Peroxidase Mimetic Activity Research Articles

Copper–Chitosan-Modified Magnetic Textile as a Peroxidase-Mimetic Catalyst for Dye Removal

Copper chitosan attached to a magnetic synthetic nonwoven textile was manufactured using a simple, rapid, and green procedure employing chitosan dissolved in diluted acetic acid and treatment with copper sulfate solution. The prepared copper–chitosan-modified textile exhibited peroxidase-mimetic activity which was subsequently used for the degradation (decolorization) of important organic dyes, namely methylene blue, Congo red, and Bismarck brown Y, in the presence of hydrogen peroxide. After 5 h of treatment at 22 °C, 87.5%, 79.5%, and 87.7% dye removal were observed for methylene blue, Congo red, and Bismarck brown Y, respectively. The textile bound catalyst can be easily recovered from the reaction mixture after the process is completed.

Uniform PtCoRuRhFe high-entropy alloy nanoflowers: Multi-site synergistic signal amplification for colorimetric assay of captopril.

Uniform PtCoRuRhFe high-entropy alloy nanoflowers (HEANFs) were fabricated by a simple wet-chemical co-reduction method in oleylamine for quantitative colorimetric determination of captopril (CAP) based on multi-site synergistic signal amplification. Specifically, the peroxidase mimetic activity of the PtCoRuRhFe HEANFs was examined through catalysis of 3,3',5,5'-tetramethylbenzidine (TMB) oxidation, whose catalytic mechanism was investigated by electron paramagnetic resonance (EPR) spectroscopy. The role of the ·O2- was figured out during the catalytic procedure. Further, the oxidation of TMB (oxTMB) can be effectively reduced by CAP, accompanied by quickly transforming the solution color from blue to colorless. More importantly, the absorbance at 652nm is linearly related to the CAP concentration in a range 5.0-50.0mM with a low detection limit of 2.82mM. The method has been applied to the determination of CAP in human urine samples. It offers a simple and high-efficiency method for facile and visual detection of CAP in hospitals.

Vanadium doped ZIF-L derived V-NC peroxidase-like nanozymes for tannic acid sensing

Transition metal-based nitrogen doping carbon nanozyme has attracted great attention owning to their high potential to replace natural enzymes. In this study, we prepared novel vanadium doped ZIF-L derived N-doped carbon nanozyme (V-NC) via facilely pyrolysis strategy. The cross-shaped morphology endows V-NC with unique V-Nx active sites, hierarchical pore character and large specific surface area, leading to its good peroxidase-mimetic activity. The steady-state kinetics trials revealed the low Km values of V-NC for TMB and H2O2, demonstrating its good affinity to TMB and H2O2. Mechanism research revealed that the excellent peroxidase-like activity of V-NC resulted from co-participation of •OH and O2•−, which were confirmed by reactive oxygen species (ROS) scavenging experiments and EPR trials. Under optimized operational conditions, and by virtue of the antioxidant properties of tannic acid (TA), a colorimetric sensing assay based on the peroxidase-like activity of V-NC was developed for sensitive detection of TA in the 0.1–2.5 µM linear range with low detection limit of 19.8 nM and the relative standard deviation (RSD, n = 3) of below 5%. This work renders a new idea for designing and developing high activity N-doped carbon nanozyme, and provides an accurate and feasible assay for the analysis of TA in real samples.

Sensitive detection of Vibrio parahaemolyticus via a dual-recognition colorimetric biosensor comprising Cefe-PEG-MNPs and apt-Fe@PDA

Highly accurate and sensitive detection of Vibrio parahaemolyticus is crucial for ensuring seafood safety and preventing the transmission of foodborne diseases. Herein, a dual-recognition strategy-driven colorimetric biosensor for the detection of V. parahaemolyticus was developed. This biosensor was based on the use of PEG-mediated cefepime-functionalized magnetic nanoparticles (Cefe-PEG-MNPs) and aptamer-modified Fe-doped polydopamine (Fe@PDA) nanozymes. The magnetic platform Cefe-PEG-MNPs was introduced to enhance the enrichment efficiency of V. parahaemolyticus, achieving a capture efficiency exceeding 90%. The Fe@PDA nanozyme exhibited notable peroxidase mimetic enzyme activity. The colorimetric biosensor developed for V. parahaemolyticus detection demonstrated good sensitivity, with a detection range spanning from 2.1 × 101 to 2.1 × 106 CFU/mL, and a limit of detection of 21 CFU/mL. Moreover, the biosensor demonstrated remarkable specificity, achieving good recovery rates from 95.80% to 103.80% in Penaeus vannamei with a relative standard deviation of less than 1.38%. The newly developed colorimetric biosensor offers a remarkable opportunity for the accurate and sensitive detection of V. parahaemolyticus in seafood.

