Superior Peroxidase-like Activity Research Articles

A highly sensitive dual-mode detection platform based on the novel copper/molybdenum bimetallic nanoclusters and Co–Fe layered doubled hydroxide nanozyme for butyrylcholinesterase activity sensing

Herein, a novel copper/molybdenum bimetallic nanoclusters (Cu/Mo NCs) with intense blue emission were synthesized by using polyvinylpyrrolidone (PVP) as template and ascorbic acid as reducing agent. Owing to the synergistic effect between Cu and Mo, the fluorescence intensity of Cu/Mo NCs was significantly improved about 6-time than monometallic copper nanoclusters. A novel and sensitive ratiometric fluorescence and colorimetric dual-mode sensing platform for monitoring butyrylcholinesterase (BChE) was strategically constructed by the integration of Cu/Mo NCs with excellent optical properties and Co–Fe layered doubled hydroxide (CoFe-LDH) with superior peroxidase-like activity for the first time. In the presence of H2O2, nonfluorescent and colorless o-phenylenediamine (OPD) was oxidized to fluorescent and yellow 2,3-diaminophenazine (DAP) with maximum fluorescence emission peak at 564 nm and ultraviolet absorption peak at 418 nm by CoFe-LDH with peroxidase-like activity. Simultaneously, the generation of DAP could effectively quench Cu/Mo NCs fluorescence at 444 nm through the inner-filter effect (IFE). The hydrolysis of S-butyrylthiocholine iodide (BTCh) can be catalyzed by butyrylcholinesterase (BChE) to generate thiocholine (TCh) that could hinder the oxidation of OPD, leading to the fluorescence and ultraviolet absorption of DAP decreased, meanwhile, the fluorescence of Cu/Mo NCs recovered. The ratiometric fluorescence signal F564/F444 and colorimetric system both performed a satisfactory response to the concentration of BChE in the range 0.5 to 90 U L−1 and 1 to 100 U L−1 with the LOD of 0.18 U L−1 and 0.36 U L−1, respectively. The dual-mode sensing for BChE exhibited outstanding application potential in biosensing.

Enhanced peroxidase-like activity based on electron transfer between platinum nanoparticles and Ti3C2TX MXene nanoribbons coupled smartphone-assisted hydrogel platform for detecting mercury ions

BackgroundHeavy metal pollution poses a serious threat to the ecological environment. Mercury ion (Hg2+) is a class of highly toxic heavy metal ions, which is bioaccumulative, difficult to breakdown, and has a significant affinity with sulfur and thiol-containing proteins, which seriously affects environmental safety and human health. Nanozyme-based sensing methods are expected to be used to detect toxic heavy metal ions. However, the application of precious metal nanozymes to develop portable sensors with simplicity, high stability, and high sensitivity has not been explored to a large extent. ResultsIn this paper, based on MXene's unique adsorption capacity for certain precious metal ions, PtNPs/Ti3C2TXNR composites were successfully prepared by in-situ growth of Pt nanoparticles (PtNPs) on the surface of Ti3C2TX MXene nanoribbons (Ti3C2TXNR) using the hydrothermal technique. Experimental data revealed PtNPs/Ti3C2TXNR exhibited superior peroxidase-like activity, attributed to the synergistic effect of well-dispersed ultrasmall PtNPs and electron transfer effect. Hg2+ can significantly inhibit enzyme-like activity of PtNPs/Ti3C2TXNR due to specific capture and partial in-situ reduction of PtNPs, so a colorimetric sensor was constructed for ultra-trace detection of Hg2+ with a linear range of 0.2 nM and 400 nM. Furthermore, using the portable detecting capabilities of smartphones and hydrogel, a smartphone-assisted hydrogel sensing platform of Hg2+ was constructed. Notably, the two-mode sensing platforms exhibited outstanding detection performance with LOD values as low as 15 pM (colorimetric) and 26 pM (hydrogel), respectively, superior to recently reported nanozyme-based Hg2+ sensors. SignificanceCompared with other methods, the PtNPs/Ti3C2TXNR-based dual-mode sensor designed in this paper has superior sensitivity, high selectivity, simple operation and portability. In particular, the dual-output sensing strategy enables self-confirmation of detection results, greatly improving the reliability of the sensor, and is expected to be used for the on-site determination of trace mercury ions.

