Drug-resistant bacterial infections in chronic wounds remain a critical challenge, particularly under persistent inflammation. Here, we report the de novo design of high-entropy alloy (HEA, PtFeCuCoNi)-based Janus artificial enzymes with pH-gated redox biocatalysis for sequential antibacterial and repair functions. The multi-metal synergy stabilizes the d-band center, allowing acidic oxidase/peroxidase-like activity and neutral antioxidase-like activity. In infection, the enzymes generate bactericidal reactive oxygen species (ROS) to eliminate methicillin-resistant Staphylococcus aureus (MRSA) and biofilms at ultralow concentrations (8 μg/mL). During healing, they scavenge ROS, alleviate oxidative injury and support cellular proliferation. In MRSA-infected wounds, this dual-action system clears bacteria and then accelerates regeneration through enhanced neovascularization and matrix remodeling. Mechanistic analyses reveal PFKFB3-mediated metabolic reprogramming, suppression of pro-inflammatory cytokines, and macrophage polarization toward the M2 phenotype. Integrating pH-gated antimicrobial and immunomodulatory repair within one nanoplatform, this strategy addresses the conflicting demands of infection control and tissue healing.

Covalent organic frameworks (COFs) exhibit considerable potential in artificial photosynthesis, notably for photoreductive generation of hydrogen peroxide (H2O2) and related aerobic oxidative synthesis of value-added chemicals. However, their widespread application is hindered by limited chemical stability, suboptimal redox active sites, and inefficient exciton dissociation. To address these challenges, we report the design of a vinylene-linked sp2-COF by introducing an electron-withdrawing and polar -CN group (sp2-COF-CN) to extend asymmetric π-conjugation and remodel the redox active sites for achieving superior H2O2 photosynthesis and aerobic oxidation reactions. Comprehensive characterization indicates that the introduction of sp-hybridized C≡N units reshapes the donor-π-acceptor configuration, promotes charge delocalization, and boosts electron density with pronounced asymmetry. These effects collectively yield a remarkable H2O2 production rate of 17,768.4 μmol g-1 h-1 using benzyl alcohol as a sacrificial agent, exceeding those of most recently reported organic and inorganic photocatalysts. Furthermore, sp2-COF-CN demonstrates high efficiency in diverse aerobic oxidation reactions, including the oxidation of furfuryl alcohol in water and the benzylamine- and thiophenol-based coupling reactions in organic solvents. This work demonstrates that extending asymmetric π-conjugation of sp2-COFs, combined with redox active site remodeling, can be an effective strategy for designing high-performance heterogeneous photocatalysts for the selective synthesis of value-added chemicals.

Inspired by the 3D microenvironment modulated precise and efficient catalytic reactions in nature enzyme systems, we designed a NiCo-based catalyst with 3D modulated microenvironments for high-performance 5-hydroxymethylfurfural (HMF) oxidation reaction by constructing metal organic frameworks (MOFs) with different side groups (SH-MOF-NiCo, OH-MOF-NiCo, and MOF-NiCo). Our research indicates that the ─SH group in the porous structure could weaken the hydrogen bonding connectivity, which enhances the adsorption of HMF* and OH* species to promote α-C-H/O-H activation. The optimized SH-MOF-NiCo electrode achieves a HMFOR current density of 463 mA cm‒2 at 1.40 V vs. RHE, 100% HMF conversion, and 100% 2,5-Furandicarboxylic acid (FDCA) selectivity at 1.45 V vs. RHE. Furthermore, the catalyst demonstrated remarkable efficiency in anion exchange membrane (AEM) electrolyzers, achieving high efficiency for high-purity FDCA and H2 production at a high current density (361 mA cm‒2) with a voltage of 2.0 V, while maintaining operational durability for 210 h and continuous FDCA production with a yield of 97%. Importantly, this strategy not only enables efficient hydrogen production and biomass upgrading but also expands the scope to other biomass-derived chemicals and high-value-added waste plastic conversion.

