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Catalysis Science & Technology · 2021 ·Vol. 12 ·期 3 ·1017-1024 · IF 6.119

The enzymatic performance derived from the lattice planes of Ir nanoparticles

Guangxia Jin,Guowei Sun,Cheng Fu,Chan Wang,Guoxia Ran,Qijun Song

Iridium nanoparticles (IrNPs) have shown intriguing enzyme-like activities; however, the mechanism behind their versatile enzymatic behaviors is still elusive. A new kind of IrNPs stabilized with β-cyclodextrin (CD) was prepared in this work, and these IrNPs show oxidase-like, catalase-like and peroxidase-like activities. Their catalytic performances were comprehensively studied both by experimental characterization and theoretical calculations. The obtained results were systematically compared with other previously reported IrNPs. It was found that the catalytic properties of the IrNPs are derived from the lattice planes. All the IrNPs could catalyze the degradation of H2O2 due to the presence of the Ir(111) plane, while only the IrNPs with the Ir(220) plane exhibit oxidase-like activity. First of all, a new mechanism for the catalase-like activity of IrNPs was proposed here. The adsorption of H2O2 on IrNPs induces the breakdown of its O–O bond to form ˙OH radicals. The produced ˙OH will then couple with another ˙OH or H2O2, forming the key intermediate species (˙O or ˙OOH) in the production of O2. According to the energy diagrams of H2O2 decomposition on different Ir planes, we suggest that the catalase-like activity is intrinsic to the Ir(111) plane and is independent of other crystal faces or coating agents. In addition, the radicals (˙OH and ˙OOH) generated on different Ir crystal planes show different stabilities and reactivities, which is responsible for the diverse peroxidase-like activities of IrNPs. Finally, the oxidase-like properties are derived from the Ir(220) plane, where the chemisorbed O2 could accept one electron to generate superoxide species. The mechanism revealed in the present work should be helpful for understanding the catalytic role of the lattice planes of IrNPs, which may also be applicable to other metal nanozymes.

研究领域: 生物化学 · 纳米生物学 · 催化科学
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Scientific Reports · 2016 ·Vol. 6 ·期 1 ·1-7 · IF 5.228

Redox enzyme-mimicking activities of CeO2 nanostructures: Intrinsic influence of exposed facets

Yang Yushi,Mao Zhou,Huang Wenjie,Liu Lihua,Li Junli,Li Jialiang,Wu Qingzhi

CeO 2 nanoparticles (NPs) have been well demonstrated as an antioxidant in protecting against oxidative stress-induced cellular damages and a potential therapeutic agent for various diseases thanks to their redox enzyme-mimicking activities. The Ce 3+ /Ce 4+ ratio and oxygen vacancies on the surface have been considered as the major originations responsible for the redox enzyme-mimicking activities of CeO 2 NPs. Herein, CeO 2 nanostructures (nanocubes and nanorods) exposed different facets were synthesized via a facile hydrothermal method. The characterizations by X-ray photoelectron spectroscopy, Raman spectroscopy, and UV-Vis spectroscopy show that the Ce 3+ /Ce 4+ ratio and oxygen vacancy content on the surfaces of as-synthesized CeO 2 nanostructures are nearly at the same levels. Meanwhile, the enzymatic activity measurements indicate that the redox enzyme-mimicking activities of as-synthesized CeO 2 nanostructures are greatly dependent on their exposed facets. CeO 2 nanocubes with exposed {100} facets exhibit a higher peroxidase but lower superoxide dismutase activity than those of the CeO 2 nanorods with exposed {110} facets. Our results provide new insights into the redox enzyme-mimicking activities of CeO 2 nanostructures, as well as the design and synthesis of inorganic nanomaterials-based artificial enzymes.

