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Analytical Methods · 2023 ·Vol. 15 ·期 33 ·4059-4065 · IF 3.1

Target-triggered ‘colorimetric-fluorescence’ dual-signal sensing system based on the versatility of MnO2 nanosheets for rapid detection of uric acid

Hao Liang,Danliang Li,Xuebing Zhang,Deshuai Zhen,Yunfei Li,Yuchen Luo,Yuyun Zhang,Dongyun Xu,Lili Chen

A simple dual-signal assay that combined colorimetric and fluorometric strategy for uric acid (UA) rapid detection was designed based on the versatility of facile synthesized MnO2 nanosheet. The oxidization of 3,3′,5,5′-tetramethylbenzidine (TMB) and the fluorescence quenching of quantum dots (QDs) occurred simultaneously in the presence of MnO2 nanosheet. UA could decompose MnO2 nanosheet into Mn2+, resulting in the fluorescence recovery of QDs, along with the fading of the blue color of ox TMB. Based on the principles above, the detection of UA could be realized by the change of the dual signals (colorimetric and fluorometric). The linear range of the colorimetric mode was 5–60 μmol L−1, and the limit of detection (LOD) was 2.65 μmol L−1; the linear range of the fluorescence mode was wide at 5–120 μmol L−1, and the LOD could be as low as 1.33 μmol L−1. The method was successfully used for analyzing UA levels in human serum samples, indicating that this new dual-signal method could be applied in clinical diagnosis.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2023 · IF 10.9

Tunning the bandgap of MnO2 homojunction by building active high-index facet to achieve rapid electron transfer for enhanced photocatalytic sterilization

Tao Zhang,Bo Li,Chaofeng Wang,Shuilin Wu,Shengli Zhu,Hui Jiang,Yufeng Zheng,Zhaoyang Li,Zhenduo Cui,Yu Zhang,Paul K Chu,Xiangmei Liu

Photocatalysis has been a research hotspot in recent years, and the design and modification of photocatalysts have been the key points. Common methods for designing photocatalysts, including constructing heterojunctions and homojunctions, have been developed on the basis of heterojunctions. In this study, two homojunctions of manganese dioxide (MnO 2 ), including a high-index crystal plane homojunction and a general homojunction, are prepared using a stepwise hydrothermal method. Using a capping agent, the high-index crystal surface of the MnO 2 is exposed. It is found that the electron transport efficiency between the two components of the homojunction with high-index planes is higher and the adsorption capacity of the oxygen is stronger, which leads to higher photocatalytic efficiency. In addition, the newly designed high-index homojunction is used for the treatment of bacterial infections, and it kills Staphylococcus aureus ( S. aureus ) and Escherichia coli ( E. coli ) at rates of 99.95% ± 0.04% and 99.31% ± 0.25%, respectively. It also has excellent therapeutic effects on mouse wounds, which implies superb practical application value. This work provides a new strategy for the improved design of homojunctions and the application of photocatalytic materials.

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JOURNAL OF ALLOYS AND COMPOUNDS · 2023 · IF 6.2

Alpha-MnO2 nanoneedle embedded in MgO-chitosan biochar for higher removal of arsenic from groundwater: Co-effects of oxidation and adsorption

