基于金属掺杂石墨烯的环境样品中多溴联苯醚及其类似物分析方法的研究

由于PBDEs具有较高亲脂性，化学性质稳定，可远距离传输，并能通过食物链进行累计放大，在生物体内蓄积产生毒性，该类物质产生的污染问题和对人类健康构成的威胁受到高度关注。因具有生物累计和放大作用，即使微量PBDEs进入环境，也会使处于高营养级的人类受到毒害。所以为保障生态安全和人类健康，必须发展高效灵敏的分析技术。但由于PBDEs样品所处基体复杂、易受环境影响、含量非常低，因此必须加大对该类物质的样品前处理技术研究。石墨烯由于具有超大比表面积，完美杂化结构、大π-π共轭体系和富电子疏水特性，被认为是样品前处理领域中的一颗新星，但由于性质稳定，其应用受到一定限制，元素掺杂被认为是有效改善其物化性质的方式之一。本项目拟通过制备金属掺杂石墨烯并结合固相萃取和固相微萃取等样品前处理技术，建立基于色谱、质谱技术的环境样品中超痕量PBDEs及其类似物的分析方法，为生态环境安全和人类健康提供基础保障。

Due to good flame-retardant properties, polybrominated diphenyl ethers (PBDEs) are widely used as additives in many types of consumer goods, such as plastics, electronics, textiles, and construction material. PBDEs pose great risk to the environment and human health because of their high persistence, high toxicity, lipophilic property and ability to get into the environment easily owing to the lack of chemical bonds with the matrix of materials. Due to high bioaccumulation, monitoring the presence of PBDEs in ecological systems at very low concentration levels is becoming more and more important. Graphene, a one-atom thick and two-dimensional carbon nanomaterial, has attracted intense interest for its unusual physical properties and great potential in various applications. Recently, graphene was considered as an excellent adsorbent in analytical sample preparation because of its exceptional properties including large surface area, π-electron-rich structure, as well as good thermal and chemical stability. Theoretical study of binding of metal-doped graphene sheet with dioxin demonstrated that graphene sheet can be effective adsorbents for dioxin moleculars in the presence of calcium atoms. This is due to cooperative formation of sandwich complexes of graphene sheet through the interaction π-Ca-π with the total binding energy of more than 3 eV. Therefore, the aim of the present project is to development of new methods by using metal-doped graphene as an absorbent for preconcentration of trace PBDEs as well as their methoxylated (MeO-) and hydroxylated (OH-) analogs from environmental samples. In this proposal, three experimental protocols based on metal-doped graphene as an sbsorbent in sample preparation were designed for the anlysis of PBDEs from environmental samples. For the first two experiment schemes, metal-doped graphene was used as an absorbent of solid-phase extraction (SPE) and coating of solid-phase microextraction (SPME) with sol-gel method, respectively.GC-MS and LC-MS methods coupling SPE and SPME with metal-doped graphene as an absorbent were developed for the analysis of he analysis of PBDEs. In the third protocol, metal-doped graphene was dispersed to environmental samples, and then metal-doped graphene was collected with certification and detected by MALDI- TOF MS. In this experiment, metal-doped graphene was used as not only absorbent for PBDEs as well as their methoxylated (MeO-) and hydroxylated (OH-) analogs, but also assisted matrix for MALDI-TOF MS that could eliminate interference from traditional matrix in low molecular weight region. In summary, the main aim of this research project is development of some new sensitive methods for the analysis of PBDEs as well as their methoxylated (MeO-) and hydroxylated (OH-) analogs by using metal-doped graphene as absorbent with increased interaction between graphene and analytes in presence of metal atoms.