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Graphene can promote plant growth and improve soil conditions, but its effectiveness in enhancing infertile soils in arid regions remains unclear. This study selected three typical shrubs from the Ulan Buh Desert Nitraria tangutorum , Xanthoceras sorbifolium , and Amygdalus mongolica as research subjects. Five graphene addition levels were set: 0 mg/L (C0), 25 mg/L (C1), 50 mg/L (C2), 100 mg/L (C3), and 200 mg/L (C4).A pot experiment was conducted in June 2023 to investigate the effects of graphene addition on shrub growth and soil nutrients. The results showed that the optimal graphene addition levels for A. mongolica , X. sorbifolium , and N. tangutorum were C2, C2, and C3, respectively. Compared with the control, the total biomass of the different shrubs increased by 185.31%, 50.86%, and 161.10%, respectively. However, when the graphene addition exceeded the optimal level, shrub biomass showed a decreasing trend with increasing graphene concentration. Total shrub biomass was positively correlated with soil available nitrogen and potassium, while redundancy analysis indicated that soil organic matter was the primary factor influencing shrub growth. This suggests that graphene promotes shrub growth by affecting soil organic matter and available nutrients. Therefore, graphene addition can enhance soil fertility in barren lands in arid regions and significantly promote shrub growth. However, due to soil leaching effects, this growth-promoting effect may decrease over time.

Aqueous asymmetric catalysis using chiral covalent organic frameworks (COFs) represents a significant advancement but remains to be explored. Herein, we present the first example of aqueous asymmetric catalysis catalyzed by a primary amine-tagged chiral D -ADP-TAPB COF. The D -ADP-TAPB COF was synthesized by the postsynthetic deprotection of D -ADP-TAPB-Boc bearing a protective tert-butoxycarbonyl (Boc) group, which was constructed by a Schiff-base reaction between an alanine-derived chiral building block ( D -ADP-Boc) and 1,3,5-tris(4-aminophenyl)benzene (TAPB). The crystalline D -ADP-TAPB COF exhibits a uniform, spherical morphology with abundant, well-distributed chiral primary amines, rendering it highly active in the asymmetric aldol reaction between cyclohexanone and 4-nitrobenzaldehyde. Notably, this reaction is conducted entirely in water, achieving impressive yields and enantiomeric excess (ee) values of up to 90 and 85%, respectively. To the best of our knowledge, D -ADP-TAPB COF represents the first chiral COF catalyst with high reactivity and enantioselectivity for an asymmetric aldol reaction solely in water, eliminating the need for conventional organic solvents. Moreover, a plausible mechanism for D -ADP-TAPB COF-mediated aqueous asymmetric aldol reactions is elucidated. This work not only expands the toolbox for designing rare primary amine-functionalized chiral COFs for asymmetric catalysis but also opens exciting avenues for developing green and water-based enantioselective catalysis.

Organic dyes are widely used in many important areas, but they also bring many issues for water pollution. To address the above issues, a reconstructed kaolinite hybrid compound (γ-AlOOH@A-Kaol) was obtained from raw kaolinite (Kaol) in this work. The product was then characterized by X-ray diffraction (XRD), Fourier-transform infrared (ATR-FTIR), Brunauer-Emmett-Teller (BET), and scanning electron microscopy (SEM), and the absorption properties of γ-AlOOH@A-Kaol for congo red were further studied. The results demonstrated that flower-like γ-AlOOH with nanolamellae were uniformly loaded on the surface of acid-treated Kaol with a porous structure (A-Kaol). In addition, the surface area (36.5 m 2 /g), pore volume (0.146 cm 3 /g), and pore size (13.0 nm) of γ-AlOOH@A-Kaol were different from those of A-Kaol (127.4 m 2 /g, 0.127 cm 3 /g, and 4.28 nm, respectively) and γ-AlOOH (34.1 m 2 /g, 0.315 cm 3 /g, and 21.5 nm, respectively). The unique structure could significantly enhance the sorption capacity for congo red, which could exceed 1000 mg/g. The reasons may be ascribed to the abundant groups of -OH, large specific surface area, and porous structure of γ-AlOOH@A-Kaol. This work provides an efficient route for comprehensive utilization and production of Kaol-based compound materials that could be used in the field of environmental conservation.

