Topochemical cross-linking of diacetylene in a highly interpenetrated three-dimensional covalent organic framework.

Topochemical polymerization is a highly promising and effective method for constructing complex three-dimensional structures and functionalized polymers. Herein, we present for the first time a topochemical reaction of diacetylene within a meticulously designed covalent organic framework (ZNUC-1). Our experimental results revealed that ZNUC-1 underwent a 1,4-addition reaction under thermal induction, forming an ene-yne-conjugated structure.

Metal-Organic Framework with Space-Partition Pores by Fluorinated Anions for Benchmark C2H2/CO2 Separation.

The efficient separation of C2H2 from C2H2/CO2 or C2H2/CO2/CH4 mixtures is crucial for achieving high-purity C2H2 (>99%), essential in producing contemporary commodity chemicals. In this report, we present ZNU-12, a metal-organic framework with space-partitioned pores formed by inorganic fluorinated anions, for highly efficient C2H2/CO2 and C2H2/CO2/CH4 separation. The framework, partitioned by fluorinated SiF62- anions into three distinct cages, enables both a high C2H2 capacity (176.5 cm3/g at 298 K and 1.0 bar) and outstanding C2H2 selectivity over CO2 (13.4) and CH4 (233.5) simultaneously. Notably, we achieve a record-high C2H2 productivity (132.7, 105.9, 98.8, and 80.0 L/kg with 99.5% purity) from C2H2/CO2 (v/v = 50/50) and C2H2/CO2/CH4 (v/v = 1/1/1, 1/1/2, or 1/1/8) mixtures through a cycle of adsorption-desorption breakthrough experiments with high recovery rates. Theoretical calculations suggest the presence of potent "2 + 2" collaborative hydrogen bonds between C2H2 and two hexafluorosilicate (SiF62-) anions in the confined cavities.

Lipocalin-2-mediated intestinal epithelial cells pyroptosis via NF-κB/NLRP3/GSDMD signaling axis adversely affects inflammation in colitis.

Ulcerative colitis (UC) is a major inflammatory bowel disease (IBD) characterized by intestinal epithelium damage. Recently, Lipocalin-2 (LCN2) has been identified as a potential fecal biomarker for patients with UC. However, further investigation is required to explore its pro-inflammatory role in UC and the underlying mechanism. The biological analysis revealed that Lcn2 serves as a putative signature gene in the colon mucosa of patients with UC and its association with the capsase/pyroptosis signaling pathway in UC. In wild-type mice with DSS-induced colitis, LCN2 overexpression in colon mucosa via in vivo administration of Lcn2 overexpression plasmid resulted in exacerbation of colitis symptoms and epithelium damage, as well as increased expression levels of pyroptosis markers (cleaved caspase1, GSDMD, IL-1ß, HMGB1 and IL-18). Additionally, we observed downregulation in the expression levels of pyroptosis markers following in vivo silencing of LCN2. However, the pro-inflammatory effect of LCN2 overexpression was effectively restrained in GSDMD-KO mice. Moreover, single-cell RNA-sequencing analysis revealed that Lcn2 was predominantly expressed in the intestinal epithelial cells (IECs) within the colon mucosa of patients with UC. We found that LCN2 effectively regulated pyroptosis events by modulating the NF-κB/NLRP3/GSDMD signaling axis in NCM460 cells stimulated by LPS and ATP. These findings demonstrate the pro-inflammatory role of LCN2 in colon epithelium and provide a potential target for inhibiting pyroptosis in UC.

A novel hydrophobic carborane-hybrid microporous material for reversed C2H6 adsorption and efficient C2H4/C2H6 separation under humid conditions.

