A Porphyrinic Metal-Organic Framework with Cooperative Adsorption Domains for PFAS Removal from Water.

The removal of toxic poly- and perfluoroalkyl substances (PFAS) as persistent pollutants from wastewater is imperative but challenging for water remediation. Many adsorbents including activated carbon, biochar, and clay minerals have been investigated for PFAS removal, but most of these materials are faced with high cost or/and low efficiency. The use of metal-organic frameworks (MOFs) as sorbents is attractive for efficient removal of PFAS due to their tailor-made structures and high surface areas. Herein, we synthesized, characterized a water stable Zr-based porphyrinic MOF (PCN-224) with cooperative adsorption domains, and demonstrated its excellent capture performance toward perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorobutane sulfonate (PFBS). PCN-224 has maximum uptake capacities of 963, 517, and 395 mg g-1 for PFOS, PFHxS, and PFBS, respectively, which are much higher than that of granular activated carbon. Moreover, coexistent anions (Cl-, SO4 2-) and humic acid have negligible effects on PFOS adsorption. The excellent adsorption performance of PCN-224 toward PFOS is due to the orthogonal cationic channel pores with a diameter of 1.9 nm, the hydrophobic porphyrin units, and the Zr6 clusters with acidic sites. PCN-224 can be readily regenerated and reused. This work highlights the potential of MOFs with multiple adsorption domains for water remediation.

Photoelectron Migration Boosted by Hollow Double-Shell Dyads Based on Covalent Organic Frameworks for Highly Efficient Photocatalytic Hydrogen Generation.

Photocatalytic hydrogen production based on noble metal-free systems is a promising technology for the conversion of solar energy into green hydrogen, it is pivotal and challenging to tailor-make photocatalysts for achieving high photocatalytic efficiency. Herein, we reported a hollow double-shell dyad through uniformly coating covalent organic frameworks (COFs) on the surface of hollow Co9S8. The double shell architecture enhances the scattering and refraction efficiency of incident light, shortens the transmission distance of the photogenerated charge carriers, and exposes more active sites for photocatalytic conversion. The hydrogen evolution rate is as high as 23.15 mmol g-1 h-1, which is significantly enhanced when compared with that of their physical mixture (0.30 mmol g-1 h-1) and Pt-based counterpart (11.84 mmol g-1 h-1). This work provides a rational approach to the construction of noble-metal-free photocatalytic systems based on COFs to enhance hydrogen evolution performance.

Exploring the therapeutic potential of Sirt6-enriched adipose stem cell-derived exosomes in myocardial ischemia-reperfusion injury: unfolding new epigenetic frontiers.

BACKGROUND: The management of myocardial ischemia-reperfusion injury (MIRI) presents continuous therapeutic challenges. NAD-dependent deacetylase Sirtuin 6 (Sirt6) plays distinct roles in various disease contexts and is hence investigated for potential therapeutic applications for MIRI. This study aimed to examine the impact of Sirt6-overexpressing exosomes derived from adipose stem cells (S-ASC-Exo) on MIRI, focusing on their influence on AIM2-pyroptosis and mitophagy processes. The sirtuin family of proteins, particularly Sirtuin 6 (Sirt6), play a pivotal role in these processes. This study aimed to explore the potential therapeutic effects of Sirt6-enriched exosomes derived from adipose stem cells (S-ASC-Exo) on regulating MIRI. RESULTS: Bioinformatic analysis revealed a significant downregulation of Sirt6 in MIRI subjected to control group, causing a consequential increase in mitophagy and pyroptosis regulator expressions. Therefore, our study revealed that Sirt6-enriched exosomes influenced the progression of MIRI through the regulation of target proteins AIM2 and GSDMD, associated with pyroptosis, and p62 and Beclin-1, related to mitophagy. The introduction of S-ASC-Exo inhibited AIM2-pyroptosis while enhancing mitophagy. Consequently, this led to a significant reduction of GSDMD cleavage and pyroptosis in endothelial cells, catalyzing a deceleration in the progression of atherosclerosis. Extensive in vivo and in vitro assays were performed to validate the expressions of these specific genes and proteins, which affirmed the dynamic modulation by Sirt6-enriched exosomes. Furthermore, treatment with S-ASC-Exo drastically ameliorated cardiac functions and limited infarct size, underlining their cardioprotective attributes. CONCLUSIONS: Our study underscores the potential therapeutic role of Sirt6-enriched exosomes in managing MIRI. We demonstrated their profound cardioprotective effect, evident in the enhanced cardiac function and attenuated tissue damage, through the strategic modulation of AIM2-pyroptosis and mitophagy. Given the intricate interplay between Sirt6 and the aforementioned processes, a comprehensive understanding of these pathways is essential to fully exploit the therapeutic potential of Sirt6. Altogether, our findings indicate the promise of Sirt6-enriched exosomes as a novel therapeutic strategy in treating ischemia-reperfusion injuries and cardiovascular diseases at large. Future research needs to underscore optimizing the balance of mitophagy during myocardial ischemia to avoid potential loss of normal myocytes.