This study aims to predict the significant duration (D5-75, D5-95) of seismic motion by employing machine learning algorithms. Based on three parameters (moment magnitude, fault distance, and average shear wave velocity), two additional parameters(fault top depth and epicenter mechanism parameters) were introduced in this study. The XGBoost algorithm is utilized for characteristic parameter optimization analysis to obtain the optimal combination of four parameters. We compare the prediction results of four machine learning algorithms (random forest, XGBoost, BP neural network, and SVM) and develop a new method of significant duration prediction by constructing two fusion models (stacking and weighted averaging). The fusion model demonstrates an improvement in prediction accuracy and generalization ability of the significant duration when compared to single algorithm models based on evaluation indicators and residual values. The accuracy and rationality of the fusion model are validated through comparison with existing research., Competing Interests: The authors have declared that no competing interests exist., (Copyright: © 2024 Li, Gao. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.)

Desert farmland provides food for desert areas, but water is the main limiting factor of this region, thus desert farmland has an extremely fragile ecological environment. This study investigated the temporal and spatial variations of vegetation NDVI (Normalized Difference Vegetation Index) in the Ulan Buh Desert, China, from 1990 to 2022, using long-term Landsat satellite data obtained from the Google Earth Engine platform and local statistical data. The results showed that from 1990 to 2022, the NDVI exhibited relatively small fluctuations and a steady increase. Furthermore, the study analyzed the impact of climate factors, namely precipitation and temperature, on NDVI, and collected the groundwater lever changes under irrigation and farmland development. The results demonstrated a positive correlation between NDVI and both precipitation and temperature from 1990 to 2006. The study area experienced an overall trend of increasing humidity. Specifically, from 1990 to 2006, significant positive correlations with precipitation and temperature were observed in 4.4% and 5.5% of the region, respectively. From 2007 to 2022, significant positive correlations were observed in 5.4% and 72.8% of the region for precipitation and temperature, respectively. These findings suggest that temperature has become increasingly influential on vegetation NDVI, while the impact of precipitation remains relatively stable. Moreover, the study assessed the impact of human activities on vegetation NDVI. The results revealed that from 1990 to 2006, human activities contributed to 43.1% of the promotion of local vegetation NDVI, which increased to 90.9% from 2007 to 2022. This study provides valuable insights into the dynamics of vegetation in the Ulan Buh Desert and its response to climatic changes and human activities. The findings highlight the significance of climate conditions and human interventions in shaping the vegetation dynamics in the region, offering essential information for ecological restoration and conservation efforts.

De novo design of peptides that bind specifically to functional proteins is beneficial for diagnostics and therapeutics. However, complex permutations and combinations of amino acids pose significant challenges to the rational design of peptides with desirable stability and affinity. Herein, we develop a computational-based evolution method, namely, peptidomimetics-driven recognition elements design (PepDRED), to derive hemoglobin-inspired peptidomimetics. PepDRED mimics the natural evolutionism pipeline to generate stable apovariant (AVs) structures for wild-type counterparts via automated point mutations and validates their efficiency through free binding energy analysis and per residue energy decomposition analysis. For application demonstration, we applied PepDRED to design de novo peptides to bind FhuA, a typical TonB-dependent transporter (TBDT). TBDTs are Gram-negative bacterial outer membrane proteins responsible for iron transport and vital for bacterial resistance. PepDRED generated a pool of AVs and proceeded to reach an optimized peptide, AV440, with a remarkable binding affinity of -21 kcal/mol. AV440 is ∼2.5-fold stronger than the existing FhuA inhibitor Microcin J25. Network energy analysis further unveils that incorporating methionine (M42) in the N-terminal region significantly enhances inter-residue contacts and binding affinity. PepDRED offers a prompt and efficient in silico approach to develop potent peptide candidates for target proteins.

