本文選題：分子印跡 + 石墨烯　； 參考：《鄭州大學(xué)》2017年碩士論文

【摘要】：分子印跡電化學(xué)傳感是將分子印跡聚合物對目標(biāo)物的特異性識別和電化學(xué)傳感技術(shù)結(jié)合為一體的一種現(xiàn)代電化學(xué)分析方法,靈敏度高、選擇性好、設(shè)備簡單。表面分子印跡是在特殊載體表面進(jìn)行的分子印跡物合成技術(shù),可以大大增加印跡位點的暴露面,加快識別位點與目標(biāo)分子之間的傳質(zhì)作用,避免傳統(tǒng)分子印跡識別位點包埋的種種弊端,日益成為研究者們的關(guān)注熱點。基于表面分子印跡和電化學(xué)傳感的優(yōu)勢,本論文以不同功能化石墨烯修飾的電極為載體,鄰苯二胺為功能單體,通過電聚合條件的控制,在修飾電極表面合成分子印跡膜,構(gòu)筑了功能化石墨烯表面分子印跡電化學(xué)傳感器,實現(xiàn)了分子印跡聚合物合成和電化學(xué)傳感器的一體化構(gòu)筑;研究了傳感器對目標(biāo)物的識別性能和傳感性能;并通過實際樣品的分析檢測,探討了傳感器在實際樣本檢測中的應(yīng)用可行性。所獲結(jié)果對于新的分子印跡電化學(xué)傳感器的構(gòu)建和應(yīng)用提供了方法學(xué)的參考和依據(jù)。具體內(nèi)容如下:1.基于聚苯乙烯磺酸鈉功能化石墨烯(PSS-GR)的大豆苷元分子印跡電化學(xué)傳感器的構(gòu)建及應(yīng)用。基于聚苯乙烯磺酸鈉(PSS)與氧化石墨烯(GO)之間的非共價作用,通過水合肼一步還原法合成PSS功能化的石墨烯(PSS-GR);采用紫外,紅外、透射電鏡、對PSS-GR進(jìn)行了表征;通過滴涂修飾技術(shù),制備了PSS-GR修飾電極(PSS-GR/GCE);利用PSS-GR與功能單體鄰苯二胺和模板分子大豆苷元之間的非共價作用,在PSS-GR/GCE界面上,通過電聚合條件的控制優(yōu)化,制備了大豆苷元分子印跡膜,探討了聚合物反應(yīng)中單體與模板分子比例、聚合濃度、聚合介質(zhì)條件及聚合強(qiáng)度的影響,確定了分子印跡膜的制備條件,構(gòu)筑了大豆苷元分子印跡電化學(xué)傳感器;以[Fe(CN)6]3-/[Fe(CN)6]4-為探針,研究了傳感器對目標(biāo)物大豆苷元的識別性能和傳質(zhì)過程;研究表明,該傳感器在11 min內(nèi),即可完成大豆苷元在電極表面的飽和富集;在0.1 mol/L的NaOH溶液中,15 min即可完成目標(biāo)分子的洗脫;相對于結(jié)構(gòu)相似的葛根素、槲皮素、染料木素、白楊素,構(gòu)筑的傳感器對大豆苷元的印跡效率高達(dá)5.25,表現(xiàn)出了較快的傳質(zhì)過程和較好的選擇識別性。在優(yōu)化的實驗條件下,大豆苷元在分子印跡膜上的識別響應(yīng)與其濃度在1×10-9~2×10-8 mol/L成線性,檢測限為8×10-10 mol/L。該方法可用于實際血樣中和葛根提取液中大豆苷元的檢測。2.基于聚苯乙烯磺酸鈉功能化石墨烯(PSS-GR)的2,4-二氯酚電化學(xué)傳感器的構(gòu)建及應(yīng)用。在第一章研究的基礎(chǔ)上,依據(jù)PSS-GR對2,4-二氯酚和鄰苯二胺強(qiáng)烈的非共價相互作用,在PSS-GR/GCE界面上,以鄰苯二胺為功能單體,2,4-二氯酚為模板分子,采用循環(huán)伏安掃描電聚合制備了2,4-二氯酚的分子印跡電化學(xué)傳感器,探討了聚合物反應(yīng)中單體與模板分子比例、聚合濃度、聚合介質(zhì)條件及聚合強(qiáng)度的影響;以[Fe(CN)6]3-/[Fe(CN)6]4-為探針,研究了傳感器的電化學(xué)行為和對目標(biāo)物2,4-二氯酚的識別性能和傳質(zhì)過程。研究表明,該傳感器在14 min內(nèi),即可完成大豆苷元在電極表面的飽和富集;在0.1 mol/L的NaOH溶液中,10 min即可完成目標(biāo)分子的洗脫;相對于結(jié)構(gòu)相似的氯酚類化合物,構(gòu)筑的傳感器對大豆苷元的印跡效率高達(dá)7.83,表現(xiàn)出了較快的傳質(zhì)過程和優(yōu)異的選擇性。在優(yōu)化的實驗條件下,傳感器對2,4-二氯酚檢測的線性范圍為5×10-9~8×10-8mol/L,檢測限為1×10-9 mol/L。該方法可以用于實際水樣(湖水、自來水和雨水)中2,4-DCP的檢測。3.基于聚多巴胺功能化石墨烯(PDA-rGO)的2,4-二氯酚分子印跡電化學(xué)傳感器的構(gòu)建及應(yīng)用�；诙喟桶返娜踹�原性和堿性條件下自聚合的性質(zhì),一步法合成了聚多巴胺功能化石墨烯(PDA-rGO)。通過通過紫外-可見吸收光譜、紅外光譜、掃描電鏡、透射電鏡、X射線衍射對PDA-rGO進(jìn)行了表征。利用滴涂修飾技術(shù),制備了PDA-rGO修飾電極(PDA-rGO/GCE);利用PDA-rGO與功能單體鄰苯二胺和模板分子2,4-DCP之間的非共價作用,在PDA-rGO界面上,通過電聚合條件的控制優(yōu)化,制備了2,4-DCP分子印跡膜;以[Fe(CN)6]3-/[Fe(CN)6]4-為探針,研究了構(gòu)筑傳感器的電化學(xué)行為和對目標(biāo)物的傳質(zhì)和識別性能;研究表明,該傳感器在6 min內(nèi)即可完成2,4-二氯酚在電極表面的飽和富集;在乙醇溶液中8min即可完成目標(biāo)分子的洗脫;相對于結(jié)構(gòu)相似的2-氯酚,三氯酚,五氯酚,鄰氨基苯酚和鄰苯二酚,印跡因子分別為上述干擾物的3.67、4.02、4.63、5.77和25倍,印跡效率為15.5,表現(xiàn)出了更快的傳質(zhì)過程和優(yōu)異的選擇性。該傳感器可以成功應(yīng)用于水樣中2,4-二氯酚檢測
[Abstract]:Molecularly imprinted electrochemical sensing is a modern electrochemical analysis method, which combines the specific recognition of the molecularly imprinted polymer and the electrochemical sensing technology of the target. The sensitivity is high, the selectivity is good, and the equipment is simple. The surface molecular imprinting is a molecularly imprinted matter synthesis technology on the surface of the special carrier, which can greatly increase the printing On the basis of the advantages of surface molecularly imprinting and electrochemical sensing, the electrode of different functional fossils as the carrier, o-benzene two, is becoming the focus