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NEW JOURNAL OF CHEMISTRY · 2019 ·Vol. 43 ·期 34 ·13430-13436 · IF 3.069

Metal–oxygen clusters as peroxidase mimics for their multifarious applications in colorimetric sensors

Mei-Jie Wei,Jia-Qi Fu,Bo Li,Kui-Zhan Shao,Hong-Ying Zang,Xiao-Hong Wang,Zhong-Min Su

A metal–oxygen cluster (Fe28) was certified to show inherent peroxidase-like performance, which could catalyze the oxidation of the peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) using H2O2 in aqueous solution for the first time. The compound Fe28 as a peroxidase mimic displayed multi-functional applications in the detection of H2O2, glucose and dopamine. The TMB/Fe28/H2O2 system supplied a simple colorimetric approach for the detection of H2O2 and glucose with good sensitivity and had a linear range from 2.62 × 10−5 mol L−1 to 1.57 × 10−4 mol L−1 and 3.92 × 10−6 mol L−1 to 3.14 × 10−5 mol L−1, respectively. Moreover, the Fe28 cluster could detect dopamine without H2O2 with a linear range from 4.62 × 10−5 mol L−1 to 4.16 × 10−4 mol L−1. Moreover, the Fe28 cluster was low-priced, easy to synthesize and extremely effective in a colorimetric assay, which could lead to new opportunities for the development and application of metal–oxygen clusters.

研究领域: 分析化学 · 材料科学 · 生物化学
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TALANTA · 2013 · IF 3.498

Detection of Hg2+ based on the selective inhibition of peroxidase mimetic activity of BSA-Au clusters

Rui Zhu,Yan Zhou,Xi-Liang Wang,Li-Ping Liang,Yi-Juan Long,Qin-Long Wang,Hai-Jie Zhang,Xiao-Xiao Huang,Hu-Zhi Zheng

It was found that Hg 2+ can inhibit the peroxidase mimetic activity of bovine serum albumin (BSA) protected Au clusters (BSA-Au) due to the specific interaction between Hg 2+ and Au + existed onto the surface of BSA-Au clusters. By coupling with 3, 3′, 5, 5′-tetramethylbenzidine (TMB)–H 2 O 2 chromogenic reaction, a novel method for Hg 2+ detection was developed based on the inhibiting effect of Hg 2+ on BSA-Au clusters peroxidase-like activity. This method exhibited high selectivity and sensitivity. As low as 3   nM (0.6   ppb, 3 σ ) Hg 2+ could be detected with a linear range from 10   nM (2   ppb) to 10   µM (2   ppm) and this method was successfully applied for the determination of total mercury content in skin lightening products.

CAS / MDL: 13453-07-1
研究领域: 分析化学 · 生物化学 · 环境科学
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ANALYST · 2019 ·Vol. 144 ·期 20 ·6041-6047 · IF 4.019

Nitro-functionalized metal–organic frameworks with catalase mimic properties for glutathione detection

Jiayan Wang,Wenying Li,Yue-Qing Zheng

In the present study, four copper-based metal–organic frameworks were facilely prepared to study the effects of the substituent groups of the ligand on the enzyme-like properties of these frameworks. It was found that all of them were capable of catalyzing the reaction between 3,3′,5,5′-tetramethylbenzidine (TMB) and H2O2; this demonstrated their enzyme-like properties. Moreover, the enzyme-like catalytic properties of all the Cu-MOFs obtained herein were studied in detail. Interestingly, the results indicate that the four Cu-MOFs should be addressed as different enzyme mimics although the chemical structures of their ligands are quite similar. Among these four MOFs, the Cu-MOF with the –NO2 group (Cu-MOF (ii)) exhibits highest catalytic activity at neutral pH, which would be beneficial for its application in real biological samples. Moreover, its catalytic activity should be ascribed to the generation of oxygen induced by Cu-MOF (ii)-catalyzed H2O2 decomposition; this accordingly indicates that this MOF should be called a catalase mimic. Under optimized conditions, the Cu-MOF (ii) was applied to develop a (GSH) colorimetric assay for glutathione (GSH). In addition, GSH detection in serum was performed, and satisfactory results were obtained. Therefore, a simple, sensitive and selective colorimetric assay based on the MOF catalase mimic for the detection of GSH was developed.

