生物分子保护的银纳米簇的合成及分析应用

发布时间：2018-01-31 20:08

本文关键词： 生物分子银纳米簇金属离子生物硫醇荧光分析法　出处：《山西大学》2015年硕士论文　论文类型：学位论文

【摘要】：银纳米簇(Ag NCs)作为一种新型的荧光团,具有制备成本低廉、化学性质活泼、表面易修饰、水溶性良好等优点,作为性能优良的荧光探针,引起了研究者广泛的兴趣。论文中,我们以不同种类的生物分子作为保护剂兼配体,合成了不同功能的发光Ag NCs,并基于荧光猝灭机制,建立了对金属离子、生物硫醇的分析检测方法。第一章：综述了Ag NCs的合成、光学性质及其应用方面的研究进展。第二章：设计了一种环状部分富含胞嘧啶碱基C,二级结构呈发卡状的单链DNA分子。以该发卡状DNA作为模板,合成了高量子产率的、发红色荧光的DNA/Ag NCs,当Hg2+存在时,能有效地将其荧光猝灭,进而发展了一种灵敏度高、选择性好的检测Hg2+的方法。该方法可在1.0×10-10mol/L-1.2×10-8mol/L的线性范围内实现对Hg2+的测定,并在S/N=3时,检出限为1.0×10-10mol/L。通过紫外可见吸收光谱的初步研究,荧光猝灭可能是由于5d10(Hg2+)-4d10(Ag+)之间的亲金属作用所致。第三章：以巯基小分子化合物——谷胱甘肽(GSH)为配体,采用超声法一步合成了发蓝色荧光的GSH@Ag NCs,并运用透射电镜(TEM)、紫外可见吸收光谱和荧光光谱对其进行了表征。发现Fe3+存在时,可使其荧光猝灭,建立了高灵敏测定Fe3+的方法,在5×10-7mol/L-2×10-5 mol/L的线性范围内对Fe3+有良好响应,S/N=3时检出限为1.2×10-7 mol/L,将该方法成功用于人血清样品中铁含量的测定。当引入络合剂EDTA时,Fe3+-GSH@Ag NCs体系的荧光恢复,这既为Fe3+与GSH@Ag NCs的作用机制提供了一种新的理解,也使GSH@Ag NCs可能被开发为off/on新型可逆荧光探针。第四章：以牛血清白蛋白(BSA)做保护剂,合成了发红色荧光的BSA-Ag NCs,其荧光能被小分子生物硫醇半胱氨酸(Cys)、同型半胱氨酸(Hcy)和谷胱甘肽(GSH)猝灭,这可能是由巯基和银之间的亲和作用所致。用BSA-Ag NCs作为纳米荧光探针,建立了生物硫醇的新型分析检测方法,测定Cys、Hey、GSH的线性范围分别为2.0×10-6mol/L-9.0×10-5mol/L、2.0×10-6mol/L-1.2×10-4mol/L、1.0×10-5 mol/L-8.0×10-5mol/L;S/N=3时,检出限分别为8.1×10-7 mol/L、1.0×10-6 mol/L、1.1×10-6mol/L。此方法可成功地用于人血浆样品中生物硫醇含量的测定,回收率94.83-105.24%,表明BSA-Ag NCs在化学和生物传感方面具有潜在的应用价值。第五章：对本论文中Ag NCs作为纳米荧光探针,在金属离子和生物硫醇分析检测方面的研究结果做了总结,并对下一步工作进行了展望。
[Abstract]:Silver nanoclusters Ag NCs, as a new type of fluorescence, have the advantages of low preparation cost, active chemical properties, easy surface modification, good water solubility and so on, so they can be used as fluorescent probes with excellent properties. In this paper, different kinds of biomolecules were used as protective agents and ligands to synthesize Ag NCswith different functions and based on fluorescence quenching mechanism. A method for the analysis and detection of metal ions and biological mercaptan was established. Chapter 1: the synthesis of Ag NCs was reviewed. Progress in optical properties and applications. Chapter 2: a circular partially cytosine C- rich single-stranded DNA molecule with a hairpin structure was designed. The hairpin DNA was used as a template. DNA/Ag NCs with high quantum yield and red fluorescence have been synthesized. In the presence of Hg2, it can effectively quench its fluorescence, thus developing a kind of high sensitivity. The method can be used to determine Hg2 in the linear range of 1.0 脳 10 ~ (-10) mol / L ~ (-1) 脳 10 ~ (-8) mol / L ~ (-1) 脳 10 ~ (-8) mol 路L ~ (-1) 路L ~ (-1). At S / N = 3:00, the detection limit is 1.0 脳 10 ~ (-10) mol / L. Fluorescence quenching may be due to the metalphilic interaction between 5 d 10 Hg2 + -4 d 10 Ag. Chapter 3: glutathione glutathione glutathione (GSH) is used as ligand. GSH@Ag NCs with blue fluorescence were synthesized by ultrasonic method. UV-Vis absorption and fluorescence spectra were used to characterize it. It was found that Fe3 can quench its fluorescence in the presence of Fe3, and a highly sensitive method for the determination of Fe3 was established. In the linear range of 5 脳 10 ~ (-7) mol / L ~ (-2) 脳 10 ~ (-5) mol/L, the detection limit for Fe3 is 1.2 脳 10 ~ (-7) mol / L at 3:00. The method was successfully applied to the determination of iron in human serum samples. The fluorescence recovery of Fe _ 3-GSH _ H NCs system was obtained when the complex agent EDTA was introduced. This provides a new understanding of the mechanism of Fe3 and GSH@Ag NCs. GSH@Ag NCs may also be developed as a novel reversible fluorescence probe for off/on. Chapter 4th: bovine Serum Albumin (BSA) as Protective Agent. A red fluorescent BSA-Ag NCS was synthesized, which can be quenched by cysteine (cysteine) and glutathione (Glutathione). This may be due to the affinity between mercapto and silver. Using BSA-Ag NCs as a nano-fluorescent probe, a new analytical method for the detection of biological mercaptan was established. The linear range of GSH is 2.0 脳 10-6 mol / L 9.0 脳 10 -5 mol / L, 2.0 脳 10 -6 mol / L -1. 2 脳 10 -4 mol / L. 1.0 脳 10-5 mol / L 8.0 脳 10-5 mol / L; S / N = 3:00, the detection limit was 8.1 脳 10 ~ (-7) mol / L ~ (-1) 脳 10 ~ (-6) mol/L. 1.1 脳 10 ~ (-6) mol 路L ~ (-1) 路L ~ (-1). The method has been successfully applied to the determination of biological mercaptan in human plasma samples with recoveries of 94.83-105.24%. It shows that BSA-Ag NCs has potential application value in chemical and biological sensing. Chapter 5th: using Ag NCs as a nano-fluorescence probe in this thesis. The results of analysis and detection of metal ions and biological mercaptan were summarized, and the future work was prospected.
【学位授予单位】：山西大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O657.3;TB383.1

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