CAS / MDL: 54827-17-7
研究领域: 生物材料学 · 纳米医学 · 催化酶学
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 8 ·1-12 · IF 5.3

Fluorescence detection of valence speciation of Cr(III) based on the catechol oxidase mimic enzyme activity of CuSeNP nanozymes

Ruan Ya,Li Qiulan,Yang Dezhi,Yang Yaling

Copper selenide nanoparticles (CuSeNP) were synthesized using histidine, ethylenediamine, and sodium selenate as precursors by one-step microwave digestion methods. The as-prepared CuSeNPs exhibit excellent catechol oxidase mimic enzyme and catalase (CAT)-like activities. Dopamine (DA) can be oxidized to aminochrome with H 2 O 2 by CuSeNPs, and the intermediate product aminochrome can further react with α -naphthol to yield a highly fluorescent derivative. It was confirmed that Cr(III) could adsorb on the surface of CuSeNPs and inhibit the production of semiquinone radicals in the reaction system, and the catalytic activity of CuSeNPs was inhibited. The detection mechanisms, kinetics, and catalytic properties of CuSeNPs were systematically investigated. As a result, a novel fluorescence method for the assay of Cr(III) was established. The feasibility of CuSeNP nanozyme in detecting speciation Cr(III) in food samples was explored with satisfactory results. It showed the obvious potential for developing effective and dependable fluorescent detection method for protecting food safety. Graphical Abstract

研究领域: 分析化学 · 食品安全 · 纳米生物学
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ACS Applied Nano Materials · 2021 · IF 5.097

CoS2/MoS2 Nanosheets with Enzymatic and Photocatalytic Properties for Bacterial Sterilization

Jin Wang,Yi Wang,Dun Zhang,Chao Chen,Zhanxu Yang

Harvesting a remarkable antibacterial performance is a major point to choose enzymatic catalytic and photocatalytic coupling catalysts. Here, Co–Mo–S mixed metal sulfides (MMSs) were composed by tailoring the composition and energy of metal organic framework (MOF)-based precursors. When n(Co)/n(Mo) = 1:1, Co/Mo-MOF is in the lowest energy state and the vulcanized CoS2/MoS2 nanosheets (NSs) exhibit the best enzymatic property. With the inherent photocatalytic activity, CoS2/MoS2 NSs can degrade more than 90% of methylene blue, methyl orange, rhodamine B, and tetracycline hydrochloride within 1 h. Promoted by intrinsic photocatalytic properties, CoS2/MoS2 NSs exhibit outstanding mimic enzyme-mimicking abilities in a neutral medium, which solve the big problem that nanozymes can only work in acidic environments. Due to the collaboration of enzymatic and photocatalytic catalysis, ·O2– can be generated in a neutral, no H2O2, and dark system, which can effectively kill Escherichia coli and Staphylococcus aureus. In all, the design of MOFs with adjustable compositions, the breakthrough of enzymatic catalysis working in a neutral medium, and the innovation of sterilization independent of external conditions encourage the utilization in an open environment and the construction of multifunctional materials in biotechnology, biosensors, and biomedicine.

CAS / MDL: 75-05-8 64-18-6
研究领域: 材料科学 · 生物医学 · 环境科学
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ACS Applied Nano Materials · 2022 · IF 6.14

TiO2 Nanoflowers Decorated with FeOx Nanocluster and Single Atoms by Atomic Layer Deposition for Peroxidase-Mimicking Nanozymes

Fengmin Qin,Jiankang Zhang,Zhan Zhou,Hao Xu,Lin Cui,Zhengxing Lv,Yong Qin

Nanozymes have great potential to replace natural enzymes due to their multiple enzyme-mimicking properties in practical applications, and the development of high-efficiency nanozymes is of great necessity. Herein, FeOx/TiO2 nanozymes with confined structures were synthesized by atomic layer deposition (ALD), among which the 70FeOx/TiO2 nanozymes with highly dispersed Fe single atoms and FeOx nanoclusters confined in the pores of TiO2 nanoflower supports exhibit optimized peroxidase activity. Furthermore, the ultrathin modification strategy of ALD (1-cycle TiO2) followed by reduction treatment was conducted to achieve the 1TiO2-70FeOx/TiO2-H nanozymes, whose enzyme-like activity is almost 2 times higher than that of 70FeOx/TiO2 counterparts. Investigation of the catalytic mechanism shows that atomic-level modification of TiO2 modifies the FeOx electron states, contributing to the stronger capability to generate hydroxyl radical, which results in remarkably enhanced peroxidase activity. The present work may provide new insights into the rational design of high-efficiency nanozymes at an atomic level.

