水体中激素类PPCPs原位富集、表面增强拉曼光谱快速检测新方法及其应用研究

The development of in-situ sampling and detection methods always attracts much interest in the field of environmental science. In this study, an in-situ sampling, preconcentration and detection method based on surface-enhanced Raman spectra (SERS) is proposed for the determination of hormonal pharmaceuticals and personal care products (PPCPs). The sampling and preconcentration device with high efficiency and selectivity is developed based on molecularly imprinted membrane. The Fe3O4@Au core shell nanoparticles modified with functional ligands based on hydrophobic, charge transfer, boric acid and molecularly imprinted interactions is prepared. The resultant hybrid nanoparticles serve as both the SERS substrates and the enrichment materials, and can be withdrawed from the matrix easily. The molecular imprinted membrane and the SERS substrates are then coupled with the Raman spectrometer for in-situ rapid determination of target analytes by a specially designed interface. The species and concentration of the hormonal PPCPs in Zhujing River in Guangzhou are investigated. The proposed technique, which has broad applications to the analysis of pollutants in environmental water, provides new method for the fast and real-time analysis of environmental samples. It is of theoretical and practical importance for the investigation of the pollution level and characteristics of hormonal PPCPs.

发展能对水体中污染物原位富集和现场监测的新技术一直是环境科学研究领域的热点问题。本项目针对激素类PPCPs这一新型微污染物，发展基于表面增强拉曼光谱(SERS)的原位富集和快速检测技术。结合分子印迹膜制备技术,研制高效、高选择性的采样/富集装置。研制集SERS活性基底和富集材料为一体的表面功能化的核壳式磁性金纳米粒子,利用疏水、电荷转移、硼酸亲和、表面印迹等功能化修饰磁性SERS基底以选择性增强检测信号，并有效实现基底回收。将富集了目标污染物的分子印迹膜和SERS基底通过接口装置的设计实现现场快速检测。在此基础上研究以珠江广州河段水体为代表的激素类PPCPs污染种类和含量水平。本项目的实施将丰富水体污染物现场快速检测方法，为探索激素类PPCPs的污染水平、特征和迁移规律提供新的技术基础，具有重要的理论研究意义和实际应用价值。

水体中低含量环境污染物尤其是药物和个人护理用品( pharmaceuticals and personal careproducts, PPCPs)环境污染物的监测成为近年来环境科学研究领域的关注重点。发展原位采样富集和现场检测新技术为痕量、超痕量水体中污染物的快速监测提供了重要途径。本项目基于表面增强拉曼光谱技术（Surface enhanced Raman scattering, SERS）发展了PPCPs环境污染物的快速、高灵敏、现场检测技术。（1）研制和开发了高效、高选择性的环境水原位采样/富集介质和装置。基于分子印迹技术高效识别、捕获水体中目标污染物，以配位桥联作用解决分子印迹的水相兼容性问题，研制共轭微孔聚合物富集介质，针对性实现不同环境污染物的高效富集。研制了基于膜分离富集的可用于现场检测的环境水大体积采样/富集装置。将富集介质与采样装置相结合构建环境水中痕量污染物高效采样/富集平台。（2）研制功能化表面增强拉曼光谱活性基底，进一步提高检测方法灵敏度。将金属有机骨架材料的高吸附富集性能与贵金属纳米粒子的高SERS活性相结合，研制了嵌入式和核壳式金纳米粒子/金属有机骨架复合SERS基底。采用一步超声电化学方法制备金/碳纳米片复合SERS活性基底，原位-还原法研制纳米氧化镁/银纳米粒子复合SERS活性基底，复合基底表现出更强的SERS活性，并提高了基底的使用稳定性。（3）基于以上研制的采样/富集介质和装置，结合高SERS活性基底，发展了一系列PPCPs污染物及其他环境污染物的表面增强拉曼光谱快速、灵敏检测方法，包括染发剂对苯二胺、抗生素磺胺二甲嘧啶、环境雌激素双酚A、多环芳烃及其代谢产物、农药残留西维因、孔雀石绿、显影剂等，并用于珠江水、污水、饮用水、鱼体、人体尿液等实际样品分析。以上研究工作分别在Analytical Chemistry、Nanoscale, Analyst等刊物发表，标注基金资助的论文共25篇，SCI收录期刊发表论文17篇，申请和授权发明专利各1项。