2D Metal Porphyrin-Based MOFs and ZIF-8 Composite-Derived Carbon Materials Containing M-Nx Active Sites as Bifunctional Electrocatalysts for Zinc-Air Batteries.

The main impediment to the development of zinc-air batteries is the sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Transition metal N-doped carbon catalysts offer a promising alternative to noble metal catalysts, with metal-organic framework (MOF)-derived carbon material catalysts being particularly noteworthy. Here, we synthesized MxP-Z-C carbon catalysts by combining two-dimensional (2D) metal porphyrin-based MOFs (MxPMFs, x = Fe, Co, Ni, Mn) and three-dimensional zeolitic imidazole framework-8 (ZIF-8) through electrostatic interaction, followed by carbonization. ZIF-8 was inserted between the layers of MxPMFs to prevent its Π-Π stacking, allowing the active sites to become fully exposed. MxP-Z-C demonstrated an impressive catalytic activity for both the ORR and the OER reactions. Among them, FeP-Z-C showed the best catalytic activity. The half-wave potential for ORR was 0.92 V (vs the reversible hydrogen electrode (RHE)), while the overpotential for the OER was 290 mV. In addition, the zinc-air battery assembled by FeP-Z-C exhibited high power density (133.14 mW cm-2) and significant specific capacity (816 mAh gZn-1), indicating considerable potential as a bifunctional catalyst for electronic devices.

Role of RNA Modifications, Especially m6A, in Aflatoxin Biosynthesis of Aspergillus flavus.

RNA modifications play key roles in eukaryotes, but the functions in Aspergillus flavus are still unknown. Temperature has been reported previously to be a critical environmental factor that regulates the aflatoxin production of A. flavus, but much remains to be learned about the molecular networks. Here, we demonstrated that 12 kinds of RNA modifications in A. flavus were significantly changed under 29 °C compared to 37 °C incubation; among them, m6A was further verified by a colorimetric method. Then, the transcriptome-wide m6A methylome and m6A-altered genes were comprehensively illuminated through methylated RNA immunoprecipitation sequencing and RNA sequencing, from which 22 differentially methylated and expressed transcripts under 29 °C were screened out. It is especially notable that AFCA_009549, an aflatoxin biosynthetic pathway gene (aflQ), and the m6A methylation of its 332nd adenine in the mRNA significantly affect aflatoxin biosynthesis in A. flavus both on media and crop kernels. The content of sterigmatocystin in both ΔaflQ and aflQA332C strains was significantly higher than that in the WT strain. Together, these findings reveal that RNA modifications are associated with secondary metabolite biosynthesis of A. flavus.

Regulation of Fungal Morphogenesis and Pathogenicity of Aspergillus flavus by Hexokinase AfHxk1 through Its Domain Hexokinase_2.

As a filamentous pathogenic fungus with high-yield of aflatoxin B1, Aspergillus flavus is commonly found in various agricultural products. It is crucial to develop effective strategies aimed at the prevention of the contamination of A. flavus and aflatoxin. Hexokinase AfHxk1 is a critical enzyme in fungal glucose metabolism. However, the role of AfHxk1 in A. flavus development, aflatoxin biosynthesis, and virulence has not yet been explored. In this study, afHxk1 gene deletion mutant (ΔafHxk1), complementary strain (Com-afHxk1), and the domain deletion strains (afHxk1ΔD1 and afHxk1ΔD2) were constructed by homologous recombination. Phenotype study and RT-qPCR revealed that AfHxk1 upregulates mycelium growth and spore and sclerotia formation, but downregulates AFB1 biosynthesis through related classical signaling pathways. Invading models and environmental stress analysis revealed that through involvement in carbon source utilization, conidia germination, and the sensitivity response of A. flavus to a series of environmental stresses, AfHxk1 deeply participates in the regulation of pathogenicity of A. flavus to crop kernels and Galleria mellonella larvae. The construction of domain deletion strains, afHxk1ΔD1 and afHxk1ΔD2, further revealed that AfHxk1 regulates the morphogenesis, mycotoxin biosynthesis, and the fungal pathogenicity mainly through its domain, Hexokinase_2. The results of this study revealed the biological role of AfHxk1 in Aspergillus spp., and might provide a novel potential target for the early control of the contamination of A. flavus.

The epigenetic regulator Set9 harmonizes fungal development, secondary metabolism, and colonization capacity of Aspergillus flavus.

