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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2015 · IF 2.912

“Switch-On” Fluorescent Sensing of Ascorbic Acid in Food Samples Based on Carbon Quantum Dots–MnO2 Probe

Juanjuan Liu,Yonglei Chen,Weifeng Wang,Jie Feng,Meijuan Liang,Sudai Ma,Xingguo Chen

This work describes a “switch-on” fluorescence approach for sensing of ascorbic acid (AA) in food samples. In the present method, the fluorescence intensity (FL) of carbon quantum dots (CQDs) was first quenched by addition of MnO2 nanosheets through an inner filter effect to form a CQDs-MnO2 probe. When reductive AA was introduced into the quenched CQDs solution, the added MnO2 was destroyed due to the redox reaction between AA and MnO2 nanosheets, and the FL of the system was recovered. Under the optimal conditions, the limit of detection for AA was 42 nM, with a wide concentration linear range of 0.18–90 μM. Furthermore, the as-fabricated fluorescent sensing system was successfully applied to the analysis of AA in fresh fruits, vegetables, and commercial fruit juices samples with satisfactory results.

CAS / MDL: 10424-65-4
研究领域: 分析化学 · 食品安全 · 生物医学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

An Up-conversion signal probe-MnO2 nanosheet sensor for rapid and sensitive detection of tetracycline in food

Rui Liu,Suleiman A. Haruna,Shujat Ali,Jing Xu,Qin Ouyang,Huanhuan Li,Quansheng Chen

The irrational use of tetracycline (TC) poses a serious threat to human health, which calls for the development of efficient and reliable detection methods. Herein, an ideal sensor based on luminescence resonance energy transfer (LRET) between aptamer modified up-conversion nanoparticles as signal probes (donors) and manganese dioxide (MnO 2 ) nanosheets (acceptors) was developed for TC detection in food samples. As a result of van der Waals forces between the nucleobases of the aptamer and the basal plane of MnO 2 nanosheets, the distance of the donors and acceptors was shortened. The emission spectrum of the signal probes and the absorption spectrum of MnO 2 nanosheets overlapped, resulting in LRET, and quenching of up-conversion luminescence. The TC-specific aptamer could fold into a complex conformational structure to provide recognition sites for TC. In the presence of TC, the aptamer was found to preferentially combine with TC due to the stacking of planar moieties, hydrogen bonding interactions and molecular shape complementarity, causing the separation of signal probes and nanosheets, and luminescence recovery. Consequently, a low detection limit of 0.0085 ng/mL was achieved with a wide detection range of 0.01–100 ng/mL. Moreover, the ability of the sensor to detect TC was confirmed in actual food samples and compared with the traditional ELISA with satisfactory results (p > 0.05).

研究领域: 食品安全检测 · 分析化学 · 生物传感
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BIOSENSORS & BIOELECTRONICS · 2019 · IF 9.518

MnO2 nanosheets as the biomimetic oxidase for rapid and sensitive oxalate detection combining with bionic E-eye

Ying Gan,Ning Hu,Chuanjiang He,Shuqi Zhou,Jiawei Tu,Tao Liang,Yuxiang Pan,Dmitry Kirsanov,Andrey Legin,Hao Wan,Ping Wang

