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SEPARATION AND PURIFICATION TECHNOLOGY · 2024 · IF 8.1

Insight into the activation of periodate by Mn(II) for rapid degradation of sulfadiazine: Performance and mechanisms

Chen-Yan Hu,Zi-Yi Dong,Zheng-Yu Dong,Yi-Hui Wu,Sheng-Jie Ji,Li-Li Hu,Xin-Yu Yang,Hao Liu,Bin Xu

The present study investigated the mechanism of manganese ion (Mn(II))-activated periodate (PI) for rapid removal of sulfadiazine (SDZ). The Mn(II)/PI system showed excellent SDZ degradation results with 99.8 % degradation efficiency within 2 min at pH = 5.5. Mechanism study reveals that the degradation of SDZ in the Mn(II)/PI system takes place mainly through an electron transfer process. Mn(II) can be oxidized by PI to formed the in-situ MnO 2 , followed by the generation of MnO 2 -PI complex. Electrochemical methods have confirmed that the generated MnO 2 -PI complex significantly contributes to the degradation of pollutants. MnO 2 -PI mediates the transfer of electrons from SDZ to PI surface through surface vacancies, thereby achieving efficient degradation of pollutants. p -methoxyphenyl sulfone (PMSO) is used as a probe compound, and almost 90 % of PMSO is converted into PMSO 2 in the Mn(II)/PI/SDZ system, manifesting that excessive PI may oxidize active Mn(IV) to Mn(V). And the generated Mn(V) also contributes to the SDZ degradation. The SDZ degradation pathway is proposed and the transformation of iodine species is detected. The final iodine species in the system are iodate. The chloride culture experiment has confirmed that the production of organic iodine is very low, indicating no significant health risks. This study reveals mechanism of periodate-based process, providing theoretical and technical implementation guidelines of periodate in water treatment.

CAS / MDL: 7790-28-5
研究领域: 环境科学 · 化学工程 · 水处理
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Nature Communications · 2018 ·Vol. 9 ·期 1 ·1-14 · IF 12.353

Biomimetic nanoflowers by self-assembly of nanozymes to induce intracellular oxidative damage against hypoxic tumors

Wang Zhenzhen,Zhang Yan,Ju Enguo,Liu Zhen,Cao Fangfang,Chen Zhaowei,Ren Jinsong,Qu Xiaogang

Reactive oxygen species (ROS)-induced apoptosis is a promising treatment strategy for malignant neoplasms. However, current systems are highly dependent on oxygen status and/or external stimuli to generate ROS, which greatly limit their therapeutic efficacy particularly in hypoxic tumors. Herein, we develop a biomimetic nanoflower based on self-assembly of nanozymes that can catalyze a cascade of intracellular biochemical reactions to produce ROS in both normoxic and hypoxic conditions without any external stimuli. In our formulation, PtCo nanoparticles are firstly synthesized and used to direct the growth of MnO 2 . By adjusting the ratio of reactants, highly-ordered MnO 2 @PtCo nanoflowers with excellent catalytic efficiency are obtained, where PtCo behaves as oxidase mimic and MnO 2 functions as catalase mimic. In this way, the well-defined MnO 2 @PtCo nanoflowers not only can relieve hypoxic condition but also induce cell apoptosis significantly through ROS-mediated mechanism, thereby resulting in remarkable and specific inhibition of tumor growth.

CAS / MDL: 9003-39-8 54827-17-7
研究领域: 纳米技术 · 癌症治疗 · 材料科学 · 生物化学
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Acta Pharmaceutica Sinica B · 2021 · IF 11.614

A smart O2-generating nanocarrier optimizes drug transportation comprehensively for chemotherapy improving

Xiaojuan Zhang,Chuanchuan He,Yun Sun,Xiaoguang Liu,Yan Chen,Chen Chen,Ruicong Yan,Ting Fan,Tan Yang,Yao Lu,Jun Luo,Xiang Ma,Guangya Xiang