The development of chiral covalent organic frameworks (COFs) by postsynthetic modification is challenging due to the common occurrences of racemization and crystallinity decrement under harsh modification conditions. Herein, we employ an effective site-selective synthetic strategy for the fabrication of an amine-functionalized hydrazone-linked COF, NH 2 -Th-Tz COF, by the Schiff-base condensation between aminoterephthalohydrazide (NH 2 -Th) and 4,4',4″-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (Tz). The resulting NH 2 -Th-Tz COF with free amine groups on the pore walls provides an appealing platform to install desired chiral moieties through postsynthetic modification. Three chiral moieties including tartaric acid, camphor-10-sulfonyl chloride, and diacetyl-tartaric anhydride were postsynthetically integrated into NH 2 -Th-Tz COF by reacting amine groups with acid, acyl chloride, and anhydride, giving rise to a series of chiral COFs with distinctive chiral pore surfaces. Moreover, the crystallinity, porosity, and chirality of chiral COFs were retained after modification. Remarkably, the chiral COFs exhibited an exceptional enantioselective adsorption capability toward tyrosine with a maximum enantiomeric excess (ee) value of up to 25.20%. Molecular docking simulations along with experimental results underscored the pivotal role of hydrogen bonds between chiral COFs and tyrosine in enantioselective adsorption. This work highlights the potential of site-selective synthesis as an effective tool for the preparation of highly crystalline and robust amine-decorated COFs, which offer an auspicious platform for the facile synthesis of tailor-made chiral COFs for enantioselective adsorption and beyond.

Background: Mori Fructus is an economical and readily available traditional Chinese medicine and food. Polysaccharides in Mori Fructus have clear antioxidant activity and have been found to alleviate oxidative stress (OS)-induced liver damage in experimental studies. The mechanism of regulation of cellular antioxidant activity by mulberry polysaccharides has been suggested to be Nrf2, but it is not clear whether the Nrf2 pathway is mediated by activation of other targets, and the exact process of effects in hepatocytes has yet to be elucidated., Methods: In this study, the basic characterization of total polysaccharides extracted from mulberry fruits (Morus nigra Linn.) was analyzed. A model of oxidative damage induced by H 2 O 2 in HepG2 cells was established. The levels of cellular oxidation-related markers, including ROS, SOD and Gpx, were then examined. Furthermore, Q-PCR and Western-blot were used to detect the expression of genes and proteins related to the PI3K/Akt-mediated Nrf2 signaling pathway., Results: The results showed that a total mulberry polysaccharides (TMP) has a molecular weight of 57.5 kDa with a pyranose ring mainly composed of glucose (48.81%), galactose (22.79%) and mannose (18.2%). TMP reduced the accumulation of ROS in HepG2 cells after H 2 O 2 treatment and modulated the activity of SOD and Gpx. Q-PCR and Western-blot showed that TMP could up-regulate the expression of p-PI3K, p-AKT, Nrf2, NQO1 and HO-1., Conclusions: This study demonstrates that TMP can reduce ROS accumulation in H 2 O 2 -treated HepG2 cells and restore cell viability by activating the PI3K/AKT-mediated Nrf2 pathway. TMP may be a potent antioxidant agent that could slow down oxidative damage to the liver., (© 2023. The Author(s).)

Sodium storage batteries are one of the ever-increasing next-generation large-scale energy storage systems owing to the abundant resources and low cost. However, their viability is severely hampered by dendrite-related hazards on anodes. Herein, a novel ultrathin (8 µm) exterior-nonporous separator composed of honeycomb-structured fibers is prepared for homogeneous Na deposition and suppressed dendrite penetration. The unhindered ion transmission greatly benefits from honeycomb-structured fibers with huge electrolyte uptake (376.7%) and the polymer's inherent transport ability. Additionally, polar polymer chains consisting of polyethersulfone and polyvinylidene customize the highly aggregated solvation structure of electrolytes via substantial solvent immobilization, facilitating ion-conductivity-enhanced inorganic-rich solid-electrolyte interphase with remarkable interface endurance. With the reliable mechanical strength of the separator, the assembled sodium-ion full cell delivers significantly improved energy density and high safety, enabling stable operation under cutting and rolling. The as-prepared separator can further be generalized to lithium-based batteries for which apparent dendrite inhibition and cyclability are accessible and demonstrates its potential for practical application., (© 2023 Wiley-VCH GmbH.)

