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MICROCHIMICA ACTA · 2020 ·Vol. 187 ·期 8 ·1-9 · IF 6.232

Rolling circle amplification promoted magneto-controlled photoelectrochemical biosensor for organophosphorus pesticides based on dissolution of core-shell MnO2 nanoflower@CdS mediated by butyrylcholinesterase

Tang Juan,Li Jingjing,Xiong Pengyuan,Sun Yuanfang,Zeng Zhiyao,Tian Xiaochun,Tang Dianping

A photoelectrochemical (PEC) aptasensing platform is devised for sensitive detection of an organophosphorus pesticide based on dissolution of core-shell MnO 2 nanoflower@CdS (MnO 2 NF@CdS) by thiocholine (TCh). TCH is produced from the butyrylcholinesterase-acetylthiocholine system, accompanied by target-triggered rolling circle amplification (RCA). The core-shell MnO 2 NF@CdS with excellent PEC performance was synthesized and employed as a photo-sensing platform. The target was detected on a functionalized magnetic probe with the corresponding aptamer. Upon malathion introduction, the aptamer was detached from the magnetic beads, while capture DNA (cDNA, with primer fragment) remained on the beads. The primer fragment in cDNA can trigger the RCA reaction to form a long single-stranded DNA (ssDNA). Furthermore, a large number of butyrylcholinesterase (BChE) were assembled on the long ssDNA strands through the hybridization with the S 2 -Au-BChE probe. Thereafter, TCh generated from hydrolysis of ATCh by BChE can reduce MnO 2 NF (core) to Mn 2+ and release the CdS nanoparticles (shell) from the platform electrode, significantly enhancing the PEC signal. Under optimal conditions, the proposed aptasensor exhibited high sensitivity for malathion with a low detection limit of 0.68 pg mL −1 . Meanwhile, it also presents outstanding specificity, reproducibility, and stability. Importantly, the sensing platform provides a new concept for detection of pesticide. Herein, this work devised a photoelectrochemical (PEC) aptasensing platform for sensitive detection of organophosphorus pesticide based on dissolution of core-shell MnO 2 nanoflower@CdS (MnO 2 NF@CdS) by the as-produced thiocholine (TCh) from the butyrylcholinesterase-acetylthiocholine system, accompanying with the target-triggered rolling circle amplification (RCA).

研究领域: 分析化学 · 环境科学 · 生物化学 · 农业科学
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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.

研究领域: 分析化学 · 纳米技术 · 生物传感器
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JOURNAL OF HAZARDOUS MATERIALS · 2020 · IF 9.038

Role of MnO2 in controlling iron and arsenic mobilization from illuminated flooded arsenic-enriched soils

Guowen Dong,Ruiwen Han,Yajing Pan,Chengkai Zhang,Yu Liu,Honghui Wang,Xiaoliang Ji,Randy A. Dahlgren,Xu Shang,Zheng Chen,Minghua Zhang

This study examined the role of intermittent illumination/dark conditions coupled with MnO 2 -ammendments to regulate the mobility of As and Fe in flooded arsenic-enriched soils. Addition of MnO 2 particles with intermittent illumination led to a pronounced increase in the reductive-dissolution of Fe(III) and As(V) from flooded soils compared to a corresponding dark treatments. A higher MnO 2 dosage (0.10 vs 0.02 g) demonstrated a greater effect. Over a 49-day incubation, maximum Fe concentrations mobilized from the flooded soils amended with 0.10 and 0.02 g MnO 2 particles were 2.39 and 1.85-fold higher than for non-amended soils under dark conditions. The corresponding maximum amounts of mobilized As were at least 92 % and 65 % higher than for non-amended soils under dark conditions, respectively. Scavenging of excited holes by soil humic/fulvic compounds increased mineral photoelectron production and boosted Fe(III)/As(V) reduction in MnO 2 -amended, illuminated soils. Additionally, MnO 2 amendments shifted soil microbial community structure by enriching metal-reducing bacteria (e.g., Anaeromyxobacter , Bacillus and Geobacter ) and increasing c -type cytochrome production. This microbial diversity response to MnO 2 amendment facilitated direct contact extracellular electron transfer processes, which further enhanced Fe/As reduction. Subsequently, the mobility of released Fe(II) and As(III) was partially attenuated by adsorption, oxidation, complexation and/or coprecipitation on active sites generated on MnO 2 surfaces during MnO 2 dissolution. These results illustrated the impact of a semiconducting MnO 2 mineral in regulating the biogeochemical cycles of As/Fe in soil and demonstrated the potential for MnO 2 -based bioremediation strategies for arsenic-polluted soils.

