食品中痕量有害物质表面增强拉曼光谱现场定量快速分析新技术研究

Food safety has become a major concern in China. Food safety analysis has characteristics such as time effectiveness and large number of sample preparation. It has great significance for food safety analysis to develop highly selective enrichment methods for trace harmful substances in food coupling with corresponding portable rapid detection techniques to establish the novel on-site quantitative rapid analytical techniques for trace harmful substances in food. Surface-enhanced Raman spectroscopy (SERS) technique is a portable rapid sensitive analytical technique. However, due to the low selectivity and anti-interference capability of SERS detection, it is still hard to actually apply SERS detection technique for the quantitative analysis during real analytical projects. In this project, trace illegal additives in food, pesticide and veterinary drug residues, hormone residues and other harmful substances will be concerned as target harmful substances in food. Molecular self-assembly and molecular imprinting technique will be used to prepare novel size-controlled, reproducible, highly selective and reusable SERS sensitive substrates in order to improve the selectivity and sensitivity of SERS rapid analysis technique during real analytical projects. Moreover, coupling with the home-made effective circular-flow SERS sampling system the statistical sampling representativeness during SERS rapid analysis will be improved, which facilitates the further improvement of precision and accuracy of SERS rapid analysis technique and the establishment of the novel on-site SERS quantitative rapid analytical techniques for food safety. It is expected the proposed on-site SERS quantitative rapid analytical techniques can be practically applied for the on-site rapid quantification of trace harmful substances in complex food samples such as fruits, vegetables, roast meat and aquatic products.

食品安全已成为重要的国计民生问题之一。食品安全检测具有样品量大、时效性强的特点，针对食品中痕量有害物质研发高选择性富集新方法，并结合相应便携快速检测技术，构建食品中痕量有害物质的现场定量快速检测新技术对食品安全检测具有重要意义。表面增强拉曼光谱（SERS）技术具有便携、快速、灵敏等特点，但抗扰能力及选择性弱，尚无法真正用于实际样品定量分析。本项目希望针对食品中痕量非法添加剂、农兽残、激素类残留等有害物质，采用自组装及分子印迹技术制备形貌尺寸可控、重复性好、选择性高、可重复使用的新型SERS敏感基底，提高SERS快速检测技术用于复杂食品分析时的选择性和灵敏度；结合自制高效SERS分析循环流动采样系统，提高采样统计代表性，进一步提高SERS快速检测的精密度和准确度，从而构建食品安全SERS现场定量快检新技术，并实际应用于蔬果、卤煮烧腊及水产品等复杂食品中痕量有害物质的现场定量快速检测。

表面增强拉曼光谱（SERS）技术能提供丰富的化学分子结构信息，灵敏度高、检测速度快，且仪器便携，非常适合于食品安全现场快速检测。但是，SERS技术抗干扰能力及选择性弱，而食品样品基体复杂，目前许多食品安全SERS快速分析方法的精密度及准确度仍有待提高。本项目针对食品中痕量非法添加剂等有害物质，制备新型SERS敏感基底，提高食品安全SERS现场快速分析技术的选择性和灵敏度；通过自制高效 SERS 分析采样系统，进一步提高食品安全SERS现场快速分析的精密度和准确度。. 项目按原计划圆满顺利完成，并达到预期目标。采用导向自组装、原子转移自由基聚合法、溶胶法、表面浸润法分别成功制备了金-聚苯乙烯-嵌段-聚4-乙烯基吡啶固有内标SERS基底、金-羟基聚苯乙烯纳米阵列SERS基底、金-十六烷基三甲基溴化铵SERS基底、金-杜邦101-聚四氟乙烯薄膜SERS基底；研制了微型热助吹扫捕集、微型气膜阵列分离、微型气膜分离环炉富集、大体积恒浓度等高效SERS采样系统；结合SERS及色谱分析技术，构建了食品中痕量柯衣定、瓜子中红2G、水果中噻苯唑、饮用水中微囊藻毒素、面粉中甲醛、味精中硫化钠、酒精制品中甲醇、蔬果中四聚乙醛与福美双、水果中植物激素乙烯、水果保鲜气中二氧化硫、干果中糖精钠等目标物的现场定量快速分析新技术。在Analytical Chemistry等国内外刊物上发表论文13篇；申请发明专利4项，1项授权、3项公开，培养博士生2名、硕士生6名。