Atomically dispersed bimetallic active sites as H2O2 self-supplied nanozyme for effective chemodynamic therapy, chemotherapy and starvation therapy.

Tumor microenvironment (TME)-responsive chemodynamic therapy (CDT) is severely hindered by insufficient intracellular H2O2 level that seriously deteriorates antitumor efficacy, albeit with its extensively experimental and theoretical research. Herein, we designed atomically dispersed FeCo dual active sites anchored in porous carbon polyhedra (termed FeCo/PCP), followed by loading with glucose oxidase (GOx) and anticancer doxorubicin (DOX), named FeCo/PCP-GOx-DOX, which converted glucose into toxic hydroxyl radicals. The loaded GOx can either decompose glucose to self-supply H2O2 or provide fewer nutrients to feed the tumor cells. The as-prepared nanozyme exhibited the enhanced in vitro cytotoxicity at high glucose by contrast with those at less or even free of glucose, suggesting sufficient accumulation of H2O2 and continual transformation to OH for CDT. Besides, the FeCo/PCP-GOx-DOX can subtly integrate starvation therapy, the FeCo/PCP-initiated CDT, and DOX-inducible chemotherapy (CT), greatly enhancing the therapeutic efficacy than each monotherapy.

Fe single atoms encapsulated in N, P-codoped carbon nanosheets with enhanced peroxidase-like activity for colorimetric detection of methimazole.

Excessive use of antithyroid drug methimazole (MMI) in pharmaceutical samples can cause hypothyroidism and symptoms of metabolic decline. Hence, it is urgent to develop rapid, low cost and accurate colorimetric method with peroxidase-like nanozymes for determination of MMI in medical, nutrition and pharmaceutical studies. Herein, Fe single atoms were facilely encapsulated into N, P-codoped carbon nanosheets (Fe SAs/NP-CSs) by a simple pyrolysis strategy, as certified by a series of characterizations. UV-vis absorption spectroscopy was employed to illustrate the high peroxidase-mimicking activity of the resultant Fe SAs/NP-CSs nanozyme through the typical catalysis of 3,3',5,5'-tetramethylbenzidine (TMB) oxidation. The catalytic mechanism was scrutionously investigated by the fluorescence spectroscopy and electron paramagnetic resonance (EPR) tests. Additionally, the introduced MMI had the ability to reduce the oxidation of TMB (termed oxTMB) as a peroxidase inhibitor, coupled by fading the blue color. By virtue of the above findings, a visual colorimetric sensor was established for dual detection of methimazole (MMI) with a linear scope of 5-50 mM and a LOD of 1.57 mM, coupled by assay of H2O2 at a linear range of 3-50 mM. According to the irreversible oxidation of the drug, its screening with acceptable results was achieved on the sensing platform even in commercial tablets The Fe SAs/NP-CSs nanozyme holds great potential for clinical diagnosis and drug analysis.

Fe-Ni dual-single atoms nanozyme with high peroxidase-like activity for sensitive colorimetric and fluorometric dual-mode detection of cholesterol.

Cholesterol is widely existed in nerve myelin sheath and various membrane structures, whose abnormal level would deteriorate human cells or even cause diseases. Herein, Fe-Ni dual-single-atom nanozyme was efficiently incorporated into N-doped carbon nanosheets (FeNi DSAs/N-CSs) by a simple calcination method. Its nanozyme activity and catalytic mechanism were investigated in details. The FeNi DSAs/N-CSs nanozyme showed superior peroxidase-like property, which was applied for the dual-mode determination of hydrogen peroxide (H2O2) and cholesterol. The colorimetric/fluorometric assays of H2O2 displayed the linear ranges of 1-50 mM and 5-40 mM with low limits of detection of 0.45 mM and 3.33 mM, respectively. In parallel, there exhibited the linear ranges of 0.5-5.0 mM and 0.25-5.0 mM for the colorimetric/fluorometric analysis of cholesterol, coupled with the limits of detection down to 0.19 mM and 0.044 mM, respectively. This work provided a rapid, cost-effectiveness and simple colorimetric/fluorometric method for sensitive dual-mode detection of cholesterol in human serum samples.

Confined synthesis of ternary FeCoMn single-atom nanozyme in N-doped hollow mesoporous carbon nanospheres for synergistic chemotherapy and chemodynamic cancer therapy.