Urolithiasis commonly occurs in kidney and ureteral, and may cause local organ/tissue damage, even kidney failure. The incidence of this disease is increasing worldwide, in which calcium oxalate is the major composition forming the urinary calculus. Therefore, to monitor this disease for the prevention and treatment, measuring the oxalate in the urine is of great significance. Here, a rapid and sensitive colorimetric method was developed based on 3,3',5,5'-tetramethylbenzidine-manganese dioxide (TMB-MnO 2 ) nanosheets for oxalate detection. MnO 2 nanosheets acted as an efficient biomimetic oxidase to catalyze the reaction with TMB and oxalate. Pale yellow TMB can be oxidized to blue oxide TMB catalyzed by BSA-stabilized MnO 2 nanosheets, and oxalate can selectively inhibit this reaction by consuming and reacting with MnO 2 nanosheets, thus achieving the quantitative detection of oxalate. Moreover, a home-made bionic electronic-eye (E-eye) system was developed as a portable in-situ detection platform to efficiently measure the oxalate concentrations in 10 s by direct photographing. By optimizing experimental conditions, this method shows a wide linear range (7.8 μM to 250 μM) and a low detection limit (0.91 μM) for oxalate detection. Besides, this method exhibits high selectivity even with 80-fold interfering chemicals. Furthermore, the performance of the method was validated by testing the artificial urine samples, indicating its great potential for monitoring and diagnosis of urolithiasis in point-of-care applications.

研究领域: 生物化学 · 分析化学 · 医学诊断
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TALANTA · 2019 · IF 4.916

Fluorescence sensor for facile and visual detection of organophosphorus pesticides using AIE fluorogens-SiO2-MnO2 sandwich nanocomposites

Xiaoli Wu,Pengsi Wang,Shaoyan Hou,Peiling Wu,Jian Xue

Organophosphorus pesticides (OPs) are frequently for pest control in the agriculture industry. Accumulation of OPs is harmful to the environment and human health. Thus, facile and portable detection of organophosphorus pesticides is of great importance. Among these methods, the fluorescence assay holds the advantages of high sensitivity, simplicity, nondestructive properties. Conventional fluorophores have the drawbacks of poor photostability and low signal-to-noise ratio due to their aggregation-caused quenching drawbacks at high concentration or in the aggregate state. Aggregation-induced emission fluorogens (AIEgens) are one key to develop next-generation fluorescence sensor due to their high emission efficiency in the aggregated state. 1,2-bis[4-(3-sulfonatopropoxyl) phenyl]-1,2-diphenylethene (BSPOTPE) is a typical AIE molecule containing two hydroxyl group . In this study, a fluorescence sensor based on BSPOTPE-SiO 2 –MnO 2 sandwich nanocomposites was fabricated. Thiocholine (TCh), which produced from acetylthiocholine(ATCh) by the hydrolysis of acetylcholinesterase (AChE), can “turn on” the fluorescence sensor. Based on the inhibition effect of OPs on AChE activity and the corresponding “turn off” effect on the fluorescence sensor, an AIE-based assay for OPs determination was developed. The fabricated sensor for paraoxon determination has a good linear relationship in the range of 1–100 μg/L and the LOD of 1 μg/L. Moreover, a simple, convenient fluorescence strip for visual semi-quantitative of OPs was fabricated, indicating this “on-off” fluorescent sensor is promising for on-site and infield detection.

研究领域: 环境科学 · 分析化学 · 生物医学
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NEW JOURNAL OF CHEMISTRY · 2020 ·Vol. 44 ·期 19 ·7838-7848 · IF 3.288

A glutathione-depleted prodrug platform of MnO2-coated hollow polydopamine nanospheres for effective cancer diagnosis and therapy

Liang Dong,Zhiai Xu,Shangjie An,Xiaodan Jia,Wen Zhang,Xiue Jiang

Currently, cancer is regarded as one of the most life-threatening diseases worldwide. To date, much attention has been paid to treating this serious disease. Among various cancer therapies, chemotherapy has been used in the clinic for more than sixty years and is regarded as an ideal choice because of its high efficiency. Herein, a biocompatible and efficient nanoplatform for tumor treatment was fabricated based on manganese oxide-coated hollow polydopamine (HPDA@MnO2). Dihydroartemisinin (DHA), a derivative of the Chinese traditional anti-malarial medicine artemisinin, was selected to be loaded into the cavity of HPDA@MnO2 to form the final nanodrug DHA@HPDA@MnO2. As a unique nanoplatform, DHA@HPDA@MnO2 showed biodegradable and controllable release of DHA and Mn ions upon reaching the tumor sites. It is worth mentioning that the reduced Mn2+ interacts with DHA to generate cytotoxic reactive oxygen species (ROS) which effectively damage proteins and nucleic acids, thereby inducing the death of tumor cells. More importantly, the Mn ions reduced from MnO2 showed selective in vivo magnetic resonance imaging capability in response to the tumor microenvironment. In vitro and in vivo therapy experiments showed that the tumor inhibition of DHA@HPDA@MnO2 was more efficient than that of free DHA, accompanied by negligible side effects; thus, the proposed nanomedicine platform is promising for application in tumor chemotherapy.

