新型量子点电致化学发光生物传感器的研究及其分析应用

发布时间：2018-09-10 14:55

【摘要】：自从Bard课题组报道了 Si量子点(Quantum Dots, QDs)的电致化学发光(Electrochemiluminescence, ECL)后,QDs的ECL研究便受到了广泛的关注。到目前为止,已经有越来越多的QDs被证明具备良好的ECL性质。由于QDs的ECL性质与材料本身的尺寸和表面状态密切相关,因而通过调节QDs的组成、结构以及分散性,合成出具有高发光强度且发光性能稳定的发光试剂,然后进一步构建多种灵敏度高、稳定性好的新型固态ECL传感器。然而,对于广大的科研工作者而言,QDs的制备及其ECL应用还具有一定的挑战性,主要表现在以下两个方面:(1)相比于三联吡啶钌([Ru(bpy)3]2+)、鲁米诺等传统ECL发光体,QDs的ECL相对较弱,这不利于高灵敏ECL传感器的构建;(2)现阶段具有ECL性质的QDs主要集中于有毒重金属镉系。因此,新型低毒且具有ECL性质的QDs材料的合成变得尤为重要。本文研究内容主要基于QDs的ECL: (1)详细研究了壳-核结构CdSe@ZnS QDs固态ECL应用;(2 )水热合成具有ECL性质的新型QDs。我们首先对一系列不同尺寸壳核结构CdSe@ZnS QDs固态ECL进行了研究。随后研究了 Ti02对不同尺寸QDs的ECL强度影响,选择最佳的条件构建了高灵敏ECL癌胚抗原生物传感器。基于掺杂元素的方法,我们合成了新型的Eu3+掺杂的CdSe QDs。基于以上的研究背景我们构建灵敏度较高、稳定性较好的新型固态ECL传感器。另外,我们合成并研究了铯铅卤钙钛矿量子点(CsPbBr3NCs)的光学性质,以期望将其用作潜在的ECL发光体。本论文的研究内容主要包括以下五个部分,概括如下:1、不同粒径、具有充核结构的多波段CdSe@ZnS QDs固态电致化学发光研究应用简单油相合成的不同核粒径的壳核CdSe@ZnS QDs。首先将一定量的CdSe@ZnSQDs直接滴涂到玻璃碳电极(GCE)表面,然后置于空气中自然晾干成膜,获得CdSe@ZnS QDs修饰的电极CdSe@ZnS/GCE,以K2S208为共反应物,研究CdSe@ZnS QDs阴极ECL行为。本章节基于不同尺寸的核壳QDs第一次实现了基于尺寸效应调控的多色半导体纳米晶体的ECL行为。这将为构建稳定和多色ECL发光提供一个崭新的途径,有望应用于ECL多组分同时分析检测。2、基于聚多巴胺修饰的金纳米粒子高效淬灭二氧化钛增强的核壳CdSe@ZnS QDs的电致化学发光定量检测癌胚抗原基于二氧化钛(TiO2)增强ECL效应以及聚多巴胺(PDA)修饰的金纳米粒子(Au@PDA NPs)对其淬灭效应,我们成功构建了基于核壳CdSe@ZnS QDs的双信号放大ECL免疫传感器,然后实现了对癌胚抗原(CEA)的超灵敏检测。起初,我们通过实验优化选择较大尺寸的核壳QDs,这主要取决于较大尺寸QDs具有更高的电子和能量转移效率,从而展现出高倍放大效应。然后,我们通过CEA构建Ab1-Au@PDA NPs-Ab2三明治结构。最后,通过Au@PDA NPs的ECL淬灭效应成功实现对癌胚抗原CEA的灵敏检测。3、基于Eu3+掺杂的CdSe QDs电致化学发光定量分析检测磷酸根本章节通过Eu3+调控3-巯基丙酸包覆的CdSe QDs的ECL定量检测磷酸阴离子(PO43-)。这主要是基于PO43-和Eu3+之间强烈的特异性相互作用使其Eu3+引导淬灭CdSe QDs的ECL得以恢复,从而实现了 PO43-的高灵敏度检测,检测的线性范围为0.1～120μM,其检测限为 0.03μM (S/N = 3)。4、基于金纳米簇和碳纤维超微电极体系电致化学发光单颗粒检测本章以硫辛酸(LA)为保护剂合成一种催化性能良好的金纳米簇(AuNCs),用碳纤维超微电极,以Ru(bpy)32+与C2042-体系为研究发光体系,研究单颗粒Au NCs的ECL性质。为贵金属簇类的单颗粒电化学发光开辟出一条新的道路。5、基于超分子巯基-β-环糊精的调控钙钛矿量子点光学性能研究本章研究报道了一种基于保护剂巯基-β-环糊精(SH-β-CD)介导的主-客体交换方法系统调控全无机铯铅卤钙钛矿量子点CsPbBr3 NCs光学性能研究。通过调节保护剂SH-β-CD的用量,我们制备出了一组发光峰位置在405～510 nm的CsPbX3量子点,调控后的量子点保持了较高的荧光量子效率(可达50～90%)。综上所述,本论文研究了不同类型QDs的ECL性质,并基于QDs的ECL信号强度的改变,将其应用于生物环境中阴离子的定量分析检测以及在免疫分析中的应用。
[Abstract]:Since Bard's team reported the electrochemiluminescence (ECL) of Si quantum dots (QDs), the ECL research of QDs has attracted much attention. Up to now, more and more QDs have been proved to have good ECL properties. Therefore, by adjusting the composition, structure and dispersion of QDs, luminescent reagents with high luminescent intensity and stable luminescent performance were synthesized, and then a variety of new solid-state ECL sensors with high sensitivity and stability were further constructed. However, for the majority of researchers, the preparation of QDs and its application in ECL still have a certain degree. The challenge lies in the following two aspects: (1) Compared with ruthenium tripyridine ([Ru(bpy)3]2+), luminol and other traditional ECL luminescent materials, the ECL of QDs is relatively weak, which is not conducive to the construction of highly sensitive ECL sensors; (2) At present, QDs with ECL properties are mainly concentrated in toxic heavy metal cadmium series. In this paper, the synthesis of QDs-based ECL is particularly important. The main research contents are as follows: (1) the application of shell-core structure CdSe@ZnS QDs solid-state ECL is studied in detail; (2) hydrothermal synthesis of new QDs with ECL properties. Based on the doping element method, we synthesized a novel Eu3+ doped CdSe QDs. Based on the above