Correction for ‘Spatial organization of an enzyme cascade in a Ni-ZIF-8 framework for efficient sugar nucleotide synthesis’ by Youbo Yu et al. , Green Chem. , 2026, https://doi.org/10.1039/D5GC06007A.
Phytopathogenic bacteria are responsible for devastating agricultural losses globally. However, the chemical control of these pathogens is compromised by escalating resistance, environmental pollution, antibiotic resistance gene transfer, and a scarcity of validated antibacterial targets. To fill this gap, this review provides a critical and chemically-focused discussion of recent breakthroughs, aiming to bridge the gap between synthetic innovation, modern target discovery, and rational, data-driven design. Herein, we delineate emerging antibacterial compounds, emphasizing their structural diversity, structure-activity relationships, novel modes of action, and molecular targets. Furthermore, advanced methodologies for discovering and validating antibacterial targets are thoroughly examined, along with deep mechanistic insights. A forward-looking perspective on transformative approaches is also provided. This review aims to guide interdisciplinary efforts and stimulate the development of effective, sustainable, and environmentally friendly next-generation phytobactericides by offering the analysis urgently required by the field.
BACKGROUND:Environmentally responsive microcapsules hold great promise for sustainable pest management by improving efficacy, lowering dosage and enhancing environmental compatibility. Herein, a pH-responsive pyraclostrobin (Pyr)-loaded microcapsule (Pyr@PU) with an isocyanate core and vanillin-Schiff base polyurethane shell were successfully fabricated via interfacial polymerization. RESULTS:The obtained microcapsules exhibited high loading capacity (80.89%) and encapsulation efficiency (96.17%), indicating excellent drug loading and encapsulation performance. In vitro release experiments confirmed that the Pyr@PU microcapsules exhibited prominent pH-responsive release behavior, with a higher cumulative Pyr release (82.81%) at pH 4.0 after 144 h. Meanwhile, the prepared Pyr@PU microcapsules possessed excellent photostability, favorable leaf wettability and superior rainfastness. Bioactivity assays revealed that the microcapsules exerted favorable antifungal effects. At 200 μg mL-1, Pyr@PU provided protective and curative efficacy of 79.62% and 67.59% against kiwifruit pathogens, as well as 57.90% and 37.89% on rice leaves, respectively. Biosafety evaluation showed that Pyr@PU reduced the 96-h acute toxicity to zebrafish by 2.3-fold and displayed no obvious adverse effects on rice seed germination. CONCLUSION:The fabricated pH-responsive Pyr@PU microcapsule exhibits superior UV resistance, leaf adhesion, rainfastness, antifungal efficacy, and biocompatibility. As a promising intelligent controlled-release platform for pesticides, Pyr@PU provides both control efficacy and environmental compatibility, showing great potential for application in sustainable agriculture. © 2026 Society of Chemical Industry.
Canker diseases such as citrus, kiwifruit, and tomato canker pose serious threats to global agriculture. Conventional pesticides often suffer from one or more limitations, including suboptimal efficacy, low utilization efficiency, and environmental concerns due to poorly defined molecular targets and weak foliar affinity. To address these challenges, this study presents a pharmacophore-guided strategy to engineer DhP9, an amphiphilic molecule with potent in vitro antibacterial activity. DhP9 co-assembles with polyoxyethylene (20) sorbitan monolaurate (Tween-20) in water to form distinctive hill-like supramolecular micelles, termed DhP9@0.1 % Tween-20. These micelles suppress genes associated with the type III secretion system (T3SS), curbing bacterial virulence, and inhibit plant sugar transporter genes, inducing bacterial starvation. Simultaneously, they activate plant defense enzymes, enhancing host immunity. Notably, the micelles exhibit strong adhesion to leaf surfaces, ensuring effective deposition and sustained retention of active ingredients at infection sites. At just 200 mu g mL- 1, DhP9@0.1 % Tween-20 achieves superior protective (47.22 %) and curative (67.12 %) efficacy against citrus canker, outperforming the thiodiazole-copper (SC, 20 %), which offers 21.27 % and 33.86 % efficacy, respectively. Moreover, this efficacy is achieved without compromising the safety for crops or non-target organisms such as earthworms and zebrafish. Further investigation reveals that a structural analogue of DhP9 also selfassembles into micelles, offering enhanced control over kiwifruit and tomato canker. With its defined mechanism, high foliar affinity, and favorable safety profile, DhP9@0.1 % Tween-20 emerges as a promising candidate for the environmentally friendly management of quarantine-relevant canker diseases.
