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JOURNAL OF ALLOYS AND COMPOUNDS · 2025 · IF 6.3

Engineering sulfur vacancies in NiCo2S4 flower-like structure to achieve exceptional peroxidase activity for advanced colorimetric biomedical diagnostics

Juan Xia,Chengying Yang,Mengdie Wang,Chenchen Liu,Dan Zheng,Ping Han,Xu Sun,Hanlin Wu,Qi Wang

NiCo 2 S 4 has garnered significant attention in biochemical analysis as an enzyme mimic due to its peroxidase-like activity. However, its catalytic properties have not been fully explored, limiting its application, particularly in biomedical diagnostics for low-abundance biomolecules. The catalytic activity of nanozymes is closely linked to their interface structure, and sulfur vacancies (SVs) have shown considerable promise in enhancing nanozyme activity. In this work, we synthesized SVs-NiCo 2 S 4 with a flower-like structure and NiCo 2 S 4 with a sphere-like structure with varying SV concentrations by modulating the reaction solvent, utilizing the NiCo-glycerate metal-organic framework as a template. The SVs-NiCo 2 S 4 demonstrated a remarkable catalytic efficiency of 3.85 times higher than NiCo 2 S 4 with fewer SVs. This nanozyme effectively facilitated the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) in H 2 O 2 , leading to a strong color response. Density functional theory (DFT) calculations and hydroxyl radicals (·OH) detection confirmed that the enhanced peroxidase-mimicking activity of SVs-NiCo 2 S 4 was attributed to its efficient adsorption of H 2 O 2 and subsequent decomposition into ·OH on the SVs sites of SVs-NiCo 2 S 4 . Based on these findings, we developed an enhanced colorimetric detection method for glutathione (GSH) utilizing the peroxidase-mimicking properties of SVs-NiCo 2 S 4 . Compared to NiCo 2 S 4 , SVs-NiCo 2 S 4 exhibited greater sensitivity for GSH detection, with a linear range spanning six orders of magnitude from 5 nM to 50 nM and 70 nM to 130 μM, alongside a detection limit of 1.55 nM. A deeper understanding of the mechanisms underlying the SVs can provide valuable insights for developing high-performance nanozymes and biosensors, thereby expanding the potential applications of NiCo 2 S 4 in biosensing and medical diagnostics.

研究领域: 生物医学诊断 · 纳米酶研究 · 材料科学
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Chemosensors · 2022 ·Vol. 11 ·期 1 ·27 · IF 4.229

Facile Preparation of Co3O4 Hollow Dodecahedron with Superior Peroxidase-like Activity for Selective Detection of Cholesterol

Meili Liu,Liuheng Xue,Qinghua Feng,Yingsha Wang,Jia Liu,Shouting Zhang,Wenping Hu

The Co3O4hollow dodecahedron (Co3O4@CN) was prepared by calcining ZIF-67 in N2and then air atmosphere. In the Co3O4@CN compound material, Co3O4nanoparticles (Co3O4NPs) are anchored in the carbon skeleton, solving the aggregation problem of Co3O4NPs. Because Co3O4@CN retains the porous structure of ZIF-67, and the presence of Co2+and Co3+favors electron transfer between the enzyme substrates, it has excellent peroxidase-like (POD-like) activity. Enzymatic kinetic tests show that Co3O4@CN has approximately six times more affinity for TMB than HRP and the maximal reaction rate is approximately three times that of HRP. The cholesterol sensor was constructed with Co3O4@CN, and its linear range was 20-1000 μM, and the detection limit was 14.33 μM. The application of Co3O4@CN to the detection of human serum cholesterol will be a valuable research direction.Keywords:Co3O4@CN compound material;peroxidase-like activity;cholesterol sensor

研究领域: 生物化学 · 医学检测 · 纳米材料科学
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MOLECULES · 2023 ·Vol. 28 ·期 12 ·4630 · IF 4.6

Sensitive and Label-Free Colorimetric Detection of Glyphosate Based on the Suppression Peroxidase-Mimicking Activity of Cu(II) Ions

Qing Li,Yumeng Guo,Xiangyi He,Guangli Li

The sensitive and accurate determination of glyphosate (Glyp) is urgently demanded because it is closely correlated with human health and environmental safety. In this work, we proposed a sensitive and convenient colorimetric assay by employing copper ion peroxidases for the detection of Glyp in the environment. Free Cu(II) ions displayed high peroxidase activity and can catalytically oxidize the colorless 3,3′,5,5′-tetramethylbenzidine (TMB) into blue oxTMB, resulting in an obviously visible discoloration reaction. Once the Glyp is added, the ability of copper ions to mimic peroxidase can be largely suppressed because of the generation of Glyp–Cu2+chelate. The favorable selectivity and sensitivity were demonstrated in the colorimetric analysis of Glyp. Furthermore, this rapid and sensitive method was successfully applied in the accurate and reliable determination of glyphosate in the real sample, holding promising applications in pesticide determination in the environment.Keywords:label-free;colorimetric analysis;copper ions;peroxidase-mimicking activity;glyphosate