The treatment of biofilm-associated drug-resistant bacterial infections remains a formidable clinical challenge, primarily due to the limited permeability of therapeutic agents through the dense extracellular matrix and the inherent drug resistance of biofilm-embedded microorganisms. Here, to overcome this challenge, we report the design of an atomic Fe-O-Mo/Fe-S-Mo homojunction photothermal nanosheet (Fe-HJPS) to synergize reactive oxygen species (ROS)-biocatalysis and biofilm penetration for eradicating drug-resistant bacterial infections. Spectroscopic and computational analyses reveal that the homojunction sites in the Fe-HJPS, comprising asymmetric Fe-S-Mo/Fe-O-Mo coordinations around Fe centers, downshift the high d-p hybrid orbital energy level compared to the original symmetric Fe-S-Mo coordination. This optimization enhances the adsorption affinity of oxygen intermediates and improves ROS-biocatalytic activities. Notably, under near-infrared (NIR) irradiation, the Fe-HJPS generates localized heat and disturbs the extracellular polymeric substances (EPS) in biofilms to increase the permeability of bacterial membranes, thereby facilitating ROS influx into bacterial cells. This dual-action mechanism of ROS production and biofilm penetration enables effective biofilm eradication at ultralow concentration (40 mu g & sdot;mL- 1), demonstrating superior efficacy against drug-resistant infections in both in vitro and in vivo models. Our findings establish atomic-scale homojunction in photothermal artificial enzymes as a versatile strategy for designing non-antibiotic antimicrobial nanomaterials that overcome drug-resistant bacterial infections.

Developing radiosensitizing agents to amplify tumor-eradicating effects on primary, regional recurrence, and distant metastases plays a transformative role in modern cancer care. Here, we report the de novo design of biocatalytic artificial metalloenzymes with an IrMn-cluster-based redox center (IMM) to achieve radiosensitized systemic antitumor responses for preventing malignant tumor metastasis and recurrence. Notably, our findings indicate that Mn-organic ligands substantially enrich the electron density of Ir clusters, thereby optimizing their interaction with oxygen species and markedly enhancing the production of both reactive oxygen species and molecular oxygen. When combined with radiotherapy, the IMM effectively amplifies DNA damage and induces pronounced apoptosis by alleviating intratumoral hypoxia. This shift reprograms the tumor microenvironment, enhancing radiosensitivity and facilitating the infiltration and activation of intratumoral CD8⁺ T cells and dendritic cells. Moreover, when integrated with anti-PD-1 therapy, this coordinated therapeutic regimen elicits potent systemic immune responses and durable antitumor memory, effectively suppressing tumor recurrence and metastasis while markedly improving therapeutic efficacy and long-term survival. We anticipate that this conceptual design could offer a promising and translationally relevant nanomedicine platform for radiotherapies.

Covalent organic frameworks (COFs) are promising photocatalysts for hydrogen peroxide (H2O2) production, yet their rational design remains challenging. Although machine learning has advanced the prediction of properties of porous materials, its application to COF-based photocatalysis faces two major challenges: the representation of multilevel structural features and the limited availability of training datasets. Here we present a comprehensive computational framework, termed 'information co-evolution', that accelerates the discovery of efficient COF structures for H2O2 photosynthesis. This framework integrates two pathways: to mitigate data limitations, we introduce data augmentation techniques and ensemble modelling; concurrently, to address the structural encoding challenge, we introduce a cross-level feature fusion strategy that integrates these fragment descriptors with mechanism-driven physical descriptors. These strategies collectively reduced the validation root mean square error from 4.70 to 3.31. Among over 10,000 candidates, our framework can successfully identify high-performance COFs for H2O2 photosynthesis, for example, COF-343 achieves a H2O2 photosynthetic rate of 12,978.7 mu mol h-1 g-1. The model interpretation further unveiled critical structural motifs, offering information for the rational design of COF photocatalysts beyond traditional trial-and-error methods.