Since ethylene (C2H4) is important feedstock in the chemical industry, developing economical and energy-efficient adsorption separation techniques based on ethane (C2H6)-selective adsorbents to replace the energy-intensive cryogenic distillation is highly demanded, which however remains a daunting challenge. While previous anionic boron cluster hybrid microporous materials display C2H4-selective features, we herein reported that the incorporation of a neutral para-carborane backbone and aliphatic 1,4-diazabicyclo[2.2.2]octane (DABCO) enables the reversed adsorption of C2H6 over C2H4. The generated carborane-hybrid microporous material ZNU-10 (ZNU = Zhejiang Normal University) is highly stable in humid air and maintains good C2H6/C2H4 separation performance under high humidity. Gas loaded single crystal structure and density-functional theory (DFT) calculations revealed that the weakly polarized carborane and DABCO within ZNU-10 induce more specific C-Hδ+⋯Hδ--B dihydrogen bonds and other van der Waals interactions with C2H6, while the suitable pore space allows the high C2H6 uptake. Approximately 14.5 L kg-1 of polymer grade C2H4 can be produced from simulated C2H6/C2H4 (v/v 10/90) mixtures under ambient conditions in a single step, comparable to those of many popular materials.

3D Covalent Organic Framework with "the" Topology.

Discovery of new topology covalent organic frameworks (COFs) is a mainstay in reticular chemistry and materials research because it not only serves as a stepwise guide to the designed construction of covalent-organic architectures but also helps to comprehend function from structural design point-of-view. Proceeding on this track, the first 3D COF, TUS-38, with the topology is constructed by reticulating a planar triangular 3-c node of D3h symmetry with a tetragonal prism 8-c node of D2h symmetry via [3 + 8] reversible imine condensation reaction. TUS-38 represents a twofold interpenetrated multidirectional pore network with a high degree of crystallinity and structural integrity. Interestingly, stemming from the nitrogen-rich s-triazine rings with electron-deficient character and ─C â• N─ linkages composing the TUS-38 framework that benefit to the charge-transfer and hence dipole-dipole electrostatic interactions between the framework and iodine in addition to exclusive topological characteristics of the exotic the net, TUS-38 achieves an exemplary capacity for iodine vapor uptake reaching 6.3 g g-1. Recyclability studies evidence that TUS-38 can be reused at least five times retaining 95% of its initial adsorption capacity; while density functional theory (DFT) calculations have heightened the understanding of the interactions between iodine molecules and the framework.

Crystalline porous organic salts.

Crystalline porous organic salts (CPOSs), formed by the self-assembly of organic acids and organic bases through ionic bonding, possess definite structures and permanent porosity and have rapidly emerged as an important class of porous organic materials in recent years. By rationally designing and controlling tectons, acidity/basicity (pKa), and topology, stable CPOSs with permanent porosity can be efficiently constructed. The characteristics of ionic bonds, charge-separated highly polar nano-confined channels, and permanent porosity endow CPOSs with unique physicochemical properties, offering extensive research opportunities for exploring their functionalities and application scenarios. In this review, we systematically summarize the latest progress in CPOS research, describe the synthetic strategies for synthesizing CPOSs, delineate their structural characteristics, and highlight the differences between CPOSs and hydrogen-bonded organic frameworks (HOFs). Furthermore, we provide an overview of the potential applications of CPOSs in areas such as negative linear compression (NLC), proton conduction, rapid transport of CO2, selective and rapid transport of K+ ions, atmospheric water harvesting (AWH), gas sorption, molecular rotors, fluorescence modulation, room-temperature phosphorescence (RTP) and catalysis. Finally, the challenges and future perspectives of CPOSs are presented.

Anhydrous Proton Conduction Through a Chemically Robust Electrolyte Enabling a High-Temperature Non-Precious Metal Catalyzed Fuel Cell.

Fuel cells offer great promise for portable electricity generation, but their use is currently limited by their low durability, excessive operating temperatures, and expensive precious metal electrodes. It is therefore essential to develop fuel cell systems that can perform effectively using more robust electrolyte materials, at reasonable temperatures, with lower-cost electrodes. Recently, proton exchange membrane fuel cells have attracted attention due to their generally favorable chemical stability and quick start-up times. However, in most membrane materials, water is required for proton conduction, severely limiting operational temperatures. Here, for the first time it is demonstrated that when acidified, PAF-1 can conduct protons at high temperatures, via a unique framework diffusion mechanism. It shows that this acidified PAF-1 material can be pressed into pellets with high proton conduction properties even at high temperatures and pellet thickness, highlighting the processibility, and ease of use of this material. Furthermore, a fuel cell is shown with high power density output is possible using a non-precious metal copper electrode. Acid-doped PAF-1 therefore represents a significant step forward in the potential for a broad-purpose fuel cell due to it being cheap, robust, efficient, and easily processible.

