The one-pot cascade conversion of biomass-derived furan alcohols into pyrroles is primarily hindered by two challenges: the intrinsic competition between selective C–O hydrogenolysis and undesired overhydrogenation of the furan ring, along with the swift poisoning of acid sites caused by aniline. To address these limitations, we developed a sulfate‑functionalized Pt–S/ZSM-5 catalyst with an intimate Pt–SO42⁻ interface. This system facilitates the conversion of furan alcohol and nitrobenzene to N-phenyl-2-methylpyrrole with an 88.1% yield at 100 ℃ under 2.0 MPa H2. Mechanistic studies reveal that the Pt–SO42⁻ interface promotes hydrogen spillover, generating transient S–O–H⁺···Pt–H⁻ pairs. These species provide poisoning‑resistant Brønsted acidity for etherification and facilitate a concerted SN2-like C–O cleavage, effectively suppressing over‑hydrogenation. Moreover, the in situ generation of water via the etherification of furan alcohol with ethanol promotes the hydrolysis of 2-methylfuran. The catalyst shows broad substrate scope, accommodating 13 nitrogen sources (e.g., 2-nitrotoluene, 3-nitrotoluene, 4-nitrotoluene, 4-halonitrobenzenes (F, Cl, Br, I), 4-nitrophenol, nitrophenylmethane, 1-nitronaphthalene, 1-nitrobutane, 1-butylamine, NH3) and various FAs (e.g., 5-methyl FA, 2,5-dihydroxymethylfuran). Interfacial hydrogen spillover thus tailors the microenvironment of the tandem active sites, offering a robust strategy for the selective construction of N‑heterocycles from renewable biomass.

The increasing use of pesticides in agricultural production has exacerbated environmental pollution. Microencapsulation enhances the water solubility and dispersibility, extends the effective duration, and regulates the precise release of pesticides, thereby reducing their application and increasing efficiency. In this study, a delivery system based on TA-Fe3+ coordination was developed to form pesticide nanocapsules, improving the stability and foliar affinity of the encapsulated citral-based acylthiourea (CA) and enhancing its resistance to harsh environmental conditions. Regular spherical nanocapsules with an average diameter of approximately 251.1 nm were fabricated by optimizing the metal-polyphenol coordination. The active ingredient CA was encapsulated within the nanocapsules, achieving an encapsulation efficiency of approximately 95.8%. The adhesion of the nanopesticide formulation to the hydrophobic surfaces of Camellia oleifera leaves was significantly improved, as indicated by the adhesion work of 92.6mJ/m2. After six months of storage at ambient temperature, the retention rate of CA within the micro-carriers remained at 60.0%. The antifungal performance of the system was superior to that of the commercial pesticide difenoconazole, as the EC50 against Colletotrichum fructicola decreased from 21.15 mg/L to 0.056 mg/L. Furthermore, the release kinetics analysis demonstrated that the release behavior of the constructed nanocapsules fully conforms to the Ritger-Peppas model, indicating a release mechanism governed by the combined effects of core diffusion and wall erosion.

Tandem rearrangement-amination of biomass-derived furan alcohols (FAs) with nitrogenous compounds to produce N-cyclopentylanilines is essential for fine chemicals. However, this process is hindered by the in situ poisoning of acidic sites by basic amines over conventional metal-acid bifunctional catalysts. Herein, Ce-doped cobalt metaphosphate catalysts (CoP2/Ce-Co2P4O12), featuring CoP2 nanoparticles and oxygen vacancies (Ov), were fabricated via the precipitation of Ce-doped Prussian blue analogs, followed by oxidation and high-temperature phosphidation. Mechanistic investigation reveals that Ov promotes in situ hydrogen spillover from CoP2 nanoparticles to the Co2P4O12 support, forming H+-H− pairs. These pairs function as both Brønsted acid sites for 1,4-pentanedione aldol condensation and unconventional active sites for C=N bond hydrogenation. Consequently, a one-pot synthesis of N-cyclopentylaniline was achieved for the first time at a low temperature (120 °C), affording an exceptional yield of 86.5%. Furthermore, the catalyst exhibited broad generality for various nitrogen sources (e.g., NH3·H2O, amino compounds, and nitrobenzene) and FAs (e.g., 5-methyl furan alcohol and 2,5-dihydroxymethyl furan) via a similar reaction route. This work demonstrates that Ov-mediated hydrogen spillover can dynamically generate robust bifunctional H+-H− pairs to overcome basic poisoning, offering a new design strategy for cascade catalysis involving basic nitrogen compounds.

