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1.
J Am Chem Soc ; 2024 Jun 10.
Artigo em Inglês | MEDLINE | ID: mdl-38859682

RESUMO

The selective splitting of hexane isomers without the use of energy-intensive phase-change processes is essential for the low-carbon production of clean fuels and also very challenging. Here, we demonstrate a strategy to achieve a complete splitting of the high-RON dibranched isomer from the monobranched and linear isomers, by using a nonlinear 3D ligand to form pillar-layered MOFs with delicate pore architecture and chemistry. Compared with its isoreticular MOFs with the same ted pillar but different linear 3D or linear 2D in-layer ligands, the new MOF constructed in this work, Cu(bhdc)(ted)0.5 (ZUL-C5), exhibited an interesting "channel switch" effect which creates pore space with reduced window size and channel dimensionality together with unevenly distributed alkyl-rich adsorption sites, contributing to a greatly enhanced ability to discriminate between mono- and dibranched isomers. Evidenced by a series of studies including adsorption equilibrium/kinetics/breakthrough tests, guest-loaded single-crystal/powder XRD measurement, and DFT-D modeling, a thermodynamic-kinetic synergistic mechanism in the separation was proposed, resulting in a record production time for high-purity 2,2-dimethylbutane along with a high yield.

2.
J Am Chem Soc ; 145(16): 9254-9263, 2023 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-37053465

RESUMO

Developing adsorbents with multiple merits in capacity, selectivity, mass transfer, and stability toward C2H2/CO2 separation is crucial and challenging for producing high-purity C2H2 for advanced polymers and the electronic industry. Here, we demonstrate a vertex strategy to create adsorbents combining these merits through rationally designing the vertex groups of a wavy-shaped framework in layered 2D metal-organic frameworks (MOFs) to finely regulate the local conformation and stacking interactions, which creates the optimal inter- and intralayer space to realize simultaneous improvement of adsorption thermodynamics and kinetics. Two new hydrolytically stable MOFs, ZUL-330 and ZUL-430, were prepared, and diverse experiments and modeling on both adsorption equilibrium and diffusion were performed. Record separation selectivities coupled with extraordinary dynamic C2H2 capacities were achieved for C2H2/CO2 mixtures with different proportions (50/50 or 10/5, v/v), along with a small diffusion barrier and fast mass transfer. Consequently, polymer-grade (99.9%) and electronic-grade (99.99%) C2H2 were obtained with excellent productivities of up to ∼6 mmol cm-3.

3.
J Autoimmun ; 141: 103050, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37120327

RESUMO

OBJECTIVES: To investigate the compositional and functional characteristics of the gut microbiota in primary Sjögren's syndrome (pSS) and compare them with those in systemic lupus erythematosus (SLE). METHODS: Stool samples from 78 treatment-naïve pSS patients and 78 matched healthy controls were detected by shotgun metagenomic sequencing and compared with those from 49 treatment-naïve SLE patients. The virulence loads and mimotopes of the gut microbiota were also assessed by sequence alignment. RESULTS: The gut microbiota of treatment-naïve pSS patients had lower richness and evenness and showed a different community distribution than that of healthy controls. The microbial species enriched in the pSS-associated gut microbiota included Lactobacillus salivarius, Bacteroides fragilis, Ruminococcus gnavus, Clostridium bartlettii, Clostridium bolteae, Veillonella parvula, and Streptococcus parasanguinis. Lactobacillus salivarius was the most discriminating species in the pSS patients, especially in those with interstitial lung disease (ILD). Among the differentiating microbial pathways, the superpathway of l-phenylalanine biosynthesis was also further enriched in pSS complicated with ILD. There were more virulence genes carried by the gut microbiota in pSS patients, most of which encoded peritrichous flagella, fimbriae, or curli fimbriae, three types of bacterial surface organelles involved in bacterial colonization and invasion. Five microbial peptides with the potential to mimic pSS-related autoepitopes were also enriched in the pSS gut. SLE and pSS shared significant gut microbial traits, including community distribution, altered microbial taxonomy and pathways, and enriched virulence genes. However, Ruminococcus torques was depleted in pSS patients but enriched in SLE patients compared to healthy controls. CONCLUSIONS: The gut microbiota in treatment-naïve pSS patients was disturbed and shared significant similarity with that in SLE patients.