CAS / MDL: 1313-13-9
研究领域: 环境科学 · 土壤学 · 微生物学 · 生物地球化学
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Journal of Cleaner Production · 2021 · IF 9.297

Bioinspired 3D hierarchical BSA-NiCo2O4@MnO2/C multifunctional micromotors for simultaneous spectrophotometric determination of enzyme activity and pollutant removal

Wenning Yang,Jia Li,Yangsai Lyu,Xiaohui Yan,Ping Yang,Min Zuo

Artificial self-propelled micro/nano-motors have emerged as a promising hot spot in the fields of water-body remediation and environmental protection. Herein, we report a novel multifunctional micromotors with dual enzyme-like activities for simultaneous colorimetric determination and removal of environmental contaminants. Thanks to the tubular morphology inherited from kapok fibers, these bovine serum albumin-functionalized NiCo 2 O 4 @MnO 2 /C (BSA-NiCo 2 O 4 @MnO 2 /C) micromotors with dual oxidase/peroxidase-like activity can move forward quickly in aqueous solutions via a bubble recoil mechanism, which can not only enhance the colorimetric sensing performance, but also improve the removal efficiency toward Cu 2+ ion by enhancing the mass transfer both in the detection and catalytic degradation systems. Moreover, the unique 3D hierarchical architecture assembled by core-shell NiCo 2 O 4 @MnO 2 nanosheets and C microtubes can provide more accessible reactive sites and thus dramatically facilitate such detection process. In combination with the autonomous motility, intrinsic oxidase/peroxidase-like activities and precisely tuned hierarchical architecture, these automatic micromachines not only are able to detect Cu 2+ selectively and sensitively with the limit of detection of 2.0 nM, but also quickly remove Cu 2+ from wastewater with maximal adsorption capacity of 161.8 mg g −1 . Furthermore, these micromotors exhibit excellent catalytic activity for the degradation of tetracycline hydrochloride. This multifunctional mobile platform will provide a new and promising strategy for the simultaneous detection and decontamination of poisonous metal ions and other pollutants in aqueous samples.

研究领域: 环境科学 · 纳米技术 · 分析化学 · 水处理
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SENSORS AND ACTUATORS B-CHEMICAL · 2022 · IF 9.221

Thermocapillary convection modulating ion migration for rapid recognition and detection of Cu (Ⅱ) based on MnO2 NSs-AuNSs modified screen printed electrode

Qing Zhang,Shangshang Ma,Li Zhang,Hongyan Wang,Xin Zhuo,Guizhi Wang,Yanyun Shen,Keying Zhang,Shao Su

Microfluidic chip for sensing heavy metal ions has been strongly attended due to its merits, but still remains a large challenge from long analysis time derived from the preconcentration process of metal ions. Herein, a heated flow channel was manufactured by 3D printing combined with a filter paper to construct a microfluidic chip, the thermocapillary convection strategy was introduced to accelerate ions migration, allowing for rapidly recognizing metal ions. The MnO 2 nanosheets-Au nanostars (MnO 2 NSs-AuNSs) film was employed as modifier to fabricate a flexible screen printed electrode (SPE) for high-efficiency detecting metal ions based on thermocapillary convection accelerating accumulation method. To verify the proposed strategy, the detection of Cu 2+ was chosen as a model. The results revealed that the proposed strategy possessed a rapid detection to Cu 2+ , which greatly improved the detection efficiency (saved 400 s of preconcentration time) and achieved a detection limit down to 0.0270 ppb. Interestingly, the constructed method was successfully used to evaluate Cu 2+ concentration in sweat samples with satisfactory results. This proposed method maybe provide new insight to develop a novel approach to rapidly and sensitively detect metal ions, which possess huge utilization potentiality for safeguarding human health.

