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.

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.

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.

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.

Designed Construction of Cluster Organic Frameworks from Lindqvist-type Polyoxovanadate Cluster.

Two unprecedented examples of cluster organic frameworks (TBA)3Cu[V6O13(L)2]2·4DEF (2) (TBA)Ag[V6O13(L)2] solvent (3) (TBA = tetrabutylammonium, H3L = tris(hydroxymethyl)-4-picoline, DEF = N, N'-diethylformamide) based on Lindqvist-type polyoxometalate (POM) secondary building units (SBUs) have been constructed successfully. Compounds 2 and 3 are the second cases of cluster organic frameworks based on Lindqvist-type POM cluster SBUs. Furthermore, the cluster organic framework of 2 exhibits efficient electrocatalytic activity and strong durability in oxygen reduction reaction.

Prefunctionalized Porous Organic Polymers: Effective Supports of Surface Palladium Nanoparticles for the Enhancement of Catalytic Performances in Dehalogenation.

Three porous organic polymers (POPs) containing H, COOMe, and COO(-) groups at 2,6-bis(1,2,3-triazol-4-yl)pyridyl (BTP) units (i.e., POP-1, POP-2, and POP-3, respectively) were prepared for the immobilization of metal nanoparticles (NPs). The ultrafine palladium NPs are uniformly encapsulated in the interior pores of POP-1, whereas uniform- and dual-distributed palladium NPs are located on the external surface of POP-2 and POP-3, respectively. The presence of carboxylate groups not only endows POP-3 an outstanding dispersibility in H2 O/EtOH, but also enables the palladium NPs at the surface to show the highest catalytic activity, stability, and recyclability in dehalogenation reactions of chlorobenzene at 25 °C. The palladium NPs on the external surface are effectively stabilized by the functionalized POPs containing BTP units and carboxylate groups, which provides a new insight for highly efficient catalytic systems based on surface metal NPs of porous materials.

Designed Assembly of Heterometallic Cluster Organic Frameworks Based on Anderson-Type Polyoxometalate Clusters.

A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework.

Solvent-Induced Facile Synthesis of Cubic-, Spherical-, and Honeycomb-Shape Palladium N-Heterocyclic Carbene Particles and Catalytic Applications in Cyanosilylation.

The facile synthesis of palladium N-heterocyclic carbene (NHC) particles with spherical, cubic, and honeycomb morphologies is accomplished. The structures of cubic and honeycomb particles are defined as an unprecedented trinuclear palladium-NHC complex. An obvious effect of particle morphologies on catalytic activity and recyclability is observed in hetero-geneous cyanosilylation.

Urea-based porous organic frameworks: effective supports for catalysis in neat water.

Two urea-based porous organic frameworks, UOF-1 and UOF-2, were synthesized through a urea-forming condensation of 1,3,5-benzenetriisocyanate with 1,4-diaminobenzene and benzidine, respectively. UOF-1 and UOF-2 possess good hydrophilic properties and high scavenging ability for palladium. Their palladium polymers, PdII/UOF-1 and PdII/UOF-2, exhibit high catalytic activity and selectivity for Suzuki­Miyaura cross-coupling reactions and selective reduction of nitroarenes in water. The catalytic reactions can be efficiently performed at room temperature. Palladium nanoparticles with narrow size distribution were formed after the catalytic reaction and were well dispersed in UOF-1 and UOF-2. XPS analysis confirmed the coordination of the urea oxygen atom with palladium. SEM and TEM images showed that the original network morphology of UOF-1 and UOF-2 was maintained after palladium loading and catalytic reactions.

Anion-directed assemblies of cationic metal-organic frameworks based on 4,4'-bis(1,2,4-triazole): syntheses, structures, luminescent and anion exchange properties.

Three cationic metal-organic frameworks (MOFs), Ag(btr)·PF6·0.5CH3CN (1), Ag2(btr)2(H2O)·2CF3SO3·H2O (2), and Ag2(btr)2(NO3)·NO3 (3), were prepared from reaction of 4,4'-bis(1,2,4-triazole) (btr) with silver salts containing different anions. Complex 1 is a three-dimensional (3-D) framework constructed from tetrahedral-shaped nanoscale coordination cages with PF6(-) as counteranions. 2 and 3 are 3-D architectures containing 1-D channels, in which charge-balancing CF3SO3(-) and NO3(-) are located in their respective channels. Luminescent emission of 1-3 shows an obvious red shift compared with the btr ligand. Anion exchange studies show that 1 is able to selectively exchange MnO4(-) in aqueous solution with a modest capacity of 0.56 mol mol(-1); the luminescent emission of 1 is quickly quenched upon MnO4(-) exchange.

