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JOURNAL OF MATERIALS SCIENCE · 2020 ·Vol. 55 ·期 23 ·10022-10034 · IF 3.553

A covalent organic framework–MnO2 nanosheet system for determination of glutathione

Qu Fei,Yan Hang,Li Kexin,You Jinmao,Han Wenli

Covalent organic frameworks (COFs) are usually synthesized by virtue of Schiff base reaction between amino and aldehyde groups. Owing to their electron-rich property, COFs are widely applied to detect electron-deficient nitroaromatic explosives through photoinduced electron transfer mechanism. However, except for these cases, the COFs-based chemosensors are rarely reported for the analysis of electron-rich biomolecules. In this work, a fluorescent platform constructed by COFs and MnO 2 nanosheets is developed for sensitive detection of glutathione (GSH). It is found that the fluorescence of COFs can be effectively quenched by MnO 2 nanosheets. The quenching mechanisms involving inner filter effect and static quenching effect are discussed in detail. Due to the reducing ability of GSH, it can trigger the reduction of MnO 2 to Mn 2+ , accompanying with the fluorescence recovery of COFs. The linear range of GSH is achieved from 0.5 to 100 µM with a detection limit of 0.28 µM. This method is further applied for GSH detection in human serum samples with satisfactory results.

研究领域: 生物化学 · 分析化学 · 材料科学
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Analytical Methods · 2016 ·Vol. 8 ·期 48 ·8492-8497 · IF 1.915

Enzyme-free fluorescent biosensor for miRNA-21 detection based on MnO2 nanosheets and catalytic hairpin assembly amplification

Wenjun Ouyang,ZhenHua Liu,GuiFeng Zhang,Zheng Chen,Longhua Guo,Zhenyu Lin,Bin Qiu,Guonan Chen

MicroRNAs (miRNAs) have attracted enormous interest due to their involvement in complex regulatory functions and for being closely linked to some cancers. Thus, qualitative and quantitative detection of miRNAs has become an urgent necessity. In this study, we report an enzyme-free fluorescent biosensor for miRNA-21 detection based on MnO2 nanosheets and catalytic hairpin assembly amplification. Results showed that the detection limit for miRNA-21 was 0.33 nM (S/N = 3) and the linearity range was from 1 to 50 nM. Compared with traditional methods, such strategy is convenient, rapid, and low-cost and it can have a promising potential for miRNA detection in cancer.

研究领域: 生物化学 · 分子生物学 · 癌症研究 · 纳米技术
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MICROCHEMICAL JOURNAL · 2021 · IF 4.821

Sensitive detection of butyrylcholinesterase activity based on a separation-free photothermal assay

Zerui Ma,Lili Cao,Yifei Xing,Anrui Feng,Peng Zhang,Wei Li,Hailiang Nie,Yu-e Shi,Zhenguang Wang

Butyrylcholinesterase (BChE), a regulator for the cholinesterase activity in serum, is an important index for clinical diagnosis of organophosphorus poisoning and liver related disease. However, the assays for BChE activity are highly dependent on expensive and bulk equipment and professional operators, which limits its straightforward and portable detection. In this work, we proposed a straightforward and sensitive photothermal assay for the detection of BChE activity, avoiding the use of expensive instrument, professional operators, and separation process. Polydopamine (PDA) nanoparticles can be produced through the oxidation of dopamine by MnO 2 nanosheets, which show a rather strong photothermal features. Hydrolyzation of substrate into thiocholine and butyrate happens after introducing BChE. The generated thiocholine and butyrate inhibit the formation of PDA nanoparticle through reducing MnO 2 into Mn 2+ and creating an acidic environment, respectively. Those effects lead to the decreasing of photothermal efficiency of the reaction system, resulting in the decreasing on temperature change. Quantitative detection of BChE activity is achieved by recording the temperature change of system, using a common device, with a limit of detection of 40.65 U/L calculated. The presented results provide a clue for developing straightforward and portable photothermal assay for BChE, which shows great potential for their clinical applications.

