金属纳米簇的制备及其在药物分析中的应用

发布时间：2018-04-27 03:17

本文选题：金属纳米团簇 + 药物分析　；参考：《西南大学》2016年硕士论文

【摘要】：本论文主要以金、银、铜纳米团簇为基础简介了贵金属纳米材料的一些物理、化学性质,贵金属纳米材料的特殊性质,一些特殊领域的应用,以及贵金属纳米材料的应用前景。以环境、人体中残留的重金属以及药品残留物为研究对象,根据金属纳米团簇的特殊效应,合成了金、银、铜三种具有荧光活性的功能纳米团簇,研究了其表面结构特征,荧光特性,荧光猝灭和表面荧光增强等效应,并探讨了它们在分析传感中的应用。第一部分铜离子(Cu~(2+))是最为丰富的过渡元素之一,对人体的健康至关重要,使人体所必须的微量元素,但当人体摄入过量Cu~(2+)时,它可以破坏蛋白质、核酸以及脂质,产生氧自由基。同时,过量的Cu~(2+)对周围生态环境也产生了日益严重的污染。目前,已有传统的针对痕量Cu~(2+)的检测的大量报道,如原子吸收法。电感耦合等离子体质谱法等,然而这些方法通常操作复杂,耗时且费用昂贵,因此发展高灵敏度、高选择性、廉价、易操作的Cu~(2+)检测方法仍然具有使用价值。多西环素(DC)是四环素类抗生素药物,被广泛应用于各种呼吸道和泌尿道感染的治疗当中。它是广谱抑菌药物,然而,过量摄入DC会严重危害人体健康,如过敏反应,肝功能损害,牙齿发黄,胃肠紊乱等。进而危害人类健康。传统检测DC的方法需要复杂的样品前处理,且操作繁琐。故发展快速、简单、灵敏的检测DC的方法具有一定的应用前景。由于L-半胱氨酸(L-Cys)的结构与Cu~(2+)非常敏感,Cu~(2+)对半胱氨酸金簇(AuNCs)的荧光信号有明显的响应,其中的-COOH与Cu~(2+)有强的结合作用,能够形成螯合物,且与Cu~(2+)呈良好的线性关系,因此本文建立了一种高灵敏度的Cu~(2+)荧光分析检测方法。另外,又由于DC与Cu~(2+)有更强的结合作用,对Cu~(2+)更敏感,因此可以构建一个由Cu~(2+)介导的“关-开”的荧光分析方法检测DC。第二部分贵金属纳米团簇中用于荧光分析检测的较多的是金、银等贵金属。而对于铜纳米团簇的研究还处于基础阶段,对于铜纳米团簇的报道至今较少。众所周知,铜是人体的必须微量元素,是一种具有良好特性的过渡金属。汞离子(Hg2+)是一种有剧毒的重金属,广泛存在于环境、甚至食物当中。它可以通过食物链富集到人体中,因此对于Hg2+的检测依旧具有现实意义,而发展一种简单、经济的Hg2+检测方法仍旧具有挑战性。本实验通过以小分子L-Cys为载体,以模板法合成具有发光性质的CuNCs,当不同浓度的Hg2+加入到CuNCs中时,CuNCs的荧光信号会呈线性变化,实验中,在信噪比为3的背景下,Hg2+的检测线性范围在1.0×10-7-1.0×10-3 mol/L,因此构建了以CuNCs荧光猝灭为基础检测Hg2+的方法。另外,合成的CuNCs还能够运用于荧光染色,拓宽了对CuNCs的在荧光应用范围。第三部分SEF是指荧光素靠近金属纳米粒子表面时,其荧光会得到增强。然而,荧光素过度接近金属纳米粒子时会发生猝灭,研究表明易产生荧光增强效应的是金、银等具有良好增强效应的贵金属表面,且最大荧光增强发生的距离为10 nm。本实验以CEA为研究对象,通过在AuPNs上修饰DNA,再以含有20个碱基(15个胞嘧啶)的DNA序列合成AgNCs,基于CEA适配体与两条DNA链两端互补配对原则,将AuNPs与AgNCs连接,使AgNCs的荧光效应增强从而构建荧光增强体系,其增强的荧光强度与CEA适配体浓度在12.25 nM-50μM范围内具有线性关系,检测限(3σ)为4.8 nM。以荧光增强后的AuNPs与AgNCs复合体系为荧光探针,并由于CEA与CEA适配体特异性结合能力使SEF体系破坏,最后导致了明显的荧光降低效应,因此可以高特异性的检测CEA。其降低的荧光强度与CEA浓度在0.01 ng·mL-1到0.1 ng·mL-1浓度范围内呈良好的线性关系,检测限为3 pg·mL-1。以上结果,对于深入研究金属纳米团簇的性质和在药物分析中的应用具有理论和现实意义。
[Abstract]:On the basis of gold, silver and copper nanoclusters, this paper introduces some physical, chemical properties, special properties of noble metal nanomaterials, the application of some special fields, and the prospect of application of precious metal nanomaterials. The research object is the environment, the residual heavy metals in the human body and the residue of drug. The special effects of metal nanoclusters have been made, and three functional nanoclusters of gold, silver and copper have been synthesized. The effects of their surface structure, fluorescence, fluorescence quenching and surface fluorescence enhancement are studied. The first part of the copper ion (Cu~ (2+)) is one of the most abundant transition elements. It is vital to the health of the human body to make the trace elements necessary for the human body, but when the human body is in excess of Cu~ (2+), it can destroy protein, nucleic acid and lipid and produce oxygen free radicals. At the same time, excessive Cu~ (2+) has also produced more and more serious pollution to the surrounding ecological environment. At present, the traditional detection of trace Cu~ (2+) has been widely used. Such as atomic absorption, inductively coupled plasma mass spectrometry and so on, these methods are usually complex, time-consuming and expensive, so the development of high sensitivity, high selectivity, cheap and easy to operate Cu~ (2+) detection method is still of use value. DC is a tetracycline antibiotic drug, and is widely used in various kinds of drugs. In the treatment of respiratory and urinary tract infections, it is a broad-spectrum antimicrobial agent. However, excessive intake of DC will seriously harm human health, such as allergic reaction, liver function damage, yellow teeth, gastrointestinal disorders, and so on. Thus, the traditional method for detecting DC needs complex