表面增强拉曼光谱技术在环境污染物检测中的应用

表面增强拉曼散射(SERS)光谱具有高灵敏性及高选择性,它已被用于科学研究及生产实践的多个领域。本文阐述了近几年来SERS技术在检测重金属离子、多环芳烃、微生物、农药等环境污染物中的发展状况,并分析了该技术在这些应用领域的优点与不足。最后,预测了SERS的发展趋势。     

Localized Collection of Airborne Analytes: A Transport Driven Approach to Improve the Response Time of Existing Gas Sensor Designs

The detection of single binding has been a recent trend in sensor research introducing various sensor designs where the active sensing elements are nanoscopic in size. Currently, transport and collection of airborne analytes for gas sensors is either diffusion based or non‐localized and it becomes increasingly unlikely for analytes to interact with sensing structures where the active area is shrunk, trading an increased sensitivity with a slow response time. This report introduces a corona discharge based analyte charging method and an electrodynamic nanolens based analyte concentration concept to effectively transport airborne analytes to sensing points to improve the response time of existing gas sensor designs. Localized collection of analytes over a wide range, including microscopic particles, nanoparticles, and small molecules, is demonstrated. In all cases, the collection rate is several orders of magnitudes higher than in the case where the collection is driven by diffusion. The collection scheme is integrated on an existing SERS (surface‐enhanced Raman spectroscopy) based sensor. In terms of response time, the process is able to detect analytes at 9 ppm (parts per million) within 1 s. As a comparison, 1 h is required to reach the same signal level when diffusion‐only‐transport is used.     

Mesostructured Arrays of Nanometer‐spaced Gold Nanoparticles for Ultrahigh Number Density of SERS Hot Spots

A novel one‐trough synthesis via an air‐water interface is demonstrated to provide hexagonally packed arrays of densely spaced metallic nanoparticles (NPs). In the synthesis, a mesostructured polyoxometalate (POM)‐silicatropic template (PSS) is first self‐assembled at the air‐water interface; upon UV irradiation, anion exchange cycles enable the free‐floating PSS film to continuously uptake gold precursors from the solution subphase for diffusion‐controlled and POM‐site‐directed photoreduction inside the silica channels. NPs ≈ 2 nm can hence be homogeneously formed inside the silica‐surfactant channels until saturation. As revealed via X‐ray diffraction, small‐angle X‐ray scattering (SAXS), grazing incidence SAXS, and transmission electron microscopy, the Au NPs directed by the PSS template are arrayed into a 2D hexagonal lattice with inter‐channel spacing of 3.2 nm and a mean along‐channel NP spacing of 2.8 nm. This corresponds to an ultra‐high number density (≈10¹⁹ NPs cm^?3) of narrowly spaced Au NPs in the Au‐NP@PSS composite, leading to 3D densely deployed hot‐spots along and across the mesostructured POM‐silica channels for surface‐enhanced Raman scattering (SERS). Consequently, the Au‐NP@PSS composite exhibits prominent SERS with 4‐mercaptobenzoic acid (4‐MBA) adsorbed onto Au NPs. The best 4‐MBA detection limit is 5 nm , with corresponding SERS enhancement factors above 10⁸.     

表面增强激光拉曼法（SERS）研究铝酞菁对不同核酸碱基的光敏损伤

将表面增强激光拉曼技术（ＳＥＲＳ）作为探针引入光敏损伤的研究。利用这种新的光谱方法研究了新光敏剂铝酞菁对几种核酸碱基分子的光敏损伤过程，发现Ｇ（乌嘌呤）对光敏化的敏感性最强，Ａ（腺嘌呤）其次，Ｃ（胞嘧啶）和Ｕ（尿嘧啶）则不敏感。实验证实，是铝酞菁的光动力反应产物单线态氧，在核酸碱基的光敏损伤中起主要作用。     

SERS Substrate-Dependent Interaction of the Anticarcinogenic Drug 5-Fluorouracil with Silver

5-Fluorouracil, an extensively used anticarcinogenic drug, was found to undergo a soft adsorption (i.e., no significant structural changes) on the metal surface of different Ag island films (35, 11, 8.7, and 6.5 nm thick). The 35 nm thick film provided the best SERS signal. The resistance of the Ag-complexed species to washing demonstrates the films' advantage over colloids and makes them very attractive for potential bio-applications.

Both deprotonated forms, which were previously detected on colloidal nanoparticles (50 nm diameter) at neutral pH, are also present in this case. However, the interaction mechanism of 5-FU species appears to be substrate dependent. While on colloidal nanoparticles they are orientated perpendicular or significantly tilted from the surface normal, on the much larger Ag-clusters of the island films (20-200 nm) they lie flat, attached through the carbonyl groups and the π-electrons. The charge-transfer mechanism significantly contributes to the rich information SERS reports for this system.     

