Metal-organic frameworks (MOFs) demonstrate considerable potential for enzyme immobilization, yet their applications are often limited by enzyme leakage or denaturation. Herein, we present a strategy for enzyme immobilization using hierarchically porous UiO-66 (a stable microporous MOF) frameworks. By partially replacing the conventional 1,4-benzenedicarboxylic acid (HBDC) linkers with monocarboxylic acids of controlled-chain lengths, we successfully engineered tailored mesopores within the stable microporous UiO-66 structure.
View Article and Find Full Text PDFDeveloping high-performance nanozymes with efficient HO activation capacity for biosensing still faces a great challenge. Here, Pt nanoparticles on a porous nitrogen-doped carbon carrier (Pt─N─C) are prepared as efficient nanozymes. By optimizing the pyridinic N content in the carbon carrier, a positive correlation has been found between the pyridinic N content and the peroxidase-like activity of Pt─N─C nanozymes.
View Article and Find Full Text PDFElectrochemiluminescence (ECL) based on luminol-HO systems presents significant potential for the accurate and reliable biosensing. However, owing to the overlap of the potential windows for activating HO and dissolved O leads to competitive reactions, which presents a significant challenge for the selective ECL sensing. Herein, single atom Co sites on nitrogen-doped hierarchically porous carbon (Co-NC SAs) as co-reaction accelerators can efficiently activate HO to generate reactive oxygen species for oxidation of luminol and thus achievement of enhanced ECL emission.
View Article and Find Full Text PDFPlatinum (Pt)-based nanozymes display exceptional stability and catalytic activity in the activation of HO, making them ideal peroxidase (POD)-like substitutes for immunoassay applications. However, specific catalytic progress is hindered by the excessive orbital overlaps between Pt and oxygen-based intermediates. Herein, a highly efficient mesoporous medium-entropy alloy (m-MEA) nanozyme is reported to selectively enhance POD activity through synergy interaction of multiple elements.
View Article and Find Full Text PDFThe identification of dominant reactive oxygen species (ROS) in the direct oxidation of benzene with HO holds crucial significance for understanding catalytic mechanisms and guiding catalyst design. Herein, we developed a sub-nanoscale Cu cluster supported on SiO (Cu/SiO) catalyst, which achieved comparable benzene conversion to its nanoparticle counterpart (46.6% vs 55.
View Article and Find Full Text PDFThe large-scale production of carbon monoxide (CO) through electrochemical CO reduction reaction (CORR) represents a promising strategy for mitigating CO emissions and energy crisis. However, the development of high-efficiency, stable, and pH-universal electrocatalysts for CORR is of utmost urgency. In this study, CoNi alloy nanoparticles encapsulated within N-doped carbon nanotubes (N-CNTs) are synthesized and employed as robust catalysts toward CORR-to-CO.
View Article and Find Full Text PDFDeveloping efficient peroxidase-like nanozymes to surpass natural enzymes remains a significant challenge. Herein, an amorphous RuO nanozyme with peroxidase-like activity is synthesized for activating HO with a specific activity of 1492.52 U mg, outperforming the crystalline RuO nanozymes by a factor of 22 and far superior to natural peroxidases.
View Article and Find Full Text PDFThe critical challenge in utilizing carbon-based nanomaterials is identifying the active site. Herein, we demonstrate the keto-oxygen on the graphitic surface as active sites for catalytic transfer hydrogenation (CTH) and present an efficient nanocrystalline diamond (ND)-derived carbon-based catalyst for metal-free CTH of nitroarenes to imine with 99.9% nitrobenzene conversion and exclusive selectivity (99.