研究领域: 分析化学 · 环境科学 · 生物医学工程
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JOURNAL OF NANOBIOTECHNOLOGY · 2024 · IF 10.6

MnO2 and roflumilast-loaded probiotic membrane vesicles mitigate experimental colitis by synergistically augmenting cAMP in macrophage

Chengjun Song,Jiamin Wu,Jinhui Wu,Fangyu Wang

Background Ulcerative colitis (UC) is one chronic and relapsing inflammatory bowel disease. Macrophage has been reputed as one trigger for UC. Recently, phosphodiesterase 4 (PDE4) inhibitors, for instance roflumilast, have been regarded as one latent approach to modulating macrophage in UC treatment. Roflumilast can decelerate cyclic adenosine monophosphate (cAMP) degradation, which impedes TNF-α synthesis in macrophage. However, roflumilast is devoid of macrophage-target and consequently causes some unavoidable adverse reactions, which restrict the utilization in UC. Results Membrane vesicles (MVs) from probiotic Escherichia coli Nissle 1917 (EcN 1917) served as a drug delivery platform for targeting macrophage. As model drugs, roflumilast and MnO 2 were encapsulated in MVs (Rof&MnO 2 @MVs). Roflumilast inhibited cAMP degradation via PDE4 deactivation and MnO 2 boosted cAMP generation by activating adenylate cyclase (AC). Compared with roflumilast, co-delivery of roflumilast and MnO 2 apparently produced more cAMP and less TNF-α in macrophage. Besides, Rof&MnO 2 @MVs could ameliorate colitis in mouse model and regulate gut microbe such as mitigating pathogenic Escherichia–Shigella and elevating probiotic Akkermansia . Conclusions A probiotic-based nanoparticle was prepared for precise codelivery of roflumilast and MnO 2 into macrophage. This biomimetic nanoparticle could synergistically modulate cAMP in macrophage and ameliorate experimental colitis. Graphical Abstract Supplementary Information The online version contains supplementary material available at 10.1186/s12951-024-02558-6.

研究领域: 药理学 · 胃肠病学 · 免疫学 · 纳米技术 · 微生物学
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INTERNATIONAL JOURNAL OF PHARMACEUTICS · 2022 · IF 6.51

Photothermal MnO2 nanoparticles boost chemo-photothermal therapy-induced immunogenic cell death in tumor immunotherapy

Zhenzhen Chen,Qian Zhang,Qinbiao Huang,Zhihong Liu,Lingjun Zeng,Lingna Zhang,Xu Chen,Hongtao Song,Jialiang Zhang

The induction of immunogenic cell death (ICD) is an attractive strategy for generating in situ autologous tumor cell-based vaccines and thus has great potential in cancer prevention and personalized immunotherapy . However, the effectiveness of ICD in tumor immunotherapy has been greatly limited, mainly by low induction efficiency and the immunosuppressive tumor microenvironment (TME). Herein, we report a new strategy for chemo-photothermal therapy-induced ICD by employing photothermal MnO 2 nanoparticles loaded with doxorubicin (DOX) in tumor immunotherapy to overcome the low efficiency of traditional ICD inducers and the immunosuppressive TME. Specifically, we prepared photothermal bovine serum albumin (BSA)-templated MnO 2 NPs (BSA/MnO 2 NPs) with good aqueous dispersibility and high biocompatibility through the direct reduction of KMnO 4 with BSA, and we then efficiently loaded DOX, an ICD inducer, onto the MnO 2 NPs through coordination (DOX-BSA/MnO 2 NPs). The DOX-BSA/MnO 2 NPs achieved high photothermal conversion efficiency, highly efficient tumor targeting, TME-responsive DOX release and modulation of the hypoxic TME. Notably, a marked in vivo synergistic therapeutic effect was achieved in a triple-negative breast carcinoma-bearing mouse model by combining chemo-photothermal therapy-induced ICD with amelioration of the immunosuppressive TME. Our research highlights the great promise of modulating the TME with photothermal MnO 2 nanosystems to enhance ICD-induced antitumor immunotherapy.