Jiangmin Song,Guanxing Huang,Dongya Han,Qinxuan Hou,Ruinan Liu

High performance and high permeability of reactive materials are crucial issues for the remedy of arsenic (As)-enriched groundwater by permeable reactive barriers. The remediation strategy integrating adsorption and oxidation has gained wide concerns due to its deep removal for As(Ⅲ). In this study, a granular bifunctional nanocomposite MgO-Chitosan-MnO 2 (MgO-CS-MnO 2 ) was fabricated as permeable reactive media for the in-situ remediation for high As groundwater. The needle structure of MnO 2 could provide adequate oxidation sites, furthermore, the multilayer porous characteristic of MgO-CS could also meet higher adsorption capacity. As a result, the estimated maximal adsorption capacity of MgO-CS-MnO 2 for As(Ⅲ) reached to 266.61 mg/g and 578.05 mg/g for arsenate (As(Ⅴ)), which are much higher than current similar adsorbents. The adsorption behaviors of As(Ⅲ/Ⅴ) follow pseudo-second-order kinetic model and Freundlich isotherm model, suggesting that both As(Ⅲ) and As(Ⅴ) are mainly chemisorbed onto MgO-CS-MnO 2 . It could perform effectively in a broad range of pH values (3−11), moreover, competing oxyanions (CO 3 2- , NO - , and SO 4 2- ), organic matters (humic acid) and ion strength exert no significant influence towards As remediation. XPS results revealed As(Ⅲ) adsorbed onto composite completely transformed to As(Ⅴ), and removal mechanisms involved oxidation and metal-O-As(Ⅲ/Ⅴ) complexation. In addition, it can be easily regenerated and recycled maintaining an excellent adsorption and oxidative ability. Besides, Column experiment demonstrated this composite column could effectively treat 1300 and 1700 bed volume (BV) of synthetic As(Ⅲ/Ⅴ)-contaminated groundwater, respectively. Therefore, MgO-CS-MnO 2 have a great potential applicability towards high As groundwater improvement as permeable reactive media.

CAS / MDL: 9012-76-4
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MICROCHEMICAL JOURNAL · 2023 · IF 4.8

Enzyme-free colorimetric detection of uric acid on the basis of MnO2 nanosheets - mediated oxidation of 3, 3′, 5, 5′- tetramethylbenzidine

Li Huang,Shangying Qin,Yuanjin Xu,Shiqi Cheng,Jin Yang,Yilin Wang

MnO 2 nanosheets (MnO 2 NSs) were prepared and used as both oxidant of 3, 3′, 5, 5′- tetramethylbenzidine (TMB) and recognizer of UA, a simple colorimetric approach for sensitive detection of uric acid (UA) was established. In the medium of weak acid, MnO 2 NSs exhibited strong oxidation capacity and could oxidize colorless TMB to generate a blue oxidation product (oxTMB) with an absorbance signal. However, the introduction of UA could inhibit MnO 2 NSs - mediated TMB oxidation and reduce the formation of oxTMB, resulting in the blue fading and the absorbance weakening. Under the conditions of incubation time 20 min, pH 3.0, TMB 0.5 mM, and MnO 2 NSs 50 μM, the decrease in absorbance was linearly dependent on UA concentration in the range of 0.5–30.0 μM with a detection limit of 0.21 μM. Furthermore, the approach has been applied for determining UA in human urine samples with recoveries between 93.1 and 102.4 % and relative standard deviation less than 3.0 %.

CAS / MDL: 69-93-2 54827-17-7
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2022 · IF 5.518

Carbon ink modified α-MnO2 as a peroxymonosulfate activator for enhanced degradation of organic pollutants via a direct electron transfer process

Long Cheng,Jiale Bai,Mingyu Wei,Shuaiqi Zhao,Aihua Xu,Xiaoxia Li

Transition metal oxides and carbon can activate peroxymonosulfate (PMS) to decompose organic contaminants. The combination of two materials can facilitate the adsorption of oxidants and pollutants on the catalyst and improve electron transfer efficiency. In this study, carbon nanoparticles-MnO 2 composites (IC-MnO 2 ) were synthesized by coating carbon ink on α-MnO 2 and applied in PMS activation for acid orange 7 (AO7) degradation. The results showed that carbon nanoparticles were uniformly loaded on the α-MnO 2 surface. Complete degradation of AO7 (20 mg/L) can be achieved in 15 min in the IC-MnO 2 /PMS system with a first-order kinetic rate constant of 0.22 min −1 . Electrochemical analysis , quenching experiments, electron paramagnetic resonance , PMS decomposition, and removal of various contaminants demonstrated that AO7 could be efficiently degraded via a direct electron transfer pathway. A galvanic oxidation system containing the salt bridge and two separate cells was further established to confirm the electron transfer mechanism of the catalytic system. The study expands MnO 2 applications by compositing nanocarbon materials in advanced oxidation processes and sheds light on the direct electron transfer mechanism.