Assuntos
Microbioma Gastrointestinal , Doenças Pulmonares Intersticiais , Lúpus Eritematoso Sistêmico , Síndrome de Sjogren , Humanos , Síndrome de Sjogren/genética , Lúpus Eritematoso Sistêmico/complicações , Metagenoma
4.
J Am Chem Soc ; 144(31): 14322-14329, 2022 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-35849509

RESUMO

The fine-tuning of the pore structure of metal-organic frameworks (MOFs) is of critical importance to developing energy-efficient processes for the challenging separation of structurally similar molecules. Herein, we demonstrate a strategy to realize a quasi-three-dimensional refinement of the pore structure that utilizes the tunability of ring size and number in polycycloalkane-dicarboxylate ligands. Two hydrolytically stable MOFs with a confined aliphatic pore environment, ZUL-C1 and ZUL-C2, were, for the first time, synthesized and applied in separating low-concentration C2-C3 hydrocarbons from natural gas and ultralow-concentration Xe from used nuclear fuel (UNF) off-gas. Validated by X-ray diffraction and modeling, an expansion of the polycycloalkane moiety enables sub-angstrom contraction in specific directions and forms a pore surface with more alkyl sites, which affords stronger trapping of guest molecules with relatively higher polarizability. The resultant material exhibits record C2H6/CH4 and C3H8/CH4 selectivities coupled with a benchmark low-pressure C2H6 capacity in alkane mixture separation and also a benchmark Xe capacity at extremely diluted feed concentration and record Kr productivity for the Xe/Kr (20:80, v/v) mixture in Xe/Kr separation.

5.
J Am Chem Soc ; 144(46): 21417-21424, 2022 11 23.
Artigo em Inglês | MEDLINE | ID: mdl-36356164

RESUMO

The separation of C8 aromatics (xylenes and ethylbenzene) remains one of the most challenging industrial separations due to their similar structures and properties. Suitable adsorbents that can distinguish the small differences among isomers are urgently demanded. Herein, we demonstrate a strategy to realize the precise discrimination of C8 aromatics by constructing a nonaromatic confined pore environment with mixed polycycloalkane-type ligands. The nonaromatic low-polar pore environment avoids strong convergent interactions between the framework and the common phenyl rings while creating possibilities to amplify the difference between host-guest/guest-guest interactions regarding the different methyl (ethyl) group positions of isomers. The resultant metal-organic framework, ZUL-C3, with either tetragonal or monoclinic lattice, exhibits outstanding separation performance for C8 aromatics, not only realizing the simultaneous separation of four isomers from each other but also setting a benchmark for the dynamic separation performance of OX/PX and OX/MX.


Assuntos
Estruturas Metalorgânicas , Isomerismo , Xilenos
6.
J Autoimmun ; 134: 102958, 2022 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-36455385