Drug transportation is impeded by various barriers in the hypoxic solid tumor, resulting in compromised anticancer efficacy. Herein, a solid lipid monostearin (MS)-coated CaO 2 /MnO 2 nanocarrier was designed to optimize doxorubicin (DOX) transportation comprehensively for chemotherapy enhancement. The MS shell of nanoparticles could be destroyed selectively by highly-expressed lipase within cancer cells, exposing water-sensitive cores to release DOX and produce O 2 . After the cancer cell death, the core-exposed nanoparticles could be further liberated and continue to react with water in the tumor extracellular matrix (ECM) and thoroughly release O 2 and DOX, which exhibited cytotoxicity to neighboring cells. Small DOX molecules could readily diffuse through ECM, in which the collagen deposition was decreased by O 2 -mediated hypoxia-inducible factor-1 inhibition, leading to synergistically improved drug penetration. Concurrently, DOX-efflux-associated P-glycoprotein was also inhibited by O 2 , prolonging drug retention in cancer cells. Overall, the DOX transporting processes from nanoparticles to deep tumor cells including drug release, penetration, and retention were optimized comprehensively, which significantly boosted antitumor benefits.

CAS / MDL: 31566-31-1
研究领域: 药学 · 纳米技术 · 癌症研究 · 化疗 · 药物递送系统
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ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH · 2020 ·Vol. 27 ·期 33 ·41437-41445 · IF 3.056

Tanning process promotes abiotic humification: separation and characterization of humic acid-like polymers complex

Zhu Chao,Wang Huiqin,Ma Hongrui,Yang Yonglin,Li Fan

Humic-like substances are essential components of soluble organic matter in tannery wastewater. However, the tannery process can promote the abiotic humification in wastewater. Therefore, it is of great significance to clarify the pathway and degree of abiotic humification and the properties of the as-derived humic acid-like (HAL) complex polymers in the tannery process in order to control the refractory organic compounds. In the present study, considering the catechol-Maillard system and commercial humic acid (HA) as control, the polyphenol-Maillard humification in the tannery process was simulated under the catalysis of MnO 2 . Moreover, physicochemical and spectroscopic techniques were used to characterize the separated fractions of HAL further. As a result, it was found that the catechol-Maillard system with small molecule organic matter as precursor had higher humification degree. Furthermore, the ultraviolet-visible (UV-Vis), Fourier transform infrared (FTIR), and excitation-emission matrix (EEM) fluorescence spectrum of humic acid-like 0 (HAL0) derived from it was different from those of humic acid-like 1 and 2 (HAL1 and HAL2) of polyphenol-Maillard system, indicating the differences of polymer structure between them. In the polyphenol-Maillard system, tannin was the skeleton of polymerization or polycondensation reaction, and the high content of N and the H/C value of HAL2 indicated that in adding to amino acids, proteins promoted the humification, forming industry-specific HAL polymers with a high degree of aliphatic nature. Therefore, it can be concluded that controlling the raw materials in the tannery process (especially tannins), in order to reduce the occurrence of abiotic humification may be the key to improve the efficiency of wastewater treatment.

CAS / MDL: 54-64-8
研究领域: 环境科学 · 化学工程 · 分析化学
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Journal of Materials Chemistry C · 2020 ·Vol. 8 ·期 16 ·5554-5561 · IF 7.059

Multi-emitting fluorescence sensor of MnO2–OPD–QD for the multiplex and visual detection of ascorbic acid and alkaline phosphatase

Qian Yang,Chuyao Li,Jinhua Li,Maryam Arabi,Xiaoyan Wang,Hailong Peng,Hua Xiong,Jaebum Choo,Lingxin Chen

