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MnO2
Drug Delivery and Translational Research · 2022 ·Vol. 12 ·期 11 ·2678-2692 · IF 5.671

Construction and evaluation of curcumin upconversion nanocarriers decorated with MnO2 for tumor photodynamic therapy

Chen Xinru,Li Quandong,Huang Zipeng,Lin Wen,Ma Yan

The limited tissue penetration depth and tumor hypoxic microenvironment have become the two pivotal obstacles that alleviate the antineoplastic efficacy in tumor photodynamic therapy (PDT). In the research, MnO 2 -decorated upconversion nanoparticles (UCSMn) have been designed to generate certain oxygen within the solid tumor, and also increase the light penetrating depth due to the optical conversion ability derived from upconversion nanoparticles. Furthermore, upconversion nanoparticles as the inner core are coated by mesoporous silica for the loading of curcumin as photosensitizer and chemotherapeutics, and then a MnO 2 shell is proceeding to grow via redox method. When reaching the tumor tissue, the MnO 2 nanoshells of UCSMn could be rapidly degraded into manganese ions (Mn 2+ ) owing to the reaction with H 2 O 2 in acidic tumor microenvironment, meanwhile producing oxygen and facilitating curcumin release. Once the tumor is illuminated by 980 nm light, the upconversion nanoparticles can transform the infrared light to visible light of 450 nm and 475.5 nm, which can be efficiently absorbed by curcumin, and then produce singlet oxygen to induce tumor cell apoptosis. Curcumin played a dual role which can not only be acted as a photosensitizer, but also a chemotherapeutic agent to further reinforce the antitumor activity. In short, the intelligent nanostructure has the potential to overcome the above-mentioned shortcomings existed in PDT and eventually do work well in the hypoxia tumors. Graphical abstract MnO 2 -decorated upconversion nanoparticle to solve the tissue penetration and tumor hypoxic microenvironment for tumor photodynamic therapy

研究领域: 纳米技术 · 癌症治疗 · 生物医学工程 · 药学
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APPLIED CATALYSIS B-ENVIRONMENTAL · 2022 · IF 24.319

Mechanochemically tailoring oxygen vacancies of MnO2 for efficient degradation of tetrabromobisphenol A with peroxymonosulfate

Sylvestre Ndayiragije,Yifan Zhang,Yuqi Zhou,Zhou Song,Nan Wang,Tetsuro Majima,Lihua Zhu

Oxygen vacancy (V O ) engineering can efficiently improve the catalytic activity of metal oxides. This work developed a solvent-free mechanochemical method to tailor V O levels on the surface of commercial MnO 2 under ambient conditions. After a typical ball milling treatment at 350 rpm for 20 min, the obtained V O -rich MnO 2 activated peroxymonosulfate (PMS) to completely degrade tetrabromobisphenol (TBBPA) with a pseudo-first-order rate constant of 0.21 min −1 , being 22 times larger than that for non-milled MnO 2 . 18 O-labeling tests confirmed that singlet oxygen was generated from both PMS and lattice oxygen of MnO 2 as dominant active species for the TBBPA degradation. It was clarified that the catalytic activity of MnO 2 depends on not only V O levels, but also the local environment of V O , i.e., V O -associated cations. The Mn 4+ /Mn 3+ redox couple is more important than Mn 3+ /Mn 2+ , and V O improves the oxygen mobility in/on MnO 2 and Mn 4+ /Mn 3+ redox reactions for the activation of PMS.

CAS / MDL: 79-94-7
研究领域: 环境科学 · 催化化学
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CELLULOSE · 2022 ·Vol. 29 ·期 13 ·7353-7363 · IF 6.123

In situ growth of MnO2 on pDA-templated cotton fabric for degradation of formaldehyde

Zhang Yali,Zhao Zhong,Li Daiqi,Cai Guangming,Tang Xiaoning,Li Wenbin,Cheng Deshan,Wang Xin

Degradation of formaldehyde (HCHO) in interior decoration has been an urgent issue due to its toxicity nature and potential threats to human health. In this work, manganese dioxide nanoparticles (MnO 2 NPs) were in situ grown on the polydopamine (pDA)-templated cotton fabrics for environmentally friendly HCHO degradation applications. The morphology, elemental composition, and crystal structure of the cotton/pDA/MnO 2 were characterized by scanning electron microscopy–energy dispersive X-ray spectrum, Fourier transform infrared, X-ray diffractometer and X-ray photoelectron spectroscopy, respectively. The degradation of HCHO by the as-developed cotton/pDA/MnO 2 was measured in a self-made quartz reactor, and the stability of adsorption was evaluated by cyclic experiments. The results showed that the HCHO removal efficiency reached to 100% within 20 min after three cycles, suggesting that the as-prepared fabrics exhibited good stability for the degradation of HCHO. The development of MnO 2 NPs coated fabrics provides new strategies in degradation HCHO in interior decoration.