Interactions among the composition changes in fungal communities and the main mycotoxins in simulated stored wheat grains.

BACKGROUND: There are significant food safety risks associated with wheat spoilage due to fungal growth and mycotoxin contamination. Nevertheless, a few studies have examined how stored wheat grain microbial communities and mycotoxins vary in different storage conditions. In this study, changes in deoxynivalenol (DON) and deoxynivalenol-3-glucoside (D3G) content were measured with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), and an amplicon sequence analysis of fungi was performed on stored wheat grains from different storage conditions using high-throughput sequencing. The detailed interactions among the composition changes in the fungal community and the DON content of simulated stored wheat grains were also analyzed. RESULTS: Alternaria, Fusarium, Mrakia, and Aspergillus were the core fungal taxa, and the fungal communities of samples stored under different conditions were observed to be different. Aspergillus relative abundances increased, whereas Fusarium decreased. This led to an increase in the content of DON. The content of DON increased about 67% with 12% moisture and at 25 °C after 2 months of storage, which was influenced by the stress response of Fusarium. Correlations in fungal and mycotoxins changes were observed. There may be potential value in these findings for developing control strategies to prevent mildew infestations and mycotoxins contamination during grain storage. CONCLUSION: In storage, the more the fungal community composition and the relative abundance of Fusarium change, the more mycotoxins will be produced. We should therefore reduce competition between fungal communities through pre-storage treatment and through measures during storage. © 2023 Society of Chemical Industry.

The Structural and Electronic Engineering of Molybdenum Disulfide Nanosheets as Carbon-Free Sulfur Hosts for Boosting Energy Density and Cycling Life of Lithium-Sulfur Batteries.

The compact sulfur cathodes with high sulfur content and high sulfur loading are crucial to promise high energy density of lithium-sulfur (Li-S) batteries. However, some daunting problems, such as low sulfur utilization efficiency, serious polysulfides shuttling, and poor rate performance, are usually accompanied during practical deployment. The sulfur hosts play key roles. Herein, the carbon-free sulfur host composed of vanadium-doped molybdenum disulfide (VMS) nanosheets is reported. Benefiting from the basal plane activation of molybdenum disulfide and structural advantage of VMS, high stacking density of sulfur cathode is allowed for high areal and volumetric capacities of the electrodes together with the effective suppression of polysulfides shuttling and the expedited redox kinetics of sulfur species during cycling. The resultant electrode with high sulfur content of 89 wt.% and high sulfur loading of 7.2 mg cm-2 achieves high gravimetric capacity of 900.9 mAh g-1 , the areal capacity of 6.48 mAh cm-2 , and volumetric capacity of 940 mAh cm-3 at 0.5 C. The electrochemical performance can rival with the state-of-the-art those in the reported Li-S batteries. This work provides methodology guidance for the development of the cathode materials to achieve high-energy-density and long-life Li-S batteries.

Covalent Organic Frameworks for Separator Modification of Lithium-Sulfur Batteries.