The age-regulation mechanism plays a crucial role throughout the entire life cycle of plants, including vegetative growth, growth phase transition, reproductive development, senescence, and regeneration. While this mechanism has been elucidated in angiosperms, it remains poorly understood in gymnosperms. DEFICIENS AGAMOUS-LIKE 1 (DAL1) is a conserved age biomarker in gymnosperms that integrates the aging pathway and reproductive development. However, the molecular regulatory mechanisms governing DAL1 expression patterns are not well understood. In this study, we revealed that DAL1 can activate its own expression through a positive feedback loop by directly binding to its own promoter region. Furthermore, the jasmonic acid (JA)-responsive transcriptional regulator TIFY25 acts as a 'brake' by directly interacting with DAL1 via protein-protein interactions. This interaction inhibits the self-activation of DAL1, ensuring that its expression increases gradually and steadily with age, thereby preventing premature or excessive activation. These findings provide insights into the age-regulation mechanism and integrate JA into the age pathway in P. tabuliformis.
Traditional control agents have long struggled with the cell wall-degrading enzymes and oxalic acid secreted by S. sclerotiorum, resulting in poor control efficacy of sclerotinia stem rot (SSR). To overcome these predicaments, we designed a high-efficiency fungicide capable of site-specifically target-controlled release of active ingredients. Specifically, amino-functionalized zeolitic imidazolate framework-8 (ZIF-8-NH2) with triazole as the bridging ligand in hexaconazole (Hex)-loaded ZIF-8 was obtained via post-synthetic modification, followed by modifying with polygalacturonic acid (PG) to construct a pH and enzyme-dual-responsive nano-pesticide controlled-release system (ZIF-8-NH2@Hex@PG), which possesses superior UV resistance, leaf adhesion properties, and rainwater wash-off resistance, and is stimuli-responsive to the microenvironment with acidity and polygalacturonases (PGs). Bioactivity tests indicate that, compared to 10% Hex formulations and 98% Hex technical grade, ZIF-8-NH2@Hex@PG exhibits better antifungal activity (EC50 = 0.086 μg/mL), as well as protective (89.42%) and curative (76.67%) efficacy at 200 μg/mL against S. sclerotiorum, and also demonstrates broad-spectrum activity against three other pathogenic fungi in vitro. The fungicidal mechanism of ZIF-8-NH2@Hex@PG involves the disruption of hyphal and cellular integrity. Moreover, ZIF-8-NH2@Hex@PG shows good biocompatibility, reducing zebrafish toxicity and promoting rapeseed plant growth. This dual-responsive nanopesticide system provides a novel strategy for rapeseed stem rot control and intelligent agrochemicals green development.