研究领域: 纳米技术 · 癌症研究 · 药学 · 生物医学工程
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Journal of Environmental Chemical Engineering · 2020 · IF 4.3

Catalytic ozonation of phenol enhanced by mesoporous MnO2 prepared through nanocasting method with SBA-15 as template

Jianlin Zhang,Tao Zhuang,Shanjun Liu,G.C. Zhang,Kaili Huo

A mesoporous MnO 2 (M-MnO 2 ) was prepared by nanocasting method with SBA-15 as the hard template, and was investigated as an ozonation catalyst. The composition and morphology of the as-prepared MnO 2 were characterized using X-ray diffraction analysis, transmission electron microscopy and surface area analysis. The ordered nanorods with high surface area (100 m 2 g −1 ) helped the mass transport and the active sites exposed, and thus enhanced the efficiency of catalytic ozonation. The adsorption capacity of M-MnO 2 on phenol was about 8 times as high as that of the control MnO 2 (C-MnO 2 ) calculated by the Langmuir adsorption model(10.47 mgg −1 vs 1.20 mgg −1 ). Hydroxyl radical was identified as the main reactive oxygen species, and the hydroxyl radical yield from M-MnO 2 is about 2-fold enhanced compared with that from C-MnO 2 . Benefiting from the high mass transport and abundant active sites exposed, the TOC removal of phenol catalyzed by M-MnO 2 (35%) was much better than that by C-MnO 2 (27%)in 30 minutes.

CAS / MDL: 3317-61-1
研究领域: 环境科学 · 催化化学
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Mechanistic understanding of electron structure regulation by Co Ion-Doping on MnO2 nanocatalyst during optimizing peroxymonosulfate activation

Aihua Xu,Runshi Chen,Wenpei Zhao,Jiajin Lin,Rongrong Hu,Aimal Khan,Wei Li,Xiaoxia Li,Shuaiqi Zhao,Yongcai Qiu

Controlling the electronic structure of the active centre through ion doping modulation has been widely recognized as an effective means to enhance catalytic activity , particularly for MnO 2 -based catalysts. However, existing models fail to fully elucidate the underlying mechanism behind this phenomenon. Here, we utilizes the quenching route to synthesize a variety of MnO 2 -based catalysts (named as Co-MnO 2 -Q) with different Co content, aiming to investigate the catalytic mechanism of MnO 2 in activating peroxymonosulfate (PMS) and establish a correlation between its electronic structure and catalytic activity. Notably, the optimal catalyst (Co-MnO 2 -Q3) exhibited a rate constant (k obs ) for Levofloxacin (LEVO) removal up to 0.105 min −1 , which is eight times higher than that of pure MnO 2 (0.013 min −1 ). Experimental and density functional theory (DFT) investigations have demonstrated that the adsorption of PMS on the constructed catalyst models is an exothermic process, which occurs spontaneously and effectively elongates the O–O bond. Meanwhile, DFT calculations reveal a positive correlation between Co-doped catalyst activity and upward shift of Mn 3d and O 2p band centres. Essentially, Co doping enhances the covalency of Mn–O bonds and increases electron density levels near the Fermi energy, thereby facilitating electron transfer from Mn sites to adsorbed PMS molecules and accelerating both PMS activation and catalytic degradation reactions. This study successfully establishes a descriptor that effectively characterizes the intrinsic activity enhancement of MnO 2 -based catalysts, providing valuable guidance for designing more advanced catalytic systems based on MnO 2 .