Lithium-sulfur (Li-S) batteries are regarded as one of the promising energy storage systems. However, rapid capacity attenuation caused by shuttle effect of soluble polysulfides is major challenge in practical application. The separator modification is regarded as one countermeasure besides the construction of sulfur host materials. Covalent organic frameworks (COFs) are one type of outstanding candidates for suppressing shuttle effect of polysulfides. Herein, recent advances of COFs in the application as commercial separator modifiers are summarized. COFs serve as ionic sieves, the importance of porous size and surface environments in inhibiting soluble polysulfides shuttling and promoting lithium ions conduction is highlighted. The superiority of charge-neutral COFs, ionic COFs, and the composites of COFs with conductive materials for improving reversible capacity and cycling stability is demonstrated. Some new strategies for the design of COF-based separator modifiers are proposed to achieving high energy density. The review provides new perspectives for future development of high-performance Li-S batteries.

Transformation of Covalent Organic Frameworks from N-Acylhydrazone to Oxadiazole Linkages for Smooth Electron Transfer in Photocatalysis.

Covalent organic frameworks (COFs) are regarded as new platforms for solar-to-chemical energy conversion due to their tailor-made functions and pre-designable structures. Their intrinsic reversibility and the high polarization of organic linkages inevitably result in poor chemical stability and weak optoelectronic properties. Herein, one N-acylhydrazone-linked COF (H-COF) was converted into a stable and π-conjugated oxadiazole-linked COF via post-oxidative cyclization. Both chemical stability and π-electron delocalization throughout the reticular framework are significantly improved, leading to a high hydrogen evolution rate of 2615 µmol g-1 h-1 upon visible light irradiation, which is over four times higher than that of H-COF. This work provides a facile protocol for the fabrication of π-conjugated COFs and the modulation of photophysical properties for photocatalytic application.

Chemically Activating Tungsten Disulfide via Structural and Electronic Engineering Strategy for Upgrading the Hydrogen Evolution Reaction.

Both improving the intrinsic activity and activating basal plane sites of the layered metal dichalcogenides are desirable to enhance their electrocatalytic performance for energy storage and conversion. Herein, we present palladium (Pd)-doped tungsten disulfide (WS2) epitaxially sheathed around linear tungsten oxide for the hydrogen evolution reaction (HER). The Pd doping is evidenced to tune the electronic structure of WS2 for activating basal sites of WS2, while the unique core-shell structure facilitates charge transfer. The as-prepared Pd-WS2/W3O with 5.65 wt % Pd content exhibits a small overpotential of only 54 mV at -10 mA cm-2 and superior stability in the acidic electrolyte, which are superior to that of the 5 wt % Pt/C benchmark and are unprecedented in the reported WS2-based electrocatalysts. Theoretical results have revealed that Pd substituting for W in coordination with four S atoms is thermodynamically stable, and the in-plane S atoms adjacent to the doped Pd represent new catalytic active centers for promoting hydrogen adsorption. This work provides a new multiscale structural and electronic engineering strategy for improving the catalytic performance of transition-metal dichalcogenides.

The Interfacial Electronic Engineering in Binary Sulfiphilic Cobalt Boride Heterostructure Nanosheets for Upgrading Energy Density and Longevity of Lithium-Sulfur Batteries.

High gravimetric, areal and volumetric capacities together with long lifetime are key indexes for the applications of lithium-sulfur (Li-S) batteries in compact space. The sulfur host materials play pivotal roles in the practical deployment. Herein, one type of new heterostructure nanosheets composed of cobalt boride (CoB) on nitrogen, boron-codoped porous carbon (NBC), which is constructed through molten salt-assisted strategy using ZIF-67-encapsulated ZIF-8 as precursors is reported on. Benefiting from strong interfacial electronic interactions between binary sulfiphilic CoB and porous NBC, the CoB/NBC-S electrode exhibits the excellent cycling stability with low average capacity decay of 0.013% in ultralong 1500 cycles at high rate of 5 C. Remarkably, the electrode with high sulfur content of 82 wt% and high sulfur loading of 5.8 mg cm-2 delivers gravimetric capacity of 1309 mA h g-1 , areal capacity of 7.59 mA h cm-2 , and volumetric capacity of 1355 mA h cm-3 at 0.1 C. The favorable electrochemical performance can rival with the state-of-the-art of those in the reported nanosheets-based sulfur cathodes. This study provides new methodology for the design of heterostructure nanosheets of metal borides to achieve energy density and longevity of Li-S batteries.