Covalent organic frameworks (COFs) have emerged as auspicious porous adsorbents for radioiodine capture. However, their conventional solvothermal synthesis demands multiday synthetic times and anaerobic conditions, largely hampering their practical use. To tackle these challenges, we present a facile microwave-assisted synthesis of 2D imine-linked COFs, Mw-TFB-BD-X, (X = -CH 3 and -OCH 3 ) under air within just 1 h. The resultant COFs possessed higher crystallinity, better yields, and more uniform morphology than their solvothermal counterparts. Remarkably, Mw-TFB-BD-CH 3 and Mw-TFB-BD-OCH 3 exhibited exceptional iodine adsorption capacities of 7.83 g g -1 and 7.05 g g -1 , respectively, placing them among the best-performing COF adsorbents for static iodine vapor capture. Moreover, Mw-TFB-BD-CH 3 and Mw-TFB-BD-OCH 3 can be reused 5 times with no apparent loss in the adsorption capacity. The exceptionally high iodine adsorption capacities and excellent reusability of COFs were mainly attributed to their uniform spherical morphology and enhanced chemical stability due to the in-built electron-donating groups, despite their low surface areas. This work establishes a benchmark for developing advanced iodine adsorbents that combine fast kinetics, high capacity, excellent reusability, and facile rapid synthesis, a set of appealing features that remain challenging to merge in COF adsorbents so far., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Co-published by University of Science and Technology of China and American Chemical Society.)

Objective: To investigate the therapeutic effects of static magnetic field (SMF) and its regulatory mechanism in the repair of osteoarthritic cartilage., Methods: Fourteen-week-old female C57BL/6 mice were randomly divided into the sham operation group and the osteoarthritis (OA) groups with and without SMF application. SMF was applied at 200 ​mT for two consecutive weeks. Changes in knee cartilage were examined by histomorphometry, and the chondrogenesis and migration of endogenous stem cells were assessed. The expression of SRY-related protein 9 (SOX9), Collagen type II (COL2), matrix metallopeptidase 13 (MMP13), stromal cell-derived factor 1/C-X-C chemokine receptor type 4 (SDF-1/CXCR4), Piezo1 and other genes was evaluated, and the mechanism of SMF's action was tested using the CXCR4 inhibitor, AMD3100, and Piezo1 siRNA., Results: SMF significantly decreased the OARSI scores after induction of OA. SMF was beneficial to chondrogenesis by elevating SOX9. In the OA mouse model, an increase in MMP13 with a decrease in COL2 led to the destruction of the cartilage extracellular matrix, which was suppressed by SMF. SMF promoted the migration of cartilage-derived stem/progenitor cells and bone marrow-derived mesenchymal stem cells (MSCs). It increased SDF-1 and CXCR4, while the CXCR4 inhibitor significantly suppressed the beneficial effects of SMF. The application of Piezo1 siRNA inhibited the SMF-induced increase of CXCR4., Conclusion: SMF enhanced chondrogenesis and improved cartilage extracellular matrices. It activated the Piezo1-mediated SDF-1/CXCR4 regulatory axis and promoted the migration of endogenous stem cells. Collectively, it attenuated the pathological progression of cartilage destruction in OA mice., The Translational Potential of This Article: The findings in this study provided convincing evidence that SMF could enhance cartilage repair and improve OA symptoms, suggesting that SMF could have clinical value in the treatment of OA., (© 2022 The Authors.)

The calcineurin B-like (CBL)-interacting protein kinases (CIPKs), a type of plant-specific genes in the calcium signaling pathway, function in response to adverse environments. However, few halophyte derived CIPKs have been studied for their role in plant physiological and developmental adaptation during abiotic stresses, which inhibits the potential application of these genes to improve environmental adaptability of glycophytes. In this study, we constructed Nitraria billardieri CIPK25 overexpressing Arabidopsis and analyzed the seedling development under salt treatment. Our results show that Arabidopsis with NbCIPK25 expression exhibits more vigorous growth than wild type plants under salt condition. To gain insight into the molecular mechanisms underlying salt tolerance, we profiled the transcriptome of WT and transgenic plants via RNA-seq. GO and KEGG analyses revealed that upregulated genes in NbCIPK25 overexpressing seedlings under salt stress are enriched in photosynthesis related terms; Calvin-cycle genes including glyceraldehyde-3-phosphate dehydrogenases (GAPDHs) are significantly upregulated in transgenic plants, which is consistent with a decreased level of NADPH (GAPDH substrate) and increased level of NADP + . Accordingly, NbCIPK25 overexpressing plants exhibited more efficient photosynthesis; soluble sugar and proteins, as photosynthesis products, showed a higher accumulation in transgenic plants. These results provide molecular insight into how NbCIPK25 promotes the expression of genes involved in photosynthesis, thereby maintaining plant growth under salt stress. Our finding supports the potential application of halophyte-derived NbCIPK25 in genetic modification for better salt adaptation., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Lu, Wu, Tang, Zhu, Hao, Zhang, Li, Shi, Chen and Cheng.)

