基于金银纳米簇和苯硼酸功能材料的传感技术

发布时间：2018-01-27 05:24

本文关键词： 金/银纳米簇乙酰胆碱酯酶重金属离子苯硼酸糖类多羟基化合物化学与生物传感技术　出处：《曲阜师范大学》2015年硕士论文　论文类型：学位论文

【摘要】：贵金属纳米簇(NCs),如金纳米簇(AuNCs)、银纳米簇(AgNCs)及其双金属纳米簇(Au/AgNCs)具有独特的化学和物理性能,被广泛的应用于化学与生物传感器中,实现了对多种目标物的检测。本论文一方面通过合成强荧光金银纳米簇,利用待测物质对其荧光的猝灭效应,建立了有机磷农药和重金属离子的传感检测体系;同时,借助苯硼酸对多羟基化合物的特异识别特性,发展了一种糖类等多羟基化合物的目视高度速测技术。(1)通过合成强荧光金纳米簇为探针,建立了一种基于“一滴溶液”免标记的荧光分析方法,用于蔬菜中有机磷残留物的分析(第二章)。该方法借助乙酰胆碱酶(AChE)催化硫代乙酰胆碱水解产生硫代胆碱引起金纳米簇的团聚,进而导致其荧光猝灭的特性,并利用敌敌畏(DDVP)对乙酰胆碱酶(AChE)催化活性的抑制效应,实现了对农药残留的快速、灵敏、特异的检测(线性范围0.032 nM-20 nM,检出限13.67 pM),其对实际蔬菜样品中残留DDVP的检出限达36 pM。该荧光分析方法通过速测有机磷感染的直接标志物自由有机磷,实现了对有机磷早期感染的预警,并为酶生理催化活性的评价提供了一种新思路。(2)采用一锅反应的生物矿化合成路线,并通过调整金/银前驱体的摩尔比例,合成了强荧光的双金属金银合金纳米簇,用以作为荧光探针实现了对血液中的铜离子和汞离子的快速、特异、超灵敏的检测(第三章)。研究表明,制备的金银合金纳米簇具有“银效应”增强的红色荧光,其荧光强度分别是常见金纳米簇和核-壳结构的金银纳米簇的6.5倍和4.7倍;特别是,“银效应”不仅提高了金银合金纳米簇响应汞离子的能力,而且赋予了其特异检测铜离子的能力;此外,通过引入铜离子络合剂,实现了对铜离子和汞离子的分别检测;所构建的荧光分析法检测血液中汞离子和铜离子的检测限分别达0.30 nM和0.60 nM,可望应用于临床实验室中血汞和血铜的检测。(3)基于功能化苯硼酸衍生物对糖类等多羟基化合物的特异识别原理以及毛细效应建立了一种目视高度的速测技术,用于血液、天然产物、农产品以及化工产品中单糖、多糖以及含有1,2-或1,3-二醇基团的多羟基化合物的检测(第四章)。将功能化苯硼酸衍生物修饰于预先氨基硅烷化处理的刻度毛细管内壁,通过毛细效应自动吸入样品,进而利用壁上苯硼酸与含有1,2-或1,3-二醇基团的多羟基化合物形成复合物后发生溶胀,导致毛细管内壁的亲疏水性的改变,进而引起刻度毛细管内液面高度的规律性上升,经目测其液面高度实现对待测样品中糖类等多羟基化合物含量的速测。该方法以功能化苯硼酸衍生物作为糖类等多羟基化合物的识别体,克服了传统酶学检测技术存在的诸多缺点(例如,酶失活问题),具有样品用量少(约20μL)、操作简单、价格低廉、适于现场速测等优点。
[Abstract]:Noble metal nanoclusters (NCs), such as gold nanoclusters (AuNCs), silver nanoclusters (AgNCs) and double metal nanoclusters (Au/AgNCs) with unique chemical and physical properties, is widely used in chemical and biological sensor, the detection of multiple targets. The article on the one hand, through the synthesis a strong fluorescence quenching effect of silver nanoparticles, using the analytes on the fluorescence, a sensing system of organophosphorus pesticide and heavy metal ions; at the same time, with the specific recognition properties of phenylboronic acid of polyhydroxy compounds, the development of a sugar polyol. Rapid detection of visual height (1) by synthesis of strong fluorescent gold nanoclusters as probe, was established based on the "one drop solution" label free fluorescence analysis method for the analysis of organic phosphorus residues in vegetables (chapter second). This method uses acetylcholine enzyme (AChE) catalyzes the thioacetyl Choline is hydrolyzed to produce thiocholine by gold nanoclusters agglomeration, leading to the characteristics of fluorescence quenching, and the use of dichlorvos (DDVP) on acetylcholinesterase (AChE) inhibitory effect on catalytic activity, the pesticide residue rapid, sensitive and specific detection (linear range of 0.032 nM-20 nM, the detection limit is 13.67 pM). The actual DDVP residues in vegetable samples detection limit of 36 pM. the fluorescence analysis method by measuring the direct signs of infection of the organic phosphorus free organic phosphorus, organic phosphorus for infection early warning, and provides a new method for evaluation of physiological enzyme catalytic activity. (2) biomineralization synthesis route the one pot reaction, and through adjusting the molar ratio of gold / silver precursor, double metal alloy of gold and silver nanoclusters strong fluorescence were synthesized and used as fluorescent probes for mercury ion and copper ion in the blood quickly, especially ISO, ultra sensitive detection (the third chapter). The research results show that the alloy of gold and silver nanoclusters prepared with red fluorescent silver enhancement effect, the fluorescence intensity was 6.5 times gold and silver nanoclusters common gold nanoclusters and core-shell structure and 4.7 times; in particular, the "silver" effect not only to improve the response ability of gold and silver alloy nanocluster mercury ion, and gives the specific detection of copper ions; in addition, through the introduction of copper ion complexing agent, the detect of copper ions and mercury ion; fluorescence detection analysis of blood mercury ion and copper ion limit of 0.30 nM and 0.60 nM respectively, the detection can be used in clinical laboratory blood mercury and blood copper. (3) functionalized phenylboronic acid derivatives of saccharide polyhydroxy compounds and the specific recognition principle is established based on the capillary effect of a high speed visual measurement technology, with In the blood, natural products, agricultural products, chemical products, monosaccharide, polysaccharide and detection of polyhydroxy compounds containing groups of 1,2- or 1,3- of the diol (Chapter fourth). The function of phenylboronic acid derivatives modified on the inner wall of capillary amino silane treatment scale in advance, automatic suction samples by capillary effect, and then by swelling on the wall of phenylboronic acid with polyhydroxy compounds containing groups of 1,2- or 1,3- glycol to form compound, lead to the inner wall of the capillary wettability change, thereby causing regular scale capillary level in the rise of the visual realization of the height of liquid level detecting sugars in samples of polyhydroxy compounds content. The method of velocity measurement the function of phenylboronic acid derivatives as recognition sugar polyol, overcomes many disadvantages of traditional enzymatic detection techniques (e.g., enzyme inactivation problem), out There are few samples (about 20 L), simple operation, low price, and suitable for field rapid measurement.

【学位授予单位】：曲阜师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：O657.3;TB34

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