Li Wenhao, Zou Ting, Wang Ziyi, Zhang Yuanyuan, Zhang Juan
School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430205, China.
School of Chemistry and Environmental Engineering, Wuhan Institute of Technology, Wuhan 430205, China.
Anal Chim Acta. 2025 Sep 15;1367:344286. doi: 10.1016/j.aca.2025.344286. Epub 2025 Jun 4.
Quercetin, a flavonoid with cis-diol moiety, is widely found in plants and exhibits significant pharmacological properties, including anti-inflammatory, antioxidant, and anti-tumor activities. Efficient adsorption and separation of quercetin from complex matrices are crucial for advancing health and nutrition research. However, the structural diversity of flavonoids poses challenges for their selective separation. Covalent organic frameworks (COFs) have emerged as promising adsorbents due to their high surface area and adsorption performance. However, most imine-linked COFs suffer from poor chemical stability under harsh conditions. There is a need for developing highly stable COFs with selective adsorption capabilities for quercetin and other cis-diol-containing compounds.
A post-synthetic modification strategy was employed to convert COF-366 into a highly stable quinoline-linked boronic acid-functionalized COF (named COF-366-BA) via the aza-Diels-Alder reaction. COF-366-BA exhibited enhanced chemical and thermal stability, withstanding strong acidic and alkaline conditions. Characterization revealed a high specific surface area and excellent crystallinity. After functionalization with BA, COF-366-BA demonstrated superior selective adsorption performance for cis-diol-containing quercetin, adenosine, and naringin, with adsorption mechanisms involving boron affinity, π-π interactions, hydrogen bonding, and hydrophobic effects. Adsorption kinetics, isotherms, and thermodynamics were thoroughly investigated. A DSPE-HPLC method using COF-366-BA as an adsorbent was developed for the selective enrichment and detection of quercetin in black tea. Green metric evaluations including GAPI, Complex GAPI, AGREE, and AGREEprep confirmed the method's eco-friendliness.
This work presents a significant advancement in the design of highly stable and functional COFs for selective adsorption cis-diol-containing compounds. COF-366-BA's robustness and selectivity make it a promising material for the enrichment and detection of cis-diols structural bioactive compounds in complex matrices. The green synthesis approach and practical application of quercetin detection in food and biological samples hold a significant importance in the health and nutrition fields.
槲皮素是一种具有顺式二醇部分的黄酮类化合物，广泛存在于植物中，并具有显著的药理特性，包括抗炎、抗氧化和抗肿瘤活性。从复杂基质中高效吸附和分离槲皮素对于推进健康与营养研究至关重要。然而，黄酮类化合物的结构多样性对其选择性分离构成挑战。共价有机框架（COFs）因其高比表面积和吸附性能而成为有前景的吸附剂。然而，大多数亚胺连接的COFs在苛刻条件下化学稳定性较差。需要开发对槲皮素和其他含顺式二醇的化合物具有选择性吸附能力的高度稳定的COFs。
采用后合成修饰策略，通过氮杂狄尔斯-阿尔德反应将COF-366转化为高度稳定的喹啉连接的硼酸功能化COF（命名为COF-366-BA）。COF-366-BA表现出增强的化学和热稳定性，能耐受强酸性和碱性条件。表征显示其具有高比表面积和优异的结晶度。用BA功能化后，COF-366-BA对含顺式二醇的槲皮素、腺苷和柚皮苷表现出优异的选择性吸附性能，吸附机制涉及硼亲和力、π-π相互作用、氢键和疏水作用。对吸附动力学、等温线和热力学进行了深入研究。开发了一种以COF-366-BA作为吸附剂的DSPE-HPLC方法用于红茶中槲皮素的选择性富集和检测。包括GAPI、Complex GAPI、AGREE和AGREEprep在内的绿色指标评估证实了该方法的生态友好性。
这项工作在设计用于选择性吸附含顺式二醇化合物的高度稳定且功能性的COFs方面取得了重大进展。COF-366-BA的稳健性和选择性使其成为在复杂基质中富集和检测含顺式二醇结构生物活性化合物的有前景的材料。绿色合成方法以及槲皮素在食品和生物样品检测中的实际应用在健康和营养领域具有重要意义。