Colorimetric detection of benzoate in the beverage using the peroxidase-like properties of single-atom Fe-N-C nanozymes

Overuse of benzoate as a preservative is bad for human health. Therefore, we need to achieve quantitative detection of benzoate. Colorimetric nanozyme sensors have garnered significant interest owing to their exceptional efficacy and affordability. In this article, Fe-N-C dodecahedral nanozymes with superior peroxidase-like catalytic activity are prepared using ZIF-8 as a precursor. Therefore, we construct a colorimetric sensor for benzoate detection with a detection limit of 0.33 μM through integrating the inhibitory impact of benzoate on D-amino acid oxidase activity with the Fe-N-C-catalyzed 3,3′,5,5′-tetramethylbenzidine (TMB)–H2O2 system, and this reaction is completed within 10 min. It is noteworthy that a recovery rate of 96.8–109 % has been attained for the detection of benzoate in beverages.

Cu2O nanoparticles with morphology-dependent peroxidase mimic activity: a novel colorimetric biosensor for deoxynivalenol detection.

Different morphological Cu2O nanoparticles including cube, truncated cube, and octahedron were successfully prepared by a selective surface stabilization strategy. The prepared cube Cu2O exhibited superior peroxidase-like activity over the other two morphological Cu2O nanoparticles, which can readily oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to form visually recognizable color signals. Consequently, a sensitive and simple colorimetric biosensor was proposed for deoxynivalenol (DON) detection. In this biosensor, the uniform cube Cu2O was employed as the vehicle to label the antibody for the recognition of immunoreaction. The sensing strategy showed a detection limit as low as 0.01ng/mL, and a wide linear range from 2 to 100ng/mL. Concurrently, the approximate DON concentration can be immediately and conveniently observed by the vivid color changes. Benefiting from the high sensitivity and selectivity of the designed biosensor, the detection of DON in wheat, corn, and tap water samples was achieved, suggesting the bright prospect of the biosensor for the convenient and intuitive detection of DON in actual samples.

Engineering nickel-supported osmium bimetallic nanozymes with specifically improved peroxidase-like activity for immunoassay

Researchers have shown significant interest in modulating the peroxidase-like activity of nanozymes. Among these, bimetallic nanozymes have shown superior peroxidase-like activity over monometallic counterparts, offering enhanced performance and cost-efficiency in nanozyme designs. Herein, bimetallic nanozymes comprising nickel (Ni) and osmium (Os) incorporated into hyaluronate (HA) have been developed, resulting in HA-Nin/Os nanoclusters. Subsequently, comprehensive characterizations have been conducted. Further investigation has revealed that HA-Nin/Os efficiently catalyzed 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation with hydrogen peroxide (H2O2), confirming its peroxidase-like behavior and role as a nanozyme. Impressively, HA-Ni2/Os (Ni/Os = 2:1) displays heightened substrate affinity, accelerated reaction rates, enhanced hydroxyl radical production in acidic conditions, and exhibits activity unit of 1224 U/mg, representing more than two-fold increase compared to non-Ni-supported Os nanozyme. Theoretical calculations indicate that Ni support enhances the peroxidase-like process of Os nanozyme by improving H2O2 adsorption and TMB oxidation. Crucially, the support of Ni does not significantly alter the other enzyme-like activities of Os nanozymes, thereby enabling Ni to selectively enhance their peroxidase-like activity. In terms of application, the peroxidase-like ability of HA-Ni2/Os, facilitated by HA's carboxyl groups enabling crosslinking, proves effective in a squamous carcinoma antigen immunoassay. Moreover, HA-Ni2/Os exhibit reliable stability, promising as a peroxidase substitute. This work underscores the advantages of incorporating Ni into Os, specifically enhancing peroxidase-like activity, highlighting the potential of Os bimetallic nanozymes for peroxidase-based applications.