Porous Materials for Atmospheric Water Harvesting.

Atmospheric Water Harvesting (AWH) using porous adsorbents is emerging as a promising solution to combat water shortage. Thus, a clearer understanding of the developing trends and optimization strategies of different porous adsorbents can be extremely helpful. Therefore, in this concept, the different types of porous adsorbents and AWH devices are briefly introduced with a focus on the factors that influence the static and kinetic properties of porous adsorbents and their respective optimization strategies. In addition, the fast transport characteristics of water molecules in micropores are studied from the perspective of superfluidity as part of the analysis of the kinetic properties of porous adsorbents. Finally, the future development of porous materials for AWH and the accompanying challenges are summarized.

Record Ultralarge-Pores, Low Density Three-Dimensional Covalent Organic Framework for Controlled Drug Delivery.

The unique structural characteristics of three-dimensional (3D) covalent organic frameworks (COFs) like high surface areas, interconnected pore system and readily accessible active sites render them promising platforms for a wide set of functional applications. Albeit promising, the reticular construction of 3D COFs with large pores is a very demanding task owing to the formation of interpenetrated frameworks. Herein we report the designed synthesis of a 3D non-interpenetrated stp net COF, namely TUS-64, with the largest pore size of all 3D COFs (47 Å) and record-low density (0.106 g cm-3 ) by reticulating a 6-connected triptycene-based linker with a 4-connected porphyrin-based linker. Characterized with a highly interconnected mesoporous scaffold and good stability, TUS-64 shows efficient drug loading and controlled release for five different drugs in simulated body fluid environment, demonstrating the competency of TUS-64 as drug nanocarriers.

Reply to the Correspondence on "Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System".

White et al., in a recent Correspondence, provided additional structural data to illustrate that CPOS-6 undergoes a single-crystal-to-single-crystal transformation during water adsorption/desorption. This finding gave a better understanding of the relevant experimental phenomena from the perspective of structural transformation and is a good complement to our previous results. However, we wish to emphasize that our research focuses on the kinetic behavior of water during ultrafast adsorption/desorption in nano-confined channels. Herein, we further interpret the rapid transport of water molecules in the nano-confined channels from the perspective of superfluidity.

Recent Advances in Porous Polymers for Solid-State Rechargeable Lithium Batteries.

The application of rechargeable lithium batteries involves all aspects of our daily life, such as new energy vehicles, computers, watches and other electronic mobile devices, so it is becoming more and more important in contemporary society. However, commercial liquid rechargeable lithium batteries have safety hazards such as leakage or explosion, all-solid-state lithium rechargeable lithium batteries will become the best alternatives. But the biggest challenge we face at present is the large solid-solid interface contact resistance between the solid electrolyte and the electrode as well as the low ionic conductivity of the solid electrolyte. Due to the large relative molecular mass, polymers usually exhibit solid or gel state with good mechanical strength. The intermolecules are connected by covalent bonds, so that the chemical and physical stability, corrosion resistance, high temperature resistance and fire resistance are good. Many researchers have found that polymers play an important role in improving the performance of all-solid-state lithium rechargeable batteries. This review mainly describes the application of polymers in the fields of electrodes, electrolytes, electrolyte-electrode contact interfaces, and electrode binders in all-solid-state lithium rechargeable batteries, and how to improve battery performance. This review mainly introduces the recent applications of polymers in solid-state lithium battery electrodes, electrolytes, electrode binders, etc., and describes the performance of emerging porous polymer materials and materials based on traditional polymers in solid-state lithium batteries. The comparative analysis shows the application advantages and disadvantages of the emerging porous polymer materials in this field which provides valuable reference information for further development.

Crystalline Porous Organic Salt for Ultrarapid Adsorption/Desorption-Based Atmospheric Water Harvesting by Dual Hydrogen Bond System.