RESUMO

OBJECTIVES: To investigate the compositional and functional characteristics of the gut microbiota in primary Sjögren's syndrome (pSS) and compare them with those in systemic lupus erythematosus (SLE). METHODS: Stool samples from 78 treatment naïve pSS patients and 78 matched healthy controls were detected by shotgun metagenomic sequencing and compared with those from 49 treatment naïve SLE patients. The virulence loads and mimotopes of the gut microbiota were also assessed by sequence alignment. RESULTS: The gut microbiota of treatment naïve pSS patients had lower richness and evenness and showed a different community distribution than that of healthy controls. The microbial species enriched in the pSS-associated gut microbiota included Lactobacillus salivarius, Bacteroides fragilis, Ruminococcus gnavus, Clostridium bartlettii, Clostridium bolteae, Veillonella parvula, and Streptococcus parasanguinis. Lactobacillus salivarius was the most discriminating species in the pSS patients, especially in those with interstitial lung disease (ILD). Among the differentiating microbial pathways, the superpathway of l-phenylalanine biosynthesis was also further enriched in pSS complicated with ILD. There were more virulence genes carried by the gut microbiota in pSS patients, most of which encoded peritrichous flagella, fimbriae, or curli fimbriae, three types of bacterial surface organelles involved in bacterial colonization and invasion. Five microbial peptides with the potential to mimic pSS-related autoepitopes were also enriched in the pSS gut. SLE and pSS shared significant gut microbial traits, including the community distribution, altered microbial taxonomy and pathways, and enriched virulence genes. However, Ruminococcus torques was depleted in pSS patients but enriched in SLE patients compared to that in healthy controls. CONCLUSIONS: The gut microbiota in treatment naïve pSS patients was disturbed and shared significant similarity with that in SLE patients.

7.
Chem Rev ; 120(16): 8814-8933, 2020 08 26.
Artigo em Inglês | MEDLINE | ID: mdl-31967791

RESUMO

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with permanent porosity and highly ordered structures. Unlike other polymers, a significant feature of COFs is that they are structurally predesignable, synthetically controllable, and functionally manageable. In principle, the topological design diagram offers geometric guidance for the structural tiling of extended porous polygons, and the polycondensation reactions provide synthetic ways to construct the predesigned primary and high-order structures. Progress over the past decade in the chemistry of these two aspects undoubtedly established the base of the COF field. By virtue of the availability of organic units and the diversity of topologies and linkages, COFs have emerged as a new field of organic materials that offer a powerful molecular platform for complex structural design and tailor-made functional development. Here we target a comprehensive review of the COF field, provide a historic overview of the chemistry of the COF field, survey the advances in the topology design and synthetic reactions, illustrate the structural features and diversities, scrutinize the development and potential of various functions through elucidating structure-function correlations based on interactions with photons, electrons, holes, spins, ions, and molecules, discuss the key fundamental and challenging issues that need to be addressed, and predict the future directions from chemistry, physics, and materials perspectives.

8.
Chem Soc Rev ; 50(1): 120-242, 2021 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-33283811

RESUMO

Covalent organic frameworks offer a molecular platform for integrating organic units into periodically ordered yet extended two- and three-dimensional polymers to create topologically well-defined polygonal lattices and built-in discrete micropores and/or mesopores. This polymer architecture is unique as it enables predesigning both primary- and high-order structures, greatly enhancing our capabilities of designing organic materials to produce predictable structures and to achieve unique properties and functions. Progress over the past 15 years in the design, synthesis and functional exploration of COFs has successively established the basis of the COF field and COFs have shown the great potential of chemistry in developing a class of amazing organic materials. In this review, we focus on analysing the historic developments of COFs to uncover a full materials and application picture by providing comprehensive yet clear guidance for molecular design, synthetic control and functional exploration. We scrutinise the structural components of COFs including building blocks, reactive sites and functional groups with the aim of finding the origins of structural designability and diversity, as well as multiple functionalities. We disclose strategies for designing and synthesising frameworks to construct various tailor-made interfaces, and for exploring skeletons and pores to design properties and functions. With well-defined skeletons, pores and interfaces that offer a chemical basis to trigger and control interactions with photons, excitons, phonons, polarons, electrons, holes, spins, ions and molecules, we illustrate the current status of our understandings of structure-property correlations, and unveil the principles for establishing a regime to design unique functions that originate from and are inherent to structures. We predict the key central issues in design and synthesis, the challenges in functional design and the future directions from the perspectives of chemistry, physics and materials science.

