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ACS Applied Materials & Interfaces · 2015 · IF 6.723

Immobilization of Enzymes by Electrochemical and Chemical Oxidative Polymerization of L-DOPA to Fabricate Amperometric Biosensors and Biofuel Cells

Mengzhen Dai,Lingen Sun,Long Chao,Yueming Tan,Yingchun Fu,Chao Chen,Qingji Xie

Electrochemical/chemical oxidative synthesis and biosensing/biofuel cell applications of poly(L-DOPA) (PD) are studied versus polydopamine (PDA) as a recent hotspot biomaterial. The enzyme electrode developed by coelectrodeposition of PD and glucose oxidase (GOx), uricase, or tyrosinase shows biosensing performance superior to that of the corresponding PDA-based enzyme electrode. The chemical oxidative polymerization of L-DOPA (PDC) by NaAuCl4 in GOx-containing neutral aqueous solution is used to immobilize GOx and gold nanoparticles (AuNPs). The thus-prepared chitosan (CS)/GOx-PDC-AuNPs/Auplate/Au electrode working in the first-generation biosensing mode responds linearly to glucose concentration with a sensitivity of 152 μA mM–1 cm–2, which is larger than those of the CS/GOx-PDAC-AuNPs/Auplate/Au electrode, the CS/GOx-poly(3-anilineboronic acid) (PABA)-AuNPs/Auplate/Au electrode, and the most reported GOx-based enzyme electrodes. This PDC-based enzyme electrode also works well in the second-generation biosensing mode and as an excellent bioanode in biofuel cell construction, probably because PD as an amino acid polymer has the higher biocompatibility and the more favorable affinity to the enzyme than PDA. The PD material of great convenience in synthesis, outstanding biocompatibility for preparing high-performance bionanocomposites, and strong capability of multifunctional coatings on many surfaces may find wide applications in diversified fields including biotechnology and surface-coating.

CAS / MDL: 59-92-7
研究领域: 生物技术 · 材料科学 · 电化学
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International Journal of Electrochemical Science · 2023 · IF 1.5

Biosensor for Detecting Uric Acid in Urine

Lan Zheng,Heng Ma,Yaohong Ma,Qingjun Meng,Junhui Yang,Binglian Wang,Yan Yang,Weili Gong,Guangheng Gao

In this work, we developed a highly sensitive electrochemical enzyme electrode that directly determines the uric acid (UA) concentration in urine. Results from cyclic voltammetry testing showed a well-defined oxidation peak at 0.35 V, but no reduction peak, indicating that an irreversible redox reaction was executed. The enzyme electrode’s modification method was optimized as follows: 0.1% chitosan, 0.3% graphene oxide, 5 mmol L -1 uricase, and 25% glutaraldehyde. Under these optimal conditions, there was a good linear relationship between the redox peak current and UA concentration in the range of 0.1-2 mmol L -1 (I=4.1661 CUA + 2.0445; R 2 =0.9995); and the detection limit was 0.023 mmol L -1 (S/N = 3.3). The modified electrode showed high repeatability (RSD = 3.34%), good stability (12 days), and strong antiinterference capability. Therefore, this electrode can quickly and accurately determine the UA concentration in urine. This study is highly significant for monitoring UA levels in gout populations and preventing kidney damage caused by gout.

CAS / MDL: 9012-76-4 111-30-8
研究领域: 生物传感器技术 · 医学诊断 · 电化学分析
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Biosensors-Basel · 2024 ·Vol. 14 ·期 8 ·403 · IF 4.9

Solid-Phase Electrochemiluminescence Enzyme Electrodes Based on Nanocage Arrays for Highly Sensitive Detection of Cholesterol