Osteoarthritis (OA) is a whole joint disorder that is characterized by cartilage damage and abnormal remodeling of subchondral bone. Injecting adipose-derived stem cells (ASCs) into the knee joint cavity can assist in repairing osteoarthritic joints, but their ability to migrate to the damaged site is limited. Our previous studies have shown that knee loading can improve the symptoms of OA, but the effect and mechanism of knee loading on the migration of ASCs in OA remain unclear. We employed a mouse model of OA in the knee and applied knee loading (1 N at 5 Hz for 6 min/day for 2 weeks) after the intra-articular injection of ASCs. The cartilage and subchondral bone repair were assessed by histopathological analysis. Immunofluorescence assays were also used to analyze the migration of ASCs. Using cell cultures, we evaluated the migration of ASCs using the transwell migration and wound healing assays. In vivo experiments showed that knee loading promoted the migration of ASCs, increased the local SDF-1 level, and accelerated the repair of the OA-damaged sites. Mechanistically, the observed effects were blocked by the SDF-1/CXCR4 inhibitor. The in vitro results further revealed that knee loading promoted the migration of ASCs and the inhibition of SDF-1/CXCR4 significantly suppressed the beneficial loading effect. The results herein suggested that the migration of ASCs was enhanced by knee loading through the SDF-1/CXCR4 regulatory axis, and mechanical loading promoted the joint-protective effect of ASCs., (© 2022. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Topochemical polymerization reactions hold the promise of producing ultra-high molecular weight crystalline polymers. However, the totality of topochemical polymerization reactions has failed to produce ultra-high molecular weight polymers that are both soluble and display variable functionality, which are restrained by the crystal-packing and reactivity requirements on their respective monomers in the solid state. Herein, we demonstrate the topochemical polymerization reaction of a family of para-azaquinodimethane compounds that undergo facile visible light and thermally initiated polymerization in the solid state, allowing for the first determination of a topochemical polymer crystal structure resolved via the cryoelectron microscopy technique of microcrystal electron diffraction. The topochemical polymerization reaction also displays excellent functional group tolerance, accommodating both solubilizing side chains and reactive groups that allow for post-polymerization functionalization. The thus-produced soluble ultra-high molecular weight polymers display superior capacitive energy storage properties. This study overcomes several synthetic and characterization challenges amongst topochemical polymerization reactions, representing a critical step toward their broader application., (© 2021. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

Covalent organic frameworks (COFs) with efficient charge transport and exceptional chemical stability are emerging as an import class of semiconducting materials for opto-/electronic devices and energy-related applications. However, the limited synthetic chemistry to access such materials and the lack of mechanistic understanding of carrier mobility greatly hinder their practical applications. Herein, we report the synthesis of three chemically stable polyarylether-based metallophthalocyanine COFs (PAE-PcM, M = Cu, Ni, and Co) and facile in situ growth of their thin films on various substrates (i.e., SiO 2 /Si, ITO, quartz) under solvothermal conditions. We show that PAE-PcM COFs thin films with van der Waals layered structures exhibit p -type semiconducting properties with the intrinsic mobility up to ∼19.4 cm 2 V -1 s -1 and 4 orders of magnitude of increase in conductivity for PAE-PcCu film (0.2 S m -1 ) after iodine doping. Density functional theory calculations reveal that the carrier transport in the framework is anisotropic, with the out-of-plane hole transport along columnar stacked phthalocyanine more favorable. Furthermore, PAE-PcCo shows the redox behavior maximumly contributes ∼88.5% of its capacitance performance, giving rise to a high surface area normalized capacitance of ∼19 μF cm -2 . Overall, this work not only offers fundamental understandings of electronic properties of polyarylether-based 2D COFs but also paves the way for their energy-related applications.

