CcPTGS2a-like gene-mediated NF-κB/ERK signaling regulation in the common carp (Cyprinus carpio).

Prostaglandin-endoperoxide synthase 2 (PTGS2), a common biological macromolecule, is pivotal for innate immunity and pathogen recognition. In this study, we identified and characterized a CcPTGS2a-like gene in the common carp (Cyprinus carpio) with an open reading frame (ORF) of 1821 bp and epidermal growth factor and peroxidase domains. Our multiple sequence analysis revealed high homology between the amino acid sequence of CcPTGS2a-like and those of its homologs in other fish. CcPTGS2a-like mRNA and protein expressions were significantly upregulated in the spleen, head kidney, liver, and gill tissues upon exposure to Aeromonas hydrophila stimulation. CcPTGS2a-like protein recognized the conserved bacterial surface components and exhibited detectable bacterial binding activity. CcPTGS2a-like overexpression before exposure to A. hydrophila notably enhanced the survival rate of common carp, concomitant with decreased bacterial burden. The NF-κB/ERK signaling pathway initiated the immune response in common carp upon infection with A. hydrophila. CcPTGS2a-like overexpression or interference in the head kidney and Epithelioma papulosum cyprinid cells could modulate the p-NF-κB (p-p-65), p-IκBα, and p-ERK1/2 levels as well as the IL-1ß and IL-6 mRNA expression. These results indicated potential CcPTGS2a-like involvement in the immune response of the common carp to bacterial infections through the NF-κB/ERK signaling pathway.

Ti-based MOFs with acetic acid pendings as an efficient catalyst in the preparation of new spiropyrans with biological moieties.

The strategy of designing heterogeneous porous catalysts by a post-modification method is a smart strategy to increase the catalytic power of desired catalysts. Accordingly, in this report, metal-organic frameworks based on titanium with acetic acid pending were designed and synthesized via post-modification method. The structure of the target catalyst has been investigated using different techniques such as FT-IR, XRD, SEM, EDX, Mapping, and N2 adsorption/desorption (BET/the BJH) the correctness of its formation has been proven. The catalytic application of Ti-based MOFs functionalized with acetic acid was evaluated in the preparation of new spiropyrans, and the obtained results show that the catalytic performance is improved by this modification. The strategy of designing heterogeneous porous catalysts through post-modification methods presents a sophisticated approach to enhancing the catalytic efficacy of desired catalysts. In this context, our study focuses on the synthesis and characterization of metal-organic frameworks (MOFs) based on titanium, functionalized with acetic acid pendants, using a post-modification method. Various characterization techniques, including Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), mapping, and N2 adsorption/desorption (BET/BJH), were employed to investigate the structure and composition of the synthesized catalyst. These techniques collectively confirmed the successful formation and structural integrity of the target catalyst. The structure of the synthesized products was confirmed by melting point, 1H-NMR and 13C-NMR and FT-IR techniques. Examining the general process of catalyst synthesis and its catalytic application shows that the mentioned modification is very useful for catalytic purposes. The presented catalyst was used in synthesis of a wide range of biologically active spiropyrans with good yields. The simultaneous presence of several biologically active cores in the synthesized products will highlight the biological properties of these compounds. The present study offers a promising insight into the rational design, synthesis, and application of task-specific porous catalysts, particularly in the context of synthesizing biologically active candidate molecules.

Dipolar Microenvironment Engineering Enabled by Electron Beam Irradiation for Boosting Catalytic Performance.

Creating a diverse dipolar microenvironment around the active site is of great significance for the targeted induction of intermediate behaviors to achieve complicated chemical transformations. Herein, an efficient and general strategy is reported to construct hypercross-linked polymers (HCPs) equipped with tunable dipolar microenvironments by knitting arene monomers together with dipolar functional groups into porous network skeletons. Benefiting from the electron beam irradiation modification technique, the catalytic sites are anchored in an efficient way in the vicinity of the microenvironment, which effectively facilitates the processing of the reactants delivered to the catalytic sites. By varying the composition of the microenvironment scaffold structure, the contact and interaction behavior with the reaction participants can be tuned, thereby affecting the catalytic activity and selectivity. As a result, the framework catalysts produced in this way exhibit excellent catalytic performance in the synthesis of glycinate esters and indole derivatives. This manipulation is reminiscent of enzymatic catalysis, which adjusts the internal polarity environment and controls the output of products by altering the scaffold structure.

Modulating confinement space in metal-organic frameworks enables highly selective indole C3-formylation.

