Integrating Multiscale Simulation with Machine Learning to Screen and Design FIL@COFs for Ethane-Selective Separation.

Efficient and economical separation of C2H6/C2H4 is an imperative and extremely challenging process in the petrochemical industry. The C2H6-selective adsorbents with high working capacity and high selectivity are highly desirable from a practical application standpoint. In this study, we constructed a database of fluorinated ionic liquid@covalent organic frameworks (FIL@COFs) and screened out the high-performing FIL@COFs for C2H6-selective separation. Utilizing the optimal machine learning (ML) algorithm (XGBoost) and hyperparameters, we further revealed the key factors influencing the separation performance. The multiscale simulation not only validated the prediction accuracy of ML but also demonstrated that adjusting the largest cavity diameter of COFs with FILs could yield FIL@COFs with high performance for C2H6-selective separation. Our work provides essential guidance for designing new FIL@COF adsorbents for value-added gas purification.

Large-Area Ultrathin Metal-Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations.

Ultrathin continuous metal-organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic-imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large-area fabrication. Here, we propose a ligand back diffusion-assisted bipolymer-directed metal ion distribution strategy for preparing large-area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross-linked two-dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large-area ultrathin MOF membranes. We report the practical fabrication of three representative defect-free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50-130 nm), including ZIFs and carboxylate-linker MOFs. Among these, the ZIF-8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale-up practicality, MOF membranes were prepared and incorporated into spiral-wound membrane modules with an active area of 4,800 cm2. The ZIF-8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).

Enhancing ion selectivity by tuning solvation abilities of covalent-organic-framework membranes.

Understanding the molecular-level mechanisms involved in transmembrane ion selectivity is essential for optimizing membrane separation performance. In this study, we reveal our observations regarding the transmembrane behavior of Li+ and Mg2+ ions as a response to the changing pore solvation abilities of the covalent-organic-framework (COF) membranes. These abilities were manipulated by adjusting the lengths of the oligoether segments attached to the pore channels. Through comparative experiments, we were able to unravel the relationships between pore solvation ability and various ion transport properties, such as partitioning, conduction, and selectivity. We also emphasize the significance of the competition between Li+ and Mg2+ with the solvating segments in modulating selectivity. We found that increasing the length of the oligoether chain facilitated ion transport; however, it was the COF membrane with oligoether chains containing two ethylene oxide units that exhibited the most pronounced discrepancy in transmembrane energy barrier between Li+ and Mg2+, resulting in the highest separation factor among all the evaluated membranes. Remarkably, under electro-driven binary-salt conditions, this specific COF membrane achieved an exceptional Li+/Mg2+ selectivity of up to 1352, making it one of the most effective membranes available for Li+/Mg2+ separation. The insights gained from this study significantly contribute to advancing our understanding of selective ion transport within confined nanospaces and provide valuable design principles for developing highly selective COF membranes.

Metal-Organic Framework Membrane Constructor: A Tool for High-Throughput Construction of Metal-Organic Framework Membrane Models.

With the rapid development of metal-organic framework (MOF) membranes for separation applications, computational screening of their separation performance has attracted increasing interest in the design and fabrication of such materials. Although bulk crystal models in MOF databases are often used to represent MOF membrane structures, membrane models in slab geometries are still essential for researchers to simulate the separation performance, particularly to understand the effects of the surface/interface structure, pore sieving, and exposed lattice plane on guest permeability. However, to date, no database or method has been established to provide researchers with numerous membrane models, restricting the further development of related theoretical studies. Herein, we propose an algorithm and develop a tool called the "MOF-membrane constructor" to realize the high-throughput construction of membrane models based on the MOF crystal structures. Using this tool, membrane models can be generated with desired sizes, reasonable surface terminations, and assigned exposed crystal planes. The tool can also deduce the most prominent surface in the Bravais-Friedel-Donnay-Harker morphology or identify the pores in MOF crystals and automatically determine an exposed plane for each membrane model. Thus, an MOF-membrane database can be established rapidly according to user simulation requirements. This study can considerably improve the efficiency of building MOF membrane models and may be beneficial for the future development of simulation studies on MOF membranes.

