【摘要】：發(fā)展快速、靈敏、高選擇性和檢測結(jié)果可靠的傳感器在諸多領(lǐng)域都有廣泛需求,在藥物分析領(lǐng)域也是同樣。分子印跡聚合物(molecularly imprinted polymer,MIP)是一種能夠特異性識別目標(biāo)物質(zhì)的高分子材料,具有預(yù)定選擇性、特異識別性和廣泛適用性的特點(diǎn),因此近年來發(fā)展迅速。本論文將分子印跡技術(shù)與電化學(xué)傳感技術(shù)相結(jié)合,制備了三種分子印跡電化學(xué)傳感器分別用于檢測雌酮硫酸鈉、甲硝唑和多巴胺。主要內(nèi)容分為以下3個(gè)部分:(1)基于分子印跡聚合物修飾的碳糊電極用于雌酮硫酸鈉的檢測本研究采用傳統(tǒng)的本體聚合方法制備雌酮硫酸鈉(estrone 3-sulfate sodium salt,ESS)分子印跡聚合物,將ESS-MIP和石墨粉混合后加入少量液體石蠟作為粘合劑,充分研磨將其混勻,隨后填充到電極管中,制備了分子印跡聚合物修飾的碳糊電極(carbon paste electrode,CPE),將其作為電化學(xué)傳感器用于ESS的檢測。其中,對ESS-MIP制備過程中模板分子、功能單體、交聯(lián)劑三者之間的比例、聚合反應(yīng)溶劑和洗脫溶劑都進(jìn)行了優(yōu)化,同時(shí)對填入碳糊電極中聚合物與石墨粉的質(zhì)量比進(jìn)行了優(yōu)化。通過掃描電子顯微鏡和傅里葉紅外光譜儀對所制備的印跡聚合物材料的形貌和結(jié)構(gòu)進(jìn)行了表征。在最佳條件下,所構(gòu)建的傳感器對ESS的檢測具有較好的選擇性和寬的線性范圍(4.0×10-12~6.0×10-9 M),檢測限可達(dá)1.2×10-12 M(S/N=3)。此外,傳感器被成功應(yīng)用于實(shí)際孕馬尿樣品中ESS的檢測,與高效液相色譜法進(jìn)行比對發(fā)現(xiàn),結(jié)果準(zhǔn)確可信,重復(fù)性好,檢測迅速,成本低廉,有望在現(xiàn)場實(shí)時(shí)檢測中發(fā)揮作用。(2)基于分子印跡聚合物修飾的納米多孔微線用于檢測甲硝唑本工作采用金銀合金線(Au-Ag alloy microrod,AMR),通過簡單的脫合金法得到表面具有納米多孔結(jié)構(gòu)的金銀合金線(nanoporous Au-Ag alloy microrod,NPAMR),將其作為工作電極,利用電聚合的方式在其表面修飾上分子印跡聚合物薄膜,得到分子印跡聚合物修飾的納米多孔金銀合金線(MIP/NPAMR)電極。該電極可以在沒有任何額外商品化電極支撐下作為工作電極使用,本工作采用這種無支撐電極完成了甲硝唑(metronidazole,MNZ)的定量分析。對傳感器制備過程中的一系列實(shí)驗(yàn)參數(shù)進(jìn)行了優(yōu)化。通過掃描電子顯微鏡和能譜分析對MNZ-MIP/NPAMR進(jìn)行了形貌表征以及元素分析,用計(jì)時(shí)電量法對脫合金前后傳感器的表面積進(jìn)行了計(jì)算,結(jié)果表明具有3D結(jié)構(gòu)的NPAMR具有高的比表面積和良好的電子傳遞能力。將[Fe(CN)6]3-/4-氧化還原對作為電流指示劑,采用循環(huán)伏安法對目標(biāo)分子MNZ進(jìn)行了定量分析并考察了MNZ-MIP/NPAMR的各項(xiàng)電化學(xué)性能。實(shí)驗(yàn)結(jié)果表明所構(gòu)建的傳感器具有超低的檢測限(2.7×10-14 M)和寬的線性范圍(8.0×10-14~1.0×10-6 M),不需要額外商品化電極支撐的特點(diǎn)也有利于降低成本。此外,傳感器被成功應(yīng)用于實(shí)際樣品(魚肉和片劑)中MNZ的檢測,結(jié)果準(zhǔn)確可信,重復(fù)性好,檢測迅速,有望在更多生物和化學(xué)物質(zhì)的痕量檢測中發(fā)揮作用。(3)基于分子印跡聚合物修飾的納米多孔微線用于檢測痕量多巴胺本工作中納米多孔金銀合金微線的制備方法同(2),同樣采用電聚合的方法,以多巴胺(dopamine,DA)為模板分子,在NPAMR表面形成了一層分子印跡聚合物膜,經(jīng)過洗脫之后得到MIP修飾的電化學(xué)傳感器(MIP/NPAMR)。對聚合過程中聚合液的pH值和模板分子與功能單體之間的比例進(jìn)行了優(yōu)化。通過掃描電子顯微鏡對NPAMR和MIP/NPAMR進(jìn)行了形貌表征,用能譜分析對NPAMR和MIP/NPAMR中元素組成進(jìn)行了分析,通過循環(huán)伏安法和阻抗分析法對MIP/NPAMR的各項(xiàng)電化學(xué)性能進(jìn)行了評價(jià)。實(shí)驗(yàn)結(jié)果表明所構(gòu)建的電化學(xué)傳感器具有超低檢測限(7.63×10-14 M)和寬的線性范圍(2.0×10-13~2.0×10-8 M)。此外,傳感器被成功應(yīng)用于實(shí)際生物樣品(家兔血清和大鼠腦組織)中DA的檢測。
[Abstract]:Molecularly imprinted polymer (MIP) is a high molecular material capable of identifying target substances specifically, with predetermined selectivity, specificity and wide suitability. In this paper, three kinds of molecularly imprinted electrochemical sensors are prepared and used to detect sodium estrone sulfate, metronidazole and dopamine, which are divided into 3 parts: (1) carbon paste electrode based on molecularly imprinted polymer modified by molecular imprinting technology. In the study of the test of estrone sodium sulfate, the traditional bulk polymerization method was used to prepare estrone 3-sulfate sodium salt (ESS) molecularly imprinted polymer, and a small amount of liquid paraffin was mixed with ESS-MIP and graphite powder as adhesive, and it was mixed well and then filled into the electrode tube, and the molecularly imprinted polymerization was prepared. The modified carbon paste electrode (carbon paste electrode, CPE) is used as an electrochemical sensor for the detection of ESS. Among them, the proportion of the template molecules, functional monomers, crosslinker three, the polymerization reaction solvent and the elution solvent in the ESS-MIP preparation process are optimized, and the polymer and graphite powder in the carbon paste electrode are filled. The mass ratio is optimized. The morphology and structure of the imprinted polymer materials are characterized by scanning electron microscope and Fourier infrared spectrometer. Under the optimum conditions, the sensor has good