Advancements and Applications of Single-Atom Nanozymes in Sensing Analysis

Single-atom nanozymes, with their atomically dispersed metal active sites, distinctive atom utilization rate, and tunable electronic structure, demonstrate great promise in the field of sensing analysis. This paper reviews the latest research progress on single-atom nanozymes in sensing applications. We classify single-atom nanozymes based on both their structural characteristics, such as carbon-based carriers, frameworks and their derivatives, metal oxides, metal sulfides, and organic polymer carriers, and their unique catalytic properties, including peroxidase, oxidase, catalase, superoxide dismutase, and multi-enzyme mimetic activities. Furthermore, we discuss the application of single-atom nanozymes in the sensitive detection of biological small molecules, antioxidants, ions, enzyme activities and their inhibitors, as well as cells and viruses. Finally, we highlight the opportunities and challenges for advancing the practical application and further research of single-atom nanozymes in the field of sensing analysis.

Paper immobilized BSA-decorated gold nanoclusters for single-step optical sensing of glucose and cholesterol without cross-reactivity

Minimally invasive methods for detecting glucose, cholesterol and hydrogen peroxide are crucial for monitoring the nutritional and health status of humans and animals. The peroxidase mimetic activity by nanozymes is one of the versatile methods for detecting glucose, cholesterol, hydrogen peroxide, and other biomolecules. However, the strict requirement of acidic pH limits their sensing and interfacing ability with natural enzymes. The present study developed bovine serum albumin (BSA) coated gold nanoclusters (AuNC) immobilized on paper fabric to enable single-step visual detection of glucose, cholesterol and hydrogen peroxide in complex biological fluids like serum and milk. The BSA-AuNC suspension and immobilized paper fabric synergistically interface with the natural oxidative enzymes, glucose oxidase or cholesterol oxidase, at physiological pH. The concomitant loss in the fluorescent intensity of BSA-AuNC-loaded paper fabric exposed to the generated hydrogen peroxide (glucose/glucose oxidase or cholesterol/cholesterol oxidase) was directly proportional to the concentration of glucose or cholesterol. These reactions enabled simple visual detection as well as quantification of hydrogen peroxide, glucose and cholesterol using Image-J software and common smartphone-based mobile applications. The detection ability of BSA-AuNC-embedded paper fabric is specific and remains unaltered in the presence of similar oxidase enzymes or similar substrate analogues. With these unique features, the BSA-AuNC embedded paper fabric stands out as a prominent analytical device with enormous potential as a simple, user-friendly detection tool for monitoring biomolecules that are important to health, nutrition, and environmental safeguarding.

Hydroxyl functionalized hexagonal boron nitride quantum dots as nanozyme for pesticides sensing through dual colorimetric and fluorometric platform: A combined experimental and theoretical study

The Hydroxyl-functionalized hexagonal boron nitride quantum dots (h-BN QDs) were synthesized using a hydrothermal technique in a water medium, exhibiting stability in water for over 90 days. The present study demonstrates two simple fluorescence and colorimetric techniques for sensing organophosphorus (OP) and organochloride (OC) pesticides (atrazine, simazine and chlorpyrifos) in an aqueous medium using hydroxyl-functionalized h-BN QDs. The sensing capability of h-BN QDs for these pesticides was determined to be in the range of 5–10 µM using both techniques. The hydroxyl groups on the surface of the QDs enhanced dispersibility and enabled peroxidase-like catalytic activity in acidic conditions. The radical generation using hydroxyl-functionalized h-BN QDs in the presence of H2O2 upon 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) oxidation plays a significant role in the peroxidase reaction. The hydrogen bonding and π-π interactions between the pesticide molecules and ABTS can enhance the pesticide sensing performance. The limit of detection (LOD) using ABTS for atrazine, simazine, and chlorpyrifos was 6.11, 6.56, and 2.47 µM, respectively. Fluorescence sensing, based on a turn ON/OFF mechanism, demonstrated high specificity and sensitivity with LODs of 5.59, 6.45, and 8.08 µM for the same pesticides. The DFT studies revealed non-covalent bonding, such as hydrogen bonding, π-π interactions between the pesticides and the h-BN QDs, indicating binding affinities and stabilization energies of the complexes which can detect pesticides effectively. Atrazine exhibited higher binding affinity towards h-BN QDs, followed by simazine and chlorpyrifos. The h-BN QDs provide a new insight into bonding with pesticides, enhancing the peroxidase mimetic and fluorescence activity.