of attention of the researchers. Amines, as functional monomers, synthesized molecular imprinted membranes on the surface of modified electrodes by the control of electropolymerization conditions, constructed a Molecularly Imprinted Electrochemical Sensor on the surface of functionalized fossils, realized the synthesis of molecularly imprinted polymers and the integration of electrochemical sensors, and studied the recognition and sensing properties of the sensor. Through the analysis and detection of the actual samples, the feasibility of the application of the sensor in the actual sample detection is discussed. The results will provide a reference and basis for the construction and application of the new molecularly imprinted electrochemical sensor. The specific contents are as follows: 1. the daidzein molecule based on the PSS-GR of polystyrene sulfonate function fossils The construction and application of the imprinted electrochemical sensor. Based on the non covalent interaction between PSS and GO, PSS functionalized graphene (PSS-GR) was synthesized by one step reduction method of hydrazine hydrate, and PSS-GR was characterized by UV, IR, transmission electron microscopy, and PSS-GR modified electricity was prepared by coating modification. Polar (PSS-GR/GCE); with the non covalent interaction between PSS-GR and functional monomers of benzyl two amine and formwork daidzein, a daidzein molecularly imprinted membrane was prepared on the PSS-GR/GCE interface through the control of electropolymerization conditions. The proportion of monomers and template molecules, polymerization concentration, polymerization medium conditions and polymerization in the polymer reaction were discussed. The preparation conditions of the molecularly imprinted membrane were determined by strength, and a daidzein Molecularly Imprinted Electrochemical sensor was constructed. The identification performance and mass transfer process of the sensor to daidzein were studied with [Fe (CN) 6]3-/[Fe (CN) 6]4- as a probe. The study showed that the sensor could finish the Daidzein on the surface of the electrode in 11 min. Saturated enrichment; in the 0.1 mol/L NaOH solution, 15 min can complete the elution of the target molecule; compared to the structure similar puerarin, quercetin, genistein and poplar, the imprinting efficiency of the daidzein is up to 5.25, showing a faster mass transfer process and better selection recognition. Under the optimized experimental conditions, The recognition response of Daidzein on molecular imprinting membrane is linear with its concentration of 1 x 10-9~2 x 10-8 mol/L, and the detection limit is 8 x 10-10 mol/L.. The method can be used for the detection of Daidzein in the actual blood sample and pueraria extract. The construction of 2,4- two chlorophenol electrochemical sensor based on the PSS-GR of sodium sulfonate (PSS-GR) and the construction of.2. On the basis of the study in the first chapter, on the basis of the strong non covalent interaction between 2,4- two Chlorophenol and phthalamines on the basis of PSS-GR, the molecular imprinting electrochemical sensor of 2,4- two chlorophenol was prepared by cyclic voltammetric scanning electropolymerization