研究领域: 癌症研究 · 纳米技术 · 免疫治疗 · 生物医学工程
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ACS Applied Nano Materials · 2022 · IF 6.14

Hollow MnO2 Nanoparticles Loaded with Functional Genes as Nanovaccines for Synergistic Cancer Therapy

Weicai Wang,Xiaozu Chen,Junwei Li,Qiu Jin,Hyung Jong Jin,Xuemei Li

Nanotechnology provides more developments and challenges for cancer immunotherapy. Nanomaterial-mediated synergistic therapy, immunosuppressive adjustment of the tumor microenvironment (TME), and nanovaccine construction can promote cancer immunotherapy. Here, based on the biodegradable hollow manganese dioxide (H-MnO2) tumor-targeted drug delivery platform, we have developed a TME-responsive nanovaccine for synergistic cancer therapy. The nanoplatform significantly enhanced photodynamic therapy (PDT)-mediated immune response by improving the hypoxic tumor microenvironment and on-demand drug release. At the same time, it was supplemented with gene therapy and chemotherapy to achieve significant in vivo combined therapy benefits. Taking full advantage of the high reactivity to the hydrogen peroxide and weak acidity of the TME, H-MnO2 loaded with chemotherapy drug doxorubicin (DOX) and photosensitizer chlorin e6 (Ce6) not only provided the required oxygen for photodynamic therapy but also reduced the side effects of chemotherapy drugs on normal tissues. Moreover, the coating of nucleic acid on H-MnO2 solved the problem of biocompatibility of nanoparticles and ensured that they could be swallowed by cancer cells. The results revealed that through the controlled release of targeted drugs and combined therapy, the synergistic nanovaccine significantly inhibited tumor growth in mice, which is expected to achieve the treatment of primary tumors.

研究领域: 纳米技术 · 癌症免疫治疗 · 药物递送系统 · 光动力疗法 · 基因治疗 · 化疗 · 生物相容性
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

Tumor microenvironment-responsive MIL-53(Fe)@MnO2- induced glutathione depletion and sustained hydroxyl radical generation for enhanced chemodynamic cancer therapy

Ying Jiang,Hao Lu,Lingli Lei,Daniel Scherman,Yingshuai Liu

The design of nanomedicines targeting specific tumor microenvironment (TME) characteristics, such as low pH, hypoxia, and elevated glutathione (GSH) concentration, holds significant potential for selectively killing cancer cells. In this study, we have developed a TME-responsive nanoparticle, i.e. , MIL-53(Fe)@MnO 2 stabilized with polyethylene glycol (FMP), which is capable of depleting GSH and sustainably generating hydroxyl radical (•OH) for enhanced chemodynamic therapy of cancer. After endocytosis, the FMP nanoparticles undergo gradual decomposition, resulting in GSH depletion while releasing Fenton-active Fe 2+ and Mn 2+ ions. These ions then subsequently catalyze a Fenton-like reaction to generate highly toxic •OH, ultimately inducing oxidative cell death. As a synergistic effect, the depletion of GSH further enhances therapeutic efficacy by inhibiting intracellular •OH scavenging. In vivo experiments demonstrated that this synergistically chemotherapeutic approach efficiently suppressed tumor growth without inducing significant systemic toxicity. This work presents a promising nanotherapeutic strategy that simultaneously depletes intracellular GSH and sustains cytotoxic •OH generation for enhanced tumor treatment.

