金银纳米簇的仿生矿化合成及其初步的荧光检测应用
本文选题:生物仿生矿化 + 金银纳米簇 ; 参考:《曲阜师范大学》2017年硕士论文
【摘要】:金银等贵金属纳米簇(NCs)凭借其独特的物理化学性质,被广泛地应用于生物分析、医学成像、催化等领域。本论文分别以谷胱甘肽(GSH)和牛血清白蛋白(BSA)为模板,借助生物仿生矿化途径,分别合成了银纳米簇(AgNCs)和金-银纳米簇(Au-AgNCs),用以建立了三种简单、快速、选择性好、灵敏度高的传感检测技术,实现了对植酸(PA)和三聚氰胺(MA)等目标物的检测以及酪氨酸酶(TYR)催化活性的研究。(一)以GSH为模板,在超声条件下,通过GSH介导银生物矿化,制备出具有强蓝色荧光的AgNCs,进而以荧光AgNCs为探针,借助Fe3+猝灭AgNCs荧光以及引入植酸络合Fe3+后可引起其荧光恢复的现象,设计了一种荧光“Turn-on”型的传感检测技术,实现了谷物中植酸的高灵敏分析(第二章)。结果表明,与传统植酸检测方法比较,本检测技术具有操作简单、选择性好、灵敏度高等优点,可望广泛应用于对谷物等农作物的营养成分植酸的分析以及水果保鲜度的评价。(二)以BSA为模板,通过“一锅式”仿生矿化途径,制备了强红色荧光的Au-AgNCs。以Au-AgNCs为荧光探针,利用Au-AgNCs与Hg2+作用引起荧光猝灭,并借助三聚氰胺与Hg2+络合形成稳定配合物,致使Au-AgNCs荧光恢复的原理,发展了一种三聚氰胺荧光传感分析技术(第三章)。实验发现,与单一金或银纳米簇比较,以BSA模板介导的金银仿生矿化途径制得的双金属型Au-AgNCs,不仅具有显著增强的荧光,而且能灵敏地响应Hg2+和三聚氰胺引起的荧光猝灭与恢复。由此研制的三聚氰胺荧光检测法,具有灵敏度高、选择性好、检测速度快等优点,经应用于奶制品中三聚氰胺的检测,获得了满意的效果。(三)以BSA模板介导合成的Au-AgNCs为荧光探针,并结合TYR催化多巴胺氧化反应原理,建立了一种快速、灵敏评价TYR活性的荧光检测方法(第四章)。在溶解氧存在的情况下,多巴胺被TYR催化氧化生成多巴醌,从而引起Au-AgNCs的荧光猝灭,借以实现了对TYR活性的检测。该方法避免了传统方法选择性差、灵敏度低等缺点,为TYR的催化活性评价、以及白癜风和白化病等疾病的临床检验诊断,提供了一种新的分析工具。
[Abstract]:Due to its unique physical and chemical properties, gold and silver nanoclusters have been widely used in biological analysis, medical imaging, catalysis and other fields. In this paper, using glutathione (GSH) and bovine serum albumin (BSA) as templates, silver nanoclusters (AgNCs) and gold-silver nanoclusters (Au-AgNCsN) were synthesized by biomimetic mineralization, respectively. The detection of phytate (PAA) and melamine malamine (MAA) and the catalytic activity of tyrosinase (TYR) with high sensitivity were achieved. (1) using GSH as template, silver biomineralization mediated by GSH was used to prepare AgNCswith strong blue fluorescence, and then fluorescent AgNCs were used as probes. Based on the phenomenon that the fluorescence of AgNCs quenched by Fe _ 3 and the fluorescence recovery caused by the introduction of Fe _ 3 complexing with phytic acid, a kind of "Turn-on" type fluorescence sensing technique was designed, which realized the highly sensitive analysis of phytic acid in cereals (Chapter 2). The results show that compared with the traditional phytic acid detection method, this method has the advantages of simple operation, good selectivity, high sensitivity and so on. It is expected to be widely used in the analysis of phytic acid in crops such as cereals and the evaluation of fruit freshness. (2) A strong red fluorescent Au-AgNCswas prepared by "one-pot" bionic mineralization using BSA as template. Using Au-AgNCs as the fluorescence probe, the fluorescence quenching was induced by the interaction of Au-AgNCs with Hg _ 2, and the stable complex was formed by the complexation of melamine with Hg _ 2, which led to the fluorescence recovery of Au-AgNCs. A fluorescence sensing analysis technique for melamine was developed (Chapter 3). Compared with single gold or silver nanoclusters, the bimetallic Au-AgNCsobtained by BSA template mediated gold and silver biomimetic mineralization pathway not only has significantly enhanced fluorescence, but also can sensitively respond to fluorescence quenching and recovery induced by Hg2 and melamine. The developed method has the advantages of high sensitivity, good selectivity and fast detection speed. It has been applied to the detection of melamine in dairy products, and satisfactory results have been obtained. (3) A rapid and sensitive method for the detection of TYR activity was established by using Au-AgNCs synthesized by BSA template as fluorescent probe and combining with the principle of TYR catalytic dopamine oxidation (TYR). In the presence of dissolved oxygen dopamine was oxidized to dopa quinone catalyzed by TYR which resulted in fluorescence quenching of Au-AgNCs and thus the detection of TYR activity was realized. This method avoids the disadvantages of poor selectivity and low sensitivity of traditional methods and provides a new analytical tool for the evaluation of catalytic activity of TYR and the clinical diagnosis of vitiligo and albinism.
【学位授予单位】:曲阜师范大学
【学位级别】:硕士
【学位授予年份】:2017
【分类号】:O657.3;TB383.1
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