Step-Nucleation In Situ Self-Repair to Prepare Rollable Large-Area Ultrathin MOF Membranes.

Ultrathin membranes with ultrahigh permeance and good gas selectivity have the potential to greatly decrease separation process costs, but it requires the practical preparation of large area membranes for implementation. Metal-organic frameworks (MOFs) are very attractive for membrane gas separation applications. However, to date, the largest MOF membrane area reported in the literature is only about 100 cm2 . In the present study, a new step-nucleation in situ self-repair strategy is proposed that enables the preparation of large-area (2400 cm2 ) ultrathin and rollable MOF membranes deposited on an inexpensive flexible polymer membrane support layer for the first time, combining a polyvinyl alcohol (PVA)-metal-ion layer and a pure metal-ion layer. The main role of the pure metal-ion layer is to act as the main nucleation sites for MOF membrane growth, while the PVA-metal-ion layer acts as a slow-release metal-ion source, which supplements MOF crystal nucleation to repair any defects occurring. Membrane modules are necessary components for membrane applications, and spiral-wound modules are among the most common module formats that are widely applied in gas separation. A 4800 cm2 spiral-wound membrane module was successfully prepared, demonstrating the practical implementation of large-area MOF membranes.

Molecular Simulation Study on the Wettability of a Surface Texturized with Hierarchical Pillars.

By using molecular dynamics simulation, we investigate the wettability of a surface texturized with a periodic array of hierarchical pillars. By varying the height and spacing of the minor pillars on top of major pillars, we investigate the wetting transition from the Cassie-Baxter (CB) to Wenzel (WZ) states. We uncover the molecular structures and free energies of the transition and meta-stable states existing between the CB and WZ states. The relatively tall and dense minor pillars greatly enhance the hydrophobicity of a pillared surface, in that, the CB-to-WZ transition requires an increased activation energy and the contact angle of a water droplet on such a surface is significantly larger.

Degradation of xylan by human gut Bacteroides xylanisolvens XB1A.

Although many polysaccharides utilization loci (PULs) have been investigated by genomics and transcriptomics, the detailed functional characterization lags severely behind. We hypothesize that PULs on the genome of Bacteroides xylanisolvens XB1A (BX) dictate the degradation of complex xylan. To address, xylan S32 isolated from Dendrobium officinale was employed as a sample polysaccharide. We firstly showed that xylan S32 promoted the growth of BX which might degrade xylan S32 into monosaccharides and oligosaccharides. We further showed that this degradation was performed mainly via two discrete PULs in the genome of BX. Briefly, a new surface glycan binding protein (SGBP) BX_29290SGBP was identified, and shown to be essential for the growth of BX on xylan S32. Two cell surface endo-xylanases Xyn10A and Xyn10B cooperated to deconstruct the xylan S32. Intriguingly, genes encoding Xyn10A and Xyn10B were mainly distributed in the genome of Bacteroides spp. In addition, BX metabolized xylan S32 to produce short chain fatty acids (SCFAs) and folate. Taken together, these findings provide new evidence to understand the food source of BX and the BX-directed intervention strategy by xylan.

Metal-Organic Framework Crystal-Glass Composite Membranes with Preferential Permeation of Ethane.

Metal-organic framework (MOF) glass is an easy to process and self-supported amorphous material that is suitable for fabricating gas separation membranes. However, MOF glasses, such as ZIF-62 and ZIF-4 have low porosity, which makes it difficult to obtain membranes with high permeance. Here, a self-supported MOF crystal-glass composite (CGC) membrane was prepared by melt quenching a mixture of ZIF-62 as the membrane matrix and ZIF-8 as the filler. The conversion of ZIF-62 from crystal to glass and the simultaneous partial melting of ZIF-8 facilitated by the melt state of ZIF-62 make the CGC membrane monolithic, eliminating non-selective grain boundaries and improving selectivity. The thickness of CGC membrane can be adjusted to fabricate a membrane without the need of a support substrate. CGC membranes exhibit a C2 H6 permeance of 41 569 gas permeation units (GPU) and a C2 H6 /C2 H4 selectivity of 7.16. The CGC membrane has abundant pores from the glassy state of ZIF-62 and the crystalline ZIF-8, which enables high gas permeance. ZIF-8 has preferential adsorption for C2 H6 and promotes C2 H6 transport in the membrane, and thus the GCG membrane exhibits ultrahigh C2 H6 permeance and good C2 H6 /C2 H4 selectivity.