The sucking pests such as aphids, planthoppers, and whiteflies pose a significant threat to global crop productivity, causing estimated losses of up to 40

In this study, we synthesized Fe, N, S co-doped hierarchically porous carbon (Fe-CSK-PCP) with a high specific surface area of 1826.34 m2/g and a pore volume of 1.14 cm3/g. This material was prepared using discarded lotus seedpods as a carbon source, potassium hydroxide (KOH) as an activator, potassium ferricyanide as both an activator and graphitization promoter, thiourea as a source of N and S dopants, and cetyltrimethylammonium bromide (CTAB) as a pore-enlarging agent. Platinum nanoparticles (PtNPs) were subsequently loaded onto the Fe-CSK-PCP surface via wet impregnation. The enhanced porosity, increased pore size, and heteroatom doping of the Fe-CSK-PCP support have significantly promoted the loading content and dispersion of PtNPs, consequently creating an abundance of active sites. Meanwhile, the hierarchical pore structure has improved the diffusion of analyte and the desorption of oxidation product. Therefore, the fabricated PtNPs/Fe-CSK-PCP sensor exhibited exceptional fouling resistance and electrocatalytic performance in indole-3-acetic acid (IAA) detection, demonstrating a high sensitivity (2.32 mu A/mu M) and a low detection limit (21.67 nM, S/N = 3) over a wide linear range (0.3-20 mu M). This sensor was successfully applied to determine IAA in apple juice samples with satisfactory recoveries.

Rhizoctonia solani is a significant soil-borne plant pathogenic fungus. Its sclerotial structure confers strong environmental adaptability and persistent infectivity, posing a serious threat to the production of numerous crops. Citral, a plant-derived monoterpene aldehyde, exhibits antifungal activity; however, its antifungal potency is limited. In this study, citral was combined with its acylthiourea derivatives, leading to the screening and construction of an efficient synergistic antifungal system, CE4. CE4 significantly inhibits mycelial growth of R. solani and reduces its capacity for sclerotia formation, with an EC50 value of 10.97 mg/L. Further research has revealed that CE4 disrupts the surface structure of hyphae, significantly increases cell membrane permeability, and reduces ergosterol content, thereby disrupting cellular membrane homeostasis. Meanwhile, CE4 induces the accumulation of ROS and lipid peroxidation products, significantly disrupts the antioxidant enzyme system, and inhibits the activity of key enzymes in energy metabolism, thereby reducing ATP levels. Cytotoxicity evaluation demonstrated that CE4 did not significantly increase cytotoxicity toward mammalian cells at the effective antifungal concentration. The above results indicate that CE4 effectively inhibits the growth of R. solani through the synergistic disruption of cell membrane homeostasis, induction of oxidative stress, and interference with energy metabolism. The results of this study provide a novel theoretical and experimental foundation for the synergistic application of plant-derived antifungal agents.

To develop citral-based botanical fungicides, 112 previously reported derivatives across 5 series were evaluated in vitro against Colletotrichum fructicola. SAR analysis identified the citral-thiourea series as the most potent group, with 3-methoxy derivative c18 showing the highest intraseries activity. Notably, intermediates d (EC50 = 0.7474 mg/L, EC90 = 6.0319 mg/L) and g (EC50 = 0.1073 mg/L, EC90 = 0.6244 mg/L) demonstrated exceptional efficacy, significantly outperforming commercial chlorothalonil (EC50 = 1.4382 mg/L, EC90 = 268.5969 mg/L), with intermediate g emerging as the most potent compound overall. A predictive QSAR model was successfully constructed (R2 = 0.8345), revealing that lower polarity, enhanced electronic stability of carbon-hydrogen bonds, higher localized solvation energy, and minimized steric hindrance favor antifungal potency. Furthermore, MTT assays confirmed that derivative g exhibits low cytotoxicity toward human liver and kidney cells, substantially lower than raw citral. This work provides a solid theoretical framework for designing highly active inhibit C. fructicola agents.