The catalytic conversion of CO2 into value-added chemicals via the reverse water-gas shift (RWGS) reaction represents a significant pathway for mitigating climate change and enabling sustainable carbon utilization. However, Pt-based catalysts, despite their superior H2 activation ability, often suffer from inadequate CO selectivity and durability under high-temperature conditions, primarily due to excessive CO adsorption at low-coordinated Pt edge sites. Herein, we present a sulfur (S)-mediated targeted passivation strategy to engineer Pt-CeO2 catalysts with atomically tailored active sites, effectively addressing the critical activity-stability-selectivity trade-off. The incorporation of S into CeO2 support induced optimized electronic modulation, as evidenced by in situ/ex situ characterizations and density functional theory (DFT) calculations, which weakened *CO adsorption strength and suppressed the methanation pathway. The optimized Pt-S-CeO2 catalyst exhibits remarkable performance at 600 °C: CO selectivity >95%, CO production rate of 8.8×10-5 mol gcat-1 s-1, and <10% activity loss over 250 h. On the other hand, this work establishes a framework for targeted dopant-mediated site engineering in heterogeneous catalysis, offering a generalizable route to reconcile conflicting performance in CO2 hydrogenation systems and beyond.

ABSTRACT Covalent organic framework (COF)‐based photocatalysts hold considerable promise for solar‐driven chemical transformations, yet their practical performance in conventional powder or membrane systems is often constrained by poor dispersibility, inefficient interfacial mass transport, and suboptimal charge utilization. Here, we report COF‐based Janus membrane photocatalysts with an extended π‐conjugation for continuous photosynthesis of H 2 O 2 and value‐added chemicals, in which COF structures bearing expanded conjugated side chains are uniformly immobilized on the polyacrylonitrile (PAN) substrate to create a Janus‐like interfacial architecture. This design integrates the efficient light‐harvesting and charge‐transport capabilities of the COF framework with a PAN‐induced planar interface and tunable surface hydrophobicity. As a result, the Janus COF‐membrane exhibits enhanced hydrophobicity, achieving an H 2 O 2 production rate of 7888 µmol·g −1 h −1 under visible‐light irradiation, which is 2.23 times that of the control group, alongside excellent recyclability and long‐term operational stability. Furthermore, this straightforward approach can be extended to a range of COF‐derived photocatalysts for the photosynthesis of value‐added chemicals, which demonstrate superior activity in benzylamine coupling (99% conversion and selectivity within 3 h) and Knoevenagel condensation reactions (90%–99% conversion and selectivity within an average of 6 h). Together, our findings underscore the effectiveness of interfacial microenvironment engineering in designing COF membrane‐based photocatalytic systems.

Selective producing CH4 by CO2 electroreduction remains challenging, primarily hindered by the complexity of reduction products, sluggish protonation kinetics, and competitive hydrogen evolution reaction. Herein, we developed a silica-copper composite catalyst (CuO/SiO2), where CuO nanoparticles are dispersed on the hydroxyl-functionalized SiO2 nanosheet. The hydroxyl-functionalized SiO2 support promotes the formation and transfer of interfacial reactive hydrogen species, lowers the energy barrier for the reduction of CO2 to CH4 by stabilizing *COOH, *CO, and *H intermediates. Meanwhile, it favors the hydrogenation of *CHO over C—C coupling between C1 intermediates, thereby shifting product selectivity from multi-carbon products towards CH4. As a result, CuO/SiO2 catalyst delivers high CH4 selectivity over a broad current density range of 0.2–0.9 A/cm2, with a peak Faradaic efficiency of 66.2