selectivity and wide linear range (4 x 10-12~6.0 x 10-9 M) for the detection of ESS, and the detection limit is up to 1.2 * 10-12. M (S/N=3). In addition, the sensor has been successfully applied to the detection of ESS in real pregnant horse urine samples. Compared with high performance liquid chromatography (HPLC), it is found that the results are accurate, reliable, reproducible, rapid and inexpensive, and it is expected to play a role in real time detection. (2) nano porous microlines based on molecularly imprinted polymer are used to detect the nail. The Au-Ag alloy microrod (AMR) is used in nitrazole to obtain the gold and silver alloy wires (nanoporous Au-Ag alloy microrod, NPAMR) on the surface of the surface with a simple dealloying method, which is used as the working electrode to modify the molecularly imprinted polymer film on its surface by electropolymerization, and the molecular imprint is obtained. A trace polymer modified nano porous gold and silver alloy wire (MIP/NPAMR) electrode. The electrode can be used as a working electrode without any additional commercialized electrode support. This work uses this unsupported electrode to complete the quantitative analysis of metronidazole (metronidazole, MNZ). A series of experimental parameters in the process of sensor preparation are carried out. The morphology and elemental analysis of MNZ-MIP/NPAMR were carried out by scanning electron microscope and energy spectrum analysis. The surface area of the Dealloyed sensor was calculated by chronoelectric method. The results showed that the NPAMR with 3D structure had high specific surface area and good electron transfer ability. [Fe (CN) 6]3-/4- was redox and redox. As an current indicator, the target molecule MNZ is quantitatively analyzed by cyclic voltammetry and the electrochemical performance of MNZ-MIP/NPAMR is investigated. The experimental results show that the sensor has a ultra low detection limit (2.7 x 10-14 M) and a wide linear range (8 x 10-14~ 1 x 10-6 M) without additional commercial electrode support. The characteristics also help to reduce the cost. In addition, the sensor has been successfully applied to the detection of MNZ in real samples (fish and tablets). The results are accurate, reproducible, and rapid detection. It is expected to play a role in the trace detection of more biological and chemical substances. (3) nano porous microlines based on molecularly imprinted polymer are used to detect trace amounts. The preparation method of nano porous gold and silver alloy microwires in dopamine is the same as (2). Also, the method of electropolymerization, using dopamine (dopamine, DA) as the template molecule, has formed a layer of molecularly imprinted polymer film on the surface of NPAMR. After elution, the MIP modified electrochemical sensor (MIP/NPAMR) is obtained. The pH of the polymerization solution in the polymerization process. The ratio of the value and the template molecule to the functional monomer was optimized. The morphology of NPAMR and MIP/NPAMR was characterized by scanning electron microscope. The composition of the elements in NPAMR and MIP/NPAMR was analyzed by energy spectrum analysis. The electrochemical properties of MIP/NPAMR were evaluated by cyclic voltammetry and impedance analysis. The results show that the proposed electrochemical sensor has a ultra low detection limit (7.63 x 10-14 M) and a wide linear range (2 x 10-13~2.0 * 10-8 M). In addition, the sensor has been successfully applied to the detection of DA in the actual biological samples (rabbit serum and rat brain tissue).
【學(xué)位授予單位】：石河子大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TP212

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本文編號：2154435