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LUMINESCENCE · 2017 ·Vol. 33 ·期 1 ·138-144 · IF 1.509

Redox luminescence switch based on Mn2+-doped NaYF4:Yb,Er upconversion nanorods

Liping Zhang,Jianguo Zhang,Hongqi Chen,Lun Wang

An redox luminescence switch was developed for the sensing of glutathione (GSH), l -cysteine (Cys) or l -ascorbic acid (AA) based on redox reaction. The Mn 2+ -doped NaYF 4 :Yb,Er upconversion nanorods (UCNRs) with an emission peak located in the red region were synthesized. The luminescence intensity of the UCNRs could be quenched due to the Mn 2+ could be oxidized to MnO 2 by KMnO 4 . Subsequently, when the AA, GSH or Cys was added into the MnO 2 modified upconversion nanosystem, which could reduced MnO 2 to Mn 2+ and the luminescence intensity was recovered. The concentration ranges of the nanosystem are 0.500–3.375 mM (R 2 = 0.99) for AA, 0.6250–11.88 mM (R 2 = 0.99) for GSH and 0.6250–9.375 mM (R 2 = 0.99) for Cys, respectively.

研究领域: 分析化学 · 纳米技术 · 生物化学
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International Journal of Electrochemical Science · 2024 · IF 1.3

Designing MnO2@amorphous carbon core-shell structure as a cathode to enhance rate performance and cycling stability of aqueous zinc-ion batteries

Zhen Zhang,Yiwen Wang,Pengbo Guo,Guilin Lu,Luchen Wu,Xinyu li

Manganese dioxide has received significant attention as a prospective cathode material in aqueous zinc-ion batteries (ZIBs) owing to its elevated working voltage and commendable energy density. Nevertheless, challenges such as structural instability, manganese dissolution, and poor electrical conductivity remain significant barriers to the practical application of research. Here, the MnO 2 nanorods encapsulated in the amorphous carbon (MnO 2 @C) with core-shell structure are prepared by a special hard template method, and investigated as cathode materials for ZIBs. The amorphous carbon, characterized by its structural defects and disorder, manifests heightened active site density, thereby establishing an efficient conduit for charge transport. Concurrently, the nano-dimensional interstitial spaces augment the active sites available for zinc insertion reactions, thereby effectively curtailing the ion diffusion path and, consequently, engendering heightened electrochemical performance. Moreover, the distinctive core-shell architecture of MnO 2 @C not only furnishes substantial spatial accommodation but also serves to alleviate volume alterations throughout charge and discharge events. Consequently, MnO 2 @C demonstrates outstanding electrochemical performance, with reversible capacities of 210 mAh·g −1 and 50 mAh·g −1 at 0.1 A·g −1 and 1.6 A·g −1 , respectively. Furthermore, even after 600 cycles at 0.8 A·g −1 , it maintains exceptional cycling performance, reaching 102 mAh·g −1 , endowing MnO 2 @C cathodes with robust competitiveness in aqueous ZIBs.

研究领域: 材料科学 · 电化学
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Design of novel dual-emitting ratiometric fluorescence system based on FMT-CDs and MnO2 NS for sensitive isoniazid detection in urine sample

Xin-Ran Guo,Yan-Xin Guo,Juan Chen,Xin-Yue Chen

In this work, a simple and sensitive ratiometric fluorescence probe to detect isoniazid (INH) was developed on the basis of carbon dots and MnO 2 nanosheets (MnO 2 NS). Nitrogen-doped carbon dots (FMT-CDs) were synthesized by microwave method using formononetin (FMT) in ammonia water. The oxidase-like activity of MnO 2 NS was utilized to oxidize non-fluorescent o -phenylenediamine (OPD) to 2, 3-diaminophenazine (DAP) with orange fluorescence. It was demonstrated that DAP could effectively quench the fluorescence of FMT-CDs through the inner filtering effect (IFE). Due to the reducing nature of INH, MnO 2 NS was decomposed and thus lost its oxidase-like activity after the addition of INH. Therefore, the production of DAP was reduced, and the fluorescence intensity was decreased, while IFE on FMT-CDs was weakened and the fluorescence of FMT-CDs was recovered. Based on the above principle, a sensitive method for the detection of INH was established based on the fluorescence intensity ratio of the two fluorescent substances, FMT-CDs and DAP, and was successfully applied to the detection of INH in human urine samples. The limit of detection (LOD) could reach to 0.16 μM in human urine samples.