Here, Selective C3-formylation of indole was achieved under mild conditions using a metal-organic framework (MOF) catalyst. The confined reaction space within the MOF pores effectively suppressed undesired side reactions and promoted the formation of the targeted product by controlling the reaction pathway. Density functional theory (DFT) calculations corroborated the experimental observations.

Skin-Inspired, Highly Sensitive, Broad-Range-Response and Ultra-Strong Gradient Ionogels Prepared by Electron Beam Irradiation.

Skin, characterized by its distinctive gradient structure and interwoven fibers, possesses remarkable mechanical properties and highly sensitive attributes, enabling it to detect an extensive range of stimuli. Inspired by these inherent qualities, a pioneering approach involving the crosslinking of macromolecules through in situ electron beam irradiation (EBI) is proposed to fabricate gradient ionogels. Such a design offers remarkable mechanical properties, including excellent tensile properties (>1000%), exceptional toughness (100 MJ m-3), fatigue resistance, a broad temperature range (-65-200°C), and a distinctive gradient modulus change. Moreover, the ionogel sensor exhibits an ultra-fast response time (60 ms) comparable to skin, an incredibly low detection limit (1 kPa), and an exceptionally wide detection range (1 kPa-1 MPa). The exceptional gradient ionogel material holds tremendous promise for applications in the field of smart sensors, presenting a distinct strategy for fabricating flexible gradient materials.

Research progress of pattern recognition receptors in red swamp crayfish (Procambarus clarkii).

Though Procambarus clarkii (red swamp crayfish) is a lower invertebrate, it has nonetheless developed a complex innate immune system. The crayfish farming industry has suffered considerable economic losses in recent years as a consequence of bacterial and viral diseases. Hence, perhaps the most effective ways to prevent microbial infections in P. clarkii are to examine and elucidate its innate immunity. The first step in the immune response is to recognize pathogen-associated molecular patterns (PAMPs) through pattern recognition receptors (PRRs). PRRs are expressed mainly on immune cell surfaces and recognize at least one PAMP. Thence, downstream immune responses are activated and pathogens are phagocytosed. To date, the PRRs identified in P. clarkii include Toll-like receptors (TLRs), lectins, fibrinogen-related proteins (FREPs), and ß-1,3-glucan-binding proteins (BGRPs). The present review addresses recent progress in research on PRRs and aims to provide guidance for improving immunity and preventing and treating infectious diseases in P. clarkii.

Catalytic Application of Functionalized Bimetallic-Organic Frameworks with Phosphorous Acid Tags in the Synthesis of Pyrazolo[4,3-e]pyridines.

Combining two different metals for the synthesis of a metal-organic framework (MOF) is a smart strategy for the architecture of new porous materials. Herein, a bimetal-organic framework (bimetal-MOFs) based on Fe and Co metals was synthesized. Then, phosphorous acid tags were decorated on bimetal-MOFs via a postmodification method as a new porous acidic functionalized catalyst. This catalyst was used for the synthesis of pyrazolo[4,3-e]pyridine derivatives as suitable drug candidates. The present study provides new insights into the architecture of novel porous heterogeneous catalysts based on a bimetal-organic framework (bimetal-MOFs). The type of final structures of catalyst and pyrazolo[4,3-e]pyridine derivatives were determined using different techniques such as fourier transform infrared (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), SEM-elemental mapping, N2 adsorption-desorption isotherm, Barrett-Joyner-Halenda (BJH), thermogravimetry/differential thermal analysis (TG/DTA), 1H NMR, and 13C NMR.

Application of Metal-Organic Frameworks with Sulfonic Acid Tags in the Synthesis of Pyrazolo[3,4-b]pyridines via a Cooperative Vinylogous Anomeric-Based Oxidation.

Herein, we report the design and synthesis of Co-MOF-71/imidazole/SO3H as a novel porous catalyst with sulfonic acid tags. The structure and morphology of the catalyst were investigated using various techniques such as Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction, scanning electron microscopy (SEM), SEM elemental mapping, energy-dispersive X-ray spectroscopy, Barret-Joyner-Halenda, and N2 adsorption-desorption isotherms. Co-MOF-71/imidazole/SO3H was studied in the preparation of novel pyrazolo[3,4-b]pyridines under mild and green conditions via a cooperative vinylogous anomeric-based oxidation. A wide range of mono and bis pyrazolo[3,4-b]pyridines were synthesized with good to excellent yields (65-82%). A hot filtration test for the heterogeneous nature of the catalyst indicated the high stability of the prepared catalyst. The recyclability of Co-MOF-71/imidazole/SO3H is another advantage of the present methodology. The structures of the final products were confirmed using FT-IR, 1H-NMR, and 13C-NMR spectroscopic techniques.