Enzyme cascade reactions hold transformative potential for sugar nucleotide biosynthesis, aligning with green chemistry principles by minimizing solvent waste and purification steps. However, their potential is often compromised by low catalytic efficiency due to inefficient intermediate utilization and instability of individual enzymes. Capitalizing on the coordinatively unsaturated Ni2+ sites and the hydrophilic nature of Ni-doped zeolitic imidazolate framework-8 (Ni-ZIF-8), we engineered a highly active nanocomposite by incorporating a hexahistidine-tagged dual-enzyme conjugate of N-acetylhexosamine 1-kinase (BlNahK) and N-acetylglucosamine 1-phosphate uridylyltransferase (PmGlmU) (His6-BlNahK-PmGlmU-His6) for efficient synthesis of uridine diphosphate N-acetylglucosamine (UDP-GlcNAc)-a pivotal sugar nucleotide. The Ni-ZIF-8 scaffold acts as a sustainable nano-reactor, not only stabilizing the dual-enzyme conjugate conformation but also elevating local substrate concentrations (ATP, UTP, and GlcNAc) via synergistic electrostatic and van der Waals interactions, thereby enhancing reaction kinetics and resource efficiency. Using stimulated Raman scattering (SRS) microscopy, we directly visualized the spatial confinement and rapid consumption of the intermediate substrate GlcNAc-1-P on the nanocomposite surface, demonstrating an engineered substrate channeling-like effect, a common mechanism in native metabolon complexes that boosts cascade efficiency. The resulting nanocomposite exhibits a 4.4-fold higher activity than free enzymes and superior stability across varying temperatures and pH conditions, and retains approximately 60% of its initial activity after five reuse cycles. This work establishes a generalizable and robust strategy for constructing metal-organic framework (MOF)-enzyme complexes with broad applicability in high-value sugar nucleotide biosynthesis and other complex bioconversion processes requiring metabolic flux control.
Conventional aromatic fluorophores in fluorescent probes can easily initiate molecular aggregation via Tr-Tr stacking, which drastically quenches fluorescence and hinders cellular permeability. To address this challenge, we developed an ingenious host-guest recognition strategy that converted detrimental Tr- Tr stacking into a relaxed molecular aggregation state, enabling the creation of a rhodamine-based supramolecular fluorescent probe called RAO@2CB[8]. This ternary conjugate, assembled by encapsulating adamantyl-modified rhodamine (RAO) with two cucurbit[8]uril (CB[8]), showcased enhanced fluorescence properties for the precise detection of salicylic acid (SA). Intriguingly, in intricate biological systems, RAO@2CB[8] demonstrated exceptional cell permeability, facilitating susceptible detection and imaging of SA in HEK-293 cells, radish roots, and salt-stressed white pea seedlings. This facile supramolecular strategy not only mitigates aggregation-induced quenching, but also provides profound insights for the precise modulation of molecular aggregation behavior. (c) 2026 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
Conifers, as long-lived gymnosperms, employ age-regulatory mechanisms distinct from the miR156-miR172 module dominant in angiosperms. The MADS-box gene DAL1 serves as a conserved age marker in conifers, yet the hormonal modulation of its activity remains elusive. Here, we reveal that gibberellin (GA) and jasmonic acid (JA) exert antagonistic control over DAL1 protein abundance through mechanistically distinct pathways in Pinus tabuliformis. GA promotes DAL1 accumulation via the conserved GA-GID1-DELLA cascade. Conversely, JA suppresses DAL1 primarily through the transcription factor MYC2, which directly interacts with DAL1 to mediate its degradation. Strikingly, we uncovered a compensatory mechanism wherein JA-induced TIFY25, a JAZ family protein, stabilizes DAL1 by competitively disrupting the DAL1-DPL1 interaction, thereby counterbalancing the negative regulation by MYC2. This dual regulatory architecture enables conifers to maintain age-dependent DAL1 expression while integrating growth-promoting (GA) and defense-related (JA) signals. Our findings establish a novel GA-JA crosstalk mechanism in conifers and provide fundamental insights into how long-lived trees coordinate developmental timing with phytohormone-mediated environmental adaptation.
Naturally hydrophobic characteristics of most pesticides seriously affect their effective deposition and bioavailability on susceptible plants, causing inevitable off-target movement and environmental pollution. To solve this problem, we employ supramolecular self-assembly strategies to deliver and remedy such defective pesticides, thereby creating a self-assembled, multifunctional delivery system-PyE28@HP-β-CD, which comprises a high-performance pyridyl ether microbicide (PyE28) complexed with 2-hydroxypropyl-β-cyclodextrin (HP-β-CD). This approach transforms insoluble hexagonal sheet structures (PyE28) into biocompatible sugar-armored spherical assemblies (PyE28@HP-β-CD) with sustained release profiles in aqueous environment, ultimately improving the physicochemical/biological properties and targeted delivery efficiency of hydrophobic pesticides. The advancement concretely manifests as: (i) markedly enhanced foliar deposition via improved wetting coverage and reduced interfacial tension (contact angle decreased by 18°), (ii) effective biofilm disruption (achieving an 81.40% biofilm reduction at 23.3 µg mL-1) through suppression of extracellular polysaccharide biosynthesis, and (iii) superior bactericidal activity against Xanthomonas pathogens mediated by oxidative damage amplification and redox homeostasis interference. In vivo evaluations demonstrated that PyE28@HP-β-CD at 200 µg mL-1 effectively suppressed citrus canker and rice bacterial blight by 79.73% and 45.53%, respectively, superior to conventional bactericides by 30.76% and 20.33%. This study presents a supramolecular self-assembly approach to optimize hydrophobic agrochemical delivery, combining sustained release with on-demand precision.