Diabetic wounds remain a major clinical challenge due to persistent inflammation and impaired tissue regeneration. In this study, we report the scalable synthesis of hyperbranched polyglycerol-b-poly(2-ethyl-2-oxazoline) star copolymers bearing terminal arginine groups (hPG-b-PEO-Arg), designed to self-assemble into nanoscale hydrocolloids (70-200 nm) in aqueous media, driven by the distinct hydrophilicity of the polymer blocks. These hydrophilic nanoparticles penetrate damaged wound tissue, facilitating in vivo healing of diabetic wounds in rats (n = 10). The copolymers were synthesized on a 300 g scale via ring-opening polymerization and demonstrated excellent cytocompatibility with primary human fibroblasts and keratinocytes at concentrations up to 15 mg/mL. In vivo, hPG-b-PEO-Arg treatment accelerated wound closure and promoted collagen-rich tissue regeneration without evidence of systemic toxicity, oxidative stress, or skin irritation. The combination of scalable synthesis, high biocompatibility, and intrinsic hydrocolloid-forming capability positions hPG-b-PEO-Arg as a promising platform for chronic wound management and broader biomedical applications.

Offshore oil spills and oily wastewater cause severe water pollution. Membrane separation offers a promising solution for efficient oil-water separation; however, conventional membranes often exhibit poor fouling resistance and face a trade-off between flux and separation efficiency due to mismatched pore sizes. To overcome these challenges, we developed a hydrolyzed polyacrylonitrile by tetraethyl orthosilicate modification (HPANT) nanofibrous membrane based on the synergistic mechanism of selective wettability and pore-size exclusion. And it achieves superhydrophilicity and underwater superoleophobicity, with the pore size regulated to ∼20 nm. This design achieves excellent fouling resistance and separation efficiencies of 98.29% for immiscible mixtures and 97.80% for surfactant-stabilized emulsions, with high fluxes of 6,941.5 L·L·m-2·h-1·bar-1 and 8,379.6 L·m-2·h-1·bar-1, respectively. Multiscale simulations (DFT, MD, FEM) further clarify the dual mechanism: the stable hydration layer resisting oil adhesion and tailored nanopores providing a physical barrier. This strategy provides guidance for the development of oil-water separation membranes.

Bacterial infection poses a significant threat to clinical treatment due to the emergence of drug resistance and the high risk of recurrence. Here, we report the de novo design of a spiky pollen-based vanadium artificial enzyme particle (VAE-Pollen) that integrates potent reactive oxygen species (ROS)-catalytic activity with immune priming to prevent both primary and secondary bacterial infections. Experimental and theoretical analyses confirm that bacteria are efficiently captured by the micro-structured surface of VAE-Pollen, and the introduction of oxygen vacancies modulates the electronic configuration of vanadium catalytic sites, significantly enhancing their versatile ROS-catalytic performance. Meanwhile, VAE-Pollen enhances bacterial capture and ROS-triggered release of bacterial antigens, which mimics the sustained allergen exposure characteristic of natural pollen, thereby potently activating systemic defensive responses and providing sustained anti-infective surveillance to prevent secondary wound infection. Notably, the VAE-Pollen demonstrates significant efficacy in treating methicillin-resistant Staphylococcus aureus (MRSA) and preventing its recurrence, offering a potent and intelligent antibacterial alternative that may circumvent the limitations of conventional antibiotics.

Radiotherapy is a cornerstone of oncological treatment and is frequently used in combination with chemotherapy or immunotherapy. However, its effectiveness is often limited by radioresistance and insufficient activation of systemic antitumor immunity. Overcoming these challenges necessitates the development of innovative radio-activable agents that can enhance therapeutic efficacy and suppress metastasis and recurrence. Here, we present the de novo design of a radio-activable gold-single-atom-based artificial enzyme (Au-RadioSAE) system with superior biocatalysis and radiosensitization to prevent metastatic recurrence. Upon activation by radiotherapy, Au-RadioSAE triggers a rapid increase in intracellular reactive oxygen species, amplifies DNA damage, and initiates potent cell necroptosis. Simultaneously, it remodels the tumor immune microenvironment by enhancing CD8+ T cell infiltration, promoting M1 macrophage polarization, and enhancing radioimmunotherapy. In a CT26 murine model, Au-RadioSAE significantly inhibited tumor growth and recurrence. When combined with an anti-PD-1 immune checkpoint inhibitor, it strongly induced immunogenic cell death in nonirradiated tumors, leading to the synergistic suppression of metastatic growth. This innovative design offers a promising strategy for developing radio-activable artificial enzymes that synergize radiotherapy and immunotherapy, particularly in preventing metastasis and recurrence in advanced malignancies.

