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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

CeO2@nanogel/Au nanozymes to enhance peroxidase activity for a novel ultrasensitive SERS assay of H2O2 determination

Yifei Li,Yucui Zhang,Huan Jiang,Mengyao Qi,Xia Zhang,Baowang Zhu,Lei Han

Although the fact that H 2 O 2 is employed in the medical, food, and chemical industries, trace detection of H 2 O 2 remains a difficult and significant problem. For the detection of H 2 O 2 residues, SERS assays based on enzyme inhibition techniques show promise. As a result, we csynthesized CeO 2 @nanogel/Au nanoparticles with dual enzyme-like capabilities to detect hydrogen peroxide in this study. CeO 2 nanozymes possess both peroxidase-like and oxidase-like activities which could oxidize colorless 3,3′,5,5′-tetramethylbenzidine to blue TMB oxide. Surprisingly, after the addition of nanogel, CeO 2 @nanogel were prepared and both of its dual enzymatic activities decreased, especially the oxidase-like enzymes almost disappeared. To better investigate the enzyme catalytic activity, Au NPs were introduced and CeO 2 @nanogel/Au nanozymes were self-assembly prepared. Based on the significantly enhancement of CeO 2 @nanogel/Au nanozymes peroxidase activity, we developed a Raman detection method for H 2 O 2 with TMB ox as the probe molecule. The Raman intensity showed good linearity for the concentration of H 2 O 2 in the range of 10 -9 M−10 −1 M with a correlation coefficient of R 2  = 0.9922 and a detection limit of 2.68 × 10 -12 M. Thus, the proposed SERS mode sensor exhibited good selectivity and interference resistance, providing a new avenue for environmental monitoring.

CAS / MDL: 1310-73-2 127-09-3
研究领域: 生物化学 · 分析化学 · 环境科学
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MICROCHIMICA ACTA · 2023 ·Vol. 190 ·期 5 ·1-10 · IF 5.7

G-/C-rich ssDNA-based Fe and Cu/Fe nanoclusters with peroxidase-like activity for intracellular ROS production and cytotoxicity applications

Wei Chunying,Lin Huiqing,Bai Hehe

Five G-/C-rich single-stranded DNA (ssDNA) with different sequences and lengths were templated to prepare the DNA-Cu, DNA-Fe, and bimetallic DNA-Cu/M nanoclusters (NCs). The peroxidase-like activities of these nanomaterials were studied using H 2 O 2 and 3,3′,5,5′'-tetramethylbenzidine (TMB) as the reaction substrates in HAc-NaAc buffer. It was found that T30-G2-Fe NCs and T30-G2-Cu/Fe NCs, with a size of about 2 nm, exhibit similar and the strongest enzyme-like activity under optimal conditions. Both NCs possess a similarly high affinity to substrates, and the Michaelis–Menten constant ( K m ) values to TMB and H 2 O 2 are about 11 and 2–3 times lower than those of natural horseradish peroxidase (HRP), respectively. The activity of both nanozymes decreases to about 70% after being kept for one week in pH 4.0 buffer at 4 °C, which is comparable with HRP. Hydroxyl radicals (•OH) are the main reactive oxygen species (ROS) produced in the catalytic reaction. Moreover, both NCs can facilitate in situ generation of ROS in HeLa cells using endogenous H 2 O 2 . MTT assays indicate that the T30-G2-Cu/Fe NCs exhibit the strong selective cytotoxicity to HeLa cells over HL-7702 cells. The cellular viability is about 70% and 50% after incubating with 0.6 M NCs for 24 h without or with 2 mM H 2 O 2 , respectively. The current study shows that the T30-G2-Cu/Fe NCs have the potential for chemical dynamic treatment (CDT). Graphical abstract

研究领域: 生物化学 · 纳米医学 · 肿瘤学
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Sensors & Diagnostics · 2023 ·Vol. 2 ·期 4 ·902-908 · IF 0

Graphitic carbon nitride with Cu2+ and triazole group co-doping for enhanced peroxidase-like activity and its application for glutathione detection

Xiaotao Liu,Xueyi Zheng,Chunqiu Xia,Liangqia Guo

Nanozymes have attracted great interest in the field of biotechnology, (bio)sensing, and environmental monitoring. Herein, a co-doping strategy is proposed to enhance the peroxidase-like activity of graphitic carbon nitride (g-C3N4). Cu2+ and triazole group co-doped graphitic carbon nitride (g-C3N5-Cu2+) was derived from thermal polymerization of 3-amino-1,2,4-triazole and then coordination with Cu2+. g-C3N5-Cu2+ nanosheets (NSs) could catalyze the oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) by H2O2 under neutral conditions, yielding 10.9-fold better catalytic activity than g-C3N4 NSs. Reactive oxygen species scavenging experiments indicated that ˙OH played a crucial role during the catalytic process. When glutathione (GSH) was introduced, the absorbance of the system decreased because of the reduction of the oxidation product of TMB by GSH. The colorimetric method demonstrated a sensitive response for GSH with a linear range of 0.8–33.3 μmol L−1 and a limit of detection of 0.3 μmol L−1. The sensitivity is higher than most other peroxidase mimetic-based colorimetric methods for GSH. Finally, the feasibility for the detection of GSH in HeLa cells was demonstrated.

