基于电化学表面增强拉曼光谱技术的近海海洋环境中痕量抗生素的快速检测方法研究

近海海洋环境中有机污染物种类多、含量低且基质复杂，其定性定量分析需在实验室中进行，但长途输运过程伴随的污染或变质将影响结果的准确性且难应对应急监测。因此，发展现场检测技术是海洋环境监测研究的趋势。电化学表面增强拉曼光谱（EC-SERS）技术能提供分子指纹信息且具有极高检测灵敏度，结合便携式拉曼光谱仪，可实现近海海洋环境中痕量有机物的现场快速检测。本项目拟：1）设计研制掌上型电化学仪、即插即用型SERS基底和电化学流动池，与便携式拉曼光谱仪集成，研制一体化船载式EC-SERS检测系统；2）发展海洋环境中典型痕量抗生素（负电性喹诺酮类和正电性磺胺类）的快速样品前处理方案；3）针对海洋环境高盐特点，结合纳米材料表面组装和电化学电位调控技术，发展灵敏稳定的固态SERS基底；4）引入内标并结合弱信号识别算法，实现海洋环境中痕量抗生素的快速定性定量分析，从而建立船载式EC-SERS现场检测系统和方法。

The qualitative and quantitative detection of emerging organic pollutants in coast seawater is typically carried out in lab using large-scale facilities, due to the extraordinary variety and the trace amount of these organic compounds and the interference from the complicated matrix in marine environment. However, the long-distance shipping and long-time storage could deteriorate or contaminate samples and give negative effect on the experimental results with the misleading information. Meanwhile, it is difficult for the long-term periodic monitoring and the analyzable data is restricted by the sampler frequency of the random sampling. Therefore, developing onsite detection technique is lacking and highly demanded and is the research tendency of marine environmental detection. Characterizing by the fingerprint resolution and high sensitivity, Electrochemical Surface-enhanced Raman Spectroscopy (EC-SERS) has the potential for the on-site, fast detection of trace emerging organic pollutants in marine environment, facilitated by the portable Raman spectrometer. Therefore, we planned to develop the EC-SERS based detection technique towards the trace emerging organic pollutants in coast region, with the trace antibiotics detection as an example. The following work would be carried out: 1) By integrating the handhold electrochemical workstation, the plug & play SERS active electrode, the electrochemical in-situ flow cell and the portable Raman spectrometer, the EC-SERS system would be formed. 2) Taking the negative quinolones and positive sulfonamides as the target molecules, the quick sample pretreatment process under the marine environment was developed. 3) considering the high salt concentration of the marine environment, the preparation of SERS active electrode with high sensitivity, selectivity, reproducibility and stability was optimized by surface ensemble and potential modulation. 4) Integration of internal SERS standard and the recognition algorithm of weak signal, the onsite EC-SERS system and related method could be realized towards the trace antibiotics in the marine environment.