Biocatalytic generation of reactive oxygen species (ROS) by artificial enzymes offers a promising strategy for treating diverse diseases, including pathogenic infections and malignancies. However, the sluggish ROS biocatalytic efficiency and unstable active sites have hindered their potential clinical translation. Here, inspired by natural vanadium haloperoxidases and NADPH oxidase-based ROS-catalytic systems, we report the de novo design of a sono-activated artificial vanadium enzyme (Vx+-SonoAE) for efficient and renewable ROS nanobiocatalytic therapies. By mimicking the electron transport chains and active VO4 centers in natural enzymes, our innovative bionic approach not only yields efficient, robust, and precise vanadium active sites on TiO2 but also enables continuous regeneration of redox centers during ROS biocatalysis via efficient electron transfer from sono-activated TiO2 to the Vx+ site. Consequently, the Vx+-SonoAE achieves remarkable ROS-catalytic performance with a superior turnover number (TON = 54 × 10-3 s-1) that far surpasses the reported state-of-the-art metal oxides-based nanobiocatalysts. Moreover, this new artificial enzyme system demonstrates exceptional therapeutic efficiency in infection control and tumor regression with sustained and sono-activated treatment properties. This work establishes a new paradigm for designing efficient and renewable nanobiocatalysts, combining fundamental insights from natural enzymatic systems with advanced materials engineering to create robust therapeutic platforms with long-term efficacy.

Ischemic stroke is a fatal cerebrovascular disease, and reperfusion, the primary approach for restoring blood supply, can lead to significant oxidative stress and subsequent damage to the cerebrovascular system. Developing strong antioxidant agents could be a solution, but it remains a Herculean challenge. Herein, inspired by the three-dimensional coordination structures and active center of natural Mn-superoxide dismutase, coupled with the synergistic monoatom/cluster sites found in antioxidases, we propose the de novo design of Mn-organic complex-supported Ru clusters (MnCP-Ru) to function as an artificial metalloenzyme for cascade elimination of reactive oxygen species (ROS), aimed at protecting against cerebral ischemic-reperfusion injury. Our studies show that Mn-organic ligands increase the electron density of Ru clusters, thereby improving their binding to oxygen species and resulting in effective, cascade-like antioxidase activities. Accordingly, the MnCP-Ru can reduce the number of apoptotic neurons by attenuating ROS-induced cell damage and exert powerful anti-inflammatory effects by inhibiting lipid peroxidation, microglial and astrocyte activation in brain tissues, thus leading to powerful protection and repair of cerebral ischemia-reperfusion injury. We believe the MnCP-Ru biocatalyst, with its synergistic sites and cascade ROS elimination, offers effective antioxidative performance, paving the way for developing materials to treat ischemic-reperfusion injury and other oxidative stress-related diseases.

