Design of Molecularly Imprinted Polymers Using Supercritical Carbon Dioxide Technology.

The design and development of affinity polymeric materials through the use of green technology, such as supercritical carbon dioxide (scCO2), is a rapidly evolving field of research with vast applications across diverse areas, including analytical chemistry, pharmaceuticals, biomedicine, energy, food, and environmental remediation. 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- and gas-like properties and an accessible critical point, offer an environmentally-friendly 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-polymerization and surface modification are commonly used in these strategies, enhancing the materials' performance and versatility. This review aims to provide an overview of the key strategies and recent advancements in the design of affinity polymeric materials using scCO2.

Biomolecular Fishing: Design, Green Synthesis, and Performance of l-Leucine-Molecularly Imprinted Polymers.

Biopurification is a challenging and growing market. Despite great efforts in the past years, current purification strategies still lack specificity, efficiency, and cost-effectiveness. The development of more sustainable functional materials and processes needs to address pressing environmental goals, efficiency, scale-up, and cost. Herein, l-leucine (LEU)-molecularly imprinted polymers (MIPs), LEU-MIPs, are presented as novel biomolecular fishing polymers for affinity sustainable biopurification. Rational design was performed using quantum mechanics calculations and molecular modeling for selecting the most appropriate monomers. LEU-MIPs were synthesized for the first time by two different green approaches, supercritical carbon dioxide (scCO2) technology and mechanochemistry. A significant imprinting factor of 12 and a binding capacity of 27 mg LEU/g polymer were obtained for the LEU-MIP synthesized in scCO2 using 2-vinylpyridine as a functional monomer, while the LEU-MIP using acrylamide as a functional monomer synthesized by mechanochemistry showed an imprinting factor of 1.4 and a binding capacity of 18 mg LEU/g polymer, both systems operating at a low binding concentration (0.5 mg LEU/mL) under physiological conditions. As expected, at a higher concentration (1.5 mg LEU/mL), the binding capacity was considerably increased. Both green technologies show high potential in obtaining ready-to-use, stable, and low-cost polymers with a molecular recognition ability for target biomolecules, being promising materials for biopurification processes.

MIP Synthesis and Processing Using Supercritical Fluids.

Supercritical fluid technology provides a clean and straightforward way for the preparation of high affinity polymeric materials. Molecularly Imprinted Polymers (MIPs) as dry, free-flowing powders are obtained in a one-step synthetic route yielding molecular recognition materials for several applications. Herein, we describe the experimental procedures involved in the scCO2-assisted MIP development: synthesis, template desorption, impregnation, and membrane preparation. MIP applications are described putting in evidence the advantages of MIP development using supercritical fluid technology.