【摘要】：農藥和有機污染物在樣品中的含量比較低,但是對人體和其它生物存在著潛在的危害。環(huán)境樣品基質復雜,一般需要通過樣品處理過程,把目標分析物從復雜基質中分離并且富集后才能進行后續(xù)的定性定量分析�，F(xiàn)有的樣品前處理方法耗時、繁瑣,常用的檢測方法通常需要比較昂貴的儀器,分析成本較高且需要專業(yè)人員操作。因此,開發(fā)簡單、快速、廉價的樣品前處理方法和檢測方法十分重要。納米材料具有巨大的比表面積和獨特的光學特性等,可以用于環(huán)境樣品的前處理和檢測。本論文主要分為三部分實驗內容。第一部分:選取水果和蔬菜樣品為基質,研究了石墨烯在農藥多殘留分析中的凈化作用。首先,制備的石墨烯通過光電子能譜和拉曼光譜進行表征。然后,選取17種農藥用GC-MS分析,研究了石墨烯作為QuEChERS方法的分散固相萃取吸附劑,對胡蘿卜、葡萄、番茄、油菜四種基質的凈化效果。實驗結果表明:目標農藥的回收率為92-120%,石墨烯對各種基質都有較好的凈化作用,且其凈化效果要優(yōu)于石墨化炭黑。第二部分:選取15種鄰苯二甲酸酯為目標分析物,研究了石墨烯對水體中環(huán)境污染物的提取作用。15種鄰苯二甲酸酯用GC-MS檢測,實驗對石墨烯用量、解吸附溶劑、吸附時間、解吸附時間及pH進行了優(yōu)化,并將該方法用于中國7個地方的河水和海水樣本的分析。實驗結果表明:在優(yōu)化條件下,15種鄰苯二甲酸酯在超純水、河水、海水中的回收率為71-117%,方法的線性關系良好,且可以用于實際樣本檢測。第三部分:選取對氧磷為代表性的農藥,研究了納米材料在有機磷農藥檢測方面的應用。對制備的MnO2納米片、碳量子點、金納米顆粒進行了 TEM、UV-Vis光譜、熒光光譜、Zeta電位等表征。MnO2納米片能夠引起異硫氰酸熒光素(FITC)的熒光淬滅且該淬滅作用會隨著H202的加入而得到恢復,H2O2可以通過乙釀膽堿酯酶和膽堿氧化酶的催化作用產生。基于有機磷農藥抑制膽堿酯酶活性的性質,以對氧磷為例,建立了 FITC-MnO2納米片熒光傳感檢測有機磷農藥的方法。該方法的線性關系良好,LOD為1μg L-1,河水和自來水中的添加回收率為89-108%。相對于有機熒光染料,碳量子點低毒,生物相容性好。金納米顆粒能夠通過熒光共振能量轉移作用(FRET)淬滅碳量子點熒光,丁酰膽堿酯酶水解硫代乙酰膽堿的產物能夠引起金納米顆粒聚沉,從而使碳量子點熒光恢復�；谟袡C磷農藥抑制丁酰膽堿酯酶活性的性質,以對氧磷為例,建立了有機磷農藥的熒光檢測方法。該方法的線性關系良好,LOD為0.05 μg L-1,河水和自來水中的添加回收率為90-103%。本論文制備了不同的納米材料,將其分別用于農藥多殘留的基質凈化、鄰苯二甲酸酯提取和有機磷農藥的熒光檢測,開發(fā)了新的樣品前處理的凈化劑、有機污染物提取方法和有機磷農藥的檢測方法。
[Abstract]:Pesticides and organic pollutants in the sample content is relatively low, but there are potential hazards to human and other organisms. The matrix of environmental sample is complex, so it is necessary to separate and enrich the target analyte from the complex matrix through the sample treatment process before the qualitative and quantitative analysis can be carried out. The existing sample pretreatment methods are time-consuming, cumbersome, and the commonly used detection methods usually need more expensive instruments, and the analysis cost is high and needs professional operation. Therefore, it is very important to develop simple, fast and cheap sample pretreatment and detection methods. Nanomaterials have a large specific surface area and unique optical properties, which can be used for pretreatment and detection of environmental samples. This thesis is divided into three parts. In the first part, the purification of graphene in pesticide multi-residue analysis was studied by using fruit and vegetable samples as substrate. Firstly, the graphene was characterized by photoelectron spectroscopy and Raman spectroscopy. Then, 17 kinds of pesticides were selected for GC-MS analysis to study the purification effect of graphene as a dispersive solid phase extraction adsorbent for carrot, grape, tomato and rape. The experimental results show that the recovery rate of the target pesticide is 92-120. Graphene has a good purification effect on all kinds of matrix, and its purification effect is better than that of graphitized carbon black. The second part: 15 phthalates were selected as target analytes to study the extraction of graphene to environmental pollutants in water. 15 phthalates were detected by GC-MS, the amount of graphene was measured, the adsorption solvent was desorbed. The adsorption time, desorption time and pH were optimized, and the method was applied to the analysis of water and sea water samples from 7 places in China. The experimental results show that under the optimized conditions, the recoveries of 15 phthalates in ultrapure water, river water and seawater are 71-117.The linear relationship of the method is good, and it can be used for the detection of practical samples. In the third part, the application of nanomaterials in organophosphorus pesticide detection was studied. The prepared MnO2 nanoparticles, carbon quantum dots and gold nanoparticles were characterized by TEM,UV-Vis and fluorescence spectra. Zeta potential. MnO2 nanoparticles can induce fluorescence quenching of fluorescein isothiocyanate (FITC) and the quenching effect will be restored with the addition of H202. H2O2 can be produced by the catalysis of ethylcholinesterase and cholinesterase. Based on the properties of organophosphorus pesticides inhibiting cholinesterase activity, a fluorescence sensing method for the detection of organophosphorus pesticides by FITC-MnO2 nanoparticles was established. The linear relationship of the method is good, the LOD is 1 渭 g / L ~ (-1), and the recovery rate of adding in river water and tap water is 89 ~ 108. Compared with organic fluorescent dyes, carbon quantum dots have low toxicity and good biocompatibility. Gold nanoparticles can quench the fluorescence of carbon quantum dots by (FRET) through fluorescence resonance energy transfer. The products of acetylcholine hydrolyzed by butyrylcholinesterase can lead to the aggregation of gold nanoparticles, which can restore the fluorescence of carbon quantum dots. Based on the properties of organophosphorus pesticides inhibiting butyrylcholinesterase activity, a fluorescence detection method for organophosphorus pesticides was established. The linear relationship of the method is good, the LOD is 0. 05 渭 g L ~ (-1), and the recovery rate in river water and tap water is 90-103. In this paper, different nanomaterials were prepared and used for the purification of multi-residue matrix, extraction of phthalate and fluorescence detection of organophosphorus pesticides, and a new purifying agent for sample pretreatment was developed. Extraction of organic pollutants and determination of organophosphorus pesticides.
【學位授予單位】：中國農業(yè)大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：X592;S481.8

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