研究领域: 材料科学 · 催化化学 · 生物医学
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Polymers · 2022 ·Vol. 14 ·期 23 ·5135 · IF 4.967

Electrospinning of n-hemin/PAN Nanocomposite Membranes and Its Photo-Enhanced Enzyme-like Catalysis

Xu Han,Yun Tao,Chao Xu,Yicong Deng,Zisen Meng,Zhenhao Dou,Peng Wang,Quan Feng

Hemin possesses great potential in eliminating organic pollutants due to its mild reaction condition, light-harvesting efficiency, and environmental friendliness. However, it has drawbacks such as being easy to aggregate and hard to recycle, and poor stability should be improved in practical application. Herein, the subject developed an electrospinning approach to enable the hemin particulates to be immobilized onto polyacrylonitrile (PAN) nanofibers stably. Hydrogen peroxide (H2O2) was adopted as an oxidant in the system to simulate the enzymatic catalysis of hemin in an organism. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), UV-Vis diffuse reflection spectroscopy (DRS), and electron spin resonance spectroscopy (ESR) analysis was employed to discuss the morphology, structure, and mechanism of the prepared n-hemin/PAN nanocomposite membranes, and 0.02 mmol L−1of the rhodamine B (RhB) removal activity in different conditions was also verified with these membranes. The kinetic studies showed that n-hemin/PAN nanocomposite membranes maintained excellent properties both in adsorption and degradation. Around 42% RhB could be adsorbed in the dark, while 91% RhB decolorized under xenon lamp irradiation in 110 min, suggesting the catalytic performance of n-hemin/PAN was greatly driven by light irradiation. Differing from the axial coordinated hemin complexes, n-hemin/PAN would catalyze hydrogen peroxide into •OH radicals rather than •OOH and high-valent metal-oxo species. This work provides an effective way to support hemin as nanocomposite membranes, in which the molecular interaction between polymer and hemin made their light adsorption an obvious red shift.Keywords:polyacrylonitrile;hemin;photocatalysis;enzyme-like catalysis;electrospinning

研究领域: 环境科学 · 材料科学 · 生物化学
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Advanced cobalt-ferrite layered double hydroxides sandwich-structured nanozymes for ROS-bloomed tumor therapy

Siyi Li,Xiucheng Zhao,He Ding,Jinhu Chang,Xiran Qin,Fei He,Xiangyang Gao,Shili Gai,Piaoping Yang

Artificial-engineered nanozymes show great promise for improving cancer therapeutic outcomes. Herein, we elaborately designed the advanced cobalt-ferrite layered double hydroxides (Co-Fe LDHs) sandwich-structured architectures that can serve as superior nanozymes with Co/Fe dual catalytic cycles and also be used as nanocarriers for loading Au nanoparticles (NPs) and maleimide (MA) to achieve the “all-in-one” reactive oxygen species (ROS)-bloomed tumor therapeutic strategy. The constructed Co-Fe LDHs@Au@MA nanozymes can not only enhance the oxidative stress in tumors through cascade enzymatic reactions but also disrupt the glutathione supply and further aggravate the tilt of the established redox homeostasis. The Co/Fe active sites are optimal by manipulating the Co/Fe-doped amount for obtaining the synergistic effect of multi-metallic enzyme-like activities. Besides, the mild photothermal effect of Au NPs facilitates the enhanced catalytic efficiency of Co-Fe LDHs but also initiates tumor cell apoptosis via the hyperthermia effect. In conclusion, this study presents a typical paradigm to utilize bi-functional LDHs-based nanozymes for tumor treatment with enhanced enzyme-like activities.