Pseudo-water-soluble Fe2O3 as Nanozyme catalyzed chemiluminescent reaction for detection of brilliant blue in gelatin and beverages

Converting solid iron oxide nanoparticles into a “pseudo-water-soluble” form before applying them to chemiluminescent reactions leads to enhance the chemiluminescence intensity. Using 8-hydroxyquinoline as a colloidal agent, a new, fast, and simple method of synthesizing pseudo-water-soluble Fe2O3 nanoparticles was developed. SEM, VSM, SAED, HRTEM, XRD, FTIR, and EDS techniques were used to characterize the synthesized Fe2O3 nanoparticles. Fe2O3 nanoparticles synthesized in this study have superior peroxidase-like activity (POD-like) and are stable under a wide range of pH and temperature. The chemiluminescence reaction of luminol-H2O2 is intensified and accelerated by a colloidal solution of Fe-nanoparticles/8-hydroxyquinoline. Reverse-flow injection analysis was employed to determine brilliant blue. A chemiluminescent sensing method based on iron oxide nanozymes was utilized for sensitive detection of the brilliant blue synthetic dye, achieving a limit of detection of 0.06 mg/L and a dynamic linear range of 0.1 to 50 mg/L. The recovery and relative standard deviations of real samples were found to be 97.83–99.93% and 0.09–3.07%, respectively. An analysis of a sample, from injection to obtaining the maximum peak, could be performed in less than one minute.

Bioenzyme-free dual-mode sensing for organophosphorus pesticides based on UiO-66-NH2 MOFs encapsulated tris(2,2′-bipyridyl) ruthenium(II)

Herein, we proposed a novel bioenzyme-free dual-mode sensing strategy for the rapid and accurate monitoring of organophosphorus pesticides (OPs) by preparing tris(2,2′-bipyridyl) ruthenium(II) (Ru(bpy)32+) encapsulated with UiO-66-NH2 MOFs as nanozyme (Ru@Zr-MOFs). The as-prepared Ru@Zr-MOFs nanozyme not only exhibits superior peroxidase-like activity which can catalyze O-phenylenediamine (OPD) oxidation to generate yellow 2,3-diaminophenazinc, but also exhibits dual-fluorescence feature (at 442 and 612 nm respectively) and specific interaction capacity with OPs. However, in the existence of OPs, the peroxidase-like activity of Ru@Zr-MOFs nanozyme is restricted and the oxidation process of OPD is stopped; meanwhile, the fluorescence of Ru@Zr-MOFs at 442 nm increases rapidly (< 10 s) while that at 612 nm is apathetic, thus a colorimetric and ratiometric fluorescent sensing strategy was first designed to detect OPs by using glyphosate (Gly) as a typical model of OPs. Then, in consideration of the benefits of smartphone which can make the sensing process more convenient, stable, rapid and sensitive feedback, a smartphone coupled with hydrogel detection platform was proposed also for OPs determination. In addition, the designed sensing strategy offers superior selectivity, stability and real application capabilities. It’s thus expected the as-designed Ru@Zr-MOFs nanozyme based dual-mode sensing strategy possesses important real application for the low-cost, rapid, sensitive and accurate determination of OPs.

Rational design of cuprofullerene bipyridine nanozyme with high peroxidase-like activity for colorimetric sensing of bleomycin.

The high catalytic activity of Cu-based nanozymes mainly depends on the efficient Fenton-like reaction of Cu+/ H2O2, but Cu+ cannot exist stably. Trying to find a material that can stably support Cu+ while promoting the electron cycle of Cu2+/Cu+ still faces serious challenges. C60 is expected to be an ideal candidate to solve this problem due to its unique structure and rich physicochemical properties. Here, we designed and synthesized a C60-doped Cu+-based nanozyme (termed as C60-Cu-Bpy) by loading high catalytic active site Cu+ onto C60 and coordinating with 2,2'-bipyridine (Bpy). The single crystal diffraction analysis and a series of auxiliary characterization technologies were used to demonstrate the successful preparation of C60-Cu-Bpy. Significantly, the C60-Cu-Bpy exhibited superior peroxidase-like activity during the catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). Then, the catalytic mechanism of C60-Cu-Bpy as peroxidase was elucidated in detail, mainly benefiting from the dual function of C60. On the one hand, C60 acted as a carrier to directly support Cu+, which has the ability to efficiently decompose H2O2 to produce reactive oxygen species. The other was that C60 acted as an electron buffer, contributing to promoting the Cu2+/Cu+ cycle to facilitate the reaction. Furthermore, a colorimetric sensor for the quantitative analysis of bleomycin was established based on the principle of bleomycin specific inhibition of C60-Cu-Bpy peroxidase-like activity, with satisfactory results in practical samples. This study provides a new strategy for the direct synthesis of Cu+-based nanozymes with high catalytic performance.

