【摘要】：本論文利用了三種不同的納米材料構建了三種光譜傳感器,把納米材料作為比色或熒光探針,并結合酶催化法、紫外可見光譜法以及熒光猝滅法等方法對環(huán)境中常見的危險物質(汞離子、有機磷農藥)進行了定量分析。該類方法操作簡單,檢測快速,靈敏度高,為納米材料在危險物質的定量檢測方面提供了一些新的思路。具體內容總結如下:闡述了銀納米粒子、石墨烯量子點、金納米簇、四氧化三鐵這幾種納米材料的發(fā)展、其常見的合成方法以及在分析化學研究領域的應用研究;介紹了幾種檢測對象的用途、現(xiàn)狀;展望了納米材料結合分子光譜法在分析檢測領域的一些動向。利用硼氫化鈉還原硝酸銀的方法制備了檸檬酸鈉保護的銀納米粒子。利用紫外-可見光譜、透射電子顯微鏡和能量彌散X射線能譜等表征手段對合成的銀納米粒子的形貌及其在反應前后的聚散程度進行表征。(1)乙酰膽堿酯酶催化底物硫代乙酰膽堿水解產(chǎn)生的硫代膽堿可以和銀納米粒子結合使其聚集;(2)這種變化會反應在體系溶液的顏色上,銀納米溶液由亮黃色變成粉紅色;(3)有機磷或氨基甲酸酯農藥能使乙酰膽堿酯酶變性失活,從而抑制這一變化的發(fā)生。依據(jù)此原理對有機磷或氨基甲酸酯農藥的含量進行測定。通過將檸檬酸在200?C下熱解合成了石墨烯量子點,在450 nm處可以發(fā)出藍色熒光。(1)通過靜電作用,帶正電的汞離子會吸附在帶負電的石墨烯量子點表面誘導其聚集,同時通過電荷轉移使其熒光猝滅;(2)繼續(xù)加入半胱氨酸后,汞離子會與其通過金屬巰基鍵結合從而脫離石墨烯量子點表面,熒光恢復。因此根據(jù)以上熒光先猝滅后增強的變化可以構建一個依次檢測汞離子和半胱氨酸的高靈敏熒光傳感器。我們將磁性四氧化三鐵和金納米簇結合,合成了一種磁性的熒光納米復合材料,四氧化三鐵的核被包裹在一層二氧化硅中,外表面再修飾上一層氨基;將牛血清白蛋白保護的金納米簇進行羧基活化;通過肽鍵,它們可以結合在一起并形成一種交聯(lián)結構。6-巰基嘌呤會吸附在金納米簇的表面并誘導其聚集產(chǎn)生更大的金納米粒子,破壞這種交聯(lián)結構,同時熒光猝滅。根據(jù)此原理可以構建一個6-巰基嘌呤的熒光傳感器。本文的創(chuàng)新點如下:1.利用了3種不同類別的納米材料對一些環(huán)境中的危險物質及藥物進行了定量檢測,都取得了非常理想的實驗結果,具有很高的靈敏度和較好的選擇性;2.構建的定量方法相對傳統(tǒng)的檢測方法操作簡單、檢測快速,具有更強的實際應用能力;3.通過先猝滅后增強的熒光“On-Off-On”體系構建了同時檢測汞離子和半胱氨酸的雙傳感器;4.結合理論,自行構建了納米復合材料的合成方法,成功將金納米簇和四氧化三鐵納米粒子兩種納米材料的性質整合到一起,大大提高了檢測效率。
[Abstract]:In this paper, three kinds of spectrum sensors were constructed by using three different nanomaterials, which were used as colorimetric or fluorescent probes, and combined with enzymatic catalysis. UV-Vis spectroscopy and fluorescence quenching methods were used to quantitatively analyze the common hazardous substances (mercury ions, organophosphorus pesticides) in the environment. This method is simple in operation, rapid in detection and high in sensitivity. It provides some new ideas for quantitative detection of hazardous substances by nanomaterials. The specific contents are summarized as follows: the development of silver nanoparticles, graphene quantum dots, gold nanoclusters, iron trioxide, their common synthesis methods and their applications in analytical chemistry are reviewed. The applications and present situation of several detection objects are introduced, and some trends of nanomaterials combined with molecular spectroscopy in the field of analysis and detection are prospected. Silver nanoparticles protected by sodium citrate were prepared by reducing silver nitrate by sodium borohydride. Using the UV-Vis spectrum, Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) were used to characterize the morphology of the synthesized silver nanoparticles and their degree of dispersion before and after the reaction. (1) acetylcholinesterase catalyzed the hydrolysis of thioacetylcholine by acetylcholinesterase. The resulting thiocholine can be combined with silver nanoparticles to aggregate it; (2) this change is reflected in the color of the solution. Silver nanoparticles changed from bright yellow to pink. (3) organophosphorus or carbamate pesticides could deactivate acetylcholinesterase and inhibit this change. According to this principle, the content of organophosphorus or carbamate pesticides was determined. Graphene quantum dots were synthesized by pyrolysis of citric acid at 200C, and blue fluorescence could be emitted at 450 nm. (1) by electrostatic action, positively charged mercury ions would be adsorbed on the surface of negatively charged graphene quantum dots to induce their aggregation. At the same time, the fluorescence was quenched by charge transfer. (2) after the addition of cysteine, mercury ions would bind to the surface of graphene quantum dots through metal sulfhydryl bonds, and the fluorescence would recover. Therefore, a highly sensitive fluorescence sensor for the detection of mercury ion and cysteine can be constructed according to the changes of fluorescence quenching and then enhancement. A kind of magnetic fluorescent nanocomposites was synthesized by combining magnetic ferric oxide with gold nanoclusters. The core of Fe _ 2O _ 3 was encapsulated in a layer of silica, and the outer surface was modified with a layer of amino. The bovine serum albumin protected gold nanoclusters are activated by carboxyl groups; by peptide bonds, they can bind together and form a cross-linking structure. 6-mercaptopurine adsorbs on the surface of the gold nanoclusters and induces their aggregation to produce larger gold nanoparticles. The crosslinking structure was destroyed and the fluorescence quenching was carried out at the same time. According to this principle, a 6-mercaptopurine fluorescence sensor can be constructed. The innovations of this paper are as follows: 1. Three different kinds of nanomaterials were used to quantitatively detect some dangerous substances and drugs in the environment. All of them obtained very ideal experimental results with high sensitivity and good selectivity. 2. Compared with the traditional detection method, the quantitative method constructed is simple, rapid and has stronger practical application ability. 3. A double sensor for the simultaneous detection of mercury and cysteine was constructed by quenching and then enhancing the fluorescence "On-Off-On" system. 4. Combining with the theory, the synthesis method of nanocomposites was constructed, and the properties of gold nanoclusters and iron trioxide nanoparticles were successfully integrated together, which greatly improved the detection efficiency.
【學位授予單位】：南昌大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：X830;TB383.1

【共引文獻】

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6 戴炳業(yè);唐清華;胡燕;史修娟;徐志祥;;電化學生物傳感器在農藥殘留檢測中的應用研究進展[J];糧油食品科技;2014年04期

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本文編號：2294031