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Science Bulletin · 2024 · IF 18.8

Unilamellar MnO2 nanosheets confined Ru-clusters combined with pulse electrocatalysis for biomass electrooxidation in neutral electrolytes

Yuanqing He,Chongyang Ma,Shiheng Mo,Chung-Li Dong,Wei Chen,Shuo Chen,Huan Pang,Ren Zhi Ma,Shuangyin Wang,Yuqin Zou

The electrochemical oxidation of 5-hydroxymethylfurfural (HMFOR) in alkaline electrolyte is a promising strategy for producing high-value chemicals from biomass derivatives. However, the disproportionation of aldehyde groups under strong alkaline conditions and the polymerization of HMF to form humic substances can impact the purity of 2,5-furandicarboxylic acid (FDCA) products. The use of neutral electrolytes offers an alternative environment for electrolysis, but the lack of OH − ions in the electrolyte often leads to low current density and low yields of FDCA. In this study, a sandwich-structured catalyst, consisting of Ru clusters confined between unilamellar MnO 2 nanosheets (S-Ru/MnO 2 ), was used in conjunction with an electrochemical pulse method to realize the electrochemical conversion of 5-hydroxymethylfurfural into FDCA in neutral electrolytes. Pulse electrolysis and the strong electron transfer between Ru clusters and MnO 2 nanosheets help maintain Ru in a low oxidation state, ensuring high activity. The increased *OH generation led to a groundbreaking current density of 47 mA/cm 2 at 1.55 V vs. reversible hydrogen electrode (RHE) and an outstanding yield rate of 98.7 % for FDCA in a neutral electrolyte. This work provides a strategy that combines electrocatalyst design with an electrolysis technique to achieve remarkable performance in neutral HMFOR.

研究领域: 电化学 · 材料科学 · 生物质转化
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Advanced Energy Materials · 2016 ·Vol. 6 ·期 18 ·1600755 · IF 15.23

Free-Standing 3D Nanoporous Duct-Like and Hierarchical Nanoporous Graphene Films for Micron-Level Flexible Solid-State Asymmetric Supercapacitors

Kaiqiang Qin,Enzuo Liu,Jiajun Li,Jianli Kang,Chunsheng Shi,Chunnian He,Fang He,Naiqin Zhao

High energy density and power density within a limited volume of flexible solid-state supercapacitors are highly desirable for practical applications. Here, free-standing high-quality 3D nanoporous duct-like graphene (3D-DG) films are fabricated with high flexibility and robustness as the backbones to deposit flower-like MnO 2 nanosheets (3D-DG@MnO 2 ). The 3D-DG is the ideal support for the deposition of large amount of active materials because of its large surface area, appropriate pore structure, and negligible volume compared with other kinds of carbon backbones. Moreover, the 3D-DG preserve the distinctive 2D coherent electronic properties of graphene, in which charge carriers move rapidly with a small resistance through the high-quality and continuous chemical vapor deposition-grown graphene building blocks, which results in a high rate performance. Marvelously, ultrathin (≈50 μm) flexible solid-state asymmetric supercapacitors (ASCs) using 3D-DG@MnO 2 as the positive electrode and 3D hierarchical nanoporous graphene films as the negative electrode display ultrahigh volumetric energy density (28.2 mW h cm −3 ) and power density (55.7 W cm −3 ) at 2.0 V. Furthermore, as-prepared ASCs show high cycle stability clearly demonstrating their broad applications as power supplies in wearable electronic devices.

CAS / MDL: 9002-89-5
研究领域: 材料科学 · 能源存储与转换
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2024 · IF 5.4

Tumor microenvironment-responsive size-changeable and biodegradable HA-CuS/MnO2 nanosheets for MR imaging and synergistic chemodynamic therapy/phototherapy

Zhen Jin,Yunkai Wang,Miaomiao Han,Li Wang,Fei Lin,Qianfang Jia,Wu Ren,Jiawei Xu,Wenhao Yang,Guo-an Zhao,Xuming Sun,Changqin Jing

Tumor microenvironment (TME)-responsive size-changeable and biodegradable nanoplatforms for multimodal therapy possess huge advantages in anti-tumor therapy. Hence, we developed a hyaluronic acid (HA) modified CuS/MnO 2 nanosheets (HCMNs) as a multifunctional nanoplatform for synergistic chemodynamic therapy (CDT)/photothermal therapy (PTT)/photodynamic therapy (PDT). The prepared HCMNs exhibited significant NIR light absorption and photothermal conversion efficiency because of the densely deposited ultra-small sized CuS nanoparticles on the surface of MnO 2 nanosheet. They could precisely target the tumor cells and rapidly decomposed into small sized nanostructures in the TME, and then efficiently promote intracellular ROS generation through a series of cascade reactions. Moreover, the local temperature elevation induced by photothermal effect also promote the PDT based on CuS nanoparticles and the Fenton-like reaction of Mn 2+ , thereby enhancing the therapeutic efficiency. Furthermore, the T 1 -weighted magnetic resonance (MR) imaging was significantly enhanced by the abundant Mn 2+ ions from the decomposition process of HCMNs. In addition, the CDT/PTT/PDT synergistic therapy using a single NIR light source exhibited considerable anti-tumor effect via in vitro cell test. Therefore, the developed HCMNs will provide great potential for MR imaging and multimodal synergistic cancer therapy.

