發(fā)布時(shí)間：2018-04-17 00:03

  本文選題：薄層色譜 + 增強(qiáng)薄層色譜板��； 參考：《第二軍醫(yī)大學(xué)》2017年碩士論文

【摘要】：表面增強(qiáng)拉曼光譜(Surface-enhanced Raman Spectroscopy,SERS)法是一種特征性強(qiáng)、靈敏度高的分析方法,其可提供大量物質(zhì)的特征光譜信息。然而,在實(shí)際應(yīng)用時(shí),目標(biāo)待測(cè)物多處在復(fù)雜體系中,SERS技術(shù)獲取繁雜光譜信息后無(wú)法進(jìn)一步提取目標(biāo)化合物的SERS光譜信息。此外,在部分復(fù)雜體系中,一些SERS響應(yīng)弱的組分的信號(hào)往往被SERS響應(yīng)強(qiáng)的組分所掩蓋。因此,在SERS檢測(cè)前,對(duì)復(fù)雜體系中待測(cè)組分進(jìn)行簡(jiǎn)單分離是十分有必要的。常用的分離方法有高效液相色譜法(HPLC)、氣相色譜法(GC)、毛細(xì)管電色譜法(CE)、薄層色譜法(TLC)等。其中,TLC-SERS聯(lián)用法因具有簡(jiǎn)單、快速及無(wú)需昂貴設(shè)備等優(yōu)點(diǎn)而備受關(guān)注。TLC-SERS法分析步驟如下:將混合樣品在TLC板上分離后,對(duì)分離后斑點(diǎn)進(jìn)行定位,然后在定位斑點(diǎn)表面滴加SERS活性基底(金屬溶膠),再將定位斑點(diǎn)置于拉曼光譜儀下進(jìn)行檢測(cè)。但是這種方法存在一些缺點(diǎn):1.金屬溶膠會(huì)對(duì)色譜分離后斑點(diǎn)重疊化合物的SERS檢測(cè)產(chǎn)生干擾;2.一些化合物在紫外燈(UV254/365)和可見(jiàn)光下均不可見(jiàn),分離后斑點(diǎn)無(wú)法定位,也就無(wú)法進(jìn)行SERS檢測(cè);3.斑點(diǎn)會(huì)發(fā)生橫向擴(kuò)散以及二次擴(kuò)散,導(dǎo)致檢測(cè)靈敏度較低。為了改善常規(guī)TLC-SERS技術(shù)的不足,本研究建立了兩種新型TLC-SERS方法。一種是:采用金屬納米粒子修飾的MIL-101骨架材料(AuNPs/MIL-101)對(duì)常規(guī)TLC板進(jìn)行功能化,使其成為一種可分離的SERS基底,本文稱這種新型TLC板為增強(qiáng)薄層色譜(enhanced Thin Layer Chromatography,簡(jiǎn)稱eTLC)板。將eTLC板與SERS技術(shù)結(jié)合,待測(cè)樣品在eTLC板上分離后,沿著展開(kāi)方向采用激光逐點(diǎn)掃描的方式進(jìn)行檢測(cè),板上所有化合物的信息都將被收集,包括斑點(diǎn)重疊和斑點(diǎn)不可見(jiàn)化合物。另一種是:采用色譜層析硅膠GF254制備寬度為2 mm的窄帶TLC板,待樣品在窄帶TLC板上分離后,在分離斑點(diǎn)表面噴灑銀溶膠,然后進(jìn)行SERS檢測(cè)。結(jié)果表明,窄帶TLC-SERS法具有簡(jiǎn)便、快速、靈敏的優(yōu)點(diǎn),可改善常規(guī)TLC-SERS法斑點(diǎn)橫向擴(kuò)散和二次擴(kuò)散的不足,而且降低了固定相用量,節(jié)約了成本。本研究分為兩個(gè)部分:1)第一部分,根據(jù)文獻(xiàn)中方法制備AuNPs/MIL-101復(fù)合材料,然后將復(fù)合材料和色譜硅膠按一定比例混合制備eTLC板;采用羅丹明6G作為探針?lè)肿?對(duì)混合比例、潤(rùn)濕劑種類及濃度、拉曼檢測(cè)參數(shù)、eTLC板信號(hào)的重現(xiàn)性及穩(wěn)定性等進(jìn)行摸索和確定,成功建立了eTLC-SERS分析技術(shù),并采用建立的eTLC-SERS分析技術(shù)對(duì)TLC分離后斑點(diǎn)重疊和斑點(diǎn)不可見(jiàn)的化合物進(jìn)行檢測(cè)。2)第二部分,制備了窄帶TLC板,然后將其和SERS技術(shù)結(jié)合,建立了窄帶TLC-SERS分析方法,并考察了固定相用量、靈敏度、檢測(cè)限等因素。本研究的結(jié)果如下:1)制備出SERS增強(qiáng)性能最佳、均一性及穩(wěn)定性好的eTLC板;2)建立eTLC-SERS法,確定最佳SERS檢測(cè)條件,其中潤(rùn)濕劑種類為鹽酸,濃度為0.01 mol/L,體積為5μL,拉曼激光功率為90 mW,積分時(shí)間為5 s;3)利用eTLC-SERS法檢測(cè)TLC分離后斑點(diǎn)重疊和斑點(diǎn)不可見(jiàn)的化合物,成功鑒別出重疊斑點(diǎn)的組分及準(zhǔn)確找出了不可見(jiàn)斑點(diǎn)的確切位置,實(shí)現(xiàn)了斑點(diǎn)重疊化合物和斑點(diǎn)不可見(jiàn)化合物的簡(jiǎn)單、快速以及靈敏的檢測(cè);4)制備出窄帶TLC板,建立了窄帶TLC-SERS法。與常規(guī)TLC-SERS法相比,該方法的靈敏度更高、檢測(cè)限更低,且固定相用量?jī)H為常規(guī)TLC板的8%。本研究首次成功建立了eTLC-SERS分析方法,并將其用于斑點(diǎn)重疊和斑點(diǎn)不可見(jiàn)化合物的檢測(cè)。研究表明,該法沒(méi)有外加金屬溶膠基底的干擾,具有簡(jiǎn)單、靈敏度高、穩(wěn)定性強(qiáng)等優(yōu)點(diǎn)。其次,本研究建立了窄帶TLC-SERS分析方法,其與常規(guī)TLC-SERS法相比,靈敏度更高,且固定相用量少,節(jié)約了成本。綜上所述,本文建立的兩種新型TLC-SERS分析方法均在一定程度上改善了常規(guī)TLC-SERS方法的不足,為TLC-SERS聯(lián)用技術(shù)注入了新的活力。
[Abstract]:Surface enhanced Raman spectroscopy (Surface-enhanced Raman Spectroscopy, SERS) is a strong feature, high sensitivity analysis method, which can provide a large number of characteristic spectral information of material. However, in practical application, the target analytes in complex systems, SERS technology gets complicated spectral information after no further extraction of SERS the spectral information of the target compounds. In addition, in the part of the complex system, some SERS response weak signal components tend to be strong SERS response components cover. Therefore, before SERS detection, it is very necessary for simple separation of analytes in complex systems. There are commonly used high performance liquid separation method chromatography (HPLC), gas chromatography (GC), capillary electrochromatography (CE), thin layer chromatography (TLC). The TLC-SERS method with simple, fast and without expensive equipment has attracted attention.TLC-SER S analysis steps are as follows: the sample on the TLC board separation after mixing, the localization of separated spots, and then add the SERS active substrate in the positioning surface spots (metal sol), and then drops will be placed under the spot detection and localization of Raman spectrometer. But this method has some disadvantages: SERS detection of 1. metal sol after