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MICROCHIMICA ACTA · 2017 ·Vol. 184 ·期 12 ·4629-4635 · IF 4.58

A bimetallic (Co/2Fe) metal-organic framework with oxidase and peroxidase mimicking activity for colorimetric detection of hydrogen peroxide

Yang Haiguan,Yang Ruitao,Zhang Peng,Qin Yuemei,Chen Tao,Ye Fanggui

A bimetallic metal-organic framework of the type MOF(Co/2Fe), synthesized by a hydrothermal method, is demonstrated to exhibit peroxidase-like activity and oxidase-like activity. The material catalyzes the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) to produce a blue product both in the absence and presence of H 2 O 2 . Its catalytic activity strongly depends on temperature and the solution pH value. With its dual enzyme mimetic activity, MOF(Co/2Fe) has the advantages of low cost, good stability, ease of preparation, and attractive Michaelis-Menten behavior. The mechanisms and kinetics of the pseudo-enzymatic activity were studied in some detail. A colorimetric method was developed for determination of H 2 O 2 that is based on the peroxidase-like activity of MOF(Co/2Fe). Under the optimal conditions, the absorbance of oxidized TMB at 652 nm increases linearly in the 10 to 100 μM H 2 O 2 concentration range, with a 5 μM limit of detection. A bimetallic metal-organic framework of the type MOF(Co/2Fe) exhibits peroxidase-like activity and oxidase-like activity. The material catalyzes the oxidation of 3,3,5,5-tetramethylbenzidine (TMB) to produce a blue product in the presence and absence of H 2 O 2 .

研究领域: 材料科学 · 生物化学
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CRYSTENGCOMM · 2018 ·Vol. 20 ·期 14 ·1978-1984 · IF 3.304

Ni-introduced CuAu nanocages: facile co-reduction synthesis of a novel magnetic multi-metallic nanostructure with high peroxidase mimetic activity

Chang Liu,Li Li,Qianqian Su,Feng Wu,Jian Dong,Weiping Qian

In this study, a simple and mild route was designed for the synthesis of novel octahedral Ni-introduced CuAu nanocages via a co-reduction process. Based on sequential reactions, Cu2O/Au nano-octahedra were firstly prepared through galvanic displacement reaction by employing octahedral Cu2O as the template, and then nickel and copper were introduced almost simultaneously to form the Ni-introduced CuAu nanocages by using N2H4·H2O as the reducing agent and excess Cu2O as the copper source. The peroxidase-like activity of the Ni-introduced CuAu nanocages was tested and the relevant parameters of their enzymatic activity were also investigated systematically. Compared with monometallic Cu2O/Au nano-octahedra, Ni-introduced CuAu nanocages have superior catalytic activity, and such a magnetic catalyst could still keep a relatively high catalytic efficiency after several cycles. The results showed that the as-prepared magnetic multi-metallic nanocages could be used as an efficient recyclable peroxidase-like catalyst.

CAS / MDL: 10031-43-3 7791-20-0
研究领域: 纳米材料科学 · 催化化学 · 生物医学工程
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TALANTA · 2023 · IF 6.1

High-loading Cu single-atom nanozymes supported by carbon nitride with peroxidase-like activity for the colorimetric detection of tannic acid

Xiaoyi Xie,Xiaofang Chen,Yaohui Wang,Maosen Zhang,Yuxiu Fan,Xiupei Yang

The design of nanozymes with high metal atom loading is of great significance to improve enzyme activity and is also the key to furthering the construction of highly sensitive colorimetric sensors. In this work, a colorimetric sensor for the quantitative analysis of tannic acid (TA) was developed based on two-dimensional carbon nanosheet carbon nitride (CN)-supported Cu single-atom nanozymes (Cu/CN). Cu/CN was synthesized by supramolecular preorganization and calcination , with an ultrathin nanosheet structure and a high density of Cu active sites, with a Cu loading of up to 14.3 wt%. Benefiting from the above characteristics, Cu/CN exhibits peroxidase-mimicking activity and excellent catalytic performance. Therefore, a colorimetric sensor was constructed for the fast and sensitive quantitative analysis of TA with good linearity in the range of 0.09–3.2 μM and a low detection limit of 30 nM. Furthermore, the sensor was successfully applied to the analysis of TA in tea samples of different varieties. This work sheds new light on the design of nanozymes with a high density of active sites and the analysis of TA in real environments.

