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MnO2
Nanoscale · 2020 ·Vol. 12 ·期 18 ·10390-10398 · IF 6.895

Enzyme activity-modulated etching of gold nanobipyramids@MnO2 nanoparticles for ALP assay using surface-enhanced Raman spectroscopy

Hua Liu,Lin Wei,Jianhao Hua,Da Chen,Hongmin Meng,Zhaohui Li,Lehui Xiao

The detection of enzyme activity can provide valuable insights into clinical diagnosis. Herein, we synthesize gold nanobipyramids@MnO2 nanoparticles (AMNS) as the surface-enhanced Raman spectroscopy (SERS) substrate for the first time and design a “turn-on” SERS strategy for the detection of enzyme activity without the need for a complicated SERS nanotag preparation process. In the presence of alkaline phosphatase (ALP), 2-phosphate-L-ascorbic acid trisodium salt (AAP) can be hydrolyzed to ascorbic acid (AA), which can etch the shell of AMNS by reducing MnO2 to Mn2+. The cracked MnO2 shell-caused electromagnetic field enhancement from AMNS can give rise to a significant increase in the Raman intensity of the adsorbed molecules (i.e., crystal violet, CV) on the surfaces of nanobipyramids. Thus, the ALP activity can be accurately quantified based on the MnO2 shell thickness dependent Raman signal output from CV. A linear dynamic range from 0.4 to 20 mU mL−1 with a detection limit of 0.04 mU mL−1 is achieved, which is more sensitive than other spectroscopic methods for ALP detection. Because of its advantages of sensitivity, convenience and versatility, this approach provides a new perspective to disease-related biomolecular detection in the future.

研究领域: 生物化学 · 医学诊断 · 纳米技术
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International Journal of Analytical Chemistry · 2019 · IF 1.682

Oxidase-Like Catalytic Performance of Nano-MnO2 and Its Potential Application for Metal Ions Detection in Water

Kai Sun,Qingzhu Liu,Rui Zhu,Qi Liu,Shunyao Li,Youbin Si,Qingguo Huang

Certain nano-scale metal oxides exhibiting the intrinsic enzyme-like reactivity had been used for environment monitoring. Herein, we evaluated the oxidase-mimicking activity of environmentally relevant nano-MnO2 and its sensitivity to the presence of metal ions, and particularly, the use of MnO2 nanozyme to potentially detect Cu2+, Zn2+, Mn2+, and Fe2+ in water. The results indicated the oxidase-like activity of nano-MnO2 at acidic pH-driven oxidation of 2,6-dimethoxyphenol (2,6-DMP) via a single-electron transfer process, leading to the formation of a yellow product. Notably, the presence of Cu2+ and Mn2+ heightened the oxidase-mimicking activity of nano-MnO2 at 25°C and pH 3.8, showing that Cu2+ and Mn2+ could modify the reactive sites of nano-MnO2 surface to ameliorate its catalytic activity, while the activity of MnO2 nanozyme in systems with Zn2+ and Fe2+ was impeded probably because of the strong affinity of Zn2+ and Fe2+ toward nano-MnO2 surface. Based on these effects, we designed a procedure to use MnO2 nanozyme to, respectively, detect Cu2+, Zn2+, Mn2+, and Fe2+ in the real water samples. MnO2 nanozyme-based detecting systems achieved high accuracy (relative errors: 2.2–26.1%) and recovery (93.0–124.0%) for detection of the four metal ions, respectively. Such cost-effective detecting systems may provide a potential application for quantitative determination of metal ions in real water environmental samples.

