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These affinity polymeric materials are specifically engineered to interact with target molecules, demonstrating high affinity and selectivity. The unique properties of scCO2, which present both liquid\u2013 and gas\u2013like properties and an accessible critical point, offer an environmentally\u2013friendly and highly efficient technology for the synthesis and processing of polymers. The design and the synthesis of affinity polymeric materials in scCO2 involve several strategies. Commonly, the incorporation of functional groups or ligands into the polymer matrix allows for selective interactions with target compounds. The choice of monomer type, ligands, and synthesis conditions are key parameters of material performance in terms of both affinity and selectivity. In addition, molecular imprinting allied with co\u2013polymerization and surface modification are commonly used in these strategies, enhancing the materials\u2019 performance and versatility. 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