Xinying Ma,Zhe Zhang,Yanyan Zheng,Jiyang Liu

The convenient and sensitive detection of metabolites is of great significance for understanding human health status and drug development. Solid-phase electrochemiluminescence (ECL) enzyme electrodes show great potential in metabolite detection based on the enzyme-catalyzed reaction product hydrogen peroxide (H2O2). Herein, a solid-phase ECL enzyme sensor was fabricated based on a confined emitter and an immobilized enzyme using electrostatic nanocage array, constructing a platform for the sensitive detection of cholesterol. The electrostatic cage nanochannel consists of a bipolar and bilayer vertically aligned mesoporous silica film (bp-VMSF). The upper layer of bp-VMSF is an amino-modified, positively charged VMSF (p-VMSF), and the lower layer is a negatively charged VMSF (n-VMSF). The most commonly used ECL probe tris(bipyridine)ruthenium(II) (Ru(bpy)32+) is fixed in n-VMSF by electrostatic adsorption from n-VMSF and electrostatic repulsion from the upper p-VMSF, generating significantly enhanced and stable ECL signals. The successful preparation of the electrostatic cage was characterized by scanning electron microscopy (SEM) and electrochemical methods. After amino groups on the outer surface of bp-VMSF were derivatized with aldehyde, cholesterol oxidase (ChOx) molecules were covalently immobilized. The successful construction of the enzyme electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). When the corresponding enzyme substrate, cholesterol, was present in the solution, the ECL signal of Ru(bpy)32+was quenched by the enzyme-catalyzed reaction product H2O2, enabling the high-sensitivity detection of cholesterol. The linear range for detecting cholesterol was from 0.05 mM to 5.0 mM, with a limit of detection (LOD) of 1.5 μM.

研究领域: 生物传感器 · 医学检测 · 材料科学
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MICROCHEMICAL JOURNAL · 2020 · IF 3.594

Facile and rapid one-step mass production of flexible 3D porous graphene nanozyme electrode via direct laser-writing for intelligent evaluation of fish freshness

Yifu Zhu,Peng Liu,Ting Xue,Jingkun Xu,Daoyang Qiu,Yingying Sheng,Weiqiang Li,Xinyu Lu,Yu Ge,Yangping Wen

In this report, we have prepared 3D porous graphene flexible nanozyme electrode on polyimide by direct laser-writing technology using a home-made computer-controlled laser scribing machine, which is a cost-efficient and one-step mass-production method. This flexible electrode exhibited outstanding mechanical flexibility, distinctive 3D porous structure, expected cycle stability, high conductivity, which was employed as a novel electrochemical nano-sensing platform for intelligent evaluation of fish freshness via simultaneous detection of both xanthine (XT) and hypoxanthine (HX) and smart analysis and digital output using machine learning (ML) model based on artificial neural network (ANN) algorithm. The as-prepared flexible electrode showed an enzyme-like kinetic (nanozyme) characteristic during the detection of XT (0.3–179.9 μM) and HX (0.3–159.9 μM) with a limit of detection (LOD) of 0.26 μM and 0.18 μM, respectively. The fish freshness was evaluated by voltammetric detection of both XT and HX in fish sample with different storage times, and ML model with ANN algorithm was built to realize smart analysis and digital output for evaluating the fish freshness. This will provide an experimental support for biomimetic flexible nano-sensing platform based on nanozyme flexible electrode via facile and rapid one-step mass production and intelligent nano-sensing platform based on ML model for intelligent operation for smart analysis and intelligent transformation for digital output.

