基于3D泡沫金属/非金属的新型固相萃取方法的构建及在污染物分析中的应用

Solid-phase extraction (SPE) is the most popular sample preparation technique for enrichment and separation in one step, and the key is the adsorbent. For the past few years, some new adsorbents had been promoted the development of SPE, but there existed some deficiencies such as expensive, inadequacy recycle, loss in reuse and difficulty in separation. The number of new SPE adsorbents commercially available is much less than that of microcolumn adsorbents. 3D foam metal/metalloid has the advantages of large surface area, light weight, high strength and easy to be separated from matrix and so on, with bonding of the specific functional groups on the surface can achieve effects of high efficiency and selective adsorption. Based on the preliminary work, this project plans to prepare modified 3D foam with alkyl, aryl, cholesterol, graphene and metal frame compounds, then characterized by means of electron microscopy, X-ray photoelectron spectroscopy and infrared spectroscopy. The adsorption effect and mechanism would be described in detail including the effects of adsorbent amount, sample pH, ion interference and so on. Finally, the adsorption of environmental pollutants was investigated. The project will expand the new SPE method and open up new avenues for the commercialization of new adsorbents.

固相萃取（SPE）集富集、分离于一步，是最常用的样品前处理技术，吸附剂是该技术的核心。近年来发展的吸附剂仍存在成本高、回收不完全、再利用有损失、不易分离等缺点。市面上商品化的新型SPE吸附剂数目远少于传统微柱式吸附剂。3D泡沫金属/非金属具有比表面积大、质轻、强度高、易与基质分离等优点，申请者率先将3D泡沫镍引入SPE，在其表面键合特异性官能团，显示出高效、选择性吸附效果。本项目拟在前期工作基础上，系统制备烷基、芳基、胆固醇及石墨烯、金属框架化合物等改性的3D泡沫新型吸附剂，利用电镜、X射线光电子能谱、红外光谱等手段表征其结构，阐述其结构与性能的关系；详细研究吸附剂用量、样品pH值、离子干扰、样品量等参数对萃取效率的影响，探索其吸附效果和机制，最后应用于对环境污染物的吸附作用。该项目将拓展SPE新方法，为新型吸附剂的商品化研制开辟新的途径。

样品前处理是样品分析过程中的关键步骤，对于复杂样品如中药，由于基体干扰的复杂性和多样性，痕量或超痕量待测组分的分离、富集需要高亲和力、高选择性的样品前处理技术。固相萃取（SPE）集富集、分离于一步，是最常用的样品前处理技术，而吸附剂是该技术的核心。近年来发展的吸附剂仍存在成本高、回收不完全、再利用有损失、不易分离等缺点。本项目将3D泡沫镍引入SPE，结合 3D泡沫镍的比表面积大、质轻、强度高、易与基质分离等优点，制备了胆固醇、石墨烯及二苯基功能化的泡沫镍复合材料，建立了基于泡沫镍吸附剂的固相萃取技术，与气相色谱-质谱联立，实现了多种中药复杂样品中痕量污染物多环芳烃的分离富集和检测分析。采用正硅酸四乙酯包覆、3-氨基丙基三乙氧基甲基硅烷功能化、胆固醇改性的方法制备了胆固醇包覆泡沫镍。联合气相色谱-质谱联用技术分析中药大青叶中16种多环芳烃(PAHs)污染物。检出限为0.6-11.5ng/mL。采用原位合成法制备石墨烯功能化的泡沫镍吸附剂材料，建立固相萃取与气相色谱-质谱联用（GC-MS）相结合的方法，对5种中药即蒲公英、枳壳、薄荷、桑叶和胎菊样品中的PAHs进行分离富集和检测分析，检测限（LOD）为0.01-0.11 ng/mL。 制备二苯基功能化泡沫镍新型吸附剂，并将其用于中药材中外源性多环芳烃（PAHs）污染物的分析。检出限(LODs)为0.5-7.6 ng mL-1，加样回收率为83-110%。项目成果对于中药样品中污染物分析及样品前处理技术的发展具有重要意义。