本文關鍵詞：基于多孔銀基底的固相微萃取與表面增強拉曼聯(lián)用技術及其在快速分析檢測中的應用　出處：《山東大學》2017年博士論文　論文類型：學位論文

  更多相關文章： 多孔銀納米結構 表面增強拉曼 固相微萃取 快速檢測

【摘要】：表面增強拉曼光譜(Surface Enhanced Raman Spectroscopy,SERS)是一種高靈敏分析技術,通過納米結構的電磁和化學效應可以有效增強光譜強度,提供吸附分子的詳細振動信息。SERS已經(jīng)廣泛的應用于環(huán)境監(jiān)測、食品分析、材料科學、生物醫(yī)學檢驗等領域中。SERS基底的制備技術是影響SERS技術實用化的關鍵科學問題,例如熱點的構建,基底的穩(wěn)定性、均勻性和耐候性等。隨著納米技術的發(fā)展,基底的制備方法也越來越多樣化,如何獲得兼具增強能力和均勻穩(wěn)定性的基底依然是制約其應用的一個關鍵性問題。固相微萃取(Solid Phase Microextraction,SPME)是一種高效、快速的樣品前處理技術。其原理是依據(jù)分析物在固相微萃取涂層和樣品基質(zhì)之間的分配平衡,將分析物從樣品基質(zhì)中富集到固相萃取涂層上。固相微萃取已經(jīng)廣泛應用于環(huán)境分析、食品分析、生物分析等領域。近年來,固相微萃取與各種分析儀器的聯(lián)用技術也在飛速發(fā)展,極大拓展了其應用范圍。本文發(fā)展了一種具有SERS活性的多孔銀納米結構固相微萃取基底,并通過Galvanization-Freec沉積反應在多孔銀表面形成超薄金膜,提高基底的穩(wěn)定性和均勻性。采用各種物理化學方法對基底進行表征,結果表明該多孔銀基底兼具良好的SERS活性和SPME萃取性能。具體如下:1利用電化學法原位合成多孔銀納米結構,采用X射線衍射(XRD),掃描電子顯微鏡(SEM),原子力顯微鏡(AFM)和接觸角測試對結構和性能進行了表征。多孔銀基底是由納米顆粒及其堆積孔構成,表面具有疏水性,兼具良好的SERS活性和吸附萃取性能。利用此基底,建立了針對有機錫化合物的SPME-SERS聯(lián)用分析方法。根據(jù)SERS的分子指紋峰,實現(xiàn)對三甲基氯化錫,二丁基二氯化錫,三丁基氯化錫,三苯基氯化錫和四苯基氯化錫快速分析識別,檢測限達到ppb水平。研究了萃取過程的吸附熱力學和動力學過程,并采用主成分分析(principal component analysis,PCA)對有機錫的分子指紋峰進行統(tǒng)計學分類,最后通過ICP-MS對以上方法進行了驗證,實現(xiàn)了有機錫化合物的現(xiàn)場快速分析檢測。2在此基礎上,通過引入鹵素離子提高Ag+電極電位,抑制Au3+/Ag之間的Galvanic replacement反應,同時利用抗壞血酸作為還原劑和穩(wěn)定劑在多孔銀表面形成超薄的金沉積膜,采用AFM,XPS,SEM和元素Mapping進行了表征。然后以巰基苯胺作為探針,考察了 porousAg@Au基底的熱穩(wěn)定性和均勻性,利用熱紅外成像儀研究了基底的實時導熱情況。采用SPME-SERS聯(lián)用方法對水產(chǎn)品中違禁藥物呋喃西林及其代謝物(氨基脲)的進行了快速分析,檢出限達到ppb水平。3采用氨基/硝基苯硫酚作為探針修飾porousAg@AuSERS基底,根據(jù)SERS光譜研究不同表面氧化態(tài)的配體與蛋白質(zhì)分子的相互作用。合成了金納米顆粒作為模型,利用毛細管電泳分離納米顆粒/蛋白質(zhì)分子復合物,計算解離常數(shù)和協(xié)同常數(shù)。同時,采用分子對接方法對particles-proteins模型的空間結合點位及作用力進行了理論計算,從分子角度為顆粒的生物毒性和代謝過程研究提供理論依據(jù)。
[Abstract]:Surface enhanced Raman spectroscopy (Surface Enhanced Raman Spectroscopy, SERS) is a high sensitive analytical technique, the electromagnetic and chemical effects of nano structure can effectively enhance the spectral intensity, provide application with vibration information of.SERS adsorption molecules have been widely in environmental monitoring, food analysis, material science and technology in the field of biomedical test preparation.SERS substrate is a key scientific problem to influence the practical use of SERS technology, such as hot construction, basal stability, uniformity and weathering resistance. With the development of nanotechnology, the substrate preparation method is becoming more and more diversified, how to obtain both enhanced basal ability and uniformity and stability is still restricting the application of a key problems. Solid phase microextraction (Solid Phase, Microextraction, SPME) is an efficient, fast sample pretreatment technique. Its principle is based on the analysis. The distribution balance between SPME coating and the sample matrix, the analyte from the sample matrix to the enrichment of solid phase extraction coatings. Solid phase microextraction has been widely used in environmental analysis, food analysis, biological analysis and other fields. In recent years, solid phase microextraction and various analytical instruments combined with technology is developing rapidly. Has greatly expanded its scope of application. This paper develops a model of SERS active porous