View Article and Find Full Text PDFSci Bull (Beijing)
May 2025
Designing three-dimensional (3D) catalytic sites in single-atom catalysts (SACs) that mimic thyroid peroxidase (TPO) function for achieving iodotyrosine coupling, although highly desirable for the synthesis of thyroid hormones, poses a great challenge. Herein, we design and synthesize a class of SACs with 3D catalytic centers composed of Cu-N as catalytic sites and BO as binding sites (BO/CuNC) for mimicking TPO in activating HO to facilitate tyrosine iodination and conjugation for producing thyroid hormones. We demonstrate that the as-prepared BO/CuNC not only provides binding sites for HO through hydrogen bond interactions but also possesses catalytic sites to promote an alternative O-O heterolysis process.
View Article and Find Full Text PDFNanozymes, as superior alternatives to natural enzymes, frequently employ the inhibition effect in turn-off sensors for analyte detection. However, limited attention has been paid to the inhibition mechanisms between analytes and nanozymes, limiting advancements in nanozyme-based sensing. Benefiting from the synergistic effects between three-dimensional network structure of aerogel and ligand effect triggered electronic regulation, PtBi aerogel nanozymes (PtBi ANs) exhibit superior peroxidase-like activity (293.
View Article and Find Full Text PDFAnal Chem
January 2025
The elementary mechanism and site studies of nanozyme-based inhibition reactions are ambiguous and urgently require advanced nanozymes as mediators to elucidate the inhibition effect. To this end, we develop a class of nanozymes featuring single Cu-N catalytic configurations and B-O sites as binding configurations on a porous nitrogen-doped carbon substrate (B/Cu) for inducing modulable inhibition transfer at the atomic level. The full redistribution of electrons across the Cu-N sites, induced by B-O sites incorporation, yields B/Cu with enhanced peroxidase-like activity versus Cu.
View Article and Find Full Text PDFThe rational design of efficient hydroxyl intermediate (*OH) adsorption catalysts for dopamine electrooxidation still faces a major challenge. To address this challenge, a CeO-loaded CuO catalyst inspired by the f-p-d orbital hybridization strategy is designed to achieve efficient *OH adsorption and improve dopamine oxidation. The experimental results and theoretical calculations demonstrate that the f-p-d orbital hybridization regulates the electron distribution at the Ce-O-Cu interface, which facilitates electron transfer and optimizes the adsorption of *OH, thereby promoting dopamine oxidation.
View Article and Find Full Text PDFChem Sci
August 2024
Regulating the performance of peroxidase (POD)-like nanozymes is a prerequisite for achieving highly sensitive and accurate immunoassays. Inspired by natural enzyme catalysis, we design a highly active and selective nanozyme by loading atomically dispersed tungsten (W) sites on Pd metallene (W-O-Pdene) to construct an artificial three-dimensional (3D) catalytic center. The 3D asymmetric W-O-Pd atomic pairs can effectively stretch the O-O bonds in HO and further promote the desorption of HO to enhance POD-like activity.
View Article and Find Full Text PDFRational design of highly active and stable catalysts for dopamine oxidation is still a great challenge. Herein, inspired by the catalytic pocket of natural enzymes, an iodine (I)-doped single Fe-site catalyst (I/FeNC) is synthesized to mimic the catalytic center of heme enzymes in both geometrical and electronic structures, aiming to enhance dopamine (DA) oxidation. Experimental studies and theoretical calculations show that electronic communication between I and FeN effectively modulates the electronic structure of the active site, greatly optimizing the overlap of Fe 3d and O 2p orbitals, thereby enhancing OH adsorption.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
The electrochemical conversion of CO into valuable chemicals is a promising route for renowable energy storage and the mitigation of greenhouse gas emission, and production of multicarbon (C) products is highly desired. Here, we report a 1.4 %Pd-Cu@CuPz comprising of dispersive CuO and PdO dual nanoclusters embedded in the MOF CuPz (Pz=Pyrazole), which achieves a high C Faradaic efficiency (FE) of 81.
View Article and Find Full Text PDFBiosens Bioelectron
October 2024
Rational design of peroxidase (POD)-like nanozymes with high activity and specificity still faces a great challenge. Besides, the investigations of nanozymes inhibitors commonly focus on inhibition efficiency, the interaction between nanozymes-involved catalytic reactions and inhibitors is rarely reported. In this work, we design a p-block metal Sn-doped Pt (p-d/PtSn) nanozymes with the selective enhancement of POD-like activity.
