基于聚酰亚胺-共价有机骨架的固相微萃取纤维的制备及性能研究

The uniform and compact coating will be prepared on the stainless steel substrate with the aromatic polyimide-covalent organic frameworks (PI-COFs) as the functional component and the adhesive PI as the transition layer. Adhesive PI plays an important role in the preparation of high quality fiber because it have good bonding force with metal and can connect with PI-COFs through chemical bonds. The synthesized fiber will be used in solid-phase microextraction (SPME) and combined with high performance liquid chromatography-mass spectrometry (HPLC-MS) for the determination of biogenic amines (histamine, cadaverine) in various foods content. The extraction performance of the fiber will be investigated, including the enrichment efficiency, sensitivity, selectivity and service life. The pore structure, size and the surface chemical environment of PI-COFs will be adjusted and controlled through the reasonable design of monomer. The interaction between PI-COFs and biogenic amines and relationship between the microstructure of PI-COFs and the extraction properties will be analyzed, in order to get the high efficiency, sensitivity,stability of SPME fibers and the efficient ,accurate detection method of biogenic amines in food.

本项目拟以多孔芳香型聚酰亚胺-共价有机骨架（PI-COFs）材料为功能组分，以与金属具有很好的粘结力并且能够与PI-COFs通过化学键相连的聚酰亚胺（PI）胶粘剂为过渡层，在不锈钢纤维基底上制备致密均一，紧密结合的涂层。拟将上述合成的纤维制成可应用于固相微萃取（SPME）的萃取头，并与高效液相色谱-质谱（HPLC-MS）联用，测定食物中各种生物胺（组胺，尸胺等）的含量，考察纤维的萃取性能，包括富集效率、灵敏度、选择性和使用寿命等。通过单体的合理设计调控PI-COFs的孔道形貌、尺寸，以及表面化学环境。解析PI-COFs材料与生物胺的相互作用关系，探讨PI-COFs微观结构与萃取性能之间的构效关系，从而进一步指导新型涂层的SPME纤维的制备，并获得高效率、高灵敏度、高稳定性的SPME纤维，实现食物中各种生物胺的高效准确检测。

本项目将具有2D平面结构的JUC-Z2和PAF-41，以及具有3D金刚石拓扑结构的COF-300和COF-DL229制成了高质量的SPME纤维，作为前处理技术与色谱联用，分别建立了1-萘胺、2-萘胺、苯丙胺、甲基苯丙胺、苯乙胺、羟基苯乙胺的检测方法。优化SPME条件，评价上述建立的分析方法（检出限、线性范围、重复性等），并与其他SPME纤维进行对比，结合孔道性质分析、DFT理论模拟等解释了COFs与上述吸附质之间的相互作用，提出了COFs吸附的主要驱动力，进而揭示了COFs在SPME过程中的主要作用机理。此外，作为项目的延伸，将具有高稳定性的JUC-505进行羧基（-COOH）和胺肟基（-AO）的功能化修饰，并用于水体中重金属离子的富集及去除，并通过DFT理论计算解释其吸附机理。