研究领域: 材料科学 · 生物传感 · 人工智能
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JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS · 2019 · IF 2.752

3D Graphene-based macro-mesoporous frameworks as enzymatic electrodes

Ling Shen,Jie Ying,Lei Ren,Yao Yao,Yi Lu,Ying Dong,Ge Tian,Xiao-Yu Yang,Bao-Lian Su

An efficient method was developed to fabricate three-dimensional (3D) graphene-based nanomaterials with hierarchical macro-mesoporous structures as novel enzymatic electrode materials. The 3D continuously interconnected macropores were generated by hydrothermal self-assembly of graphene oxide sheets to form 3D graphene-based frameworks, and uniform mesopores on the surface of graphene frameworks were obtained by replicating the previously synthesized mesoporous silica . Due to the integration of macropores that can promote the efficiency of mass transfer, and mesopores that can facilitate enzyme immobilization and electron transfer , the unique 3D graphene-based macro-mesoporous frameworks with narrow mesopore size distribution, large surface area and high electrical conductivity can be applied as an excellent platform to immobilize glucose oxidase as enzymatic electrodes, displaying enhanced glucose-sensing properties. This approach can be utilized to fabricate various 3D hierarchical macro-mesoporous nanomaterials for application in a broad range of sensors, supercapacitors , batteries and catalysis.

CAS / MDL: 57-09-0 78-10-4
研究领域: 材料科学 · 生物传感器 · 电化学
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Scientific Reports · 2020 ·Vol. 10 ·期 1 ·1-10 · IF 3.998

Core-shell gold-nickel nanostructures as highly selective and stable nonenzymatic glucose sensor for fermentation process

Gao Xuejin,Du Xinzhao,Liu Danye,Gao Huihui,Wang Pu,Yang Jun

Non-enzymatic electrodes based on noble metals have excellent selectivity and high sensitivity in glucose detection but no such shortcomings as easy to be affected by pH, temperature, and toxic chemicals. Herein, spherical gold-nickel nanoparticles with a core-shell construction (Au@Ni) are prepared by oleylamine reduction of their metal precursors. At an appropriate Au/Ni ratio, the core-shell Au@Ni nanoparticles as a sensor for glucose detection combine the high electrocatalytic activity, good selectivity and biological compatibility of Au with the remarkable tolerance of Ni for chlorine ions (Cl − ) and poisoning intermediates in catalytic oxidation of glucose. This electrode exhibits a low operating voltage of 0.10 V vs. SCE for glucose oxidation, leading to higher selectivity compared with other Au- and Ni-based sensors. The linear range for the glucose detection is from 0.5 mmol L −1 to 10 mmol L −1 with a rapid response time of ca. 3 s, good stability, sensitivity estimated to be 23.17 μA cm −2 mM −1 , and a detection limit of 0.0157 mM. The sensor displays high anti-toxicity, and is not easily poisoned by the adsorption of Cl − in solution.

研究领域: 生物传感器 · 材料科学 · 分析化学
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Journal of Inorganic and Organometallic Polymers and Materials · 2017 ·Vol. 27 ·期 5 ·1162-1176 · IF 1.577

Dependence of Catalytic Dynamics on Structural and Operational Parameters of Enzymatic Electrodes Based on Nano-composite

Zeng Han,Yang Yang,Zhao Shu Xian,Zhang Yu He

Abstract Dependences of structural parameters and operational conditions on enzymatic catalysis of substrates (glucose and oxygen) for basal electrodes over-coated by composite consisting of nano-gold particle and polymer, were investigated systematically by the means of electrochemistry and spectrometry. Rate constants of steps involved in the whole catalytic cycle were estimated under the same dimension and were compared to confirm the limiting factor in the whole catalytic cycle. Results from experiments indicated that nano-gold particle surface anchored with aromatic ring as conductive support played the important role in achieving direct electron transfer between cofactors in redox protein molecules and electrical wired matrix. Complexations between components of nano-composite and redox sites within incorporated enzyme molecules acted as the paradoxical role in promoting the catalytic efficiency in the long term. Electrochemical conversion of substrates into product was identified to be the rate limiting step in the whole catalytic cycle for both enzyme based electrodes. Other parameters such as enzyme loading amounts in matrix, size of nano-particle and proportion of component in nano-composite only posed impact on magnitude of catalytic effect rather than the mechanism of catalysis. Graphical Abstract Transformation of substrate into product was ascribed to the limiting step in the whole catalysis for enzyme-based electrodes which resulted from great impact of interactions between enzyme carrier and redox protein on configuration of cofactors in enzyme molecules and binding ability to substrate for proteins.