Traditional bio-based vitrimers generally suffer from unsatisfactory mechanical properties and poor degradability. To address these issues, epoxidized maleopimaric acid (EMPA) was synthesized using rosin as the raw material, and then blended with castor oil triglycidyl ether (CGE), a series of degradable rosin-castor oil-based vitrimers containing dynamic ester bonds and disulfide bonds were fabricated via curing reaction with 4,4'-dithiodibutyric acid (DBA), 3,3'-dithiodipropionic acid (DPA) and 4-aminophenyl disulfide (APD). The experimental results demonstrate that EMPA-CGE-APD vitrimers exhibit outstanding mechanical performances owing to the simultaneous incorporation of rigid hydrogenated phenanthrene skeletons from rosin and flexible aliphatic chains from castor oil. The material achieves a tensile strength of 64.5 MPa, a Tg of 108 °C, and and a toughness of 45.07 MJ/m³. Moreover, the simultaneous introduction of dynamic ester bonds and disulfide bonds into the cross-linked network endows the vitrimers with excellent self-healing, physical reprocessing and chemical degradation capabilities. Scratch healing tests demonstrate that the healing efficiency of EMPA-CGE-APD vitrimer can reach 95.0%. After being shredded and remolded, the tensile strength and Tg of the recycled vitrimer retain 87.6% and 84.2% of the original values, respectively. In addition, the as-prepared rosin-castor oil-based vitrimers can be degraded completely in mercaptoethanol (ME) and ethanolamine (EA) through disulfide exchange reaction and amidation reaction of ester groups, respectively. Specifically, the EMPA-CGE-APD vitrimer is fully dissolved in ME at 100 °C within 16 h, and completely degraded in EA at 100 °C in only 140 min. The rosin-castor oil-based vitrimers developed in this work are expected to promote the sustainable development of degradable bio-based resins.

Developing a cost-effective catalyst for the selective tandem conversion of furfural (FFA) to ethyl levulinate (EL) is important for synthesizing biofuels and fine chemicals from biomass. However, traditional catalysts prefer the hydrogenation-dehydration-hydrolysis pathway and are slow due to high activation energy requirement. Herein, a NiCoP/LaPO4 catalyst was prepared via calcination of layered double hydroxide (LDH) precursor, followed by hydrogen reduction, and phosphating. When applied to the tandem of FFA for EL production, it exhibited a high selectivity of 90.1% at 160 degrees C under ethanol and water via acetalization-hydrogenolysis-hydrolysis route. Catalytic mechanism investigation indicated that in situ hydrogen spillover from NiCoP nanoparticles to the LaPO4 support, leading to the formation of H+-H- pairs. These H+-H- pairs not only provide Br & oslash;nsted acid sites to drive FFA acetalization and 2-ethoxymethyl furan (EMF) hydrolysis but also activate the C-O bonds of the key intermediate 2-diethoxymethyl furan (DEMF) via the SN2 mechanism, markedly accelerating the hydrogenolysis step. Moreover, the NiCoP/LaPO4 catalyst shows remarkable catalytic versatility for the synthesis of different alkyl levulinates from a range of alcohols (i.e., methanol, propanol, isopropanol, butanol and benzyl alcohol). This study presents an efficient bifunctional catalysis approach for complex tandem reaction pathways aimed at synthesizing alkyl levulinate by hydrogen spillover to generate transient H+-H- pairs.