Bacterial biofilms formed by phytopathogens confer formidable resistance to chemical pesticides, underscoring an urgent need for innovative antimicrobial solutions. Antimicrobial peptides (AMPs), exemplified by the potent bee venom derivative melittin, offer a promising alternative owing to their broad-spectrum activity and intrinsic biofilm-disrupting capacity. However, the agricultural application of melittin is severely hindered by rapid environmental degradation, susceptibility to enzymatic degradation, and non-selective cytotoxicity. Here, we report a metal-coordination-driven nanoassembly strategy to enhance the stability and efficacy of melittin. Engineering an N-terminal hexahistidine tag enabled a one-step assembly of melittin into uniform nanoparticles (NanoMel) via Zn²⁺ coordination. This nanoformulation improved the antibacterial potency, lowering the half-maximal effective concentration (EC₅₀) values against Xanthomonas oryzae pv. oryzae (Xoo), Xanthomonas oryzae pv. oryzicola (Xoc) to 3.795 µg/mL and 3.202 µg/mL, representing a 1.59- and 1.38-fold enhancement over its linear counterpart. Furthermore, NanoMel demonstrated superior biofilm eradication, degrading 86.9
Self-assembly is a canonical process for generating ordered, functional architectures, with the structural 'blueprint' encoded in the component design and interaction thermodynamics. While external stimuli such as concentration and chemical guests might shift the equilibrium between predefined ordered states, the structural memory remains embedded in the assembly (thermodynamic control). In this work, we employ mechanical force as a unique stimulus to dismantle thermodynamic order, accessing a structural “erasing” state and resetting the assembly landscape. Specifically, ball-milling of a thermodynamically-preferred Pd6L14 coordination cage (c-Pd6L14) drives it to a disordered, ligand-exchanged state (PdxL1y), which upon dissolution undergoes a conversion to a transient and metastable tubular Pd6L14 isomer (t-Pd6L14), thermodynamically inaccessible from conventional pathways from c-Pd6L14.We generalize such “mechanochemical reset” by transforming a complex double-walled Pd12L28 knot-like cage into a triply interlocked [Pd3L22]2 complex via a similar force-generated disordered PdxL2y state. To highlight the uniqueness of the reset process, this strategy was further employed in two confinement catalytic settings: 1) thermal; and 2) photochemical C-H oxidation reactions, where the analogous reactions suffer from product inhibition in conventional conditions. This work establishes mechanochemistry as not merely a green synthetic tool, but a powerful strategy for escaping deep thermodynamic minima and navigating the self-assembly energy landscape toward non-thermodynamic, otherwise-inaccessible states.