CAS / MDL: 50-99-7
研究领域: 生物化学 · 电化学
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ANALYST · 2015 ·Vol. 140 ·期 15 ·5205-5215 · IF 4.107

Nanoporous copper oxide ribbon assembly of free-standing nanoneedles as biosensors for glucose

Shaodong Sun,Yuexia Sun,Anran Chen,Xiaozhe Zhang,Zhimao Yang

Inspired by a sequential hydrolysis–precipitation mechanism, morphology-controllable hierarchical cupric oxide (CuO) nanostructures are facilely fabricated by a green water/ethanol solution-phase transformation of Cux(OH)2x−2(SO4) precursors in the absence of any organic capping agents and without annealing treatment in air. Antlerite Cu3(OH)4(SO4) precursors formed in a low volume ratio between water and ethanol can transform into a two-dimensional (2D) hierarchical nanoporous CuO ribbon assembly of free-standing nanoneedle building blocks and hierarchical nanoneedle-aggregated CuO flowers. Brochantite Cu4(OH)6(SO4) precursors formed in a high volume ratio between water and ethanol can transform into hierarchical nanoplate-aggregated CuO nanoribbons and nanoflowers. Such 2D hierarchical nanoporous CuO ribbons serving as a promising electrode material for nonenzymatic glucose detection show high sensitivity, a low detection limit, fast amperometric response and good selectivity. Significantly, this green water-induced precursor-hydrolysis method might be used to control effectively the growth of other metal oxide micro-/nanostructures.

研究领域: 材料科学 · 生物传感 · 化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2015 · IF 4.097

Graphene nanodots encaged 3-D gold substrate as enzyme loading platform for the fabrication of high performance biosensors

Jianmei Wang,Huihui Zhu,Yuanhong Xu,Wenrong Yang,Ao Liu,Fukai Shan,Mengmei Cao,Jingquan Liu

Herein, a uniform three-dimensional (3-D) graphene nanodots-encaged porous gold electrode was prepared via ion beam sputtering deposition (IBSD) and mild corrosion chemistry for efficient enzyme electrode fabrication. Enzymes, like glucose oxidase and catalase , were modified with pyrene functionalities and then loaded into the graphene nanodots encaged porous gold electrode via non-covalent π–π stacking interaction between pyrene and graphene. The fabricated enzyme electrodes showed profound reusability and repeatability, high sensitivity, inherent selectivity and enhanced detection range. As for glucose analysis a broad linear range from 0.05 to 100   mM was obtained and the linear range for hydrogen peroxide was 0.005 to 4   mM. Detection limits of 30   μM for glucose and 1   μM for hydrogen peroxide were achieved ( S / N   =   3), respectively. These electrodes can be applied to analyze the clinical samples with reliable results. The formation mechanism and 3-D structure of the porous electrode were investigated using high resolution transmission electron microscope (HRTEM), atomic force microscopy (AFM), scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS). Most importantly, various other ideal biosensors can be fabricated using the same porous electrode and the same enzyme modification methodology.

CAS / MDL: 9001-05-2
研究领域: 生物传感器 · 材料科学 · 分析化学
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2017 ·Vol. 164 ·期 13 ·G112 · IF 3.259

Three-Dimensional Nickel Foam Based Enzymatic Electrode and Its Glucose/O2 Biofuel Cell with High Power Density