研究领域: 环境科学 · 生物化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2019 · IF 6.393

A FRET biosensor based on MnO2 nanosphere/copper nanocluster complex: From photoluminescence quenching to recovery and magnification

Tianzi Li,Zhenguang Wang,Dafeng Jiang,Henggang Wang,Wing-Fu Lai,Yunkai Lv,Yongqing Zhai

A Förster resonance energy transfer (FRET)-based biosensor using Cu nanoclusters (NCs) as energy donors and signal magnifiers and MnO 2 nanospheres as both energy acceptors and target recognizers for selective detection of glutathione (GSH) was developed. MnO 2 nanospheres, synthesized through an ultrasonication assisted top down method, can quench the photoluminescence (PL) of Cu NCs through FRET, after forming complex through electrostatic interactions. GSH can recover PL of Cu NCs by triggering the decomposition of complex through digesting MnO 2 nanospheres into Mn 2+ . Additionally, the PL can be further magnified through the host-guest interactions between GSH and Cu NCs, with around 25 times higher than the original intensity and 3 times higher than the initial PL intensity of Cu NCs. Under the optimum conditions, the FRET based sensor can detect GSH in the concentration range from 0 to 140 μM, with a detection limit of 17 μM. Moreover, the proposed method shows a strong anti-interference ability, achieving the sensitive directly detection of GSH in human whole blood samples. Our results provide insights in designing FRET based sensors. Moreover, all the components are nontoxic and biodegradable, demonstrating their potential applications in other fields such as nanomedicine and environmental science.

研究领域: 生物传感 · 分析化学 · 纳米医学
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SENSORS AND ACTUATORS B-CHEMICAL · 2023 · IF 8.4

AND logic-gate-based Au@MnO2 sensing platform for tetracyclines with fluorescent and colorimetric dual-signal readouts

Mingcong Rong,Yi Huang,Xiaoting Zhuang,Yingming Ma,Haijiao Xie,Yanfang Wu,Li Niu

Tetracyclines (TCs) are the most common antibiotic drugs in the world. However, due to the overuse and difficulty of degradation, TCs pollution is becoming a global threat to aquatic and terrestrial biodiversity. Current methods for detecting TCs mainly rely on fluorescent probes or nanomaterials with enzyme-mimicking catalytic activities , which only provide a single signaling mode and are vulnerable to experimental factors. Herein, this study reports the development of an AND logic-gate-based sensing platform for TCs with fluorescent and colorimetric dual-signal readouts using Au@MnO 2 nanoparticles that could be mutually verified for the selective sensing of TCs. It was found that Au@MnO 2 nanoparticles could oxidize TC into its oxidation state (oxTC), resulting in significant green fluorescence emission . Meanwhile, the MnO 2 shell was etched away, and the released Au core nanoparticles gradually aggregated, with a color change from brown to light blue. As such, we established the fluorescence “turn-on” and colorimetric quantitative relationships towards TC with detection limits of 21.9 and 83.3 nM, respectively. Furthermore, Au@MnO 2 -based analytical paper devices were prepared and demonstrated successfully for the fluorescent and colorimetric dual-signal readout detection of TC in real samples. This paper sheds light on the on-site detection of tetracycline using paper-based analytical devices and smartphones.

研究领域: 分析化学 · 环境科学 · 生物医学工程
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Journal of Materials Chemistry A · 2015 ·Vol. 3 ·期 32 ·16695-16707 · IF 7.443

Hybrid MnO2/C nano-composites on a macroporous electrically conductive network for supercapacitor electrodes

Dajun Wu,Shaohui Xu,Mai Li,Chi Zhang,Yiping Zhu,Yuwei Xu,Weiwei Zhang,Rong Huang,Ruijuan Qi,Lianwei Wang,Paul K. Chu