研究领域: 环境科学 · 分析化学
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2019 · IF 3.973

Effect of surface modification on the peroxidase-like behaviors of carbon dots

Jing Shi,Tianxiang Yin,Weiguo Shen

Carbon dots (CDs) have drawn much attention in recent decades due to their outstanding biocompatibility and environmental friendliness. In this work, the surface modifications of peroxidase-like carbon dots were carried out to show the influence of surface structure on the catalytic activity . Poly(ethyleneimine) and citric acid modified CDs, i.e. PEI-CDs and CA-CDs, were obtained and used in the catalytic oxidation of two different substrates 3,3',5,5'-tetramethylbenzidine (TMB) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS). The catalytic activity of CA-CDs for TMB is greater than that of unmodified CDs while the catalytic activity of PEI-CDs for ABTS is greater than that of unmodified CDs. These results may be ascribed to that TMB shows stronger affinity to negatively charged CA-CDs and ABTS shows stronger affinity to positively charged PEI-CDs. These results clearly suggested that the surface charge plays an important role in the catalytic activity of nanoenzyme. Furthermore, the mechanism of peroxidase-like activity of all CDs was investigated and both the generation of hydroxyl radical and enhanced electron transfer were involved in the catalytic process.

研究领域: 纳米生物学 · 生物化学
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FOOD CHEMISTRY · 2022 · IF 9.231

Simple and rapid detection of calcium peroxide in flour based on methanobactin peroxidase-like activity

Xin Jia-ying,Lu Xue-chun,Sun Li-rui,Zhang Jia-yu,Xia Chun-gu

Calcium peroxide is forbidden to be added to flour as brightener in many countries. A rapid and sensitive spectrophotometric method for the detection of calcium peroxide in flour was proposed. Methanobactin (Mb), a copper-binding small peptide of methanotrophs with excellent peroxidase-like activity, has been successfully applied for H 2 O 2 -mediated co-oxidation between phenol and 4-aminoantipyrine to give a colored product that can be detected at 505 nm. When the concentration of Mb-Cu was 6.5 × 10 −6 mol/L, the detection temperature was 50 ℃, and the detection time was 5 min, the linear range for quantification of calcium peroxide concentration was observed between 0.4 and 10.0 mg/L with R 2  = 0.99397. The limit of detection was 0.027 mg/L (3.34 mg/kg flour) and the average recovery of standard addition was 99.6%–100.5%. Mb was very stable and still maintained catalytic activity even at 50 ℃ in acidic medium, which gave the proposed method has simple process and rapid detection speed.

研究领域: 食品科学 · 生物化学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2021 · IF 4.098

Iodide-enhanced Co/Fe-MOFs nanozyme for sensitively colorimetric detection of H2S

Xiao-Lan Zhao,Jia-Li Liu,Fa-Ting Xie,Tong Yang,Rong Hu,Yun-Hui Yang

In this paper, a simple, rapid, and low-cost colorimetric method was designed based on Co/Fe-MOFs-iodide composite for the quantitative detection of H 2 S. It is know that iodide can improve the catalytic activity of bimetallic porous material Co/Fe-MOFs via adsorption into the framework of MOFs. Herein, we demonstrate a novel strategy to enhance the peroxidase-like activity of MOFs. Compared to horseradish peroxidase (HRP), the kinetic measurement results show that Co/Fe-MOFs-iodide exhibits excellent affinity to substrates, promoting electron transfer. Due to the synergetic effect of Co/Fe-MOFs and iodide, and rapid electron transfer process, Co/Fe-MOFs-iodide demonstrates improved peroxidase-like activity. As a proof-of-concept application, a novel, highly sensitive H 2 S colorimetric method is established with a detection limit (LOD) of 0.33 nM. In the absence of iodide, LOD is approx. 200-fold higher than that of the amplified colorimetric assay. The proposed method can also accurately detect traces of H 2 S in serum samples.