研究领域: 生物化学 · 材料科学 · 分析化学
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ANALYST · 2013 ·Vol. 138 ·期 16 ·4526-4531 · IF 3.969

A nanosized metal–organic framework of Fe-MIL-88NH2 as a novel peroxidase mimic used for colorimetric detection of glucose

Ya Li Liu,Xi Juan Zhao,Xiao Xi Yang,Yuan Fang Li

In this paper, a nanosized porous metal–organic framework, Fe-MIL-88NH2, was facilely prepared with a uniform octahedral shape by the addition of acetic acid, and for the first time was demonstrated to possess intrinsic peroxidase-like activity. Kinetic analysis and electron spin resonance measurements indicated that the catalytic behavior was consistent with typical Michaelis–Menten kinetics and follows a ping-pong mechanism. As a novel peroxidase mimic material, Fe-MIL-88NH2 shows the advantages of high catalytic efficiency, ultrahigh stability and high biocompatibility in aqueous medium compared with natural enzymes and other peroxidase nanomimetics. Here, Fe-MIL-88NH2 was used to quickly catalyze oxidation of the peroxidase substrate 3,3′,5,5′-tetramethylbenzidine (TMB) in the presence of H2O2 to produce a colored product, which provided a simple, sensitive and selective method for the colorimetric detection of glucose. Glucose could be linearly detected in the range from 2.0 × 10−6 to 3.0 × 10−4 M with a detection limit of 4.8 × 10−7 M, and the color variation for glucose response was also obvious by visual observation at concentrations as low as 2.0 × 10−6 M. More importantly, the colorimetric method could be successfully applied to the determination of glucose in diluted serum samples.

研究领域: 生物分析化学 · 纳米生物技术 · 酶模拟 · 临床检验 · 分子诊断
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ANALYTICA CHIMICA ACTA · 2021 · IF 6.558

N-doped MoS2-nanoflowers as peroxidase-like nanozymes for total antioxidant capacity assay

Jing Chen,Fanghong Xu,Qian Zhang,Shuying Li

Total Antioxidant Capacity (TAC) Assay plays an important role in evaluating the quality of antioxidant food and monitoring the oxidative stress level of human body. It is mainly achieved by measuring the contents of antioxidants such as AA , L-Cys and GSH, while TAC can be detected by using peroxidase-like activity of artificial nanoenzyme materials. In this work, the N-Doped, defect-rich N–MoS 2 NFs nano-materials were used to build the nano enzyme , which has strong stability and high peroxidase-like activity. H 2 O 2 was detected because it can be catalyzed to generate the intermediate ·OH and make TMB appears blue. However, when H 2 O 2 , AA, L-Cys and GSH coexist in solution, due to the oxidation resistance of AA, L-Cys and GSH, they can competitively react with ·OH in solution or reduce TMB in oxidation state (oxTMB), which reduces the characteristic absorption of oxTMB, indirectly achieves the purpose of detecting AA, L-Cys and GSH, and finally realizes the determination of TAC, even in actual serum and saliva samples. At the same time, the N–MoS 2 NFs/NH 2 -MIL-53(Al)+OPD system is further constructed. Based on the fluorescence resonance energy transfer (FRET) between NH 2 -MIL-53(Al) and oxidized OPD (oxOPD), the purpose of detecting TAC by fluorescence method was realized.