研究领域: 生物医学工程 · 纳米医学 · 肿瘤治疗
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Foods · 2024 ·Vol. 13 ·期 13 ·2009 · IF 4.7

Enzyme Cascade Amplification-Based Immunoassay Using Alkaline Phosphatase-Linked Single-Chain Variable Fragment Fusion Tracer and MnO2 Nanosheets for Detection of Deoxynivalenol in Corn Samples

Guifang Xie,Fujing Mao,Yirui Huang,Li Wen,Zhichang Sun,Zhenyun He,Xing Liu

Deoxynivalenol (DON) is a common mycotoxin that contaminates cereals. Therefore, the development of sensitive and efficient detection methods for DON is essential to guarantee food safety and human health. In this study, an enzyme cascade amplification-based immunoassay (ECAIA) using a dual-functional alkaline phosphatase-linked single-chain fragment variable fusion tracer (scFv-ALP) and MnO2nanosheets was established for DON detection. The scFv-ALP effectively catalyzes the hydrolysis of ascorbyl-2-phosphate (AAP) to produce ascorbic acid (AA). This AA subsequently interacts with MnO2nanosheets to initiate a redox reaction that results in the loss of oxidizing properties of MnO2. In the absence of ALP, MnO2nanosheets can oxidize 3,3′,5,5′-tetramethylbenzidine (TMB) to produce the blue oxidized product of TMB, which exhibits a signal at a wavelength of 650 nm for quantitative analysis. After optimization, the ECAIA had a limit of detection of 0.45 ng/mL and a linear range of 1.2–35.41 ng/mL. The ECAIA exhibited good accuracy in recovery experiments and high selectivity for DON. Moreover, the detection results of the actual corn samples correlated well with those from high-performance liquid chromatography. Overall, the proposed ECAIA based on the scFv-ALP and MnO2nanosheets was demonstrated as a reliable tool for the detection of DON in corn samples.

CAS / MDL: 13446-34-9 75-59-2
研究领域: 食品安全 · 分析化学 · 生物技术
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

A convenient smartphone-assisted colorimetric for 6-Mercaptopurine detection using enhanced oxidase-like activity of β-cyclodextrin modified MnO2 nanosheets

Ruiqi Huang,Yingfeng Qin,Yanqin Huang,Zengqiong Huang,Gao-Jie Ye

6-mercaptopurine (6-MP) is widely used in the treatment of many diseases, but exhibits some serious side effects due to its toxicity. Therefore, it is important and imperative to effectively control and monitoring concentration of 6-MP. Herein, we designed a smartphone-assisted colorimetric sensing platform for 6-MP detection, based on an excellent β-cyclodextrin modified MnO 2 nanosheets (β-CD@MnO 2 NNS) mediated oxidase-like activity. β-CD@MnO 2 NNS can directly oxidizes 3,3′,5,5′-tetramethylbenzidine (TMB) into oxidized TMB with color changes, yielding more than 3-fold higher oxidase-like catalytic activity compared with individual MnO 2 NNS. After adding 6-MP, β-CD@MnO 2 NNS can be reduced to Mn 2+ and lose their oxidase-like properties, resulting in a color and absorbance change for sensitive and selectivity detection of 6-MP. Meanwhile, the smartphone-based color recognition application can intuitively and simply measure the concentration of 6-MP. The limits of detection UV–vis instrument and smartphone were 0.35 μM and 0.86 μM, respectively. This method has also been successfully applied to the detection of real samples. Finally, this study provides a new promising platform for detection of 6-MP and is expected to be used in application of pharmaceutical analysis and biomedicine.