研究领域: 生物医学工程 · 癌症治疗 · 纳米医学
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CRYSTAL GROWTH & DESIGN · 2025 · IF 3.4

Bimetallic Fe3Cu-MOFs as Mimetic Enzyme and Fluorescent Probes for the Dual-Mode Detection of Uric Acid

Jiali Zhong,Rou Cheng,Ziyi Guo,Zhixiang Yue,Zhengyue Xiao,Chunyan Yan,Xiaomin Tang,Ping Qiu

In recent years, the global burden of gout has been increasing, and an excessively high level of blood uric acid is an important cause of gout attacks. The rapid detection of uric acid (UA) is of great significance for the auxiliary diagnosis of disease. We synthesized bifunctional Fe3Cu-MOFs that combined excellent peroxidase activity and fluorescence probe. UA reacts with uricase to generate H2O2, which could be catalyzed by the Fe3Cu-MOF to involve hydroxyl radicals (•OH) and singlet oxygen (1O2). And these free radicals can oxidize o-phenylenediamine (OPD) to 2,3-diaminophenazine (DAP) and the solution changes from colorless to yellow. Meanwhile, there is fluorescence resonance energy transfer (FRET) between DAP and Fe3Cu-MOF, resulting in the weakening of the blue fluorescence of Fe3Cu-MOF. Based on these mechanisms, we constructed a dual-mode sensor for UA detection. The detection ranges of the colorimetric method and the ratiometric fluorescence method of this sensor are 1–250 and 0.5–250 μM, respectively, and the limits of detection are 0.43 and 0.30 μM, respectively. These results indicate that the sensor has excellent sensitivity for UA detection. In addition, we have also successfully applied this sensor to the detection of UA content in human serum samples and urine samples.

研究领域: 生物医学工程 · 分析化学 · 纳米材料 · 临床检验
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2020 · IF 3.232

The intrinsic enzyme mimetic activity of platinum oxide for biosensing of glucose

Xueliang Liu,Yingmin Zhou,Jin Liu,Hongjun Xia

Given the enzymatic properties and the oxidized surface of Pt nanomaterials, we demonstrated the intrinsic oxidase-like and peroxidase-like activities of platinum oxide (PtO 2 ). The surface clean PtO 2 nanoparticles with high water dispersibility were synthesized by a simple and green method. X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS) results demonstrated that the prepared PtO 2 nanoparticles mainly consisted of Pt (Ⅳ) state without Pt(0) chemical state. The enzymatic activity of PtO 2 nanoparticles was verified by catalytic oxidation of several chromogenic substrates. Catalytic mechanism analysis suggested that PtO 2 nanopartiles acted as peroxidase and oxidase enzyme mimics by promoting the generation of the reactive oxygen species (ROS). By combining glucose oxidase, a colorimetric assay for glucose detection was developed with the limit of detection of 10.8 μM. The successful application of the proposed detection assay in human serum samples demonstrated the promising practical application in clinical diagnosis, pharmacy and food.

研究领域: 生物传感 · 材料科学 · 临床诊断
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CHEMISTRY OF MATERIALS · 2018 · IF 9.89

Nitrogen-Doped Carbon Nanomaterials as Highly Active and Specific Peroxidase Mimics

Yihui Hu,Xuejiao J. Gao,Yunyao Zhu,Faheem Muhammad,Shihua Tan,Wen Cao,Shichao Lin,Zhong Jin,Xingfa Gao,Hui Wei

Nanozymes, the enzyme-mimicking nanomaterials, have been developed to overcome the low stability and high cost of natural enzymes. Unlike highly active and specific enzymes, however, the catalytic activities of nanozymes are moderate and lack specificity. To address these issues, herein we demonstrated an effective and general strategy to specifically enhance the peroxidase-mimicking activities of carbon nanozymes. By doping heteroatom nitrogen (N) into reduced graphene oxide (rGO) and mesoporous carbon (MC), their peroxidase-mimicking activities were enhanced by over 100- and 60-fold, respectively. Moreover, N-doping did not significantly affect the oxidase-, superoxide dismutase (SOD)-, or catalase-mimicking activities of rGO and MC, demonstrating a specific enhancement of the peroxidase-mimicking activities. To understand the origin of the specific enhancement, we performed density functional theory calculations to examine the catalytic reaction mechanisms responsible for the peroxidase-, catalase-, oxidase-, and SOD-mimicking activities of N-doped rGO (N-rGO). We revealed that N-rGO selectively activated H2O2 rather than O2 and •O2– by forming and stabilizing radical oxygen species adjacent to the N sites of N-rGO. The radical oxygen species then oxidized peroxidase substrates, endowing N-rGO with peroxidase-mimicking activity. This study will aid in the rational design of highly active and specific peroxidase mimics and help elucidate the catalytic mechanisms of nanozymes.