研究领域: 生物化学 · 分析化学 · 纳米技术 · 临床诊断
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FOOD CONTROL · 2021 · IF 5.548

Sensitive detection of patulin based on DNase Ⅰ-assisted fluorescent aptasensor by using AuNCs-modified truncated aptamer

Hualin Guo,Yuhan Sun,Pengfei Ma,Imran Mahmood Khan,Nuo Duan,Zhouping Wang

Patulin (PAT) is a mycotoxin that exists in a wide range and is harmful to human health, which has aroused great attention to food safety. In this study, we established a novel assay to detect food samples contaminated by PAT. First of all, we proposed a truncation protocol based on the secondary structure of aptamer. By removing the stem-loop structure one by one, an optimized truncated PAT aptamer (P-30) was obtained. To the best of our knowledge, the mechanism between PAT and P-30 was elaborated in the assisting of molecular docking and circular dichroism for the first time. Furthermore, we developed a sensitive aptasensor platform to detect PAT in food samples. The aptamer modified with gold nanoclusters (AuNCs) was used as fluorescent probe, and BSA-directed synthesized MnO 2 nanoflakes (MnO 2 NFs) as fluorescence receptor. Additionally, fluorescence signal amplification strategy assisted by DNase Ⅰ successfully improved the sensitivity of aptasensor. The developed assay had a low detection limit of 8.5 ng/L, and can be effectively used in apple and grape juice samples. Thus, the established aptasensor shows a broad application prospect in PAT detection.

研究领域: 食品科学 · 分析化学 · 毒理学
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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 9 ·1-10 · IF 6.232

A nanoprobe for ratiometric imaging of glutathione in living cells based on the use of a nanocomposite prepared from dual-emission carbon dots and manganese dioxide nanosheets

Deng Zhiwei,Li Xiufang,Liu Hui,He Yao,Zhang Jie,Yuan Jing,Gao Peiru,Jiang Xuling,Yang Yanjing,Zhong Shian

A ratiometric fluorescence assay for glutathione (GSH) was developed. The novel assay is based on a nanoprobe composed of manganese dioxide nanosheets (MnO 2 NS) and dual-emission carbon dots (de-CDs) with intrinsic GSH-response property. After construction of the nanoprobe, two emission peaks of de-CDs were suppressed to varying degrees by MnO 2 NS. The suppression was relieved and the two emission peaks recovered proportionally when MnO 2 NS was decomposed by GSH, thus realizing the ratiometric assay for micromolar GSH. The intrinsic responsiveness of de-CDs to millimolar GSH broadens the analytical range of the nanoprobe. An appropriate precursor, calcon-carboxylic acid, was screened out to synthesize de-CDs via one-step hydrothermal treatment. The de-CD@MnO 2 NS nanoprobe can measure GSH concentrations through the fluorescence intensity ratio between 435 and 516 nm excited at 365 nm. The range of response was from 1 μM to 10 mM and the detection limit reached 0.6 μM (3σ criterion). Benefiting from its good biocompatibility, the proposed nanoprobe has excellent applicability for intracellular GSH imaging. Graphical abstract Schematic representation of glutathione (GSH) ratiometric detection. The nanoprobe is prepared from dual-emission carbon dots (de-CDs) and manganese dioxide nanosheets (MnO 2 NS). GSH removes quenching effect by decomposing MnO 2 NS and induces intrinsic response of de-CDs, which realizes ratiometric detection.