Regulating Utilization Efficiency of the Photogenerated Charge Carriers by Constructing Donor-π-Acceptor Polymers for Upgrading Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction offers a promising approach for managing global carbon balance. The smooth delivery of the photoexcited electrons to the active sites without the extra photosensitizers is still challenging. Herein, a series of donor-π-acceptor conjugated organic polymers (COPs) were produced using anthracene, cobalt-coordinated bipyridyl, and benzene as donor, acceptor, and π linker units, respectively. The introduction of phenyl linker significantly improved the activities of photocatalytic CO2 reduction upon visible light illumination. Structure-performance relationship examinations uncovered that donor-π-acceptor structure promotes mobility of charge carriers and utilization efficiency on the catalytically active sites, resulting in high photocatalytic activity and durability for CO2 photoreduction. The in-depth insights into the electron transport processes open new perspectives for further optimization and rational design of photoactive polymers with high efficiency for solar-energy conversion.

The Electrostatic Attraction and Catalytic Effect Enabled by Ionic-Covalent Organic Nanosheets on MXene for Separator Modification of Lithium-Sulfur Batteries.

It is of great significance to mediate the redox kinetics and shuttle effect of polysulfides in pursuit of high-energy-density and long-life lithium-sulfur (Li-S) batteries. Herein, a new strategy is proposed based on the electrostatic attraction and catalytic effect of polysulfides for the modification of the polypropylene (PP) separator. Guanidinium-based ionic-covalent organic nanosheets (iCON) on the surface of Ti3 C2 is presented as a coating layer for the PP separator. The synergetic effects of Ti3 C2 and iCON provide new platforms to suppress the shuttle effect of polysulfides, expedite the redox kinetics of sulfur species, and promote efficient conversion of the intercepted polysulfides. The functional separator endows carbon nanotube/sulfur cathodes with excellent electrochemical performance. The average capacity decay per cycle within 2000 cycles at 2 C is as low as 0.006%. The separator is even effective in the case of sulfur content of 90 wt% and sulfur loading of 7.6 mg cm-2 ; the reversible capacity, areal capacity, and volumetric capacity at 0.1 C are as high as 1186 mA h g-1 , 9.01 mA h cm-2 , and 1201 mA h cm-3 , respectively. This work provides a promising approach toward separator modification for the development of high-performance Li-S batteries.

Ammonia-free fabrication of ultrafine vanadium nitride nanoparticles as interfacial mediators for promoting electrochemical behaviors of lithium-sulfur batteries.

Transition metal nitrides are promising mediators for improving the electrochemical performance of lithium-sulfur (Li-S) batteries, but the synthesis of ultrafine and durable nanoparticles in the absence of ammonia gas is still a great challenge. Herein, we reported a new method for the fabrication of ultrafine vanadium nitride (VN) nanoparticles uniformly embedded into N-doped porous carbon using a main-chain imidazolium-based ionic polymer (ImIP) containing metavanadate anions as a precursor. ImIP not only serves as sole carbon and nitrogen sources, but also effectively inhibits the aggregation and coalescence of VN nanoparticles during pyrolysis. Benefiting from the ultrafine particle size, high polarity and good electrocatalytic effects of VN, both redox kinetics of sulfur species and chemical adsorbability toward polysulfides are greatly expedited. The resultant electrode exhibits superior cycling stability with a low average capacity decay rate of 0.035% for 1200 cycles at a high rate of 5 C. This work develops a facile ammonia-free approach to fabricate ultrafine VN nanoparticles for improving electrochemical behaviors of Li-S batteries.