9.
Angew Chem Int Ed Engl ; 60(35): 19419-19427, 2021 Aug 23.
Artigo em Inglês | MEDLINE | ID: mdl-34143926

RESUMO

The ordered π skeletons of covalent organic frameworks make them viable light-emitting materials but their limited tunability has precluded further implementation. Here we report the synthesis of hydrazone-linked frameworks which are stable in water, acid, and base, and demonstrate their utility as a platform for light emission. The polygonal backbone is designed to be luminescent and partially π conjugated while the pore wall is docked with single atom or unit to induce resonance, hyperconjugation, and tautomerization effects. These effects can be transmitted to the backbone, so that the framework can emit three primary colors of light. The wall can be perturbated with multiple surface sites, rendering the material able to edit diverse emission colors in a predesignable and digital way. The systems show high activity, stability, tunability, and sensibility: a set of features attractive for light-emitting and sensing applications.

10.
J Autoimmun ; 106: 102336, 2020 01.
Artigo em Inglês | MEDLINE | ID: mdl-31601476

RESUMO

Excessive inflammatory cytokines play crucial roles in the pathogenesis of rheumatoid arthritis (RA), however, the underlying mechanism remains unclear. In this study, we demonstrated that pentaxin 3 (PTX3), an essential component of innate immunity, was elevated in RA and preferentially bound to CD14+ monocytes. C1q promoted the binding and resulted in increased cell proliferation, activation and caspase-1-related late apoptotic cells (7-AAD+annexin V+), as well as enhanced release of inflammatory cytokines including TNF-α, IL-1ß and IL-6. Serum from RA patients, compared with healthy controls, induced gasdermin D (GSDMD)-dependent pyroptosis in monocytes, and this ability was associated with disease activity. Moreover, PTX3 synergized with C1q to promote pyroptosis in RA-serum pre-incubated monocytes by coordinately enhancing NLRP3 inflammasome over-activation and inducing GSDMD cleavage, cell swelling with large bubbles, caspase-1-dependent cell death and inflammatory cytokine release including IL-6. On the other hand, IL-6 promoted PTX3 plus C1q-induced pyroptosis in both normal and RA serum pre-incubated monocytes. These findings collectively implicated an important role of IL-6 in driving PTX3 plus C1q-mediated pyroptosis in RA and shed lights on a potential new treatment strategy targeting pyroptosis-mediated persistent inflammatory cytokine release.


Assuntos
Artrite Reumatoide/imunologia , Proteína C-Reativa/imunologia , Complemento C1q/imunologia , Inflamassomos/imunologia , Proteína 3 que Contém Domínio de Pirina da Família NLR/imunologia , Piroptose/imunologia , Componente Amiloide P Sérico/imunologia , Adulto , Idoso , Apoptose/imunologia , Caspase 1/imunologia , Citocinas/imunologia , Feminino , Humanos , Inflamação/imunologia , Receptores de Lipopolissacarídeos/imunologia , Masculino , Pessoa de Meia-Idade , Monócitos/imunologia , Adulto Jovem
11.
Angew Chem Int Ed Engl ; 59(31): 12725-12730, 2020 Jul 27.
Artigo em Inglês | MEDLINE | ID: mdl-32329164

RESUMO

C2 -C3 alkyne/alkene separation is of great importance; however, designing materials for an efficient molecular sieving of alkenes from alkynes remains challenging. Now, two hydrolytically stable layered MOFs, [Cu(dps)2 (GeF6 )] (GeFSIX-dps-Cu, dps=4,4'-dipyridylsulfide) and [Zn(dps)2 (GeF6 )] (GeFSIX-dps-Zn), can achieve almost complete exclusion of both C3 H6 and C2 H4 from their alkyne analogues. GeFSIX-dps-Cu displays a notable advanced threshold pressure for alkynes adsorption and thus substantial uptakes at lower pressures, providing record C3 H4 /C3 H6 uptake ratios and capacity-enhanced C2 H2 /C2 H4 sieving for a wide composition range. Metal substitution (Zn to Cu) affords fine tuning of linker rotation and layer stacking, creating slightly expanded pore aperture and interlayer space coupled with multiple hydrogen-bonding sites, allowing easier entrance of alkyne while excluding alkene. Breakthrough experiments confirmed tunable sieving by these MOFs for C3 H4 /C3 H6 and C2 H2 /C2 H4 mixtures.