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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2019 · IF 4.784

Multi-templates based molecularly imprinted sodium alginate/MnO2 for simultaneous enantiorecognition of lysine, alanine and cysteine isomers

Jie Zhang,Jihong Hu,Datong Wu,Jianfeng Ma,Yongxin Tao,Yong Qin,Yong Kong

Sodium alginate (SA) was electrodeposited onto the surface of a glassy carbon electrode (GCE), and then l -lysine ( l -Lys), l -alanine ( l -Ala) and l -cysteine ( l -Cys) were simultaneously introduced to the surface of SA via electrostatic attractions. γ-MnO 2 film was deposited potentiostatically onto the multi-templates immobilized SA from an aqueous mixture of K 2 SO 4 and MnSO 4 . The templates of l -Lys, l -Ala and l -Cys were then oxidized and removed by cyclic voltammetry (CV) while maintaining the crystalline structures of SA and MnO 2 . Finally, the molecularly imprinted SA/MnO 2 was successfully applied in the simultaneous recognition of the isomers of Lys, Ala and Cys by differential pulse voltammetry (DPV). This work opens a new avenue in the construction of SA-based multi-templates molecularly imprinted systems for electrochemical simultaneous recognition of the isomers of several chiral amino acids .

研究领域: 生物化学 · 材料科学 · 分析化学
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2021 · IF 4.539

Fabrication of porous carbon nanofibril/MnO2 composite aerogels from TEMPO-oxidized cellulose nanofibrils for high-performance supercapacitors

Yu Chen,Yang Hu,Jisi Chen,Yao Lu,Zhenghui Zhao,Abdul Rehman Akbar,Quanling Yang,Zhuqun Shi,Chuanxi Xiong

Supercapacitors have played a key role in energy storage field due to their fast charge-discharge processes and long cycle life. Here, 2,2,6,6-tetramethylpiperidine-1-oxylradical (TEMPO)-oxidized cellulose nanofibrils were carbonized to fabricate carbon nanofibrils (CTOCN). CTOCN/manganese dioxide (MnO 2 ) composite aerogels were then obtained via a simple hydrothermal method , through which MnO 2 strongly attached to the surface of CTOCN, thus maintaining the highly porous 3-dimensional (3D) structure. CTOCN/MnO 2 with MnO 2 content of 20.8 wt% exhibited the most outstanding electrochemical performance . It possessed a maximum specific capacitance of 171.1 F g −1 at 0.5 A g −1 and could still remain 98.4% of the initial value after 5000 cycles at 3 A g −1 . Moreover, an asymmetric supercapacitor using the CTOCN/MnO 2 composite as positive electrode and activated carbon (AC) as negative electrode was assembled. The assembled supercapacitor delivered an energy density of 8.6 W h kg −1 at a power density of 619.2 W kg −1 , and could still remain 4.13 W h kg −1 at a power density of 6.8 kW kg −1 . Additionally, it possessed an excellent cycle life with 99.4% retention of the first cycle after 4500 cycles at 3 A g −1 , suggesting an available method for designing a promising electrode material for supercapacitors.

研究领域: 材料科学 · 能源存储技术
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Surfaces and Interfaces · 2023 · IF 6.2

Carbon/MnO2-x nanofibrous membrane for superior O/W emulsions purification with robust and comprehensive-fouling mitigation

Hongwei Su,Xin Chen,Hua Hu,Xiaofang Zhang,Guilong Yan,Zhenyu Li,Li Wang,Dong Xiang,Chunxia Zhao,Yuanpeng Wu,Yong Du,Jingyu Chen