研究领域: 生物技术 · 环境监测 · 分析化学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2021 · IF 4.539

Zwitterionic daptomycin stabilized palladium nanoparticles with enhanced peroxidase-like properties for glucose detection

Ying Liang,Hongchen Li,Liyuan Fan,Ruyu Li,Yanshuai Cui,Xianbing Ji,Haiyan Xiao,Jie Hu,Longgang Wang

Mimic enzymes , especially noble metal nanomaterials , replace natural horseradish peroxidase due to the artificial regulation of catalytic activity by adjusting particle size and morphology. However, the existing mimic enzymes still have disadvantages such as large particle size, easy clustering and poor biocompatibility . Herein, well-dispersed daptomycin stabilized palladium nanoparticles (Dap-Pd n NPs) were synthesized by using daptomycin as a biological template . The average particle size of palladium nanoparticles of Dap-Pd 0.25 NPs was 1.73 nm, the hydrodynamic size of Dap-Pd 0.25 NPs detected by DLS method was 49.97 nm, Dap-Pd 0.25 NPs were stable in fibrinogen solution. In addition, Dap-Pd 0.25 NPs had excellent peroxidase-like activity, which effectively catalyzed the colorimetric oxidation reaction of 3,3′,5,5′-tetramethylbenzidine (TMB) by H 2 O 2 . Dap-Pd 0.25 NPs were used to detect glucose concentration based on the colorimetric reaction of TMB, which had a wide detection range (0.02–1 mM) and low detection limit (5.6 μM) for glucose. Besides, fluorescence experiments proved that Dap-Pd n NPs catalyzed H 2 O 2 to generate·OH. Taken together, a simple, green and inexpensive synthesis method of palladium nanoparticles with enhanced peroxidase-like activity was proved in this research. Dap-Pd n NPs will have great application prospects in biological detection in the future.

研究领域: 生物化学 · 纳米医学 · 分析化学
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Nano Research · 2018 ·Vol. 11 ·期 9 ·4905-4913 · IF 7.994

Prussian blue with intrinsic heme-like structure as peroxidase mimic

Chen Jinxing,Wang Qingqing,Huang Liang,Zhang Hui,Rong Kai,Zhang He,Dong Shaojun

Despite the intrinsic peroxidase-like activity of Prussian blue nanoparticles (PBNPs), their enzyme-mimic mechanism has been scarcely investigated to date. Herein, we probed the catalytic site of PBNPs for the first time, by comparing their peroxidase-like activity with that of a series of Prussian blue analogs (PBAs) in which Fe atoms were replaced by Co, Ni, and Cu. The PBNPs exhibited the highest maximal reaction velocity (1.941 μM·s −1 ), which was at least 13 times higher than that of the PBAs, demonstrating that the peroxidase-like properties of PBNPs could be ascribed to the FeN x ( x = 4–6) instead of the FeC 6 units. Notably, the PBNPs/H 2 O 2 couple also showed much higher oxidizability than ·OH radicals produced from the Fenton reaction, implying that a high active Fe(IV)=O intermediate might be formed in the FeN x units. This study can thus pave the way for the wider application of PBNPs in biomimetic reactions.

研究领域: 生物化学 · 材料科学 · 仿生学
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ANALYST · 2020 ·Vol. 145 ·期 6 ·2191-2196 · IF 3.978

Au–Hg/rGO with enhanced peroxidase-like activity for sensitive colorimetric determination of H2O2

Fen-Ying Kong,Lei Yao,Xin-Yang Lu,Heng-Ye Li,Zhong-Xia Wang,Hai-Lin Fang,Wei Wang

The Au–Hg amalgam anchored on the surface of reduced graphene oxide nanosheets (Au–Hg/rGO) has been synthesized successfully and characterized by various techniques such as transmission electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The Au–Hg/rGO nanocomposites were found to possess excellent peroxidase-like catalytic activity and can quickly catalyze the oxidation of colorless 3,3′,5,5′-tetramethylbenzidine (TMB) to blue oxTMB in the presence of H2O2. The obvious color change offered accurate determination of the H2O2 concentration by recording the absorbance at 652 nm using a UV-vis spectrophotometer. The linear response range for H2O2 was from 5 μM to 100 μM and the detection limit was 3.25 μM (S/N = 3). Furthermore, a kinetic study indicated that the catalytic behavior of Au–Hg/rGO nanocomposites followed the typical Michaelis–Menten theory and Au–Hg/rGO nanocomposites showed good affinity for H2O2. We envision that the simple and sensitive colorimetric detection system holds great promising applications in clinical diagnostics and food and environment monitoring.