A two-step hydrothermal process is designed to synthesize hybrid MnO2/C nano-composites on a macroporous electrically conductive network (MECN) via a redox reaction in a 30 mM KMnO4 solution with carbon microspheres. The microstructure, surface morphology, and electrochemical properties of the MnO2/C coated on MECN are determined systematically. The MnO2 nanoflakes, which are about 40–200 nm, are deposited regularly on the carbon microspheres coated on the MECN electrode. The MnO2 nano-lamellas offer fast ion transport and adsorption–desorption to/from the MnO2 surface, and the microporous carbon microspheres enhance the electrical storage and ion transfer. The in situ growth of MnO2 on the carbon microspheres on the MECN substrate leads to a small contact resistance and short current transfer length. The materials are demonstrated to be excellent electrodes in supercapacitors boasting a high capacitance of 497 F g−1 at 1 A g−1 with a 1 cm2 electrode and excellent long-term cycling stability over 5000 cycles in 1 M Na2SO4. The MnO2/C/MECN||active carbon/Ni-foam asymmetrical supercapacitors (ASCs) deliver an energy density of 0.50 mW h cm−3 (55.5 W h kg−1 at a power density of 4000 W kg−1) with 87.6% retention of the specific capacitance after 5000 cycles.

研究领域: 材料科学 · 电化学
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BIOSENSORS & BIOELECTRONICS · 2019 · IF 9.518

Ratiometric fluorescence sensor for organophosphorus pesticide detection based on opposite responses of two fluorescence reagents to MnO2 nanosheets

Tiantian Yao,Anran Liu,Yong Liu,Min Wei,Wei Wei,Songqin Liu

The detection of organophosphorus pesticides (OPs) has received considerable attention for their great harm to human beings. Herein, a novel ratiometric fluorescence biosensor was constructed for the determination of OPs by using Scopoletin (SC) and Amplex Red (AR) as probe pairs that have opposite responses to MnO 2 nanosheets (MnO 2 NS). MnO 2 NS possess peroxidase-like catalytic activity , which could quench the fluorescence of SC as well as enhance the fluorescence of the non-fluorescent substance AR by oxidation . In the absence of OPs, acetylcholinesterase (AChE) hydrolyzed acetylcholine chloride (ATCh) into choline (TCh) and acetate. TCh led the decomposition of MnO 2 NS to manganese ions (Mn 2+ ), increasing signal of SC and decreasing signal of AR. In the presence of OPs, the activity of AChE was inhibited and the decomposition of MnO 2 NS was hindered, therefore the fluorescence intensity of SC was weak and the fluorescence intensity of AR had an obvious increase. Moreover, under the optimal conditions, the ratio of fluorescence intensity response recorded on the AR/SC increases with increasing the concentration of DDVP. The method has wider linear range of 5.0 pg/mL ∼500 ng/mL with a detection limit of 1.6 pg/mL, which is superior to previously reported methods. This strategy has also been applied to a visual observation based on the color change of the solution under UV light.

CAS / MDL: 119171-73-2 7722-84-1
研究领域: 分析化学 · 环境科学 · 生物传感技术
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Materials Science & Engineering C-Materials for Biological Applications · 2019 · IF 4.959

Rapid fabrication of electrode for the detection of alpha fetoprotein based on MnO2 functionalized mesoporous carbon hollow sphere

Xiaodong Zhu,Yuxue Dai,Yuanling Sun,Hao Liu,Weiyan Sun,Yanna Lin,Dandan Gao,Rui Han,Xueying Wang,Chuannan Luo

The concentration of alpha-fetoprotein (AFP) rises greatly in patients with liver cancer and it is a challenge to construct a sensitive AFP detection method with wide range. Therefore, an easy and label-free sensing electrochemical platform for AFP detection with wide concentration range had been designed in this work. Firstly, MnO 2 functionalized mesoporous carbon hollow sphere (MCHS@MnO 2 ) with optimal performance was synthesized by regulating experimental conditions and characterized by scanning electron microscope (SEM), high resolution transmission electron microscopy (HRTEM), x-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV), etc. Then, it was immobilized on glassy carbon electrode (MCHS@MnO 2 /GCE) to build an immunosensor for the detection of AFP. The MCHS@MnO 2 /GCE can catalyze decomposition of H 2 O 2 to generate electrochemical signal, and the signal will decrease after capturing AFP. Due to good electrocatalytic activity of MCHS@MnO 2 to H 2 O 2 , the immunosensor achieved indirect detection of AFP with wide sensing range from 0.10 ng mL −1 to 420 ng mL −1 and a detection limit of 0.03 ng mL −1 . Furthermore, the method had been proven to be satisfactory selectivity and reproducibility, and it was successfully applied to determine the content of AFP in human serum samples with satisfactory results. This method is expected to be used for early diagnosis and prognosis examination of liver cancer patients.