Two frontier crystalline porous framework materials, namely, metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), have been widely explored owing to their outstanding physicochemical properties. While each type of framework has its own intrinsic advantages and shortcomings for specific applications, combining the complementary properties of the two materials allows the engineering of new classes of hybrid porous crystalline materials with properties superior to the individual components. Since the first report of MOF/COF hybrid in 2016, it has rapidly evolved as a novel platform for diverse applications. The state-of-art advances in the various synthetic approaches of MOF/COF hybrids are hereby summarized, together with their applications in different areas. Perspectives on the main challenges and future opportunities are also offered in order to inspire a multidisciplinary effort toward the further development of chemically diverse, multi-functional hybrid porous crystalline materials., (© 2021 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Non-alcoholic fatty liver disease (NAFLD) is the most common liver disorder and frequently exacerbates in postmenopausal women. In NAFLD, the endoplasmic reticulum (ER) plays an important role in lipid metabolism, in which salubrinal is a selective inhibitor of eIF2α de-phosphorylation in response to ER stress. To determine the potential mechanism of obesity-induced NAFLD, we employed salubrinal and evaluated the effect of ER stress and autophagy on lipid metabolism. Ninety-five female C57BL/6 mice were randomly divided into five groups: standard chow diet, high-fat (HF) diet, HF with salubrinal, HF with ovariectomy, and HF with ovariectomy and salubrinal. All mice except for SC were given HF diet. After the 8-week obesity induction, salubrinal was subcutaneously injected for the next 8 weeks. The expression of ER stress and autophagy markers was evaluated in vivo and in vitro. Compared to the normal mice, the serum lipid level and adipose tissue were increased in obese mice, while salubrinal attenuated obesity by blocking lipid disorder. Also, the histological severity of hepatic steatosis and fibrosis in the liver and lipidosis was suppressed in response to salubrinal. Furthermore, salubrinal inhibited ER stress by increasing the expression of p-eIF2α and ATF4 with a decrease in the level of CHOP. It promoted autophagy by increasing LC3II/I and inhibiting p62. Correlation analysis indicated that lipogenesis in the development of NAFLD was associated with ER stress. Collectively, we demonstrated that eIF2α played a key role in obesity-induced NAFLD, and salubrinal alleviated hepatic steatosis and lipid metabolism by altering ER stress and autophagy through eIF2α signaling.

Two-dimensional polyimide covalent organic framework (2D PI-NT COF) films were constructed on indium tin oxide-coated glass substrates to fabricate two-terminal sandwiched resistive memory devices. The 2D PI-NT COF films condensated from the reaction between 4,4',4″-triaminotriphenylamine and naphthalene-1,4,5,8-tetracarboxylic dianhydride under solvothermal conditions demonstrated high crystallinity, good orientation preference, tunable thickness, and low surface roughness. The well-aligned electron-donor (triphenylamine unit) and -acceptor (naphthalene diimide unit) arrays rendered the 2D PI-NT COF films a promising candidate for electronic applications. The memory devices based on 2D PI-NT COF films exhibited a typical write-once-read-many-time resistive switching behavior under an operating voltage of +2.30 V on the positive scan and -2.64 V on the negative scan. A high ON/OFF current ratio (>10 6 for the positive scan and 10 4 -10 6 for the negative scan) and long-term retention time indicated the high fidelity, low error, and high stability of the resistive memory devices. The memory behavior was attributed to an electric field-induced intramolecular charge transfer in an ordered donor-acceptor system, which provided the effective charge-transfer channels for injected charge carriers. This work represents the first example that explores the resistive memory properties of 2D PI-COF films, shedding light on the potential application of 2D COFs as information storage media.

Ordered interlayer stacking is intrinsic in two-dimensional covalent organic frameworks (2D COFs) and has strong implications on COF's optoelectronic properties. Reversible interlayer sliding, corresponding to shearing of 2D layers along their basal plane, is an appealing dynamic control of both structures and properties, yet it remains unexplored in the 2D COF field. Herein, we demonstrate that the reversible interlayer sliding can be realized in an imine-linked tetrathiafulvalene (TTF)-based COF TTF-DMTA . The solvent treatment induces crystalline phase changes between the proposed staircase-like sql net structure and a slightly slipped eclipsed sql net structure. The solvation-induced crystallinity changes correlate well with reversible spectroscopic and electrical conductivity changes as demonstrated in oriented COF thin films. In contrast, no reversible switching is observed in a related TTF-TA COF, which differs from TTF-DMTA in terms of the absence of methoxy groups on the phenylene linkers. This work represents the first 2D COF example of which eclipsed and staircase-like aggregated states are interchangeably accessed via interlayer sliding, an uncharted structural feature that may enable applications such as chemiresistive sensors.