ABSTRACT The management of bacterial plant diseases is impeded by biofilm fortifications and the poor foliar affinity of conventional antimicrobials. Supramolecular assemblies have recently emerged as promising biofilm‐eradicating agents with enhanced surface adhesion. Yet, supramolecular polymers, although endowed with comparable or even greater potential, remain largely untapped in this arena. Herein, we introduce NOP@CB[8], a flower‐like supramolecular polymer self‐assembled in water from a de novo designed cationic pyridinium salt (NOP) and cucurbit[8]uril (CB[8]). Acting as a multifunctional agent, NOP@CB[8] disrupts bacterial membranes, perturbs redox equilibrium, disintegrates biofilms, and concurrently enhances foliar affinity. These combined attributes endow NOP@CB[8] with potent in vivo efficacy, exhibiting protective and curative efficacies of 56.1% and 51.2%, respectively, at 200 µg mL −1 against rice bacterial leaf blight, thereby surpassing both free NOP (47.9%/43.1%) and thiodiazole copper (TC, 36.2%/33.7%). Remarkably, NOP@CB[8] delivers high control efficacy with uncompromised safety toward both target and non‑target organisms, even demonstrates enhanced safety in zebrafish relative to free NOP. Extending its scope to citrus and kiwifruit cankers, NOP@CB[8] achieves approximately 80% protective and over 60% curative efficacy, consistently outperforming NOP and TC. Together, this study delineates a green alternative for crop protection and a conceptual framework for next‐generation functional supramolecular polymers.
Developing low-cost bifunctional electrocatalysts with efficient catalytic activity on both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is crucially important for practical water splitting technology. Herein, the interstitial Boron (B)-doped CoFe2O4 with enriched oxygen vacancy as bifunctional electrocatalysts for OER and HER was synthesized by strategy of in-situ diffusion combined with NaBH4 reduction method. Besides metalloid B doping could regulate the electronic structure, the constructed disorder by B doping further leads to massive oxygen vacancies of CoFe2O4. Therefore, the synergistic effect of boron doping and oxygen vacancy endows CoFe2O4 electrocatalysts with marvelous intrinsic electrocatalytic activities on both OER and HER in alkaline electrolyte. For OER, the overpotential of r-B-CoFe2O4/NF is 244.27 mV with a Tafel slope of 31.68 mV dec- 1, which is lower than that of commercial IrO2 electrocatalyst. For HER, the overpotential of r-B-CoFe2O4/NF is as low as 103.42 mV with a Tafel slope of 141.01 mV dec- 1. To stabilize the oxygen vacancy by boron-oxygen bond, the r-B-CoFe2O4/NF electrocatalyst exhibits an excellent stability during long-term running of 100 h at a current density of 50 mA cm- 2. Furthermore, the water splitting performance of r-BCoFe2O4/NF || r-B-CoFe2O4/NF is overwhelming that of commercial IrO2 || Pt/Ti in both two-electrode and anion exchange membrane (AEM) electrolytic cell.
The development of nanopesticides with minimized carriers (NMCs) through prodrug design and molecular self-assembly represents a transformative strategy for enhancing pesticide utilization efficiency and addressing global food security challenges. As a proof of concept, we developed A12@DES, a water-based nanodelivery system that combines a target-specific pesticide with a deep eutectic solvent (DES). The system utilizes a laccase inhibitor (A12, structurally optimized from lead compound PMDD-5Y) to self-assemble into monodisperse nanospheres (∼160 nm diameter) with an alkaline phosphatase (ALP)-responsive DES matrix. The formulation demonstrates multiple functional advantages: (1) a simple preparation process, (2) substantially reduced droplet bouncing and splashing, (3) enhanced foliar wetting performance, and (4) ultimately improved pesticide deposition efficiency. Intriguingly, A12@DES supports rice growth and demonstrates minimal toxicity to nontarget organisms. At a low dose of 200 μg/mL, A12@DES exhibits superior in vivo curative and protective efficacies (74.43%/85.53%) against Magnaporthe oryzae compared to both the commercial fungicide isoprothiolane (57.48%/63.29%) and A12 alone (66.69%/69.95%). This study provides a reference for the development of multipurpose water-based nanopesticide delivery systems based on prodrug technology and DES conception, improving the comprehensive utilization efficiency of fungicides for high-risk rice blast control.