研究领域: 生物医学工程 · 肿瘤学 · 分析化学
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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

Construction of silver nanoparticles anchored flower-like magnetic Fe3O4@SiO2@MnO2 hybrids with antibacterial and wound healing activity

Hang Jia,Xiao Zhang,Xuejun Zeng,Rui Cai,Zhouli Wang,Yahong Yuan,Tianli Yue

With the increased risk of wound infection caused by pathogenic bacteria, silver nanoparticles have been considered as potential antibacterial nanosystem. However, the challenge of size control and agglomeration of silver nanoparticles need to be considered. Herein, the application of flower-like silver nanoparticles (Ag NPs) anchored Fe 3 O 4 @SiO 2 @MnO 2 hybrids (Ag/FSM) in the control of pathogenic bacteria and promotion of wound healing were reported. TEM results indicated the ultrafine Ag NPs were uniformly dispersed onto the surface of FSM. In vitro experimental results showed the Minimum inhibitory concentration (MIC) of Ag/FSM against Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ) were 60 and 100 μ g mL −1 , respectively. Furthermore, in vivo investigation in mice demonstrated that the hybrids showed low toxicity and effectively promoted wound healing caused by the infection of E. coli . In summary, the results supported the possibility that Ag/FSM could be considered as an antibacterial agent with potential for the treatment of bacterial infections.

研究领域: 材料科学 · 生物学 · 医学
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Polymers · 2022 ·Vol. 14 ·期 12 ·2504 · IF 4.967

Gradient Porous Structured MnO2-Nonwoven Composite: A Binder-Free Polymeric Air Filter for Effective Room-Temperature Formaldehyde Removal

Zijian Dai,Jianyong Yu,Yang Si

Recently, MnO2-coated polymeric filters have shown promising performance in room-temperature formaldehyde abatement. However, a commonly known concern of MnO2/polymer composites is either MnO2crystal encapsulation or weak adhesion. This work reports a low-cost high-throughput and green strategy to produce binder-free MnO2-nonwoven composite air filters. The production approach is energy saving and environmentally friendly, which combines MnO2crystal coating on bicomponent polyolefin spunbond nonwovens and subsequent heat immobilizing of crystals, followed by the removal of weakly bonded MnO2. The binder-free MnO2-nonwoven composites show firm catalyst-fiber adhesion, a gradient porous structure, and excellent formaldehyde removal capability (94.5% ± 0.4%) at room temperature, and the reaction rate constant is 0.040 min−1. In contrast to the MnO2-nonwoven composites containing organic binders, the HCHO removal of binder-free filters increased by over 4%. This study proposes an alternative solution in producing catalyst/fabric composite filters for formaldehyde removal.Keywords:MnO2;bicomponent polyolefin nonwovens;polymeric filter;binder-free;HCHO removal

CAS / MDL: 50-00-0 9002-89-5
研究领域: 材料科学 · 环境科学
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APPLIED SURFACE SCIENCE · 2022 · IF 7.392

Two-dimensional Fe3O4-MnO2 hollow fiber ceramic membrane for hybrid catalytic ozonation-membrane filtration process for TCH degradation