chromatography spots overlap compounds interference; 2. compounds (UV254/365) in the UV light and visible light are not visible, separated spots can't locate cannot be detected by SERS; 3. spots occur lateral diffusion and two diffusion, leading to low detection sensitivity. In order to improve the shortcomings of conventional TLC-SERS Technology, this study established two new TLC-SERS methods. One is: MIL-101 matrix material using metal nanoparticles modified (AuNPs/MIL-101) function of the conventional TLC plate, make it become a branch SERS from the base, the new board is called TLC (enhanced Thin Layer enhanced TLC plate Chromatography, referred to as eTLC). Combining the eTLC board and the SERS technology, the sample was separated on a eTLC board, measured along the direction by laser point scanning mode, all information compound board will be collected, including spot overlap and spots invisible compounds. The other is: using silica gel GF254 chromatography preparation for narrowband TLC 2 mm in width, the sample separation in narrowband TLC board, the separation is sprayed on the surface of silver sol spots, and then detected by SERS. The results show that the narrow band TLC-SERS method is simple, rapid, sensitive, can improve the conventional TLC-SERS method and two spots transverse diffusion diffusion, but also reduces the amount of fixed phase, saves the cost. This research is divided into two parts: the first part according to the literature, 1) In the preparation method of AuNPs/MIL-101 composite materials, and composite materials and silica gel are mixed in certain proportion and preparation of eTLC board; by Luo Danming 6G as a probe molecule, the mixing ratio, type and concentration of wetting agent, Raman detection parameters, to explore and determine the eTLC board signal reproducibility and stability, eTLC-SERS has been successfully established analysis of technology, and use eTLC-SERS analysis technology to build on TLC after the separation of overlapping spots is not visible spots and compounds were detected.2) the second part, the preparation of narrowband TLC plate, and then combining with the SERS technology, a narrowband TLC-SERS analysis method, and the effects of the amount of stationary phase, sensitivity, detection limit and other factors. The results of this study are as follows: 1) the preparation of SERS to enhance the performance of the best, uniformity and stability of the eTLC board; 2) to establish a eTLC-SERS method to determine the optimum SERS detection conditions, the type of wetting agent for salt Acid concentration of 0.01 mol/L, Volume 5 L, Raman laser power is 90 mW, the integration time is 5 s; 3) was detected by eTLC-SERS TLC after the separation of spot overlap and spots invisible compounds, able to identify overlapping spots components and find out the exact spot indeed completely invisiable cutting position, realizes the spot overlapping spots is not visible and compound compounds is simple, rapid and sensitive detection; 4) prepared by narrowband TLC board, a narrowband TLC-SERS method. Compared with the conventional TLC-SERS method, the sensitivity of the method is higher, lower detection limit, and the amount of stationary phase of only conventional TLC board 8%. for the first time successfully established the eTLC-SERS analysis method, and used for detecting spot overlap and spots invisible compounds. The results show that the method without external interference, metal sol substrate has the advantages of simplicity, high sensitivity, strong stability and other advantages. Secondly, this study A narrowband TLC-SERS analysis method, compared with the conventional TLC-SERS method, higher sensitivity, and fixed phase consumption, saving the cost. To sum up, are established in this paper two methods of model TLC-SERS analysis to improve the shortcomings of the conventional TLC-SERS method in a certain extent, as TLC-SERS technology has injected new vitality.

