基于表面分子印迹石墨烯整体纤维阵列固相微萃取的有机磷酸酯阻燃剂环境分析新方法

The increasing amount of organophosphate flame retardants (OPFRs) attracted great attention worldwide. It is urgent to develop the simultaneously efficient enrichment and analytical method of many OPFRs in the environment. Although solid phase microextraction (SPME) was always applied in the pretreatment of the residual analysis of environmental pollutants, the non-imprinted fiber of SPME has some disadvantages, such as brittle and broken, long extraction equilibrium time and low extraction amount when the fiber was applied to sampling and enrichment in environment. The traditional molecularly imprinted coating of SPME is easy to be fallen off, and it is difficult to be accessible and to be desorbed because of the location of imprinted sites are deep. All this can not meet the requirements of environmental analysis of OPFRs. The project planed to assemble the two dimensional graphene oxide and the molecularly imprinted polymer of OPFRs to three dimensional surface molecularly imprinted fibers. It will be clarified the structure-function relationship between the structure of OPFR molecularly imprinted graphene fiber and the performance of SPME, then further to assemble OPFRs surface imprinted graphene fibers array. We will study systematically the SPME performance of different fibers array to realize the fast enrichment of OPFRs in the real environment and develop the new environmental analytical method based on SPME of the surface molecularly imprinted graphene fibers array coupled to GC/MS. We hope the study will provide the analytical method for the pollution status and environmental behaviour of OPFRs.

有机磷酸酯阻燃剂（OPFRs）用量持续增长引起了广泛关注，其环境行为研究迫切需要发展真实环境中多种OPFRs同时高效富集和分析方法。虽然固相微萃取（SPME）常用于环境污染物残留分析前处理，但无分子印迹的SPME纤维环境采样富集时易折断，萃取平衡时间长且容量低；而传统SPME分子印迹涂层易脱落，印迹位点深难以接近和脱附，无法满足OPFRs环境分析需求。本项目拟将二维氧化石墨烯和OPFRs分子印迹聚合物组装成三维表面分子印迹石墨烯纤维，阐明OPFR分子印迹石墨烯纤维结构与固相微萃取效果之间的构效关系，进一步组装出OPFRs表面分子印迹石墨烯整体纤维阵列，系统研究模拟环境条件下不同纤维阵列固相微萃取效果，实现环境中不同OPFRs的快速富集，并与GC/MS联用，建立基于表面分子印迹石墨烯整体纤维阵列固相微萃取的OPFRs环境分析新方法。籍此研究为OPFRs的污染现状和环境行为研究提供分析方法。

石墨烯表面有机磷酸酯阻燃剂分子印迹聚合物整体纤维阵列固相微萃取-气相色谱/质谱检测新方法的建立为环境中痕量的不同种类、不同性质有机污染物的高选择性、高灵敏、高通量同时测定提供了新途径。本项目四年来以整体纤维阵列固相微萃取环境分析新方法的建立为目标，开展了不同有机磷酸酯阻燃剂的分子印迹聚合物石墨烯整体纤维的研制及其在环境中有机磷酸酯阻燃剂的检测等应用研究工作。取得的主要研究成果包括（1）研制成功了石墨烯表面磷酸三甲酯分子印迹聚合物整体纤维及其石墨烯表面非分子印迹聚合物整体纤维、石墨烯表面磷酸三苯酯分子印迹聚合物整体纤维及其石墨烯表面非分子印迹聚合物整体纤维、石墨烯表面磷酸三（2-氯乙基）酯分子印迹聚合物整体纤维及其石墨烯表面非分子印迹聚合物整体纤维、石墨烯整体纤维及石墨烯掺杂的聚合物整体纤维等固相微萃取整体纤维，并建立了磷酸三甲酯分子印迹聚合物纤维、石墨烯掺杂的聚合物纤维、石墨烯表面磷酸三苯酯分子印迹聚合物纤维和气相色谱质谱联用测定环境中痕量有机磷酸酯阻燃剂的分析方法。（2）将各种石墨烯表面有机磷酸酯阻燃剂分子印迹聚合物整体纤维按各自最佳萃取模式组合成萃取阵列，建立了同时测定不同种类、不同性质有机磷酸酯阻燃剂的高选择性、高灵敏、高通量的新方法。（3）在包括Chemical Communications, Analytica Chimica Acta, Journal of Chromatography A, RSC Advance, Journal of Separation Science (Front cover) 等国际学术刊物发表论文6篇，申请专利3项，申请号分别为201910655156.6, 201910536776.8，201910553146.1.，并参加国内外学术会议13次。（4）通过本项目的研究，培养硕士研究生6人。