Highly selective colorimetric determination of glutathione based on sandwich-structured nanoenzymes composed of gold nanoparticle-coated molecular imprinted metal-organic frameworks.

Asandwich-structured composite nanoenzyme (NH2-MIL-101(Fe)@Au@MIP) was prepared using molecularly imprinted polymers, metal-organic frameworks, and gold nanoparticles and a highly selective glutathione (GSH) colorimetric sensor was constructed. The inner part of the composite nanoenzymes is a metal-organic framework loaded with gold nanoparticles (AuNPs), NH2-MIL-101(Fe)@Au, which has superior peroxidase-like activity compared with NH2-MIL-101(Fe). This is due to the surface plasmon resonance effect of AuNPs. GSH can form strong Au-S bonds with AuNPs, which can significantly reduce the enzymatic activity of NH2-MIL-101(Fe)@Au, thereby changing the absorbance at 450nm of the sensing system. The degree of change in absorbance is correlated with the concentration of GSH. In the outer part, the molecularly imprinted polymer with oxidized glutathione (GSSG) as a dummy template provided specific pores, which significantly improved the selectivity of the sensing system. The sensor showed good GSH sensing performance in the range 1 ~ 50μM with a lower limit of detection (LOD) of 0.231μM and good sensing performance in fetal bovine serum, indicating its highpotential for clinical diagnostic applications.

Employing Noble Metal-Porphyrins to Engineer Robust and Highly Active Single-Atom Nanozymes for Targeted Catalytic Therapy in Nasopharyngeal Carcinoma.

Single-atom nanozymes (SANzymes) emerge as promising alternatives to conventional enzymes. However, chemical instability limits their application. Here, a systematic synthesis of highly active and stable SANzymes is presented by leveraging noble metal-porphyrins. Four noble metal-porphyrins are successfully synthesized to mimic the active site of natural peroxidases through atomic metal-N coordination anchored to the porphyrin center. These noble metal-porphyrins are integrated into a stable and biocompatible Zr-based metal-organic framework (MxP, x denoting Ir, Ru, Pt, and Pd). Among these, MIrP demonstrates superior peroxidase-like activity (685.61 U mg-1 ), catalytic efficiency, and selectivity compared to horseradish peroxidase (267.71 U mg-1 ). Mechanistic investigations unveil heightened catalytic activity of MIrP arises from its robust H2 O2 adsorption capacity, unique rate-determining step, and low energy threshold. Crucially, MIrP exhibits remarkable chemical stability under both room temperature and high H2 O2 concentrations. Further, through modification with (-)-Epigallocatechin-3-Gallate, a natural ligand for Epstein-Barr virus (EBV)-encoded latent membrane protein 1, targeted SANzyme (MIrPHE) tailored for EBV-associated nasopharyngeal carcinoma is engineered. This study not only presents an innovative strategy for augmenting the catalytic activity and chemical stability of SANzymes but also highlights the substantial potential of MIrP as a potent nanomedicine for targeted catalytic tumor therapy.

Shape-Regulated Photothermal-Catalytic Tumor Therapy Using Polydopamine@Pt Nanozymes with the Elicitation of an Immune Response.

Recently, nanozyme-based photothermal-catalytic therapy has emerged as a promising strategy for antitumor treatment. Extensive research has focused on optimizing the catalytic activity and photothermal conversion performance of nanozymes through size, morphology, and surface property regulations. However, the biological effects of nanozymes, such as cellular uptake and cytotoxicity, resulting from their physicochemical properties, remain largely unexplored. In this study, two types of polydopamine/platinum (PDA@Pt) nanozymes, flower-like (FPDA@Pt) and mesoporous spherical-like (MPDA@Pt), to comprehensively compare their enzyme-mimicking activity, photothermal conversion capacity, and antitumor efficiency are designed. These findings revealed that FPDA@Pt exhibited superior peroxidase-like activity and higher photothermal conversion efficiency compared to MPDA@Pt. This led to enhanced production of reactive oxygen species (ROS) and increased heat generation at tumor sites. Importantly, it is observed thatthe flower-like structure of FPDA@Pt facilitated enhanced cellular uptake, leading to an increased accumulation of nanozymes within tumor cells. Furthermore, the light irradiation on tumors also triggered a series of anti-tumor immune responses, further enhancing the therapeutic efficacy. This work provides a possible design orientation for nanozyme-based photothermal-catalytic tumor therapy, highlighting the importance of considering the physicochemical properties of nanozymes to optimize their therapeutic potential in antitumor strategies.