In recent years, the porous sorbent-assisted atmospheric water harvesting (AWH) method has emerged as an effective approach for solving water crises without geographical restrictions. However, there is a limited array of porous adsorbent materials that can be used for AWH, which are inadequate to meet the needs under different climatic conditions. In light of this, herein, we synthesize a new crystalline porous organic salt (CPOS; denoted as CPOS-6) possessing a dual hydrogen bond system and verify its applicability toward AWH for the first time. Unlike other reported CPOSs, CPOS-6 displays an S-shaped water sorption isotherm owing to the presence of the dual hydrogen bond system. Under simulated drought conditions in Xinjiang Uygur Autonomous Region, CPOS-6 exhibits long-term water adsorption-desorption cycling stability, low water desorption temperature, and ultrarapid adsorption-desorption kinetics. The results confirm that CPOS-6 is an effective sorbent material for AWH.

Biomimetic KcsA channels with ultra-selective K+ transport for monovalent ion sieving.

Ultra-selective and fast transport of K+ are of significance for water desalination, energy conversion, and separation processes, but current bottleneck of achieving high-efficiency and exquisite transport is attributed to the competition from ions of similar dimensions and same valence through nanochannel communities. Here, inspired by biological KcsA channels, we report biomimetic charged porous subnanometer cages that enable ultra-selective K+ transport. For nanometer to subnanometer scales, conically structured double-helix columns exhibit typical asymmetric transport behaviors and conduct rapid K+ with a transport rate of 94.4 mmol m-2 h-1, resulting in the K+/Li+ and K+/Na+ selectivity ratios of 363 and 31, respectively. Experiments and simulations indicate that these results stem from the synergistic effects of cation-π and electrostatic interactions, which impose a higher energy barrier for Li+ and Na+ and lead to selective K+ transport. Our findings provide an effective methodology for creating in vitro biomimetic devices with high-performance K+ ion sieving.

Direct realization of an Operando Systems Chemistry Algorithm (OSCAL) for powering nanomotors.

Systems chemistry focuses on emergent properties in a complex matter. To design and demonstrate such emergent properties like autonomous motion in nanomotors as an output of an Operando Systems Chemistry Algorithm (OSCAL), we employ a 2-component system comprising porous organic frameworks (POFs) and soft-oxometalates (SOMs). The OSCAL governs the motion of the nanocarpets by the coding and reading of information in an assembly/disassembly cascade switched on by a chemical stimulus. Assembly algorithm docks SOMs into the pores of the POFs of the nanocarpet leading to the encoding of supramolecular structural information in the SOM-POF hybrid nanocarpet. Input of a chemical fuel to the system induces a catalytic reaction producing propellant gases and switches on the disassembly of SOMs that are concomitantly released from the pores of the SOM-POF nanocarpets producing a ballast in the system as a read-out of the coded information acquired in the supramolecular assembly. The OSCAL governs the motion of the nanocarpets in steps. The assembly/disassembly of SOM-POFs, releasing SOMs from the pores of SOM-POFs induced by a catalytic reaction triggered by a chemical stimulus coupled with the evolution of gas are the input. The output is the autonomous linear motion of the SOM-POF nanocarpets resulting from the read-out of the input information. This work thus manifests the operation of a designed Systems Chemistry algorithm which sets supramolecularly assembled SOM-POF nanocarpets into autonomous ballistic motion.

Self-Assembly and Cascade Catalysis by a Soft-Oxometalate (SOM) System.

Cascade catalysis has gained importance due to its various applications. In this work, cascade catalysis was performed using a self-assembled soft-oxometalate (SOM) as a model system. At first, we synthesized an oxometalate (OM) hybrid with a polymerizable organic cation, namely tetrakis(4-aminophenyl)methane, and an OM, K8[SiW11O39]. The hybrid in turn was converted into SOM in water, DMSO mixture, and characterized by different techniques, ranging from electron microscopy to DLS. The SOM state is endowed with the ability to polymerize the aniline based counter ions associated with it in the presence of UV-light. This polymerization is possible due to the presence of photocatalytic OMs (oxometalates) in the SOMs. The polymer-SOM hybrid in cascade oxidizes selectively aniline to nitrobenzene and nitrite to nitrate owing to the residual oxidizing property of the OM constituents in it. This is the first example of cascade catalysis in SOM chemistry.