研究领域: 分析化学 · 纳米技术 · 生物医学工程 · 细胞生物学
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ACS Omega · 2021 · IF 3.512

CDs–MnO2–TPPS Ternary System for Ratiometric Fluorescence Detection of Ascorbic Acid and Alkaline Phosphatase

Hongzhi Lu,Shoufang Xu

Manganese dioxide (MnO2) nanosheet-based fluorescence sensors often use oxidase-like activity or wide absorption spectrum for detection of antioxidants. In those strategies, MnO2 nanosheets were reduced to Mn2+ by antioxidants. However, few strategies emphasize the role of Mn2+ obtained from MnO2 reduction in the design of the fluorescence sensor. Herein, we expanded the application of a MnO2 nanosheet-based fluorescence sensor by involving Mn2+ in the detection process using ascorbic acid (AA) as a model target. In this strategy, carbon dots (CDs), MnO2 nanosheets, and tetraphenylporphyrin tetrasulfonic acid (TPPS) comprise a ternary system for ratiometric fluorescence detection of AA. Initially, CDs were quenched by MnO2 nanosheets based on the inner filter effect, while TPPS maintained its fluorescence intensity. After the addition of AA, MnO2 nanosheets were reduced to Mn2+ so that the fluorescence intensity of CDs was recovered and TTPS was quenched by coordination with Mn2+. Overall, AA triggered an emission intensity increase at 440 nm for CDs and a decrease at 640 nm for TPPS. The ratio intensity of CDs to TPPS (F440/F640) showed a good linear relationship from 0.5 to 40 μM, with a low detection limit of 0.13 μM for AA detection. By means of the alkaline phosphatase (ALP)-triggered generation of AA, this strategy can be applied for the detection of ALP in the range of 0.1–100 mU/mL, with a detection limit of 0.04 mU/mL. Furthermore, this sensor was applied to detect AA and ALP in real, complex samples with ideal recovery. This novel platform extended the application of MnO2 nanosheet-based fluorescence sensors.

研究领域: 分析化学 · 纳米技术 · 生物传感器
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2025 · IF 3.8

In situ generation of polydopamine as photothermal reporter for on-site testing of azodicarbonamide in flour using an integrated 3D-printed device

Guo Lan,Zhao Dong-Mei,Hu Bao-Hua,Wu Shuo,Chen Shuai,Yu Yong-Liang

The detection of the illegal additive azodicarbonamide (ADA) in flour and related products is crucially important due to the harmful effects of excessive consumption on human health. However, the requirement for expensive instruments and trained operators poses a major challenge for on-site testing of ADA, particularly in field enforcement and consumer self-monitoring. Herein, an economical and portable 3D-printed photothermal (PT) device constructed by a 3D-printed sample bracket, a separable 96-well plate, an 808 nm laser, and a thermometer was rationally designed for quantitative on-site testing of ADA in flour. Since the target ADA could convert reducing glutathione (GSH) into non-reducing glutathione disulfide (GSSG), manganese dioxide nanosheets (MnO 2 NSs) in this sensing system remain intact to catalyze the conversion of dopamine (DA) into polydopamine nanoparticles (PDA NPs). During the detection process, the PT signal changes induced in the sample driven by the 808 nm laser could be easily recorded with a digital thermometer. The proposed PT method demonstrates an excellent linear response for ADA in the range of 30–1000 μM, with a detection limit as low as 10 μM, which was significantly lower than the maximum allowable ADA level in flour extracts (388 μM). This portable and cost-effective PT sensing system shows great potential for quantitative on-site testing, enabling immediate food safety identification in resource-limited regions. Graphical

研究领域: 食品安全 · 分析化学 · 传感器 · 纳米技术 · 生物医学工程
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NEW JOURNAL OF CHEMISTRY · 2023 ·Vol. 47 ·期 15 ·7198-7204 · IF 3.3

An “off–on”-type electrochemiluminescent immunosensor based on resonance energy transfer and a liposome-assisted strategy for signal amplification