Switchable adhesives hold great potential in fields like flexible electronics, soft robotics, and tissue repair, etc. However, creating bio-based switchable adhesives for biomedical use remains challenging due to the difficulty in balancing high strength and a broad adhesion span. Here, we report a dynamic chemical modification strategy based on biorefinery-derived hyperbranched nanoconfinement to fabricate a switchable adhesive for biomedical applications. Microbial fermentation produces hyperbranched biorefinery molecules with nanostructures that address common biomass-related issues like long production cycles, unstable batches, and by-product generation, while also providing abundant binding sites for high-density dynamic bonds. This hyperbranched nanoconfinement enables substantial energy dissipation, facilitating efficient stress redistribution and interfacial reconfiguration at fracture sites, thereby achieving simultaneously excellent adhesive strength and switchable adhesion. The resulting switchable wound bioadhesive exhibits a wide switching span (296 to 17 N/m) and high stability, enabling non-invasive repair with a 94.80% wound closure rate after 10 days, significantly higher than the control (76.07%). This work explores the application of biorefinery molecules in the field of bio-based adhesives and develops a promising candidate for innovating adhesion solutions in the biomedical field.

Iron-doped Carbon-based nanoparticles (Fe-CBNs) are emerging as highly versatile platforms for precision oncology by integrating catalytic, magnetic, optical, and immunomodulatory functions within a single construct. This review first outlines the fundamentals of Fe incorporation into graphitic and amorphous carbon matrices, emphasizing how iron speciation, heteroatom (e.g., N) co-doping, and carbon architecture tune electronic structure, surface polarity, and redox microenvironments. We then survey key synthetic routes, including biomass pyrolysis, plasma, sol–gel, chemical vapor deposition, hydrothermal and microwave-assisted methods that afford precise control over core–shell morphology, pore structure, and Fe–N–C active sites. These structural attributes underpin unique properties relevant to cancer therapy including enhanced Fenton/Fenton-like catalysis for chemodynamic therapy, efficient near-infrared photothermal conversion, robust magnetic responsiveness for targeting and hyperthermia, high drug-loading capacity, and multimodal MRI/fluorescence/photoacoustic imaging. Mechanistic sections detail how Fe-CBNs exploit the acidic, H₂O₂-rich tumor microenvironment to generate reactive oxygen species, trigger ferroptosis and apoptosis, and amplify heat-induced cytotoxicity under alternating magnetic fields or light irradiation. We further describe their roles as smart drug carriers, and as immunomodulators that repolarize tumor-associated macrophages, inhibit epithelial–mesenchymal transition, and synergize with chemotherapy and immune checkpoint blockade. Finally, we discuss translational challenges and future opportunities, including stimuli-responsive and ligand-targeted designs, logic-gated therapeutic cascades, and machine-learning-guided materials optimization. The evidence positions Fe-CBNs as promising next-generation theranostic nanoplatforms capable of uniting chemodynamic therapy, photothermal/photodynamic and magnetic hyperthermia, ferroptosis induction, drug delivery, immunotherapy, and image guidance within integrated, patient-tailored cancer treatments.

Among CO2 emission mitigation strategies, the reverse water-gas shift (RWGS) reaction represents a promising route for selective CO2-to-CO conversion, enabling subsequent valorization. However, designing selective and stable non-noble metal catalysts for RWGS remains a persistent challenge. In this study, we report a Ni site-induced localized accelerated carbonization process to produce noble metal-like active Ni-WC nano-islands for high-performance RWGS catalysis. Benefiting from the unique structures, the Ni0.02WC/WO2-NIs catalyst exhibits exceptionally high RWGS activities, with a CO production rate of 2340 molCO·molWC-1·h-1 and over 97% CO selectivity. Even after 100 hours of continuous testing at 500 °C, the activity loss of Ni0.02WC/WO2-NIs was only 0.5%. Unlike the conventional catalyst structure in the RWGS reaction, we demonstrate that the nano-island WC structure with stretch strain ensures the space limitation of electron-rich Ni sites for CO desorption and H2 dissociation. Integrated in-situ DRIFTS, Raman spectroscopy, and DFT calculations reveal that dual-functional WC/WOx interfaces enhance catalyst activity through bidentate carbonate formation and intensified hydrogen spillover. We suggest that the design of new, efficient, and selective Ni-based noble-metal-like catalysts with nano-island structure through interface synergistic effects offers a promising path to engineering superior RWGS catalysts for CO2 reduction.