研究领域: 生物化学 · 纳米材料科学 · 分析化学
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NEW JOURNAL OF CHEMISTRY · 2023 · IF 3.3

Highly selective detection and differentiation of aminophenol isomers based on a bimetallic metal–organic-framework with peroxidase-like activity

Yujie Zhang,Yingjiang Wang,Zhaohui Li,Lingbo Qu,Lanlan Yu

Nanozymes, which possess similar catalytic activities to natural enzymes, are considered promising alternatives to natural enzymes. In the present study, a new bimetallic Fe/Mn metal–organic framework (MOF) nanomaterial was synthesized by doping Mn in MIL-101(Fe). Despite the low doping amount of Mn, the Fe/Mn MOF displayed remarkably enhanced peroxidase-like activity, catalyzing the conversion of chromogenic substrate ABTS to blue-green ABTS˙+. Subsequently, the addition of environmental pollutant aminophenol isomers induced different color changes in a solution, which provided a simple and feasible approach to differentiate them by the naked eyes. Based on the effect of aminophenol isomers on the absorption spectrum of ABTS˙+, colorimetric methods were developed to quantitatively determine m-AP and p-AP with detection limits of 0.13 μM and 0.20 μM, respectively. Furthermore, taking advantage of a smart phone software-color recognizer to analyze the RGB value, a rapid detection method for m-AP was proposed, offering a solution to detect m-AP in the absence of any analytical instruments. This work verified the essential role of doping Mn in enhancing the enzyme-like activity of nanozymes. Simultaneously, the proposed simple, rapid, and accurate sensing method provided a new option to differentiate and determine aminophenol isomers, which has great potential for environmental application.

研究领域: 环境科学 · 材料科学 · 生物化学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Facilely fabricating triple-atom Fe/Zn/Ir luminescent nanozymes with peroxidase-like activity for dual mode melatonin detection

Li Yin,Baixue Xing,Ziyuan Liu,Lihua Lu

Herein, a novel ternary-atomic Fe/Zn/Ir nanozyme (Fe/Zn/Ir TAzyme) with peroxidase (POD)-like and luminescence properties is fabricated through coordinating Ir(III) complex into the as-prepared Fe/ZIF-8. The preparation procedures avoid high-temperature and pyrolysis which endue Fe/Zn/Ir nanocomposite with high stability and can be scaled up. Once Fe/Zn/Ir TAzyme catalyzes the substrate TMB to produce blue oxidized TMB (oxTMB), its luminescence is quenched by the generated oxTMB. Ascribed to its high POD-like activity and interesting luminescence property, a dual-mode sensing platform for the detection of melatonin (MT) is fabricated. In the presence of increasing concentrations of MT, the absorbance of the detection system declines, while the emission of the detection system grows. The detection platform exhibits the limits of detection (LODs) in colorimetric and luminescence detections are 8.9 nM and 8.8 nM, respectively, which can mutually validate the assay results. More importantly, Fe/Zn/Ir TAzyme has been fabricated into test swabs to monitor MT in the way of portable and naked-eye detection. This double-role TAzyme provides new conceptions for researchers to explore novel and highly efficient nanozymes in future.

研究领域: 生物化学 · 纳米医学 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

Ligand density-optimized peroxidase-like activity of gold nanoclusters for colorimetric sensing of biothiols and acetylcholinesterase

Yunyan Liang,Fangying Sun,Shaohua Qu,Xiaomeng Zhou,Li Shang

Nanozymes are emerging as an attractive alternative to natural enzymes for a wide range of biological applications, but the effect of surface ligands’ density on the catalytic activity of nanozymes remains largely unclear. Herein, taken gold nanoclusters (AuNCs) as a model nanozyme, glutathione-protected AuNCs (GSH-AuNCs) with three different ligand densities: low ( l -AuNCs), medium ( m -AuNCs), and high ( h -AuNCs) were synthesized and the role of ligand density on the catalytic activity of GSH-AuNCs was systematically investigated. It was disclosed that a relatively lower ligand density is favorable for the peroxidase-like catalytic activity due to weaker steric hindrance effects. Consequently, colorimetric detection of biothiols (e.g., cysteine) and acetylcholinesterase activity was successfully achieved based on the peroxidase property of ligand density-optimized AuNCs , which exhibit a detection limit of 0.08 μM and 0.005 mU/mL, respectively. Moreover, application of the present system for detection of acetylcholinesterase activity in human serum samples was successfully demonstrated. This study provides new avenues for designing robust nanozymes with enhanced catalytic performances for application in biocatalysis as well as biosensing.