研究领域: 生物化学 · 纳米医学 · 分析化学
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 2 ·1-11 · IF 6.232

Oligonucleotide-induced regulation of the oxidase-mimicking activity of octahedral Mn3O4 nanoparticles for colorimetric detection of heavy metals

Wang Jiajia,Wang Jinlong,Zhou Pei,Tao Han,Wang Xueli,Wu Yuangen

A colorimetric assay for the determination of heavy metal ions is presented that is based on the regulation of the oxidase-mimicking activity of Mn 3 O 4 nanoparticles (NPs) by oligonucleotides. The chromogenic agent tetramethylbenzidine (TMB) is oxidized by the catalytic action of Mn 3 O 4 NPs to generate products that have a yellow color in acidic solution, with a peak at 450 nm. It is found that random oligonucleotides are absorbed on the regular surface of the Mn 3 O 4 NPs and temporarily inhibit the oxidation of TMB. This leads to a decrease in absorbance and a light-green coloration of the solution. The results show that the purine bases in oligonucleotides play a key role in their regulation of the activity of the NPs. The regulatory effect is assumed to be of the noncompetitive type. In the presence of heavy metal ions like Hg(II) or Cd(II), the inhibition is canceled due to the binding of heavy metal ions to thymine bases, and the color of the solution changes from light green to yellow. The increase in absorbance at 450 nm is related to the amount of heavy metal ions present. The method allows Hg(II) and Cd(II) to be determined visually in concentrations as low as 20 μg·L −1 . The detection limit of the colorimetric assay is 3.8 and 2.4 μg·L −1 of Hg(II) and Cd(II), respectively. The assay displays good selectivity over other heavy metal ions. The method was successfully validated by analyzing several water samples. Schematic representation of the colorimetric assay for Hg(II) and Cd(II) based on the intrinsic oxidase-mimicking activity of Mn 3 O 4 nanoparticles that is regulated by oligonucleotides.

研究领域: 分析化学 · 纳米技术 · 环境科学 · 生物化学
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JOURNAL OF FOOD COMPOSITION AND ANALYSIS · 2025 · IF 4.6

Multicolorimetric detection of histamine via nanozyme-mediated gold nanorod etching for food freshness monitoring

Xiaohao Gan,Yan Zhang,Lina Zheng,Yuxuan Wang,Xuancheng Shen,Feiyan Wu,Wenxiang Wang,Ye He

Histamine is usually regarded as an important indicator for monitoring food freshness, and the detection of histamine is crucial for ensuring food safety. Herein, a high-resolution colorimetric assay for histamine determination based on nanozyme-inhibited TMB 2 + -mediated etching of gold nanorods (AuNRs) was proposed. Hydrothermal synthesis yielded CDsEDTA@Fe³ ⁺ nanozymes with Fe³ ⁺ active sites, with Vₘ = 11.17 × 10⁻⁸ M·s⁻¹ for TMB oxidation. The strong chelation between Fe 3+ and the imidazole group on histamine modulates the catalytic activity of the carbon dot nanozymes, thereby regulating the production of the oxidative end product TMB 2+ . Upon the introduction of AuNRs as the final colorimetric substrate, a rainbow-like spectrum of 5--6 distinct color changes was observed, enabling simple and rapid visual monitoring of food freshness. The limits of detection and quantification are 13.16 μM and 18.49 μM, respectively. This strategy has been effectively applied to track the genuine spoilage of shrimp and mackerel under diverse storage situations, with a recovery rate of 94.64 %-110.65 % and an RSD (n = 3) < 6 %, showing significant promise for swift and convenient detection of histamine in food products, thereby enabling the assessment of food freshness onsite.

CAS / MDL: 108-67-8
研究领域: 食品科学与技术 · 分析化学 · 纳米技术 · 生物传感器 · 食品安全
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MICROCHIMICA ACTA · 2024 ·Vol. 191 ·期 2 ·1-11 · IF 5.3

A portable intelligent hydrogel platform for multicolor visual detection of HAase

Zhao Zhe,Li Zhixin,Huang Jiahui,Deng Xiaoyu,Jiang Fan,Han Ray P.S.,Tao Yingzhou,Xu Shaohua

