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RSC Advances · 2014 ·Vol. 4 ·期 67 ·35500-35504 · IF 3.708

CoxFe3−xO4 hierarchical nanocubes as peroxidase mimetics and their applications in H2O2 and glucose detection

Wenshu Yang,Jinhui Hao,Zhe Zhang,Baoping Lu,Bailin Zhang,Jilin Tang

A facile approach was proposed for the synthesis of hierarchical CoxFe3−xO4 nanocubes (CF nanocubes), using Prussian Blue (PB) as precursor. The method consists of the synthesis of hierarchical cobalt–iron Prussian blue analogues (PBAs) through the reaction of PB nanocubes with CoCl2 in a water bath and subsequently calcining the corresponding PBA precursor. The obtained CF nanocubes were characterized using transmission electron microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and N2 adsorption–desorption isotherm measurements. It is found that the hierarchical CF nanocubes have a large specific surface area (108 m2 g−1). Considering the hierarchical structure and the doping of Co in Fe3O4 are beneficial for the catalytic activity of the catalyst, an efficient and simple colorimetric biosensor for H2O2 and glucose was fabricated using CF nanocubes as a peroxidase mimetic. The good catalytic activity and low-cost make the hierarchical CF nanocubes a useful biocatalyst for a wide range of potential applications in medicine and biotechnology.

CAS / MDL: 9001-37-0 54827-17-7
研究领域: 生物传感 · 材料科学 · 医学诊断
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2023 · IF 4.5

Trimetallic metal–organic framework nanosheets as nanozymes for the electrochemical sensing of H2O2

Ying Ma,Ping Wei,Mengjie Chen,Xianhua Shi,Xiange Lu,Xuanxuan Zhang,Duanping Sun

A variety of two-dimensional (2D) metal–organic framework (MOF) nanosheets have been discovered with excellent peroxidase-like activity due to their merits of accessible active sites and large surface area. However, few methods can be used for the large-amount production of 2D MOF nanosheets. Herein, we report a simple room temperature solution phase method for the high-yield synthesis of 2D trimetallic MOF nanosheets with three kinds of metal ions as ligands. The as-synthesized NiCoM (M = Cu, Fe, and Zn) nanosheets showed markedly enhanced electrochemical activity due to the synergistic effect. Among these obtained nanosheets, NiCoFe showed the highest electrocatalytic activity, demonstrating that Fe played a dominant role in determining the activities of nanozymes. As a proof-of-concept application, 2D NiCoFe nanosheets are used as modified materials for the electrochemical detection of H 2 O 2 . The results showed that the fabricated sensor can detect  hydrogen peroxide (H 2 O 2 ) with a detection range of 5.0 μM − 15 mM, a detection limit of 2.1 μM, excellent selectivity and stability. Moreover, the fabricated NiCoFe nanosheet-based electrochemical sensor can be used for the detection of H 2 O 2 in serum samples. Our work provides a scalable method for the large-scale synthesis of 2D trimetallic MOF nanosheets as enhanced nanozymes for various applications.

研究领域: 材料科学 · 分析化学 · 生物医学工程
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RSC Advances · 2016 ·Vol. 6 ·期 97 ·95199-95203 · IF 3.289

In situ synthesis and analytical investigation of porous Hb–Mn3(PO4)2 hybrid nanosheets and their biosensor applications

Shi-Yu Lu,Sheng-Hui Liao,Shu-Juan Bao,Meng Jin,Bo Weng,Chang-Ming Li

The excellent selectivity and anti-interference ability of enzyme-based biosensors have attracted considerable attention by researchers. However, the short lifetime, difficult electron transfer, and easily leak from the supporting materials restrict the practical applications of enzyme. In this study, an enzyme–inorganic hybrid biosensor constructed from slack Hb–Mn3(PO4)2·3H2O nanosheets was prepared by a simple and effective in situ immobilization method. Designed as an H2O2 sensor, it exhibits a fast electron transfer rate constant (ks = 4.16 s−1), an ultra-wide linear range for H2O2 detection (20 to 56 100 μM), and long life-time (85% of initial response after 29 days), which may be attributed to the effective immobilization of the enzyme and the good biocompatibility of Mn3(PO4)2·3H2O. For the detection of a real sample, the range of recovery of our designed biosensor was around 98.2–102.6%, confirming that our proposed method presents a promising immobilization enzyme-based biosensor for use in practical applications.