研究领域: 纳米生物学 · 生物传感 · 酶学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2021 · IF 4.539

Peroxidase-like and oxidase-like nanozyme activities of reusable Mn–Co–S–Se/Ni foam for antibacterial application

Yumeng Lian,Yi Wang,Dun Zhang,Likun Xu

Developing a stable and reusable material for antibacterial application in an enzyme-like system is still a challenge. Herein, Mn–Co–S–Se (MnCo 2 S x Se 4–x )/Ni foam (NF) are synthesized by introducing S 2– and Se 2– in MnCo 2 O 4 /NF with a facile hydrothermal approach. With the different molar ratios of S/Se, the surface morphology of MnCo 2 S x Se 4–x /NF shows different growth and the catalytic activity also presents regular changes. MnCo 2 S 3.1 Se 0.9 /NF possesses a high enzyme-like ability with higher V max than natural horseradish peroxidase . Due to the outstanding peroxidase-like activity, MnCo 2 S 3.1 Se 0.9 /NF also exhibits broad-spectrum bactericidal performance towards Escherichia coli and Staphylococcus aureus which stems from the formation of ·O 2 – from H 2 O 2 . In the reutilization experiment, the enzyme-like activity keeps a stable value after 25 cyclic tests and the bactericidal performance is still stable after 10 cyclic tests, proving that MnCo 2 S 3.1 Se 0.9 /NF possesses relative stability and reusability. This research showed the great prospect of new energy and environmental catalysis.

研究领域: 生物材料学 · 环境催化 · 纳米酶研究
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SENSORS AND ACTUATORS B-CHEMICAL · 2021 · IF 7.46

Amorphous RuTe2 nanorods as efficient peroxidase mimics for colorimetric immunoassay

Hongye Yan,Yifeng Chen,Lei Jiao,Wenling Gu,Chengzhou Zhu

With great progress in the development of nanozymes, the effect of size, composition and structure on the catalytic activity of nanozymes have been studied extensively, while the effect of phase has rarely been reported. Herein, phase-engineered RuTe 2 nanorods are synthesized with different phase structures and peroxidase (POD)-like activities, which enables an in-depth understanding of their structure-activity relationship. Amorphous RuTe 2 (a-RuTe 2 ) nanorods exhibit superior POD-like activity, which is 3.77 times higher than that of their crystalline counterpart (c-RuTe 2 nanorods). The amorphous phase composed of a large amount of disordered atoms endows the a-RuTe 2 nanozyme with impressive performance. Significantly, given many POD-like nanozymes also show oxidase (OXD)-like activities, the interferences of O 2 limit their applications in colorimetric assay. The proposed a-RuTe 2 nanorods were found to possess negligible OXD-like activity. As a proof-of-concept, an enzyme-linked immunosorbent assay (ELISA) was constructed utilizing a-RuTe 2 nanorods as labels for the detection of prostate-specific antigen (PSA). This a-RuTe 2 nanorods-based ELISA possesses a low detection limit of 32.6 pg mL −1 , which is at least one order of magnitude lower than that of conventional ELISA based on natural horseradish peroxidase. This work provides new insights into the design of high-performance nanozymes based on phase engineering.

研究领域: 纳米材料 · 生物医学工程 · 催化化学
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INORGANIC CHEMISTRY COMMUNICATIONS · 2020 · IF 1.943

Fast colorimetric sensing of H2O2 and glutathione based on Pt deposited on NiCo layered double hydroxide with double peroxidase-/oxidase-like activity

Xiaoyan Cao,Hui Yang,Qiulian Wei,Yanting Yang,Mei Liu,Qingyun Liu,Xianxi Zhang

The Pt/NiCo layered double hydroxides nanocomposites (Pt/NiCo-LDH NCs) have been successfully prepared by a one-pot hydrothermal method. Pt/NiCo-LDH was demonstrated to possess an excellent peroxidase-like activity together with a weak oxidase-like activity, evaluating in virtue of rapid catalytic oxidization of 3, 3′, 5, 5′-tetramethylbenzidine (TMB) by H 2 O 2 into a blue oxidation product (oxTMB) only in 30 s. The short response time is very important for designing colorimetric sensors to realize real time detection. The catalytic behaviors of Pt/NiCo-LDH followed the Michaelis-Menten kinetics, possessing a good affinity towards both TMB and H 2 O 2 . The catalytic mechanism of Pt/NiCo-LDH is due to OH radicals from decomposing of H 2 O 2 . Based on the high peroxidase mimetic activity of Pt/NiCo-LDH, a rapid and convenient colorimetric sensing platform for H 2 O 2 and glutathione has been successfully constructed. Under optional conditions, the colorimetric platform shows a sensitive response to H 2 O 2 and glutathione in the linear range of 10–90 mM and 50–500 mM with a limit of detection of 0.76 mM and 3.77 mM, respectively.