12.
Angew Chem Int Ed Engl ; 59(9): 3423-3428, 2020 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-31746086

RESUMO

The separation of xenon/krypton (Xe/Kr) mixture is of great importance to industry, but the available porous materials allow the adsorption of both, Xe and Kr only with limited selectivity. Herein we report an anion-pillared ultramicroporous material NbOFFIVE-2-Cu-i (ZU-62) with finely tuned pore aperture size and structure flexibility, which for the first time enables an inverse size-sieving effect in separation along with record Xe/Kr selectivity and ultrahigh Xe capacity. Evidenced by single-crystal X-ray diffraction, the rotation of anions and pyridine rings upon contact of larger-size Xe atoms adapts cavities to the shape/size of Xe and allows strong host-Xe interaction, while the smaller-size Kr is excluded. Breakthrough experiments confirmed that ZU-62 has a real practical potential for producing high-purity Kr and Xe from air-separation byproducts, showing record Kr productivity (206 mL g-1 ) and Xe productivity (42 mL g-1 , in desorption) as well as good recyclability.

13.
Angew Chem Int Ed Engl ; 59(49): 21954-21958, 2020 12 01.
Artigo em Inglês | MEDLINE | ID: mdl-32851781

RESUMO

A tandem Bischler-Napieralski/semipinacol rearrangement reaction has been developed for the purpose of assembling a bis(spirocyclic) indole framework, a privileged structural unit of aspidofractinine-type monoterpenoid indole alkaloids, and was used in combination with a subsequent Mannich reaction to expeditiously construct the central bridged bicyclo[2.2.1]heptane ring system of these molecules with contiguous quaternary centers. The development of this novel strategy culminated in the collective total synthesis of four aspidofractinine alkaloids.

14.
Angew Chem Int Ed Engl ; 59(13): 5050-5091, 2020 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-31144373

RESUMO

A new approach has been developed to design organic polymers using topology diagrams. This strategy enables covalent integration of organic units into ordered topologies and creates a new polymer form, that is, covalent organic frameworks. This is a breakthrough in chemistry because it sets a molecular platform for synthesizing polymers with predesignable primary and high-order structures, which has been a central aim for over a century but unattainable with traditional design principles. This new field has its own features that are distinct from conventional polymers. This Review summarizes the fundamentals as well as major progress by focusing on the chemistry used to design structures, including the principles, synthetic strategies, and control methods. We scrutinize built-in functions that are specific to the structures by revealing various interplays and mechanisms involved in the expression of function. We propose major fundamental issues to be addressed in chemistry as well as future directions from physics, materials, and application perspectives.

15.
ACS Appl Mater Interfaces ; 16(17): 22455-22464, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38642370

RESUMO

Improving the gas separation performance of metal-organic frameworks (MOFs) by crystal downsizing is an important but often overlooked issue. Here, we report three different-sized flexible ZUL-520 MOFs (according to the crystal size from large to small, the three samples are, respectively, named ZUL-520-0, ZUL-520-1, and ZUL-520-2) with the same chemical structure for optimizing trace acetylene (C2H2) removal from acetylene/ethylene (C2H2/C2H4) mixture. The three differently sized activated ZUL-520 (denoted as ZUL-520a) exhibited almost identical C2H2 uptake of 4.8 mmol/g at 100 kPa, while the C2H2 uptake at 1 kPa increased with a downsizing crystal. The C2H2 uptake of activated ZUL-520-2 (denoted as ZUL-520-2a) at 1 kPa was ∼55% higher than that of activated ZUL-520-0 (denoted as ZUL-520-0a). The adsorption isotherms and adsorption kinetics validated that gas adsorptive separation is governed not only by adsorption thermodynamics but also by adsorption kinetics. In addition, all three different-sized ZUL-520a MOFs showed high C2H2/C2H4 selectivity. Grand canonical Monte Carlo (GCMC) simulations and dispersion-corrected density functional theory (DFT-D) computations illustrated a plausible mechanism of C2H2 adsorption in MOFs. Importantly, breakthrough experiments demonstrated that ZUL-520a can effectively separate the C2H2/C2H4 (1/99, v/v) mixture and the C2H4 productivity obtained by ZUL-520-2a was much higher than that by ZUL-520-0a. Our work may provide an easy but powerful strategy for upgrading the performance of gas adsorptive separation in MOFs.