研究领域: 生物化学 · 分析化学 · 材料科学
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NEW JOURNAL OF CHEMISTRY · 2021 ·Vol. 45 ·期 41 ·19565-19571 · IF 3.591

The robust peroxidase mimics within metal–organic frameworks for the sensitivity detection of H2O2 and glucose in serum

Peipei Yang,Qingfan Ren,Yuying Chen,Sixue Ouyang,Zhipeng Huang,Peng Zhao,Jia Tao

Alloy nanoparticle-based nanozymes exhibit unique catalytic properties resulting from their tailored atomic coordination numbers and geometric parameters. The development of ultrafine alloy nanozymes is effective for improving their catalytic activities and promoting multifunction. However, it remains a challenge because of the aggregation of alloy nanoparticles resulting from the high surface free energy. This paper reports a strategy for stabilizing ultrafine and uniform CuPd alloy nanoparticles (2.18 ± 0.53 nm) in MIL-101 as a biosensor platform. The steady-state kinetic studies show that CuPd@MIL-101 can serve as a robust peroxidase-like nanozyme with a lower Michaelis constant (Km) than horseradish peroxidase (HRP). H2O2 and glucose were chosen as model targets to develop a sensitive label-free colorimetric method using CuPd@MIL-101. The linear detection of H2O2 in the range of 0.25–700 μM was achieved with a detection limit of 0.043 μM and that of glucose in the linear range of 0.5–400 μM with a detection limit of 0.16 μM. The catalytic activity of CuPd@MIL-101 can remain stable in the dulbecco's modified eagle's medium (DMEM) high-glucose medium and phosphate buffer solution (PBS) for at least five days. This study provides a meaningful reference for developing ultrafine nanozymes without affecting their stability.

研究领域: 生物传感 · 纳米医学 · 催化化学
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MICROCHIMICA ACTA · 2022 ·Vol. 189 ·期 11 ·1-10 · IF 6.408

Sensitive colorimetric assay of hydrogen peroxide and glucose in humoral samples based on the enhanced peroxidase-mimetic activity of NH2-MIL-88-derived FeS2@CN nanocomposites compared to its precursors

Fan Ru,Tian Jinrong,Wang Huili,Wang Xuedong,Zhou Peipei

By employing NH 2 -MIL-88 as a template, we synthesized the intermediate Fe@CN under high-temperature calcination and further fabricated the FeS 2 @CN nanocomposites in the presence of sulfur powder. Under varying temperatures (300–600 °C) and Fe@CN-to-S ratios (1:3–6), FeS 2 @CN 500-5 nanocomposites had the highest peroxidase-mimetic activity. Under optimized conditions (incubation temperature 40 °C; solution pH 4.0 and nanocomposite concentration 10 μg/mL; 652-nm absorption), the Michaelis-Menten constant ( K m ) of FeS 2 @CN was much lower than that of horseradish peroxidase (HRP), therefore demonstrating that it had a higher affinity for both chromogenic substrates than conventional HRP. The limits of detection for H 2 O 2 and glucose were 0.15 and 0.30 μmol/L, respectively, and the recoveries for glucose were 91.8–103% with RSDs <5.2%. The novelty of this study lies in (1) the FeS 2 @CN was confirmed to possess stronger enzyme-mimetic activity than its precursors (NH 2 -MIL-88 and Fe@CN); (2) the enhanced activity resulted from the unsaturated sites of N and S doping and the plentiful defects on the porous carbon surface; and (3) free radical trapping experiments evidenced that •OH played a major role in the catalytic reaction, while h + and •O 2 − simultaneously participated in the catalytic process. These convincing performance metrics lead us to postulate that the FeS 2 @CN-based colorimetric biosensor provides a promising approach for several real-world applications, such as point-of-care diagnosis and workplace health evaluations. Graphical abstract