sample pretreatment and complicated operation. The method of sensitive detection of DC has a certain application prospect. Because the structure of L- cysteine (L-Cys) is very sensitive to Cu~ (2+), Cu~ (2+) has an obvious response to the fluorescence signal of cysteine gold cluster (AuNCs), in which -COOH and Cu~ (2+) have a strong binding effect and can form a chelate and have a good linear relationship with Cu~. A high sensitivity Cu~ (2+) fluorescence analysis method was established. In addition, because of the stronger binding of DC and Cu~ (2+), Cu~ (2+) is more sensitive. Therefore, a "close to open" fluorescence analysis method mediated by Cu~ (2+) can be used to detect the fluorescence analysis of DC. second part of the noble metal nanoclusters. The research on copper nanoclusters is still in the basic stage, and there are few reports on the copper nanoclusters. It is known that copper is a necessary trace element of the human body and is a kind of transition metal with good properties. The mercury ion (Hg2+) is a highly toxic heavy metal, widely existed in the environment and even in food. In order to enrich the human body through the food chain, the detection of Hg2+ is still of practical significance, and it is still challenging to develop a simple and economical method of Hg2+ detection. By using small molecule L-Cys as the carrier, the CuNCs with luminescent properties is synthesized by template method. When different concentrations of Hg2+ are added to CuNCs, the fluorescence of CuNCs In the experiment, in the experiment, in the background of the signal to noise ratio of 3, the linear range of Hg2+ is 1 x 10-7-1.0 x 10-3 mol/L. Therefore, the method of detecting Hg2+ based on CuNCs fluorescence quenching is constructed. In addition, the synthesized CuNCs can also be used in fluorescence staining, widening the application range for CuNCs in fluorescence. Third part SEF is When fluorescein is near the surface of the metal nanoparticles, its fluorescence is enhanced. However, the fluorescein will be quenched when it is too close to the metal nanoparticles. The study shows that the fluorescence enhancement effect is the precious metal surface with good enhancement effect, such as gold, silver, and the distance of the maximum fluorescence enhancement is 10 nm.. This experiment is based on CEA. The study object, by modifying DNA on AuPNs, and then synthesizing AgNCs with 20 bases (15 cytosine) DNA sequences, based on the principle of complementary pairing of CEA aptamers and two DNA chains, connecting AuNPs with AgNCs so that the fluorescence effect of AgNCs is enhanced and the fluorescence enhancement system is constructed. The enhanced fluorescence intensity and CEA aptamer concentration are 12.25 n. There is a linear relationship in the range of M-50 mu M. The detection limit (3 sigma) is 4.8 nM., and the AuNPs and AgNCs composite system after fluorescence enhancement is a fluorescent probe, and the SEF system is destroyed by the specific binding ability of CEA and CEA aptamers. Finally, the obvious fluorescence reduction effect is caused. Therefore, the fluorescence intensity and CEA of CEA. can be detected by high specificity and CEA. The concentration range from 0.01 ng mL-1 to 0.1 ng / mL-1 has a good linear relationship, and the detection limit is 3 pg. ML-1.. It is of theoretical and practical significance for the in-depth study of the properties of the metal nanoclusters and the application of the drug in the drug analysis.

【学位授予单位】：西南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O657.3;R917

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