新型多功能印迹复合材料的制备及对环境中甲状腺素干扰物的识别研究

Thyroid-disrupting chemicals may disturb the overall activity of thyroid hormones by interference with the receptors. The potential effect may facilitate their transport to thyroid dependent tissues such as the brain or the fetus, and then affect the formation of neuronal circuit and subsequent behavioral functions. It is difficult to decide which chemicals are the key causative toxic pollutants, but it is an essential precondition for environmental risk assessment and pollution control. In this study, a novel method is proposed to synthesize molecularly imprinted polymers (MIPs) with highly selective for the target molecule (thyroid hormones), using random peptides as the monomers and glutamine transaminase as the cross-linker. Then, MIPs are introduced into the effect-directed analysis, because the properties are determined by their structure. For one thing, MIPs are used instead of biological assay to identify thyroid-disrupting effects in environmental samples. For another thing, MIPs are used as solid-phase extraction adsorbents to determine thyroid-disrupting chemicals, which can be helpful in identifying the compound groups responsible for the measured effect in city cluster in the middle reaches of the Yangtze River. This study offers new facilities for the effect-directed analysis, which is conducive to confirm the suspected cause of toxicity and decrease potentially dangerous. Furthermore, we find a way to loosen the bonds of tradition and change the recognition model of molecularly imprinted polymers for complex mixtures of different chemicals.

甲状腺素干扰物能影响脑部发育与认知功能，对婴幼儿健康威胁极大。识别环境中主要贡献污染物是环境风险评价与污染控制和削减的前提，遗憾的是缺乏相应的生物学筛查元件。本研究提出一种随机多肽为单体，谷氨酰胺转氨酶为交联剂的新型合成体系，以甲状腺素为模板，在磁性@荧光功能材料表面构筑模拟甲状腺素受体/结合蛋白的仿生识别孔穴，依据结构决定效应理论，实现对甲状腺素干扰物（为甲状腺素结构类似物）的识别，系统研究其合成规律和识别机理。并将其引入甲状腺素干扰效应引导污染物的识别和分析中，作为筛查元件完成环境水样甲状腺素干扰效应的甄别，判断是否需要检测相应的污染物；随后，可以作为固相萃取吸附剂，开展甲状腺素干扰物的鉴定和分析，为长江中游城市群主要贡献污染物及来源确定提供基础数据。本项目摆脱了目标物为导向的传统分析思路，转变分子印迹识别模式，实现对多种甲状腺素干扰物的识别，预防其对潜在人群的危害。

效应引导污染物识别以特定的生物学毒性效应为标尺，引导组分分离、化学分析与污染物鉴定，能够快速高效地筛选样本中已知/未知主要贡献污染物，处于环境化学领域的研究前沿。本项目制备了一种甲状腺素印迹仿生材料，能够代替甲状腺素转运蛋白甄别干扰甲状腺素转运的污染物，结合色谱分离技术，以保留因子为评价指标，建立一种全新的干扰甲状腺素转运毒性引导污染物的识别和分析方法，表现出高通量、低成本、兼容性好的优势。新方法不仅能够用于已知污染物的分析，比常规固相萃取柱表现出更加优越的性能，而且能够用于未知污染物的筛选。此外，我们提出了已知甲状腺素干扰物的毒性因子数据库，为利用效能因子法研究污染物复合暴露及其健康危害研究奠定基础。随后，我们开始关注干扰甲状腺素合成污染物的筛选方法研究。服务于“十四五环境与化学领域培育学科未来生长点（化学品高通量毒性筛查）。此基础上，以已知主要贡献干扰物四溴双酚A和对羟基苯甲酸酯为研究对象，创新分子印迹技术，建立灰尘和个人用品中痕量目标物的快速检测方法，服务于环境污染物暴露与评估研究。基于此，发表5篇SCI论文，授权/申请发明专利3项，在高水平国际会议上做大会报告3次，完成了申请书预期要求。