Membrane-based separations can mitigate the capital- and energy-intensive challenges associated with traditional thermally driven processes. To further push the boundary of gas separations, mixed matrix membranes (MMMs) have been extensively exploited; however, identifying an optimal nanofiller to boost the separation performance of MMMs beyond Robeson permeability-selectivity upper bounds remains an ongoing challenge. Here, a new class of MMMs based on pyrazine-fused crystalline porous graphitic frameworks (PGFs) is reported. At a loading of 6 wt % PGFs, the MMMs surpass the current H 2 /CH 4 Robeson upper bound, ideally suited for applications such as H 2 regeneration. In addition, the fabricated MMMs exhibit appealing CO 2 separation performance, closely approaching the current Robeson upper bounds for CO 2 separation. Compared with the pristine polymeric membranes, the PGF-based MMMs display a record-high enhancement of gas permeability over 120% while maintaining intrinsic gas selectivities. Highlighting the crucial role of the crystallinity of nanofillers, this study demonstrates a facile and effective approach in formulating high-performance MMMs, complementing state-of-the-art membrane formation processes. The design principles open the door to energy-efficient separations of gas mixtures with enhanced productivity compatible with the current membrane manufacturing.

Bone loss in postmenopausal osteoporosis is induced chiefly by an imbalance of bone-forming osteoblasts and bone-resorbing osteoclasts. Salubrinal is a synthetic compound that inhibits de-phosphorylation of eukaryotic translation initiation factor 2 alpha (eIF2α). Phosphorylation of eIF2α alleviates endoplasmic reticulum (ER) stress, which may activate autophagy. We hypothesized that eIF2α signaling regulates bone homeostasis by promoting autophagy in osteoblasts and inhibiting osteoclast development. To test the hypothesis, we employed salubrinal to elevate the phosphorylation of eIF2α in an ovariectomized (OVX) mouse model and cell cultures. In the OVX model, salubrinal prevented abnormal expansion of rough ER and decreased the number of acidic vesiculars. It regulated ER stress-associated signaling molecules such as Bip, p-eIF2α, ATF4 and CHOP, and promoted autophagy of osteoblasts via regulation of eIF2α, Atg7, LC3, and p62. Salubrinal markedly alleviated OVX-induced symptoms such as reduction of bone mineral density and bone volume fraction. In primary bone-marrow-derived cells, salubrinal increased the differentiation of osteoblasts, and decreased the formation of osteoclasts by inhibiting nuclear factor of activated T-cells cytoplasmic 1 (NFATc1). Live cell imaging and RNA interference demonstrated that suppression of osteoclastogenesis is in part mediated by Rac1 GTPase. Collectively, this study demonstrates that ER stress-autophagy axis plays an important role in OVX mice. Bone-forming osteoblasts are restored by maintaining phosphorylation of eIF2α, and bone-resorbing osteoclasts are regulated by inhibiting NFATc1 and Rac1 GTPase.

Osteoarthritis (OA) is a disease characterized by cartilage damage and abnormal remodeling of subchondral bone. Our previous study showed that in the early stage of OA, knee loading exerts protective effects by suppressing osteoclastogenesis through Wnt signaling, but little is known about loading effects at the late OA stage. Endoplasmic reticulum (ER) stress and autophagy are known to be involved in the late OA stage. We determined the effects of mechanical loading on ER stress and autophagy in OA mice. One hundred seventy-four mice were used for a surgery-induced OA model. In the first set of experiments, 60 mice were devoted to evaluation of the role of ER stress and autophagy in the development of OA. In the second set, 114 mice were used to assess the effect of knee loading on OA. Histologic, cellular, microcomputed tomography, and electron microscopic analyses were performed to evaluate morphologic changes, ER stress, and autophagy. Mechanical loading increased phosphorylation of eukaryotic translation initiation factor 2α (eIF2α) and regulated expressions of autophagy markers LC3II/I and p62. Osteoarthritic mice also exhibited an elevated ratio of calcified cartilage to total articular cartilage (CC/TAC), and synovial hyperplasia with increased lining cells was found. At the early disease stage, subchondral bone plate thinning and reduced subchondral bone volume fraction (B.Ar/T.Ar) were observed. At the late disease stages, subchondral bone plate thickened concomitant with increased B.Ar/T.Ar. Mice subjected to mechanical loading exhibited resilience to cartilage destruction and a correspondingly reduced Osteoarthritis Research Society International score at 4 and 8 wk, as well as a decrease in synovitis and CC/TAC. While chondrocyte numbers in the OA group was notably decreased, mechanical loading restored chondrogenic differentiation. These results demonstrate that mechanical loading can retard the pathologic progression of OA at its early and late stages. The observed effects of loading are associated with the regulations of ER stress and autophagy.-Zheng, W., Li, X., Liu, D., Li, J., Yang, S., Gao, Z., Wang, Z., Yokota, H., Zhang, P. Mechanical loading mitigates osteoarthritis symptoms by regulating endoplasmic reticulum stress and autophagy.

