Molecularly imprinted polymers： novel green preparation methods and cutting-edge applications review

Molecular imprinting technology is an emerging technique that achieves specific recognition of imprinted molecules by simulating the interactions between antibody and antigen or between enzyme and substrate. The core of this technology lies in the preparation of molecularly imprinted polymers （MIPs）. However， traditional preparation methods of MIPs face severe challenges due to drawbacks such as uneven morphology， limited conformational choices for molecular recognition， random and uncontrollable polymerization， and environmental safety hazards， making the innovation of synthesis methods urgent. In recent years， with the proposal of green chemistry concepts and the development of green synthesis methods， the preparation technology of MIPs has gradually transitioned towards resource-saving and environment-friendly directions. The preparation of green molecularly imprinted polymers （GMIPs） aims to replace traditional methods by reducing the use of solvents and the generation of waste liquids during the synthesis process， employing safe and non-toxic reagents and solvents， and developing efficient synthesis methods to improve energy efficiency. Green solvents such as water， supercritical carbon dioxide， deep eutectic solvents， and ionic liquids are used to replace organic solvents in the synthesis of traditional MIPs. Functional monomers with biocompatibility and environmental friendliness， including chitosan， cellulose， itaconic acid， dopamine， and cyclodextrin， have found increasing applications in the preparation of MIPs. In addition， the preparation technology of MIPs is gradually transitioning towards resource conservation and environmental friendliness. The development of novel synthesis methods such as green precipitation polymerization， microwave-assisted synthesis， supercritical fluid technology， ultrasound-assisted polymerization， and computer simulation-assisted design and characterization has promoted the popularity of GMIPs preparation methods. These novel preparation methods significantly improve the functionality and environmental compatibility of MIPs by precisely regulating reaction conditions， reducing energy consumption， and minimizing harmful by-products. They not only optimize the synthesis efficiency of MIPs， but also provide new ideas for solving the bottlenecks of traditional methods in morphology control and large-scale production. GMIPs， with their high selectivity， stability， and tunability， have shown breakthrough applications in multiple frontier fields. For example， in environmental monitoring， GMIPs are applied to detect heavy metal ions （such as lead and arsenic）， organic pollutants （such as pesticides and antibiotics）， and explosives in aqueous environments. In the field of food safety analysis， GMIPs enable efficient enrichment and detection of trace pollutants （such as pesticide residues， veterinary drugs， and mycotoxins） in food matrices， significantly outperforming traditional methods. In biomedical applications， GMIPs are developed as drug controlled-release systems， biomarker detection platforms， and targeted therapeutic carriers. In addition， the efficient performance of GMIPs in sample pretreatment （such as solid-phase extraction） further reduces analysis costs and reduces reliance on organic solvents. This paper reviews the novel preparation methods of GMIPs and their applications in environmental monitoring， food safety， and biomedicine in recent years， and provides an outlook on the development of GMIPs.

分子印迹技术（Molecular imprinting technology）是一种新兴技术，通过模拟抗体与抗原、酶与底物之间的相互作用，实现对印迹分子的特异性识别。该技术的核心在于分子印迹聚合物（MIPs）的制备。然而，传统MIPs制备方法存在形貌不均一、分子识别构象选择受限、聚合过程随机且不可控、存在环境安全隐患等缺陷，面临严峻挑战，因此开发新型合成方法迫在眉睫。近年来，随着绿色化学理念的提出与绿色合成方法的发展，MIPs制备技术逐渐向节约资源、环境友好的方向转型。绿色分子印迹聚合物（GMIPs）的制备旨在通过减少合成过程中溶剂使用与废液产生、采用安全无毒的试剂与溶剂、开发高效合成方法以提升能源利用效率，来替代传统制备方法。研究人员采用水、超临界二氧化碳、低共熔溶剂、离子液体等绿色溶剂，替代传统MIPs合成中的有机溶剂。壳聚糖、纤维素、衣康酸、多巴胺、环糊精等具备生物相容性与环境友好性的功能单体，在MIPs制备中的应用日益广泛。此外，MIPs制备技术正逐步向节约资源与环境友好的方向发展。绿色沉淀聚合、微波辅助合成、超临界流体技术、超声辅助聚合、计算机模拟辅助设计与表征等新型合成方法的开发，推动了GMIPs制备方法的普及。这些新型制备方法通过精准调控反应条件、降低能耗、减少有害副产物生成，显著提升了MIPs的功能特性与环境相容性。它们不仅优化了MIPs的合成效率，更为解决传统方法在形貌调控与大规模生产中的瓶颈问题提供了新思路。GMIPs凭借其高选择性、稳定性与可调控性，在多个前沿领域展现出突破性应用。例如在环境监测领域，GMIPs可用于检测水环境中的重金属离子（如铅、砷）、有机污染物（如农药、抗生素）与爆炸物；在食品安全分析领域，GMIPs能够对食品基质中的痕量污染物（如农药残留、兽药、真菌毒素）实现高效富集与检测，性能显著优于传统方法；在生物医学应用中，GMIPs被开发为药物控释系统、生物标志物检测平台与靶向治疗载体。此外，GMIPs在样品前处理（如固相萃取）中的优异表现，进一步降低了分析成本，减少了对有机溶剂的依赖。本文综述了近年来GMIPs的新型制备方法及其在环境监测、食品安全与生物医药领域的应用，并对GMIPs的发展前景进行了展望。