食品中羟基多氯联苯类特异性识别及超敏传感基础研究

Hydroxylated polychlorinated biphenyls (OH-PCBs) are a group of chemical compounds with strong toxicity and endocrine disruption. Food which is contaminated with OH-PCBs has resulted in serious effect on food safety and human health. Generally, the rapid testing technologies for OH-PCBs included sensing based on whole cell and electrochemical sensors. However, the above developed methods were only applied into detection of single OH-PCBs and were difficult to detect multi residues of OH-PCBs. Meanwhile, the above methods were suffering from complicated operation and lower stability and so on. In this study, novel sensing system for OH-PCBs in food based on molecularly imprinted polymer (MIP), metal-organic frame materials (MOFs) and up conversion phosphor (UCP) to realize sensitive and multi target analysis is studied. The study intends to focus on the following aspects: the recognition mechanism, mass transfer and interaction parameters of MIPs with 4,4’-dihydroxydiphenyl (DHB) as template for OH-PCBs are demonstrated. The relations of constitution and molar ratios of rare earth elements with luminescent properties of UCP and the effects of MOFs on luminescence property of UCP are studied in detail. The construction of sensing system based on MIP-UCP@MOFs will be conducted and the sensing amplification mechanism of MOFs for sensing system is ascertained. Finally, the MIP-UCP@MOFs sensing system is fabricated to detect multi OH-PCBs target analytes with some advantages, including homogeneous phase reaction, high sensitive as well as quantitative detection and so on. This study can provide novel strategy for the quantitative analysis of other contanminants in food.

羟基多氯联苯（OH-PCBs）是一类具有强内分泌干扰作用的化合物，污染OH-PCBs的食品严重威胁人类健康。目前，已有的食品中OH-PCBs速测方法主要是全细胞免疫技术和电化学传感，其操作复杂，稳定性不足，且只对单种OH-PCBs速测，难以实现多种OH-PCBs同时检测。针对上述问题，拟基于分子印迹材料（MIP）类特异识别、金属有机框架材料（MOFs）增敏和上转换发光材料（UCP）光谱特性构建多靶标、高灵敏的传感体系。主要内容包括揭示以4,4’-二羟基联苯为模板的MIP对OH-PCBs的识别机理、传质效率及作用参数；探明UCP中稀土元素组成、摩尔比及包被MOFs与发光特性间关系；创建MIP-UCP@MOFs超敏传感体系，揭示传感机理及MOFs增敏机制，研究其传感性能与实际应用。通过组装高灵敏、均相传感体系，实现对食品中OH-PCBs多靶标同时检测，同时也为其他污染物均相传感分析提供新思路。

羟基多氯联苯（OH-PCBs）是一类具有强内分泌干扰作用的化合物，污染OH-PCBs的食品严重威胁人类健康。目前，已有的食品中OH-PCBs速测方法主要是全细胞免疫技术和电化学传感，其操作复杂，稳定性不足，且只对单种OH-PCBs速测，难以实现多种OH-PCBs同时检测。针对上述问题，本项目开展了金属有机框架材料（MOFs）的光谱行为和传感效应，创制了一种同时具有“turn on”和“turn off”光谱性能的镓（Ga）基MOFs；探明了镓（Ga）基MOFs对双酚类的逻辑传感机理以及性能；设计并合成了两种新型稳定荧光铝（Al）基MOFs，考察了BUT-17对内分泌干扰物的传感性能；进一步开展了锆基MOFs材料分子调控设计，合成出具有调控空间位阻能力的MOFs材料，具有大的比表面积和良好的吸附能力。在此基础上，合成制备了对羟基多氯联苯（OH-PCBs）具有良好识别能力的分子印迹聚合物（MIP），考察了MIP对OH-PCBs识别能力，基于时间读数构建了OH-PCBs超敏传感器，检测灵敏度达到0.3 ng/mL。进而，基于纳米条带分子识别材料与邻苯二甲酸酯类化合物的π-π作用，提高了荧光信号，研制出具有类特异性识别传感能力的传感器，根据邻苯二甲酸酯类化合物的浓度与荧光强度，实现对邻苯二甲酸酯类化合物的高效和高灵敏传感分析。该传感器对邻苯二甲酸酯类化合物的检测能达到0.03 ppb，且具有良好的选择性，其他类似分子对邻苯二甲酸酯类化合物不存在明显的干扰作用。该研究也为其他污染物均相传感分析提供新思路。相关研究成果在Chemical Reviews，Analytical Chemistry和Biosensors and Bioelectronics等国际权威刊物上共发表SCI论文11篇，申请国家发明专利7项，授权国家发明专利3项，培养硕士研究生5名，2名研究生获得硕士学位；1人入选中国农业科学院D类人才。对照项目任务书要求，全面完成了相关研究目标和考核指标。