研究领域: 分析化学 · 医学诊断 · 材料科学
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ACS Sustainable Chemistry & Engineering · 2022 · IF 9.224

Fabricating a Gel Electrolyte Based on Lignin-Coated Nanosilica to Enhance the Reversibility of Zinc Anodes for Rechargeable Aqueous Zn/MnO2 Batteries

Jingliang Xu,Minghai Wang,Md. Asraful Alam,Gul Muhammad,Yongkun Lv,Chenjie Zhu,Haoran Zhang,Wenlong Xiong

When a conventional aqueous ZnSO4 solution is used as the electrolyte, rechargeable aqueous Zn/MnO2 batteries suffer from inferior electrochemical performance because of the corrosion, dendrites, and passivation on zinc anodes. Herein, a novel gel electrolyte was fabricated by adding lignin/fumed silica composites to the reference aqueous electrolyte (RAE) (2 M ZnSO4 + 0.2 M MnSO4) for the purpose of mitigating the aforementioned issues of zinc anodes. Results of linear polarization and chronoamperometry showed that the as-prepared gel electrolyte reduced deterioration on zinc (up to 38.9%) and supported planar zinc deposits. Batteries using this gel electrolyte presented a higher open-circuit voltage after 24 h of monitoring and superior rate performance compared to batteries using the RAE. Most importantly, the discharge capacity of the batteries using this gel electrolyte after 3000 cycles at 1.5 A g–1 was still up to 106.2 mA h g–1, which was much higher than that (39.6 mA h g–1) of the batteries using the RAE. Observation through X-ray diffraction and scanning electron microscopy characterizations of the post-run zinc anodes revealed that this gel electrolyte could strongly inhibit the formation of zinc dendrites and reduce the production of byproducts (3Zn(OH)2·ZnSO4·xH2O) during the operation of the battery. This study is highly significant to the development of advanced aqueous batteries with high safety.

研究领域: 材料科学 · 电化学
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JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS · 2021 · IF 3.935

A ratiometric electrochemical biosensor via alkaline phosphatase mediated dissolution of nano-MnO2 and Ru(III) redox recycling for the determination of dimethoate

Li Hou,Xuanhan Zhang,Yuxiu Huang,Min Wang,Xiaoyu Chen,Tianran Lin,Yanhui Tan,Shulin Zhao

A sensitive and ratiometric electrochemical biosensor was developed for the determination of dimethoate via alkaline phosphatase (ALP) mediated dissolution of nano-MnO 2 and [Ru(NH 3 ) 6 ] 3+ (Ru(III)) redox recycling. The electroactive probe Ru(III) was adsorbed on the nano-MnO 2 with the high specific surface area through electrostatic interaction to form the MnO 2 -Ru(III) nanocomposite, which was then fixed on the surface of the glassy carbon electrode. When the dimethoate inhibited the catalytic activity of ALP in a homogeneous system, the hydrolysate L -ascorbic acid (AA) produced by ALP hydrolysis of L -ascorbic acid-trisodium 2-phosphate (AAP) decreased. The solution was then incubated with a glassy carbon electrode modified by MnO 2 -Ru(III). At this time, only a small amount of MnO 2 -Ru(III) was decomposed and Ru(III) was rapidly electroreduced to Ru(II) on the surface of the electrode. The in-situ produced Ru(II) was chemically oxidized back to Ru(III) by Fe(III). The redox recycling of Ru(III) was completed and the Ru(III) reduction current signal was amplified. The process consumed part of Fe(III) to reduce the reduction current signal of Fe(III), and the ratio of the two reduction currents (I Ru(III) /I Fe(III) ) increased significantly. The I Ru(III) /I Fe(III) value increased with the increase of dimethoate concentration in the linear range of 0.01–300 ng mL −1 , and the detection limit was 6.3 pg mL −1 . It has been successfully applied to the determination of dimethoate in oilseed rape and lettuce with a satisfactory result.

