金属有机框架/聚合物复合材料用于环境和生物介质中新兴全氟和多氟化合物富集、检测方法的研究

Emerging per- and polyfluoroalkyl substances in the environment have attracted much attention in recent years due to their persistence in the environment and bioaccumulation effect. It is essentially significant to study the potential health effects of environmental exposure to these compounds. Currently, only limited sample preparation methods are available for the emerging per- and polyfluoroalkyl contaminants. Moreover, the conventional methods suffer from several aspects, such as tedious operation procedures, low extraction efficiency and consumption of a large amount of organic solvents. Hence, the project aims to synthesize nanocomposites of metal-organic framework nanoparticles and functional polymers via electrospinning. The ideal metal-organic framework candidates should be stable in water and organic solvents, and the polymers having ion-exchange functional groups are preferred. The as-synthesized nanocomposites will be employed as the sorbent material and packed in a pipette tip that could be used for solid-phase extraction. By optimizing the metal-organic framework and polymer components, as well as the experimental conditions for the extraction, an effective and sensitive extraction method coupled to liquid-phase chromatography-mass spectrometry analysis will be established for newly emerging per- and polyfluoroalkyl substances from environmental samples and human urine and breast milk samples. The methods developed in this project will provide new analytical tools for environmental monitoring for assessing human exposure to these emerging per- and polyfluoroalkyl substances, and scientific evidence for investigating the potential adverse effects on human health.

近年来，环境中不断涌现出多种新兴全氟和多氟化合物，该类有机污染物的暴露对人体健康的影响不容忽视。目前适用于该类化合物的分析检测方法较少，且存在样品处理操作繁琐，富集能力弱，溶剂消耗多的缺点。本项目拟以化学稳定性好的金属有机框架材料为基础，选取具有离子交换能力和选择性吸附性能的聚合物基体，采用利用静电纺丝技术制备功能化的金属框架/聚合物复合纤维材料，将其填充于移液器吸头制成微型化的固相萃取装置。通过优化复合纤维材料的结构组成和化学性质，以及萃取实验参数，建立一种适合于新兴全氟和多氟化合物的微型化样品前处理和色谱-质谱分析检测方法，实现对基质成分复杂的实际样品（如环境水样、人体尿液和乳汁）中痕量全氟和多氟类污染物的快速高效分离、富集和测定。本项目的实施可为环境和生物基质中新兴全氟和多氟化合物的实时监测提供技术手段，更可为进一步研究人体暴露水平与不良健康效应之间的关系提供重要依据。

利用静电纺丝技术和表面化学修饰的方法，设计制备了多种新型复合纳米材料，包括氟基金属有机框架UiO-66与聚丙烯腈、胺基/氟基修饰联合修饰金属有机框架-聚丙烯腈、氟化碳纳米管修饰丝素蛋白纳米纤维、磁性葫芦脲纳米颗粒等。将它们用于简便固相萃取方法，实现了对环境、生物等复杂样品基质中全氟多氟化合物，包括全氟多氟烷基羧酸、磺酸、磺酰胺、膦酸等的高效富集和定性定量分析，为痕量污染物检测中灵敏度低、前处理繁琐、高成本的问题提供了解决方法。通过材料表征揭示材料结构、功能基团种类与吸附性能的关系。优化实验条件，并通过多种实际样品测试验证了所建方法的可靠性和优势。基于优化的方法，对生活污水、工厂排放废水以及湖泊水和自来水进行了环境全氟多氟化合物的现状调查。考察了多种潜在全氟多氟化合物暴露来源，包括奶茶、方便面等快餐食品、国产化妆品、个人卫生护理产品，获得了这些消费品全氟多氟化合物分布特征及潜在健康风险，为产品安全和公共卫生监管等提供了科学信息。通过文献梳理和统计学分析，发现全氟多氟化合物与儿童过敏性疾病、儿童接种疫苗后抗体水平、孕产结局、肠道屏障等健康问题之间存在关联。建立了基于近400对母婴样本的出生队列数据库和标本库，收集母血、脐血、胎盘及随访母乳和胎粪样本，同时评估了母乳中多种全氟多氟化合物的污染现状及随时间动态变化的趋势。这些工作为全氟多氟化合物的暴露水平监测、相关卫生决策和疾病预防提供了科学依据。