Chromosome-level genome assembly of Dastarcus helophoroides provides insights into CYP450 genes expression upon insecticide exposure.

BACKGROUND: Dastarcus helophoroides is an important natural enemy of cerambycids, and is wildly used in biological control of pests. Nevertheless, the absence of complete genomic information limits the investigation of the underlying molecular mechanisms. Here, a chromosome-level of Dastarcus helophoroides genome is assembled using a combination strategy of Illumina, PacBio, 10x™ Genomics, and Hi-C. RESULTS: The final assembly is 609.09 Mb with contig N50, scaffold N50 and GC content of 5.46 Mb, 42.56 Mb and 31.50%, respectively, and 95.25% of the contigs anchor into 13 chromosomes. In total 14 890 protein-coding genes and 65.37% repeat sequences are predicted in the assembly genome. The phylogenetic analysis of single-copy gene families shared among 20 insect species indicates that Dastarcus helophoroides is placed as the sister species to clade (Nitidulidae+Curculionoidea+Chrysomeloidea) + Tenebrionoidea, and diverges from the related species ~242.9 Mya. In total 36 expanded gene families are identified in Dastarcus helophoroides genome, and are functionally related to drug metabolism and metabolism of xenobiotics by cytochrome P450. Some members of CYP4 Clade and CYP6 Clade are up-regulated in Dastarcus helophoroides adults upon insecticide exposure, of which expressions of DhCYP4Q, DhCYP6A14X1 and DhCYP4C1 are significantly up-regulated. The silencing of the three genes leads to adults more sensitive to insecticide and increased knocked-down rate, which may indicate their critical roles in stress resistance and detoxication. CONCLUSION: Our study systematically integrated the chromosome-level genome, transcriptome and gene expression of Dastarcus helophoroides, which will provide valuable resources for understanding mechanisms of pesticide metabolism, growth and development, and utilization of the natural enemy in integrated control. © 2022 Society of Chemical Industry.

Coordination-driven structure reconstruction in polymer of intrinsic microporosity membranes for efficient propylene/propane separation.

Polymers of intrinsic microporosity (PIMs), integrating unique microporous structure and solution-processability, are one class of the most promising membrane materials for energy-efficient gas separations. However, the micropores generated from inefficient chain packing often exhibit wide pore size distribution, making it very challenging to achieve efficient olefin/paraffin separations. Here, we propose a coordination-driven reconstruction (CDR) strategy, where metal ions are incorporated into amidoxime-functionalized PIM-1 (AO-PIM) to in situ generate coordination crosslinking networks. By varying the type and content of metal ions, the resulting crosslinking structures can be optimized, and the molecular sieving capability of PIM membranes can be dramatically enhanced. Particularly, the introduction of alkali or alkaline earth metals renders more precise micropores contributing to superior C3H6/C3H8 separation performance. K+ incorporated AO-PIM membranes exhibit a high ideal C3H6/C3H8 selectivity of 50, surpassing almost all the reported polymer membranes. Moreover, the coordination crosslinking structure significantly improves the membrane stability under higher pressure as well as the plasticization resistant performance. We envision that this straightforward and generic CDR strategy could potentially unlock the potentials of PIMs for olefin/paraffin separations and many other challenging gas separations.

Rare Species-Driven Diversity-Ecosystem Multifunctionality Relationships are Promoted by Stochastic Community Assembly.