A blue-, yellow- and red-emitting fluorescence sensor was constructed via the synergy of manganese dioxide (MnO2) nanosheets, o-phenylenediamine (OPD) and red-fluorescent quantum dots (r-QDs), namely MnO2–OPD–QD, for visualization of ascorbic acid (AA) and alkaline phosphatase (ALP). Initially, by virtue of the oxidase-like activity of MnO2 nanosheets, OPD was oxidized into yellow-fluorescent OPDox (emission: 569 nm), which quenched the r-QDs (emission: 659 nm). After interaction with AA, one reaction product of ALP and 2-phospho-L-ascorbic acid (AA2P), the MnO2 nanosheets were reduced and lost the oxidase-like activity, so that the generation of OPDox was lessened and the fluorescence of the r-QDs was thereupon recovered. Further increasing AA or ALP, the MnO2 nanosheets were fully decomposed so that OPD was not oxidized but was reduced into blue-fluorescent OPDred (emission: 441 nm), while the r-QDs were not affected. Overall, AA or ALP triggered emission intensity changes at 441, 569 and 659 nm and led to profuse color variation over the yellow–orange–red–purple range, realizing multiplex and visual determination of AA and ALP in the ranges of 0.5–70 μM and 0.1–100 mU mL−1, respectively. The color variation range of the ternary-emission mode was greatly enlarged, especially compared with that of the single-/dual-emission mode. Accordingly, the MnO2–OPD–QD sensor provided detection limits for AA and ALP as low as 0.18 μM and 0.06 mU mL−1, respectively. Furthermore, the highly selective/sensitive measurement and accurate readout of AA and ALP were accomplished in complicated food and serum samples. The multi-emitting fluorescence sensor held great potential for onsite visualization of various targets in more fields.

研究领域: 分析化学 · 生物传感器 · 材料科学 · 生物化学
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Journal of Physical Chemistry C · 2020 · IF 4.189

Opposite Effects of Co and Cu Dopants on the Catalytic Activities of Birnessite MnO2 Catalyst for Low-Temperature Formaldehyde Oxidation

Abubakar Yusuf,Yong Sun,Yong Ren,Colin Snape,Chengjun Wang,Hongpeng Jia,Jun He

Defect engineering is an effective strategy to enhance the activity of catalysts for various applications. Herein, it was demonstrated that in addition to enhancing surface properties via doping, the influence of dopants on the surface–intermediate interaction is a critical parameter that impacts the catalytic activity of doped catalysts for low-temperature formaldehyde (HCHO) oxidation. The incorporation of Co into the lattice structure of δ-MnO2 led to the generation of oxygen vacancies, which promoted the formation of surface active oxygen species, reduced activation energy, and enhanced catalytic activity for low-temperature oxidation of HCHO. On the contrary, Cu doping led to a drastic suppression of the catalytic activity of δ-MnO2, despite its enhanced redox properties and slight increase in the surface concentration of active oxygen species, compared to pristine δ-MnO2. Diffuse reflectance infrared Fourier transform analysis revealed that in the presence of Cu, carbonate intermediate species accumulate on the surface of the catalysts, leading to partial blockage of active sites and suppression of catalytic activity.

研究领域: 材料科学 · 环境科学
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY · 2026 · IF 4.1

Tyndall-effect-based colorimetric enzyme-linked aptamer assay for instrument-free thrombin detection via enzyme-triggered degradation of MnO2 nanosheets

Hu Jiale,Li Wei,Luo Pei,Nan Yihong,Liu Yimin,Yang Yashi,Zou Jianmei,He Huijun,Zhang Yun

In this work, an innovative Tyndall-effect-based (TE-based) colorimetric strategy was developed to detect the activity of alkaline phosphatase (ALP) via enzyme-triggered degradation of MnO₂ nanosheets (MnO₂ NSs), and it was further extended to construct a TE-based colorimetric enzyme-linked aptamer assay (ELAA) for monitoring thrombin (TB) concentrations. In the presence of ALP, ascorbic acid 2-phosphate (AAP) was hydrolyzed to ascorbic acid (AA), which in turn reduced MnO₂ NSs to Mn 2+ and led to their structural decomposition. Under the irradiation of a handheld laser pointer, the TE signal of the detection solution gradually diminished with increasing ALP concentration. The quantitative measurement of ALP was further achieved using a smartphone to read out the TE signal, with a limit of detection (LOD) of 0.35 mU/mL. Furthermore, this strategy effectively functioned as an exquisite signal generation mechanism to devise a TE-based colorimetric ELAA for TB detection. The results demonstrated that the proposed method exhibited high specificity and sensitivity for TB, capable of linear detection over a concentration range of 1–25 nM with a LOD of 0.38 nM (3σ). In actual human serum samples, the recovery of TB ranged from 93.40 to 109.30%. To our knowledge, this work presents the first TE-based colorimetric ELAA for instrument-free protein analysis by leveraging enzyme-triggered MnO₂ nanosheet degradation. This approach establishes a novel signal transduction mechanism for colorimetric ELAA, thereby offering significant potential to expand the theoretical scope of this assay format and broaden its applications in various resource-limited settings. Graphical abstract