Recently, nanozymes show increasing biological applications and promising possibilities for therapeutic intervention, while their mediated therapeutic outcomes are severely compromised due to their insufficient catalytic activity and specificity. Herein, ternary FeCoMn single atoms were incorporated into N-doped hollow mesoporous carbon nanospheres by in situ confinement pyrolysis at 800 °C as high-efficiency nanozyme. The confinement strategy endows the as-prepared nanozyme with the enhanced catalase- and oxidase-like activities. Specifically, the FeCoMn TSAs/N-HCSs nanozyme can decompose intracellular H2O2 to generate O2 and subsequently convert O2 to cytotoxic superoxide radicals (O2∙-), which can initiate cascade enzymatic reactions in tumor microenvironment (TME) for chemodynamic therapy (CDT). Moreover, the cancer therapy was largely enhanced by loading with doxorubicin (DOX). Impressively, the FeCoMn TSAs/N-HCSs nanozyme-mediated CDT and the DOX-induced chemotherapy endow the DOX@FeCoMn TSAs/N-HCSs with effective tumor inhibition, showing the superior therapeutic efficacy.

N-Doped Carbon Nanotubes Supported Fe-Mn Dual-Single-Atoms Nanozyme with Synergistically Enhanced Peroxidase Activity for Sensitive Colorimetric Detection of Acetylcholinesterase and Its Inhibitor.

Monitoring acetylcholinesterase (AChE) and its inhibitors is of importance for early diagnosis and therapy of neurological diseases. Herein, N-doped carbon nanotubes supported Fe-Mn dual-single-atoms (FeMn DSAs/N-CNTs) were fabricated by a simple pyrolysis, as thoroughly figured out by a series of the characterization techniques. The peroxidase-like activity of FeMn DSAs/N-CNTs was investigated by catalytic oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) to generate rich hydroxyl radicals (·OH) in the H2O2 system, which effectively catalyzed colorless TMB oxidation to blue oxidized TMB (ox-TMB). Besides, the peroxidase-like activity was greatly weakened by thiocholine (derived from AChE), accompanied by making blue ox-TMB fade. Impressively, the highly improved peroxidase-like property is further evidenced by density functional theory (DFT) calculations, where the dual-single atoms show a lower energy barrier (0.079 eV) and their interactions with the N-CNTs played critical roles for producing the oxygen radicals. By virtue of the nanozyme, a low-cost, specific, and sensitive colorimetric sensor was built for detection of AChE with a broader linear range of 0.1-30 U L-1 and a lower limit of detection (LOD, 0.066 U L-1), combined with its feasible analysis in human serum samples. Also, this platform was applied for measuring huperzine A inhibitor with a wide linear scope of 5-500 nM and a LOD down to 4.17 nM. This strategy provides a low-cost and convenient approach for early clinical diagnosis and drug development.

Bimetallic AuPt alloy/rod-like CeO2 nanojunctions with high peroxidase-like activity for colorimetric sensing of organophosphorus pesticides.

Organophosphorus pesticides (OP) have extensive applications in agriculture, while their overuse causes inevitable residues in food, soil, and water, ultimately being harmful to human health and even causing diverse dysfunctions. Herein, a novel colorimetric platform was established for quantitative determination of malathion based on peroxidase mimic AuPt alloy decorated on CeO2 nanorods (CeO2@AuPt NRs). The synthesized nanozyme oxidized colorless 3,3',5,5'-tetramethylbenzidine (TMB) in the presence of H2O2. Besides, the oxidized TMB was inversely reduced by ascorbic acid (AA), which were originated from hydrolysis of L-ascorbic acid-2-phosphate (AA2P) with the assistance of acid phosphatase (ACP). Based upon this observation ACP analysis was explored by colorimetry, showing a wid linear range of 0.2 ~ 3.5 U L-1 and a low limit of detection (LOD = 0.085 U L-1, S/N = 3). Furthermore, malathion present in the colorimetric system inhibited the activity of ACP and simultaneously affected the generation of AA, in turn promoting the recovery of the chromogenic reaction. Based on this, the LOD was decreased to 1.5 nM (S/N = 3) for the assay of malathion with a wide linear range of 6 ~ 100 nM. This simple colorimetric platform provides some informative guidelines for determination of other pesticides and disease markers.