The relative functional importance of rare and abundant species in driving relationships between biodiversity and ecosystem functions (BEF) remains unknown. Here, we investigated the functional roles of rare and abundant species diversity (multitrophic soil organism groups) on multifunctionality derived from 16 ecosystem functions in 228 agricultural fields relating to soil and crop health. The results revealed that the diversity of rare species, rather than of abundant species, was positively related to multifunctionality. Abundant taxa tended to maintain a larger number of functions than rare taxa, while rare subcommunity contributed more phylotypes supporting to the single ecosystem functions. Community assembly processes were closely related to the ecosystem functional performance of soil biodiversity, only observed in rare subcommunity. Higher relative contributions of stochastic assembly processes promoted the positive effects of diversity of rare taxa on multifunctionality, while reducing their diversity and multifunctionality overall. Our results highlight the importance of rare species for ecosystem multifunctionality and elucidate the linkage between ecological assembly processes and BEF relationships. IMPORTANCE The relative functional importance of rare and abundant species in driving relationships between biodiversity and ecosystem functions remains unknown. Here, we highlighted the importance of rare species for ecosystem multifunctionality. In addition, community assembly processes were closely related to the ecosystem functional performance of soil biodiversity in rare subcommunity. Stochastic assembly processes promoted the positive effects of diversity of rare taxa on multifunctionality, while reducing their diversity and multifunctionality overall. This study expands current understanding of the mechanisms underpinning the relationships between biodiversity and ecosystem functions and suggests that stochastic community assembly enhances BEF relationships.

Streptomyces gobiensis sp. nov., an antimicrobial producing actinobacterium isolated from soil under black Gobi rocks.

A novel actinomycete, strain 1_25T, was isolated from soil under a black Gobi rock sample from Shuangta, PR China, and characterized using a polyphasic taxonomic approach. The results of comparative analysis of the 16S rRNA gene sequences indicated the 1_25T represented a member of the genus Streptomyces. Chemotaxonomic data revealed that 1_25T possessed MK-9(H8) as the major menaquinone. The cell wall contained ll-diaminopimelic acid (ll-DAP) and the whole-cell sugar pattern consisted of ribose, glucose and galactose. Major fatty acid methyl esters were observed to be iso-C16 : 0 (23.6 %), and anteiso-C15 : 0 (10.4 %). The genomic DNA G+C content of 1_25T was 69 mol %. The results of phylogenetic analysis based on 16S rRNA gene sequence indicated that 1_25T had high sequence similarity with Streptomyces qinglanensis 172205T (98.1 %), Streptomyces lycii TRM 66187T (98 %), and Streptomyces griseocarneus JCM4580T (98 %). In addition to the differences in phenotypic characters, the average nucleotide identity (ANI) and digital DNA-DNA hybridization (dDDH) values between 1_25T and closely related species were below the recommended threshold values for assigning strains to the same species. The fermentation product of 1_25T in ISP2 had an inhibitory effect on Staphylococcus aureus. On the basis of these genotypic and phenotypic characteristics, strain 1_25T (=JCM 34936T=GDMCC 4.216T) represents a novel species of the genus Streptomyces, for which the name Streptomyces gobiensis sp. nov. is proposed.

Confined Ionic Liquid-Built Gas Transfer Pathways for Efficient Propylene/Propane Separation.

The separation of light olefins from paraffins using membrane technology is highly desired; however, synthetic polymer membranes generally suffer a pernicious trade-off between permeability and selectivity. Herein, we show that this limitation can be overcome by constructing selective gas transfer pathways in a polymer matrix, as demonstrated by incorporating composites of ionic liquids and zeolitic imidazolate frameworks (ZIFs) to form mixed-matrix membranes. Using propylene/propane separation as a model system, dramatic improvements in the propylene permeability of 218.4 Barrer and propylene/propane separation factor of 45.7 were achieved compared to the values obtained using individual components as a filler. The synergy between the high solubility of the gas molecules in ionic liquids and the size screening ability of ZIF exacerbates the difference in the transmission of propylene and propane, thus leading to superior separation performance. This work presents a promising strategy for the design of membranes for efficient gas separation.

Obesity induces morphological and functional changes in female reproductive system through increases in NF-κB and MAPK signaling in mice.

