-1 at 180 °C. Importantly, remarkable long-term durability is achieved as well, with no obvious loss of catalytic activity in the run of 460 h, outperforming most of the reported catalysts. The short bond length and strong cooperation of Co-N are beneficial to improve the structural stability of the Co-N4 centers, and significantly enhanced resistance of water and sulfation over single-atom Co-catalyst. The present mechanism involves the stepwise hydrogen transfer process via the adsorbed *HOO and *HS intermediates.
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Iron-based catalysts have been widely studied for the oxidation of H2 S into elemental S. However, the prevention of iron sites from deactivation remains a big challenge. Herein, a facile copolymerization strategy is proposed for the construction of isolated Fe sites confined in polymeric carbon nitride (CN) (Fe-CNNχ). The as-prepared Fe-CNNχ catalysts possess unique 2D structure as well as electronic property, resulting in enlarged exposure of active sites and enhancement of redox performance. Combining systematic characterizations with density functional theory calculation, it is disclosed that the isolated Fe atoms prefer to occupy four-coordinate doping configurations (Fe-N4 ). Such Fe-N4 centers favor the adsorption and activation of O2 and H2 S. As a consequence, Fe-CNNχ exhibit excellent catalytic activity for the catalytic oxidation of H2 S to S. More importantly, the Fe-CNNχ catalysts are resistant to water and sulfur poisoning, exhibiting outstanding catalytic stability (over 270 h of continuous operation), better than most of the reported catalysts.
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Visible light active and stable nanoporous polymeric base-crystalline TiO2 nanocomposites were solvothermally synthesized from in situ copolymerization of divinylbenzene (DVB) with 1-vinylimidazolate (VI) or 4-vinylpyridine (Py) in the presence of tetrabutyl titanate without the use of any other additives (PDVB-VI-TiO2-x, PDVB-Py-TiO2-x, where x stands for the molar ratio of TiO2 to VI or Py), which showed excellent activity with respect to catalyzing the degradation of organic pollutants of p-nitrophenol (PNP) and rhodamine-B (RhB). TEM and SEM images show that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x have abundant nanopores, and TiO2 nanocrystals with a high degree of crystallinity were homogeneously embedded in the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x, forming a stable 'brick-and-mortar' nanostructure. PDVB-VI and PDVB-Py supports act as the glue linking TiO2 nanocrystals to form nanopores and constraining the agglomeration of TiO2 nanocrystals. XPS spectra show evidence of unique interactions between TiO2 and basic sites in these samples. UV diffuse reflectance shows that PDVB-VI-TiO2-x and PDVB-Py-TiO2-x exhibit a unique response to visible light. Catalytic tests show that the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were active in catalyzing the degradation of PNP and RhB organic pollutants under visible light irradiation. The enhanced activities of the PDVB-VI-TiO2-x and PDVB-Py-TiO2-x were ascribed to synergistic effects between abundant nanopores and the unique optical adsorption of visible light in the samples.
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High-frequency, high-power, and high-speed telecommunication in a complex environment promotes the development of dielectric materials toward a low dielectric constant, low dielectric loss, good thermal properties, and long-term reliability. Here, polyimide/polytetrafluoroethylene (PI/PTFE) nanofiber membranes with an inherent super hydrophobicity, excellent dielectric properties, good thermal stability, and enhanced tensile strength were prepared via a simple electrospinning strategy and an imidization reaction. The obtained PI/PTFE membranes demonstrate a superlow average dielectric constant of 1.22-1.27 and a dielectric loss of 0.032-0.048 in high frequency, together with an enhanced tensile strength, benefiting from the special nanofiber-bead structure formed in the composite membrane. The mixing of polyamic acid (PAA) and PTFE in the electrospinning solution endows the obtained PI/PTFE nanofiber membrane with a uniform distribution of PTFE and thus an inherent superhydrophobicity with a water contact angle of 156.1 and 159.2° for PI/PTFE-30% and PI/PTFE-40%, respectively. Besides, the hydrophobicity could be kept even after standing more than 10,000 water drops, and the thermal properties exhibited promising results with Tmax = 587 °C and Td5% = 423 °C, rendering these PI/PTFE membranes favorable alternatives for prospective telecommunication.