Yu-Ling Wang,Yi-Zhuo Fu,Hui-Jin Xiao,Pan Wu,Shu-Wei Ren,Jun-Tao Cao,Yan-Ming Liu

An “off–on”-type electrochemiluminescence (ECL) system for a myoglobin (Myo) assay was proposed by coupling a resonance energy transfer (RET) strategy with functional liposomes as probes. Specifically, black-phosphorus nanosheets (BP NSs), as energy-donors, were introduced into an ECL system, and MnO2 NSs (energy-acceptors) were reduced on the surface of BP NSs in situ to form the BP/MnO2 nanocomposites. Thanks to a perfect spectral match between BP NSs and MnO2 NSs, efficient ECL-RET occurred in BP/MnO2 nanocomposites. Glutathione (GSH)-loaded liposomes (as probes for the regulation and amplification of signals) were immobilized in a 96-well plate through a sandwich immunoreaction. The abundant GSH lysed from liposomes could reduce MnO2 to Mn2+ effectively and destroy the RET, thus regulating the degree of recovery of the ECL signal from BP NSs. The absence and presence of GSH generated the “signal-off” and “signal-on” states of the BP/MnO2 nanocomposites-based ECL system. The amount of Myo could be estimated by the degree of recovery of the signal. Benefiting from these phenomena, a good linear relationship ranging from 1.0 × 10−13 to 1.0 × 10−7 g mL−1 was found and the limit of detection was down to 2.5 × 10−14 g mL−1 for Myo. Furthermore, the ECL system revealed a favorable performance for the determination of Myo in samples of human serum.

CAS / MDL: 70-18-8
研究领域: 生物分析化学 · 医学诊断
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ACS Applied Materials & Interfaces · 2016 · IF 7.145

Layered-MnO2 Nanosheet Grown on Nitrogen-Doped Graphene Template as a Composite Cathode for Flexible Solid-State Asymmetric Supercapacitor

Yongchuan Liu,Xiaofei Miao,Jianhui Fang,Xiangxin Zhang,Sujing Chen,Wei Li,Wendou Feng,Yuanqiang Chen,Wei Wang,Yining Zhang

Flexible solid-state supercapacitors provide a promising energy-storage alternative for the rapidly growing flexible and wearable electronic industry. Further improving device energy density and developing a cheap flexible current collector are two major challenges in pushing the technology forward. In this work, we synthesize a nitrogen-doped graphene/MnO2 nanosheet (NGMn) composite by a simple hydrothermal method. Nitrogen-doped graphene acts as a template to induce the growth of layered δ-MnO2 and improves the electronic conductivity of the composite. The NGMn composite exhibits a large specific capacitance of about 305 F g–1 at a scan rate of 5 mV s–1. We also create a cheap and highly conductive flexible current collector using Scotch tape. Flexible solid-state asymmetric supercapacitors are fabricated with NGMn cathode, activated carbon anode, and PVA–LiCl gel electrolyte. The device can achieve a high operation voltage of 1.8 V and exhibits a maximum energy density of 3.5 mWh cm–3 at a power density of 0.019 W cm–3. Moreover, it retains >90% of its initial capacitance after 1500 cycles. Because of its flexibility, high energy density, and good cycle life, NGMn-based flexible solid state asymmetric supercapacitors have great potential for application in next-generation portable and wearable electronics.

研究领域: 材料科学 · 电化学 · 纳米材料 · 能源存储 · 柔性电子学
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ACS Applied Materials & Interfaces · 2018 · IF 8.097

FRET Effect between Fluorescent Polydopamine Nanoparticles and MnO2 Nanosheets and Its Application for Sensitive Sensing of Alkaline Phosphatase