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Nanoscale · 2021 ·Vol. 13 ·期 25 ·11120-11127 · IF 7.79

A mild reduction of Co-doped MnO2 to create abundant oxygen vacancies and active sites for enhanced oxygen evolution reaction

Jincan Jia,Lei Li,Xiao Lian,Mingzai Wu,Fangcai Zheng,Li Song,Guangzhi Hu,Helin Niu

Efficient and non-precious-metal-based catalysts (e.g., manganese-based oxides) for the oxygen evolution reaction (OER) remain a substantial challenge. Creation of oxygen vacancies of manganese-based oxides with the aim to enhance their intrinsic activities is rarely reported, and there is a critical requirement for a mild and facile synthesis strategy to create abundant oxygen vacancies on manganese-based oxides. Herein, Co-doped MnO2 nanowires were reduced by NaBH4 solution at room temperature; then, MnCo2O4.5 nanosheets with abundant oxygen vacancies and active sites were formed on the surface of Co-doped MnO2 nanowires. Benefiting from the reduction strategy, the fabricated hierarchical Co-doped-MnO2@MnCo2O4.5 nanowire/nanosheet nanocomposites exhibit higher catalytic activity (an overpotential of 250 mV at a current density of 10 mA cm−2 in 1.0 M KOH solution) than pristine Co-doped MnO2 nanowires. The calculated TOF of Co-doped-MnO2@MnCo2O4.5 is 0.034 s−1 at the overpotential of 300 mV, which is 136-fold higher than that of Co-doped-MnO2. The excellent OER performance was attributed to the synergistic advantages of abundant oxygen vacancies and active sites over the hierarchical nanowire-nanosheet architectures.

研究领域: 材料科学 · 电化学
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MICROCHIMICA ACTA · 2016 ·Vol. 183 ·期 9 ·2597-2604 · IF 4.831

Highly improved sensing of dopamine by using glassy carbon electrode modified with MnO2, graphene oxide, carbon nanotubes and gold nanoparticles

Rao Dejiang,Zhang Xinjin,Sheng Qinglin,Zheng Jianbin

A composite material obtained by ultrasonication of graphene oxide (GO) and multi-walled carbon nanotubes (MWCNTs) was loaded with manganese dioxide (MnO 2 ), poly(diallyldimethylammonium chloride) and gold nanoparticles (AuNPs), and the resulting multilayer hybrid films were deposited on a glassy carbon electrode (GCE). The microstructure, composition and electrochemical behavior of the composite and the modified GCE were characterized by transmission electron microscopy, Raman spectra, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and cyclic voltammetry. The electrode induces efficient electrocatalytic oxidation of dopamine at a rather low working voltage of 0.22 V (vs. SCE) at neutral pH values. The response is linear in the 0.5 μM to 2.5 mM concentration range, the sensitivity is 233.4 μA·mM‾ 1 ·cm‾ 2 , and the detection limit is 0.17 μM at an SNR of 3. The sensor is well reproducible and stable. It displays high selectivity over ascorbic acid, uric acid and glucose even if these are present in comparable concentrations. Gold nanoparticles were self-assembled onto the surface of the MnO 2 decorated graphene oxide-carbon nanotubes composites with poly(diallyldimethylammonium chloride) (PDDA) as a coupling agent. Further, a sensitive electrochemical sensor of dopamine was developed via immobilizing this nanocomposite on a glassy carbon electrode (GCE).