BACKGROUND: Recently, human infertility incidence is increasing in obese women causing it to become an emerging global health challenge requiring improved treatment. There is extensive evidence that obesity caused female reproductive dysfunction is accompanied by an endocrinological influence. Besides, systemic and tissue-specific chronic inflammatory status are common characteristics of obesity. However, the underlying molecular mechanism is unclear linking obesity to infertility or subfertility. METHODS: To deal with this question, we created an obese mouse model through providing a high fat diet (HFD) and determined the fertility of the obese mice. The morphological alterations were evaluated in both the reproductive glands and tracts, such as uterus, ovary and oviduct. Furthermore, to explore the underlying mechanism of these functional changes, the expressions of pro-inflammatory cytokines as well as the activations of MAPK signaling and NF-κB signaling were detected in these reproductive tissues. RESULTS: The obese females were successful construction and displayed subfertility. They accumulated lipid droplets and developed morphological alterations in each of their reproductive organs including uterus, ovary and oviduct. These pathological changes accompanied increases in pro-inflammatory cytokine expression levels of interleukin-6 (IL-6) and tumor necrosis factor-α (TNF-α) in all of these sites. Such effects also accompanied increases in nuclear factor kappa B (NF-kB) expression and mitogen-activated protein kinase (MAPK) signaling pathway stimulation based on uniform time dependent increases in the NF-κB (p-NF-κB), JNK (p-JNK), ERK1/2 (p-ERK) and p38 (p-p38) phosphorylation status. CONCLUSIONS: These HFD-induced increases in pro-inflammatory cytokine expression levels and NF-κB and MAPKs signaling pathway activation in reproductive organs support the notion that increases of adipocytes resident and inflammatory status are symptomatic of female fertility impairment in obese mice.

Pressure-Responsive Two-Dimensional Metal-Organic Framework Composite Membranes for CO2 Separation.

The regulation of permeance and selectivity in membrane systems may allow effective relief of conventional energy-intensive separations. Here, pressure-responsive ultrathin membranes (≈100 nm) fabricated by compositing flexible two-dimensional metal-organic framework nanosheets (MONs) with graphene oxide nanosheets for CO2 separation are reported. By controlling the gas permeation direction to leverage the pressure-responsive phase transition of the MONs, CO2 -induced gate opening and closing behaviors are observed in the resultant membranes, which are accompanied with the sharp increase of CO2 permeance (from 173.8 to 1144 gas permeation units) as well as CO2 /N2 and CO2 /CH4 selectivities (from 4.1 to 22.8 and from 4 to 19.6, respectively). The flexible behaviors and separation mechanism are further elucidated by molecular dynamics simulations. This work establishes the relevance of structural transformation-based framework dynamics chemistry in smart membrane systems.

Fungi show broader environmental thresholds in wet than dry agricultural soils with distinct biogeographic patterns.

It is critical to establish response thresholds for fungal communities to global environmental change and assess the relationship between fungal diversity and nutrient cycling in soils. However, these have not yet been evaluated in agro-ecosystems. Here we report the findings of a survey across eastern China on the soil fungi and physicochemical properties in adjacent maize and rice fields. The results revealed a wider range of environmental thresholds for soil fungi in rice than maize fields. We found that the dominant fungal taxa only accounted for 0.6% of all taxa, but constituted >50% of total fungi. Based on their habitat preferences, distinct distribution maps between maize and rice fields were constructed, which indicated niche differentiation of soil fungi between dry and waterlogged soils. Rice fields showed higher fungal richness in low latitude regions, consistent with latitudinal richness patterns found in natural terrestrial ecosystems; however, no such trend was observed in maize fields. Fungal richness was positively correlated with nutrient cycling in rice soils and fungal beta diversity with nutrient cycling in maize soils. These findings provide response thresholds for fungal community change across environmental gradients, advancing our understanding of soil fungal diversity patterns in agricultural ecosystems. Differences between wetland and dryland should be taken into consideration when formulating sustainable management plans and baselines for assessments of future global change and resilience of agricultural fields.