研究领域: 生物化学 · 分析化学 · 材料科学
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APPLIED CLAY SCIENCE · 2021 · IF 5.467

Palygorskite@Co3O4 nanocomposites as efficient peroxidase mimics for colorimetric detection of H2O2 and ascorbic acid

Ping Chen,Hui Zhong,Xiao-rong Li,Meisheng Li,Shouyong Zhou

Nanomaterials with intrinsic enzyme-like activities have attracted extensive research interest as promising alternatives to natural biological enzymes due to their advantages of low cost and high stability. Many artificial enzyme mimics have been successfully applied in the fields of sensing, environmental treatment, and oncotherapy. Herein, novel [email protected] 3 O 4 nanocomposites ( [email protected] 3 O 4 NCs) were fabricated by modifying Pal with Co 3 O 4 nanoparticles through a facile hydrothermal method . The obtained [email protected] 3 O 4 nanocomposites as nanozymes displayed enhanced peroxidase-like activity, which can catalyze the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) in the presence of hydrogen peroxide (H 2 O 2 ) to obtain colored products. Kinetic assay indicated that the [email protected] 3 O 4 peroxidase mimics showed a higher affinity towards TMB than that of natural horseradish peroxidase (HRP). Moreover, a sensitive and selective sensor for colorimetric determination of H 2 O 2 and ascorbic acid (AA) was successfully constructed by using [email protected] 3 O 4 nanocomposites as peroxidase mimics. Furthermore, the proposed assay for sensing of AA in model samples was evaluated with satisfactory results, demonstrating the potential applications in complex biological systems.

研究领域: 生物传感 · 纳米材料科学 · 医学诊断
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Applied Materials Today · 2019 · IF 8.013

Ordered mesoporous CoO/CeO2 heterostructures with highly crystallized walls and enhanced peroxidase-like bioactivity

Jiachen Ge,Xuanyu Yang,Jiahang Luo,Junhao Ma,Yidong Zou,Jichun Li,Wei Luo,Xiaowei Cheng,Yonghui Deng

With increasing requirements of replacing the high-cost and unstable natural enzymes, the rational design of highly efficient inorganic mimetic enzymes (nanozymes), as one of the most important bioactive materials, has attracted more and more attention in recent years. In our work, using the solvent evaporation induced co-assembly strategy with high-molecular weight poly(ethylene oxide)-block-polystyrene (PEO- b -PS) diblock copolymer as the template and two metal salts as the co-precursors in one-pot system, we synthesized ordered mesoporous heteroatom-doped CeO 2 with high surface area, bimodal pore sizes and highly crystallized walls. The composite materials were then constructed as the mimetic enzymes to investigate their peroxidase-like catalytic performance and detect H 2 O 2 and glucose as bioactive materials in diverse systems including complex biological samples. It was demonstrated that mesoporous 5%CoO/CeO 2 catalyst was the best peroxidase mimic, following the typical Michaelis–Menten kinetics and exhibiting the excellent peroxidase-like catalytic performance toward 3,3′,5,5′-tetramethylbenzidine (TMB) with comparable K m and V m values to horseradish peroxidase (HRP) enzyme. A highly sensitive and selective colorimetric assay was developed to detect H 2 O 2 and glucose with detection limits of 0.88 and 19.6   μM, respectively. The promising catalytic behavior of mesoporous 5%CoO/CeO 2 as the peroxidase-like bioactive catalyst could be ascribed to its interconnected large mesopores, rich exposed surface defects and oxygen vacancies introduced by the heterojunction interface of ultrasmall CeO 2 and CoO nanocrystals within pore walls.