Hyaluronidase (HAase) is an important endoglycosidase involved in numerous physiological and pathological processes, such as apoptosis, senescence, and cancer progression. Simple, convenient, and sensitive detection of HAase is important for clinical diagnosis. Herein, an easy-to-operate multicolor visual sensing strategy was developed for HAase determination. The proposed sensor was composed of an enzyme-responsive hydrogel and a nanochromogenic system (gold nanobipyramids (AuNBPs)). The enzyme-responsive hydrogel, formed by polyethyleneimine-hyaluronic acid (PEI-HA), was specifically hydrolyzed with HAase, leading to the release of platinum nanoparticles (PtNPs). Subsequently, PtNPs catalyzed the mixed system of 3,3′,5,5′-tetramethylbenzidine (TMB) and H 2 O 2 to produce TMB 2+ under acidic conditions. Then, TMB 2+ effectively etched the AuNBPs and resulted in morphological changes in the AuNBPs, accompanied by a blueshift in the localized surface plasmon resonance peak and vibrant colors. Therefore, HAase can be semiquantitatively determined by directly observing the color change of AuNBPs with the naked eye. On the basis of this, the method has a linear detection range of HAase concentrations between 0.6 and 40 U/mL, with a detection limit of 0.3 U/mL. In addition, our designed multicolor biosensor successfully detected the concentration of HAase in human serum samples. The results showed no obvious difference between this method and enzyme-linked immunosorbent assay, indicating the good accuracy and usability of the suggested method. Graphical Abstract

研究领域: 生物化学 · 纳米技术 · 分析化学 · 生物医学工程 · 临床诊断
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 2 ·1-7 · IF 6.232

A colorimetric method for determination of the prostate specific antigen based on enzyme-free cascaded signal amplification via  peptide-copper(II) nanoparticles

Sun Ting,Xia Ning,Yuan Fang,Liu Xiaoman,Chang Yong,Liu Shudi,Liu Lin

Biotinylated peptide-Cu 2+ nanoparticles (Cu-P NPs) were synthesized via “one-pot” self-assembly. The peptide P conststs of a hydrophobic dipeptide (FF), a tripeptide (KGH), and a biotin moiety attached to the terminal amino group of the Lys residue. The Cu-P NPs contain abundant catalytically active Cu 2+ ions which are liberated by acid-induced dissolution. The released Cu 2+ ions catalyze the oxidization of 3,3′,5,5′-tetramethylbenzidine (TMB) by H 2 O 2 because of their intrinsic peroxidase activity, and this results in the formation of a blue-green coloration. Based on the streptavidin–biotin interaction, the Cu-P NPs were employed to establish an enzyme-free colorimetric method for determination of prostate-specific antigen (PSA) as a model biomarker. Under optimal conditions, the linear response range is 0.001–1 ng mL −1 , with a limit of detection as low as 1 pg mL −1 . Schematic illustration of a colorimetric immunoassay for the prostate specific antigen (PSA) with biotinylated peptide-Cu 2+ nanoparticle (Cu-P NP) as the signal label based on the streptavidin (SA)–biotin interaction. The signal was produced by Cu 2+ -catalyzed oxidization of 3,3′,5,5′-tetramethylbenzidine (TMB). P: KGHFF

CAS / MDL: 54827-17-7
研究领域: 分析化学 · 生物标志物检测 · 纳米技术 · 癌症诊断
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FOOD CHEMISTRY · 2022 · IF 9.231

A label-free visual aptasensor for zearalenone detection based on target-responsive aptamer-cross-linked hydrogel and color change of gold nanoparticles

Mei Liu,Jinxin Zhang,Shasha Liu,Baoxin Li

ZEN-responsive hydrogel was prepared using ZEN aptamer and a cationic conjugated skeleton which was formed by the electrostatic interaction between acrylamide and poly (diallyldimethylammonium chloride) (PDDA). In the presence of ZEN, the binding of aptamer and ZEN caused the hydrogel to dissociate, releasing the gold nanoparticles (AuNPs) encapsulated in the hydrogel into supernatant, whose color changes serving as response instructions were observed by eyes. To realize low dose visual detection, the TMB-H 2 O 2 was used for quantitative readout by AuNPs released from the hydrogel which can efficiently catalyze the reaction to generate a obvious change.There was a good linear relationship between the changed absorbance and concentration of ZEN within 2.5–100 ng/mL, a detection limit of 0.98 ng/mL, recovery rates of 98.8%-101.3% and 99.8%-101.5% for corns and beer, respectively. This developed sensing strategy would provide a promising application for other mycotoxins by replacing the corresponding aptamer sequences.