16.
Nat Commun ; 15(1): 2620, 2024 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-38521770

RESUMO

Extensive efforts have been made to improve the separation selectivity of hydrocarbon isomers with nearly distinguishable boiling points; however, how to balance the high regeneration energy consumption remains a daunting challenge. Here we describe the efficient separation of hexane isomers by constructing and exploiting the rotational freedom of organic linkers and inorganic SnF62- anions within adaptive frameworks, and reveal the nature of flexible host-guest interactions to maximize the gas-framework interactions while achieving potential energy storage. This approach enables the discrimination of hexane isomers according to the degree of branching along with high capacity and record mono-/di-branched selectivity (6.97), di-branched isomers selectivity (22.16), and upgrades the gasoline to a maximum RON (Research Octane Number) of 105. Benefitting from the energy regulation of the flexible pore space, the material can be easily regenerated only through a simple vacuum treatment for 15 minutes at 25 °C with no temperature fluctuation, saving almost 45% energy compared to the commercialized zeolite 5 A. This approach could potentially revolutionize the whole scenario of alkane isomer separation processes.

17.
Endocr Connect ; 13(5)2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38552311

RESUMO

Objective: Hashimoto's thyroiditis is an inflammatory disease, and research suggests that a low-carbohydrate diet may have potential anti-inflammatory effects. This study aims to utilize Dixon-T2-weighted imaging (WI) sequence for a semi-quantitative assessment of the impact of a low-carbohydrate diet on the degree of thyroid inflammation in patients with Hashimoto's thyroiditis. Methods: Forty patients with Hashimoto's thyroiditis were recruited for this study and randomly divided into two groups: one with a normal diet and the other with a low-carbohydrate diet. Antibodies against thyroid peroxidase (TPOAb) and thyroglobulin (TgAb) were measured for all participants. Additionally, thyroid water content was semi-quantitatively measured using Dixon-T2WI. The same tests and measurements were repeated for all participants after 6 months. Results: After 6 months of a low-carbohydrate diet, patients with Hashimoto's thyroiditis showed a significant reduction in thyroid water content (94.84 ± 1.57% vs 93.07 ± 2.05%, P < 0.05). Concurrently, a decrease was observed in levels of TPOAb and TgAb (TPOAb: 211.30 (92.63-614.62) vs 89.45 (15.9-215.67); TgAb: 17.05 (1.47-81.64) vs 4.1 (0.51-19.42), P < 0.05). In contrast, there were no significant differences in thyroid water content or TPOAb and TgAb levels for patients with Hashimoto's thyroiditis following a normal diet after 6 months (P < 0.05). Conclusion: Dixon-T2WI can quantitatively assess the degree of thyroid inflammation in patients with Hashimoto's thyroiditis. Following a low-carbohydrate diet intervention, there is a significant reduction in thyroid water content and a decrease in levels of TPOAb and TgAb. These results suggest that a low-carbohydrate diet may help alleviate inflammation in patients with Hashimoto's thyroiditis.

