新型光电化学生物传感器中若干关键问题的研究

项目来源

国家自然科学基金(NSFC)

项目主持人

张剑荣

项目受资助机构

南京大学

项目编号

21375059

立项年度

2013

立项时间

未公开

项目级别

国家级

研究期限

未知 / 未知

受资助金额

80.00万元

学科

化学科学-化学测量学-电分析化学

学科代码

B-B04-B0402

基金类别

面上项目

关键词

共敏化 ; 分析 ; 光电化学生物传感器 ; 光电转换材料 ; 量子点 ; photoelectrochemical biosensor ; photoelectric conversion material ; quantum dots ; co-sensitization ; analysis

参与者

范高超;王文静;盖盼盼;班睿;何莉;李思远

参与机构

青岛农业大学;贵州师范学院;青岛科技大学;华中农业大学

项目标书摘要:光电化学生物传感是以光电化学过程与电化学生物传感器相结合为基础发展起来的新一代传感器。它以光为激发信号,而电信号则作为检测信号。由于采用了两种不同形式的激发和检测信号,使得该技术背景信号低,具有更高的灵敏度。因此作为一种理想的新型传感机制,它已成为当前研究热点之一。但在已有的光电化学生物传感器中大都采用单一的光电转换材料,受光电转换材料能带宽度的限制,每种光电转换材料均对应有最佳的吸光波段,因此不能充分利用光源的能量。为此,本项目提出用具有不同能隙宽度的光电转换材料组成光电转换复合材料,使之能够对白光等连续光源中各个波段的光均充分的利用,从而显著提高光电信号和光电化学生物传感器性能。本项目主要围绕(1)高光电转换功能纳米材料及量子点的制备;(2)新型光电化学生物传感方式与机理探索;(3)光电化学生物传感电极的修饰与组装等关键问题进行基础研究,争取有所新突破。

Application Abstract: Photoelectrochemical biosensor(PEC biosensor)is a newly appeared biosensor which developed on the basis of combining photoelectrochemical process with electrochemical biosensor.In photoelectrochemical biosensor system,light is employed as excitation signal and current is utilized as detection signal.Because of the total separation of excitation signal and detection signal,this technique possesses potentially higher sensitivity because of the reduced background signals.Accordingly,photoelectrochemical biosensor,as an ideal and novel sensing mechanism,has received more and more attention and become a research focus.However,in most previously reported literatures,only single photoelectric conversion material was employed in PEC biosensor system.As a result,the energy of light source can not be fully utilized because different photoelectric conversion materials have different energy band gaps and each photoelectric conversion material possess its own optimal light absorption band.Based on the situation mentioned above,photoelectric conversion composite materials,which consist of photoelectric conversion materials with different energy band gaps,were proposed to adopt in PEC biosensor system to solve this problem and significantly improve the performance of PEC biosensor.Specifically,this project is mainly focused on the following key issues:(1)preparation of functional nanomaterials and quantum dots with high photoelectric conversion efficiency;(2)construction and mechanism of new type of photoelectrochemical biosensor;(3)modification and assembly of photoelectrochemical biosensing electrode.Believably,new breakthroughs will be produced on the aspects of photoelectric conversion efficiency of functional materials and detection performance of photoelectrochemical biosensor.

项目受资助省

江苏省

项目结题报告(全文)

