本文選題：農(nóng)藥　切入點(diǎn)：分子印跡　出處：《鄭州大學(xué)》2016年碩士論文　論文類(lèi)型：學(xué)位論文

【摘要】：農(nóng)藥在生產(chǎn)和生活中應(yīng)用十分廣泛。有相關(guān)統(tǒng)計(jì)顯示全世界每年大約有200萬(wàn)人因農(nóng)藥污染而患病,工業(yè)排放的污水中農(nóng)藥超標(biāo)、大棚蔬菜施藥不當(dāng)及施用違禁高毒農(nóng)藥對(duì)環(huán)境安全和人類(lèi)身體健康造成極大威脅,成為亟待解決的重大社會(huì)問(wèn)題。傳統(tǒng)的農(nóng)藥檢測(cè)手段大多設(shè)備昂貴、操作復(fù)雜,需要使用大量有機(jī)溶劑進(jìn)行預(yù)處理,并且無(wú)法實(shí)時(shí)監(jiān)測(cè)。目前,市場(chǎng)迫切需要能實(shí)現(xiàn)對(duì)工業(yè)廢水、食品生產(chǎn)加工聚集區(qū)、農(nóng)藥生產(chǎn)和施用現(xiàn)場(chǎng)農(nóng)藥遠(yuǎn)程監(jiān)檢的方法。因此研究無(wú)需樣品預(yù)處理,能簡(jiǎn)單、快速、實(shí)時(shí)地監(jiān)檢水中農(nóng)藥及農(nóng)藥噴施過(guò)程的檢測(cè)手段具有十分重要的意義。本文首次提出并構(gòu)筑了農(nóng)藥現(xiàn)場(chǎng)檢測(cè)監(jiān)控系統(tǒng)的理念和方法,并以制備簡(jiǎn)單、易于分離、特異性好的分子印跡聚合物為識(shí)別手段;以超靈敏、非標(biāo)記性和能實(shí)時(shí)在線檢測(cè)的石英晶體微天平為檢測(cè)手段;以最常用的有機(jī)磷農(nóng)藥毒死蜱為模板分子,制備具有樣品無(wú)需預(yù)處理,高特異性和高靈敏度,可直接檢測(cè)水相以及蔬菜大棚噴霧中的毒死蜱乳油的功能的石英晶體微天平傳感器,努力實(shí)現(xiàn)農(nóng)藥實(shí)施現(xiàn)場(chǎng)及農(nóng)藥污染源實(shí)施遠(yuǎn)程檢測(cè)監(jiān)控的設(shè)計(jì)目的。本課題的研究?jī)?nèi)容和結(jié)果具體包括以下三個(gè)方面:1.設(shè)計(jì)并通過(guò)電化學(xué)聚合方法以毒死蜱乳油為模板分子,吡咯為功能單體,磷酸鹽緩沖溶液作溶劑,制備了毒死蜱分子印跡聚吡咯修飾的石英晶體微天平傳感器,并對(duì)其制備條件進(jìn)行了優(yōu)化;通過(guò)電化學(xué)循環(huán)伏安、交流阻抗、靜態(tài)水接觸角、石英晶體微天平、掃描電子顯微鏡和原子力顯微鏡分別對(duì)聚吡咯印跡薄膜的性質(zhì)及表面形貌進(jìn)行了表征。2.通過(guò)毒死蜱聚吡咯印跡傳感器測(cè)定毒死蜱乳油水溶液,同時(shí)制備的兩個(gè)傳感器檢出限分別為1.30 ppm和1.72 ppm,表明傳感器制備重現(xiàn)性良好。從特異性、溫度穩(wěn)定性、實(shí)際樣品實(shí)驗(yàn)和再生性方面對(duì)傳感器的性能進(jìn)行分析。結(jié)果表明印跡傳感器對(duì)毒死蜱乳油的檢測(cè)是對(duì)毒死蜱分子的特異性識(shí)別,檢測(cè)結(jié)果受溫度影響較小,該傳感器能檢測(cè)蔬菜汁液等復(fù)雜基質(zhì)中的毒死蜱,加標(biāo)回收率92%~104%,相對(duì)標(biāo)準(zhǔn)偏差為4%,傳感器可再生13次。此外,在水相檢測(cè)時(shí)探索施加DEP對(duì)毒死蜱乳膠微粒進(jìn)行富集,加快識(shí)別速率,降低檢出限。3.首先采用聚吡咯毒死蜱印跡傳感器對(duì)毒死蜱乳油噴霧進(jìn)行測(cè)定,結(jié)果顯示頻率響應(yīng)受水影響較大,與農(nóng)藥的濃度沒(méi)有線性關(guān)系且特異性不好。繼而選擇強(qiáng)疏水性的聚偏氟乙烯(PVDF)作為成膜物質(zhì)制備了PVDF毒死蜱印跡傳感器,其測(cè)定農(nóng)藥噴霧有一定的特異性但仍未達(dá)到預(yù)期效果。進(jìn)而又選擇有機(jī)硅絕緣漆為成膜物質(zhì),從水接觸角在酸洗后增大及掃描電子顯微鏡圖中的大量微米亞微米凹槽推測(cè)其可能是形成了一種類(lèi)荷葉的疏水結(jié)構(gòu)。識(shí)別過(guò)程中共振頻率變化呈鋸齒狀,可能是印跡位點(diǎn)包埋所致,也可能與凹槽中存有空氣相關(guān)。
[Abstract]:Pesticide is widely used in production and daily life. Some statistics show that every year about 2 million people in the world get sick because of pesticide pollution. The improper application of pesticides in greenhouse vegetables and the application of banned high toxic pesticides pose a great threat to environmental safety and human health and become a major social problem to be solved urgently. Most of the traditional pesticide detection methods are expensive in equipment and complex in operation. Need to use a large number of organic solvents for pretreatment, and can not be monitored in real time. At present, the market urgently needs to be able to achieve industrial wastewater, food production and processing areas, Methods for remote monitoring and inspection of pesticides in the field of pesticide production and application. It is of great significance to monitor and inspect the pesticide and pesticide spraying process in water in real time. The idea and method of pesticide field detection and monitoring system are put forward and