研究领域: 分析化学 · 电化学 · 生物传感器 · 环境监测
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ELECTROCHIMICA ACTA · 2024 · IF 5.5

Improving of the electrochemical performance of acacia wood porous carbon/MnO2 nanocomposite as an advanced electrode for supercapacitor and oxygen evolution reaction

Hamouda Adam Hamouda,Anas Ramadan,Leila Mahmoud Mokhtar,Suad Atitalla Ageeb,Mohammed Hassan Ibrahim,Abir EM Ajab,Mohammed Bahreldin Hussein,Adam A. Farah,Elfatih A Hassan,Guofu Ma

Effective energy storage has now become increasingly critical as global energy demand has skyrocketed. Asymmetric supercapacitors using electrodes made of acacia wood-derived carbon doped with MnO 2 . A hydrothermal process was used to synthesize the AWPC/MnO 2 composite. Techniques such as XRD , SEM, TEM, XPS, FTIR spectra, Ramman spectra, and N 2 adsorption-desorption isotherms. We looked at the electrochemical properties of the materials we made in an electrolyte using cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS). A hydrothermal synthesis approach is used to graft MnO 2 wire-like nanostructures onto acacia wood-derived activated carbon. Good electrochemical performance is shown by the carbon/MnO 2 hybrid composite electrode, which has high specific capacitances of 301 F g − 1 at 500 mA s − 1 , low Tafel slope of 54 mV dec −1 , which is attributed to the synergistic influences between MnO 2 and waste biomass-produced carbon. Moreover, an asymmetric supercapacitor operating in the voltage range of 1.8 V and exhibiting a high energy density of 25 Wh kg −1 at a power density of 450 W kg −1 demonstrates the significant potential of the activated carbon/MnO 2 composite generated from synthesized biomass. The AWPC/MnO 2 's oxygen evolution reaction (OER) activity was checked to see how well the improved nanostructure could be used. The results offer a fresh perspective on the fabrication of electrochemical energy storage devices with outstanding performance.

CAS / MDL: 7697-37-2
研究领域: 能源材料科学 · 电化学
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FREE RADICAL BIOLOGY AND MEDICINE · 2026 · IF 8

A multifunctional injectable hydrogel co-delivering GDF6 and MnO2 nanozymes alleviates intervertebral disc degeneration by mitigating oxidative stress and promoting anabolic repair

Chao Wei,Qin Tang,Yanlin Tan,Qianshi Zhang,Qimu Tang,Fubin Liu,Wenzhe Li,Yuhao Zheng,Xiaobin Wang,Jing Li

Intervertebral disc degeneration (IDD) is a primary cause of low back pain, characterized by cell loss, extracellular matrix (ECM) degradation, and a harsh microenvironment with excessive oxidative stress, creating an urgent need for regenerative therapies. This study aimed to develop and evaluate a multifunctional injectable hydrogel (Gel@MnO 2 /GDF6) co-delivering growth differentiation factor 6 (GDF6) for anabolic stimulation and manganese dioxide (MnO 2 ) nanozymes for reactive oxygen species (ROS) scavenging to treat IDD. The MnO 2 nanorods and the chitosan-arginine/oxidized dextran-based hydrogel were synthesized and characterized, demonstrating sustained GDF6 release and pH-responsive degradation. In vitro , Gel@MnO 2 /GDF6 protected nucleus pulposus (NP) cells from H 2 O 2 -induced oxidative stress by reducing ROS, upregulating antioxidant enzymes, promoting anabolic ECM metabolism (increasing Aggrecan and Collagen II while decreasing ADAMTS-4 and MMP-13), reducing key inflammatory cytokine expression (TNF-α and IL-6), and activating the Smad pathway. In vivo , intra-discal injection of Gel@MnO 2 /GDF6 into a rat IDD model significantly attenuated disc degeneration over 12 weeks, as evidenced by improved histological scores, preserved disc height and hydration on radiological and MRI assessments, restoration of ECM protein homeostasis, reduced cellular apoptosis, mitigated inflammatory marker expression, and activated Smad pathway, with these therapeutic effects being superior to those achieved with hydrogels containing only MnO 2 or GDF6. Importantly, all tested hydrogel formulations, including Gel@MnO 2 /GDF6, demonstrated good systemic biocompatibility. These findings collectively demonstrate that the multifunctional Gel@MnO 2 /GDF6 hydrogel effectively promotes intervertebral disc regeneration by concurrently mitigating oxidative stress and fostering an anabolic, anti-inflammatory microenvironment, validating its potential as a promising therapeutic method for IDD.