研究领域: 医学诊断 · 药物分析 · 生物传感
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Energy storage smart window with transparent-to-dark electrochromic behavior and improved pseudocapacitive performance

Sijie Xie,Yongbo Chen,Zhijie Bi,Shasha Jia,Xiangxin Guo,Xiangdong Gao,Xiaomin Li

A carefully designed energy storage smart window (ESSW) was successfully demonstrated with transparent-to-dark electrochromic behavior and improved pseudocapacitive performance that constructed by Mo-doped WO 3 film electrode and MnO 2 nanoflake film electrode. These two electrodes were all synthesized by facile electrodeposition method which is simple, economic and easy-to-production. The proposed ESSW could change its color between transparent and dark with over 60% optical modulations in all visible bands (420–800 nm), which is satisfactory to the applications toward energy saving. Also, the areal capacitance of the ESSW reaches 19.1 mF cm −2 with working voltage window of 2.0 V so that just one single ESSW could power an LED bulb for more than 90 s. The complementary electrochromic behavior of the two electrodes guarantees the commendable electrochromic performance of the proposed ESSW, and the well-matched working potentials and areal capacitances of the asymmetric electrodes improve the pseudocapacitive performance. Such ESSW could have widely future applications toward energy saving and storing fields.

研究领域: 材料科学 · 能源技术
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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 Materials Chemistry A · 2019 ·Vol. 8 ·期 4 ·2021-2032 · IF 10.733

A composite solid polymer electrolyte incorporating MnO2 nanosheets with reinforced mechanical properties and electrochemical stability for lithium metal batteries

Yuhan Li,Zongjie Sun,Dongyu Liu,Yiyang Gao,Yuankun Wang,Huaitian Bu,Mingtao Li,Yanfeng Zhang,Guoxin Gao,Shujiang Ding

A solid polymer electrolyte is expected to be useful for safe and high energy density lithium-metal batteries owing to its good flexibility and high degree of safety. The development of a polyethylene oxide (PEO) based solid electrolyte is still restrained by low ionic conductivity and unsatisfactory mechanical strength. Since MnO2 could combine with PEO chains and Li ions could undergo long-range migration on MnO2 nanosheets, MnO2 nanoflakes are chosen as fillers to improve the electrochemical and mechanical properties of a solid polymer electrolyte. A PEO/MnO2 composite solid polymer electrolyte (CSPE) displays a higher lithium ion transference number (0.378), higher ionic conductivity (1.5 times higher at 60 °C) and better tensile strength (2.3 times) than a PEO solid electrolyte. Density functional theory calculations reflect the fact that the binding energy between the PEO/Li complex and MnO2 is small and there is easy desorption of Li from PEO and migration on MnO2 nanosheets, indicating enhanced lithium ion transport in the electrolyte system. A solid-state lithium metal battery using a PEO/MnO2 CSPE delivers higher capacity (143.5 mA h g−1 after 300 cycles) than an electrolyte without fillers (61.2 mA h g−1 after 90 cycles). Soft-package lithium metal batteries with an MnO2 CSPE reveal high safety after cutting, nail and bending tests.

研究领域: 材料科学 · 能源存储与转换
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SENSORS AND ACTUATORS B-CHEMICAL · 2024 · IF 8

One-step detection of glutathione based on MnO2 nanosheet and pregnancy test strip

Huai Yang,Xiao-Shuai Zhang,Kai Cheng,Bo Liu,Wei Chen,Jin-Xuan Fan,Yuan-Di Zhao

Low cost and rapid detection of glutathione (GSH) has important clinical reference value for the diagnosis and treatment of related diseases. In this study, a one-step method for rapid detection of GSH is developed based on the characteristics of low cost, simple operation and rapid color development of pregnancy test strip. In this method, magnetic Fe 3 O 4 -doped MnO 2 nanosheet is first synthesized, and colloidal gold probe modified with hCG and ssDNA is absorbed on the surface of the nanosheet. Based on the oxidase-like properties of MnO 2 nanosheet, in the presence of GSH, a redox reaction between GSH with MnO 2 occurs to release hCG signal probe into the solution. The supernatant solution is loaded on pregnancy test strip after magnetic separation, and the test line develops color. Then the smartphone App developed in our lab is used to quantitatively detect GSH. The results show that under the optimal conditions, the GSH in the range of 40~800   μM has a good linear relationship with the color intensity of the test line on pregnancy test strip and the detection limit for GSH is 40   μM. So, this method can realize the detection of GSH with low cost, simple, rapid and sensitive, and it can meet the requirements of GSH detection in actual samples.