Utilizing ferrocene for doping iron into graphitic carbon nitride (FeIII/g-C3N4): an internal dual photocatalyst for tandem oxidation/cyclization of toluene to benzimidazoles under visible light conditions.

Recently, doping metals into graphitic carbon nitride (g-C3N4) is considered for environmental applications and organic reactions. In this study, we used ferrocene as a source of Fe3+ to dope iron onto g-C3N4. The scaffold of the internal electric field is presented as an impressive strategy to increase photocatalytic activities. Fe3+ was doped onto graphitic carbon nitride (FeIII/g-C3N4) by the calcination method, which was well characterized by FT-IR, Raman, XRF, XRD, XPS, UV-visible DRS, photo-luminescence (PL), photocurrent, SEM, HR-TEM, EDX, BET, EIS, and cyclic voltammetry analyses. The synthesis of benzimidazole derivatives as pharmaceutically active compounds was introduced by using a suitable method under mild reaction conditions without using a base, oxidant, and other reagents or additives. The modification by using iron had a considerable effect on the optical and electronic characteristics in contrast to g-C3N4. The nanocomposite FeIII/g-C3N4 could be employed as a multifunctional photocatalyst to perform the tandem process, oxidation of toluene, and then cyclization with o-phenylenediamines to prepare benzimidazoles under visible light conditions. The existence of the dynamic equilibrium of Fe3+/Fe2+ helped in significantly improving the activity. By changing the reaction conditions and different control experiments as well as Mott-Schottky plot analysis, the superoxide ion (O2˙-) can be obtained as the reactive species in this reaction. The photocatalytic activity of FeIII/g-C3N4 for this one-pot reaction is also investigated in detail.

Electron Beam Etching of Cellulose Microgels for Absorptive Separation of DMSO from Reactions of 5-Hydroxymethylfurfural Synthesis.

Invited for this month's cover is the groups of Jiang Huang and Yanlong Gu at Huazhong University of Science and Technology. The image shows a new method for the separation of dimethyl sulfoxide from a reaction solution of synthesizing 5-hydroxymethylfurfural by means of using a cellulose microgel fabricated by electron beam irradiation as a bio-based absorbant. The Research Article itself is available at 10.1002/cssc.202201755.

Induction and potential molecular mechanism of the enhanced immune response in Procambarus clarkii after secondary encountered with Aeromonas veronii.

For a long time, it was believed that invertebrates do not possess acquired immunity and mainly rely on innate immunity for protection against pathogens infection. However, an increasing number of studies have suggested that some form of "immune memory" can be initiated in invertebrates after primary exposure to the pathogen, which was defined as "specific immune priming". In the present study, two experiments were carried out to determine whether specific immune priming can be induced in crayfish (Procambarus clarkii) by Aeromonas veronii, if so, to identify the underlying mechanism. Once being "preimmunization" by formalin-killed A. veronii, the survival rate, in vitro antibacterial activity and haemocyte phagocytosis rate of crayfish were enhanced, which indicated that better immune protection was obtained. Furthermore, at some time points, the expression of antimicrobial peptide (AMP) and Down syndrome cell adhesion molecule (Dscam) genes was significantly higher in P. clarkii individuals that underwent stimulation twice than in those that were only stimulated once. Taken together, the results suggest that enhanced specific immune protection can be obtained in primed crayfish and that the Dscam molecule, haemocyte phagocytosis function, and AMPs may be involved in this immune priming. The present study provides a better understanding of the molecular mechanism of immune priming in invertebrates.

Electron Beam Etching of Cellulose Microgels for Absorptive Separation of DMSO from Reactions of 5-Hydroxymethylfurfural Synthesis.

In this study, an efficient method for the separation of 5-hydroxymethylfurfural by the specific adsorption of dimethyl sulfoxide (DMSO) with cellulose microgels fabricated by electron beam irradiation was developed. The cellulose microgel was recovered and reused although this was accompanied by a decrease in the separation efficiency. A series of characterizations, including ultraviolet and infrared spectroscopy, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and swelling ability tests, were performed to determine the adsorption behavior of the chemical structures of the microgel toward DMSO. The results showed that after the first run, the chemical structure of the recovered microgel did not change significantly. Electron-beam etching played a pivotal role in conferring a special capacity for enriching DMSO in its matrix on the microgel.