CAS / MDL: 7647-01-0 7722-64-7
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Advanced Science · 2026 · IF 14.1

Versatile Co-Engineering of Immunogenic Cell Death-Primed Dead Tumor Cell Bodies With Tumor-Activated MnO2 for cGAS-STING-Potentiated Personalized Immunotherapy

Bolun Xu,Xuan Lu,Yuquan Wang,Haihua Ji,Ying Zhang,Yiqun Wan,Hao Wan

Immunogenic cell death (ICD)-based whole-cell personalized cancer immunotherapies present full tumor antigens but suffer from poor immunogenicity, early clearance, and a glutathione (GSH)-rich immunosuppressive tumor microenvironment (TME). Here, we report a TME-responsive immunotherapeutic platform, DTBEI@CS@MnO 2 , which integrates immunogenicity-enhanced dead tumor cell bodies (DTBEI) with Mn 2 + -potentiated innate immunity. Tumor cells preloaded with indocyanine green (ICG) are sequentially functionalized with a chitosan (CS) interlayer followed by MnO 2 adsorption (CS@MnO 2 ) via electrostatic interactions. Upon near-infrared laser irradiation, ICG-mediated photodynamic/photothermal effect induces potent ICD, generating DTBEI. Within the acidic and GSH-enriched TME, the CS@MnO 2 coating disassembles to release DTBEI and MnO 2 . DTBEI provides endogenous antigens and ICD-associated danger signals, while MnO 2 is reduced by GSH to Mn 2 + . The resulting Mn 2 + amplifies DTBEI- and tumor-derived deoxyribonucleic acid-triggered cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) activation and downstream immune-stimulatory effects, thereby synergistically promoting dendritic cell maturation, antigen cross-presentation, and tumor-specific T-cell priming. Consequently, DTBEI@CS@MnO 2 elicits durable anti-tumor immunity, effectively inhibiting tumor growth and suppressing recurrence and metastasis, while establishing T-cell memory responses. Importantly, this strategy shows broad applicability in multiple tumor models, including CT26 colon cancer, 4T1 breast cancer, and B16F10 melanoma, while maintaining favorable biocompatibility. Overall, these findings highlight a materials-based approach for personalized cancer immunotherapy.

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FOOD CHEMISTRY · 2026 · IF 10.4

Beyond single-mechanism: A three-channel MnO2 nanozyme array for point-of-care flavonoid isomers discrimination and proof-of-concept Citrus differentiation

Bingjing Xu,Mengyao Shi,Li Zou,Huaping Xu,Hanqi Ruan,Wuxiang Ye,Dan Shou,Chaoying Tong

Constructing a three-channel MnO 2 nanozyme array with multi-mechanism synergy. • Revealing structure/coordination-mediated radical scavenging and electron transfer. • Discriminating flavonoid isomers sensitively down to 1 μg/mL. • Identifying adulterated samples accurately from 0 to 100%. • Demonstrating proof-of-concept Citrus differentiation on a paper-based platform. The rapid differentiation of closely related Citrus plants remains a challenge due to their highly similar physicochemical profiles. This study developed a three-channel colorimetric sensor array based on morphologically distinct MnO 2 -I/II/III nanozymes with diverse oxidase-like activity. Synergistic free radical scavenging and electron transfer during catalysis induce specific absorbance changes of TMB/oxTMB (green, yellow, and blue) at 370, 450, and 652 nm, which may be synergistically mediated by flavonoid structures and coordination interactions. The multi-mechanism three-channel design provides a highly cross-reactive dataset on a paper-based platform, enabling HCA, PCA, and 3D LDA to: (i) discriminate flavonoid isomers (1–500 μg/mL), (ii) identify adulterated samples (0–100%), and (iii) achieve 100% accuracy on an independent test set for multi-batch Citrus samples. This work presents a mechanism-distinctive MnO 2 nanozyme array, which, coupled with chemometric analysis, serves as a promising proof-of-concept platform for point-of-care screening of structurally similar flavonoids and closely related plant samples. Download: Download high-res image (117KB) Download: Download full-size image

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SENSORS AND ACTUATORS B-CHEMICAL · 2025 · IF 7.7

Novel triethylamine sensor with low operating temperature and low detect limit using the nano n-p heterojunction of δ-MnO2 and WO3