Yuchen Hui,Xiaoyan Ma,Fengjin Qu,Fang Chen,Ying Chen

A practical strategy is developed to fabricate stable glucose/O2 biofuel cells with high power density assembled by enzymatic bio-electrodes based on three-dimensional nickel foam. The porous three-dimensional nickel foam is used as a substrate to enhance the enzyme loading, while the reduced graphene oxide and gold nanoparticles decorating on the nickel foam are employed as the direct electron transfer system for bio-anodes and bio-cathodes. The ferrocenecarboxylic acid serves for the mediated electron transfer to further increase electron transfer rate for glucose oxidase electrodes. Covalent bond is employed to immobilize the mediator and enzymes for improving the stability of bio-electrodes and biofuel cells. As the results, the surface glucose oxidase loading reaches to 4.03 × 10−7 mol cm−2 with good enzymatic activity. Additionally, the obtained glucose/O2 biofuel cells exhibit an outstanding maximum power density of 2.84 ± 0.09 mW cm−2, with a remarkable long-term operational stability for retaining 85.5% of its performance after 70 days. In human blood, the biofuel cell shows a favorable output performance of 0.39 ± 0.04 mW cm−2, implying the appropriateness for practical applications.

研究领域: 生物化学 · 材料科学 · 能源技术
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BIOSENSORS & BIOELECTRONICS · 2024 · IF 10.7

Controllable radical polymerization of TEMPO redox for stable and sensitive enzyme electrode interface

Nan Ma,Shuqi Wang,Mengyuan Liu,Hao Zhu,Qianzuo Liu,Jinming Kong,Ting Zhang

Assembling functional molecules on the surface of an enzyme electrode is the most basic technique for constructing a biosensor. However, precise control of electron transfer interface or electron mediator on the electrode surface remains a challenge, which is a key step that affects the stability and sensitivity of enzyme-based biosensors. In this study, we propose the use of controllable free radical polymerization to grow stable 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) polymer as electron mediator on enzyme surface for the first time. Through scanning electron microscopy (SEM), Raman spectroscopy , electrode surface coverage measurement, static contact angle (SCA), and a series of electrochemical methods , it has been demonstrated that the TEMPO-based enzyme electrode exhibits a uniform hydrophilic morphology and stable electrochemical performance. Furthermore, the results show that the sensor demonstrates high sensitivity for detecting glucose biomolecules in artificial sweat and serum. Attributing to the quantitative and controllable radical polymerization of TEMPO redox assembled enzyme electrode surface, the as-proposed biosensor providing a use, storage, and inter-batch sensing stability, providing a vital platform for wearable/implantable biochemical sensors .

研究领域: 生物化学 · 材料科学 · 分析化学
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SENSORS AND ACTUATORS B-CHEMICAL · 2016 · IF 4.758

A sensitive electrochemiluminescent cholesterol biosensor based on Au/hollowed-TiO2 nano-composite pre-functionalized electrode

Shan Tang,Qun Zhao,Yifeng Tu

This paper describes a novel approach to promote the analytical performance of electrochemiluminescent (ECL) biosensor of cholesterol by a nanocomposite (Au nanoparticles/ion liquid/hollowed TiO 2 nano-shell) pre-functionalized indium tin oxide glass to load the cholesterol oxidase. Here the enzymatically produced hydrogen peroxide greatly intensified the ECL of luminol under the catalysis of the nanocomposite. The quantification of cholesterol was directly accomplished by calibrating the ECL sensing output. The formation and properties of the nanocomposite and the functionalized electrode have been confirmed by electrochemistry , spectroscopy and electron-microscopy. The prepared biosensor exhibits a linear regression ranged from 8.33   ×   10 −9   M to 4.17   ×   10 −7   M with an ultralow detection limit (LOD) of 6.30   ×   10 −9   M. It also possesses the excellent specificity for cholesterol from potential interferents , the favorable repeatability/stability for use or storage, the good reproducibility and adequate recovery for real sample test. In addition, for the detection of clinical serum sample, it is well consistent with the datum from medical cholesterol kit, indicating its reliability. It is in promising of the application for the cholesterol detection in those clinical specimens of teeny amount of sample and limited concentration.

研究领域: 生物医学工程 · 分析化学
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