Ag-MXene as peroxidase-mimicking nanozyme for enhanced bacteriocide and cholesterol sensing

Reactive oxygen species (ROS) are ideal alternative antibacterial reagents for rapid and effective sterilization. Although a variety of ROS-based antimicrobial strategies have been developed, many are still limited by their inefficiency. Herein, we report the synthesis of the Ag-MXene nanozyme, which have superior peroxidase-like activity for antibacterial applications. As a result, Ag-MXene nanozyme can efficiently increase the level of intracellular ROS, converting H2O2 into hydroxyl radicals that effectively kill both Gram-negative and Gram-positive bacteria and disrupting the bacterial biofilm formation. Moreover, a sensitive and selective colorimetric biosensor was constructed for assaying cholesterol based on the Ag-MXene’s prominent peroxidase-mimicking activity and the cholesterol oxidase cascade reaction. The biosensor exhibits high performance with a linear cholesterol detection range of 2–800 μM, and a detection limit of 0.6 μM. Ag-MXene nanozyme can be used for the rapid detection of cholesterol in serum without complicated sample pretreatment. Collectively, it is conceivable that the proposed Ag-MXene nanozyme could be used as a biocide and as a cholesterol sensor. This study provides a broad prospect for the rapid detection and sterilization of MXene nanozymes in the biomedical field.

Highly adhesive and catalytic VOxC nanosheets with strong antibacterial activity

Peroxidase-like nanozymes represent fascinating agents that can treat bacterial infections by oxidative attack. Challengingly, many antibacterial nanozymes only perform well at high concentrations because the low affinity to attach on bacterial surface, short lifetime and working distance for hydroxyl radicals largely limit the applications of antibacterial nanozymes. The potential safety/toxicity should be also considered under an exposure of high concentrations of nanomaterials. In this work, we proposed a “Melee attack” strategy to strikingly enhance antibacterial activity by using peroxidase-like VOxC nanosheets (NSs) that prefer to chemically contact bacterial cell surface. The strategy combines the structure properties of VOxC NSs by coordinating with functional groups on bacteria cell wall with high affinity and the superior peroxidase-like activity of VOxC that can generate hydroxyl radicals for bacterial killing. The VOxC NSs are prepared by controlling the auto-oxidation of V2C NSs, possessing multivalent, ultrathin, flexible and entangled texture as well as good hydrophilicity and biocompatibility. VOxC NSs exhibit efficiently antibacterial activity toward E. coli and S. aureus. This study provides a promising strategy by using adhesive nanozymes in close proximity to the surface of targeted bacteria via chemical bonds, which will inspire the design and application of powerful antibacterial nanozymes with high efficiency.

Rapid and user-friendly detection of selenium-rich foods using a THEATER colorimetric device with Pt-Co-N-C as viewing glasses

The consumption of Se-rich foods is a highly effective means of augmenting a person’s intake of Se, which plays a critical role in human health; however, excessive Se consumption can be toxic. The determination of Se levels is therefore of paramount importance to ensure the safety of both the production and consumption of selenium-rich foods. In this study, a rapid and user-friendly method is developed for the analysis of selenium-rich foods wherein the detection process is similar to watching three-dimensional movies in a theater. A portable 3D-printed colorimetric device called the Detection THEATER (Time-saving, High-sensitive, Easy, Accurate, Telling, Economical, and Rapid) is first constructed for the rapid and visually accessible colorimetric analysis of samples in nonlaboratory settings. Subsequently, the Co-N-C nanozyme is doped with Pt to produce a Pt-Co-N-C nanozyme with superior peroxidase-like activity, which serves as the viewing glasses for signal amplification in the Detection THEATER. The Detection THEATER exhibits excellent sensitivity and accuracy, including a linear range of 0.5–1.2 μg/mL and a low detection limit of 0.026 μg/mL. The pretreatment of food samples is also optimized and simplified, thereby reducing processing times three-fold and enhancing accessibility and usability. The Pt-Co-N-C nanozyme-based Detection THEATER, demonstrated outstanding specificity and practicality, opening up a new avenue for the analysis of selenium-rich foods.

