多孔有机骨架材料对顺式二醇化合物富集分离的研究进展

基于在碱性环境下硼酸能与顺式二醇化合物可逆共价结合形成稳定的五元或六元环酯,而在酸性环境下环酯开环释放顺式二醇化合物这一特性,设计合成高效、高选择性、高富集性能的硼亲和材料的研究备受关注。近年来,许多研究工作者合成了各种类型的硼亲和材料,应用于高选择性富集顺式二醇化合物。金属有机骨架(MOFs)和共价有机骨架(COFs)由于具有孔径可调、高孔隙率、高比表面积、骨架结构可调和化学及热稳定性良好等特点,被广泛应用于色谱分离和样品前处理领域。为赋予MOFs和COFs材料对顺式二醇化合物的富集选择性,各种不同结构和不同种类的硼酸修饰的MOFs和COFs被合成出来。该综述主要是对近几年来80余篇源于科学引文索引关于硼酸功能化MOFs和COFs的种类、合成方法及其应用文章的总结,包括“金属配体-片段共组装”“合成后修饰”和“自下而上”的硼酸功能化多孔材料的修饰策略,以及硼酸功能化MOFs和COFs的种类,介绍了其在化学分析和生物分析领域的发展概况和应用前景,客观评价了硼酸功能化MOFs和COFs的区别和优缺点。该文旨在让研究人员能够充分了解近几年硼酸功能化多孔有机骨架材料的研究现状、掌握合成思路和方法,为其应用提供一定的理论指导和技术支撑,为加快硼酸功能化多孔有机骨架材料的商业化脚步贡献绵薄之力。

Advances in enrichment and separation of cis-diol-containing compounds by porous organic frameworks

The design and synthesis of boronate affinity materials that show high efficiency, high selectivity, and high enrichment performance have gained significant attention. The principle of boronate affinity relies on the reversible covalent reactions, including the formation of stable five-membered or six-membered cyclic esters with cis-diol-containing compounds in alkaline aqueous media and dissociation of cyclic esters in an acidic surrounding to release cis-diol-containing compounds. Recently, various boronate affinity materials have been synthesized and utilized for selective enrichment of these compounds. Metal organic frameworks (MOFs) and covalent organic frameworks (COFs) have been widely used in chromatographic separation and sample pretreatment because of their adjustable pore size, high porosity, high specific surface area, tunable skeleton structure, and favorable chemical and thermal stability. To promote the enrichment selectivity of MOFs and COFs for cis-diol-containing compounds, boronic acid-functionalized MOFs and COFs with various structures and categories have been synthesized. This review summarizes more than 80 investigations into the categories, synthetic strategies, and applications of boronic acid-functionalized MOFs and COFs from the Science Citation Index. These synthesis methods include metal ligand-fragment co-assembly, post-synthetic modification, and bottom-up modification of boronic acid-functionalized porous materials. Although two modification strategies (post-synthetic and metal ligand-fragment co-assembly) have been introduced for the preparation of boronic acid-functionalized MOFs, the latter is more commonly adopted as it improves the enrichment selectivity and enrichment efficiency of MOFs. The common limitations of MOFs such as aggregation and aperture issues were also resolved. Boron affinity MOFs possessing favorable properties according to the characteristics of cis-diol-containing compounds, have also been synthesized. Furthermore, to facilitate enrichment and separation, many boronic acid-functionalized magnetic material MOFs have been developed for the enrichment and analysis of cis-diol-containing compounds. Additionally, the luminescent properties of Ln-MOFs have been used in combination with boronic acid affinity for the enrichment, separation, and subsequent detection of cis-diol-containing compounds. Post-synthetic modification and the bottom-up strategy are the primary methods for the preparation of boronic acid-functionalized COFs. Boronic acid-functionalized COFs are less investigated than boronic acid-functionalized MOFs, likely due to the greater complexity of COF synthesis. This work aims to summarize the research advances, synthesis ideas, and synthesis methods related to boric acid-functionalized porous organic frameworks, which will provide theoretical guidance and technical support for its applications while accelerating the commercialization of such organic frameworks.