Filtration membranes (FMs), with high separation efficiency, robust/comprehensive anti-fouling capacities, and highly anti-corrosive performance, are highly desirable for practical complex oil/water emulsions purification, but still a challenge unsolved. Herein, FM containing oxygen vacancy engineered MnO 2-x nanolayer on the outer surface of carbon nanofibrous membrane has been fabricated to address this challenge. Given the existence of oxygen vacancy of the MnO 2-x nanolayer, multiple functions have been realized simultaneously: (i) stronger water affinity than oils; (ii) robust anti-corrosion towards diverse corrosive media (e.g., 1M HCl, 1M NaOH, 10 wt % NaCl, N,N-dimethylformamide, and dimethyl sulfoxide); (iii) efficient degradation of organic dyes (methylene blue and rhodamine B) via photocatalytic process; (iv) comprehensive anti-fouling capacities for oils, organic dyes, bovine serum albumin, and humic acid . Consequently, our FM displays superior separation efficiencies (≥ 99.3 %) towards complex oil/water emulsions with high flux (the maximum: 41,557 ± 350 L m −2 h −1 bar −1 ), robust and comprehensive anti-fouling capacity for different pollutants (e.g., oils, bovine serum albumin, humic acid, and organic dyes) via simple water rinse or photocatalytic degradation to 100 % recover permeation flux for 40 cycles. These outstanding functions make our FM with great potential in practically complex O/W emulsions treatments under harsh conditions.

CAS / MDL: 119171-73-2
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ANALYTICA CHIMICA ACTA · 2023 · IF 6.2

MnO2 nanoflowers based colorimetric and fluorescent dual-mode aptasensor for sensitive detection of aflatoxin B1 in milk

Shuofeng Li,Fangfang Wang,Bin Zhao,Chun Wang,Zhi Wang,Qiuhua Wu

Aflatoxin B1 (AFB1) with tremendous toxic effects has caused a serious threat to food security. Accurate quantification of AFB1 in food can effectively prevent the risk of human intake of AFB1. Herein, a colorimetric and fluorescent dual-mode aptasensor for accurate and sensitive detection of AFB1 has been developed based on MnO 2 nanoflowers (MnO 2 NFs) for the first time. MnO 2 NFs could catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB) into blue oxidation product (TMBox) by H 2 O 2 , which would be used for visible detection of AFB1. Simultaneously, MnO 2 NFs can be served as a signal amplifier and reduced by ascorbic acid to generate lots of Mn 2+ which would quench the fluorescence of calcein for fluorescent detection of AFB1. Both colorimetric and fluorescent methods have been successfully applied for determination of AFB1 in milk samples with satisfactory results. The proposed dual-mode detection method with high detection sensitivity and accuracy showed great promise for monitoring AFB1 in food.

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Regenerative Biomaterials · 2023 · IF 6.7

Mesoporous polydopamine delivery system for intelligent drug release and photothermal-enhanced chemodynamic therapy using MnO2 as gatekeeper

Wang Zhaoyang,Li Zekai,Shi Yuehua,Zeng Leyong

The non-specific leakage of drugs from nanocarriers seriously weakened the safety and efficacy of chemotherapy, and it was very critical of constructing tumor microenvironment (TME)-responsive delivery nanocarriers, achieving the modulation release of drugs. Herein, using manganese dioxide (MnO2) as gatekeeper, an intelligent nanoplatform based on mesoporous polydopamine (MPDA) was developed to deliver doxorubicin (DOX), by which the DOX release was precisely controlled, and simultaneously the photothermal therapy (PTT) and chemodynamic therapy (CDT) were realized. In normal physiological environment, the stable MnO2 shell effectively avoided the leakage of DOX. However, in TME, the overexpressed glutathione (GSH) degraded MnO2 shell, which caused the DOX release. Moreover, the photothermal effect of MPDA and the Fenton-like reaction of the generated Mn2+ further accelerated the cell death. Thus, the developed MPDA-DOX@MnO2 nanoplatform can intelligently modulate the release of DOX, and the combined CDT/PTT/chemotherapy possessed high-safety and high-efficacy against tumors.

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