用于复杂基质中痕量有害物质特异性识别、富集的新型杯(杂)芳烃固相萃取技术研究

In the project, a series of functionalized heterocalixarenes will be synthesized, and then novel solid-phase extraction materials will be prepared by bonding the heterocalixarenes onto silica gel or organic substrate surface. The recognition and enrichment ability of the functionalized heterocalixarenes solid phase extraction (SPE) materials for trace hazards will be studied, the target analytes including sulfonamides, fluoroquinolones, imidazole, nitrogen-containing organic pesticides in the foods, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and nitro-substituted benzenes in environmental samples. The effect of thermodynamics and kinetics parameters in the extraction process will be studied, the enrichment performance of the SPE materials will be clarified based on the structures of heterocalixarene and the target analytes. Quantum chemical calculation method will be introduced to study the intercation between the novel heterocalixarene materials and target analytes, the specific recognition of heterocalixarene toward guest molecules meodels, efficient extraction and enrichment models will be constructed. By introducing specific functional groups onto the main skeleton of heterocalixarene and adjusting the cavity size of the main structure, the design of the molecular structure will be optimized, which will guide the synthesis of new heterocalixarene SPE materials, and increase the enrichment efficiency. By using GC, CE, LC, GC-MS, LC-MS and other techniques, the enrichment and analytical methods of trace hazards in food, environment and other real samples will be studied.

本项目合成一系列具有不同功能化基团的杯(杂)芳烃，将杯(杂)芳烃键合到硅胶或有机基质表面制备新型的固相萃取材料；研究功能化杯(杂)芳烃萃取材料对食品中痕量磺胺、氟喹诺酮、咪唑类药物、含氮有机农药等，环境样品中多环芳烃、硝基取代苯、多氯联苯等有害物质的的识别能力和富集效果；探讨各种热、动力学参数对目标物的萃取效率的影响，阐明杯（杂）芳烃、目标物结构与富集效能之间的关系；采用量子化学计算方法研究固相萃取材料与目标化合物分子间的相互作用机制，构建杯（杂）芳烃对客体分子特异性识别、高效萃取和富集的模型；在杯杂（芳）烃主体结构中引入特定的功能团，调节杯芳烃结构空腔大小，优化分子结构设计，指导新的杯（杂）芳烃固相萃取材料的合成，提高富集效率。结合GC、CE、LC、GC-MS和LC-MS等手段，研究食品、环境等实际样品中痕量有害物质的富集、分离分析新方法。

本项目制备了10种不同功能化基团的杯(杂)芳烃，2种固相萃取材料和2种以Fe3O4@SiO2为核的磁性纳米材料（ Fe3O4@SiO2@NCS and Fe3O4@SiO2@MAsp-HEMA）；并利用Gaussian 09程序的DFT/B3LYP/6–31+G基组研究分析了目标化合物（咖啡因，植物生长激素等）与杯芳烃固相萃取材料之间的识别富集作用机理。结果表明，杯芳烃固相萃取材料与目标化合物之间存在多重相互作用，包括π-π作用，包结作用，氢键作用等，功能化的杯芳烃材料对含苯环、羟基、硝基、氨基类的化合物具有优异的识别作用，富集效率高。结合GC、CE、LC、GC-MS和LC-MS等手段，我们开发建立了10种食品、环境、生物体液等实际样品中痕量有害物质的富集、分离分析新方法。取得的结果令人满意，且具有潜在的应用价值。