constructed for the first time in this paper, and the preparation is simple and easy to separate. Specific molecularly imprinted polymers are used as recognition methods; quartz crystal microbalance, which is hypersensitive, unlabeled and can be detected online in real time; chlorpyrifos, the most commonly used organophosphorus pesticide, as template molecule. A quartz crystal microbalance sensor with the functions of no pretreatment, high specificity and high sensitivity for direct detection of chlorpyrifos emulsifiable oil in vegetable greenhouse spray was prepared. The research contents and results of this paper include the following three aspects: 1.Design and use chlorpyrifos emulsifiable oil as template molecule by electrochemical polymerization method. Using pyrrole as a functional monomer and phosphate buffer solution as solvent, the imprinted polypyrrole modified quartz crystal microbalance sensor modified by chlorpyrifos was prepared and its preparation conditions were optimized. The properties and surface morphology of polypyrrole imprinted films were characterized by static water contact angle, quartz crystal microbalance, scanning electron microscope and atomic force microscope. 2. Chlorpyrifos emulsion aqueous solution was determined by chlorpyrrosine polypyrrole imprinting sensor. The detection limits of the two sensors were 1.30 ppm and 1.72 ppm, respectively, which indicated that the reproducibility of the two sensors was good. The results show that the detection of chlorpyrifos by imprinting sensor is a specific recognition of chlorpyrifos molecules, and the detection results are less affected by temperature. The sensor can detect chlorpyrifos in complex matrix, such as vegetable juice. The recovery rate of chlorpyrifos is 920.The relative standard deviation is 4. The sensor can regenerate 13 times. In addition, the application of DEP in water phase detection is explored to enrich chlorpyrifos latex particles. Firstly, the polypyrrole chlorpyrifos imprinted sensor was used to determine the chlorpyrifos emulsion spray. The results showed that the frequency response of chlorpyrifos was greatly affected by water. There was no linear relationship with the concentration of pesticides and the specificity was not good. Then the hydrophobic polyvinylidene fluoride (PVDF) was used as the membrane material to prepare PVDF chlorpyrifos imprinting sensor. The determination of pesticide spray has a certain specificity, but still does not reach the desired effect. Then, the silicone insulating paint is selected as the film forming material. Based on the increase of water contact angle after pickling and the large number of micron submicron grooves in the scanning electron microscope (SEM), it is speculated that the water contact angle may form a hydrophobic structure of a kind of lotus leaf. It may be caused by imprinting site entrapping, or it may be related to the existence of air in the grooves.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類(lèi)號(hào)】：O631.3

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