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TALANTA · 2022 · IF 6.556

An MnO2-ZIF-67 immobilized acetylcholinesterase method for acetylcholinesterase activity assay and inhibitor screening from Inula macrophylla based on capillary electrophoresis

Jia Liu,Rui Ma,Wei Ha,Hai-Xia Zhang,Yan-Ping Shi

The inhibition of acetylcholinesterase (AChE) from decomposing acetylcholine (ACh) is regarded as a common therapeutic strategy for Alzheimer's disease (AD). Screening AChE inhibitors is of great significance for AD treatment . In this work, AChE was physically absorbed on the synthesized MnO 2 -ZIF-67 through electrostatic interaction for the first time, and the fabricated MnO 2 -ZIF-67 immobilized AChE coupled with capillary electrophoresis (CE) was applied to screening AChE inhibitor. The established MnO 2 -ZIF-67 immobilized AChE with excellent pH, thermal and organic solvents tolerance stability was evaluated by Ellman's method. Huperzine A was used as model inhibitor to investigate the inhibition kinetics of the immobilized AChE, which possess the feasibility and applicability for its inhibitor screening. The screening mechanism of AChE inhibitor was based on the Ellman's method and measured by the changes of 5-thio-2-nitrobenzoic acid (TNB), which was produced by the reaction of thiocholine (TCh) with 5,5-dithiobis-(2-nitrobenzoic acid) (DTNB). Benefiting from the advantages of convenience and high sensitivity, the proposed platform was employed to screen AChE inhibitors from 11 compounds isolated from Inula macrophylla , and macrophyllic acid A (compound 1 ), dibutyl phthalate (compound 2 ) exhibited strong AChE inhibitory activity. Thus, this work not only provides a promising platform for monitoring AChE activity, but also holds great potential for the further exploration of active components with AChE inhibitory activity from Inula macrophylla .

CAS / MDL: 69-78-3
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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.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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ACS Applied Nano Materials · 2022 · IF 6.14

Carbon Nanofibers Coated with Fe3O4 Nanoparticles and MnO2 Nanosheets further Modified with Molecularly Imprinted Polydopamine for Fluorescence Sensing of Carcinoembryonic Antigen

Hongzhi Lu,Shoufang Xu

Nanoparticles are effective tools for signal amplification in chemical sensor construction. Herein, we present molecularly imprinted polymer (MIP)-based sandwich-structured fluorescence sensors for ultrasensitive detection of trace carcinoembryonic antigen (CEA) based on MnO2 nanosheet and MoS2 nanoflower dual signal amplification. MIPs were used as synthetic antibodies and prepared by a surface imprinting method using MnO2 nanosheet-loaded magnetic carbon fibers (CF/Fe3O4/MnO2) as solid supports by the self-polymerization of dopamine. The obtained CF/Fe3O4/MnO2/MIPs can specifically absorb the target CEA from complex samples, which can then be specifically labeled with boronic acid-modified MoS2-curcumin nanotags (BA-MoS2-CUR). Under alkaline conditions, CUR was detached from MoS2 and used as a fluorescence reporter molecule. Due to the high binding capacity of the MnO2 nanosheets and the high loading capacity of the MoS2 nanoflowers, the detection sensitivity of the molecularly imprinted fluorescence sensors was remarkably improved. Specific detection of CEA in the linear range of 0.01 ng/mL–10 μg/mL with a low LOD of 3.5 pg/mL (S/N = 3) was achieved. In addition, based on the MIPs and boronic affinity dual specific recognition ability, the detection selectivity was also improved. Finally, the concentration of CEA in human serum was determined by this approach.

