[Recent progress in constructions and applications of chiral porous framework-based chromatographic stationary phases].

Abstract

Chirality， as an inherent property of nature， plays a central role in the complexity and precision of biological systems. The stereochemistry of molecules profoundly impacts their pharmacological activities， metabolic pathways， and toxicological effects. Enantiomers， which are mirror-image forms of the same compound， often exhibit significantly different behaviors， making the accurate separation and trace analysis of racemates crucial in modern pharmaceutical research， as well as in the production of high-value chiral intermediates. The precise enantioseparation of compounds has therefore become an essential component of drug development， environmental monitoring， and chemical synthesis. Among various separation methods， chiral chromatography has emerged as the most dominant technique due to its high efficiency， versatility， and rapid analytical capabilities. Conventional chiral stationary phases （CSPs） have been primarily based on materials such as polysaccharides， proteins， and synthetic polymers. However， recent advancements in materials science have led to the development of chiral porous frameworks， particularly metal-organic frameworks （MOFs） and covalent organic frameworks （COFs）， which offer remarkable advantages. These materials feature ultra-high surface areas， well-ordered porous structures， and tunable chiral microenvironments， making them ideal candidates for the next generation of chiral stationary phases in chromatography. This review provides a comprehensive summary of the recent progress made by domestic scholars from 2023 to 2025 on the application of MOFs and COFs in chiral separation， specifically in high performance liquid chromatography （HPLC）， gas chromatography （GC）， and capillary electrochromatography （CEC）. It begins by discussing the construction strategies for these chiral porous frameworks， highlighting their synthesis and functionalization methods. Next， it focuses on the preparation techniques for incorporating these materials into chromatographic stationary phases， emphasizing the challenges and innovations involved in optimizing their performance. The review then examines the practical applications of MOFs and COFs in the separation of racemates， showcasing their use in the enantioseparation of pharmaceuticals， agrochemicals， and natural products. The separation performance is evaluated based on key metrics such as resolution， selectivity， and enantioselectivity. Comparisons with traditional commercial columns highlight the superior performance of MOF- and COF-based stationary phases， including their higher efficiency， broader selectivity， and better adaptability to a wider range of compounds. Finally， the review discusses the future directions and challenges in the field. These include the need for scalable synthesis methods， enhancing the stability of MOFs and COFs under practical chromatographic conditions， and improving the selectivity of these materials. Future research may also focus on hybrid MOF-COF composites， further functionalization techniques， and the integration of these materials with advanced detection technologies to broaden their applications. Indeed， this review aims to provide an insightful summary of the current state of chiral separation materials， particularly MOFs and COFs， offering a valuable resource for researchers in this field. We hope this work will inspire future innovations， driving the advancement of chiral separation technologies to new levels of precision and efficiency.