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Cancer Nanotechnology · 2023 ·Vol. 14 ·期 1 ·1-19 · IF 5.7

Boosting immunogenic cell death via hollow MnO2-based multiple stimuli-responsive drug delivery systems for improved cancer immunotherapy

Wu Yueyao,Wang Runtian,Shen Peiliang,Zhou Weijia,Chen Chao,Yang Kaiyong,Yang Jingjing,Song Yujun,Han Xin,Guan Xiaoxiang

Cancer treatment by inducing tumor cell immunogenic cell death (ICD) is critical for tumor therapy. However, ICD activation by single pathway is often limited in practical application due to its low efficiency. In addition, the low pH and anoxic microenvironments in solid tumors greatly limit the effective activation of ICD. Herein, hollow manganese dioxide (H-MnO2) nanomaterials were selected to load both Mitoxantrone (MTZ) and Chlorin e6 (Ce6) due to its hollow structure and ability to release drugs in the acidic environments. Thus, the synergy of photodynamic therapy (PDT), photothermal therapy (PTT) and chemotherapy can induce the process of immunogenic cell death, stimulate the maturation of dendritic cells (DCs), and activate the immune response to kill tumor cells dramatically. Efficient immunotherapeutic effects were obtained when MnO2-C/M-HA was given intravenously to 4T1 tumor-bearing BALB/c mice with 660 nm near-infrared laser irradiation. This study overcame the limitations of monotherapy and provided a multifunctional platform for tumor immunotherapy.

CAS / MDL: 108-46-3 78-10-4
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2023 · IF 7.2

Ag nanoparticle-loaded to MnO2 with rich oxygen vacancies and Mn3+ for the synergistically enhanced oxygen reduction reaction

Minghua He,Zulhumar Turup,Xuekun Jin,Fengjuan Chen

MnO 2 is considered to be one of the most promising electrocatalysts for oxygen reduction reactions (ORR) in alkaline media and can be applied to various electrochemical energy conversion and storage devices. However, it is limited by the relatively slow kinetics of the cathodic electrochemical reactions . In addition, it is difficult to control the presence state of Ag during the modification of MnO 2 . To this end, an efficient ORR electrocatalyst of Ag nanoparticles supported by MnO 2 nanorods was successfully synthesized by using NH 3 ·H 2 O as a complexing agent to inhibit the Ag +  intercalating into the tunnels of MnO 2 . The half-wave potential ( E 1/2 ) and limiting current density ( J lim ) of the obtained Ag/MnO 2 electrocatalysts are 0.81 V and −5.6 mA cm −2 , respectively, showing comparable ORR catalytic activity to commercial Pt/C catalysts. The excellent catalytic performances can be attributed to the presence of abundant oxygen vacancies and Mn 3+ species on the MnO 2 surface, as well as the synergistic effect between MnO 2 substrates and Ag nanoparticles. Among them, oxygen vacancies enhances the adsorption of O 2 , Mn 3+ facilitates the displacement of O 2 2− /OH − , MnO 2 inhibits the accumulation of peroxide species to improving the oxygen environment on the Ag surface and Ag accelerates the electron transfer in the whole process. This work provides a useful guide for the design of efficient Mn-based ORR electrocatalysts.

CAS / MDL: 31175-20-9
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JOURNAL OF HAZARDOUS MATERIALS · 2023 · IF 13.6

Insight into the electron transfer regime of periodate activation on MnO2: The critical role of surface Mn(IV)

Liwei Yang,Fashan Yang,Heng Zhang,Hongyu Zhou,Mengfan Luo,Yunmei Liu,Chuanliang Zhao,Lu Zheng,Bo Lai