研究领域: 材料科学 · 环境科学
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Materials Today Communications · 2022 · IF 3.662

One-step preparation of MnO2 electrode for secondary aqueous zinc ion batteries by electrodeposition

Qihang Dai,Longyan Li,Bingjie Hu,Yiyang Jia,Tiancheng Tu,Tuan K.A. Hoang,Mingdao Zhang,Li Song

As the cathode material , manganese oxides have been a research hotspot in the secondary aqueous zinc ion batteries due to their various advantages such as multiple crystal structures, low-cost, and environmentally friendliness. However, most of the current research focuses on the material modification, and little research has been done on the development of synthesis methods. Herein, a MnO 2 electrode is directly prepared by a one-step electrodeposition method from the aqueous solution containing manganese ions. It is found that a porous electrode with the nano MnO 2 particulates as the active material can be obtained from the 0.3 M MnSO 4 solution. The porous structure provides numerous reaction sites that facilitates the electrochemical processes on the electrode. As a result, it delivers the area specific capacity of 0.35 mAh cm −2 at the current density of 0.5 mA cm −2 and a high coulombic efficiency of 100% after 1000 cycles at 1.5 mA cm −2 . These excellent electrochemical properties suggest that this convenient one-step electrodeposition method can be effectively applied for the large-scale commercialization of the aqueous zinc ion batteries.

CAS / MDL: 638-38-0 7785-87-7
研究领域: 材料科学 · 电化学
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JOURNAL OF HAZARDOUS MATERIALS · 2022 · IF 14.224

Tributyl phosphate degradation and phosphorus immobilization by MnO2: Reaction condition optimization and mechanism exploration

Wenhua Tong,Jiepeng Wang,Xinhang Du,Xuqian Wang,Yabo Wang,Yongkui Zhang

The treatment of tributyl phosphate (TBP) extractant waste from specific industry, eg., nuclear industry, is a great challenge due to its stability and high environmental risk of phosphorus-containing species releasing. Inspired by chemical looping combustion (CLC) technology , a MnO 2 -assisted thermal oxidation strategy is proposed for TBP degradation and simultaneously P immobilization. Under recommended reaction conditions of 220 °C, 10 g MnO 2 mL −1 TBP and 3 h reaction duration, a high P immobilization efficiency of 93.99% is achieved. Material characterization results indicate that P is mainly immobilized in the form of Mn 2 P 2 O 7 , which greatly reduces the environmental risk of P-containing species. TBP degradation intermediates are further identified by thermogravimetric-gas chromatography-mass spectrometry (TG-GC-MS), liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS), which facilitates understanding of reaction mechanisms as well as proposing possible pathways of TBP degradation. It is suggested that MnO 2 provides essential oxygen as oxygen carrier for flameless combustion. Meantime, MnO 2 reduction leads to the generation of Mn(III) species. The existence of oxygen vacancy in MnO 2 also facilitates •O 2 - radical generation. Under flameless combustion and attacks of Mn(III) and •O 2 - , TBP is firstly degraded into intermediates and finally mineralized into CO 2 and H 2 O, while P is mainly immobilized as pyrophosphate.

CAS / MDL: 126-73-8
研究领域: 环境科学 · 化学工程
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Materials · 2021 ·Vol. 14 ·期 16 ·4402 · IF 3.623

Removal Performance and Mechanism of Benzo(b)Fluorathene Using MnO2 Nanoflower/Graphene Oxide Composites

Qingqing Cao,Siqi Lu,Wenjun Yin,Yan Kang,Naihao Yang,Yudong Hou,Zizhang Guo

High-ring polycyclic aromatic hydrocarbons (PAHs, Benzo[b]fluorathene (BbFA), etc.) are difficult to biodegrade in the water environment. To address this issue, an innovative method for the preparation of MnO2nanoflower/graphene oxide composite (MnO2NF/GO) was proposed for adsorption removal of BbFA. The physicochemical properties of MnO2NF/GO were characterized by SEM, TEM, XRD, and N2adsorption/desorption and XPS techniques. Results show that the MnO2NF/GO had well-developed specific surface area and functional groups. Batch adsorption experiment results showed that adsorption capacity for BbFA was 74.07 mg/g. The pseudo-second-order kinetic model and Freundlich isotherm model are fitted well to the adsorption data. These show electron-donor-acceptor interaction; especially π-π interaction and π complexation played vital roles in BbFA removal onto MnO2NF/GO. The study highlights the promising potential adsorbent for removal of PAHs.Keywords:MnO2nanoflower;graphene oxide;PAHs;adsorption

研究领域: 环境科学 · 材料科学
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2021 ·Vol. 168 ·期 8 ·080524 · IF 4.316