研究领域: 生物化学 · 分析化学
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INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES · 2023 ·Vol. 24 ·期 4 ·3173 · IF 5.6

Different Dimensional Copper-Based Metal–Organic Frameworks with Enzyme-Mimetic Activity for Antibacterial Therapy

Chuyan Lin,Xiangjian Guo,Fayin Mo,Duanping Sun

Fighting against bacterial infection and accelerating wound healing remain important and challenging in infected wound care. Metal–organic frameworks (MOFs) have received much attention for their optimized and enhanced catalytic performance in different dimensions of these challenges. The size and morphology of nanomaterials are important in their physiochemical properties and thereby their biological functions. Enzyme-mimicking catalysts, based on MOFs of different dimensions, display varying degrees of peroxidase (POD)-like activity toward hydrogen peroxide (H2O2) decomposition into toxic hydroxyl radicals (•OH) for bacterial inhibition and accelerating wound healing. In this study, we investigated the two most studied representatives of copper-based MOFs (Cu-MOFs), three-dimensional (3D) HKUST-1 and two-dimensional (2D) Cu-TCPP, for antibacterial therapy. HKUST-1, with a uniform and octahedral 3D structure, showed higher POD-like activity, resulting in H2O2decomposition for •OH generation rather than Cu-TCPP. Because of the efficient generation of toxic •OH, both Gram-negative Escherichia coli and Gram-positive methicillin-resistantStaphylococcus aureuscould be eliminated under a lower concentration of H2O2. Animal experiments indicated that the as-prepared HKUST-1 effectively accelerated wound healing with good biocompatibility. These results reveal the multivariate dimensions of Cu-MOFs with high POD-like activity, providing good potential for further stimulation of specific bacterial binding therapies in the future.Keywords:metal–organic frameworks;POD-like activity;antibacterial therapy;wound healing

研究领域: 材料科学 · 生物学 · 医学
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ACS Sustainable Chemistry & Engineering · 2020 · IF 7.632

Copper-Sensitized “Turn On” Peroxidase-Like Activity of MMoO4 (M = Co, Ni) Flowers for Selective Detection of Aquatic Copper Ions

Linpin Luo,Zehui Su,Junchen Zhuo,Lunjie Huang,Ying Nian,Lihong Su,Wentao Zhang,Jianlong Wang

Improving the catalytic performance of nanozymes is currently one of the hot topics in the field of analytical chemistry. Metal ions can be an ideal way for the regulation of enzyme activity because of its unique advantages. Although great advances have been achieved, the efficiency and selectivity of nanozymes still has big room to improve. Herein, we found that the copper ions (Cu2+) could selectively and sensitively regulate the peroxidase-like activity of flower-like transition-metal-based material MMoO4 (M = Co, Ni). The peroxidase-like activity of MMoO4 could obviously be activated by Cu2+, which accelerated the effective oxidation of common chromogenic substrates represented by 3,3′,5,5′-tetramethylbenzidine. The catalytic activity of MMoO4–Cu2+ strongly relies on the reaction temperature and the pH of solution. Moreover, the kinetic behavior follows the Michaelis–Menten kinetics. Then, a simple, sensitive, and selective colorimetric strategy using CoMoO4 as the probe for detecting Cu2+ was established. The obvious color change can be discerned by the naked eye or detected by the absorption spectroscopic method. In the range of Cu2+ concentration of 0.1–24 μM, the absorbance at 652 nm exhibited a linear relationship to the concentration of Cu2+. The low detection limit of our method could achieve 0.024 μM, and our strategy can also be well applied in the real sample with good recoveries. Our work implied the promising use of nanozymes in heavy metal ion detection.

研究领域: 分析化学 · 纳米生物学
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MICROCHEMICAL JOURNAL · 2019 · IF 3.206

Rapid and sensitive colorimetric sensor for H2O2 and Hg2+ detection based on homogeneous iodide with high peroxidase-mimicking activity

Yang Wang,Liujing Xu,Wen Xie

Peroxidase reaction is known as a classical reaction that is widely used in the analytical chemistry field because of not only the important peroxide analytes but also the key role of H 2 O 2 detection in various coupled enzyme systems. For this reason, exploiting appropriate enzymes with good catalytic properties, low cost, easy preparation, and simple operation for the reaction becomes extremely important for acquiring desired analytical performance. Herein, we proposed a simplified, rapid, and universal colorimetric platform based on the peroxidase-mimicking activity of I − for sensing applications. The I − species exhibited the peroxidase-like ability to catalyze the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to blue TMBox in the presence of H 2 O 2 via the I 2 intermediate. Compared with natural bio-enzymes and emerging nanozymes , the homogeneous I − mimic provided excellent activity to trigger the color reaction faster. More importantly, commercial reagents were able to be used directly, thus avoiding the tedious preparation and purification processes required in bio-enzymes and nanozymes. As a result, the fabricated platform could be used to detect H 2 O 2 within 3 min, providing a linear range of 1.7–166.7 μM and a detection limit of 1.1 μM. Given that Hg 2+ could suppress the color reaction through formation HgI 2 , the Hg 2+ target (20–80 nM) was also determined rapidly. Practical measurements demonstrated the reliability of the colorimetric assay . It is believed that the general platform based on the H 2 O 2  + TMB + I − reaction holds broader applications in other analytical systems.

