可控SERS增强基底的构筑和机理及在饲料质量安全中的应用研究

发布时间：2018-06-08 03:10

本文选题：表面增强拉曼光谱 + 构筑　；参考：《中国农业科学院》2017年博士论文

【摘要】：目前,饲料与畜产品质量安全快速分析技术亟需补充和完善。基于纳米结构的表面增强拉曼光谱技术发展迅速,其中也面临众多技术难点,如基底均一性、增强信号稳定性以及对目标分子靶向富集等问题。若将SERS技术引入到饲料与畜产品快速分析领域,解决其中关键技术问题,将会是一个巨大的飞跃。本论文制备了深度氧化石墨烯负载纳米金复合物、纳米银阵列和纳米金溶胶等三种SERS增强基底,研究了它们的光学性质、稳定性、均一性及增强活性,探究了关键制备参数、形貌参数对基底增强性能调控规律,揭示了影响基底增强信号稳定性的关键因素和控制方法。论文还以纳米银阵列为例,阐明了三聚氰胺关键结构在纳米银阵列表面作用的系统属性及作用方式,重点研究了纳米银阵列对三聚氰胺的两种SERS增强作用机制:一是基于纳米银棒间“热点”形成的电磁场局域增强,二是基于Ag-Melamine之间电荷转移的化学增强。论文所得的结论可为SERS在实际应用中提供科学参考。论文选取了三聚氰胺、克伦特罗等常见违禁添加物,首次构建了饲料中三聚氰胺的两种SERS快速分析方法。方法一是以均一性良好的AgNR为增强基底,以甲醇为提取净化溶剂一步法处理,以Δv=682 cm~(-1)处特征拉曼吸收为定性定量峰,检测限和定量限分别为0.9,2μg·g~(-1),分析时间约3 min/样;二是以AuNPs为增强基底,以pH=3~4 HCl水溶液及混合溶剂(正丁醇:乙酸乙酯,6:1 v/v)为两相溶剂,两次液液萃取进行样品前处理,以731 cm~(-1)为归一化峰,707 cm~(-1)作为定量峰进行计算,检测限和定量限分别为0.5,2μg·g~(-1),分析时间约5 min/样。论文还建立了动物尿液中克伦特罗的SERS快速分析方法,以深度氧化石墨烯负载纳米金为增强体系,利用克伦特罗抗体标记磁珠富集净化尿液中的克伦特罗目标物,以Δv=1474 cm~(-1)为定性定量峰,检测限和定量限分别为0.5,1 ng·mL~(-1),分析时间约15 min/样。建立的三套SERS速测方法为饲料和畜产品质量安全监管提供技术支撑。
[Abstract]:At present, feed and animal products quality and safety analysis technology needs to be supplemented and improved. Surface enhanced Raman spectroscopy based on nanostructures has been developed rapidly, among which many technical difficulties are faced, such as homogeneity of substrate, enhancement of signal stability and targeted enrichment of target molecules. If SERS technology is introduced into the field of fast analysis of feed and livestock products, it will be a great leap forward to solve the key technical problems. In this paper, three kinds of SERS enhanced substrates, such as deep graphene oxide supported nano-gold complex, nano-silver array and nano-gold sol, were prepared. Their optical properties, stability, homogeneity and enhancement activity were studied, and the key preparation parameters were investigated. The regulation of morphology parameters on the performance of substrate enhancement reveals the key factors and control methods that affect the stability of substrate enhancement signal. Taking the nano-silver array as an example, the system properties and action modes of the key structure of melamine on the surface of the nano-silver array are expounded in this paper. Two kinds of SERS enhancement mechanisms of nano-silver arrays on melamine are studied: one is based on the local enhancement of electromagnetic field formed by "hot spot" between silver nanorods, the other is based on the chemical enhancement of charge transfer between Ag-Melamine. The conclusion can provide scientific reference for the application of SERS. In this paper, melamine, clenbuterol and other common prohibited additives were selected, and two rapid SERS analysis methods of melamine in feed were constructed for the first time. The first method was to take the homogeneous AgNR as the enhanced substrate, methanol as the extraction solvent, and the characteristic Raman absorption as the qualitative and quantitative peak. The detection limit and the quantitative limit were 0.9 ~ 2 渭 g / g, respectively, and the analytical time was about 3 min/. The results were as follows: (1) the analytical time was about 3 min/, and the detection limit and the quantitative limit were 0.9 ~ 2 渭 g / g ~ (-1) ~ (-1), respectively, with the characteristic Raman absorption at 螖 V ~ (682) cm ~ (-1). Secondly, the AuNPs was used as the enhancement substrate, the pH ~ (3 +) ~ (4) HCl solution and the mixed solvent (n-butanol: ethyl acetate 6: 1 / v) were used as two-phase solvent, the sample was pretreated by twice liquid-liquid extraction, and the normalized peak of 731 cm ~ (-1) was taken as the peak of 707 cm ~ (-1) as the quantitative peak. The detection limit and the quantitative limit were 0.5 ~ 2 渭 g / g ~ (-1) ~ (-1), respectively, and the analysis time was about 5 min/. A rapid SERS method for the determination of clenbuterol in animal urine was established, in which deep graphene oxide loaded nanocrystalline gold was used as an enhanced system, and clenbuterol antibody was used to label magnetic beads to enrich and purify clenbuterol target in urine. The detection limit and the quantitative limit were 0.5 ~ (1) ng / mL ~ (-1), respectively, and the analytical time was about 15 min/ for the sample with 螖 V ~ (1) 1474 cm ~ (-1) 路m ~ (-1) ~ (-1) as the qualitative and quantitative peak. The established three sets of SERS methods provide technical support for the quality and safety supervision of feed and animal products.
【学位授予单位】：中国农业科学院
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB383.1;O657.37

【相似文献】