Flexible Supercapacitors Based on CNT/MnO2-BP Composite Yarn Synthesized by In Situ Reduction

Qiang Zhou,Gongbin Tang,Xiuhang Chen,Fenghua Su

Solid-state flexible supercapacitors are considered significant prospective energy storage devices, and carbon nanotube (CNT) yarn is an ideal electrode material for constructing linear flexible supercapacitors because of its high electrical conductivity and flexibility. However, the relatively low specific capacitance and energy density of a supercapacitor made of pure CNT yarn limits its application. Here, we prepared a CNT/MnO2-BP composite yarn via a facile one-step liquid deposition method by the innovative introduction of few-layer black phosphorous (BP) nanosheets. The redox reaction between the BP and the potassium permanganate forms MnO2 and an electrolyte of phosphorus acids (HxPOy). The two-ply yarn supercapacitor composed of the CNT/MnO2-BP composite yarn shows excellent electrochemical properties with a volumetric capacitance of 441.79 F cm−3 at the scanning rate of 0.01 V s−1 and an energy density of 9.82 mWh cm−3 at a power density of 441.79 mW cm−3. Herein, this work provides a way to improve the electrochemical performance of CNT yarn-based supercapacitors that can act as flexible energy storage devices for wearable electronics.

CAS / MDL: 7723-14-0
研究领域: 材料科学 · 能源存储技术
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ENERGY & FUELS · 2021 · IF 3.605

Strongly Coupled MnO2 Nanosheets/Silver Nanoparticles Hierarchical Spheres for Efficient Oxygen Reduction Reaction Electrocatalysis

Longchao Wang,Dingding Kong,Fengshang Chen,Lisan Cui,Yezheng Cai,Hongqiang Wang,Xinxian Zhong,Youguo Huang,Qingyu Li,Zhaoling Ma,Sijiang Hu

Manganese dioxide (MnO2) represents a promising oxygen reduction reaction (ORR) electrocatalyst, but its catalytic activity is largely limited by the essentially low electronic conductivity and large geometric size. Herein, hierarchical ε-MnO2 nanosheets (MnO2-H) strongly coupled with silver nanoparticle spheres (Ag NPs) were developed. The introduced Ag NPs can not only enhance the electronic transfer but also tune the electronic structure of MnO2 and act as active sites for ORR. Owing to the large electrochemically active surface area, good mass/electronic transfer, and a strong coupled interface between MnO2-H and Ag NPs, the optimal Ag-MnO2-H-1.53 showed much higher catalytic activity than MnO2-H, Ag microparticles, and commercial Pt/C catalyst for ORR. Moreover, Ag-MnO2-H-1.53 displayed robust catalytic stability with negligible shift in the half-wave potential after 5000 cycles. As a cathode catalyst, a homemade zinc–air battery (ZAB) based on Ag-MnO2-H-1.53 showed a high open circuit voltage (1.52 V), maximum peak power density (120.2 mW/cm2), and specific capacity (646 mAh/g) superior to those of Pt/C-based ZAB (1.48 V, 82.3 mW/cm2, and 612 mAh/g), along with a long lifetime. This work highlights the significance of strong interface coupling between MnO2-H and Ag NPs for boosting the ORR electrocatalysis, which will inspire more work for the rational design of efficient carbon-free transition metal electrocatalysts for energy conversion.

CAS / MDL: 1310-58-3
研究领域: 材料科学 · 电化学
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Biosensors-Basel · 2023 ·Vol. 13 ·期 6 ·613 · IF 5.4

Development and Validation of Aptasensor Based on MnO2 for the Detection of Sulfadiazine Residues

Xiaoling Zheng,Lulan Yang,Qi Sun,Lei Zhang,Tao Le

The monitoring of sulfadiazine (SDZ) is of great significance for food safety, environmental protection, and human health. In this study, a fluorescent aptasensor based on MnO2and FAM-labeled SDZ aptamer (FAM-SDZ30-1) was developed for the sensitive and selective detection of SDZ in food and environmental samples. MnO2nanosheets adsorbed rapidly to the aptamer through its electrostatic interaction with the base, providing the basis for an ultrasensitive SDZ detection. Molecular dynamics was used to explain the combination of SMZ1S and SMZ. This fluorescent aptasensor exhibited high sensitivity and selectivity with a limit of detection of 3.25 ng/mL and a linear range of 5–40 ng/mL. The recoveries ranged from 87.19% to 109.26% and the coefficients of variation ranged from 3.13% to 13.14%. In addition, the results of the aptasensor showed an excellent correlation with high-performance liquid chromatography (HPLC). Therefore, this aptasensor based on MnO2is a potentially useful methodology for highly sensitive and selective detection of SDZ in foods and environments.Keywords:aptamer;MnO2;aptasensor;sulfadiazine