II-Scheme Heterojunction Frameworks Based on Covalent Organic Frameworks and HKUST-1 for Boosting Photocatalytic Hydrogen Evolution.

Covalent organic frameworks (COFs) are one type of promising polymer semiconductors in solar-driven hydrogen production, but majority of COFs-based photocatalytic systems show low photocatalytic efficiency owing to lack of metal active sites. Herein, we reported II-Scheme heterojunction frameworks based on COF (TpPa-1) and metal-organic framework (HKUST-1) for highly efficient hydrogen production. The coordination bonding directed self-assembly of HKUST-1 on the surface of TpPa-1 endows the heterojunction frameworks (HKUST-1/TpPa-1) with strong interface interaction, optimized electronic structures and abundant redox active sites, thus remarkably boosting photocatalytic hydrogen evolution. The hydrogen evolution rate for optimal HKUST-1/TpPa-1 is as high as 10.50 mmol g-1 h-1, which is significantly enhanced when compared with that of their physical mixture (4.13 mmol g-1 h-1), TpPa-1 (0.013 mmol g-1 h-1) and Pt-based counterpart (6.70 mmol g-1 h-1). This work offers a facile approach to the construction of noble-metal-free II-Scheme heterojunctions based on framework materials for efficient solar energy conversion.

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.

Analysis of wheat fungal community succession in traditional storage structures using Illumina MiSeq sequencing technology.

The diversity of fungi in wheat with different deoxynivalenol (DON) content at various periods post-harvest and in the environment of storage were investigated. The changes in DON content were measured with ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS), and an amplicon sequence analysis of fungi was performed in traditional storage structures using high-throughput sequencing. The changes in temperature, humidity, and CO2 concentration were collected by sensors. In addition, we analyzed principal component analysis, species composition, species differences, and community differences of fungi. There was an obvious separation of the fungal communities under different storage conditions and times. Many fungal genera were gradually decreasing during storage and were eventually undetectable, and many fungal genera that were undetectable at first gradually increased during storage and even became dominant fungal genera. The competition between fungi was fierce. The competition between fungi were affected by the presence of DON. As the initial DON content increased, the contribution of inter-group differences became more obvious. The temperature, humidity, and CO2 concentration of wheat in the silo's environment changed with extended storage time. The content of DON decreased with extended storage time. We had investigated the changes in DON content and their correlation with the changes in fungal communities and environmental factors, which showed a high degree of correlation. This study offers theoretical justification for optimizing safe wheat grain in traditional storage conditions.

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.

A cationic metal-organic framework consisting of nanoscale cages: capture, separation, and luminescent probing of Cr(2)O7(2-) through a single-crystal to single-crystal process.

Dichromate capture: A 3D cationic metal-organic framework consisting of distorted octahedral and tetrahedral cages was constructed by using Ag(I) and 4,4'-bis(1,2,4-triazole). The complex exhibits fast exchange, high trapping capacity, and good selectivity for Cr2 O7 (2-) through single-crystal to single-crystal transformation. The complex also features a bluish violet luminescence that is distinctly quenched after Cr2 O7 (2-) exchange.

Click ionic liquids: a family of promising tunable solvents and application in Suzuki-Miyaura cross-coupling.

A series of click ionic salts 4 a-4 n was prepared through click reaction of organic azides with alkyne-functionalized imidazolium or 2-methylimidazolium salts, followed by metathesis with lithium bis(trifluoromethanesulfonyl)amide or potassium hexafluorophosphate. All salts were characterized by IR, NMR, TGA, and DSC, and most of them can be classified as ionic liquids. Their steric and electronic properties can be easily tuned and modified through variation of the aromatic or aliphatic substituents at the imidazolium and/or triazolyl rings. The effect of anions and substituents at the two rings on the physicochemical properties was investigated. The charge and orbital distributions based on the optimized structures of cations in the salts were calculated. Reaction of 4 a with PdCl(2) produced mononuclear click complex 4 a-Pd, the structure of which was confirmed by single-crystal X-ray diffraction analysis. Suzuki-Miyaura cross-coupling shows good catalytic stability and high recyclability in the presence of PdCl(2) in 4 a. TEM and XPS analyses show formation of palladium nanoparticles after the reaction. The palladium NPs in 4 a are immobilized by the synergetic effect of coordination and electrostatic interactions with 1,2,3-triazolyl and imidazolium, respectively.

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 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.