Abiotic stress severely hinders plant growth and development, resulting in a considerable reduction in crop yields. Salicylic acid (SA) serves as a central signal mediating abiotic stress responses in plants. Real-time fluorescence tracking using specific probes can enhance our understanding of the SA-triggered modulation underlying these events. However, in complicated living plant microenvironments, selective recognition and bioimaging of SA is a great challenge for scientists due to the severe background interference and SA analogues. Herein, an efficient fluorescence probing technology employing a highly selective rhodamine probe-phoxrodam was developed, which realizes the precise bioimaging of SA in salt-stressed plant seedlings. Experimental findings reveal that phoxrodam demonstrates exceptional selectivity (fluorescence intensity: IPhoxrodam+SA/IPhoxrodam+SA analogues > 4.29-fold), high sensitivity (limit of detection = 6.42 nM, fluorescence quantum yield: ΦPhoxrodam+SA = 0.36) and good anti-interference properties. Furthermore, we confirmed that phoxrodam accurately detects SA in the roots of salt-stressed wheat seedlings, the low-temperature resistance of Nicotiana benthamiana and the heavy metal resistance of pea seeds, using in vivo confocal imaging. This study provides a feasible strategy for efficiently tracking plant signalling molecules and promotes the in-depth research of SA-mediated physiological mechanisms, laying a key foundation for the future development of new immune activation inducers.
Electronic structure tuning in metal oxides is a facile and effective strategy on boosting their catalytic oxygen evolution reaction (OER) performance. Here, we demonstrate the electronic structure tuning of CuCo2O4 by phosphorus (P) doping via in-situ diffusion method. The results suggest that due to more electrons transferred from P to the neighboring Co3+, the tuned Co is served as catalytic active sites for the enhanced OER performance. The synthesized P3.85-CCO/NF exhibits an overpotential of 250 mV at a current density of 10 mA cm-2, and a Tafel slope of 27 mV dec- 1, which performs an enhanced OER activity than that of IrO2/NF. Moreover, the P3.85-CCO/NF presents stable electrochemical performances upon long-time running for 30 h. Thus, the electronic structure tuning strategy by in-situ P diffusion method emerges as an effective approach on enhancing the catalytic OER performance for metal oxide electrocatalysts.
Introduction With the COVID-19 pandemic becoming endemic, vigilance for Long COVID-related cardiovascular issues remains essential, though their specific pathophysiology is largely unexplored. Objectives Our study investigates the persistent cardiovascular symptoms observed in individuals long after contracting SARS-CoV-2, a condition commonly referred to as “Long COVID”, which has significantly affected millions globally. Methods We meticulously describe the cardiovascular outcomes in five patients, encompassing a range of severe conditions such as sudden cardiac death during exercise, coronary atherosclerotic heart disease, palpitation, chest tightness, and acute myocarditis. Results All five patients were diagnosed with myocarditis, confirmed through endomyocardial biopsy and histochemical staining, which identified inflammatory cell infiltration in their heart tissue. Crucially, electron microscopy revealed widespread mitochondrial vacuolations and the presence of myofilament degradation within the cardiomyocytes of these patients. These findings were mirrored in SARS-CoV-2-infected mice, suggesting a potential underlying cellular mechanism for the cardiac effects associated with Long COVID. Conclusion Our findings demonstrate a profound impact of SARS-CoV-2 on mitochondrial integrity, shedding light on the cardiovascular implications of Long COVID.
Chiral pesticides have captivated considerable interest in agriculture, yet the integration of chirality into multifunctional supramolecular materials within this sector remains uncharted. Here, we show the fabrication of chiral AIM-12S/R@β-CD by encapsulating AIM-12S/R within β-cyclodextrin (β-CD), designed to enhance foliar adhesion and biofilm disruption for effective management of rice bacterial blight. Upon assembly in aqueous media, the chiral disparities in foliar affinity and biofilm disruption, initially present in AIM-12S/R, are amplified, as evidenced by a 67° lower contact angle for AIM-12R@β-CD relative to its S-enantiomer, and an 8.5-fold increase in biofilm eradication at 12.5 μg·mL⁻¹. Despite comparable in vitro potency, which often obscures chiral influences on other traits, enantioselective interactions between the enantiomers with leaf surfaces and biofilms dictate the divergence in in planta efficacy. This work provides a demonstration of chiral discrimination in supramolecular agrochemicals, presenting valuable insights into the further deployment of chiral supermolecules in agriculture.