本项目按照计划书规划顺利完成研究任务,以通讯作者发表SCI论文29篇,其中Nature指数刊物论文12篇,影响影子大于10论文3篇。代表性论文:Chem.Soc.Rev.1篇,Angew.Chem.Int.Ed.1篇,Anal.Chem.5篇,Chem.Commun.4篇,Chem.Sci.1篇,Biosensors and Bioelectronics 3篇,Journal of Materials Chemistry A 3篇;专利1件。毕业博士生5名,硕士生1名。达到了预期研究目标。主要成果如下:成功制备了一批具有各个能带宽度(如~3.2 eV、~2.4 eV、~1.4 eV)的光电复合纳米材料,例如TiO2/CdS/CdSe二元共敏化光电材料、尺寸不同的CdTe 量子点共敏化TiO2/CdS:Mn 杂合物、SiO2@Ab2信号放大和CdS:Mn/CdTe共敏化TiO2纳米管、CdSeTe合金量子点和SiO2@Au纳米复合物之间高效的激子能量转移复合物、CdSe@ZnS核壳量子点敏化TiO2NWs/Au 纳米复合物、CdS:Mn@Ru(bpy)2(dcbpy)纳米复合物等,并将他们作为光电活性材料,显著提高了光电化学系统的光电转换效率。在此基础上,设计了多种新颖的信号放大元件,采用标记性策略构建了高灵敏的光电化学免疫传感、DNA传感以及适配体传感。光电免疫分析方法通常以光电阳极为传感电极,但是,该方法在实际样品分析中具有抗干扰能力差的固有弱点。以光电阴极为基础的光电免疫分析方法可以有效地避免了实际样品中测定干扰的问题。我们设计了由光电阳极和光电阴极组成、以光电阴极作为免疫传感电极,分析生物标志物的新颖光电免疫分析方法。所设计的分析方法具有二个明显的优点:第一,由于在光阴极上进行生物识别和传感,所以,在检测实际生物样品时,阴极传感具有良好的抗干扰能力。第二,由于引入了光阳极,提高了检测目标分析物Ag的光电流和检测限。设计构建了新型光电生物燃料电池,将氮掺杂3D石墨烯作为阳极基地电极种植和生长微生物。同时,对可见光有响应的p-型CuS纳米材料作为光敏化剂用于制备生物燃料电池的阴极。该光助微生物燃料电池既能从燃料又能从光能中获得电能,在电池中同时实现了二种能量的转变,功率输出达到2607 mW m-2,显示出良好的应用潜力。

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  • 3.Ultrasensitive cathode photoelectrochemical immunoassay based on TiOO-2 photoanode-enhanced 3D Cu2 nanowire array photocathode and signal amplification by biocatalytic precipitation

    • 关键词:
    • Biomolecules;Nanobelts;Indium compounds;Silver compounds;Photocathodes;Amplification;Tin oxides;Anodes;Immunology;Nanowires ;TiO2 nanoparticles;3D Cu2O NWA;Biocatalytic precipitation;Carcinoembryonic antigen;Horseradish peroxidase;Immunoassay;Indium tin oxide electrodes;Photo-electrochemistry;Photoelectrochemicals
    • Liu, Li-Xia;Fan, Gao-Chao;Zhang, Jian-Rong;Zhu, Jun-Jie
    • 《Analytica Chimica Acta》
    • 2018年
    • 1027卷
    • 期刊

    Cathode photoelectrochemical immunoassay usually shows better anti-interference capacity toward real samples than anode photoelectrochemical immunoassay. However, its poor photocurrent response has greatly restricted the detection sensitivity. Herein, a promising ultrasensitive cathode photoelectrochemical immunoassay was developed based on TiO2 photoanode-enhanced 3D Cu2O nanowire array (NWA) photocathode, and coupled with signal amplification by horseradish peroxidase (HRP)-induced biocatalytic precipitation (BCP). Carcinoembryonic antigen (CEA, Ag) was used as a detection model, TiO2 nanoparticle-modified indium tin oxide (ITO) electrode served as the photoanode, and Cu2O NWAs grown in situ on Cu mesh was both the photocathode and photoelectrochemical matrix to immobilize the capture CEA antibodies (Ab1). The signal CEA antibodies (Ab2) were labeled with HRP to form Ab2-HRP bioconjugates, and employed as signal amplifiers when the specific immunoreaction occurred. The developed photoanode-enhanced cathode photoelectrochemical immunoassay has good anti-interference capability, outstanding photocurrent response, and high sensitivity for target Ag detection, which was attributed to the synergistic effects of the 3D nanostructure of Cu2O NWA photocathode, the introduction of TiO2 photoanode as counter electrode, and the signal amplification of Ab2-HRP bioconjugate-induced BCP. The developed cathode photoelectrochemical immunoassay showed a low limit of detection (0.037 pg mL−1) with a wide linear range (from 0.1 pg mL−1 to 50 ng mL−1) for CEA detection. © 2018 Elsevier B.V.

    ...
  • 4.Ultrasensitive cathode photoelectrochemical immunoassay based on TiOO-2 photoanode-enhanced 3D Cu2 nanowire array photocathode and signal amplification by biocatalytic precipitation

    • 关键词:
    • Biomolecules;Nanobelts;Indium compounds;Silver compounds;Photocathodes;Amplification;Tin oxides;Anodes;Immunology;Nanowires ;TiO2 nanoparticles;3D Cu2O NWA;Biocatalytic precipitation;Carcinoembryonic antigen;Horseradish peroxidase;Immunoassay;Indium tin oxide electrodes;Photo-electrochemistry;Photoelectrochemicals
    • Liu, Li-Xia;Fan, Gao-Chao;Zhang, Jian-Rong;Zhu, Jun-Jie
    • 《Analytica Chimica Acta》
    • 2018年
    • 1027卷
    • 期刊