Single-stranded DNA regulated peroxidase mimetic activity of MCOF@AuNPs for colorimetric detection of carcinoembryonic antigen

Rapid, accurate, simple and portable monitoring of carcinoembryonic antigen (CEA) in serum is important for assessing the occurrence, development, and prognosis of cancer. In this work, we developed a colorimetric method based on the peroxidase-like activity of MCOF@AuNPs functionalized by complementary sequences of CEA-specific aptamer (MCOF@AuNPs-apt*) enhancing by G-terminated CEA-specific aptamer (G-apt). The enhancement of catalytic activity depends on the increase affinity of MCOF@AuNPs-apt*-G-apt to the TMB via promoting electron transfer. Based on this strategy, we successfully detected CEA at 0.1 ng/mL with high accuracy and anti-interference ability. Importantly, combined with the smartphone app based on the smartphone app RGB color model, the results can be visualized directly without expensive equipment, which meets the demand for point of care testing of CEA. This study also explored the enhancement of catalytic activity of nanozyme by ssDNA and the application potential in aptamer biosensor.

Performance-complementary colorimetric/electrochemical bimodal detection of Hg2+ based on analyte-accelerated peroxidase-mimicking activity of GO-AuNPs

As a highly toxic heavy metal pollutant, mercury ions cause substantial risks to the environment and human health, and developing high-performance and convenient analytical approaches becomes quite important. Here we propose a performance-complementary colorimetric/electrochemical dual-mode Hg2+ sensing method based on the analyte accelerating the peroxidase-mimetic activity of gold nanoparticles (AuNPs) loaded on graphene oxide (GO). The GO-AuNPs composite was readily fabricated via mechanically mixing AuNPs and GO with controllable proportions, exhibiting a weak peroxidase-like activity in catalyzing the oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB). Upon the introduction of Hg2+, it combined with AuNPs rapidly, significantly enhancing the peroxidase-mimicking activity of GO-AuNPs. By capturing the color signal of the generated blue oxTMB and the electro-oxidation response of residual TMB, a “turn-on” colorimetric and “turn-off” electrochemical bimodal method was established for Hg2+ measurement, providing a linear range of 10–60 μg/L in colorimetric detection and 0.001–20 μg/L in electrochemical analysis. Different from common bimodal assays mainly improving detecting reliability due to their cross-validation ability, our dual-mode sensor exhibits the unique feature of complementary sensitivity and detection range, thus enabling its flexible use in analyzing different levels of the target in a broad scope with no requirement for sample enrichment and dilution.

Nitrogen Vacancy Modulation of Tungsten Nitride Peroxidase-Mimetic Activity for Bacterial Infection Therapy.

