Rational design and preparation of dibenzothiophene‐targeting molecularly imprinted polymers with molecular dynamics approaches and surface‐initiated activators regenerated by electron‐transfer atom‐transfer radical polymerization

Nine molecular dynamic simulations of molecular‐imprinting prepolymerization systems were performed to investigate the effects of the type and concentration of crosslinkers (CLs) on key template (T)–functional monomer (FM) complexes. Subsequent analyses revealed that the system with divinylbenzene as the CL had the most stable T–FM complexes, and the mass percentage concentration of divinylbenzene in the prepolymerization system was 9.4%. Nine corresponding imprinted polymers were synthesized by the coupling of the surface‐initiated activator regenerated by electron‐transfer atom‐transfer radical polymerization technique with the hierarchical‐imprinting technique to validate the reliability of the simulation results. The structural properties of the optimal adsorbent were characterized by IR spectrophotometry, scanning electron microscopy, and nitrogen sorption measurements. The Langmuir isotherm fitted the equilibrium data best, and the kinetic data (within 30 min) were well described by the pseudo‐second‐order model. Meanwhile, the prepared adsorbent displayed a higher selectivity to dibenzothiophene compared with other analogs. Finally, the adsorbent was successfully applied for the deep desulfurization of the gasoline sample. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42629.