新型溴代阻燃剂分子印迹纳米纤维膜传感器的研制

Neurotoxicity induced by environmental pollutants has been of major public and scientific concern due to the serious health threats to humans, especially infants and children. Brominated flame retardants (BFRs) have been beneficially used in many consumer products such as polymers, furniture, computers, and television sets. However, large production volumes, modes of application, and intrinsic chemical-physical properties of some BFRs have also rendered these to be found at increasing levels in the environment, wildlife, and humans. Some of the BFRs have recently attracted much attention due to their persistence in the environment and widespread global distribution. BFRs have also been studied in regard to their potential as developmental neurotoxicants. However, there is no effective means to identify the compounds in the environment. On the basis of our previous work in molecular imprinting technique, we want to screen molecularly imprinted systems and forecast performance of imprinted polymers by Theoretical and Computational Chemistry, it is to provide theoretical guidance for the preparation and application of imprinted polymers; then, in order to achieve efficient separation of these substances, this project will focus on the preparation of the novel BFRs molecular imprinted nanofibers by combinating the imprinting technique with electrospinning method, and explore the key facts; at last, coupling means of electrochemical tests, functional nanofibers will be immobilized on electrochemical sensing interface, to establish a rapid, high sensitivity and high stability of novel BFRs molecular detection. This project has practical significance on the determination of emergency monitoring and easy monitoring of novel BFRs pollution.

新型溴代阻燃剂(Bromide Flame Retardants, BFRs)是样品中神经毒性风险的主要来源，目前尚无有效手段对环境中神经毒性效应化合物进行有效识别。本项目在我们前期从事分子印迹技术工作的基础上，拟运用理论化学计算方法，筛选分子印迹体系以及预测印迹聚合物的性能，为印迹聚合物的制备和应用提供理论指导；结合印迹技术与电纺丝方法，重点研究制备新型BFRs分子印迹纳米纤维膜，摸索其制备的关键技术，实现高效分离此类物质；将功能化的纳米纤维固定于电化学传感界面上，偶联电化学测试手段，以期建立起对新型BFRs分子的快速、高灵敏和高稳定检测方法。项目研究对新型BFRs污染物的应急监测和简易监测具有实际意义。

新型溴代阻燃剂是神经毒性风险的主要来源，目前尚无有效手段对环境中神经毒性化合物进行有效识别。在掌握静电纺丝和分子印迹技术相结合的基础上，我们主要对两种新型溴代阻燃剂进行了较深入的印迹传感研究。. 首先，以芳香族化合物—三溴苯酚（TBP)为印迹分子，分别以具有生物相容性好、无毒、廉价的天然高分子壳聚糖、聚乙烯亚胺(PEI)及具有“内疏水，外亲水”这一独特空间结构的环糊精分子作为功能体，采用传统的滴涂法和电聚合法，以及核壳纳米粒子负载，纳米纤维负载等方法，制备了基于壳聚糖、聚乙烯亚胺和环糊精的三溴苯酚分子印迹聚合物，研究了三溴苯酚分子传感器的相关性能。通过比较各传感器的检出限[D(滴涂法)=1.61×10-8 mol/L (5.32 µg/L)； D(电聚合法)=1.32×10-8 mol/L (4.36 µg/L)；D(纳米粒子)=1.51×10-8 mol/L （4.99 µg/L)；D(纳米纤维)=9.62×10-10 mol/L (0.32 µg/L)，得出：结合电纺技术和分子印迹技术制备的分子印迹纳米纤维传感器的检出限远低于由纳米粒子构建或直接成膜构建的传感器。生活饮用水卫生标准对水中挥发酚的含量规定为≤2µg/L，而对微量挥发性酚的传统检测改进色谱法的检出限可达到0.5 µg/L，印迹纳米纤维构建的传感器检出限与色谱法相当，且因具有快速检测、操作简单、仪器便携可进行现场检测的特点，该传感器有望具有较好的应用前景。. 其次，以杂环化合物——三-（2,3-二溴丙基）异氰脲酸酯为研究对象，耦合分子印迹技术和电化学技术，实验利用多功能基团的电活性单体邻氨基苯酚 (OAP)和对苯二胺 (OPD) 为功能单体，制备新型溴代阻燃剂TBC分子印迹传感器，并与以苯胺为功能单体构建的TBC传感器作对比，结果为检出限D(OPD)=6.26×10-13 mol/L ; D(OAP)=6.64×10-11 mol/L ; D(苯胺)=5.22×10-10 mol/L ，这一结果明显优于电化学发光(ECL)方法构建的TBC传感器，其中，OPD构建的优于光电化学免疫(PCI)方法构建的，OAP 与其相当。实验证实多功能基团的协同效应可超灵敏检测TBC。由于TBC在环境中的浓度较低，该项工作有望为快速测定相似于TBC的可持续污染物的应急监测和简易监测提供借鉴意义。