Synthesis of pyrimidine-6-carbonitriles, pyrimidin-5-ones, and tetrahydroquinoline-3-carbonitriles by new superb oxovanadium(V)-[5,10,15,20-tetrakis(pyridinium)-porphyrinato]-tetra(tricyanomethanide) catalyst via anomeric based oxidation.

Oxovanadium(V)-[5,10,15,20-tetrakis(pyridinium)-porphyrinato]-tetra(tricyanomethanide) [(VO)TPP][(TCM)4] was designed, synthesized and characterized by various techniques such as FT-IR, EDX, SEM equipped with EDX mappings, CHN elemental analysis, ICP-OES, XRD, SEM, TEM, TGA, DTA, DRS, Kubelka-Munk function (Tauc's plot), and UV-Vis analyses. Then, [(VO)TPP][(TCM)4] was used as a benign and expedient catalyst for the synthesis of numerous heterocyclic compounds such as 5-amino-7-(aryl)-4,7-dihydro-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitriles, 5-amino-7-(aryl)-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitriles, 7-(aryl)-7,12-dihydro-5H-isochromeno[4,3-d][1,2,4]triazolo[1,5-a]pyrimidin-5-ones, and 4-(aryl)-2-(1H-indol-3-yl)-5,6,7,8-tetrahydroquinoline-3-carbonitriles under solvent-free conditions at 100 °C via a cooperative geminal-vinylogous anomeric based oxidation.

Synthesis of N-(4-chlorophenyl) substituted pyrano[2,3-c]pyrazoles enabling PKBß/AKT2 inhibitory and in vitro anti-glioma activity.

A series of N-(4-chlorophenyl) substituted pyrano[2,3-c]pyrazoles was synthesised and screened for their potential to inhibit kinases and exhibit anticancer activity against primary patient-derived glioblastoma 2D cells and 3D neurospheres. A collection of 10 compounds was evaluated against glioma cell lines, with compound 4j exhibiting promising glioma growth inhibitory properties. Compound 4j was screened against 139 purified kinases and exhibited low micromolar activity against kinase AKT2/PKBß. AKT signalling is one of the main oncogenic pathways in glioma and is often targeted for novel therapeutics. Indeed, AKT2 levels correlated with glioma malignancy and poorer patient survival. Compound 4j inhibited the 3D neurosphere formation in primary patient-derived glioma stem cells and exhibited potent EC50 against glioblastoma cell lines. Although exhibiting potency against glioma cells, 4j exhibited significantly less cytotoxicity against non-cancerous cells even at fourfold-fivefold the concentration. Herein we establish a novel biochemical kinase inhibitory function for N-(4-chlorophenyl) substituted pyrano[2,3-c]pyrazoles and further report their anti-glioma activity in vitro for the first time.KEY MESSAGEAnti-glioma pyrano[2,3-c]pyrazole 4j inhibited the 3D neurosphere formation in primary patient-derived glioma stem cells. 4j also displayed PKBß/AKT2 inhibitory activity. 4j is nontoxic towards non-cancerous cells.

Diversity-Oriented Metal-Free Synthesis of Nitrogen-Containing Heterocycles Using Atropaldehyde Acetals as a Dual C3/C2-Synthon.

A highly efficient and elegant diversity-oriented reaction paradigm employing atropaldehyde acetals as new dual C2/C3 synthons was developed under metal-free conditions using glycine esters as the counterpart reagents, which allowed rapid synthesis of two important nitrogen-containing heterocycles, pyrrolo[1,2-a]quinolines and 3,5-diarylpyridines. The divergent products are subtly controlled by the manipulation of the substitutional groups of glycine esters. When a N-arylglycine ester was used, pyrrolo[1,2-a]quinolines can be formed through cascade oxidative C-C cleavage/multiple cyclization. Instead, N-benzylglycine ester as the counter-reagent led to the synthesis of 3,5-diarylpyridines via two key C-N cleavages. Mild conditions, broad substrate scope, scalability and environmentally acceptable organic solvents rendered this method practical and attractive.

A magnetic porous organic polymer: catalytic application in the synthesis of hybrid pyridines with indole, triazole and sulfonamide moieties.

Herein, the synthesis and characterization of a triazine-based magnetic ionic porous organic polymer are reported. The structure, morphology, and components of the prepared structure have been investigated with several spectroscopic and microscopic techniques such as FT-IR, EDX, elemental mapping, TGA/DTA, SEM, TEM, VSM, and BET analysis. Also, catalytic application of the prepared triazine-based magnetic ionic porous organic polymer was investigated for the synthesis of hybrid pyridine derivatives bearing indole, triazole and sulfonamide groups. Furthermore, the prepared hybrid pyridine systems were characterized by FT-IR, 1H NMR, 13C NMR and mass analysis. A cooperative vinylogous anomeric-based oxidation pathway was suggested for the synthesis of target molecules.