Rational synthesis of FeNiCo-LDH nanozyme for colorimetric detection of deferoxamine mesylate

The accurate surveillance and sensitive detection of deferoxamine mesylate (DFO) is of great significance to ensure the safety of thalassemia major patients. Herein, we report a new nanozyme-based colorimetric sensor platform for DFO detection. First, a metal-organic framework (ZIF-67) was used as a precursor for the synthesis of FeNiCo-LDH (Layered Double Hydroxide, LDH) via an ion exchange reaction stirring at room temperature. The results of electron microscopy and nitrogen adsorption-desorption showed that FeNiCo-LDH exhibited a 3D hollow and mesopores structure, which supplied more exposed active sites and faster transfer of mass. The as-prepared FeNiCo-LDH showed superior peroxidase-like activity with a low Km and high υmax. It can catalyze the decomposition of H2O2 to generate reactive oxygen species (ROS) and further react with 3,3′,5,5′-tetramethylbenzidine (TMB) to form blue oxidized TMB (oxTMB), which has a characteristic absorption at 652 nm. Once DFO was introduced, it can complex with FeNiCo-LDH and inhibit the peroxidase-like activity of FeNiCo-LDH, making the color of oxTMB lighter. The quantitative range of DFO was 0.8–28 μM with a detection limit of 0.71 μM. This established method was applied to the detection of DFO content in urine samples of thalassemia patients, and the spiked recoveries were falling between 97.7% and 109.6%, with a relative standard deviation was less than 5%, providing a promising tool for the clinical medication of thalassemia patients.

A smartphone-assisted colorimetric sensor based on Fe1-xS nanozyme for detection of glucose and ascorbic-acid in soft drinks

Due to their distinct enzyme-like catalytic activity, iron-based nanomaterials have attracted considerable attention from researchers in the field of biomolecular detection. However, the current literature predominantly focuses on iron oxide nanozymes, with limited attention given to iron sulfide (FexSy) nanozymes. In this work, a glutathione-modified Fe1-xS nanoparticles (Fe1-xS NPs) with a diameter of 4–6 nm was synthesized in one-pot aqueous solution at room temperature. The resulting Fe1-xS NPs exhibited superior peroxidase-like (POD) activity compared to natural horseradish peroxidase, indicating their potential as a promising alternative for POD applications. A sensor utilizing the POD activity of Fe1-xS NPs was developed for detecting glucose and ascorbic-acid (AA) in soft drinks. The detection limits for glucose and AA were determined to be 37 and 5.3 μM, respectively, with broader linear ranges of 200–700 and 10–500 μM. Moreover, Fe1-xS NPs demonstrated exceptional selectivity and anti-interference properties in detecting glucose and AA in soft drinks. Furthermore, this study proposed a smartphone-assisted colorimetric sensor based on Fe1-xS nanozymes for rapid and specific detection of glucose and AA. This technique has the potential to be utilized in the future for convenient and efficient detection of glucose and AA.

Coacervate-Based Plexcitonic Assembly toward Peroxidase-like Activity and Ultrasensitive Glucose Sensing

Inbuilt catalytic centers anchored inside the confined architecture of artificial nanoreactors have gained tremendous attention owing to their vast applicability in various catalytic transformations. However, designing homogeneously distributed catalytic units with exposed surfaces in confined environment is a challenging task. Here, we have utilized quantum dot (QD)-embedded coacervate droplets (QD-Ds) as a confined compartment for the in situ synthesis of gold nanoparticles (Au NPs) without any additional reducing agent. High-resolution transmission electron microscopy images reveal homogeneous distribution of 5.6 ± 0.2 nm-sized Au NPs inside the QD-Ds (Au@QD-Ds). The in situ synthesized Au NPs are found to be stable over a period of 28 days without any agglomeration. Control experiments reveal that the free surface carboxylic acid groups of embedded QDs simultaneously act as reducing and stabilizing agents for Au NPs. Notably, these Au@QD-Ds exhibit superior peroxidase-like activity compared to bulk aqueous Au NPs and Au@QDs under similar experimental conditions. The observed peroxidase-like activity follows the classical Michaelis–Menten model inside the Au@QD-Ds via the fast electron-transfer pathway. The enhanced peroxidase-like activity has been explained by considering confinement, mass action, and the ligand-free surface of embedded Au NPs. The present plexcitonic nanocomposites exhibit excellent recyclability over several consecutive cycles without any compromise in their catalytic activity. Finally, a cascade reaction with glucose oxidase (GOx)-loaded Au@QD-Ds have been utilized for colorimetric detection of glucose with a limit of detection of 272 nM in solution as well as on filter paper. The present work highlights a facile and robust methodology for the fabrication of optically active functional hybrid plexcitonic assemblies and may find importance in various fields including bioanalytical chemistry and optoelectronics.