The facile pyrolysis of a bipyridyl metal-organic framework, MOF-253, produces N-doped porous carbons (Cz-MOF-253), which exhibit excellent catalytic activity in the Knoevenagel condensation reaction and outperform other nitrogen-containing MOF-derived carbons. More importantly, by virtue of their high Lewis basicity and porous nature, Cz-MOF-253-supported Pd nanoparticles (Pd/Cz-MOF-253-800) show excellent performance in a one-pot sequential Knoevenagel condensation-hydrogenation reaction., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Osteonecrosis of the femoral head is a serious orthopedic problem. Moderate loads with knee loading promote bone formation, but their effects on osteonecrosis have not been investigated. Using a rat model, we examined a hypothesis that knee loading enhances vessel remodeling and bone healing through the modulation of the fate of bone marrow-derived cells. In this study, osteonecrosis was induced by transecting the ligamentum teres followed by a tight ligature around the femoral neck. For knee loading, 5 N loads were laterally applied to the knee at 15 Hz for 5 min/day for 5 weeks. Changes in bone mineral density (BMD) and bone mineral content (BMC) of the femur were measured by pDEXA, and ink infusion was performed to evaluate vessel remodeling. Femoral heads were harvested for histomorphometry, and bone marrow-derived cells were isolated to examine osteoclast development and osteoblast differentiation. The results showed that osteonecrosis significantly induced bone loss, and knee loading stimulated both vessel remodeling and bone healing. The osteonecrosis group exhibited the lowest trabecular BV/TV (p b 0.001) in the femoral head, and lowest femoral BMD and BMC (both p b 0.01). However, knee loading increased trabecular BV/TV (p b 0.05) as well as BMD (pb 0.05) and BMC (p b 0.01). Osteonecrosis decreased the vessel volume (pb 0.001), vessel number (pb 0.001) and VEGF expression (p b 0.01), and knee loading increased them (pb 0.001, pb 0.001 and p b 0.01). Osteonecrosis activated osteoclast development, and knee loading reduced its formation, migration, adhesion and the level of “pit” formation (pb 0.001, pb 0.01, pb 0.001 and pb 0.001). Furthermore, knee loading significantly increased osteoblast differentiation and CFU-F (both p b 0.001). A significantly positive correlation was observed between vessel remodeling and bone healing (both p b 0.01). These results indicate that knee loading could be effective in repair osteonecrosis of the femoral head in a rat model. This effect might be attributed to promoting vessel remodeling, suppressing osteoclast development, and increasing osteoblast and fibroblast differentiation. In summary, the current study suggests that knee loading might potentially be employed as a non-invasive therapy for osteonecrosis of the femoral head.

A new porphyrin-based microporous MOF, {Mn(II)0.5[Mn(II)4Cl(Mn(III)Cl-ttzpp)2(H2O)4]}·(DEF)20·(CH3OH)18·(H2O)12 (UTSA-57), has been constructed from {5,10,15,20-tetrakis[4-(2,3,4,5-tetrazolyl)phenyl]porphyrinato} manganese(III) chloride as the metalloligand. The MOF adopts the rare scu topology with one-dimensional square nanotube-like channels of about 20 Å. UTSA-57a exhibits permanent porosity and displays moderately high performance for C2H2/CH4 separation at room temperature.