Litsea cubeba is an important industrial plant valued for its pericarp essential oil and kernel oil. However, variation in seed traits and kernel oil characteristics among wild populations and their relationships with ecological factors remain insufficiently understood. Wild germplam from 21 provenances across eight provinces in southern China was evaluated for seed traits, kernel oil content, and fatty acid composition, and variance analysis, correlation and path analysis, and multivariate ecological analyses were used to characterize phenotypic diversity and examine its associations with environmental variables. Analysis of variance showed that the investigated provenances differed significantly in seed traits and kernel oil characteristics (P < 0.05). Provenances ZJ-LY and SC-KJ exhibited relatively high kernel oil content (≥ 35

In the fields of agriculture and forestry, there are major unknown risks associated with the toxicity of chemical pesticide residues and pathogen resistance. To address this issue, in this study, 52 novel pyrazole monoterpene compounds were obtained by organic synthesis of highly active monoterpene natural products and evaluated for their in vitro and in vivo antifungal activities and crystal structure analysis of compound 5b. The results showed that compounds 4g and 8f exhibited remarkable antifungal activities against Rhizoctonia solani, with the corresponding EC50 values reaching 4.27 and 4.81 mg/L. At the same time, the results of in vivo and in vitro experiments showed that both compounds 4g and 8f had good control effects against rice sheath blight. The antifungal activity of these compounds was preliminarily explored by scanning electron microscopy, molecular docking, enzyme activity determination, and cytotoxicity, indicating that these compounds have the potential for development into low-toxic antifungal drugs.

BACKGROUND:Pear anthracnose, caused by Colletotrichum fructicola, is a highly destructive disease that inflicts substantial economic losses worldwide. However, current antifungal agents mainly target known target proteins, and long-term use leads to increased resistance of C. fructicola. Thus, developing multitargeted antifungal agents based on new targets is an effective way to solve the problem of drug resistance. RESULTS:Twenty camphor derivatives containing thiosemicarbazide groups were synthesized and evaluated for antifungal activity against C. fructicola. Among them, compound 1a [median effective concentration (EC50) = 3.76 mg L-1] exhibited the strongest antifungal activity, superior to kresoxim-methyl (EC50 = 9.69 mg L-1). The in vivo antifungal test demonstrated that 1a had better protective and curative effects against pear anthracnose than kresoxim-methyl. The toxicity results showed that 1a exhibited low toxicity to LO2 and HEK293 cell lines. Mechanistically, 1a can destroy hyphae morphology and cell ultrastructure, increase cell membrane permeability, affect the normal expression pathway of soluble proteins and destroy the normal metabolic function of phospholipase C. Additionally, the laccase inhibitory activity results showed that 1a [Median inhibitory concentration (IC50) = 7.14 mg L-1) had stronger laccase inhibitory activity than cysteine (IC50 = 23.99 mg L-1). Furthermore, molecular docking studies showed that 1a interacted with laccase by forming hydrogen bonds with amino acid residues ASP444 and ARG442. CONCLUSION:This study showed that compound 1a can serve as a promising multitarget fungicide candidate for controlling C. fructicola, with its targets at least including the cell membrane and laccase of the C. fructicola. © 2025 Society of Chemical Industry.

In this study, we systematically investigated the mechanisms of the antioxidation and anti-lipid accumulation effects of antioxidant peptides from Litsea cubeba on a free fatty acid (FFA)-induced NAFLD model of HepG2 cells. The NAFLD cell model was constructed by inducing the HepG2 hepatocellular carcinoma cell line with 0.5 mmol/L FFAs, and AQRDAGLL, QEGPFVR, and DVPPPRGPL were given to the culture to study their lipid-lowering and antioxidant activities on NAFLD cells. The lipid-lowering activities of the three antioxidant peptides were evaluated by Oil Red O staining and TG and TC content assays, and the results showed that all three peptides had strong ameliorating effects on FFA-induced lipid accumulation in NAFLD cells. The intracellular antioxidant protease (CAT, GSH, and SOD) activity levels and lipid peroxidation (MDA) content were measured and intracellular ROS levels were detected. The results showed that after intervention with the antioxidant peptides, the intracellular ROS levels in the NAFLD model cells were significantly reduced, the SOD and CAT activities were increased, the GSH content was elevated, and the MDA content was reduced, which indicated that AQRDAGLL, QEGPFVR, and DVPPPRGPL were able to inhibit the oxidative stress of the cells effectively and to achieve the effect of intervening in NAFLD. JC-1 fluorescence staining experiments showed that the mitochondrial membrane potential function of NAFLD cells was restored under the effect of the antioxidant peptides. Molecular dynamics simulations revealed that the main driving force between QEGPFVR and Keap1 protein was van der Waals forces, ΔG = −62.11 kcal/mol, which indicated that QEGPFVR was capable of spontaneously binding to Keap1 protein.