应用置换反应制备高效SERS活性基底研究

利用预处理的铝片和铜片还原硝酸银溶液的方法获得了具有不同表面形貌的银纳米结构.扫描电子显微镜(SEM)图表明反应产物分别为花样和树枝状的银纳米结构.以对羟基苯甲酸(PHBA)作为探针分子,对这种新体系的表面增强拉曼散射(SERS)活性进行了研究,发现该体系是一种非常高效的SERS活性增强基底,并且其SERS活性优于用化学方法制备的银胶.本文对这种新型SERS活性基底的增强机制进行了讨论.     

TLC-SERS法快速筛查猪尿中磺胺类抗生素

采用薄层色谱法(TLC)与表面增强拉曼光谱(SERS)联用技术,建立猪尿中磺胺类抗生素残留的快速筛查方法。用阴性猪尿样本模拟阳性样品,以氯仿-乙醇-石油醚(1:1:2)为展开剂,利用TLC将猪尿中的抗生素与猪尿基质初步分离。以785 nm激光为激发波长,金溶胶为表面增强剂,采用SERS技术对分离出的抗生素沉积斑点进行检测。结合密度泛函理论,得到定性定量分析猪尿中磺胺嘧啶分子特征峰877 cm~(-1)和994 cm~(-1)、磺胺二甲嘧啶分子特征峰661 cm~(-1)、磺胺噻唑分子特征峰862 cm~(-1)和1127 cm~(-1)。该方法检测猪尿中磺胺嘧啶、磺胺二甲嘧啶和磺胺噻唑的最低检测浓度分别为0.1、0.1、0.2 mg/L。且TLC技术可实现猪尿中混合抗生素的分离,当猪尿中3种混合抗生素点样沉积量为0.01μg时,各抗生素的特征峰均清晰可辨。由此可见,TLC-SERS技术可用于猪尿中混合抗生素残留的快速筛查。     

叶菜中多类农药残留的SERS快速无损检测

有机磷、有机硫和烟碱类农药常应用于叶菜的种植和生产中,常规的检测方法前处理复杂、检测时间长、成本高等特点,难以满足快速检测的需求,为了实现农药残留的在线检测,本文提出一个基于SERS技术进行定量和定性分析叶菜中农药残留的检测方法,选取农药的特征拉曼峰作为校正峰,制定农药残留的浓度与校正峰强度的线性校准方程,将最低检测限对应SERS光谱的校正峰的强度代入线性校准方程,计算出定量检测限。研究表明,小白菜中亚胺硫磷农药的检测限能达到0.5mg/kg以下,相关系数R~2为0.95273,标准偏差为2.89%～13.63%,回收率为96.00%～121.33%;大白菜中福美双农药残留的检测限能达到0.5mg/kg以下,相关系数R~2为0.8905,标准偏差为3.90%～8.39%,回收率为88.80%～112.44%;空心菜中啶虫脒农药残留的检测限能达到1mg/kg以下,相关系数R~2为0.93858,标准偏差为2.12%～9.29%,回收率为87.67%～107.17%。这些结果说明,基于SERS技术进行定量和定性分析叶菜中农药残留的检测方法是一种有效的方法,可以实现叶菜农药残留的快速无损检测。     

表面增强拉曼散射技术对白酒中克百威残留的定性检测

建立表面增强拉曼散射（surface enhanced Raman scattering,SERS）技术对白酒中的克百威残留进行定性检测方法。制备金溶胶（Au nanoparticles,Au NPS）和不同Ag壳厚度的银包金纳米粒子（Au@Ag NPS）,通过探测分子罗丹明B（R6G）比较Au NPS和不同Ag壳厚度Au@Ag NPS的SERS增强效果;碱性条件下,向克百威分子引入标记物2,6-二氯醌-4-氯亚胺,再与增强效果较好的NPS按比例混合进行拉曼测试,讨论SERS信号采集条件,并对拉曼谱峰进行比较和归属,计算克百威在Au@Ag NPS增强基底上的增强因子。结果表明：克百威、标记物和Au@Ag NPS的比例为1∶0.225∶7,约7 nm Ag壳厚度Au@Ag NPS效果最好,克百威的检测下限为1×10－16 mol/L,Au@Ag NPS增强因子为2×108,用此方法检测3 种市售白酒中均含有微量的克百威,方法快速、简便、结果可靠。