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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2022 · IF 4.831

In-situ formation of MnO2 nanoparticles on Ru@SiO2 nanospheres as a fluorescent probe for sensitive and rapid detection of glutathione

Hongding Zhang,Sifei Wu,Mengwei Sun,Jiaoyu Wang,Man Gao,Hai-Bo Wang,Linxia Fang

Glutathione (GSH)-switched fluorescent assays have appealed much attention due to rapid signal changes of fluorescent probes. However, exposure to exterior environment of fluorescent probe causes photobleaching and premature leakage, leading to low sensitivity and poor photostability. Herein, luminescent SiO 2 nanoparticles encapsulated with Ru(bpy) 3 2+ ( [email protected] 2 ) were designed and synthesized as fluorescent probe to construct a GSH-switched fluorescent assay. The encapsulation of Ru(bpy) 3 2+ in the SiO 2 nanoparticles could effectively prevent the leakage of Ru(bpy) 3 2+ molecules, improving the photostability of probe. The fluorescence of [email protected] 2 nanoparticles was quenched by coating MnO 2 nanoparticles on [email protected] 2 surface ( [email protected] 2 @MnO 2 nanocomposites) through an in situ growth approach, which reduced background of the assay. The MnO 2 nanoparticles not only further inhibited the leakage of Ru(bpy) 3 2+ molecules, but also could serve as a recognition unit of GSH. In the presence of GSH, the MnO 2 nanoparticles on the surface of [email protected] 2 nanoparticles were reduced to Mn 2+ , resulting the fluorescence recovery of [email protected] 2 nanoparticles. Thus, a signal-on fluorescent strategy was constructed for GSH detection. The assay displayed good analytical performance for GSH detection with a low detection limit of 16.2 nM due to excellent fluorescence quenching ability of MnO 2 nanoparticles and special role of [email protected] 2 nanoparticles to block probe leakage. The proposed assay was also applied to measure GSH levels in human serum samples. This work paves a new way to detect GSH with high sensitivity.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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CERAMICS INTERNATIONAL · 2022 · IF 5.532

A free-standing flexible sensor MnO2–Co/rGO-CNT for effective electrochemical hydrogen peroxide sensing and real-time cancer biomarker assaying

Alan Meng,Xiaocheng Hong,Yue Zhang,Wenman Liu,Zhenhui Zhang,Liying Sheng,Zhenjiang Li

Research on flexible biosensors is mainly concentrated on their application in acquiring information on physical signals including temperature, pH, and so on. However, there are hardly any studies on using flexible biosensors for assaying biomolecules and biomarkers caused diseases. Herein, a free-standing flexible sensor is designed for H 2 O 2 sensing and cancer biomarker assaying, in which reduced graphene oxide and carbon nanotubes (rGO-CNT) flexible hybrid film is first obtained through self-assembly, then MnO 2 nanoflowers and Co nanospheres are anchored on rGO-CNT by electrodeposition . rGO-CNT has good flexibility and conductivity . MnO 2 uniformly distributed on rGO-CNT has excellent catalytic performance towards H 2 O 2 . Co not only improve the conductivity, but also supply a second active material for H 2 O 2 sensing. Profiting from these advantages, MnO 2 –Co/rGO-CNT sensor shows an expanded detection range, high sensitivity, low detection limit, excellent repeatability, reproducibility, stability and selectivity. Surprisingly, it can maintain 100% of the original signal after folding 100 times, indicating deformation stability. Moreover, it can real-time monitor H 2 O 2 released by HepG2 cells. The strategy of introducing flexible substrate material and transition metals as well as transition metal compounds provides new insight into the design of flexible electrodes and greatly promote the development of real-time detection of cancer biomarkers.