on the PSS-GR/GCE interface, with phthalic two amine as functional monomer and 2,4- two chlorophenol as the template molecule. The effects of the proportion of the monomers and the template molecules, the concentration of the polymerization, the conditions of the polymerization medium and the polymerization strength were investigated. The electrochemical behavior of the sensor and the identification performance and mass transfer process of the target 2,4- two chlorophenol were studied with [Fe (CN) 6]3-/[Fe (CN) 6]4- as a probe. The results showed that the sensor could complete the daidzein in the electrode in 14 min. The surface saturation enrichment; in the 0.1 mol/L NaOH solution, 10 min can complete the elution of the target molecule; compared with the structure similar chlorophenols, the imprinting efficiency of the constructed sensor to daidzein is up to 7.83, showing a rapid mass transfer process and excellent selection. Under the optimized experimental conditions, the sensor is to 2,4- two chlorine. The linear range of phenol detection is 5 x 10-9~8 x 10-8mol/L and the detection limit is 1 x 10-9 mol/L.. The method can be used for the detection of 2,4-DCP in real water samples (lake water, tap water and rainwater)..3. based on the 2,4- two chlorophenol Molecularly Imprinted Electrochemical Sensor Based on the dopamine functional fossil Mo (PDA-rGO) and its application. The property of self polymerization under alkaline conditions, polydopamine functionalized fossil mo (PDA-rGO) was synthesized by one step method. PDA-rGO was characterized by UV visible absorption spectroscopy, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and X ray diffraction. The PDA-rGO modified electrode (PDA-rGO/GCE) was prepared by the coating modification technique; and PDA-rGO and function were used. The non covalent interaction between the mono two amine and the template molecule 2,4-DCP was used to prepare the 2,4-DCP molecularly imprinted membrane on the PDA-rGO interface through the control of the electropolymerization conditions. The electrochemical behavior of the sensor and the mass transfer and recognition performance of the target were studied with [Fe (CN) 6]3-/[Fe (CN) 6]4- as the probe. The saturated enrichment of 2,4- chlorophenol on the surface of the electrode can be completed in 6 min, and the elution of the target molecule can be completed in the ethanol solution; compared with the structure similar 2- chlorophenol, three chlorophenol, pentachlorophenol, O aminophenol and catechol, the imprinting factor is 3.67,4.02,4.63,5.77 and 25 times of the interferon, and the imprinting efficiency is 15.5. A faster mass transfer process and excellent selectivity has been achieved. The sensor can be successfully applied to the detection of 2,4- two chlorophenol in water samples.
【學(xué)位授予單位】：鄭州大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.1

【參考文獻(xiàn)】

相關(guān)期刊論文 前3條

1 張進(jìn);王超英;李小平;牛延慧;;聚鄰氨基苯硫酚/納米金復(fù)合膜分子印跡傳感器測定2,4-二氯苯酚[J];高等學(xué)�；瘜W(xué)學(xué)報;2013年10期

2 丁俊紅;張艷;龔樹文;;輻射引發(fā)懸浮聚合制備香草醛分子印跡聚合物[J];輻射研究與輻射工藝學(xué)報;2012年01期

3 黃寶美;姚程煒;邊清泉;王秀峰;王志國;;大豆黃素的電化學(xué)行為及其循環(huán)伏安測定[J];理化檢驗(化學(xué)分冊);2009年03期

相關(guān)博士學(xué)位論文 前1條

1 趙s钅，

本文編號：1930775