新型银、金纳米簇的制备及其应用
本文选题:银纳米簇 + 银纳米粒子 ; 参考:《湖南科技大学》2017年硕士论文
【摘要】:纳米簇因其超小尺寸而具备分离的能级结构,显示出独特的光学、电学、化学性质,与较大尺寸的纳米粒子有明显区别。贵金属纳米簇,如金纳米簇、银纳米簇,因其高量子产率、良好的光稳定性和优良的生物相容性等特点,使其在环境监测、生物标记、生化传感、离子检测等领域具有广阔的应用前景。本文设计新方法成功制备新型银、金纳米簇,并将其应用于环境和生物检测,具体包括以下内容:(1)以热变性的天然鱼精DNA为稳定剂合成了荧光银纳米簇,不同于其它人工设计合成的寡核苷酸模板法,该方法经济便捷,便于大规模合成。所制备的银纳米簇的最大激发波长为585 nm,最大发射波长为650 nm。在p H为3.78时,银纳米簇的荧光增强了三倍。加入汞离子时,体系的荧光猝灭,且其降低的程度与汞离子的浓度在2.0-3000nmol L-1范围内呈线性关系,检出限为0.7 nmol L-1。由此建立了一种快速的、灵敏的检测汞离子的方法。(2)研究发现盐酸小檗碱能显著猝灭以变性鱼精DNA为稳定剂合成的银纳米簇的荧光。盐酸小檗碱可有效的与银纳米簇表面的DNA结合使其表面电荷发生变化,致使银纳米簇团聚。且银纳米簇体系的红色荧光随着盐酸小檗碱的浓度逐渐增大,荧光颜色逐渐变为棕黄色。当盐酸小檗碱的浓度在1.0-2000 nmol L-1范围内与其体系的荧光猝灭程度呈线性关系,检出限为0.3 nmol L-1。由此建立一种灵敏度较高、精确的检测盐酸小檗碱的方法。同时,盐酸小檗碱的浓度在5.0-2000 nmol L-1范围可以实现半定量可视化检测。其余药物中常见的氨基酸和金属离子对检测没有干扰,说明该方法具有较好的选择性。该方法成功测定了复方黄连素片中盐酸小檗碱的含量。(3)以变性鱼精DNA为稳定剂,在碱性条件下利用抗坏血酸为还原剂合成了较大尺寸(45 nm)的银纳米粒子。该纳米粒子具有强散射,硫化氢的加入可导致其粒径变小,散射强度降低。通过测量共振散射光谱研究发现,硫化氢的浓度在5.0-100 nmol L-1范围内与其散射降低程度呈现良好的线性关系,检出限为2.8 nmol L-1。基于此,我们建立了简单、高灵敏的检测水溶液中硫化氢的方法,并可以用于实际水样的分析。(4)以柠檬酸三钠稳定的氯化亚锡为稳定剂和还原剂,通过微波法快速合成了新型荧光金纳米簇,并利用该纳米簇建立了一种同时检测汞离子和铜离子的双功能探针,其中铜离子可使金纳米簇的荧光猝灭,汞离子可使金纳米簇散射增强,同一体系中荧光光谱和散射光谱互不影响,可实现独立检测。铜离子的浓度在5.0′10-7-7.0′10-5 mol L-1范围时,金纳米簇的荧光猝灭程度与铜离子的浓度呈现良好的线性关系,检出限为0.38mmol L-1;当汞离子的浓度范围在2.5′10-7-1.0′10-5 mol L-1时,金纳米簇的散射增加值与汞离子的浓度呈现良好的线性关系,检出限为0.05mmol L-1。基于此,我们建立了一种简单、快速的同时检测水溶液中铜离子和汞离子的方法,并可以用于实际水样的分析。
[Abstract]:Because of its ultra small size nanoclusters with energy structure separation, showing a unique optical, electrical and chemical properties, has the obvious difference with the larger size of the nanoparticles. Noble metal nanoclusters, such as gold nanoparticles, silver nanoparticles, because of its high quantum yield, compatibility and good light stability excellent in the biological, environmental monitoring, biological markers, biochemical sensing, has broad application prospects. This paper designs a new ion detection method for the successful preparation of new silver and gold nanoclusters, and its application in environmental and biological samples, including the following: (1) the synthesis of fluorescent silver nanoclusters the stabilizer of salmon milt DNA thermal denaturation, oligonucleotide template method in other synthetic, this method is economical and convenient, and is convenient for large-scale synthesis. The silver nanoclusters prepared by the maximum excitation wavelength was 585 nm, the maximum emission wavelength of 650 Nm. in P H 3.78, fluorescent silver nanoclusters increased three times. With mercury ions, fluorescence quenching system, and the degree of concentration of mercury ions and the decrease of a linear relationship in the range of L-1 2.0-3000nmol, the detection limit was 0.7 nmol L-1. established a rapid method for detection of mercury. Ion sensitive. (2) study found that berberine hydrochloride can significantly to protamine DNA fluorescence quenching modified silver nanoclusters synthesized stabilizer. Berberine hydrochloride can effectively and silver nanoclusters DNA on the surface of the surface charge changes, resulting in the silver nanoclusters. Red fluorescence and silver cluster system increases with the concentration of berberine hydrochloride, fluorescent color gradually turned brown. There was a linear relationship between the fluorescence intensity when the concentration of berberine hydrochloride in the range of L-1 and 1.0-2000 nmol system, a detection limit of 0.3 nmol L-1. from the building A method of high sensitivity, accurate detection of berberine hydrochloride. At the same time, the concentration of berberine hydrochloride can achieve semi quantitative visual detection in 5.0-2000 nmol L-1. The common amino acids and metal ions did not interfere with the detection of other drugs, indicating that the method has good selectivity. The method is successfully applied to determination of berberine hydrochloride in compound berberine tablet. (3) with modified fish DNA as a stabilizer in alkaline conditions using ascorbic acid as reducing agent was synthesized with large size (45 nm) of the silver nanoparticles. The nanoparticles have strong scattering, adding hydrogen sulfide can lead to smaller particle diameter, scattering intensity decreased. By measurement of resonance scattering spectra found 5.0-100 nmol, the hydrogen sulfide concentration in the range of L-1 and reduce the degree of scattering showed a good linear relationship. The detection limit was 2.8 nmol L-1. based on this, we set up A simple, sensitive method for the detection of hydrogen sulfide in aqueous solution, and can be used for analysis of real samples. (4) with three citric acid stable sodium stannous chloride as stabilizer and reducing agent, through microwave synthesized novel fluorescent gold nanoclusters, and the nano cluster built a simultaneous detection of two probes for mercury ion and copper ion, copper ion which can make the fluorescence quenching of gold nanoclusters, mercury ions can make the gold nanoclusters scattering enhancement in the same system, fluorescence spectrum and scattering spectra do not influence each other, can realize independent detection. Copper ion concentration in the 5 '10-7-7.0' is in the range of L-1 10-5 mol that shows a good linear relationship between the concentration of fluorescence quenching degree and copper ions of gold nanoclusters, the detection limit is 0.38mmol L-1; when the concentration of mercury ion in the 2.5 '10-7-1.0' 10-5 mol L-1, scattering of gold nanoclusters and increase the value of mercury ions. The concentration has a good linear relationship with a detection limit of 0.05mmol L-1.. Based on this, we have established a simple and rapid method for simultaneous detection of copper and mercury ions in aqueous solutions, and can be applied to the analysis of real water samples.
【学位授予单位】:湖南科技大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:TB383.1;O657.3
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