Tong Ding,Wenxiao Zhao,Yuqing Sun,Shilong Li,Tianxiang Yu,Wenheng Jing

In this work, a novel 2D Fe 3 O 4 -MnO 2 hollow fiber ceramic membrane (HFCM) with both excellent separation performance and high catalytic activity was constructed. The Fe 3 O 4 nanoparticles were deposited on 2D MnO 2 nanoplates to increase the Mn 3+ content, and then the nanoplates were pressure-driven and sintered on the surface of the hollow fiber ceramic supports to obtain 2D Fe 3 O 4 -MnO 2 -HFCMs. Electron spin resonance analysis confirmed that hydroxyl radicals and superoxide radicals played a major role in oxidative degradation and tetracycline hydrochloride (TCH) removal was 86.9 %. Noteworthily, TCH was concentrated on the membrane interface due to the concentration polarization effect, which increases the probability of binding free radicals from the catalytic membrane layer, thus enhancing the catalytic performance and the anti-fouling capability of the membrane. The 2D Fe 3 O 4 -MnO 2 -HFCM can be applied in wastewater treatment due to its superior catalytic ozonation activity and high separation performance.

研究领域: 环境科学 · 材料科学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2023 · IF 22.1

Efficient HCHO oxidation at room temperature via maximizing catalytic sites in 2D coralloid δ-MnO2@GO

Yiheng Li,Tao Dong,Pingli Huang,Jian Ji,Haibao Huang

Airborne formaldehyde (HCHO) in indoor environments causes serious health problems and needs to be efficiently eliminated. However, the efficient and stable catalytic oxidation of HCHO can be hardly achieved at room temperature over transition metal oxides due to the limited exposure of active sites. Herein, δ-MnO 2 @GO catalysts were originally synthesized via a facile in situ growth of δ-MnO 2 on the trace graphene oxide (GO) substrate (1%) and stably exhibited nearly 100% HCHO elimination at room temperature. δ-MnO 2 @GO showed the unique 2D coralloid structure with uniformly dispersed δ-MnO 2 nanorod on planar-structured GO, which greatly enhanced the exposure of catalytic sites and mass transfer of reactants. The abundant surface reactive oxygen species (ROS) and hydroxyl (-OH) groups were rapidly generated from the activation of O 2 and surface-adsorbed water over highly exposed catalytic sites. The ROS and -OH groups cooperated well cooperated to maintain the exceptional catalytic activity and stability towards HCHO degradation. In-situ DRIFTS results showed that catalytic HCHO oxidation predominantly follows the Langmuir-Hinshelwood (L-H) mechanism over the δ-MnO 2 @GO. This study presents a simple yet effective strategy for maximizing exposure to catalytic active sites and rational design of efficient catalysts for indoor HCHO elimination.

研究领域: 环境科学 · 催化材料
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Biomed Research International · 2021 · IF 3.411

The Promotional Effect of Hollow MnO2 with Brucea Javanica Oil Emulsion (BJOE) on Endometrial Cancer Apoptosis

Qin Hu,Shu Zhang,Jun Zhu,Lina Yin,Suping Liu,Xiaowei Huang,Guihao Ke

Endometrial cancer (EC) is a common gynecological malignancy worldwide whose therapy mainly depends on chemotherapy. In past years, an increasing number of studies indicate that hollow MnO2 could serve as a nanoplatform in the drug delivery system. The Brucea javanica oil emulsion (BJOE) has been illustrated to play a vital role in cancers. However, knowledge about the combined effect of H-MnO2-PEG/BJOE in endometrial cancer remains ambiguous up to now. In the present work, we prepared a drug-delivery vector H-MnO2-PEG by chemical synthesis and found that H-MnO2-PEG significantly inhibited cell proliferation in endometrial cancer cells. Moreover, the combination of H-MnO2-PEG/BJOE could repress cell proliferation more efficiently and promote cell apoptosis. Mechanistically, we found that BJOE exerted its role as a promoter of endometrial apoptosis by regulating relative protein expressions. In general, the present study demonstrates that H-MnO2-PEG functions as a critical vector in the tumor microenvironment of endometrial cancer and the significant effect of H-MnO2-PEG/BJOE on cancer cells, suggesting a new paradigm for the treatment of endometrial cancer.

研究领域: 肿瘤学 · 药学 · 纳米技术 · 癌症生物学
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