At present, the potential mechanism of manganese oxide (MnO 2 ) activation of PI and the key active sites of PI activation are still unclear and controversial. To this end, three different crystal forms of MnO 2 were prepared in this study and used to activate PI to degrade pollutants. The results showed that different crystal types of MnO 2 showed different catalytic abilities, and the order was γ-MnO 2 > α-MnO 2 > β-MnO 2 . Through quenching experiments, EPR tests, Raman experiments and in situ electrochemical experiments, it has been confirmed that electron transfer-mediated non-free radical process is the main mechanism of pollutant degradation , in which the active substance is the highly active metastable intermediate complex (MnO 2 /PI*). Hydroxyl radical (HO • ), superoxide radical (O 2 •− ), singlet oxygen ( 1 O 2 ) and iodine radical (IO 3 • ) did not participate in pollutant degradation. The quantitative structure-activity relationship analysis confirmed that the catalytic performance of MnO 2 was highly positively correlated with the surface Mn(IV) content, which indicated that the surface Mn(IV) site was the main active site. Overall, this study will be of great help to the design and application of manganese dioxide activation for periodate degradation of pollutants.

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NEW JOURNAL OF CHEMISTRY · 2022 ·Vol. 47 ·期 3 ·1094-1104 · IF 3.925

Synthesis of dual function Fe3O4@MnO2@HKUST-1 magnetic micromotors for efficient colorimetric detection and degradation of hydroquinone

Hui Luo,Yang Han,Kaiyuan Hu,Jia Li,Dickon H. L. Ng,Xiaodi Ma,Kairui Luan,Mingkang Yang

Herein, we demonstrate a novel Fe3O4@MnO2@HKUST-1 magnetic micromotor with excellent peroxidase-like activity for highly efficient colorimetric detection and degradation of hydroquinone. Such micromotors had unique flower-like morphology with highly exposed active sites. The resulting MnO2-based micromotor was propelled by O2 bubbles generated from hydrogen peroxide fuel catalyzed by MnO2, and the velocity could be adjusted by the H2O2 fuel concentration. The self-propelled motion of the Fe3O4@MnO2@HKUST-1 could effectively increase the collision probability between active sites and pollutant molecules, and thus, enhanced the sensitivity of the colorimetric detection as well as the degradation efficiency. These excellent results confirm that this Fe3O4@MnO2@HKUST-1 micromotor has good prospects for future use in water treatment applications.

CAS / MDL: 54827-17-7 554-95-0
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Biomaterials Science · 2023 ·Vol. 11 ·期 6 ·2243-2252 · IF 6.6

A dual-modal ROS generator based on multifunctional PDA–MnO2@Ce6 nanozymes for synergistic chemo-photodynamic antibacterial therapy

Anni Cui,Ying Bao,Haitao Xu,Xin Mu,Xiahua Zhong,Wynn Wee,Fanqi Wu,Guiye Shan

The rapid emergence of drug-resistant bacteria has attracted great attention to exploring advanced antibacterial methods. However, single-modal antibacterial therapy cannot easily eliminate drug-resistant bacteria completely due to its low efficacy. Therefore, it is essential to achieve multi-modal antibacterial therapy effectively. Herein, a dual-modal ROS generator was designed based on photosensitive PDA–MnO2@Ce6/liposome (PMCL) nanozymes for synergistic chemo-photodynamic therapy. PMCL nanozymes adhere to bacteria through liposome–membrane fusion. Meanwhile, PMCL catalyzes endogenous hydrogen peroxide (H2O2) to generate hydroxyl radicals (˙OH) and singlet oxygen (1O2) under laser irradiation. Furthermore, the photothermal effect can accelerate the generation of ROS. Based on dual-enzyme activities (mimicking peroxidase and catalase) and photodynamic properties, PMCL achieves powerful antibacterial efficacy and mature bacterial biofilm eradication. With the synergistic chemo-photodynamic effects, bacterial populations decrease by >99.76% against Gram-positive S. aureus and Gram-negative E. coli. Notably, the synergistic antibacterial properties of PMCL nanozymes are further explored using a mouse wound model of S. aureus infection. This work fabricated an efficient dual-modal ROS generator to kill bacteria, further providing a new strategy for treating wound infection.

CAS / MDL: 5471-63-6 10602-37-6
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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.