Disrupted pathways from frontal-parietal cortex to basal ganglia and cerebellum in patients with unmedicated obsessive compulsive disorder as observed by whole-brain resting-state effective connectivity analysis - a small sample pilot study.

OBJECTIVE: To date, a systematic characterization of abnormalities in resting-state effective connectivity (rsEC) in obsessive-compulsive disorder (OCD) is lacking. The present study aimed to systematically characterize whole-brain rsEC in OCD patients as compared to healthy controls. METHODS: Using resting-state fMRI data of 50 unmedicated patients with OCD and 50 healthy participants, we constructed whole-brain rsEC networks using Granger causality analysis followed by univariate and multivariate comparisons between patients and controls. Similar analyses were performed for resting-state functional connectivity (rsFC) networks to examine how rsFC and rsEC differentially capture abnormal brain connectivity in OCD. RESULTS: Univariate comparisons identified 10 rsEC networks that were significantly disrupted in patients, and which were mainly associated with frontal-parietal cortex, basal ganglia, and cerebellum. Conversely, abnormal rsFC networks were widely distributed throughout the whole brain. Multivariate pattern analysis revealed a classification accuracy as high as 80.5% for distinguishing patients from controls using combined whole-brain rsEC and rsFC. CONCLUSIONS: The results of the present study suggest disrupted communication of information from frontal-parietal cortex to basal ganglia and cerebellum in OCD patients. Using combined whole-brain rsEC and rsFC, multivariate pattern analysis revealed a classification accuracy as high as 80.5% for distinguishing patients from controls. The alterations observed in OCD patients could aid in identifying treatment mechanisms for OCD.

Disrupted pathways from the frontal-parietal cortices to basal nuclei and the cerebellum are a feature of the obsessive-compulsive disorder spectrum and can be used to aid in early differential diagnosis.

A marker for distinguishing patients with obsessive-compulsive disorder (OCD) spectrum has not yet been identified. Whole-brain resting-state effective and functional connectivity (rsEC and rsFC, respectively) networks were constructed for 50 unmedicated OCD (U-OCD) patients, 45 OCD patients in clinical remission (COCD), 47 treatment-resistant OCD (T-OCD) patients, 42 chronic schizophrenia patients who exhibit OCD symptoms (SCHOCD), and 50 healthy controls (HCs). Multivariate pattern analysis (MVPA) was performed to investigate the accuracy of using connectivity alterations to distinguished among the aforementioned groups. Compared to HCs, rsEC connections were significantly disrupted in the U-OCD (n = 15), COCD (n = 8), and T-OCD (n = 19) groups. Additionally, 21 rsEC connections were significantly disrupted in the T-OCD group compared to the SCHOCD group. The disrupted rsEC networks were associated mainly with the frontal-parietal cortex, basal ganglia, limbic regions, and the cerebellum. Classification accuracies for distinguishing OCD patients from HCs and SCHOCD patients ranged from 66.6% to 98.0%. In conclusion, disrupted communication from the frontal-parietal cortices to subcortical basal nuclei and the cerebellum may represent a functional pathological feature of the OCD spectrum. MVPA based on both abnormal rsEC and rsFC patterns may aid in early differential diagnosis of OCD.

Ultrathin Low-Crystallinity MOF Membranes Fabricated by Interface Layer Polarization Induction.

Practical, ultrathin metal-organic framework (MOF) membranes have the potential to achieve otherwise difficult separations, but current fabrication methods still face challenges in the simultaneous improvement of both selectivity and permeance. Here, ultrathin, low-crystallinity-state MOF (LC-MOF) membranes are realized by a facile general method of interface layer polarization induction. This is achieved using an interface layer having metal ions with dense and uniform distribution, resulting in the creation of abundant open metal sites. Three types of LC-MOF membranes (45-150 nm) are fabricated, among which ZIF-8 membranes modified in situ with diethanolamine (DZIF-8) display the best performance for propylene/propane separation, showing unprecedented propylene permeance (2000-3000 Gas Permeance Units) with very high propylene/propane selectivity (90-120).

Author Correction: Bacterial and fungal gut communities of Agrilus mali at different developmental stages and fed different diets.

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