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Bioretention systems are one of the most widely used stormwater control measures for urban runoff treatment. However, stable and effective dissolved nutrient treatment by bioretention systems is often challenged by complicated stormwater conditions. In this study, pyrite-only (PO), pyrite-biochar (PB), pyrite-woodchip (PW), and pyrite-woodchip-biochar mixed (M) bioretention systems were established to study the feasibility of improving both stability and efficiency in bioretention system via multi-media interaction. PB, PW, and M all showed enhanced dissolved nitrogen and/or phosphorus removal compared to PO, with M demonstrating the highest efficiency and stability under different antecedent drying durations (ADD), pollutant levels, and prolonged precipitation depth. The total dissolved nitrogen and dissolved phosphorus removal in M ranged between 64%-86% and 80%-95%, respectively, with limited organic matter and iron leaching. Pore water, microbial community, and material analysis collectively indicate that pyrite, woodchip, and biochar synergistically facilitated multiple nutrient treatment processes and protected each other against by-product leaching. Pyrite-woodchip interaction greatly increased nitrate removal by facilitating mixotrophic denitrification, while biochar further enhanced ammonium adsorption and expanded the denitrification area. The Fe3+ generated by pyrite aerobic oxidation was adsorbed on the biochar surface and potentially formed a Fe-biochar composite layer, which not only reduced Fe3+-induced pyrite excessive oxidation but also potentially increased organic matter adsorption. Fe (oxyhydr)oxides intermediate product formed by pyrite oxidation, in return, controlled the phosphorus and organic matter leaching from biochar and woodchip. Overall, this study demonstrates that multi-media interaction may enable bioretention systems to achieve stable and effective urban runoff treatment.
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Carvão Vegetal , Ferro , Nitrogênio , Sulfetos , Nitrogênio/análise , Fósforo/análise , ChuvaRESUMO
In the last decade human iPSC-derived cardiomyocytes (hiPSC-CMs) proved to be valuable for cardiac disease modeling and cardiac regeneration, yet challenges with scale, quality, inter-batch consistency, and cryopreservation remain, reducing experimental reproducibility and limiting clinical translation. Here, we report a robust cardiac differentiation protocol that uses Wnt modulation and a stirred suspension bioreactor to produce on average 124 million hiPSC-CMs with >90% purity using a variety of hiPSC lines (19 differentiations; 10 iPSC lines). After controlled freeze and thaw, bioreactor-derived CMs (bCMs) showed high viability (>90%), interbatch reproducibility in cellular morphology, function, drug response and ventricular identity, which was further supported by single cell transcriptomes. bCMs on microcontact printed substrates revealed a higher degree of sarcomere maturation and viability during long-term culture compared to monolayer-derived CMs (mCMs). Moreover, functional investigation of bCMs in 3D engineered heart tissues showed earlier and stronger force production during long-term culture, and robust pacing capture up to 4 Hz when compared to mCMs. bCMs derived from this differentiation protocol will expand the applications of hiPSC-CMs by providing a reproducible, scalable, and resource efficient method to generate cardiac cells with well-characterized structural and functional properties superior to standard mCMs.
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Homogeneous catalysts usually show higher catalytic activities than heterogeneous catalysts because of their high dispersion of catalytically active sites. We demonstrate here that heterogeneous catalysts of ionic liquids functionalized on superhydrophobic mesoporous polymers exhibit much higher activities in transesterification to form biodiesel than homogeneous catalysts of the ionic liquids themselves. This phenomenon is strongly related to the unique features of high enrichment and good miscibility of the superhydrophobic mesoporous polymers for the reactants. These features should allow the design and development of a wide variety of catalysts for the conversion of organic compounds.