Ting Xiao,Jian Sun,Jiahui Zhao,Shuang Wang,Guoyong Liu,Xiurong Yang

As an essential and universal hydrolase, alkaline phosphatase (ALP) has been identified as a crucial indicator of various diseases. Herein, we, for the first time, expanded the application of fluorescent polydopamine (F-PDA) nanoparticles to nanoquencher-based biosensing system, as well as discovered the reversible quenching effect of manganese dioxide (MnO2) nanosheets on the fluorescence of F-PDA nanoparticles and intensively confirmed the quenching mechanism of Förster resonance energy transfer by using transmission electron microscopy, UV–vis, Fourier transform infrared spectroscopy, and fluorescence lifetime experiments. By means of the ALP-triggered generation of ascorbic acid (AA) from the substrate ascorbic acid 2-phosphate, the AA-triggered reduction of MnO2 nanosheets to Mn2+, as well as the clear quenching mechanism of F-PDA nanoparticles by MnO2 nanosheets, we have developed a label-free, low-cost, visual, and facile synthetic fluorescent biosensor for convenient assay of ALP activity. The fluorescent bioassay shows a good linear relationship from 1 to 80 mU/mL (R2 = 0.999), with a low detection limit of 0.34 mU/mL, and the excellent applicability in human serum samples demonstrates potential applications in clinical diagnosis and biomedical research.

CAS / MDL: 66170-10-3 75-59-2
研究领域: 生物化学 · 纳米医学 · 临床诊断
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

Monitoring of glutathione using ratiometric fluorescent sensor based on MnO2 nanosheets simultaneously tuning the fluorescence of Rhodamine 6G and thiamine hydrochloride

Tian Zhang,Zhiwen Gan,Shujun Zhen,Yongmei Hu,Xiaoli Hu

L-glutathione (GSH) which has reducibility and integrated detoxification plays an important role in maintaining normal immune system function. Its abnormal levels are relevant to some clinical diseases. In this work, a facile ratiometric fluorescence sensor for GSH was designed based on MnO 2 nanosheets, Thiamine hydrochloride (VB 1 ) and Rhodamine 6G (R6G). VB 1 could be oxidized into fluorescent ox-VB 1 due to the strong oxidizing property of MnO 2 , and MnO 2 nanosheets simultaneously could quench the fluorescence of R6G based on the inner filter effect (IFE). MnO 2 could react with GSH to form Mn 2+ , which caused its losing oxidizing property and quenching capacity. According to this principle, the concentration of ox-VB 1 diminished, resulting in its fluorescence intensity decreasing at 455 nm and the fluorescence of R6G recovering at 560 nm. Under optimal conditions, the VB 1 -MnO 2 -R6G detection system showed a wide linear range towards GSH in the range of 1.0–300.0 µmol   L −1 with a low detection limit reaching 0.52 µmol   L −1 . Furthermore, the method was also applied in the determination of GSH in human serum.

研究领域: 分析化学 · 纳米技术 · 生物医学工程 · 生物化学
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MICROCHEMICAL JOURNAL · 2022 · IF 5.304

MnO2 nanosheet-assisted ratiometric fluorescent sensor for ascorbic acid based on Pyronin Y and thiamine

Bohong Li,Meiyu Wang,Jingjin Zhao

Ascorbic acid (AA) which can be supplemented by exogenous sources such as food and beverage, plays an important role in human health. Abnormal level of AA in human body usually leads to various diseases. A facile MnO 2 nanosheet-assisted ratiometric fluorescent sensor for AA was constructed in this work. MnO 2 nanosheet (MnO 2 NS) could not only greatly quench the fluorescence of Pyronin Y (PY) by inner filter effect (IFE) but also oxidize non-fluorescent thiamine (vitamin B 1 , VB 1 ) to blue fluorescent thiochrome (oxVB 1 ) by taking advantage of the oxidase-mimicking activity simultaneously. However, MnO 2 NS could be reduced to Mn 2+ in the presence of AA, inhibiting the IFE and oxidase-mimicking activity. According to this principle, the fluorescence intensity of oxVB 1 decreasing at 440 nm and the fluorescence of PY recovering at 560 nm. Under optimal conditions, the MnO 2 NS-PY-VB 1 system showed a wide linear range towards AA in the range of 0.25–110 µM with a low detection limit reaching 0.1 µM. Furthermore, it was also applied for sensitive detection of AA in orange juice and human serum.

CAS / MDL: 7722-84-1
研究领域: 分析化学 · 生物化学 · 传感器与执行器 · 材料科学
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