Two-Dimensional COF-Three-Dimensional MOF Dual-Layer Membranes with Unprecedentedly High H2/CO2 Selectivity and Ultrahigh Gas Permeabilities.

Composite membranes embodying multilayered architecture have been on an uptrend to tap the synergy between different materials to attain new heights in gas separation performance. In the light of sustainable materials research, covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) have emerged as cutting-edge platforms for molecular-sieving membranes owing to their phenomenal surface areas, ultrahigh porosities, and precise control over chemical functionalities. In this study, we report for the first time a three-dimensional (3D) MOF-mediated strategy where a specially designed MOF film provides the binding sites along the vertical direction to anchor the two-dimensional (2D) COF structural building units. The strong chemical bonding between the 3D MOF and 2D COF provides a new outlook to fabricate 2D COF-based composite membranes. The π-stacked columns of 2D H2P-DHPh COF that can contribute to direct pathways for gas transport render the resulting membrane incredibly promising for high-flux gas separation. Besides, the chemical synergy between the MOF and COF endows the thus-developed H2P-DHPh COF-UiO-66 composite membrane with unprecedented H2/CO2 gas mixture selectivity (32.9) as well as ultrahigh H2 (108 341.3 Barrer) and CO2 permeabilities, which significantly outperform the present Robeson upper bound and polymer membranes hitherto reported.

Crystalline Porous Organic Salts: From Micropore to Hierarchical Pores.

Crystalline porous organic salts (CPOSs), as an emerging class of porous organic materials, combining the uniform microporous system and distinct polarized channels, have become a highly evolving field of important current interest. The unique ionic bond of a CPOS endows the confined channels with high polarity, making CPOSs distinct from other organic frameworks. CPOSs show many fascinating properties, such as proton conductivity and fast transport of polar molecules, which involve the interaction between highly polarized guest molecules and host frameworks. Substantial progress has been made in the synthesis and applications of CPOSs. Herein, an overview is provided to impart a comprehensive understanding of the link between the synthetic approaches and the resultant microporous structure, the structure-function correlation and the state-of-the-art applications of CPOSs. The enhanced mass-transport performance of hierarchically porous structure in combination with the intrinsic polarized channels of CPOSs is very promising to create new applications and contribute to a new research upsurge. The perspective to construct porous hierarchy within the crystalline porous organic salts is assessed and will open a new research avenue. In the conclusion, the current challenges on the synthesis, structural regulation, and applications of CPOSs and the future of hierarchically porous crystalline organic salts are discussed.

Colossal Negative Linear Compressibility in Porous Organic Salts.

Negative linear compressibility (NLC) is a common sense violation (that is, crystal phases expand in one or more directions under hydrostatic compression). The excellent NLC performance of crystal materials is intrinsically related to the geometric structure of its skeleton. Here, we discovered a crystalline porous organic salt (CPOS-1); high-pressure X-ray diffraction experiments reveal that the CPOS-1 shows colossal NLC (Kc = -90.7 T Pa-1) behavior along the c axis. This incredible performance arises from the flexible "supramolecular spring" formed by the charge-enhanced N-H+···-O-S hydrogen bond interaction between the anionic sulfonate and the cationic ammonium ion. Furthermore, we reveal the relationship between this rare NLC behavior and single crystal proton conductivity using high-pressure electrochemical impedance spectroscopy (EIS) method. We believe that NLC behavior research on such inexpensive and readily available porous organic materials is of great significance for accelerating the research and application of NLC materials, especially in organic system.

High Uptake and Fast Transportation of LiPF6 in a Porous Aromatic Framework for Solid-State Li-Ion Batteries.

Solid-state Li-ion batteries (SSLIBs) have recently attracted substantial attention from scientists for the advantages of better safety performance. However, there are still several key challenges in SSLIBs that need to be addressed, such as low energy density, poor thermal stability or cycle stability, and large interface resistance. This contribution introduces a novel SSLIB with a porous aromatic framework (PAF-1) accommodating LiPF6 that was used as the solid-state electrolyte (SSE) replacing the liquid electrolyte and diaphragm of traditional Li-ion batteries. The charge, discharge capacity, rate performance and cycle stability of the SSLIB were remarkably enhanced.