發(fā)布時(shí)間：2019-03-06 07:58

【摘要】：隨著硝基芳香類爆炸物在軍事和民間的應(yīng)用逐漸廣泛,其對(duì)環(huán)境造成的污染也日益顯露。爆炸物在生產(chǎn)、制造與運(yùn)輸?shù)倪^(guò)程中難免會(huì)發(fā)生泄露,殘留在土壤與水環(huán)境中的爆炸物成分不僅危害環(huán)境,還會(huì)間接地對(duì)人類的生命健康造成威脅。另外,爆炸物是恐怖主義危害社會(huì)穩(wěn)定與人民安全的最直接手段,因而爆炸物的檢測(cè)也是反恐與維穩(wěn)工作的重點(diǎn)。近年來(lái),表面增強(qiáng)拉曼光譜(SERS)技術(shù)因其具有可便攜、分析速度快和高靈敏度等優(yōu)點(diǎn),已經(jīng)成為檢測(cè)爆炸物最重要的光譜方法之一。其中,具有超高靈敏度的SERS基底是SERS技術(shù)實(shí)現(xiàn)微痕量爆炸物成功檢出的前提。因此,本論文研發(fā)了一種簡(jiǎn)單、省時(shí)、低成本的方法制備超高靈敏度SERS基底并實(shí)現(xiàn)硝基類爆炸物的檢測(cè)。首先,為了提高SRES基底的靈敏度,本論文選用化學(xué)試劑修飾納米粒子的方法,制備具有超高靈敏度的SERS基底。在實(shí)驗(yàn)中通過(guò)對(duì)納米粒子種類、化學(xué)試劑以及制備條件等優(yōu)化,最終獲得了 SERS基底的制備方法:1 mL的AgNPs(還原劑為檸檬酸三鈉)離心濃縮得5 μL左右納米粒子濃縮膠體,再加入25 μL的KI(10 mM)溶液混勻,在避光條件下反應(yīng)20 min獲得Ag IMNPs基底。在波長(zhǎng)為632.8 nm的激發(fā)光條件下檢測(cè)了硝基類爆炸物TNT和2,4-DNT。結(jié)果表明:碘離子修飾后的銀納米粒子具有良好的SERS活性,2,4-DNT和TNT的最低檢出濃度為0.1 nM,換算為質(zhì)量的檢出限分別約為0.364 pg和0.454 pg。然后,本論文嘗試探討了 AgIMNPs基底的增強(qiáng)機(jī)理,結(jié)果表明AgIMNPs基底的增強(qiáng)機(jī)理有兩個(gè)方面的原因。其一,本文在對(duì)Ag NPs的紫外掃描中發(fā)現(xiàn),KI修飾AgNPs會(huì)使其最大紫外吸收波長(zhǎng)發(fā)生紅移,這可能是因?yàn)镵I使AgNPs團(tuán)聚,而這種團(tuán)聚能夠使爆炸物的SERS信號(hào)得到增強(qiáng)。其二是KI對(duì)Ag NPs表面雜質(zhì)的清除作用,在納米粒子的表面產(chǎn)生了更多的"空位",為爆炸物分子與納米粒子表面的接觸提供了更多的機(jī)會(huì)。在這兩種增強(qiáng)機(jī)制的共同影響下,AgIMNPs較AgNPs的靈敏度得到了大幅度的提升。而且Ag IMNPs基底對(duì)多種硝基類芳香族化合物都有不同程度的增強(qiáng)效果,這表明AgIMNPs基底能適用于多種硝基類爆炸物的快速檢測(cè)。由于AgIMNPs基底的高靈敏度,將其與他材料聯(lián)用能夠擴(kuò)大其在環(huán)境監(jiān)測(cè)、安檢工作以及食品安全等領(lǐng)域的應(yīng)用。
[Abstract]:With the wide application of nitroaromatic explosives in military and civilian fields, the environmental pollution caused by nitroaromatic explosives is becoming more and more obvious. Explosives will inevitably leak in the process of production, manufacture and transportation. The explosive residues in the soil and water environment will not only harm the environment, but also indirectly threaten the life and health of human beings. In addition, explosives are the most direct means of terrorism to endanger social stability and people's security, so the detection of explosives is also the focus of counter-terrorism and maintenance of stability. In recent years, surface-enhanced Raman spectroscopy (SERS) has become one of the most important spectral methods for detecting explosives due to its portability, high analytical speed and high sensitivity. Among them, the SERS substrate with ultra-high sensitivity is the prerequisite for the successful detection of micro-trace explosives by SERS technology. Therefore, this paper develops a simple, time-saving and low-cost method to prepare ultra-high sensitivity SERS substrates and realize the detection of nitroexplosives. Firstly, in order to improve the sensitivity of SRES substrate, the SERS substrate with ultra-high sensitivity was prepared by chemical reagent modification. In the experiment, the preparation method of SERS substrate was obtained by optimizing the kinds of nanoparticles, chemical reagents and preparation conditions. The preparation methods were as follows: (1) AgNPs (reducing agent was trisodium citrate) centrifugally concentrated 5 渭 L nanoparticles concentrated colloid; After mixing with 25 渭 L KI (10 mM) solution, the Ag IMNPs substrate was obtained by the reaction of 20 min under the condition of avoiding light. Nitroexplosives TNT and 2,4-DNT were detected at a wavelength of 632.8 nm. The results showed that the silver nanoparticles modified by iodine ion had good SERS activity. The detection limits of the minimum detection concentrations of 2,4-DNT and TNT were about 0.364 pg and 0.454 pg., respectively. The detection limits were about 0.364 pg and 0.454 pg., respectively. The detection limits of the silver nanoparticles modified by iodine ion were about 0.364 pg and 0.454 pg., respectively. Then, the enhancement mechanism of AgIMNPs substrate is discussed in this paper. The results show that there are two reasons for the enhancement mechanism of AgIMNPs substrate. First, in the UV scanning of AgNPs, it is found that the maximum UV absorption wavelength of AgNPs modified by KI is red-shifted, which may be due to the aggregation of AgNPs by KI, which can enhance the SERS signal of explosives. The other is the removal of impurities on the surface of Ag NPs by KI, which creates more "vacancies" on the surface of nano-particles, which provides more opportunities for the contact of explosive molecules with the surface of nano-particles. Under the influence of these two enhancement mechanisms, the sensitivity of AgIMNPs is greatly improved than that of AgNPs. Moreover, AgIMNPs substrates have different enhancement effects on various nitro aromatic compounds, which indicates that AgIMNPs substrates can be used for the rapid detection of various nitroexplosives. Due to the high sensitivity of AgIMNPs substrate, its application in environmental monitoring, security inspection and food safety can be expanded by combining it with other materials.
【學(xué)位授予單位】：西南交通大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TQ560.72;TB383.1;O657.37

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