研究领域: 纳米医学 · 癌症治疗 · 生物无机化学 · 活性氧治疗 · 靶向药物递送
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DALTON TRANSACTIONS · 2024 · IF 3.5

Alleviating hypoxia by integrating MnO2 with metal–organic frameworks coated upconversion nanocomposites for enhanced photodynamic therapy in vitro

Junxun Zhou,Mengyue Jiang,Qiangqiang Zhang,Yuan Jiang,Haifang Wang,Lining Sun

Photodynamic therapy (PDT) requires the participation of abundant oxygen while the hypoxic tumor microenvironment limits the efficacy of PDT. Here, upconversion luminescent nanocomposites coated with metal–organic frameworks (MOFs) were synthesized and modified with MnO2 (named UMMnP) to alleviate hypoxia of the tumor microenvironment. Under 980 nm light irradiation, the upconversion nanoparticles (UCNPs) achieve upconversion emission to excite porphyrin MOFs, which then transfer energy to oxygen to produce singlet oxygen for PDT. At the same time, the MnO2 in the UMMnP nanocomposites can catalyze the generation of O2 from H2O2, which could increase singlet oxygen production in a hypoxic environment, thus enhancing the PDT effect. The HeLa cell viability assay shows that the UMMnP nanocomposites possess good biocompatibility, while after irradiation with 980 nm light, the cell viability decreases dramatically, demonstrating efficient PDT. Furthermore, the nanocomposites can be successfully applied for upconversion luminescence imaging in vitro. Thus, this work provides a promising application of bioimaging and enhanced photodynamic therapy by alleviating hypoxia in tumor treatment.

研究领域: 纳米技术 · 生物医学工程 · 癌症治疗 · 材料科学
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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
研究领域: 癌症治疗 · 纳米技术 · 免疫学 · 药物递送系统
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SEPARATION AND PURIFICATION TECHNOLOGY · 2022 · IF 9.136

Construction of novel maple leaf-like MnO2–SiO2@PDA composites for highly efficient removal of Cu(II), Cd(II) and Ni(II) from aqueous solution

Zhiqiang Guo,Lei Sun,Hui Hou,Jian Zhou,Yuan Li,Liangliang Hu,Jinzhang Xu

The preparation of the maple leaf-like MnO 2 –SiO 2 @PDA biomimetic composites not only overcame the problem of easy agglomeration of nanoparticles, but also provided rich functional groups, large specific surface areas and good stability, achieving the efficient sorption of Cu(II), Cd(II) and Ni(II) from aqueous solution. The maximum sorption capacities of the MnO 2 –SiO 2 @PDA towards Cu(II), Cd(II) and Ni(II) attained from the Langmuir model were 218.788, 383.420 and 148.939 mg·g −1 , respectively. The sorption of Cu(II), Cd(II) and Ni(II) on the MnO 2 –SiO 2 @PDA were strongly affected by pH, but not by ionic strength, showing good resistance to salt interference. The main sorption mechanism of the MnO 2 –SiO 2 @PDA towards Cu(II), Cd(II) and Ni(II) was the strong surface complexation of the functional groups on the MnO 2 –SiO 2 @PDA with Cu(II), Cd(II) and Ni(II). Moreover, the radii of Cu(II), Cd(II) and Ni(II) ions and their complexation strength with the MnO 2 –SiO 2 @PDA jointly determined the order of the competitive sorption capacities as Cu(II) > Cd(II) > Ni(II). Given the above analyses, the maple leaf-like MnO 2 –SiO 2 @PDA biomimetic composites have excellent application prospects in practical wastewater treatment.

研究领域: 环境科学 · 材料科学 · 化学工程
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