研究领域: 材料科学 · 生物催化 · 纳米医学
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CHEMICAL ENGINEERING JOURNAL · 2021 · IF 13.273

Co-tuning composition and channel-rich structure of Ag-Pd alloys toward sensitive electrochemical biosensing

Yang Yang,Yijin Shu,Yinqiong Wu,Qingsheng Gao

Noble-metal nanostructures are promising for biosensing applications owing to their fantastic physicochemical properties, but the rational design of their easy-accessible and reactive surface is still challenging. This work is devoted to the interfacial engineering of Ag-Pd alloys, including tuning alloy composition and geometric structure, to promote the electrochemical biosensing performance. Through a co-tuning tactic with controlled reduction, channel-rich Ag 1 Pd 3 alloys with optimal electronic configurations and accessible active surface are successfully obtained, which afford high sensitivity, outstanding selectivity and excellent repeatability to detect H 2 O 2 and glucose biomarkers. As experimentally and theoretically evidenced, tailoring the composition of Ag-Pd alloys ameliorates electronic configurations due to ligand effects, which can optimize the binding with the key intermediate of OH*, and thereby boost electrochemical kinetic steps on surface. Meanwhile, tuning geometric structure with abundant channels enables fast transport of analytes toward largely-exposed active sites. Providing an atomic-level interpretation of structure-dependent biosensing, this work is anticipated to offer guidelines for the development of efficient sensing platforms.

CAS / MDL: 50-81-7 7761-88-8
研究领域: 材料科学 · 分析化学 · 生物传感器
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2019 ·Vol. 412 ·期 4 ·963-972 · IF 3.286

Preparation of palladium/carbon dot composites as efficient peroxidase mimics for H2O2 and glucose assay

Zhuo Shujuan,Fang Jing,Zhu Changqing,Du Jinyan

In this study, palladium/carbon dot composites (Pd-CDs) were fabricated via a facial hydrothermal route using ethanediamine and palladium chloride dihydrate as precursors. The obtained Pd-CDs showed an excellent intrinsic peroxidase-like activity, which could catalyze the oxidization of 3,3′5,5′-tetramethylbenzidine with the assistance of hydrogen peroxide (H 2 O 2 ) and thus resulted in color change, accompanied by an absorption peak which appeared at 652 nm. Such response is H 2 O 2 concentration–dependent and allows for the assay of H 2 O 2 in the range of 0.1 to 30 μM with a limit of detection of 0.03 μM. Simultaneously, by combination of enzymatic oxidation of glucose with glucose oxidase and Pd-CD catalytic reaction, a colorimetric sensing platform was also constructed for glucose detection with high selectivity and sensitivity (limit of detection as low as 0.2 μM). Additionally, the proposed method exhibited capability for determination of glucose in real samples (fruit juice) with satisfactory recovery (98.5–103%), indicating potential application prospects in biochemical analysis.

研究领域: 生物化学 · 分析化学 · 纳米材料科学
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Nanoscale · 2017 ·Vol. 9 ·期 47 ·18699-18710 · IF 7.367

Fe3O4-AuNPs anchored 2D metal–organic framework nanosheets with DNA regulated switchable peroxidase-like activity