CAS / MDL: 57-09-0 7722-64-7
研究领域: 食品安全检测 · 环境科学 · 生物化学
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ACS ES&T Water · 2022 · IF 0

Dual-Path Oxidation of Phenolic Organic Contaminants Triggered by the β-MnO2/Bisulfite System

Yi Zhou,Xia Li,Xinyu Chen,Jian Lu,Yanbo Zhou

Manganese dioxide (MnO2) is often used to treat pollutants in water owing to its high oxidative activity. Bisulfite (BS) as an activator can promote the degradation efficiency of MnO2. However, the mechanism of different crystalline MnO2 in the presence of BS is still controversial. The oxidation performance of the tunnel type (α-MnO2, β-MnO2) and the two-dimensional lamellar type (δ-MnO2) in the presence of BS was investigated. β-MnO2/BS exhibited the highest oxidative activity under optimal conditions. The bisphenol A (BPA) oxidation kinetic constant of β-MnO2/BS (0.737 min–1) was 6 and 2.3 times higher than that of δ-MnO2/BS and α-MnO2/BS, respectively. The mineralization efficiency of BPA reached 80.05% within 15 min, owing to the high content of Mn(IV) in β-MnO2. BS could rapidly reduce β-MnO2 to produce a high concentration of Mn(III). Soluble Mn(III) directly participates in the BPA oxidation, and the surface Mn(III) can react with the surface adsorbed oxygen molecules (Oad) to generate superoxide radicals (O2•–) to promote the deep mineralization of target contaminants. Moreover, the β-MnO2/BS system can efficiently oxidate various phenolic organic pollutants even in natural water. This research can provide new insights for better understanding of the oxidation process of different crystalline-phase MnO2/BS.

研究领域: 环境科学 · 化学
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APPLIED CATALYSIS A-GENERAL · 2023 · IF 5.5

Carbon nanoplating stabilization of hierarchical MXene@C@MnO2 catalyst for effective Fenton-like reaction

Sisheng Guo,Yuqi Zheng,Xinyue Zhang,Xinying Lei,Hongfei Sun,Tao Wen

MXenes materials are burgeoning candidates for advanced water purification . However, the self-restacking and surface passivation of MXenes severely hamper the utilization of their electronic properties and surface reactivity. Herein, we employed the strategy of carbon nanoplating stabilization of MXenes for not only effectively stabilizing the structure of MXenes but also providing nucleation growth of MnO 2 . The MXene@C@MnO 2 -activated PMS system was able to degrade ∼ 100% of bisphenol A (BPA) (20 mg/L) within 4 min with the turnover frequency (TOF) of 8.14 min −1 . Specifically, the generation of superoxide radicals by activation of peroxymonosulfate (PMS) through reversible redox cycling between Mn(IV) and Mn(III) cations was regarded as the crucial driver of BPA removal. The scale-up experiment in actual water bodies achieved more than 90% BPA removal at 1200-bed volumes with stable catalytic properties during 20 h continuous operation. This work offers a potential macroscopic MXene-based nanohybrids for advanced oxidation processes .

研究领域: 环境科学 · 材料科学 · 水处理技术
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Analytical Methods · 2023 · IF 3.1

Ultrasensitive fluorescence immunoassay of pepsinogen I based on enzyme-triggered decomposition of AuNCs/MnO2

Huanzong Zhang,Binhuang Cai,Fan Cai,Mingzhe Lian,Yinghui Wang

Gastric cancer is a prevalent malignant tumor of the gastrointestinal tract accompanied by a high mortality rate; therefore, early gastric cancer screening is critical for improving patient survival. In this study, we present a facile fluorescence immunoassay for highly sensitive screening of pepsinogen I (PG I) based on a one-pot biomimetic mineralization process for the synthesis of gold nanocluster-anchored manganese dioxide (AuNCs/MnO2) nanosheets. MnO2 first quenches the fluorescence of AuNCs through the Förster resonance energy transfer effect, whereas the introduction of ascorbic acid (AA) leads to the decomposition of MnO2 and rapidly recovers the fluorescence of AuNCs. Based on the above principles and phenomena, we developed a sensitive fluorescence immunoassay for the in situ generation of AA to detect PG I. Specifically, in the presence of PG I, the sandwich-type immunoreactivity-enriched alkaline phosphatase-labeled secondary antibody catalyzes the production of AA from the substrate, which enhances the fluorescence intensity. Under optimized conditions, the fluorescence intensity increased linearly with the concentration of PG I (0.05 to 200 ng mL−1) with a limit of detection (LOD) of 0.013 ng mL−1 (S/N = 3). The designed sensing platform has good stability (more than one year) and excellent anti-interference capability and demonstrates satisfactory accuracy for detection in real samples compared to commercial ELISA kits.

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