Carbon Dioxide Conversion Upgraded by Host-guest Cooperation between Nitrogen-Rich Covalent Organic Framework and Imidazolium-Based Ionic Polymer.

Invited for this month's cover are the groups of Rongjian Sa and Ruihu Wang at Minjiang University and the Chinese Academy of Sciences. The image shows how host-guest composite catalysts with task-specific components for the cycloaddition of CO2 with epoxides have been developed through integrating nitrogen-rich covalent organic framework and imidazolium-based ionic polymer. The Full Paper itself is available at 10.1002/cssc.202006158.

Recent Advances on Metalloporphyrin-Based Materials for Visible-Light-Driven CO2 Reduction.

Photocatalytic CO2 reduction is a promising technology to mitigate environmental issue and the energy crisis. The four nitrogen atoms in the porphyrin ring can incorporate transition metals to form stable active sites for CO2 activation and photoreduction. Nevertheless, the photocatalytic efficiency of metalloporphyrins is still low due to the insufficient photoelectron injection to drive CO2 photoreduction upon visible light irradiation. To address this issue, considerable efforts have been made to introduce photosensitizers for constructing homogeneous or heterogeneous metalloporphyrin-based photocatalytic systems. In this Review, recent advances of metalloporphyrin-based materials for visible-light-driven CO2 reduction were summarized. The methods for the modulation of photosensitizing process at molecular level were presented for the promotion of photocatalytic performance. The mechanism of CO2 activation and photocatalytic conversion was illustrated. Better insight into the structure-activity relationship provides guidance to the design of metalloporphyrin-related photocatalytic systems.

Carbon Dioxide Conversion Upgraded by Host-guest Cooperation between Nitrogen-Rich Covalent Organic Framework and Imidazolium-Based Ionic Polymer.

The chemical conversion of CO2 into value-added chemicals is one promising approach for CO2 utilization. It is crucial to explore highly efficient catalysts containing task-specific components for CO2 fixation. Here, a host-guest catalytic system was developed by integrating nitrogen-rich covalent organic framework (TT-COF) and imidazolium-based ionic polymer (ImIP), which serve as hydrogen-bonding donor and nucleophilic agent, respectively, for cooperatively facilitating the activation of the epoxides and subsequent CO2 cycloaddition. The catalytic activity of the host-guest system was remarkably superior to those of ImIP, TT-COF, and their physical mixture. Furthermore, selective adsorption for CO2 over N2 rendered this catalytic system effective for the cycloaddition reaction of the simulated flue gas. The protocols for the unification of two catalytically active components provide new opportunities for the development of composite systems in multiple applications.

Flexible Porous Organic Polymer Membranes for Protonic Field-Effect Transistors.

Artificial transistors represent an ideal means for meeting the requirements in interfacing with biological systems. It is pivotal to develop new proton-conductive materials for the transduction between biochemical events and electronic signals. Herein, the first demonstration of a porous organic polymer membrane (POPM) as a proton-conductive material for protonic field-effect transistors is presented. The POPM is readily prepared through a thiourea-formation condensation reaction. Under hydrated conditions and at room temperature, the POPM delivers a proton mobility of 5.7 × 10-3 cm2 V-1 s-1 ; the charge carrier densities are successfully modulated from 4.3 × 1017 to 14.1 × 1017 cm-3 by the gate voltage. This study provides a type of promising modular proton-conductive materials for bioelectronics application.

Ionic-Liquid-Modified Click-Based Porous Organic Polymers for Controlling Capture and Catalytic Conversion of CO2.

Capture and catalytic conversion of CO2 into value-added chemicals is a promising and sustainable approach to relieve global warming and the energy crisis. Nitrogen-rich porous organic polymers (POPs) are promising materials for CO2 capture and separation, but their application in the additive-free catalytic conversion of CO2 into cyclic carbonates is still a challenge. Herein, a nitrogen-rich click-based POP (CPP) was developed for the cycloaddition reaction of CO2 with epoxides in the absence of metal, solvents, and additives. The introduction of imidazolium-based ionic liquids on the CPP host backbone could modulate the porosity, CO2 adsorption/desorption, CO2 selectivity over N2 , and catalytic activity in the chemical transformation. A tentative catalytic pathway was proposed to account for the superior catalytic activity of the catalytic systems, in which the incorporated ionic liquid and porous properties of CPP synergistically contributed to the catalytic reaction. This study provides a platform to understand the cooperative effects of porous properties and nucleophilic anions on the cycloaddition reaction of CO2 with epoxides.