Yolk-shell structured nanoreactor Au@Co3O4/CeO2@mSiO2 with superior peroxidase-like activity as nanozyme for ultra-sensitive colorimetric biosensing

For yolk-shell structured nanoreactors, multiple active components can be precisely positioned on core and/or shell that can afford more exposed accessible active sites, and the internal voids can guarantee sufficient contact of reactants and catalysts. In this work, a unique yolk–shell structured nanoreactor Au@Co3O4/CeO2@mSiO2 was fabricated and applied as nanozyme for biosensing. The Au@Co3O4/CeO2@mSiO2 exhibited superior peroxidase-like activity with a lower Michaelis constant (Km) and a higher affinity to H2O2. The enhanced peroxidase-like activity was attributed to the unique structure and the synergistic effects between the multiple active components. Colorimetric essays were developed based on Au@Co3O4/CeO2@mSiO2 for the ultra-sensitive sensing of glucose in the range of 3.9 nM–1.03 mM with the limit of detection as low as 3.2 nM. In the detection of glucose-6-phosphate dehydrogenase (G6PD), the cooperation between G6PD and Au@Co3O4/CeO2@mSiO2 triggered the redox cycling between NAD+ and NADH, thereby achieving the amplification of the signal and enhancing the sensitivity of the assay. The assay showed superior performance as compared to other methods with linear response of 5.0 × 10−3–15 mU mL−1 and lower detection limit of 3.6 × 10−3 mU mL−1. The fabricated novel multi-enzyme catalytical cascade reaction system allowed rapid and sensitive biodetection, demonstrating its potential in biosensors and biomedical applications.

Bioinspired Hierarchical Self-Assembled Nanozyme for Efficient Antibacterial Treatment.

Along with the rapid development and ever-deepening understanding of nanoscience and nanotechnology, nanomaterials hold promise to mimic the highly evolved biological exquisite nanostructures and sophisticated functions. Here, inspired by the ubiquitous antibacterial nanostructures on the wingsurfacesofsome insects, a NiCo2 O4 nanozyme with self-adaptive hierarchical nanostructure is developed that can capture bacteria of various morphotypes via the physico-mechanical interaction between the nanostructure and bacteria. Moreover, the developed biomimetic nanostructure further exhibits superior peroxidase-like catalytic activity, which can catalytically generate highly toxic reactive oxygen species that disrupt bacterial membranes and induce bacterial apoptosis. Therefore, the mechano-catalytic coupling property of this NiCo2 O4 nanozyme allows for an extensive and efficient antibacterial application, with no concerns of antimicrobial resistance. This work suggests a promising strategy for the rational design of advanced antibacterial materials by mimicking biological antibiosis.

Mesoporous silica-encapsulated Co-doped ceria nanodots with enhanced peroxidase-like activity enable intensive and long-lasting chemiluminescence for glutathione detection

Chemiluminescence (CL) assay has been considered as a sensitive method for quantitative detection of glutathione (GSH), a significant regulatory metabolite in cells. However, most reported CL assays present flash-type CL emission with limited detection accuracy and repeatability. Herein, an intensive and long-lasting glow-type CL system was proposed based on a novel bimetallic Co-doped ceria mesoporous nanocomposite (Co-ceria@MSN), which was prepared by in-situ growth of sub-3 nm ultrasmall Co-ceria nanodots within the pore channels of mesoporous silica nanospheres (MSN). Attributing to the confinement effect of MSN and the superior peroxidase-like catalytic activity of Co-ceria nanodots, this nanocomposite could function as a nanozyme to catalyze luminol/H2O2 CL reaction, producing a robust and long-lasting CL emission with a long plateau for over 1.2 h at physiological pH. Surprisingly, both the CL intensity and duration time were found to exist a strong dependence on GSH concentration. Accordingly, the proposed glow-type CL platform was further applied for GSH determination with a limit of detection down to 10 nM. This strategy was successfully utilized for quantitative evaluation of cellular GSH levels, indicating its broad prospects in clinical diagnosis.