研究领域: 生物化学 · 分析化学 · 材料科学
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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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ANALYTICA CHIMICA ACTA · 2024 · IF 5.7

Enhanced peroxidase-like activity based on electron transfer between platinum nanoparticles and Ti3C2TX MXene nanoribbons coupled smartphone-assisted hydrogel platform for detecting mercury ions

Gangbing Zhu,Jieling Hou,Juan Xu,Jing Li,Chenxu Wang,Yinhui Yi

Background Heavy metal pollution poses a serious threat to the ecological environment. Mercury ion (Hg 2+ ) is a class of highly toxic heavy metal ions, which is bioaccumulative, difficult to breakdown, and has a significant affinity with sulfur and thiol-containing proteins, which seriously affects environmental safety and human health. Nanozyme-based sensing methods are expected to be used to detect toxic heavy metal ions. However, the application of precious metal nanozymes to develop portable sensors with simplicity, high stability, and high sensitivity has not been explored to a large extent. Results In this paper, based on MXene's unique adsorption capacity for certain precious metal ions, PtNPs/Ti 3 C 2 T X NR composites were successfully prepared by in-situ growth of Pt nanoparticles (PtNPs) on the surface of Ti 3 C 2 T X MXene nanoribbons (Ti 3 C 2 T X NR) using the hydrothermal technique. Experimental data revealed PtNPs/Ti 3 C 2 T X NR exhibited superior peroxidase-like activity, attributed to the synergistic effect of well-dispersed ultrasmall PtNPs and electron transfer effect. Hg 2+ can significantly inhibit enzyme-like activity of PtNPs/Ti 3 C 2 T X NR due to specific capture and partial in-situ reduction of PtNPs, so a colorimetric sensor was constructed for ultra-trace detection of Hg 2+ with a linear range of 0.2 nM and 400 nM. Furthermore, using the portable detecting capabilities of smartphones and hydrogel, a smartphone-assisted hydrogel sensing platform of Hg 2+ was constructed. Notably, the two-mode sensing platforms exhibited outstanding detection performance with LOD values as low as 15 pM (colorimetric) and 26 pM (hydrogel), respectively, superior to recently reported nanozyme-based Hg 2+ sensors. Significance Compared with other methods, the PtNPs/Ti 3 C 2 T X NR-based dual-mode sensor designed in this paper has superior sensitivity, high selectivity, simple operation and portability. In particular, the dual-output sensing strategy enables self-confirmation of detection results, greatly improving the reliability of the sensor, and is expected to be used for the on-site determination of trace mercury ions.

研究领域: 环境科学 · 纳米技术 · 生物传感
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ANALYST · 2022 ·Vol. 147 ·期 11 ·2388-2395 · IF 5.227

Mimetic peroxidase based on a gold amalgam for the colorimetric sensing of trace mercury(II) in water samples

Jing Jiang,Xianwen Kan

The development of an efficient protocol to achieve the precise monitoring of trace Hg2+ is of great significance. In this work, a colorimetric sensing platform for Hg2+ monitoring was constructed via modifying gold nanoparticles (Au NPs) and hemin/reduced graphene oxide (H-rGO) onto carbon cloth (CC) (AuNPs/H-rGO/CC). The Au NPs, anchored on the surface of the interlaced fibers of CC without aggregation, showed high peroxidase-mimetic catalytic activity. The formed Au amalgam and the synergistic effect of Au NPs and H-rGO enhanced the peroxidase-mimetic activity of AuNPs/H-rGO/CC and enabled the sensing platform to achieve the colorimetric detection of Hg2+ over a wide range of 3.2 × 10−10 M–1.0 × 10−6 M. AuNPs/H-rGO/CC exhibited high selectivity towards Hg2+ due to the high special affinity between Au NPs and Hg2+. The sensing platform was further successfully applied to the determination of Hg2+ in different water samples via a simplified operation involving just tweezers. The present sensing protocol is expected to provide an efficient way to construct colorimetric sensors and to promote the sensitive determination of Hg2+ for a variety of relevant applications.

