Computer Simulation-Guided Rational Design of Sulfadiazine-Imprinted Polymers for High-Efficiency Adsorption of Antibiotics in Complex Aquatic Matrices

To address the limited selectivity of conventional membrane materials toward sulfonamide antibiotics, this study employed a DFT calculation approach to optimize the design of a molecularly imprinted system for sulfadiazine (SDZ). A hierarchical set of template molecules—aniline (ANL), sulfanilamide (SNM), and SDZ—was introduced to systematically elucidate structure-dependent template–monomer matching mechanisms in sulfonamide imprinting systems. Through rational screening, trifluoroethyl methacrylate (TFEMAA) was identified as the optimal functional monomer, with an optimal imprinting molar ratio of 1:4 (SDZ to TFEMAA). Guided by the simulation results, SDZ molecularly imprinted polymers (MIPs) were synthesized via precipitation polymerization and systematically characterized for their morphology and recognition properties. The MIPs exhibited a well-defined spherical morphology with abundant imprinted cavities, achieving adsorption equilibrium within 1.5 h. The adsorption kinetics followed a pseudo-second-order model, indicating a chemisorption-dominated process. Scatchard analysis revealed the presence of both high- and low-affinity binding sites in the MIPs. Selectivity experiments, quantified by distribution coefficients (Kd) and selectivity coefficients (k), demonstrated a significantly higher adsorption capacity for SDZ than for structural analogs and non-analogs. In real water samples, the MIPs outperformed conventional HLB sorbents and showed strong anti-interference capability (RSD < 3%). This work provides a material foundation for developing highly selective SDZ-imprinted membranes and advances the application of molecular imprinting technology in membrane separation systems.