Pd-Catalyzed direct C-H arylation of pyrrolo[1,2-a]quinoxalines.

An efficient Pd-catalyzed direct C-H arylation of pyrrolo[1,2-a]quinoxalines with aryl iodides is described, providing a selective route toward a series of 1-arylated and 1,3-diarylated pyrrolo[1,2-a]quinoxalines in good yields. This method features a broad substrate scope, good functional group tolerance and gram-scale synthesis. Furthermore, the C3-thiocyanation of the arylated product is also achieved. We believe that these novel aryl-substituted pyrrolo [1,2-a]quinoxalines will have a variety of applications in organic synthesis and medicinal chemistry.

CcGSDMEa functions the pore-formation in cytomembrane and the regulation on the secretion of IL-lß in common carp (Cyprinus carpio haematopterus).

GSDME is the only direct executor of caspase-dependent pyroptosis in both canonical and non-canonical inflammasomes known to date in fish, and plays an important role in anti-bacterial infection and inflammatory response. In order to determine the regulation of GSDMEa on antibacterial infection in innate immune response, the CcGSDMEa gene in common carp (Cyprinus carpio haematopterus) was first identified and characterized, and then its function related to immune defense was investigated. Our results showed that the expressions of CcGSDMEa at the mRNA and protein levels were both significantly increased after Aeromonas hydrophila intraperitoneal infection at the early stage than that in the control group. We found that CcGSDMEa could be cleaved by inflammatory caspase (CcCaspase-1b) and apoptotic caspases (CcCaspase-3a/b and CcCaspase-7a/b). Interestingly, only the CcGSDMEa-NT (1-252 aa) displayed bactericidal activity to Escherichia coli and could punch holes in the membrane of HEK293T cells, whereas CcGSDMEa-FL (1-532 aa) and CcGSDMEa-CT (257-532 aa) showed no above activity and pore-forming ability. Overexpression of CcGSDMEa increased the secretion of CcIL-1ß and the release of LDH, and could reduce the A. hydrophila burdens in fish. On the contrary, knockdown of CcGSDMEa reduced the secretion of CcIL-1ß and the release of LDH, and could increase the A. hydrophila burdens in fish. Taken together, the elevated expression of CcGSDMEa was a positive immune response to A. hydrophila challenge in fish. CcGSDMEa could perform the pore-formation in cell membrane and the regulation on the secretion of IL-lß, and further regulate the bacterial clearance in vivo. These results suggested that CcGSDMEa played an important role in immune defense against A. hydrophila and could provide a new insight into understanding the immune mechanism to resist pathogen invasion in teleost.

Acid-catalyzed cleavage of C-C bonds enables atropaldehyde acetals as masked C2 electrophiles for organic synthesis.

Acid-catalyzed tandem reactions of atropaldehyde acetals were established for the synthesis of three important molecules, 2,2-disubstituted indolin-3-ones, naphthofurans and stilbenes. The synthesis was realized using novel reaction cascades, which involved the same two initial steps: (i) SN2' substitution, in which the atropaldehyde acted as an electrophile; and (ii) oxidative cleavage of the carbon-carbon bond of the generated phenylacetaldehyde-type products. Compared with literature methods, the present protocol not only avoided the use of expensive noble metal catalysts, but also enabled a simple operation.

Novel nano-architectured carbon quantum dots (CQDs) with phosphorous acid tags as an efficient catalyst for the synthesis of multisubstituted 4H-pyran with indole moieties under mild conditions.

In this work, a new nano-structured catalyst with phosphorus acid moieties, synthesized by the reaction of carbon quantum dots (CQDs) and phosphorus acid under refluxing EtOH. The structure and morphology of CQDs-N(CH2PO3H2)2 were fully characterized using various techniques such as Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, thermogravimetric (TG) analysis, fluorescence and X-ray diffraction (XRD) measurements. The new CQDs-N(CH2PO3H2)2 catalyst was successfully used for the synthesis of 2-amino-6-(2-methyl-1H-indol-3-yl)-4-phenyl-4H-pyran-3,5-dicarbonitriles by the one-pot reaction of various aromatic aldehydes, 3-(1H-indol-3-yl)-3-oxopropanenitrile derivatives and malononitrile in refluxing EtOH and/or ultrasonic irradiation conditions.