silver nano structure of solid phase micro extraction and substrate deposited by Galvanization-Freec reaction form a thin gold film on porous silver surface, improve the stability and uniformity of the substrate by various physical and chemical methods were used to characterize the substrate. The results show that the porous silver the basal activity of SERS and SPME had good extraction performance. The details are as follows: 1 using electrochemical method for in situ synthesis of porous silver nanostructures by X ray diffraction (XRD), scanning electron microscope Micro mirror (SEM), atomic force microscopy (AFM) and contact angle measurements on the structure and properties were characterized. The porous silver substrate is composed of nano particles and the accumulation of holes, with hydrophobic surface, good adsorption performance. The activity of SERS and extraction using this substrate, SPME-SERS was established for organic tin compounds the analysis method combined with molecular fingerprint. According to the peak of SERS, to achieve the three methyl tin chloride, butyl two two three tin chloride, stannous chloride, rapid analysis identified three fentin chloride and four phenyl tin chloride, the detection limit can reach ppb level. The adsorption kinetics and thermodynamics of the extraction process, and the main component analysis (principal component analysis, PCA) molecular fingerprint peaks of organic tin were classified, and finally through the ICP-MS of the method was verified, the spot of organotin compounds rapid detection and analysis of the.2 in On this basis, through the introduction of halogen ions increase Ag+ electrode potential, inhibition of Galvanic replacement reaction between Au3+/Ag, while using ascorbic acid as the gold deposited film, reducing agent and stabilizer in the formation of thin porous silver surface by AFM, XPS, SEM and Mapping elements were characterized. Then with mercapto aniline were investigated as probe. The stability of the porousAg@Au substrate and the uniformity of heat transfer on the substrate by using real-time thermal infrared imager. Using SPME-SERS coupling method of illicit drugs in aquatic products of nitrofurazone and its metabolite (amino urea) was used for rapid analysis, the detection limit of ppb.3 level reached by the amino modified porousAg@AuSERS / nitrobenzene Thiophenol as the probe substrate, according to the interaction of the ligand SERS spectroscopic studies on the oxidation of different surface states and protein molecules. Gold nanoparticles were synthesized as model, the use of hair The separation of nanoparticle / protein molecular complex capillary electrophoresis, calculation of dissociation constants and cooperativity constants. At the same time, using the molecular docking method to the particles-proteins model combined with the space position and force are calculated from the molecular point of view for the biological toxicity of particles and metabolic process research and provide a theoretical basis.

【學位授予單位】：山東大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O657.37;O658.2

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