    Cathode photoelectrochemical immunoassay usually shows better anti-interference capacity toward real samples than anode photoelectrochemical immunoassay. However, its poor photocurrent response has greatly restricted the detection sensitivity. Herein, a promising ultrasensitive cathode photoelectrochemical immunoassay was developed based on TiO2 photoanode-enhanced 3D Cu2O nanowire array (NWA) photocathode, and coupled with signal amplification by horseradish peroxidase (HRP)-induced biocatalytic precipitation (BCP). Carcinoembryonic antigen (CEA, Ag) was used as a detection model, TiO2 nanoparticle-modified indium tin oxide (ITO) electrode served as the photoanode, and Cu2O NWAs grown in situ on Cu mesh was both the photocathode and photoelectrochemical matrix to immobilize the capture CEA antibodies (Ab1). The signal CEA antibodies (Ab2) were labeled with HRP to form Ab2-HRP bioconjugates, and employed as signal amplifiers when the specific immunoreaction occurred. The developed photoanode-enhanced cathode photoelectrochemical immunoassay has good anti-interference capability, outstanding photocurrent response, and high sensitivity for target Ag detection, which was attributed to the synergistic effects of the 3D nanostructure of Cu2O NWA photocathode, the introduction of TiO2 photoanode as counter electrode, and the signal amplification of Ab2-HRP bioconjugate-induced BCP. The developed cathode photoelectrochemical immunoassay showed a low limit of detection (0.037 pg mL−1) with a wide linear range (from 0.1 pg mL−1 to 50 ng mL−1) for CEA detection.
    © 2018 Elsevier B.V.

    ...
  • 5.Ultrasensitive cathode photoelectrochemical immunoassay based on TiO2 photoanode-enhanced 3D Cu2O nanowire array photocathode and signal amplification by biocatalytic precipitation

    • 关键词:
    • Photoelectrochemistry; Photocathode; Immunoassay 3D Cu2O NWA;Biocatalytic precipitation;REDUCED GRAPHENE OXIDE; PBS QUANTUM DOTS; VISIBLE-LIGHT; ASCORBIC-ACID;PLATFORM; IMMUNOSENSOR; NANOCOMPOSITES; BIOSENSOR; MATRIX; CDS
    • Liu, Li-Xia;Fan, Gao-Chao;Zhang, Jian-Rong;Zhu, Jun-Jie
    • 《ANALYTICA CHIMICA ACTA》
    • 2018年
    • 1027卷
    • 期刊

    Cathode photoelectrochemical immunoassay usually shows better anti-interference capacity toward real samples than anode photoelectrochemical immunoassay. However, its poor photocurrent response has greatly restricted the detection sensitivity. Herein, a promising ultrasensitive cathode photoelectrochemical immunoassay was developed based on TiO2 photoanode-enhanced 3D Cu2O nanowire array (NWA) photocathode, and coupled with signal amplification by horseradish peroxidase (HRP)induced biocatalytic precipitation (BCP). Carcinoembryonic antigen (CEA, Ag) was used as a detection model, TiO2 nanoparticle-modified indium tin oxide (ITO) electrode served as the photoanode, and Cu2O NWAs grown in situ on Cu mesh was both the photocathode and photoelectrochemical matrix to immobilize the capture CEA antibodies (Ab(1)). The signal CEA antibodies (Ab(2)) were labeled with HRP to form Ab(2)-HRP bioconjugates, and employed as signal amplifiers when the specific immunoreaction occurred. The developed photoanode-enhanced cathode photoelectrochemical immunoassay has good anti-interference capability, outstanding photocurrent response, and high sensitivity for target Ag detection, which was attributed to the synergistic effects of the 3D nanostructure of Cu2O NWA photocathode, the introduction of TiO2 photoanode as counter electrode, and the signal amplification of Ab(2)-HRP bioconjugate-induced BCP. The developed cathode photoelectrochemical immunoassay showed a low limit of detection (0.037 pgmL(-1)) with a wide linear range ( from 0.1 pgmL(-1) to 50 ng mL(-1)) for CEA detection. (C) 2018 Elsevier B.V. All rights reserved.