Shuwen Zhu,Huiqing Fan,Lin Lei,Yongbo Fan,Weijia Wang

Developing triethylamine (TEA) sensors using metal oxide semiconductors (MOS) presents challenges such as achieving high sensitivity, low operating temperatures, and reliable detection of trace TEA. In this study, a novel two-step solvothermal synthesis strategy was developed for the sequential fabrication of δ-MnO 2 nanosheets and δ-MnO 2 /WO 3 (WMn) heterojunction composites. The resulting WMn heterostructure features a unique morphology, where δ-MnO 2 nanosheets are encapsulated within a WO 3 matrix, forming well-defined layered interfaces and abundant active sites. This tailored structure significantly enhances the TEA sensing performance. In particularly, WMn1 sensor achieves an ultrahigh response of 515.37 to 20 ppm TEA at 140 °C. The sensor also exhibits an exceptionally low detection limit of 15.91 ppb, along with rapid response/recovery kinetics and long-term stability. The superior performance is attributed to the formation of n–p heterojunction and the synergistic effects of electronic and chemical sensitization, which optimize charge carrier dynamics, reduce interfacial resistance, and enhance surface reactivity. By focusing on interface engineering in heterojunction-based gas sensors, this study contributes to the strategic design of high-performance sensing materials, with potential applications in environmental monitoring and industrial safety.

CAS / MDL: 13283-01-7 64-19-7
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MICROCHIMICA ACTA · 2025 ·Vol. 192 ·期 7 ·1-10 · IF 5.3

A smartphone-assisted colorimetric paper sensor based on MnO2 nanozymes as oxidase mimetics for rapid evaluation of total antioxidant capacity in foods

Shi Ruirui,Wang Chao,Zhu Mingyue,Xie Chen,Cui Wenyu,Zhou Qing

Manganese dioxide nanozymes (MnO 2 -zymes) with excellent oxidase-like properties were synthesized via a one-step solvothermal method. A rapid, portable smartphone-assisted colorimetric paper sensor based on MnO 2 -zymes/TMB chromogenic system was developed for total antioxidant capacity (TAC) evaluation. The MnO 2 -zymes immediately catalyzed the oxidation of colorless TMB to generate blue oxidation products (oxTMB), while antioxidants can quickly reduce oxTMB to TMB, causing noticeable fading of the blue color. Integrated with a smartphone-based RGB mode, ascorbic acid (AA) was quantified in the range 2.5–125.00 μM with a limit of detection (LOD) of 3.03 μM. Furthermore, using AA as a model analyte, the paper sensor was successfully applied to evaluate TAC in fruits and beverages, with results closely matching those obtained from a microplate reader-assisted colorimetric sensor and an ABTS free radical scavenging capacity assay kit. This high-performance sensor is simple, rapid, and accurate, showing great potential in practical application for TAC determination. Graphical

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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2025 · IF 9.7

Vanadium dopant induced the small and low crystallinity layered MnO2 supported on the carbon Nanosheets for high-performance aqueous zinc-ion batteries

Yingyuan Zhao,Yinfeng Zhang,Xinlei Ma,Anpeng Su,Zhengbo Chen,Xu Zhang

Manganese dioxide (MnO 2 ), with its high theoretical capacity, environmental benignity, and low cost, is a promising cathode material for aqueous zinc-ion batteries (ZIBs). Nevertheless, its practical application is hindered by sluggish electrochemical kinetics and poor electrical conductivity. Herein, we report a facile synthesis of Vanadium (V) doping MnO 2 supported on carbon nanosheets (CN) with reduced crystallinity and nanoscale dimensions (V-MnO 2 /CN). The CN substrate not only enhances the conductivity but also provides abundant nucleation sites for the uniform growth of MnO 2 nanosheets. The incorporation of V regulates the electronic structure of MnO 2 , lowers its crystallinity, and generates plentiful oxygen vacancies. These structural and compositional synergies enhance electronic conductivity, accelerate ion diffusion, and expose more electrochemically active sites. As a result, the prepared V-MnO 2 /CN cathode delivers a high specific capacity of 352.9 mAh g −1 at 0.5 A g −1 and excellent cycling stability with 83.2 % capacity retention after 1000 cycles at 1 A g −1 . Further ex-situ analysis reveals that the charge storage mechanism is governed by reversible Zn 2+ /H + co-insertion and extraction. This study provides a simple yet effective design principle for constructing low crystallinity, heteroatom-doped MnO 2 nanosheets for high-performance and durable ZIBs cathodes.

研究领域: 材料科学 · 电化学 · 能源存储 · 纳米材料 · 电池技术
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