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銀納米線膜試紙條與表面增強(qiáng)拉曼光譜聯(lián)立用于快速現(xiàn)場(chǎng)檢測(cè)

發(fā)布時(shí)間:2018-11-25 14:34
【摘要】:對(duì)日常生活中環(huán)境污染物中有效成分的評(píng)定至關(guān)重要,這與環(huán)境發(fā)展和人類的健康都緊密相關(guān)。所謂有效成分,就是可以被溶解或易于被萃取的物質(zhì)部分,被認(rèn)為是與有機(jī)體的生物累積、生物吸附和生物轉(zhuǎn)換關(guān)聯(lián)最深的部分。對(duì)于環(huán)境污染物有效成分進(jìn)行快速現(xiàn)場(chǎng)分析,可以在短時(shí)間內(nèi)完成違規(guī)物的初步篩選,實(shí)現(xiàn)高效監(jiān)測(cè)過程。在檢測(cè)前進(jìn)行的分離純化及富集過程對(duì)其后的檢測(cè)影響很大,這也使得發(fā)展簡(jiǎn)便省時(shí)的樣品前處理手段十分必要。貴金屬基底可與巰基或氨基等官能團(tuán)形成化學(xué)鍵作用,被基底直接吸附而完成對(duì)含硫/氮物質(zhì)的樣品分離和富集。貴金屬表面也可利用化學(xué)鍵自組裝形成修飾層,例如金、銀和銅均可結(jié)合硫醇分子,由于硫醇的烷基鏈端聚集形成憎水區(qū)域而將各自表面由原本的親水性改為疏水性。這樣的疏水性基底可以利用范德華力吸附憎水性有機(jī)物,實(shí)現(xiàn)樣品的前處理。表面增強(qiáng)拉曼光譜(SERS)在拉曼光譜的基礎(chǔ)上發(fā)展而來,可以在在粗糙金屬表面上檢測(cè)被吸附的分子的拉曼特性,是目前最靈敏的檢測(cè)手段之一。SERS常是以粗糙的Ag、Cu或Au金屬表面作為增強(qiáng)基底,現(xiàn)今已發(fā)展了多種復(fù)合材料的新型基底體系。增強(qiáng)拉曼基底的結(jié)構(gòu)和形貌直接影響著檢測(cè)靈敏度,制備適合用于實(shí)際環(huán)境分析的SERS基底意義十分重大。便攜式拉曼光譜儀可以與多種樣品前處理手段聯(lián)用,從而能夠形成快速高效的檢測(cè)體系,用于環(huán)境或醫(yī)學(xué)等方面的監(jiān)測(cè)。本文以過濾法負(fù)載在濾紙上的銀納米線膜作為SERS基底,主要進(jìn)行了以下工作:(1)將銀納米線膜作為樣品前處理-SERS聯(lián)用基底,當(dāng)磺胺分子接觸到銀納米線膜時(shí),磺胺分子的氨基和可以銀形成相互作用力,使得它可以吸附在銀納米線膜上而完成待測(cè)分子的富集,用便攜式拉曼儀直接得到SERS信號(hào)。我們用該基底檢測(cè)了 4種常見的磺胺藥品,通過定性和定量分析,證明其對(duì)于磺胺類藥品有實(shí)際檢測(cè)功能。同時(shí),我們采用過濾法制作的銀納米線膜可以進(jìn)行重復(fù)性利用,保證了基底的實(shí)用以及經(jīng)濟(jì)性。此種樣品富集與SERS聯(lián)用的分析手段減少了復(fù)雜的樣品前處理步驟,大大縮短了分析時(shí)間,是一種原位快速檢測(cè)磺胺類藥物的方法。(2)我們提供了一種疏水性的丙硫醇修飾的銀納米線膜(PTH-Ag NMs)聯(lián)立便攜式拉曼光譜儀用于柔性原位擦拭萃取檢測(cè)PAHs的方法。PTH通過銀和硫之間的共價(jià)鍵修飾在銀納米線膜上,產(chǎn)生了疏水性膜結(jié)構(gòu)。使用溶劑進(jìn)行擦拭萃取的過程,與幼兒口鼻和玩具的接觸過程相似,可以做到玩具中PAHs的溶出模擬。通過儀器的表征分析探究了基底疏水性與修飾硫醇的鏈長和修飾濃度的關(guān)系,并解釋了硫醇在銀納米線膜上修飾的機(jī)理。玩具表面幾種典型的多環(huán)芳烴例如熒蒽、蒽和芘,都可以用PTH-Ag NMs進(jìn)行富集和靈敏地檢測(cè)。
[Abstract]:It is very important to evaluate the effective components of environmental pollutants in daily life, which is closely related to environmental development and human health. The so-called active component, which can be dissolved or easily extracted, is considered to be the most relevant part of organism bioaccumulation, biosorption and bioconversion. The rapid field analysis of the active components of environmental pollutants can complete the preliminary screening of the illegal substances in a short time and realize the high efficiency monitoring process. The process of separation, purification and enrichment before detection has great influence on the subsequent detection, which makes it necessary to develop a simple and time-saving method for sample pretreatment. Precious metal substrates can form chemical bonds with functional groups such as sulfhydryl or amino groups and are directly adsorbed by the substrate to separate and enrich the samples containing sulfur / nitrogen. The surface of precious metals can also be self-assembled by chemical bonds to form modified layers, such as gold, silver and copper, which can bind to mercaptan molecules. Because the alkyl end of mercaptan aggregates to form a hydrophobic region, the respective surfaces are changed from the original hydrophilicity to hydrophobicity. This