基于巯基点击聚合反应制备新型有机聚合物整体柱及应用研究

The chromatographic column, honored as the “heart” of chromatographic technique, is always one of research focuses in chromatographic field. As a kind of novel separation medium, monolithic column has developed in the recent decade. Due to the merits of easy preparation, wide pH tolerance and so on, organic monolith played vitally important roles in pretreatment and analysis of complicated samples in HPLC. However, the organic monolith presents poor chromatographic resolution and column efficiency for small molecules especially in isocratic elution. It is urgently necessary to improve the chromatographic efficiency of organic monolith. Although great efforts have been made on the thiol-based click chemistry, especially in reactivity, controllability and specificity, there are very few papers on the direct fabrication of monolithic columns via thiol-based click polymerization reaction. More recently, fast preparation of two kinds of organic monoliths with high column efficiency for small molecules was successfully developed via photo-initiated thiol-yne click polymerization. In this project, based on the success of thiol-yne click chemistry, the applicant will focus on further developing novel methods to fabricate well-controlled 3D skeletal organic monolithic materials via thiol–epoxy, thiol–ene and thiol–yne click reactions and so on. It is expected the efficiencies of the novel organic monolithic columns would be superior to those of common organic monolithic columns via free-radical polymerization, and reach or be superior to those of silica-based monolithic columns. The resulting organic monolithic columns will be applied for highly efficient separation and analysis of complicated environmental samples with HPLC-MS. The research results of this project will potentially extend the innovative approaches to fabricate novel monolithic columns, which are also expected to pioneer the research field of preparation and application of monolithic materials.

色谱柱被誉为色谱技术的“心脏”,一直是色谱研究的热点。整体材料是近十年来发展起来的一种新型色谱分离介质，其中有机整体柱具有制备简单和pH使用范围宽等优点，已经在复杂样品的预处理和高效液相色谱分析中发挥重要作用。但是有机整体柱存在对小分子化合物的分离柱效低的缺点，迫切需要开发新型性能优良的有机整体柱。虽然针对巯基的点击化学的反应活性、可控性和专一性等方面已有大量的研究，但直接应用于制备多孔整体材料却鲜有报道。本项目拟在我们前期发展的采用光引发巯基-炔聚合反应快速制备新型高柱效的有机整体柱的基础上，继续深入开展基于巯基-炔/烯/环氧等点击聚合反应制备新型毛细管有机聚合物整体柱的研究，发展和建立快速、简便、高效的有机整体柱制备方法，最后与质谱联用实现复杂环境样品的分离分析。该项工作的实施可以极大拓宽整体材料制备的思路，其研究成果有望为整体柱的制备和应用开辟新的研究方向。

色谱柱被誉为色谱技术的“心脏”,一直是色谱研究的热点。整体材料是近十年来发展起来的一种新型色谱分离介质，其中有机整体柱具有制备简单和pH使用范围宽等优点，已经在复杂样品的预处理和高效液相色谱分析中发挥重要作用。但是目前有机整体柱存在对小分子化合物的分离柱效低的缺点，迫切需要开发新型性能优良的有机整体柱。虽然针对巯基的点击化学的反应活性、可控性和专一性等方面已有大量的研究，但直接应用于制备多孔整体材料却鲜有报道。通过本项目的资助，我们在有机整体柱的制备方法和应用方面取得了重大进展，（1）建立以多巯基硫醇为原料，与二元或多元烯/炔等光引发聚合快速制备毛细管有机整体柱的新方法；(2) 建立碱催化巯基马来酰亚胺点击化学聚合反应体系制备有机整体柱的新方法，并在cLC中柱效达到140,000 N/m以上，最高可达到180,500 N/m；(3)通过考察制备条件对整体材料相分离、形貌和结构等方面的影响规律，发展建立了多级孔道整体材料制备的新方法；(4)建立离线和在线样品预处理方法，实现复杂生物样品和环境样品的高通量和高灵敏度分析。并且还发展和建立了多种制备过程简便、性能优良的杂化整体材料制备新方法，极大地拓宽了整体材料的制备方法，为整体柱的研制和应用开辟新的方向。至今已在国内外学术刊物上发表SCI论文18篇（均标注基金号），其中8篇IF>5.0，包括在Advanced Materials 1篇、Analytical Chemistry 2篇、Trends in Analytical Chemistry 1篇、Journal of Hazardous Materials 2篇、和Analytica Chimica Acta 2篇。正申请中国发明专利16件。