CAS / MDL: 10034-85-2 56570-89-9
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Advanced Therapeutics · 2022 ·Vol. 5 ·期 12 ·2200108 · IF 5.003

Oxygen-Generated Hierarchical-Structured AuNRs@MnO2@SiO2 Nanocarrier for Enhanced NIR- and H2O2-Responsive Mild-Hyperthermia Photodynamic/Photothermal Combined Tumor Therapy

Wen-Jie Zheng,Ze-Lei Zhou,Qi-Yan Lv,Xiaojie Song,Wen-Xing Zhang,Hui-Fang Cui

Tumor hypoxia greatly restricts photodynamic therapy (PDT) efficiency. Photothermal therapy (PTT) implemented at high temperatures induces local skin burning and surrounding tissue damage. Herein, an near-infrared (NIR)- and H 2 O 2 -double responsive heat- and O 2 -generating core–shell–shell AuNRs@MnO 2 @SiO 2 nanocarrier with Au nanorods (AuNRs) as core and MnO 2 as sandwiched nanolayer is developed to realize enhanced photodynamic/photothermal combined tumor therapy at mild-hyperthermia temperatures. Coating poly- l -lysine on AuNRs is capable of preventing AuNRs from aggregation and facilitating the on-site growth of MnO 2 . The mesoporous SiO 2 nanoshell provides large loading sites for payload indocyanine green (ICG). The MnO 2 nanolayer greatly enhances the singlet oxygen ( 1 O 2 ) generation efficiency of ICG both in testing tubes and in cancer cells. Consequently, the O 2 -enhanced PDT endows the AuNRs@MnO 2 @SiO 2 -ICG nanoparticles (NPs) dramatically stronger antitumor effect both in vitro and in vivo. Their tumor growth inhibition ratio (67.6%) is significantly higher than that of AuNRs@SiO 2 -ICG (28.5%) after one dose intratumor injection and NIR irradiation. Together with their good biosafety, the AuNRs@MnO 2 @SiO 2 -ICG is promisingly translational. The multifunctionality should provide the AuNRs@MnO 2 @SiO 2 NPs a nanocarrier platform for various therapeutic agents to modulate the tumor microenvironment and enhance tumor therapy efficiency.

CAS / MDL: 57-09-0
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Three-dimensional rattan-derived electrodes with directional channels and large mass loadings for high-performance aqueous zinc-ion batteries

Hanrui Zhao,Minfeng Chen,Jiaqi Yu,Bifu Sheng,Xiang Han,Qinghua Tian,Junling Xu,Jizhang Chen

Aqueous zinc-ion batteries (AZIBs) have emerged as prospective candidates for wide-scale energy storage, benefiting from their exceptional reliability and budget-friendliness. To tackle the challenge of limited energy density of AZIBs, it is pivotal to explore cathodes with substantial mass loadings. In this study, rattan is converted into a three-dimensional (3D) current collector with directional channels, high compressive strength, good electrolyte affinity, and superior electrochemical stability through a process involving ultraviolet light irradiation-assisted delignification followed by high-temperature carbonization. Using this current collector and a straightforward slurry pasting method, a 3D MnO 2 cathode featuring substantial loading amount of 10 mg cm −2 for active material can be constructed. This cathode’s rich channel structure allows the carbon nanotube/MnO 2 composite material to establish full contact with the electrolyte, significantly facilitating interfacial charge transfer. The optimized cathode achieves an outstanding areal capacity of 3.65 mAh cm −2 at 0.1 A/g and sustains 1.52 mAh cm −2 at 1 A/g. Besides, the capacity retention remains at 60.2 % after 1000 cycles, even under such large mass loading. Notably, the fabrication procedure of the 3D cathode is simple, and the associated costs are relatively low compared to other 3D cathodes for AZIBs. These findings present an effective strategy for developing cost-effective and high-performance electrodes with large areal capacities, advancing energy storage technologies.

研究领域: 材料科学 · 电化学 · 能源存储
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