研究领域: 分析化学 · 生物传感器 · 即时检测
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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Machine-Learning-Assisted CRISPR/Cas12a Biosensors for Monitoring Organophosphorus Pesticide Degradation

Jiaqi Xue,Kang Mao,Zihui Tang,Jiming Hu,Hua Zhang

Owing to the severe environmental and health issues posed by organophosphorus pesticides (OPs), a dual-enzyme cascade biosensing platform based on manganese dioxide (MnO2) and CRISPR/Cas12a was developed in this study. Smartphones were innovatively integrated with a stacked ensemble learning (SEL) model for ultrasensitive detection and dynamic monitoring of OPs in environmental water samples. A dual-enzyme cascade signal amplification strategy was used to construct this sensing platform. Acetylcholinesterase (AChE) catalyzes the generation of thiocholine (TCh), which, in turn, regulates the degradation of MnO2 nanosheets, releasing Cas12a activators and generating a fluorescence signal. Owing to the irreversible inhibition of AChE activity by OPs, dichlorvos (DDVP) was successfully detected, with a detection limit as low as 4.62 pg/mL. Additionally, the SEL model, integrated into the smartphone biosensing platform and incorporating random forest (RF), XGBoost, and ridge regression algorithms, exhibited strong performance in detecting OPs after optimization (R2 = 0.9985). In real water samples, the SEL model achieved a recovery rate of 93.1–103.1%, and the degradation kinetics of DDVP were successfully monitored over 24 h, revealing significant differences in DDVP degradation rates across various water matrices. This study is the first to report the integration of CRISPR/Cas12a biosensing technology with an SEL model-driven smartphone detection platform, providing a novel approach for sensitive, portable, and intelligent monitoring of OPs and offering new insights for water quality monitoring and early detection of environmental risks.

研究领域: 环境监测 · 分析化学 · 生物传感 · 分子生物学 · 环境毒理学 · 水污染控制
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ANALYTICA CHIMICA ACTA · 2019 · IF 5.256

A novel smartphone-based CD-spectrometer for high sensitive and cost-effective colorimetric detection of ascorbic acid

Liubing Kong,Ying Gan,Tao Liang,Longjie Zhong,Yuxiang Pan,Dmitry Kirsanov,Andrey Legin,Hao Wan,Ping Wang

As a powerful tool for medical diagnosis and bioanalysis , conventional optical spectrometers are generally expensive, bulky and always require an accompanying data processing device. In this work, we developed a novel smartphone-based CD-spectrometer (SCDS) for high sensitive and ultra-portable colorimetric analysis , with the advantage of cost-effective and simplicity. The distance between the light source and slit, the structure of SCDS and the parameters of camera in the smartphone were all optimized to ensure the best analytical performance. Besides, the SCDS employed HSV color model and utilized the overall intensity calculated by summing V-value of adjacent position for the absorbance measurement. In this way the errors caused by the low resolution of CD-grating can effectively be eliminated to promote the sensitivity of the SCDS. The performance of the SCDS was first validated for colorimetric detection of BSA with a detection limit of 0.0073 mg/mL, which is superior compared to that of the microtiter plate reader (MTPR). Moreover, by combining with 3,3′,5,5′-tetramethylbenzidine-manganese dioxide (TMB-MnO 2 ) nanosheets reaction, a high sensitive and specific system for ascorbic acid detection was established. The SCDS gives a detection range from 0.6250 μM to 40 μM with a detection limit of 0.4946 μM for AA detection. Compared to other studies, the SCDS features wide detection range and very low detection limit with low cost instrument. Therefore, the SCDS will be an ideal and promising colorimetric system for point-of-care (POC) application in food security, disease diagnosis and environmental monitoring.

研究领域: 医学诊断 · 生物分析 · 分析化学 · 即时检测 · 环境监测 · 食品安全
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Scientific Reports · 2018 ·Vol. 8 ·期 1 ·1-9 · IF 4.122

MRI/Fluorescence bimodal amplification system for cellular GSH detection and tumor cell imaging based on manganese dioxide nanosheet

Yuan Dandan,Ding Lairong,Sun Zhaomei,Li Xuemei

Here, we report a novel magnetic resonance imaging (MRI)/fluorescence bimodal amplification platform for the detection of glutathione (GSH) on the basis of redoxable manganese dioxide (MnO 2 ) nanosheets, which can be readily applied as a DNA nanocarrier, fluorescence quencher, and intracellular GSH-activated MRI contrast agent. The binding of aptamers that absorbed on the MnO 2 nanosheets to their target can facilitating the endocytosis of target-nanoprobes. Once endocytosed, the MnO 2 nanosheets can react with cellular GSH, resulting in the disintegration of nanosheets to generate plenty of Mn 2+ ions for MRI and releases the primers which were adsorbed on the MnO 2 nanosheets. Then the rolling circle amplification (RCA) reaction was initiated to amplify the fluorescence signal. In addition, after treatment with GSH, the MnO 2 nanosheets were reduced and then most of the fluorescence was recovered. Therefore, this MnO 2 nanoprobe exhibits excellent selectivity, suggesting a potential detection platform for analyzing the glutathione level in cells.

CAS / MDL: 13446-34-9
研究领域: 生物医学工程 · 纳米技术 · 癌症研究 · 分子成像
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