研究领域: 生物化学 · 分析化学 · 纳米材料科学
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MICROCHIMICA ACTA · 2019 ·Vol. 186 ·期 7 ·1-10 · IF 5.479

A nanocomposite prepared from copper(II) and nitrogen-doped graphene quantum dots with peroxidase mimicking properties for chemiluminescent determination of uric acid

Shi Bingfang,Su Yubin,Duan Yan,Chen Shengyu,Zuo Weiyuan

Nitrogen-doped graphene quantum dots (N-GQD) were employed along with Cu(II) ions under alkaline conditions and room temperature to synthesize nanocomposites of type Cu(II)/Cu 2 O/N-GQDs. These nanocomposites exhibit excellent stability and dispersity, and also display a peroxidase-like activity that is superior to pure Cu 2 O nanoparticles and natural peroxidase (POx). A chemiluminescence (CL) method was designed that is based on the use of uricase which oxidizes uric acid under formation of H 2 O 2 . The nanocomposites were used as a POx mimic in the luminol-H 2 O 2 CL system. Under optimized conditions, a linear relationship between CL intensity and the uric acid (UA) concentration in the range of 0.16—4.0 μM, and a detection limit of 0.041 μM (at S/ N  = 3) were obtained. The CL method was applied to the determination of UA in spiked serum and urine, and recoveries ranged from 85.0 to 121.3%. Schematic presentation of synthesis strategy of Cu(II)/Cu 2 O/N-GQDs and the CL method based Cu(II)/Cu 2 O/N-GQDs for H 2 O 2 -meidated uric acid detection. The method can be used for the determination of uric acid (UA) with the detection limit of 0.041 μM.

研究领域: 生物化学 · 医学检验 · 纳米材料科学
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RSC Advances · 2016 ·Vol. 6 ·期 40 ·33636-33642 · IF 3.289

Palladium nanoparticles modified electrospun CoFe2O4 nanotubes with enhanced peroxidase-like activity for colorimetric detection of hydrogen peroxide

Zezhou Yang,Zhen Zhang,Yanzhou Jiang,Maoqiang Chi,Guangdi Nie,Xiaofeng Lu,Ce Wang

Herein, we report a simple procedure to decorate small palladium nanoparticles (Pd NPs) on the surface of CoFe2O4 nanotubes; the decorated nanotubes possess intrinsic peroxidase-like activity for the sensitive detection of H2O2. The CoFe2O4 nanotubes are prepared via an electrospinning technique, followed by a calcination process in air. The functionalization of Pd NPs on the surface of CoFe2O4 nanotubes was achieved through an in situ reduction process using ascorbic acid (AA) as a reducing agent. The synthesized Pd nanoparticles, which are small in size, are evenly dispersed on the surface of the CoFe2O4 nanotubes. The hollow structure of the CoFe2O4 nanotubes and the uniform distribution of the Pd nanoparticles enhance peroxidase-like activity toward the catalytic oxidation of the peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H2O2. The peroxidase-like property of the Pd/CoFe2O4 composite nanotubes provides a facile approach for the colorimetric detection of H2O2 with a low detection limit. This work provides great potential for Pd/CoFe2O4 nanotubes as enzyme-like nanocatalysts to sensitively detect H2O2 in biological systems.

CAS / MDL: 13820-53-6
研究领域: 材料科学 · 生物医学工程 · 分析化学
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JOURNAL OF HAZARDOUS MATERIALS · 2022 · IF 14.224

Nano-scale minerals in-situ supporting CeO2 nanoparticles for off-on colorimetric detection of L–penicillamine and Cu2+ ion

Jiajia Lian,Pei Liu,Qingyun Liu

Realizing the high value-added utilization of cheap minerals in environmental catalysis has important practical significance. Herein, four nano-scale minerals, namely halloysite (Hal) nanotubes , palygorskite (Pal) nanorods , and montmorillonite (Mon) and hydrotalcite (LDH) nanosheets , were selected for in-situ supporting CeO 2 nanoparticles (NPs) by a facile one-pot hydrothermal method. Among various nanocomposites (NCs), CeO 2 /Pal behaves the highest peroxidase-like activity, attributing to larger surface area for uniformly dispersing CeO 2 NPs and more exposed active oxygen vacancy (O vac ) defects. A novel off-on colorimetric strategy was constructed for detecting toxic L -penicillamine (LPA) and Cu 2+ ion with limit of detections (LODs) of 8.37 and 9.80 μM, respectively. Density functional theory (DFT) calculations show that the O vac defect on CeO 2 (111) surface can catalyze the heterolytic cleavage of H 2 O 2 into H 2 O and oxygen radical (•O), instead of being two hydroxyl radicals (•OH) on clean surface. It can also act as trapping site for O 2 and H 2 O adsorption, improving the oxygen affinity and hydrophilicity of CeO 2 /Pal. This study provides a feasible strategy for designing mineral-based nanozymes and an insight into the possible catalytic mechanism.

CAS / MDL: 1113-41-3 54827-17-7
研究领域: 环境催化 · 材料科学 · 生物分析化学
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