Enhanced Chemisorption and Catalytic Effects toward Polysulfides by Modulating Hollow Nanoarchitectures for Long-Life Lithium-Sulfur Batteries.

Hollow nanostructures with intricate interior and catalytic effects hold great promise for the construction of advanced lithium-sulfur batteries. Herein, a double-shelled hollow polyhedron with inlaid cobalt nanoparticles encapsulated by nitrogen-doped carbon (Co/NC) nanodots (Co-NC@Co9 S8 /NPC) is reported, which is acquired by using imidazolium-based ionic-polymer-encapsulated zeolitic imidazolate framework-67 as a core-shelled precursor. The Co/NC nanodots promote redox kinetics and chemical adsorbability toward polysulfides, while the interconnected double shells serve as a nanoscale electrochemical reaction chamber, which effectively suppresses the polysulfide shuttling and accelerates ion/electron transport. Benefiting from structural engineering and reaction kinetics modulation, the Co-NC@Co9 S8 /NPC-S electrode exhibits high cycling stability with a low capacity decay of 0.011% per cycle within 2000 cycles at 2 C. The electrode still shows high rate performance and cyclability over 500 cycles even in the case of high sulfur loading of 4.5 mg cm-2 and 75 wt% sulfur content. This work provides one type of new hollow nanoarchitecture for the development of advanced Li-S batteries and other energy storage systems.

A Covalent Triazine-Based Framework Consisting of Donor-Acceptor Dyads for Visible-Light-Driven Photocatalytic CO2 Reduction.

Photocatalytic conversion of CO2 into value-added chemical fuels is a promising approach to address the depletion of fossil energy and environment-related concerns. Tailor-making the electronic properties and band structures of photocatalysts is pivotal to improve their efficiency and selectivity in photocatalytic CO2 reduction. Herein, a covalent triazine-based framework was developed containing electron-donor triphenylamine and electron-acceptor triazine components (DA-CTF). The engineered π-conjugated electron donor-acceptor dyads in DA-CTF not only optimized the optical bandgap but also contributed to visible-light harvesting and migration of photoexcited charge carriers. The activity of photocatalytic CO2 reduction under visible light was significantly improved compared with that of traditional g-C3 N4 and reported covalent triazine-based frameworks. This study provides molecular-level insights into the mechanism of photocatalytic CO2 reduction.

Engineering MoS2 Basal Planes for Hydrogen Evolution via Synergistic Ruthenium Doping and Nanocarbon Hybridization.

Promoting the intrinsic activity and accessibility of basal plane sites in 2D layered metal dichalcogenides is desirable to optimize their catalytic performance for energy conversion and storage. Herein, a core/shell structured hybrid catalyst, which features few-layered ruthenium (Ru)-doped molybdenum disulfide (MoS2) nanosheets closely sheathing around multiwalled carbon nanotube (CNT), for highly efficient hydrogen evolution reaction (HER) is reported. With 5 at% (atomic percent) Ru substituting for Mo in MoS2, Ru-MoS2/CNT achieves the optimum HER activity, which displays a small overpotential of 50 mV at -10 mA cm-2 and a low Tafel slope of 62 mV dec-1 in 1 m KOH. Theoretical simulations reveal that Ru substituting for Mo in coordination with six S atoms is thermodynamically stable, and the in-plane S atoms neighboring Ru dopants represent new active centers for facilitating water adsorption, dissociation, and hydrogen adsorption/desorption. This work provides a multiscale structural and electronic engineering strategy for synergistically enhancing the HER activity of transition metal dichalcogenides.