【作者】 张丽霞；

【导师】 田媛；

【作者基本信息】 吉林大学 ， 分析化学， 2018， 硕士

【摘要】 表面增强拉曼光谱（SERS）作为分子检测定性、定量的强有力的分析手段,可以提供待测分子的结构和含量信息。SERS在分析检测方面具有简单、快速、无损以及灵敏度高等优点,为此其应用的领域十分广泛,如生物医学、艺术品鉴定、食品安全、公共安全等领域。基于SERS表现出的潜力,将其应用到调味品及保健品中非法添加物的检测。本论文利用SERS技术,基于银纳米线和环糊精包裹的银纳米粒子作为基底,检测调味品中的罗丹明B和保健品中的芳香族类药物盐酸苯乙双胍。通过多元醇法制备了形貌均一的银纳米线（Ag NWs）,并将其通过自组装的方法组装在玻璃片（Glass）上形成Ag NWs@Glass,用来作为表面增强共振拉曼光谱基底。罗丹明B可以通过静电作用吸附在银纳米线的表面,从而可以在532纳米激发线下检测罗丹明B。对该SERS基底进行了TEM、SEM、XRD的表征,并计算了该基底的增强因子（4.01×10⁶）,证明Ag NWs@Glass基底具有较好的SERS增强能力。本实验对pH值以及基底的浸泡时间进行了优化。在罗丹明B的浓度范围为1.0×10^-9-1.0×10^-55 mol L^-1时,SERS信号与浓度呈线性关系,检测限为0.3 nmol L^-1（r²=0.996）。该方法成功的应用到辣椒面、辣椒酱、花椒三种调味品中非法添加罗丹明B的检测,回收率分别为89.0-93.6%,85.0-98.7%,和80.0-94.0%。在碱性条件下制备了β-环糊精（β-CD）包裹的AgNP（AgNP@β-CD）,由于β-环糊精的疏水腔可以捕获含有疏水基团的分子,所以可将合成的AgNP@β-CD用于带有疏水基团分子的检测。本实验将AgNP@β-CD与待测物的混合液滴加在经疏水处理后的硅片上,形成高热点的咖啡环,用于盐酸苯乙双胍（PHE）的检测。该方法操作简单、灵敏度高,并且形成的咖啡环基底产生了大量的热点从而提高了SERS增强能力。以邻苯二胺做为探针分子,得到了邻苯二胺的浓度依赖曲线,计算AgNP@β-CD基底的增强因子（1.58×10⁶）,该数据表明该咖啡环基底的增强效果较好。对一些实验条件（激发波长和pH值）进行了优化,在优化条件下,该方法对PHE的检测在7.0×10^-8-1.0×10^-66 mol·L^-1浓度范围内呈线性响应,检测限低至8.0×10^-99 mol·L^-1。该方法成功应用于人参苦瓜软胶囊保健品和市售药片中PHE的检测,保健品和药片中PHE的回收率分别为95.3%-102.0%,96.3%-105.0%,相对标准偏差分别为2.64%-5.16%,2.87%-4.08%,表明该方法在检测实际样品中的PHE具有可信性和令人满意的结果。且对于含有疏水基团的芳香族类药物阿司匹林的检测效果良好。更多还原

【Abstract】 As a powerful analytical tool for qualitative and quantitative detection of molecules,surface-enhanced Raman spectroscopy（SERS）can also provide much structure and content information of molecule.SERS is simple,fast,non-destructive,and highly sensitive in terms of analysis and detection.For this reason,its application is very wide in fields,such as biomedicine,art identification,food safety,and public safety.Based on the potential of SERS,it is applied to the illegal addition of foods and drugs.In this paper,SERS was used for detection Rhodamine B in condiments and aromatic compound of phenformin hydrochloride（PHE）.The silver nanowires were prepared through the improved method of polyol.Ag NWs were assembled onto glass slides through self-assembly method.Moreover,in our experiment as-prepared Ag NWs@Glass were used as a SERRS substrate to detect Rhodamine B at the excitation wavelength of 532 nm.Rhodamine B can be adsorbed on the surface of silver nanowires by electrostatic interaction.The SERS substrate was characterized by TEM,SEM and XRD,and the enhancement factor of the substrate was calculated（4.01×10⁶）,which proved that the Ag NWs@Glass substrate has a good SERS enhancement ability.Experimental conditions such as pH value and soaking time on SERRS performance were studied and optimized.Under the optimized conditions,the SERRS intensity at 1648 cm^-（1） exhibited a linear relationship with the concentration of Rhodamine B in the range of 1.0×10^-9-1.0×10^-55 mol L^-1 and detection limit（S/N=3）is as low as 0.3 nmol L^-1.The corresponding correlation coefficient of the linear equation was 0.996.This method based on Ag NWs@Glass for the detection of Rhodamine B in three kinds of condiment was investigated and the recoveries were 89.0-93.6%,85.0-98.7%,and80.0-94.0%,respectively.The AgNP@β-CD were synthesized by a simple and direct one-step methodology.Since the hydrophobic cavity ofβ-cyclodextrin traps molecules containing hydrophobic groups,the substrate and the analytes are measured.The mixed droplets of the material are added to the hydrophobically treated silicon wafer to form a highly hot coffee ring for the detection of phenylephrine hydrochloride（PHE）.Furthermore,densely-packed substrate produced a large number of hot-spots to improve the SERS effect.The SERS performance of AgNP@β-CD substrate was characterized by using o-Phenylenediamine dihydrochloride as the probe molecule,the concentration dependence curve of o-phenylenediamine was obtained and the enhancement factor（1.58×10⁶）of AgNP@β-CD substrate was calculated,indicating that the coffee ring substrate has a good enhancement effect.The excitation wavelength and the pH value were optimized.The method displays a linear response for PHE in the 7.0×10^-8-1.0×10^-6 mol L^-11 concentration range,and the limit of detection is as low as 8.0×10^-9mol L^-1.The method was applied to the detection of PHE in healthcare products and commercial tablets,with recoveries between 95.3-105.0%and 96.3%-105.0%,relative standard deviations between 2.64%-5.16%and 2.87%-4.08%,respectively.It can be seen that the method has a credible and satisfactory result in the detection of PHE in actual samples.In addition,the aspirin,which is an aromatic compound containing a hydrophobic group,has a good detection effect.更多还原