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Líquidos Iônicos/química , Polímeros/química , Catálise , Domínio Catalítico , Interações Hidrofóbicas e Hidrofílicas , Estrutura Molecular , Porosidade , Propriedades de SuperfícieRESUMO
The relatively small and sole micropores in zeolite catalysts strongly influence the mass transfer and catalytic conversion of bulky molecules. We report here aluminosilicate zeolite ZSM-5 single crystals with b-axis-aligned mesopores, synthesized using a designed cationicamphiphilic copolymer as a mesoscale template. This sample exhibits excellent hydrothermal stability. The orientation of the mesopores was confirmed by scanning and transmission electron microscopy. More importantly, the b-axis-aligned mesoporous ZSM-5 shows much higher catalytic activities for bulky substrate conversion than conventional ZSM-5 and ZSM-5 with randomly oriented mesopores. The combination of good hydrothermal stability with high activities is important for design of novel zeolite catalysts. The b-axis-aligned mesoporous ZSM-5 reported here shows great potential for industrial applications.
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Herein, we develop a low temperature gas template route for in situ growth of highly nitrogen-doped (5.68 wt%), multi-walled carbon nanotubes (N-MWCNTs). The N-MWCNTs exhibit superior sulfur compatibility in hydrogen sulfide (H2S) resource utilization, thus resulting in their enhanced functionality as Li-S cathodes with high sulfur-specific capacity and retention rate.
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Metal-organic frameworks (MOFs) are regarded as the next-generation, disruptive membrane materials, yet the straightforward fabrication of ultrathin MOF membranes on an unmodified porous support remains a critical challenge. In this work, we proposed a facile, one-step electrophoretic deposition (EPD) method for the growth of ultrathin zeolitic imidazole framework-8 (ZIF-8) membranes on a bare porous support. The crystallinity, morphology and coverage of ZIF-8 particles on support surface can be optimized via regulating EPD parameters, yet it is still difficult to ensure the integrity of a ZIF-8 membrane with the constant voltage mode. In contrast, the constant current mode is more beneficial to the growth of a defect-free ZIF-8 membrane due to the steady migration rate of colloid particles toward the electrode. With a current of 0.65 mA/cm2 and deposition time of 60 min, a 300 nm thick ZIF-8 membrane was obtained, which exhibits a CO2 permeance of 334 GPU and a CO2/CH4 separation factor of 8.8, evidencing the defect-free structure.
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The development of porous solid adsorbents for selective adsorption and separation of SO2 has attracted much attention recently. Herein, we design porous organic polymers (POPs) decorated with pyridine ligands as building units (POP-Py) through a radical polymerization of the 2,5-divinylpyridine (v-Py) monomer. Due to its high BET surface area, nanoporosity, and excellent stability, the prepared POP-Py can be used for reversible adsorption and efficient separation of SO2. The POP-Py possesses a SO2 capacity of 10.8 mmol g-1 at 298 K and 1.0 bar, which can be well retained after 6 recycles, showing an excellent reversible adsorption capacity. The POP-Py also shows superior separation performance for SO2 from a ternary SO2/CO2/N2 mixture (0.17/15/84.83v%), giving a breakthrough time and a saturated SO2 capacity at 178 min g-1 and 0.4 mmol g-1. The retention time was well maintained even under high moisture conditions, confirming its superior water resistance. Furthermore, when other vinyl-functionalized organic ligand monomers (bipyridine, pyrimidine, and pyrazine) were employed for radical polymerization, all of the resultant porous organic ligand polymers (POP-BPy, POP-PyI, and POP-PyA) exhibited superior performance for reversible adsorption and efficient separation of SO2. The combined features of reversible adsorption, efficient separation, and water resistance are important for the industrial applications of these materials as SO2 adsorbents.