Bacterial infections claim millions of lives every year, with the escalating menace of microbial antibiotic resistance compounding this global crisis. Nanozymes, poised as prospective substitutes for antibiotics, present a significant frontier in antibacterial therapy, yet their precise enzymatic origins remain elusive. With the continuous development of nanozymes, the applications of elemental N-modulated nanozymes have spanned multiple fields, including sensing and detection, infection therapy, cancer treatment, and pollutant degradation. The introduction of nitrogen into nanozymes not only broadens their application range but also holds significant importance for the design of catalysts in biomedical research. The synergistic interplay between W and N induces pivotal alterations in electronic configurations, endowing tungsten nitride (WN) with a peroxidase-like functionality. Furthermore, the introduction of N vacancies augments the nanozyme activity, thus amplifying the catalytic potential of WN nanostructures. Rigorous theoretical modeling and empirical validation corroborate the genesis of the enzyme activity. The meticulously engineered WN nanoflower architecture exhibits an exceptional ability in traversing bacterial surfaces, exerting potent bactericidal effects through direct physical interactions. Additionally, the topological intricacies of these nanostructures facilitate precise targeting of generated radicals on bacterial surfaces, culminating in exceptional bactericidal efficacy against both Gram-negative and Gram-positive bacterial strains along with notable inhibition of bacterial biofilm formation. Importantly, assessments using a skin infection model underscore the proficiency of WN nanoflowers in effectively clearing bacterial infections and fostering wound healing. This pioneering research illuminates the realm of pseudoenzyme activity and bacterial capture-killing strategies, promising a fertile ground for the development of innovative, high-performance artificial peroxidases.

Ultrasensitive detection of mycotoxins using a novel single-Atom, CRISPR/Cas12a-Based nanozymatic colorimetric biosensor

Aflatoxin B1 (AFB1) is a typical mycotoxin in cereals, posing a significant threat to the ecology and public health. Overall, the development of nanozymatic sensors with good specificity, high sensitivity, and a clear catalytic mechanism seems to be a challenge for CRISPR/Cas detection of non-nucleic acid targets. In this study, a series of Fe-N-C single-atom enzymes (SAzymes) and Fe-Co magnetic nanoparticles (MNPs) were synthesized via pyrolysis. Fe-N-C SAzymes with high peroxidase-mimetic activity were successfully utilized as TMB chromogenic catalysts for detecting AFB1 via the CRISPR/Cas12a colorimetric aptamer sensor. In the absence of the AFB1 target, its aptamer bound to crRNA and activated the trans-cleavage activity of Cas12a, indiscriminately cutting single-stranded DNA and releasing significant amounts of Fe-N-C SAzymes into the supernatant, which catalyzed the change of TMB to blue. The synthesized Fe-Co MNPs not only effectively reduced the background signal but also significantly reduced the assay cost. This study combined SAzymes with CRISPR/Cas12a technology for the first time for non-nucleic acid target detection. The combination of Fe-N-C SAzymes’ high catalytic activity and stability, and the CRISPR/Cas12a system’s high specificity and signal amplification, significantly improved the detection system’s sensitivity and specificity, enabling the detection of other targets by substituting the aptamers. Additionally, the potential active sites and catalytic mechanism of Fe-N-C SAzymes were investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional theory (DFT) simulations. This scheme provides a general method for constructing high-density Fe-N-C SAzymes and offers both experimental and theoretical guidance for understanding their catalytic mechanism.

A H₂S-Evolving Alternately-Catalytic Enzyme Bio-Heterojunction with Antibacterial and Macrophage-Reprogramming Activity for All-Stage Infectious Wound Regeneration.

The disorder of the macrophage phenotype and the hostile by-product of lactate evoked by pathogenic infection in hypoxic deep wound inevitably lead to the stagnant skin regeneration. In this study, hydrogen sulfide (H2S)-evolving alternately catalytic bio-heterojunction enzyme (AC-BioHJzyme) consisting of CuFe2S3 and lactate oxidase (LOD) named as CuFe2S3@LOD is developed. AC-BioHJzyme exhibits circular enzyme-mimetic antibacterial (EMA) activity and macrophage re-rousing capability, which can be activated by near-infrared-II (NIR-II) light. In this system, LOD exhausts lactate derived from bacterial anaerobic respiration and generated hydrogen peroxide (H2O2), which provides an abundant stock for the peroxidase-mimetic activity to convert the produced H2O2 into germicidal •OH. The GPx-mimetic activity endows AC-BioHJzyme with a glutathione consumption property to block the antioxidant systems in bacterial metabolism, while the O2 provided by the CAT-mimetic activity can generate 1O2 under the NIR-II irradiation. Synchronously, the H2S gas liberated from CuFe2S3@LOD under the infectious micromilieu allows the reduction of Fe(III)/Cu(II) to Fe(II)/Cu(І), resulting in sustained circular EMA activity. In vitro and in vivo assays indicate that the CuFe2S3@LOD AC-BioHJzyme significantly facilitates the infectious cutaneous regeneration by killing bacteria, facilitating epithelialization/collagen deposition, promoting angiogenesis, and reprogramming macrophages. This study provides a countermeasure for deep infectious wound healing via circular enzyme-mimetic antibiosis and macrophage re-rousing.