As a widely distributed food-borne pathogenic fungus, Aspergillus flavus and its secondary metabolites, mainly aflatoxin B1 (AFB1), pose a great danger to humans. It is urgent to reveal the complex regulatory network of toxigenic and virulence of this fungus. The bio-function of Set9, a SET-domain-containing histone methyltransferase, is still unknown in A. flavus. By genetic engineering means, this study revealed that, through catalyzing H4K20me2 and -me3, Set9 is involved in fungal growth, reproduction, and mycotoxin production via the orthodox regulation pathway, and regulates fungal colonization on crop kernels through adjusting fungal sensitivity reactions to oxidation stress and cell wall integrity stress. Further domain deletion and point mutation inferred that the SET domain is the core element in catalyzing H4K20 methylation, and D200 site of the domain is the key amino acid in the active center of the methyltransferase. Combined with RNA-seq analysis, this study revealed that Set9 regulates the aflatoxin gene cluster by the AflR-like protein (ALP), other than traditional AflR. This study revealed the epigenetic regulation mechanism of fungal morphogenesis, secondary metabolism, and pathogenicity of A. flavus mediated by the H4K20-methyltransferase Set9, which might provide a potential new target for early prevention of contamination of A. flavus and its deadly mycotoxins.

SWD1 epigenetically chords fungal morphogenesis, aflatoxin biosynthesis, metabolism, and virulence of Aspergillus flavus.

As the main producer of aflatoxins, Aspergillus flavus is also one of the most important causes of invasive and non-invasive aspergillosis. Therefore, it is crucial to unravel the regulatory mechanisms of growth, metabolism, and pathogenicity of A. flavus. SWD1 is highly conserved across species for maintaining COMPASS methyltransferase activity, but the bio-function of SWD1 in A. flavus has not been explored. Through genetic analysis, this study revealed that SWD1 is involved in fungal morphogenesis and AFB1 biosynthesis by regulating the orthodox pathways through H3K4me1-3. Stresses sensitivity and crop models analysis revealed that SWD1 is a key regulator for the resistance of A. flavus to adapt to extreme adverse environments and to colonize crop kernels. It also revealed that the WD40 domain and 25 aa highly conserved sequence are indispensable for SWD1 in the regulation of mycotoxin bio-synthesis and fungal virulence. Metabolomic analysis inferred that SWD1 is crucial for the biosynthesis of numerous primary and secondary metabolites, regulates biological functions by reshaping the whole metabolic process, and may inhibit fungal virulence by inducing the apoptosis of mycelia through the inducer sphingosine. This study elucidates the epigenetic mechanism of SWD1 in regulating fungal pathogenicity and mycotoxin biosynthesis, and provides a potential novel target for controlling the virulence of A. flavus.

Synthesis of ß-cyanoalkylsulfonylated vinyl selenides through a four-component reaction.

A mild copper-catalyzed four-component selenosulfonylation of alkynes, cycloketone oxime esters, DABCO (SO2)2 and diselenides has been developed. This method enables the rapid assembly of ß-cyanoalkylsulfonylated vinyl selenides in moderate to good yields. Advantages of this protocol include a broad substrate scope, good functional group tolerance and the late-stage functionalization of complex molecules. Moreover, the potential utility of this methodology is demonstrated through simple oxidation of the products to access synthetically important alkynyl sulfones. Mechanistic studies suggest that a cyanoalkylsulfonyl radical intermediate is involved in this process.

Photoinduced intramolecular carbosulfonylation of alkynes: access to sulfone-containing dibenzazepines from sulfur dioxide.

A photoinduced three-component reaction of N-benzyl-N-(2-ethynylaryl)amides, sulfur dioxide and aryldiazonium tetrafluoroborates is developed, providing an efficient and straightforward approach for the synthesis of diverse vinylsulfonylated dibenzazepine derivatives in moderate to good yields under mild conditions. This transformation proceeds smoothly at room temperature in the presence of visible light, which shows a wide range of substrate scope with good functional group compatibility. The synthetic utility of this methodology is further demonstrated through Suzuki coupling. Mechanistic studies show that this reaction is triggered by the addition of an arylsulfonyl radical to an alkyne from sulfur dioxide, followed by vinyl radical cyclization to afford the desired sulfonated dibenzazepines.

Photoredox-catalyzed sulfonylation of difluoroenoxysilanes with the insertion of sulfur dioxide.

A photoredox-catalyzed three-component reaction of aryldiazonium tetrafluoroborates with sodium metabisulfite and 2,2-difluoro enol silyl ethers is described. By using sodium metabisulfite as the source of sulfur dioxide, this method provides an elegant access to α,α-difluoro-ß-ketosulfones in moderate to good yields under mild conditions, and features a broad substrate scope and wide functional group tolerance. Both of the difluoromethyl group and sulfone moiety can be introduced in a single step. Based on the experimental results, a single-electron transfer pathway is proposed with the insertion of sulfur dioxide.