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Polímeros , Água , Adsorção , Ligantes , PorosidadeRESUMO
Micelles with well-defined nanostructures were generally formed in the presence of a suitable solvent. We report herein the accelerated construction of micelles with ordered nanostructures without assistance of additional solvents. The micelles were employed for ultrafast fabrication of ordered mesoporous silicas (OMS) using tetramethyl orthosilicate (TMOS) as silica source. When γ-aminopropyl triethoxysilane precursor was introduced, we obtained amine group (-NH2) decorated ordered mesoporous silicas (OMS-NH2-x, where x stands for the molar ratio of γ-aminopropyl triethoxysilane to TMOS). The resulted materials are large in BET surface area and tunable in content of -NH2 site, which are highly efficient for catalytic elimination of gaseous carbonyl sulfide and hydrogen sulfide. Using this strategy, other functionalized groups such as thiol and benzene can be also introduced into OMS. Furthermore, the introducing of phenolic precursor into the system leads to multiphase co-assembly for the formation of ordered mesoporous silica-polymer nanocomposites. It is demonstrated that the solvent-free ultrafast assembly offers a sustainable route for preparation of ordered mesoporous functional materials.
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The present study aimed to explore the effectiveness of endoscopic submucosal dissection (ESD) in the treatment of early gastric cancer (EGC) and its effect on serum tumor-associated trypsin-2 (TAT-2) and Golgi protein 73 (GP73) expression levels to provide a reference for the treatment of EGC. TAT-2 is a proteolytic target enzyme for tumor-associated trypsin inhibitor that has been previously reported to enhance invasion by promoting extracellular matrix degradation. GP73 is a novel type II Golgi membrane protein of unknown function that is expressed in the hepatocytes of patients with adult giant-cell hepatitis. A total of 161 patients with EGC treated at our hospital from April 2013 to February 2014 were selected as the study subjects. Among these, 86 patients underwent ESD (group A) and the remaining 75 underwent endoscopic mucosal resection (group B). Treatment effectiveness, incidence of complications and adverse reactions, operation time, intraoperative blood loss and length of hospital stay, as well as serum TAT-2 and GP73 expression levels, were compared between the two groups. The treatment effectiveness was significantly higher in group A than in group B (P<0.05). However, there was no significant inter-group difference in terms of incidence of complications/adverse reactions (P>0.05). After treatment, serum TAT-2 expression levels decreased in both groups (P<0.05) and serum TAT-2 expression levels were lower in group A than in group B (P<0.05). Furthermore, serum GP73 expression levels were significantly elevated in both groups (P<0.05). Kaplan-Meier survival analysis indicated no significant inter-group difference in the 5-year survival rate (P>0.05). In conclusion, ESD had a good therapeutic effect on EGC and is able to decrease serum TAT-2 expression levels and increase serum GP73 expression levels. The present study was registered into the Chinese Trials Registry (registration no. NCT02157534).
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In the present work, we report a facile oxalate-derived hydrothermal method to fabricate α-, ß- and δ-MnO2 catalysts with hierarchically porous structure and study the phase-dependent behavior for selective oxidation of H2S over MnO2 catalysts. It was disclosed that the oxygen vacancy, reducibility and acid property of MnO2 are essentially determined by the crystalline phase. Systematic experiments demonstrate that δ-MnO2 is superior in active oxygen species, activation energy and H2S adsorption capacity among the prepared catalysts. As a consequence, δ-MnO2 nanosphere with a hierarchically porous structure shows high activity and stability with almost 100% H2S conversion and sulfur selectivity at 210⯰C, better than majority of reported Mn-based materials. Meanwhile, hierarchically porous structure of δ-MnO2 nanosphere alleviates the generation of by-product SO2 and sulfate, promoting the adoptability of Mn-based catalysts in industrial applications.