Fabrication of Highly Sensitive and Selective Nitrite Colorimetric Sensor Based on the Enhanced Peroxidase Mimetic Activity of Using Acetic Acid Capped Zinc Oxide Nanosheets.

Nitrite ions (NO2-), as one of the leading type-A inorganic-anion, showing significant-effects in the aquatic environment and also to humans health. Whereas, the higher uptake causes detrimental threat to human health leading to various chronic diseases, thus demanding efficient, reliable and convenient method for its monitoring. For this purpose, in the present research study we have fabricated the mimetic nonozyme like catalyst based colorimetric nitrite sensor. The acetic acid capped Zinc Oxide (ZnO) nanosheets (NSs) were introduce as per-oxidase mimetic like catalyst which shows high efficiency towards the oxidative catalysis of colorless tetramethylbenzidine (TMB) to oxidized-TMB (blue color) in the presence of Hydrogen-peroxide (H2O2). The present nitrite ions will stimulate the as formed oxidized-TMB (TMBox), and will caused diazotization reaction (diazotized-TMBox), which will not only decreases the peak intensity of UV-visible peak of TMBox at 652nm but will also produces another peak at 446nm called as diazotized-TMBox peak, proving the catalytic reaction between the nitrite ions and TMBox. Further, the prepared colorimetric sensor exhibits better sensitivity with a wider range of concentration (1 × 10-3-4.50 × 10-1 µM), lowest limit of detection (LOD) of 0.22 ± 0.05 nM and small limit of quantification (LOQ) 0.78 ± 0.05 nM having R2 value of 0.998. Further, the colorimetric sensor also manifest strong selectivity towards NO2- as compared to other interference in drinking water system. Resultantly, the prepared sensor with outstanding repeatability, stability, reproducibility, re-usability and its practicability in real water samples also exploit its diverse applications in food safety supervision and environmental monitoring.

Dual-recognition colorimetric platform based on porous Au@Pt nanozymes for highly sensitive washing-free detection of Staphylococcus aureus.

Adual-recognition strategy is reportedto construct a one-step washing and highly efficient signal-transduction tag system for high-sensitivity colorimetric detection of Staphylococcus aureus (S. aureus). The porous (gold core)@(platinum shell) nanozymes (Au@PtNEs) as the signal labels show highly efficient peroxidase mimetic activity and arerobust. For the sake of simplicity the detection involved the use of a vancomycin-immobilized magnetic bead (MB) and aptamer-functionalized Au@PtNEs for dual-recognition detection in the presence of S. aureus.In addition, we designed a magnetic plate to fit the 96-well microplate to ensure consistent magnetic properties of each well, which can quickly remove unreacted Au@PtNEs and sample matrix while avoiding tedious washing steps. Subsequently, Au@PtNEs catalyze hydrogen peroxide (H2O2) to oxidize 3,3',5,5'-tetramethylbenzidine (TMB) generating a color signal. Finally, the developed Au@PtNEs-based dual-recognition washing-free colorimetric assay displayed a response in the range of S. aureus of 5 × 101-5 × 105 CFU/mL, and the detection limit was 40 CFU/mL within 1.5 h. In addition, S. aureus-fortified samples were analyzed to further evaluate the performance of the proposed method, which yielded average recoveries ranging from 93.66 to 112.44% and coefficients of variation (CVs) within the range 2.72-9.01%. These results furnish a novel horizon for the exploitation of a different mode of recognition and inexpensive enzyme-free assay platforms as an alternative to traditional enzyme-based immunoassays for the detection of other Gram-positive pathogenic bacteria.

Bioclay Enzyme with Bimetal Synergistic Sterilization and Infectious Wound Regeneration.