The citral-based acylthiourea derivative e14 was identified as a potent synergist for chlorothalonil (CT) against Colletotrichum fructicola. The optimized mixture (ECS, 25% e14) exhibited strong synergistic activity (synergistic ratio (SR) = 2.30), significantly enhancing disease control efficacy while enabling reduced fungicide dosage. Mechanistic studies revealed that e14 specifically targets mitochondrial complex I by binding to the NADH dehydrogenase subunit 5 (ND5), thereby disrupting oxidative phosphorylation and inducing energy depletion and oxidative stress. This distinct mode of action differs from that of CT, minimizing the risk of cross-resistance. Importantly, e14 exhibits low mammalian cytotoxicity. This study elucidates the synergistic mechanism of ECS and the enhancing role of e14, thereby providing a solid foundation for the development of effective fungicide synergists.

BACKGROUND:Rhizoctonia solani, the fungal pathogen causing rice sheath blight, threatens global food security. Prolonged use of Kresoxim-methyl (KM), a common fungicide, has led to resistance and reduced effectiveness. This study investigates the synergistic effects of citral-based amide derivatives with KM and explains the underlying mechanisms. RESULT:Among the tested derivatives, compound d25 exhibited the most pronounced synergistic effect, achieving a peak synergistic ratio (SR = 2.66 ± 0.67) at a molar ratio of 25% in the mixture. At a molar ratio of 10%, the mixture (Mix) demonstrated significant antifungal activity both in vitro and in vivo, effectively reducing mycelial dry weight and enhancing rice leaf protection. Mechanistic studies revealed that Mix disrupted the tricarboxylic acid (TCA) cycle, thereby inhibiting energy metabolism. Additionally, d25 interfered with arachidonic acid metabolism, impairing cell membrane repair mechanisms and enhancing the fungicidal efficacy of KM. Toxicity assessments revealed that d25 exhibited minimal cytotoxicity against human cell lines and low acute toxicity toward Apis mellifera L. and zebrafish. CONCLUSION:The findings elucidate the synergistic mechanisms of d25 and Mix, underscoring their potential as effective fungicide synergists. This study establishes a robust theoretical and practical foundation for enhancing the efficacy of chemical control strategies against R. solani, providing new insights into the development of safe and efficient fungicide formulations. © 2025 Society of Chemical Industry.

Litsea cubeba essential oil (EO)-encapsulated SiO2 (SiO2-EO) nanocapsules were fabricated by in situ biosilicification for the treatment of biofilms on food-contact surfaces. By optimizing the synthesis conditions (0.5 mg/mL EO and 50 mM silicic acid), SiO2-EO nanocapsules exhibited a uniform size distribution (150-200 nm) with a distinct core-shell structure. The characterization of nanocapsules was elucidated using a scanning electron microscope (SEM), transmission electron microscope, Fourier transform infrared, and x-ray diffraction analyses. The minimal inhibitory concentrations of SiO2-EO nanocapsules were 5 and 1.25 mg/mL for Escherichia coli and Staphylococcus aureus, respectively. Compared to free EO, the SiO2-EO nanocapsules showed more significant inhibition activity against both Gram-negative and Gram-positive bacterial biofilms. Confocal experiments and SEM demonstrated that the nanocapsules efficiently penetrate biofilms within 30 min and deliver EO to destroy the membrane structure of bacteria. Eventually, SiO2-EO nanocapsules were also applied to four kinds of food-contact surfaces. The populations in biofilms exposed to 2.5 mg/mL of nanocapsules decreased 1.51-1.56 log CFU/cm2 and 2.15-2.22 log CFU/cm2 for E. coli and S. aureus, respectively. This study provides an innovative strategy to treat bacterial biofilms with EO-based nanocomposites.