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As a highly toxic and corrosive waste gas in the industry, hydrogen sulfide (H2S) usually originates from the utilization of coal, petroleum, and natural gas. The selective catalytic elimination of H2S shows great significance to ensure the safety of industrial processes and health of human beings. Herein, we report efficiently selective oxidation of H2S to elemental sulfur over covalent triazine framework (CTF-1-x, x = 400, 500, 600, 400-600 °C) catalysts. CTF-1-x samples were prepared from polymerization of 1,4-dicyanobenzene to form polyaryl triazine networks under ion solidothermal conditions in the presence of ZnCl2, which acts as both an initiator and a porogen. The resultant CTF-1-x samples possess abundant micro-mesoporosity, large Brunauer-Emmett-Teller (BET) surface areas, and tunable structural base sites with edge amine and graphitic nitrogen characteristics, which were homogeneously decorated onto their frameworks. As a result, CTF-1-x samples act as efficient and long-lived catalysts in selective oxidation of H2S to sulfur under ambient conditions (100% H2S conversion, 100% sulfur selectivity at 180 °C, 12â¯000 mL/(g·h)), and their activities were superior to those of commercial Fe2O3 and g-C3N4 desulfurization catalysts. Abundant nitrogen structural base sites of CTF-1-x effectively activate the reactants, and abundant micro-mesoporosity facilitates mass transfer in and out of CTF-1-x. The improved design of the nitrogen-doped carbon material for H2S activation and conversion could enhance the development of more active and robust nitrogen-doped carbon catalysts.
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BACKGROUND: The cAMP response element-binding protein 1 (CREB1) was initiated as a potential target for cancer treatment. This research was conducted to probe the effect of CREB1 in the progression of gastric cancer (GC) and the molecules involved. MATERIALS AND METHODS: CREB1 expression in GC tissues and cell lines (AGS and MKN-45) as well as that in normal tissues and in gastric mucosa cell line (GES-1) was detected. The correlation between CREB1 expression and prognosis of GC patients was determined. Artificial silencing of CREB1 was introduced to evaluate its effect on biological behaviors of GC cells. The target microRNA (miRNA) of CREB1 and the target mRNA of miR-186 were predicted and validated. Altered expression of miR-186, KRT8 and HIF-1α was introduced to confirm their functions in GC progression. RESULTS: CREB1 was abundantly expressed in GC tissues and cells and linked to dismal prognosis in patients. Silencing of CREB1 or upregulation of miR-186 suppressed the malignant behaviors such as growth, epithelial-mesenchymal transition (EMT) and invasion of GC cells, while artificial overexpression of KRT8 led to reversed trends. KRT8 was a target mRNA of miR-186, and CREB1 transcriptionally suppressed miR-186 expression to further up-regulate KRT8. KRT8 was also found to increase HIF-1α expression. Upregulation of HIF-1α was found to block the suppressing role of CREB1 silencing in GC cell malignancy. CONCLUSION: This study evidenced that silencing of CREB1 inhibits growth, invasion, EMT and resistance to apoptosis of GC cells involving the upregulation of miR-186 and the following downregulation of KRT8 and HIF-1α.
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The development of highly efficient oxygen reduction reaction (ORR) catalysts is of great significance for the large-scale commercialization of fuel cells. In this work, honeycomb-like Fe-N co-doped porous carbon materials (Fe-N-PC) were prepared through a facile one-step pyrolysis strategy using soybean straw biomass as the precursor. The obtained Fe-N-PC catalyst exhibits excellent ORR performance with an onset potential of 0.989 V and a half-wave potential of 0.854 V in alkaline conditions, which positively shift only by 5 mV and 27 mV, respectively than those of the commercial Pt/C catalyst. Furthermore, the onset potential and the half-wave potential of the Fe-N-PC catalysts are up to 0.886 V and 0.754 V, respectively, under acidic conditions, which are superior to those of many other Fe, N-doped electrocatalysts. The ORR process can be regarded as a four-electron transfer process based on RRDE measurements. Moreover, the Fe-N-PC catalyst also shows greater stability and satisfactory methanol tolerance than the Pt/C catalyst. The superior electrocatalytic performance of Fe-N-PC may be attributed to the abundant nanoporous structure, large BET surface area, and Fe-N co-doping, which provide abundant and highly efficient active sites.