Bacteria invasion is the main factor hindering the wound-healing process. However, current antibacterial therapies inevitably face complex challenges, such as the abuse of antibiotics or severe inflammation during treatment. Here, a drug-free bioclay enzyme (Bio-Clayzyme) consisting of Fe2+-tannic acid (TA) network-coated kaolinite nanoclay and glucose oxidase (GOx) was reported to destroy harmful bacteria via bimetal antibacterial therapy. At the wound site, Bio-Clayzyme was found to enhance the generation of toxic hydroxyl radicals for sterilization via cascade catalysis of GOx and Fe2+-mediated peroxidase mimetic activity. Specifically, the acidic characteristics of the infection microenvironment accelerated the release of Al3+ from kaolinite, which further led to bacterial membrane damage and amplified the antibacterial toxicity of Fe2+. Besides, Bio-Clayzyme also performed hemostasis and anti-inflammatory functions inherited from Kaol and TA. By the combination of hemostasis and anti-inflammatory and bimetal synergistic sterilization, Bio-Clayzyme achieves efficient healing of infected wounds, providing a revolutionary approach for infectious wound regeneration.

Integration of Myrica rubra-based N-doped carbon dots with Fe3S4 as excellent peroxidase mimics for colorimetric assay and smartphone-based intelligent sensing of p-aminophenol in waters.

To realize the reutilization of waste Myrica rubra in the analytical field, we synthesized Myrica rubra-based N-doped carbon dots (MN-CDs) and further anchored them onto the surface of Fe3S4 to fabricate Fe3S4@MN-CD nanocomposites. The as-fabricated nanocomposites possessed higher peroxidase-mimetic activity than its two precursors, resulting from the synergistic effect between them, and could catalyze colorless 3,3',5,5'-tetramethylbenzidine (TMB) into deep blue oxTMB with a strong 652-nm absorption. Under optimized conditions (initial solution pH, 3.5; incubation temperature, 35 ℃; Fe3S4@MN-CD concentration, 50µg mL-1, and 652-nm absorption), Fe3S4@MN-CDs were employed for colorimetric assay of p-aminophenol (p-AP) with wide linear range (LR, 2.9-100 µM), low detection limit (LOD, 0.87 µM), and satisfactory recoveries (86.3-105%) in environmental waters. Encouragingly, this colorimetric assay provided the relative accuracy of 97.0-99.4% as compared withconventional HPLC-UV detection. A portable smartphone-based colorimetric application was developed by combining the Fe3S4@MN-CD-based visually chromogenic reaction with a "Thing Identify" APP software. Besides, we engineered an image-capturing device feasible for field use, in which the internal-compact sealing prevented external light source from entering photography chamber, thereby reducing light interference, and also the bottom light source enhanced the intensity of blue imaging. This colorimetric platform exhibited satisfactory LR (1-500 µM), low LOD (0.3 µM), and fortification recoveries (86.6-99.6%). In the chromogenic reaction catalyzed by Fe3S4@MN-CDs, ·O2- played a key role in concomitant with the participation of •OH and h+. Both the colorimetric assay and smartphone-based intelligent sensing show great promising in on-site monitoring of p-AP under field conditions.

Development of ATP-modified CoFe2O4@ZIF-8@ZIF-67 core–shell nanozyme for sensitive colorimetric detection of dopamine

Core-shell nanostructures (NSs) are a type of nanozyme broadly used in various fields due to their significant physicochemical advantages. In the present study, the CoFe2O4@ZIF-8@ZIF-67 core–shell were fabricated by a consecutive two-step synthesis method, including hydrothermal for CoFe2O4 metal spinel and epitaxial solvothermal growth of ZIFs bilayers on the metal spinel NSs. The core–shell surface was modified using ATP inspired by the active site of the natural peroxidase enzyme. The nanocomposites were characterized by XRD, FT-IR, SEM, EDX, and Dot-mapping techniques. The peroxidase-like activity of the ATP/CoFe2O4@ZIF-8@ZIF-67 was assessed by a colorimetric method. Modified nanocomposite displayed desirable peroxidase mimetic activity and could enzymatically generate hydroxyl radicals from H2O2 and oxidize TMB. The high catalytic activity of ATP-modified nanocomposite and its ability to oxidize TMB provides a rapid and sensitive platform for the colorimetric detection of dopamine. Dopamine consumes hydroxyl radicals, prevents TMB oxidation, and causes a color change in the detection solution, which the naked eye can recognize. The presented colorimetric test provided an excellent LOD for dopamine (0.4 µM) with a good linear range (0.2–18 µM) and selectivity, which was prosperously applied to dopamine assay in serum blood samples.

