三維仿生柔性SERS基底構(gòu)建及其用于果蔬表皮農(nóng)藥殘留檢測
發(fā)布時(shí)間:2018-03-05 14:20
本文選題:表面增強(qiáng)拉曼光譜 切入點(diǎn):柔性SERS基底 出處:《華中農(nóng)業(yè)大學(xué)》2017年碩士論文 論文類型:學(xué)位論文
【摘要】:表面增強(qiáng)拉曼光譜(SERS)技術(shù)是一種高靈敏的分析工具,以其獨(dú)具的譜帶窄、抗光漂白、無水干擾、取樣量小、原位無損以及提供指紋圖譜信息等優(yōu)勢廣泛地應(yīng)用于公共安全、食品安全、環(huán)境監(jiān)測、生命科學(xué)等領(lǐng)域。創(chuàng)制一種可用于現(xiàn)場樣品快速高效采集,并直接檢測的SERS基底一直是表面增強(qiáng)拉曼光譜領(lǐng)域研究的熱點(diǎn)和關(guān)鍵。近年來,柔性基底因更加滿足實(shí)用化基底的諸多需求而備受矚目。然而,目前的柔性SERS基底大都是以纖維濾紙、膠布、石墨烯等為襯底,信號(hào)的增強(qiáng)效果和重現(xiàn)性都難以令人滿意。此外,得到的基底表面不具有三維(3D)的納米結(jié)構(gòu),這嚴(yán)重限制了它對表面殘留樣品的采集效率。這使得柔性SERS基底在實(shí)用化的過程中面臨著不小的挑戰(zhàn);谝陨媳尘凹艾F(xiàn)狀,本文致力于發(fā)展柔性材料與仿生學(xué)相結(jié)合的制備SERS基底的新方法;構(gòu)建使用方便,可用于現(xiàn)場直接快速采樣檢測的,靈敏度高,重現(xiàn)性好,穩(wěn)定性強(qiáng)的3D仿壁虎腳的納米“觸角”SERS新基底(G-SERS);并將其應(yīng)用于果蔬表皮農(nóng)藥殘留的快速、高效采集和非標(biāo)記、無損檢測;具體研究內(nèi)容如下:1.采用表面超疏水處理的有序陽極氧化鋁(AAO)為模板,聚二甲基硅氧烷(PDMS)為注塑材料旋涂于AAO表面,加熱成型后物理剝離得到高密度類壁虎腳的3D納米“觸角”陣列。這些有序的“觸角”結(jié)構(gòu)能夠?yàn)镾ERS活性納米粒子在不同維度的沉積提供高密度的支架。在此基礎(chǔ)上利用種子沉積法將銀納米粒子修飾到“觸角”陣列上,經(jīng)時(shí)間優(yōu)化,產(chǎn)生了大面積的“熱點(diǎn)”區(qū)域,制備出3D結(jié)構(gòu)的仿生基底。本章中我們研究了不同類型陽極氧化鋁的脫模效果,優(yōu)化了銀納米粒子沉積時(shí)間并對基底的各項(xiàng)SERS性能進(jìn)行了表征。這種新型仿生基底使用方便,不僅擁有出眾的SERS活性(IF=1.2×107),優(yōu)越的重現(xiàn)性(RSD=5.8%)和出色的穩(wěn)定性還具有眾多柔軟靈活的納米“觸角”(6.7×108/cm~2)。2.利用SERS基底表面高密度的3D納米“觸角”,采用直接“粘貼-揭起”的方法,對黃瓜、蘋果和葡萄表面的甲基對硫磷、福美雙、孔雀石綠殘留以及它們的混合物進(jìn)行快速采樣檢測。與傳統(tǒng)的柔性SERS基底相比,G-SERS基底表面擁有高密度靈活的納米“觸角”,這些“觸角”能夠像壁虎腳底的剛毛一樣能夠自由地到達(dá)實(shí)際樣品表面的微區(qū)域,通過簡單的“粘貼-揭起”對復(fù)雜表面的微量樣品進(jìn)行原位、無損地直接收集,并實(shí)現(xiàn)現(xiàn)場檢測。本章研究了上述三種果蔬表面甲基對硫磷、福美雙、孔雀石綠各自的檢出限,考察了基底對果蔬表皮農(nóng)藥殘留的采集效率,檢測結(jié)果的重現(xiàn)性以及穩(wěn)定性。研究發(fā)現(xiàn)G-SERS基底對福美雙、孔雀石綠、甲基對硫磷的檢測限分別達(dá)到1.6 ng/cm~2、0.4 ng/cm~2、25 ng/cm~2,在已完成樣品采集的果皮表面并沒有再檢出農(nóng)藥殘留,且基底在實(shí)際應(yīng)用中表現(xiàn)出較好的重復(fù)性(RSD=9.3%)和穩(wěn)定性。以上結(jié)果表明G-SERS基底在食品安全領(lǐng)域具有巨大的應(yīng)用前景。
[Abstract]:Surface enhanced Raman spectroscopy (SERS) technology is a high sensitive analysis tool, with its unique narrow bands, resistance to photobleaching, no interference, little sampling, and in situ nondestructive fingerprint information and other advantages are widely used in public safety, food safety, environmental monitoring, life sciences and other fields of creation. A can be used for fast and efficient collection of field samples, and the direct detection of SERS substrate has been a hot and key research on the surface enhanced Raman spectrum field. In recent years, because of the more flexible substrates to meet the needs of many practical base has attracted attention. However, most of the current flexible SERS substrate with fiber filter paper, adhesive tape, graphite substrate as the signal enhancement effect of graphene, and reproducibility are not satisfactory. In addition, the surface of the substrate are not with three-dimensional (3D) nano structure, which seriously limits its surface residual sample collection. This makes SERS flexible rate. In the practical process of substrate in a challenge. The above background and based on the current situation, this