    ...
  • 8.Nanostructured material-based biofuel cells: recent advances and future prospects

    • 关键词:
    • ;MICROBIAL FUEL-CELLS; EXTRACELLULAR ELECTRON-TRANSFER; WASTE-WATERTREATMENT; NITROGEN-DOPED GRAPHENE; HIGH-PERFORMANCE ANODES;CARBON-NANOTUBE; 3-DIMENSIONAL GRAPHENE; GLUCOSE-OXIDASE;ELECTRICITY-GENERATION; OXYGEN REDUCTION

    During the past decade, biofuel cells (BFCs) have emerged as an emerging technology on account of their ability to directly generate electricity from biologically renewable catalysts and fuels. Due to the boost in nanotechnology, significant advances have been accomplished in BFCs. Although it is still challenging to promote the performance of BFCs, adopting nanostructured materials for BFC construction has been extensively proposed as an effective and promising strategy to achieve high energy production. In this review, we presented the major novel nanostructured materials applied for BFCs and highlighted the breakthroughs in this field. Based on different natures of the bio-catalysts and electron transfer process at the bio-electrode surfaces, the fundamentals of BFC systems, including enzymatic biofuel cells (EBFCs) and microbial fuel cells (MFCs), have been elucidated. In particular, the principle of electrode materials design has been detailed in terms of enhancing electrical communications between biological catalysts and electrodes. Furthermore, we have provided the applications of BFCs and potential challenges of this technology.

    ...
  • 9.Graphene/Fe3O4 Nanocomposites as Efficient Anodes to Boost the Lifetime and Current Output of Microbial Fuel Cells

    • 关键词:
    • electron transfer; graphene; fuel cells; microbial activity;nanoparticles;SHEWANELLA-ONEIDENSIS MR-1; ELECTRON-TRANSFER; REDUCED-GRAPHENE; OXIDE;PERFORMANCE; FABRICATION; MEMBRANE; ARCHITECTURE; ELECTRICITY;GENERATION
    • Song, Rong-Bin;Zhao, Cui-e;Gai, Pan-Pan;Guo, Dan;Jiang, Li-Ping;Zhang, Qichun;Zhang, Jian-Rong;Zhu, Jun-Jie
    • 《CHEMISTRY-AN ASIAN JOURNAL》
    • 2017年
    • 12卷
    • 3期
    • 期刊

    The enhancement of microbial activity and electrocatalysis through the design of new anode materials is essential to develop microbial fuel cells (MFCs) with longer lifetimes and higher output. In this research, a novel anode material, graphene/Fe3O4 (G/Fe3O4) composite, has been designed for Shewanella-inoculated MFCs. Because the Shewanella species could bind to Fe3O4 with high affinity and their growth could be supported by Fe3O4, the bacterial cells attached quickly onto the anode surface and their long-term activity improved. As a result, MFCs with reduced startup time and improved stability were obtained. Additionally, the introduction of graphene not only provided a large surface area for bacterial attachment, but also offered high electrical conductivity to facilitate extracellular electron transfer (EET). The results showed that the current and power densities of a G/Fe3O4 anode were much higher than those of each individual component as an anode.

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  • 10.A Fe3O4-carbon nanofiber/gold nanoparticle hybrid for enzymatic biofuel cells with larger power output

    • 关键词:
    • GRAPHENE OXIDE; BILIRUBIN OXIDASE; CARBON NANOFIBERS; GLUCOSE-OXIDASE;ASCORBIC-ACID; IMMOBILIZATION; DOPAMINE; NANOTUBES; ELECTRODES;SUBSTRATE
    • Ji, Yusheng;Gai, Panpan;Feng, Jun;Wang, Linlin;Zhang, Jianrong;Zhu, Jun-Jie
    • 《JOURNAL OF MATERIALS CHEMISTRY A》
    • 2017年
    • 5卷
    • 22期
    • 期刊

    Enzymatic biofuel cells (EBFCs) are considered as a promising approach to meet the requirements of power sources. Electrode materials, which are significant factors to affect the power output of EBFCs, have aroused great interest. Herein, we developed an EBFC using a Fe3O4-carbon nanofiber/gold nanoparticle hybrid as the substrate electrode for improving the performance of the power output. The open-circuit voltage (E-OCV) of the designed EBFC reached 0.68 +/- 0.03 V, and the maximum power density (P-max) reached 126 +/- 4.5 mu W cm(-2). The as-prepared EBFC showed 3 times higher P-max compared to the EBFC based on the carbon nanofiber/gold nanoparticle hybrid, which was ascribed to the good electrocatalytic activity of Fe3O4 NP loaded carbon nanofibers (CNFs), the 3D porous structure of CNFs as well as the uniform distribution of Au NPs. The Fe3O4-CNF/gold nanoparticle hybrid is considered as a promising candidate for constructing electrochemical biosensors and biofuel cells.

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