Bing Tan,Huimin Zhao,Weihao Wu,Xuan Liu,Yaobin Zhang,Xie Quan

Two-dimensional (2D) metal–organic framework (MOF) nanosheets emerging as a new member of the 2D family have received significant research interest in recent years. Herein, we have successfully synthesized 2D copper-based MOF nanosheets with bimetallic anchorage using a facile two-step process at room temperature and ambient pressure, denoted as Cu(HBTC)-1/Fe3O4-AuNPs nanosheets. The as-synthesized 2D bimetallic MOF nanosheets displayed enhanced peroxidase-like activity with relatively high catalytic velocity and affinity for substrates compared with previously reported peroxidase mimics. Furthermore, their intrinsic peroxidase-like catalytic activity could be flexibly regulated by single-stranded DNA (ssDNA), exhibiting the enhancement of 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation or inhibition of 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)diammonium salt (ABTS) oxidation due to the adsorption of ssDNA via π–π stacking. Accordingly, on the basis of their peroxidase-like activity, our prepared 2D bimetallic immobilized MOF nanosheets achieved ultra-sensitive detection of H2O2 with a linear range of 2.86 to 71.43 nM, and comparable detection performance for glucose with a linear range of 12.86 to 257.14 μM. By means of their controllable peroxidase-like activity, a versatile colorimetric sensing platform was developed which realized the detection of sulfadimethoxine (SDM) with a linear range of 3.57 to 357.14 μg L−1 and the limit of detection (LOD) of 1.70 μg L−1. With the multiplexed performance for detecting various targets, our as-synthesized bimetallic MOF nanosheets hold great promise for applications in environmental monitoring, as well as bioassays by virtue of their good biocompatibility.

研究领域: 纳米材料科学 · 生物医学工程 · 分析化学
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BIOSENSORS & BIOELECTRONICS · 2016 · IF 7.476

Reconstituting redox active centers of heme-containing proteins with biomineralized gold toward peroxidase mimics with strong intrinsic catalysis and electrocatalysis for H2O2 detection

Liyan Zhang,Shuai Li,Minmin Dong,Yao Jiang,Ru Li,Shuo Zhang,Xiaoxia Lv,Lijun Chen,Hua Wang

A facile and efficient enzymatic reconstitution methodology has been proposed for high-catalysis peroxidase mimics by remolding the redox active centers of heme-containing proteins with the in-site biomineralized gold using hemoglobin (Hb) as a model. Catalytic hemin (Hem) was extracted from the active centers of Hb for the gold biomineralization and then reconstituted into apoHb to yield the Hem-Au@apoHb nanocomposites showing dramatically improved intrinsic catalysis and electrocatalysis over natural Hb and Hem. The biomineralized gold, on the one hand, would act as “nanowires” to promote the electron transferring of the nanocomposites. On the other hand, it would create a reactivity pathway to pre-organize and accumulate more substrates towards the active sites of the peroxidase mimics. Steady-state kinetics studies indicate that Hem-Au@apoHb could present much higher substrate affinity (lower Michaelis constants) and intrinsic catalysis even than some natural peroxidases. Moreover, the application feasibility of the prepared artificial enzymes was demonstrated by colorimetric assays and direct electrocatalysis for H 2 O 2 sensing, showing a detection limitation low as 0.45   μM. Importantly, such a catalysis active-center reconstitution protocol may circumvent the substantial improvement of the intrinsic catalysis and electrocatalysis of diverse heme-containing proteins or enyzmes toward the extensive applications in the chemical, enviromental, and biomedical catalysis fields.

研究领域: 生物化学 · 纳米生物学 · 酶工程 · 分析化学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2015 · IF 3.368

Metal–organic frameworks-derived synthesis of porous FeP nanocubes: An effective peroxidase mimetic

Wenshu Yang,Jinhui Hao,Zhe Zhang,Bailin Zhang

Starting with metal–organic frameworks (MOFs), a facile process was demonstrated toward the synthesis of porous FeP nanocubes. Herein, Prussian blue nanocubes were used as iron-based MOFs precursors, and converted into FeP nanocubes through the thermal phosphidation reaction. Then, the FeP nanocubes were exploited as a peroxidase mimetic, which not only has the advantages of low cost, high stability, and easy preparation, but also follows Michaelis–Menten behaviors and shows strong affinity to substrates. On the basis of high catalytic activity of FeP nanocubes, a rapid, and convenient approach was developed for the colorimetric detection of H 2 O 2 from 2   μM to 130   μM and with a detection limit of 0.62   μM. The good catalytic activity and high stability make the porous FeP nanocubes a useful catalyst for a wide range of potential applications in catalysis and biotechnology.

CAS / MDL: 54827-17-7 7681-53-0
研究领域: 材料科学 · 生物技术 · 催化化学
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