基于MOFs纳米酶的SERS传感平台构建及其在中药材有机磷农药残留检测的研究

With the vigorous development of the Traditional Chinese Medicine (TCM) industry, the safety of TCM caused by organophosphorus pesticides (OPPs) has become increasingly prominent. Although the rapid detection technology for OPPs has been developed rapidly and continuously, the enzyme-based analytical method has many limitations in the application of TCM samples, such as high utilization of biological recognition ligands, low environmental adaptability, difficult on multi-residues detection. In the present study, we aim to comprehensively apply Metal-Organic Framework (MOFs), Nanozyme, and Surfaces Enhanced Raman Scattering (SERS) techniques to develop the new detection technologies and platforms. The research mainly covers two aspects: 1. The study and development of novel MOFs with enzyme-like activity for replacing of the biological recognition ligands and the enhancement of environmental adaptability; 2. The preparation of Au@Ag@MOFs within SERS metal substrate, the exploration of the featured spectra of OPPs and the analysis of multiple pesticide residues; 3. The establishment of rapid discrimination algorithm between SERS spectral data and pesticide by combining with chemometrics methods. The designed and synthesized Au@Ag@MOFs are the systems with “Catalysis-Enrichment-Detection” functions. It is expected to improve the quality assessment system for TCM, and promote the healthy and sustainable development of the TCM industry.

随着中医药行业的蓬勃发展，有机磷农药残留导致的中药材安全性问题日益突出。虽然目前农药残留的快检技术推陈出新，但以生物酶为基础的分析方法在中药材的应用中还有很多局限性，如生物类识别配体使用率高、环境适应性低、多农药同时检测难等特征。本研究拟综合运用金属框架材料（MOFs）、纳米酶、表面增强拉曼（SERS）多技术优势，构建高灵敏检测技术和平台。研究包括：1. 新型MOFs的纳米酶活性研究，以替代生物酶类识别配体，并增强环境适应性；2.集成SERS金属基底，优化合成多功能Au@Ag@MOFs复合物，探索其对于有机磷农药的拉曼特征识别，实现对于多种农药残留的拉曼信号同步稳定输出；3. 结合化学计量学方法，建立SERS光谱数据分析与农药快速区分算法。本项目利用设计合成的Au@Ag@MOFs体系，可实现“催化-富集-检测”三位一体的快速分析，不断完善中药材质量评估体系，有效促进中医药行业的持续发展。

以有机磷农药为主的污染物残留导致的中药安全性问题严重威胁中药产业发展和人类健康。2020年最新版《中国药典》颁布，其中中药材中农药残留限量标准由7种增加到33种，有机磷和氨基甲酸酯类农药品种和数量增幅明显，显示对中药安全性问题的极大关注。本项目旨在建设中药中农药残留物快速监测体系，加强中药质量评价和安全监管。首先，我们设计核壳式MOFs表面增强拉曼（SERS）基底以期为痕量农药残留提供高灵敏和准确性的拉曼芯片分析方法。以纳米金（Au NPs）为核，普鲁士蓝（PB）MOFs为骨架复合材料，可控制备了一系列具有不同程度均匀包覆PB壳层的MOFs SERS基底，同时显著改善了SERS分析的准确性和灵敏度。与此同时，通过系统评价MOFs复合物等多种纳米酶材料的催化性能，我们构建了以Au@PB MOFs为代表的几种农药残留分析技术，可实现百草枯、福美双不同农药残留或不同种类污染物的同步时空分辨分析。在中药材复杂基质存在的情况下，纳米酶的仿生识别特性保障了分析方法的环境适应性、检测准确性，这也有望实现大规模制备和技术推广。基于本项目的研发成果，相信可为中药“种植-采收-加工-流通”全产业链监管提供有效和快速的风险评估工具。