【學(xué)位授予單位】：第二軍醫(yī)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TB33;O657

【參考文獻(xiàn)】

相關(guān)期刊論文 前6條

1 張彬彬;史毅;朱青霞;陸峰;;窄帶薄層色譜-表面增強(qiáng)拉曼光譜聯(lián)用法的建立及應(yīng)用[J];光散射學(xué)報(bào);2017年02期

2 李丹;呂狄亞;陳輝;陸峰;陳強(qiáng);褚克丹;;紙基-表面增強(qiáng)拉曼光譜法檢測(cè)染色摻偽的紅花藥材[J];藥物分析雜志;2015年08期

3 Junmin Li;Jiangfeng Yang;Libo Li;Jinping Li;;Separation of CO_2/CH_4 and CH_4/N_2 mixtures using MOF-5 and Cu_3(BTC)_2[J];Journal of Energy Chemistry;2014年04期

4 董前民;楊艷敏;梁培;李曉艷;王樂(lè);;表面增強(qiáng)拉曼散射(SERS)襯底的研究及應(yīng)用[J];光譜學(xué)與光譜分析;2013年06期

5 郭紅燕;蘆玲慧;吳超;潘建高;胡家文;;SERS標(biāo)記的金納米棒探針用于免疫檢測(cè)[J];化學(xué)學(xué)報(bào);2009年14期

6 張進(jìn)治;汪瑗;陳惠;邵會(huì)波;;吳茱萸生物總堿的TLC-SERS研究[J];光譜學(xué)與光譜分析;2007年05期

相關(guān)碩士學(xué)位論文 前1條

1 陳艷瓊;TLC-SERS法在黃連等中藥鑒別中的應(yīng)用研究[D];江蘇大學(xué);2016年

，

本文編號(hào)：1761150