research background, we constructed a new solid-state ECL sensor with high sensitivity and good stability. In addition, we synthesized and studied cesium lead. The optical properties of CsPbBr3NCs are expected to be used as potential ECL luminescent materials. The main contents of this paper are summarized as follows: 1. Multi-band CdSe@ZnS QDs solid-state electrochemiluminescence with different particle sizes and core-filling structures synthesized by simple oil-phase method CdSe@ZnS QDs.First, a certain amount of CdSe@ZnSQDs was dried directly onto the surface of glass carbon electrode (GCE) and then dried in air to form a film. Then CdSe@ZnS QDs modified electrode CdSe@ZnS/GCE was obtained. The ECL behavior of CdSe@ZnS QDs cathode was studied using K2S208 as a co-reactant. In this chapter, the scale-based QDs were first realized. ECL behavior of multicolor semiconductor nanocrystals regulated by inch effect. This will provide a new way to construct stable and multicolor ECL luminescence. It is hopeful to be applied to simultaneous analysis and detection of multicomponent ECL. 2. Quantitative detection of CdSe@ZnS QDs in core-shell by electrochemiluminescence based on polydopamine modified gold nanoparticles quenched titanium dioxide Based on the enhanced ECL effect of titanium dioxide (TiO2) and the quenching effect of gold nanoparticles (Au@PDA NPs) modified by polydopamine (PDA), we successfully constructed a dual-signal amplified ECL immunosensor based on core-shell CdSe@ZnS QDs, and then realized the hypersensitive detection of carcinoembryonic antigen (CEA). Selection of larger core-shell QDs depends on higher electron and energy transfer efficiencies of larger QDs, thus exhibiting a high magnification effect. Then, we constructed Ab1-Au@PDA NPs-Ab2 sandwich structure through CEA. Finally, we successfully detected CEA by ECL quenching effect of Au@PDA NPs.3, based on Eu3+ Doped CdSe QDs Electrochemiluminescence Quantitative Analysis Detection of Phosphoric Acid Basic Chapter Quantitative Detection of Phosphoric Acid Anion (PO43-) by Eu3+ Regulated 3-Mercaptopropionic Acid-coated CdSe QDs ECL. This is mainly based on the strong specific interaction between PO43-and Eu3+, so that Eu3+ guided quenching of CdSe QDs ECL can be restored, thereby achieving PO43- Highly sensitive detection with a linear range of 0.1-120 mu M and a detection limit of 0.03 mu M (S/N=3). In order to study the ECL properties of single-particle Au NCs and C2042-system, a new way for electrochemiluminescence of noble metal clusters was opened up. 5. Supramolecular sulfhydryl-beta-cyclodextrin-based modulated perovskite quantum dots optical properties. In this chapter, a protective agent based on sulfhydryl-beta-cyclodextrin (SH-beta-CD) was reported. By adjusting the dosage of protectant SH-beta-CD, a group of CsPbX3 quantum dots with luminescent peaks of 405-510 nm were fabricated, and the quantum efficiency of CsPbBr3 quantum dots was kept high (up to 50-90%). In this paper, we studied the ECL properties of different types of QDs, and based on the change of ECL signal intensity of QDs, we applied it to the quantitative analysis of anions in biological environment and its application in immunoassay.
【学位授予单位】：东南大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TP212.3;O657.3

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