Catalytic valorization of biomass into aromatic cyclic oxygen fine chemicals is crucial for reducing reliance on fossil resources and opens up new possibilities in sustainable chemistry. In this study, a series of mesoporous ZSM-5 zeolites catalyst was prepared via alkali and acid solution etching and showed an efficient catalytic performance for synthesizing 4-hydroxy-2-cyclopentenone with an extraordinary yield of 91.2% from bioderived furfuryl alcohol at 140 degrees C. Moreover, they demonstrated outstanding catalytic efficiency in the synthesis of cyclopentenones, achieving yields exceeding 65% from various furan derivatives (i.e., 2-furan methyl alcohol, 2-furan ethyl alcohol, and 5-methylfurfuryl alcohol). Additionally, in the Diels-Alder cycloaddition of DMF, ZSM-5-Si/Al170-OH0.3-HCl treated with NaOH and HCl exhibited excellent catalytic activity, presenting 63.7% selectivity of PX, which are also far superior to commercial ZSM-5. This synergistic effect of mesoporous property, more Alsingle sites, suitable Lewis/Br & oslash;nsted acid sites greatly improves the catalytic isomerization. Furthermore, ZSM-5-Si/Al170-OH0.3-HCl demonstrated the ability to be reused for four reaction cycles while maintaining its catalytic activity without notable decline. This study offers an effective and environmentally friendly catalytic system for synthesizing cyclopentenones and P-xylene, while also showcasing the catalytic improvement achieved through modification of zeolites.

Conventional glass fiber reinforced composites (GFRCs) are usually difficult to degrade and the matrix usually exhibit low Tg. To address this dilemma, a degradable catalyst-free self-healing vitrimer matrix with a high Tg was fabricated using turpentine-derived terpene maleic acid (TMA) as a curing agent and epoxidized menthane diamine (EMDA) with a tertiary amine structure as an epoxy resin. Due to the introduction of a rigid terpene ring skeleton of turpentine, EMDA-TMA vitrimer exhibits a Tg of up to 201.8 degrees C. Due to the tertiary amine groups in the EMDA-TMA, the vitrimer can achieve self-healing and recycling properties by dynamic transesterification reaction without the addition of catalysts. More importantly, the EMDA-TMA-GF composite prepared using EMDA-TMA vitrimer as a matrix also shows a high Tg (223.6 degrees C), and excellent mechanical properties. In addition, under the synergistic action of potassium hydroxide (KOH) and ethanolamine (EA), the EMDA-TMA-GF composite can be rapidly degraded by a KOH/EA solution to realize non-destructive recovery of glass fibers.

Rhizoctonia solani is a highly destructive fungal pathogen of rice, and effective management currently depends heavily on chemical fungicides such as thiophanate-methyl (TM). To establish a sustainable approach for enhancing fungicide efficacy, we screened 22 citral-based acylthiourea derivatives and identified compound e3 as a highly effective synergist of thiophanate-methyl (TM), achieving a synergistic ratio of 3.88. When the molar ratio of e3 is 20 %, the mixture of e3 and TM (SETM) exhibits a pronounced antifungal activity against R. solani, both in vivo and in vitro. Integrated transcriptomic and metabolomic analyses demonstrated that steroid biosynthesis and membrane lipid metabolism were the primary pathways affected following the addition of e3. Notably, genes including Cytochromes P450 and sterol reductase ERG24 were significantly upregulated and exhibited strong correlations with multiple membrane lipid metabolites. Physiological and biochemical analyses revealed that e3 could induce an increase in ergosterol content, promote the accumulation of reactive oxygen species (ROS), and enhance the activity of antioxidant enzymes. Furthermore, SETM exhibited additional effects by increasing membrane permeability, causing intracellular substance leakage, and inhibiting energy metabolism. Importantly, the incorporation of e3 did not enhance the cytotoxicity of TM toward mammalian cells. These findings show that e3 is a highly effective synergist that disrupts fungal membrane lipid homeostasis and impairs key physiological functions, significantly enhancing TM's antifungal activity. The study advances understanding of fungicide-synergist interactions and offers a sustainable strategy to improve efficacy without sacrificing safety.