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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
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Catalysis of MnO2-cellulose acetate composite films in DBD plasma system and sulfamethoxazole degradation by the synergistic effect

Huihui Zhang,Sisi Xiao,Yansheng Du,Shilin Song,Kun Hu,Yuyue Huang,Huijuan Wang,Qiangshun Wu

Herein, dielectric barrier discharge (DBD) plasma and MnO 2 -cellulose acetate (MnO 2 /CA) composite films was coupled together to degrade sulfamethoxazole (SMX) in water. The MnO 2 /CA composite films were firstly prepared successfully though heating blending method in this study and then characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Raman spectra, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TG). Catalytic effect of the MnO 2 /CA films was investigated by comparing the removal percentages, the kinetic constants, the energy utilization efficiencies ( G 50 ) as well as the COD and TOC removal during the SMX degradation in the DBD plasma system with or without the MnO 2 /CA films addition under different reaction conditions. The optimal catalytic performance was obtained by adding the 3% MnO 2 /CA films into the DBD plasma system and the alkaline solution condition was favorable for the SMX degradation. After four times using, the MnO 2 /CA composite films still maintained the catalytic activity. Catalytic mechanism of the MnO 2 /CA films was speculated by analyzing the changes of solution pH and conductivity during the reaction, concentrations of the formed O 3 and H 2 O 2 in water and the generated active species ( 1 O 2 and ·OH) in both the DBD plasma system and the DBD-MnO 2 /CA films system. The quenching test was also carried out to figure out the important effect of the ·O 2 − , 1 O 2 and ·OH for the SMX degradation in the synergistic system. Finally, LC-MS was used to analyze the main intermediates generated during the SMX degradation and the possible degradation pathways were accordingly speculated. The research could provide a new direction for the development and application of the DBD plasma technology as well we the composite films catalyst.

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NEW CARBON MATERIALS · 2022 · IF 3.7

A high-frequency flexible symmetric supercapacitor prepared by the laser-defocused ablation of MnO2 on a carbon cloth

Guang-yao Zhao,Fang-cheng Wang,Ming-jie Liu,Yi-ming Sui,Zhuo Zhang,Fei-yu Kang,Cheng Yang

The rapid development of flexible electronics has produced an enormous demand for supercapacitors. Compared to batteries, supercapacitors have great advantages in terms of power density and cycling stability. They can also respond well on a time scale of seconds, but most have a poor frequency response, and behave more like pure resistors when used at high frequencies (e.g., above 100 Hz). It is therefore challenging to develop supercapacitors that work at a frequency of over 100 Hz. We report a high-frequency flexible symmetrical supercapacitor composed of a MnO 2 @carbon cloth hybrid electrode (CC@MnO 2 ), which is synthesized by the defocused-laser ablation method. This CC@MnO 2 -based symmetric supercapacitor has an excellent specific areal capacitance of 1.53 mF cm −2 at a frequency of 120 Hz and has good cycling stability with over 92.10% capacitance retention after 100 000 cycles at 100 V s −1 . This remarkable electrochemical performance is attributed to the combined effect of the high conductivity of the 3D structure of the carbon cloth and the exceptional pseudo-capacitance of the laser-produced MnO 2 nanosheets. The defocused laser ablation method can be used for large-scale production using roll-to-roll technology, which is promising for the wide use of the supercapacitor in high-frequency electronic devices.

CAS / MDL: 638-38-0
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Journal of Environmental Chemical Engineering · 2022 · IF 7.968

In situ construction of MnO2 @CeO2 catalyst with a cake-like hierarchical nanosheets structure for efficient toluene oxidation

Pijun Gong,De Fang,Feng He,Junlin Xie,Haitao Wu

Cake-like MnO 2 @CeO 2 catalyst with hierarchical nanosheets structure has been successfully constructed by in situ methods. The relationship between structure and activity of the MnO 2 @CeO 2 catalyst was characterized using various analytical techniques. It is identified that rich surface oxygen species and better reducibility were generated due to the strong synergistic effect between MnO 2 and CeO 2 , and hence nearly T 90 toluene conversion can be obtained for the 10%-MnO 2 @CeO 2 catalyst under 240–300 °C. In addition, it is found that after loading MnO 2 on the multi-layer CeO 2 support to form a hierarchical cake-like structure, the oxygen vacancies, Ce 3+ /Ce 4+ and BET surface area of MnO 2 @CeO 2 increased significantly, which is beneficial to toluene adsorption and reaction. Furthermore, the in situ DRIFTS study demonstrated that the lattice oxygen and surface oxygen both participate in the toluene oxidation , whereas surface active oxygens adsorbed on the oxygen vacancies will lead to deep oxidation by forming abundance intermediates.