研究领域: 生物化学 · 纳米医学 · 材料科学
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Chemosensors · 2024 ·Vol. 12 ·期 6 ·104 · IF 3.7

Bimetallic Fe3O4@Co3O4/CN as a Nanozyme with Dual Enzyme-Mimic Activities for the Colorimetric Determination of Mercury(II)

Yanyan Xing,Pingping He,Deyong Wang,Yuan Liang,Xing Gao,Xiaohong Hou

Colorimetric biosensor-based nanozymes have received considerable attention in various fields thanks to the advantages of the simple preparation, good stability, and regulable catalytic activity of nanozymes. In this study, a bimetallic nanozyme Fe3O4@Co3O4/CN was prepared via the high-temperature calcination of Fe3O4-PVP@ZIF-67. The material retained its skeletal structure before calcination, which prevented the aggregation of nanoparticles and exposed more active sites of the nanozyme, substantially enhancing the intrinsic dual enzyme-mimetic activities, including peroxidase- and oxidase-like activities. In particular, Fe3O4@Co3O4/CN with oxidase-like activity catalyzed the colorless tetramethylbenzidine (TMB) to become blue oxTMB with oxygen. Reducing glutathione (GSH) could inhibit the above oxidation reaction. In contrast, with respect to the existence of mercury(II), GSH bound to mercury(II) due to the strong affinity between mercury(II) and -SH, thus eliminating the inhibition and restoring the oxTMB signal. A simple and effective colorimetric sensor was fabricated to detect mercury(II) based on the above principles. The proposed measurement had a linear range of 0.1–15 μM and a limit of detection (LOD) of 0.017 μM. It was shown that the established colorimetric sensing system could be successfully applied to detect mercury(II) in water samples, and the Fe3O4@Co3O4/CN nanozyme proved to be a promising candidate for biosensing application.

研究领域: 生物传感 · 材料科学 · 环境监测
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ACS Nano · 2024 · IF 15.8

CuCo2O4 Nanoflowers with Multiple Enzyme Activities for Treating Bacterium-Infected Wounds via Cuproptosis-like Death

Wenqi Wang,Yuyu Cui,Xiaolong Wei,Ying Zang,Xulin Chen,Liang Cheng,Xianwen Wang

Nanozyme-driven catalytic therapy provides a promising treatment strategy for bacterial biofilm-infected wounds. However, the single functionality and limited catalytic efficiency of nanozyme-based materials often restrict the effectiveness of wound infection treatment. In this study, CuCo2O4 nanoflowers with multiple enzymatic activities were prepared for antibacterial/antibiofilm treatment by cuproptosis-like death. CuCo2O4 exhibited peroxidase-like (POD-like) and oxidase-like (OXD-like) dual enzyme activities that generated large amounts of •OH and O2•–. Moreover, the glutathione peroxidase-like (GSH-Px-like) activity of CuCo2O4 was able to reduce the overexpression of GSH in the wound microenvironment, enhancing the therapeutic effects of reactive oxygen species (ROS). The morphology of CuCo2O4 was modified using a hydrothermal method with PEG4000 as the solvent, resulting in the exposure of more active center sites and a significant improvement in enzyme catalytic activity. The in vitro results demonstrated the pronounced disruption effect of CuCo2O4 on biofilms formed by bacteria. In vivo, CuCo2O4 significantly promoted angiogenesis, collagen deposition, and cell proliferation. Transcriptome sequencing revealed that elevated ROS levels in bacteria led to cell membrane damage and metabolic disruption. In addition, Cu2+ overload in bacteria induces lipid peroxidation accumulation and disrupts the respiratory chain and tricarboxylic acid (TCA) cycle, ultimately leading to bacterial cuproptosis-like death. This therapeutic strategy, which combines the synergistic effects of multiple enzyme-like activities with cuproptosis-like death, provides an approach for treating biofilm infections.

CAS / MDL: 70-18-8 54827-17-7
研究领域: 生物医学工程 · 材料科学 · 微生物学
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