研究领域: 分析化学 · 纳米技术 · 食品安全 · 毒理学
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NEW JOURNAL OF CHEMISTRY · 2021 ·Vol. 46 ·期 5 ·2526-2533 · IF 3.591

Green and facile synthesis of iron-doped biomass carbon dots as a dual-signal colorimetric and fluorometric probe for the detection of ascorbic acid

Pengfei Fan,Can Liu,Congcong Hu,Feifei Li,Xi Lin,Shengyuan Yang,Fubing Xiao

Iron-doped carbon dots (Fe-CDs) were greenly synthesized via a one-step hydrothermal method using the eco-friendly materials milk powder and FeCl3. It was found that the synthesized biomass Fe-CDs have photoluminescence properties and strong mimetic oxidase activity, which enables catalysis of the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) to produce a blue product, oxidized TMB (oxTMB). The presence of ascorbic acid (AA) could reduce the oxTMB and make the solution color lighter to realize the colorimetric determination of AA. In addition, the absorption peak of the oxTMB generated at 370 nm overlaps with the excitation spectrum of Fe-CDs, and oxTMB quenched the fluorescence of Fe-CDs based on the internal filtration effect (IFE). The presence of AA will reduce oxTMB and restore the fluorescence of Fe-CDs, and the change of fluorescence intensity is positively correlated with the concentration of AA. Accordingly, a novel method for colorimetric/fluorometric dual-signal detection of AA was developed. The linear range of the colorimetric assay was 25.0–500.0 μM, and the detection limit was 8.59 μM. The linear range of the fluorometric assay was 20.0–500.0 μM with an LOD of 5.13 μM. The method took advantage of different signals to achieve complementarity and eliminate false positives of single signals and improve the accuracy with great application prospects in the detection of AA.

研究领域: 材料科学 · 分析化学 · 环境科学
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BIOSENSORS & BIOELECTRONICS · 2023 · IF 12.6

Interfacial deposition of Ag nanozyme on metal-polyphenol nanosphere for SERS detection of cellular glutathione

Yuxin Li,Ping Li,Yiqing Chen,Yue Wu,Jing Wei

The low polarization and low Raman cross section characteristics of glutathione (GSH) make it challenging to directly detect GSH molecules through surface enhanced Raman scattering (SERS) technology. Development of nanostructures for indirect detection of GSH applied to the SERS platform is of great interest. Herein, silver nanoparticles (Ag NPs)/copper-polyphenol colloidal spheres (denoted as CuTA@Ag) with adjustable Ag NPs coverage are prepared by deposition of Ag NPs on the metal-polyphenol colloidal spheres via an interfacial polyphenol reduction method. The size and density of the Ag NPs deposited on the out layer can be readily adjusted by tailoring the concentrations of silver precursor. It leads to activity difference for the nanozyme and SERS characteristics. The SERS properties of the obtained CuTA@Ag are studied using oxTMB , catalytic products of nanozyme, as the probing molecules. They provide satisfactory SERS performance with a low detection limit of 10 −7  M (S/N = 3) and linear determination in the 1–100 μM range for GSH. Moreover, it is further able to detect the glutathione content in cancer cells with well accurate and reproducible capability, catching the signs of rising cancer marker levels. This work proposes structurally tunable nanomaterials platform for a catalytic-based SERS assay, which is expected to utilize the high sensitivity of SERS tool for GSH detection in the cellular environment.

研究领域: 纳米技术 · 分析化学 · 生物传感器 · 癌症研究
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