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ACS Sustainable Chemistry & Engineering · 2022 · IF 9.224

Dendritic Mesoporous Silica Nanoparticle-Tuned High-Affinity MnO2 Nanozyme for Multisignal GSH Sensing and Target Cancer Cell Detection

Yuan Zhang,Weina Meng,Xiao Li,Dong Wang,Shaomin Shuang,Chuan Dong

Development of multifunctional enzymatic nanomaterials with rapid and sensitive characteristics for glutathione determination is extremely urgent for early cancer diagnosis. Herein, a core–shell ultrasensitive nanozyme (denoted as CPT/DM-FA) for triple-mode glutathione sensing and specific in vitro cancer detection is constructed. The dendritic mesoporous silica nanoparticle (DMSN) core not only acts as a camptothecin carrier, but also offers the nanoplatform to synthesize the MnO2 shell. Due to the DMSN-regulated high dispersion of MnO2, the atomic utilization efficiency of MnO2 is surprisingly enhanced, and leads to notable enzymatic activity with Km 0.136 μM and Vmax 0.59 μM/s. In addition, by integrating the quenching ability based on fluorescence resonance energy transfer and oxidase-mimic-mediated 1O2, O2– generation of MnO2, the fluorescence, UV–vis, and colorimetric method for glutathione sensing is established with a comprehensive linear range from 2 to 250 μM and a limit of detection of 0.654 μM. Besides, after surface folic acid modification, the CPT/DM-FA could also specifically detect cancer cells from 25 to 1 50 000 through the color reaction of 3,3′,5,5′-tetramethylbenzidine. We believe this nanozyme could afford a potential strategy to amplify the nanozyme activity for further biomedical applications.

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JOURNAL OF MATERIALS SCIENCE · 2022 ·Vol. 57 ·期 16 ·7909-7922 · IF 4.682

An ultrasensitive MnO2-S,O-doped g-C3N4 nanoprobe for “turn-on” detection of glutathione and cell imaging

Chai Chaofan,Yang Xuefang,Yang Xiaohua,Dong Chuan,Bian Wei,Choi Martin M. F.

Abstract The utilization of nanomaterial-based probes in detecting glutathione (GSH) and cell imaging has aroused extensive attention owing to the excellent properties of nanoprobes. Herein, we have synthesized manganese dioxide-S, O co-doped graphitic carbon nitride quantum dots (MnO 2 -S, O-CNQDs) nanocomposite by in situ synthesis of MnO 2 nanosheets in S,O-CNQDs dispersion solution. It was found that GSH could specifically bind to MnO 2 -S, O-CNQDs so that the fluorescence of S, O-CNQDs could be recovered. As such, a “turn-on” MnO 2 -S, O-CNQDs nanoprobe can be fabricated and applied to rapidly determine trace amounts of GSH. Under the optimal conditions, MnO 2 -S, O-CNQDs shows sensitive response to GSH in the range 10–270 μM with a detection limit of 0.307 μM ( S / N  = 3). The developed MnO 2 -S, O-CNQDs probe has demonstrated great potential to detection of GSH in biological samples and glutathione injections. What is more, MTT assay indicates that MnO 2 -S, O-CNQDs has low biotoxicity. The non-fluorescence MnO 2 -S, O-CNQDs reacts with GSH to recover the fluorescence of S, O-CNQDs in HepG2 cells. Thus, the “turn-on” fluorescence change of MnO 2 -S, O-CNQDs offers a potentially useful tool to monitor GSH of cancer cells. Graphical Abstract

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