Molecularly imprinted polymers have received wide attention from various fields owing to their pre-designable, recognition ability, and practicality. However, the disadvantages of the traditional embedding method, which include a slow recognition rate, uneven site recognition, low binding capacity, and incomplete template molecule elution, limit the development of molecular imprinting technology. Surface molecular imprinting techniques have been developed to effectively solve these problems, and different materials are used as carriers in the synthesis of molecularly imprinted polymers. Metal-organic frameworks (MOFs) show great potential as carriers. Because of their high porosity and specific surface area, MOFs can provide a large number of active sites for molecular imprinting, which can improve their detection sensitivity. The variable metal centers and organic ligands of MOF materials can also lead to multiple structures and functions. Numerous types of MOF materials have been synthesized, and the properties of these materials can be tailored by adjusting their pore size and introducing functional groups. MOFs and molecular imprinting technology can be combined to take full advantage of the specific adsorption of molecular imprinting technology and the large specific surface area and multiple active sites of MOFs, thereby expanding the application range of the resulting materials. In this paper, five aspects of the concept of MOF functionalization are discussed: introduction of special ligands, regulation of metal central sites, formation of MOF complexes, derivatization of MOFs, and sacrificial MOFs. The applications of MOF-based molecularly imprinted materials in catalysis, sample pretreatment, drug carriers, fluorescence sensors, and electrochemical sensors are also reviewed. Finally, the existing problems and future development of MOF-based molecularly imprinted materials are discussed and prospected.
分子印迹聚合物具有预定性、识别性和实用性等优点,受到各领域的广泛关注。但传统制备方法包埋法具有识别速率慢、位点不均匀、结合容量低、模板分子洗脱不彻底等缺点,限制了分子印迹技术的发展。为了有效解决上述问题,表面分子印迹合成策略应运而生。随后各种不同的材料作为载体应用于表面印迹聚合物的合成中,其中金属有机框架(MOFs)作为载体表现出极大的潜力。金属有机框架因具有较大的空隙率和较高的比表面积,可以为分子印迹提供大量的印迹位点,有利于提高检测的灵敏度。同时,由于金属中心和有机配体可变,还可以通过调节孔径及引入功能基团等手段,合成不同结构及性能的金属有机框架材料。金属有机框架与分子印迹技术相结合制备的材料同时兼具分子印迹技术特异性吸附和金属有机框架比表面积大、活性位点多的优势,扩大了材料的应用范围。本文从引入特殊配体、调控金属中心位点、生成MOFs复合物、MOFs衍生化、缺陷的MOFs设计等方面介绍了金属有机框架功能化的策略,并综述了MOFs基分子印迹材料在催化、样品前处理、药物载体、荧光传感器和电化学传感器领域的应用,并对MOFs基分子印迹材料存在的问题及未来发展进行了讨论与展望。
Keywords: catalysis; drug carriers; fluorescent sensors; metal-organic frameworks (MOFs); molecular imprinting technology; sample preparation.