View Article and Find Full Text PDFAlthough oxygen reduction reaction (ORR) as an effective signal amplification strategy has been extensively investigated for the improvement of sensitivity of electrochemical sensors, their activity and stability are still a great challenge. Herein, single-atom Fe (FeSA) and Fe nanoparticles (FeNP) on nitrogen-doped carbon (FeSA/FeNP) catalysts demonstrate a highly active and stable ORR performance, thus achieving the sensitive and stable electrochemical sensing of organophosphorus pesticides (OPs). Experimental investigations indicate that FeNP in FeSA/FeNP can improve the ORR activity by adjusting the electronic structure of FeSA active sites.
View Article and Find Full Text PDFChem Commun (Camb)
March 2024
ZnO quantum dots (QDs) supported on porous nitrogen-doped carbon (ZnO/P-NC) exhibited excellent electrochemical performance for the electroreduction of CO to CO with a faradaic efficiency of 95.3% and a current density of 21.6 mA cm at -2.
View Article and Find Full Text PDFNano Lett
March 2024
Nanozymes with peroxidase-like activity have been extensively studied for colorimetric biosensing. However, their catalytic activity and specificity still lag far behind those of natural enzymes, which significantly affects the accuracy and sensitivity of colorimetric biosensing. To address this issue, we design PdSn nanozymes with selectively enhanced peroxidase-like activity, which improves the sensitivity and accuracy of a colorimetric immunoassay.
View Article and Find Full Text PDFAs a fundamental product of CO conversion through two-electron transfer, CO is used to produce numerous chemicals and fuels with high efficiency, which has broad application prospects. In this work, it has successfully optimized catalytic activity by fabricating an electrocatalyst featuring crystalline-amorphous CoO-InO interfaces, thereby significantly expediting CO production. The 1.
View Article and Find Full Text PDFNanozymes with peroxidase (POD)-like activity have garnered significant attention due to their exceptional performance in colorimetric assays. However, nanozymes often possess oxidase (OD) and POD-like activity simultaneously, which affects the accuracy and sensitivity of the detection results. To address this issue, inspired by the catalytic pocket of natural POD, a single-atom nanozyme with FeN configuration is designed, exhibiting enhanced POD-like activity in comparison with a single-atom nanozyme with FeN configuration.
View Article and Find Full Text PDFAnal Chim Acta
December 2023
Development of highly sensitive and accurate biosensors still faces a great challenge. Herein, glucose oxidase (GOx) is efficiently immobilized on the AuCu hydrogels owing to their porous structure and interfacial interaction, demonstrating enhanced catalytic activity, satisfactory stability and recyclability. Besides, by integration of AuCu@GOx and electrochromic material of Prussian blue, a sensitive and stable biosensing platform based on the excellent electrochromic property of Prussian blue and the enhanced enzyme activity of AuCu@GOx is developed, which enables the electrochemical and visual dual-mode detection of glucose.
View Article and Find Full Text PDFPharmaceutics
September 2023
Diabetic ulcers are the second largest complication caused by diabetes mellitus. A great number of factors, including hyperchromic inflammation, susceptible microbial infection, inferior vascularization, the large accumulation of free radicals, and other poor healing-promoting microenvironments hold back the healing process of chronic diabetic ulcer in clinics. With the increasing clinical cases of diabetic ulcers worldwide, the design and development of advanced wound dressings are urgently required to accelerate the treatment of skin wounds caused by diabetic complications.
View Article and Find Full Text PDFChem Commun (Camb)
August 2023
A novel and tunable synthesis of Fe/CuO bimetallic catalysts has been achieved a simple Fe-precipitation and calcination method, which was used for highly efficient CO electroreduction to control the wide-ranging CO to H ratio by simply changing the ratio of metals. The faradaic efficiency of CO could reach 86.1% with a current density of 49.
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