CAS / MDL: 54827-17-7
研究领域: 分析化学 · 环境科学 · 纳米技术
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Signal Transduction and Targeted Therapy · 2022 ·Vol. 7 ·期 1 ·1-9 · IF 38.104

POD Nanozyme optimized by charge separation engineering for light/pH activated bacteria catalytic/photodynamic therapy

Cao Changyu,Zhang Tingbo,Yang Nan,Niu Xianghong,Zhou Zhaobo,Wang Jinlan,Yang Dongliang,Chen Peng,Zhong Liping,Dong Xiaochen,Zhao Yongxiang

The current feasibility of nanocatalysts in clinical anti-infection therapy, especially for drug-resistant bacteria infection is extremely restrained because of the insufficient reactive oxygen generation. Herein, a novel Ag/Bi 2 MoO 6 (Ag/BMO) nanozyme optimized by charge separation engineering with photoactivated sustainable peroxidase-mimicking activities and NIR-II photodynamic performance was synthesized by solvothermal reaction and photoreduction. The Ag/BMO nanozyme held satisfactory bactericidal performance against methicillin-resistant Staphylococcus aureus (MRSA) (~99.9%). The excellent antibacterial performance of Ag/BMO NPs was ascribed to the corporation of peroxidase-like activity, NIR-II photodynamic behavior, and acidity-enhanced release of Ag + . As revealed by theoretical calculations, the introduction of Ag to BMO made it easier to separate photo-triggered electron-hole pairs for ROS production. And the conduction and valence band potentials of Ag/BMO NPs were favorable for the reduction of O 2 to ·O 2 − . Under 1064 nm laser irradiation, the electron transfer to BMO was beneficial to the reversible change of Mo 5+ /Mo 6+ , further improving the peroxidase-like catalytic activity and NIR-II photodynamic performance based on the Russell mechanism. In vivo, the Ag/BMO NPs exhibited promising therapeutic effects towards MRSA-infected wounds. This study enriches the nanozyme research and proves that nanozymes can be rationally optimized by charge separation engineering strategy.

CAS / MDL: 2044-85-1
研究领域: 生物医学工程 · 纳米医学 · 感染性疾病
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Self-template synthesis of mesoporous vanadium oxide nanospheres with intrinsic peroxidase-like activity and high antibacterial performance

Ping Li,Youyou Feng,Dong Cheng,Jing Wei

Mesoporous vanadium oxide nanospheres are a very promising nanozyme for antibacterial and chemical sensing. However, controllable synthesis of mesoporous vanadium oxide nanospheres with uniform structure and small diameter (<200 nm) remains challenging. Herein, mesoporous vanadium oxide nanospheres (MVONs) with a small, uniform and adjustable particle size (52–105 nm), large mesopore size (5.1–5.8 nm), and high specific surface area (up to 63.7 m 2 g −1 ) are constructed via a self-template strategy using tannic acid, formaldehyde and vanadium compounds as a polymerizable ligand, cross-linking agent and metal source, respectively. The relationships between synthesis conditions and material nanostructure are systematically investigated. The particle size and peroxidase-like activity of MVONs can be easily changed by adding different amounts of Pluronic block copolymer F127. Owing to the mesoporous structure, high specific surface area and small particle size, MVONs can effectively convert H 2 O 2 into extremely toxic reactive oxygen species, and further kill Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ). This research establishes a universal, reliable method for synthesizing mesoporous vanadium oxide nanospheres, which might be used in catalysis, biosensors, and antibacterial treatment.

研究领域: 材料科学 · 生物学 · 纳米医学
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ACS Nano · 2025 · IF 16

HCP-to-FCC Phase Transformation of Ruthenium Nanocrystals Selectively Activate Hydrogen Peroxide for Boosting Peroxidase-like Activity

Xilin Ding,Jin Liu,Hongxiang Chen,Yu Zhou,Chengzhou Zhu,Hongye Yan

Due to the simultaneous activation of hydrogen peroxide (H2O2) and oxygen, Ru nanocrystals exhibit inherent peroxidase- and oxidase-like activities, thereby limiting their extensive application in biosensing. Phase engineering of Ru nanocrystals holds great promise for enhancing catalytic activity and selectivity but remains a challenge. Here, highly active Ru nanocrystals with a metastable face-centered cubic (fcc) structure were successfully synthesized via a facile wet-chemical method followed by an etching step, enabling selective activation of H2O2 and demonstrating promising peroxidase-like activity. Compared to the thermodynamically favored hexagonal close-packed Ru nanocrystals, the resultant fcc Ru shows an over 5-fold enhancement in the maximum reaction velocity of the peroxidase-like catalysis, while its oxidase-like performance exhibits a minor decline, indicating a transition from multienzyme activity to specificity. Theoretical calculations reveal that the phase transformation of Ru not only results in an upward shift of the d-band center to enhance H2O2 adsorption but also regulates the O–O bonding strength of H2O2 to achieve selective H2O2 activation. As a proof of concept, a colorimetric sensor based on fcc Ru nanocrystals was successfully constructed, achieving accurate and sensitive detection of organophosphorus pesticides. This work not only offers promising prospects for phase engineering of Ru nanocrystals but also highlights the significance of the Ru phase transition in hydrogen peroxide activation.

研究领域: 材料科学 · 生物传感 · 催化化学
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