paper is a new preparation method of SERS base on the development of flexible material and bionics combination; the construction is convenient to use, can be used directly in the field of fast sampling detection, high sensitivity and reproducibility. Well, the strong stability of 3D nano imitation house lizard foot tentacles SERS base (G-SERS); and its application in fruit and vegetable residues on the surface of the fast, efficient acquisition and non marking, nondestructive testing; the specific contents are as follows: 1. using ordered anodic alumina super hydrophobic surface treatment (AAO) as template, poly two methyl siloxane (PDMS) for injection molding material spin coated on the surface of AAO, heating after forming physical stripping 3D nano "high density house lizard foot antenna array. These" orderly "tentacles" structure to the activity of SERS nanoparticles in The deposition of different dimensions provide support with high density. On the basis of the seed deposition of silver nanoparticles were modified to the "tentacles" array, the optimization time, produced a large area of the "hot spots", prepared by the biomimetic substrate 3D structure. In this chapter, we study the effect of different types of anodic alumina stripping the optimization of the silver nanoparticles and the deposition time on the performance of SERS substrate were investigated. The new bionic base is easy to use, not only has the SERS activity of superior (IF=1.2 * 107), good reproducibility and stability (RSD=5.8%) color also has many nano flexible antennae "(6.7 x 108/cm~2.2.) the use of 3D nano SERS substrate with high density of tentacles, using direct" paste - lift "method of cucumber, apple and grape surface with methyl parathion, thiram, malachite green residue and A mixture of fast sampling. Compared with the traditional flexible SERS substrate, G-SERS substrate with nano "high density flexible tentacles, the tentacles can be like house lizard foot setae can freely reach the micro regional actual sample surface, in the micro sample complex surface through a simple" paste ", without a direct lift collection, and realize the scene detection. This chapter studies the above three kinds of vegetable surface methyl parathion, thiram, malachite green, their detection limits were investigated base on fruit and vegetable residues on the surface of collection efficiency, reproducibility and stability test results. The study found that the G-SERS substrate of thiram. Malachite green, methyl parathion detection reached 1.6 ng/cm~2,0.4 ng/cm~2,25 ng/cm~2 respectively, the pericarp surface has completed the sample collection and no detection of pesticides Residue and substrate have good reproducibility (RSD=9.3%) and stability in practical application. The above results show that G-SERS substrate has great application potential in food safety field.
【學(xué)位授予單位】:華中農(nóng)業(yè)大學(xué)
【學(xué)位級別】:碩士
【學(xué)位授予年份】:2017
【分類號(hào)】:O657.37;TS255.7
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