Colorimetric sensing based on silver nanoparticle-functionalized copper porphyrin nanozyme for glyphosate

Glyphosate, a widely used herbicide due to the broad-spectrum and high-efficiency properties, has the potential to accumulate in the human body via agricultural food and water sources throughout the food chain. Its safety for both human health and aquatic ecosystems remains a topic of significant debate. In this study, the presence of glyphosate could be directly detected through a notable colorimetric change in an aqueous solution. For this purpose, a silver nanoparticle-functionalized copper porphyrin metal-organic framework (AgNPs/Cu-TCPP) nanozyme was conveniently prepared for colorimetric sensing of glyphosate. The as-synthesized nanozyme that modified AgNPs with Cu-TCPP metal-organic framework as the precursor, has excellent peroxidase mimetic activity and specific recognition performance of glyphosate. The nanozyme demonstrated the ability to catalyze the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) using H2O2, resulting in a marked change in color. When glyphosate was added, which bonded with Cu2+, led to the occupation of the surface-active sites of the nanozyme, thereby making its catalytic performance ineffective. The concentration of glyphosate exhibited a linear range spanning from 2 to 400 μmol L−1, and the limit of detection was 0.67 μmol L−1 (S/N = 3). The colorimetric sensing approach employing AgNPs/Cu-TCPP nanozyme exhibits remarkable selectivity and reproducibility, enabling the detection of real samples with recovery rates of 98.3%–103.5%, indicating its potential applicability in safeguarding water and food quality.

Natural product nanozymes of herbal extract galangin in managing hepatocellular carcinoma.

Numerous local herbal extract species have been investigated as potential medicinal ingredients due to their promising anti-cancer properties. However, the primary constraint of the class of plant flavonoids lies in their low solubility and limited membrane permeability, leading to chemical instability and restricted bioavailability that impede biomedical applications. In this study, we have developed an ideal nanozyme-Galazyme, comprising galangin-loaded copper Nanozyme coated by DSPE-PEG, which amplifies oxidative stress to induce apoptosis via the regulation of reactive oxygen species (ROS) generation and mitogen-activated protein kinase (MAPK) activation. Galazyme exhibited significant peroxidase mimetic activity, demonstrating its potential to generate ROS and elevate oxidative stress. Upon uptake by HepG-2 cells, Galazyme efficiently converts excess hydrogen peroxide (H2O2) into highly reactive •OH radicals and upregulates MAPK expression, leading to the activation of Bax and Caspase 3, thereby promoting irreversible tumor cell apoptosis. Both in vitro and in vivo results demonstrate that Galazyme inhibits tumor cell growth and induces apoptosis by generating ample ROS and activating the MAPK pathway. Our study offers novel evidence supporting the enhancement of Galazyme-induced apoptosis through the upregulation of Bax and Caspase 3, along with the elucidation of the interaction between MAPK and apoptosis.

Photothermal and ferroptosis synergistic therapy for liver cancer using iron-doped polydopamine nanozymes

An innovative nanozyme, iron-doped polydopamine (Fe-PDA), which integrates iron ions into a PDA matrix, conferred peroxidase-mimetic activity and achieved a substantial photothermal conversion efficiency of 43.5 %. Fe-PDA mediated the catalysis of H2O2 to produce toxic hydroxyl radicals (•OH), thereby facilitating lipid peroxidation in tumour cells and inducing ferroptosis. Downregulation of solute carrier family 7 no. 11 (SLC7A11) and solute carrier family 3 no. 2 (SLC3A2) in System Xc- resulted in decreased intracellular glutathione (GSH) production and inactivation of the nuclear factor erythroid 2-related factor 2 (NRF2)-glutathione peroxidase 4 (GPX4) pathway, contributing to ferroptosis. Moreover, the application of photothermal therapy (PTT) enhanced the effectiveness of chemodynamic therapy (CDT), accelerating the Fenton reaction for targeted tumour eradication while sparing adjacent non-cancerous tissues. In vivo experiments revealed that Fe-PDA significantly hampered tumour progression in mice, emphasizing the potential of the dual-modality treatment combining CDT and PTT for future clinical oncology applications.