研究领域: 电化学 · 纳米材料 · 生物传感器 · 分析化学
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ELECTROCHIMICA ACTA · 2017 · IF 4.798

Nitrogen-doped hierarchical carbon spheres derived from MnO2-templated spherical polypyrrole as excellent high rate anode of Li-ion batteries

Chunhai Jiang,Jingxia Wang,Zhonghui Chen,Zhiyang Yu,Zhenyu Lin,Zhimin Zou

Hierarchical nitrogen-doped carbon spheres (NCSs) prepared by annealing the MnO 2 -templated spherical polypyrrole (PPy) at 450 or 600   °C were tested as anode materials of Li-ion batteries. The NCSs annealed at 450   °C exhibited higher nitrogen content, more amorphous carbon structure, and lower surface area as compared to the sample annealed at 600   °C. The specific capacities and rate performances of both NCSs samples were much higher than that of commercial mesocarbon microbeads (MCMBs). The NCSs annealed at 600   °C exhibited higher capacity at low current density (<0.5   A   g −1 ) but more rapid capacity decay at elevated current rates referring to the sample annealed at 450   °C. The NCSs annealed at higher temperature also possessed inferior cycling stability, possibly due to its lower electronic conductivity and higher degree of graphitization. A high specific capacity of 250.8   mAh   g −1 was achieved on the NCSs annealed at 450   °C at 3   A   g −1 , demonstrating their high potentiality as anode of high power Li-ion batteries.

研究领域: 材料科学 · 电化学 · 纳米材料 · 能源存储 · 碳材料
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TALANTA · 2017 · IF 4.162

A label-free fluorescence turn-on assay for glutathione detection by using MnO2 nanosheets assisted aggregation-induced emission-silica nanospheres

Xiaobin Zhang,Rongmei Kong,Qingqing Tan,Fei Qu,Fengli Qu

Glutathione (GSH) serves several vital biological functions and its abnormal levels are associated with many diseases. Simple and sensitive methods capable of detecting GSH are desired for better understanding the mechanism of diseases. In this work, a label-free MnO 2 nanosheets assisted aggregation-induced emission (AIE)-silica nanospheres (SiO 2 NPs) nanoprobe for fluorescent “turn-on” detection of GSH with high sensitivity was reported for the first time. The anionic tetraphenylethylene derivative 3 (TPE3) was synthesized and employed as the AIE-active probe, which can be aggregated on the uncoated amino-functionalized SiO 2 NPs to form AIE-SiO 2 NPs and emitted strong fluorescence. Negatively charged MnO 2 nanosheets were employed as both positive charge protectors for amino-functionalized SiO 2 NPs and recognition units for GSH. The presence of GSH could selectively reduce MnO 2 nanosheets to Mn 2+ , thus releasing the amino-functionalized SiO 2 NPs and exposure its positive charges. Accordingly, the TPE3 could be aggregated on the exposured amino-functionalized SiO 2 NPs to form AIE-SiO 2 NPs and emitted strong fluorescence. The proposed assay is simple, fast, low cost, and highly sensitive with a detection limit of 200   nM for GSH. The assay was further applied in human serum samples for the detection of GSH with satisfactory results, demonstrating its promising application in practical biological samples.

研究领域: 生物化学 · 分析化学 · 纳米医学
✓ 已验证 DOI 高影响因子
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BIOMASS & BIOENERGY · 2020 · IF 3.551

Removal of uranium using MnO2/orange peel biochar composite prepared by activation and in-situ deposit in a single step

Dai Ying,Peng Hong,Fan Jiali,Tao Qinqin,Liu Yuhui,Wang Youqun,Zhang Zhibin,Cao Xiaohong,Liu Yunhai

Orange peel is an important resource in view of its low-cost and universal nature. A novel material (MnO 2 /orange peel carbon, MnO 2 /OPC) was yielded via a single step involving activation and in situ deposit. The feasibility of uranium removal using MnO 2 /OPC was tested by varying MnO 2 loading amount, pH, ionic strength , uranium initial concentration and temperature. 1.2MnO 2 /OPC yielded the most competitive uptake value as 246.3 mg g −1 . The pH beneficial for adsorption was 5.5. The adsorption taken the way of inner-sphere surface complexation and the process was an endothermic, entropy increasing and spontaneous process in nature. The work gave enlightening results for reusing orange peel as raw materials to produce a kind of scavenger materials of economy and effectivity in the field of treating radioactive aqueous solution.

研究领域: 环境科学 · 材料科学
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