高效萃取X-PAHs的功能化共轭多孔聚合物SPME探针的研制及构效关系研究

The widespread polycyclic aromatic hydrocarbons (PAHs) in environment show the properties of strong toxicity and low concentration. Nevertheless, the carcinogenicity and mutagenicity of X-substituted polycyclic aromatic hydrocarbons (X-PAHs) are likely to be a hundred thousand times higher than their parent, resulting in urgent need for the analysis and monitoring of X-PAHs with ultralow concentrations. Solid phase microextraction (SPME), as a kind of sample pre-treatment technique integrating sampling, extraction and injection into one step, has demonstrated the advantages of high level automation, strong anti-interference capability and efficient enrichment, which is very promising to be employed for the high-sensitive analysis of X-PAHs. In this project, a series of functional conjugated porous polymers (CPPs) with high surface area, unique pore structure, different functional groups will be synthesized and prepared as novel SPME fiber coatings by different methods. Moreover, the structure-performance relationship of CPPs between their pore structure, functional group, surface area and adsorption efficiency will be investigated based on the adsorption thermodynamics and kinetics, theoretical calculations and enrichment results. Finally, the CPPs with excellent performance will be designed and synthesized for the preparation of high-efficient SPME fibers, which will be used for high-sensitive analysis of X-PAHs in water sample, as well as in vivo experiment. This project will not only be of great importance to expand SPME application and develop methods with high sensitivity, but also be beneficial for the study of relationship between the microstructure and adsorptive property of CPPs.

环境中广泛分布的多环芳烃具有毒性强、浓度低的特点，而官能团取代多环芳烃(X-PAHs)的致癌和致突变性可增大至母体的数十万倍，迫切需要针对环境中浓度极低的X-PAHs进行分析和监控。固相微萃取(SPME)作为一种集采样、萃取和进样于一体的样品前处理技术，具有绿色环保、自动化程度高、抗基质干扰能力强和富集效率高等优点,十分有潜力用于X-PAHs的高灵敏分析。本项目拟制备具有高比表面、特定孔径和官能团的功能化共轭多孔聚合物，并通过不同方法将其发展为新型SPME探针涂层材料；进而通过吸附热力学和动力学模型、理论计算与富集实验相结合的方法，探明材料的孔径、官能团、比表面积与其对X-PAHs吸附性能之间的构效关系；最终，用于水体和动植物活体中X-PAHs的高灵敏分析。本项目研究有利于探明共轭多孔聚合物的微观结构与吸附性能之间的关系，对拓展SPME应用范围及开发高灵敏环境分析技术也有重要的推动作用。

环境中广泛分布的多环芳烃(PAHs)和官能团取代多环芳烃(X-PAHs)具有毒性强和浓度低的特点，迫切需要发展绿色环保、省时省力的样品前处理技术对其高效富集，以实现高灵敏度分析的目的。本项目旨在基于SPME探讨共轭多孔聚合物对PAHs/X-PAHs的吸附性能与其孔径、官能团、比表面积之间的关系，最终研制出性能优异的共轭多孔聚合物，实现PAHs和X-PAHs的高效富集和高灵敏度分析。.项目完成了系列多孔聚合物的设计、合成与表征，并对其构效关系进行了系统研究，丰富了多孔聚合物对有机污染物的吸附机理；重点研究了将多孔材料制备为SPME器件（探针和薄膜）时，胶粘剂的使用对其萃取性能的影响；基于累积的吸附机理和优化的SPME器件设计方案，研制出高性能多孔聚合物，并将其发展成富集因子高、富集速度快的SPME器件；将新型SPME器件与高灵敏GC-MS、LC-MS/MS联用，实现了多种环境水样、血液及尿样中PAHs和 X-PAHs的高灵敏分析。基于本项目的成果，在Chem. Eng. J.、J. Hazard. Mater、Anal. Chim. Acta等国际主流期刊上共计发表论文7篇，申请专利2项。