基于COFs材料磁固相萃取技术的食品中晚期糖基化终末产物分析研究

Advanced glycation end-products (AGEs) exist in foods widely and could cause a variety of foodborne diseases. Thus, the analysis study on AGEs in foods is very important. Commercial solid phase columns usually have been used to purify food samples, which show some limitations, such as lower adsorption capacity, poorer selectivity, more complicated operation, etc. A magnetic nanoparticles doping on sulfonic acid functionalized covalent organic frameworks (COFs) porous materials will be synthesized in this work, which will be used in the magnetic solid phase extraction (MSPE) technique for AGEs in foods. Coupled with high performance liquid chromatography time of flight mass spectrometry (HPLC-TOF-MS) and high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) techniques, the qualitative and quantitative analysis methods of various AGEs in foods will be established. Selectively high efficiency adsorption of AGEs in foods will be achieved since macromolecule compounds such as proteins will be eliminated for the pore size confinement effect of COFs, and electronegative compounds will be eliminated owing to the sulfonic acid groups. The influence of MSPE conditions on extraction efficiency will be investigated for the preliminary study on extraction mechanism. The characterization of analytical method will be investigated also. The types and amounts of different AGEs in typical foods in Chinese resident diet (meat, drink, milk, tobacco, etc) will be studied. It would be as a technical support and data accumulation for the health risk assessment of AGEs in foods.

晚期糖基化终末产物（AGEs）广泛存在于食品中，引发多种食源性疾病。分析食品中AGEs具有重要的意义，其样品净化通常采用商品化固相萃取柱，存在吸附容量低、选择性较差、操作复杂等问题。本项目拟合成磁性纳米粒子掺杂磺酸基功能化的COFs多孔材料，建立食品中AGEs高效、高选择性的磁固相萃取技术（MSPE）；并结合高效液相色谱-飞行时间质谱和高效液相色谱-串联质谱技术，建立食品中多种AGEs定性、定量分析方法。旨在分别利用COFs孔径限域作用和磺酸基的静电作用排除蛋白质等大分子和负电性化合物的吸附，实现食品中AGEs选择性高效富集。考察MSPE条件对萃取效率的影响，对萃取机制进行初步探讨，对分析方法进行表征。采用所建立的分析方法考察中国居民膳食中典型食品（包括肉类、饮料、乳制品、烟草等）中AGEs种类及含量水平差异，为准确评估食品中AGEs的健康风险提供技术支撑和数据积累。

本项目首次采用基于磁性纳米粒子掺杂的COFs材料（Fe3O4@COF（TpTph））的磁固相萃取技术实现了烘焙食品中2种AGEs（CML和CEL）衍生物的选择性高效富集，结合HPLC-MS/MS法实现了烘焙食品中CML和CEL的定量分析，比较了不同烘焙食品中AGEs含量差异，所建立的方法表现出基质效应低、回收率高、精密度高、检出限低等优点。同时，本项目建立了一种阳离子交换固相萃取柱净化-HPLC-MS/MS法测定口含烟制品中CML和CEL游离态和总量的定量分析方法，并首次对不同类型口含烟制品进行了普查分析。另外，本项目采用所建立的阳离子交换固相萃取柱净化-HPLC-MS/MS分析方法还考察了不同焙烤条件（如焙烤温度、焙烤时间）对花生中CML、CEL及中间体乙二醛（GO）、丙酮醛（MGO）含量的影响，并研究了酚酸种类和浸渍浓度对焙烤花生中CML和CEL形成的影响。本项目所建立的磁性COFs材料磁固相萃取技术适用于复杂基质中痕量化学成分的富集分离，同时本项目为食品加工过程中AGEs的控制和抑制提供了科学的数据支撑。