18.
ACS Appl Mater Interfaces ; 15(2): 3387-3394, 2023 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-36608268

RESUMO

The selective capture of C2H6 from C2H6/C2H4 mixtures is of critical importance to realize the efficient one-step purification of C2H4 but remains challenging due to their similar properties and smaller quadrupole moment of C2H6 that usually result in C2H4-preferring adsorption. Herein, we reported two isostructural pillared-layer metal-organic frameworks, ZUL-C3 and ZUL-C4, which were constructed by mixed polycycloalkane-type ligands. Their low-polar pore environment along with more accessible low-polar C-H binding sites on the pore surface are conducive to generate more van der Waals interactions with C2H6 while the carboxylic groups distributed at four corners of pores form stronger and more dipolar interactions with C2H6, cooperatively resulting in a good C2H6/C2H4 uptake ratio of 1.50 for ZUL-C3 and 1.72 for ZUL-C4 in static adsorption experiments and a high C2H4 (>99.99% purity) productivity of 10.1 L/kg for ZUL-C3 and 14.6 L/kg for ZUL-C4 from an equimolar C2H6/C2H4 mixture in breakthrough experiments.

19.
Huan Jing Ke Xue ; 44(8): 4519-4529, 2023 Aug 08.
Artigo em Zh | MEDLINE | ID: mdl-37694646

RESUMO

Trichloroethylene is a typical organic contaminant that has widely existed in industry sites and groundwater. Biochar-supported zero-valent iron material has been used to remove trichloroethylene in groundwater; however, it could affect the microbial communities in aquifer soil, leading to changes in the environmental behavior of trichloroethylene. In this study, biochar was prepared under oxygen-limited conditions and modified by NaOH and HNO3 agents. Then, a modified biochar-supported zero-valent iron composite (BC composites) was synthesized using ball milling technology. The effects of BC composites on the removal of trichloroethylene and the responses of the microbial community were investigated under the condition of simulated aquifer soil. The results showed that the specific surface areas of BC composites were increased after the modification with NaOH. The highest removal rate of trichloroethylene was observed in the BC_2 treatment, up to 90.01%. Except in the BC_1 treatment, the diversity and abundance of soil microorganisms were increased, and the microbial community structure was changed after the addition of different BC composites, in which Bacillus, Thiobacillus, and Pseudomonas might have been the potential degrading bacteria of trichloroethylene. The abundance of Thiobacillus and Pseudomonas increased under the BC_2 treatment, which was favorable to the removal of trichloroethylene. The stabilization of the microbial community structure was probably maintained by Nocardioideas, Thermincola, Lysobacter, Gemmatimonas, Microvirga, and Pseudomonas. According to the predictive analysis of microbial metabolic pathways, the abundance of xenobiotics biodegradation and metabolism genes and the folding, sorting, and degradation of genes were the highest under the BC_2 treatment. Thus, the NaOH-modified BC composite could prompt the removal of trichloroethylene in simulated aquifer soil, probably due to the increase in the abundance of soil-degrading bacteria and the expression of degradation genes, demonstrating that the NaOH-modified BC composite could be used for the remediation of the organic-contaminated industry sites as a new composite material.


Assuntos
Microbiota , Tricloroetileno , Solo , Hidróxido de Sódio , Ferro
20.
Nat Commun ; 13(1): 2955, 2022 May 26.
Artigo em Inglês | MEDLINE | ID: mdl-35618705

RESUMO

Refineries generally employ multiple energy-intensive distillation/adsorption columns to separate and purify complicated chemical mixtures. Materials such as multi-functional molecular separators integrating various modules capable of separating molecules according to their shape and chemical properties simultaneously may represent an alternative. Herein, we address this challenge in the context of one-step removal of alkynes and propadiene from cracking gases (up to 10 components) using a multi-functional and responsive material ZU-33 through a guest/temperature dual-response regulation strategy. The responsive and guest-adaptive properties of ZU-33 provide the optimized binding energy for alkynes and propadiene, and avoid the competitive adsorption of olefins and paraffins, which is verified by breakthrough tests, single-crystal X-ray diffraction experiments, and simulation studies. The responsive properties to different stimuli endow materials with multiple regulation methods and broaden the boundaries of the applicability of porous materials to challenging separations.

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