hydrophobic substrate can be used to adsorb hydrophobic organic compounds by van der Waals force to achieve sample pretreatment. Surface-enhanced Raman spectroscopy (SERS) has been developed on the basis of Raman spectroscopy. It can be used to detect the Raman properties of molecules adsorbed on rough metal surfaces, which is one of the most sensitive detection methods at present. SERS is usually determined by rough Ag,. The metal surface of Cu or Au has been used as a reinforced substrate, and a variety of new composite substrates have been developed. The structure and morphology of enhanced Raman substrate directly affect the detection sensitivity. It is very important to prepare a SERS substrate suitable for environmental analysis. The portable Raman spectrometer can be combined with a variety of sample pretreatment methods to form a rapid and efficient detection system for environmental or medical monitoring. In this paper, silver nanowire membrane loaded on filter paper was used as SERS substrate. (1) silver nanowire membrane was used as sample pretreatment and SERS substrate, when sulfonamide molecule came into contact with silver nanowire membrane, The sulfanilamide molecule can form an interaction force with silver, which can be adsorbed on the silver nanowire film to achieve the enrichment of the molecule to be tested. The SERS signal can be obtained directly by the portable Raman spectrometer. Four common sulfanilamide drugs were detected by using this substrate. It was proved by qualitative and quantitative analysis that it has practical function for the detection of sulfonamides. At the same time, the silver nanowire membrane prepared by filter method can be used repeatedly, which ensures the practicality and economy of the substrate. This method of sample enrichment combined with SERS reduces the complex sample pretreatment steps and greatly shortens the analysis time. It is a rapid in situ detection of sulfanilamides. (2) We provide a hydrophobic silver nanowire film (PTH-Ag NMs) modified with propanol for flexible in situ wipe extraction. (2) We provide a novel portable Raman spectrometer for the detection of hydrophobic propyl thiol modified silver nanowires (PTH-Ag NMs). PTH is modified on silver nanowires by covalent bonds between silver and sulfur. Hydrophobic membrane structure was produced. The process of wiping and extracting with solvent is similar to the contact process of toddler's mouth, nose and toy, which can simulate the dissolution of PAHs in toy. The relationship between the hydrophobicity of the substrate and the chain length and the modified concentration of modified mercaptan was investigated by means of the characterization analysis of the instrument, and the mechanism of the modification of mercaptan on silver nanowires was explained. Several typical PAHs on toy surfaces such as fluoranthene anthracene and pyrene can be enriched and detected sensitively by PTH-Ag NMs.
【學(xué)位授予單位】:山東大學(xué)
【學(xué)位級(jí)別】:碩士
【學(xué)位授予年份】:2017
【分類號(hào)】:X830;O657.37

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