CAS / MDL: 9007-43-6
研究领域: 分析化学 · 生物医学工程
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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Controllable doping of Fe atoms into MoS2 nanosheets towards peroxidase-like nanozyme with enhanced catalysis for colorimetric analysis of glucose

Luping Feng,Lixiang Zhang,Su Chu,Sheng Zhang,Xi Chen,Zhongling Du,Yushuang Gong,Hua Wang

MoS 2 nanosheets were doped with Fe elements simply via the one-pot hydrothermal route resulting in the peroxidase-like nanozymes with dramatically enhanced catalysis. It was discovered that the resulted Fe-MoS 2 could display controllable catalysis activities depending on the Mo-to-Fe molar ratios, among which the highest one was achieved at 3/1 with catalysis efficiency over three folds higher than that of pristine MoS 2 . The greatly improved catalysis performances of Fe-MoS 2 nanozyme are thought to be resulted from the synergistic effects of the doped Fe atom and Mo-S sites. On the one hand, herein, the Fe sites might serve as the electron transferring mediators to facilitate the peroxidase-like catalytic reactions, as confirmed by the cytochrome C -based electron transportation experiments. On the other hand, the Mo-S sites might conduct the catalytic behavior of Fenton-like reactions, as revealed by the hydroxyl radicals-capturing experiments. Furthermore, the feasibility of practical applications for the developed Fe-MoS 2 nanozyme based colorimetric methods was demonstrated for glucose in blood sample. Importantly, an insight can be thereby obtained into the design of different nanozymes with enhanced catalysis designed by doping heteroatoms like Fe, promising for the catalysis-based applications in the biomedical analysis, food safety, and environmental monitoring fields.

研究领域: 生物医学 · 材料科学 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2020 · IF 7.1

Cu-CDs/H2O2 system with peroxidase-like activities at neutral pH for the co-catalytic oxidation of o-phenylenediamine and inhibition of catalytic activity by Cr(III)

Dezhi Yang,Qiulan Li,Sai Kumar Tammina,Zhe Gao,Yaling Yang

The construction of highly efficient nanozyme activities in a simple means is vital for the wide biological and chemical applications. Present work describes a Cu-based carbon dots (Cu-CDs) with oxidase- and peroxidase-like activity for the catalytic oxidation of o -phenylenediamine (OPD) at neutral pH. The peroxidase-like activity of Cu-CDs was finely tuned and enhanced by changing the ascorbic acid (AA) content and reduction temperature to increase the Cu + content. The oxidation of OPD was significantly accelerated by the addition of Fe 2+ ions (i.e., Cu-CDs + Fe 2+ /H 2 O 2 system) and presented a smaller K m (Michaelis constant) and a higher V max (maximum rate) than horseradish peroxidase (HRP) at the same mass concentration. The Cu-CDs with oxidase- and peroxidase-like activities could catalyze to produce the superoxide radical ( · O 2 - ) and hydroxyl radical (·OH) in the system. Interestingly, the catalytic oxidation of OPD to 2,3-diaminophenazine (DAP) could be inhibited by Cr(III) ions in Cu-CDs + Fe 2+ /H 2 O 2 system. Therefore, a new fluorescent detection strategy was developed for the detection of Cr(III) with the linear range of 0.2−100 μM, and the detection limit of 36 nM (S/N = 3). This work provides new insight into the mechanism and kinetics of low-valence copper–carbon dots peroxidase-like and Fenton co-catalyst system.

研究领域: 生物化学 · 纳米生物学 · 分析化学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2020 · IF 3.232

Platinum (II)-doped graphitic carbon nitride with enhanced peroxidase-like activity for detection of glucose and H2O2

Guo Zeng,Minghui Duan,Yifan Xu,Fahuan Ge,Weiguo Wang

A platinum (II)-doped graphitic carbon nitride (Pt 2+ @g-C 3 N 4 ) nanozyme was prepared in this work. Compared to g-C 3 N 4 , Pt 2+ @g-C 3 N 4 shows enhanced peroxidase-like activity. According to DFT calculations and ESR measurements, the Pt on the surface of g-C 3 N 4 accelerates the decomposition of H 2 O 2 into OH and consequently accelerates TMB oxidation. Furthermore, as a proof of concept, the obtained Pt 2+ 2.30 @g-C 3 N 4 was applied in the detection of glucose with an LOD of 0.01 mM. The reproducibility and precision tests of the glucose detection method based on Pt 2+ 2.30 @g-C 3 N 4 show that this method is reliable and feasible for the detection of glucose.

研究领域: 生物化学 · 材料科学 · 分析化学
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