Preparation of monodispersed macroporous core–shell molecularly imprinted particles and their application in the determination of 2,4-dichlorophenoxyacetic acid

• Monodispersed macroporous core–shell PGMA@MIP particles for 2,4-dichlorophenoxyacetic acid (2,4-D) were prepared via si-ATRP.
• Monodispersed macroporous PGMA particles were synthesized as the supporting matrix.
• PGMA@MIP exhibited excellent selectivity, accessibility and affinity toward 2,4-D.
• PGMA@MIP particles were used to selectively enrich 2,4-D from tap water.

Porous polymers have aroused extensive attention due to their controllable porous structure in favor of mass transfer and binding capacity. In this work, the novel macroporous core–shell molecularly imprinted polymers (MIP) for selective recognition of 2,4-dichlorophenoxyacetic acid (2,4-D) were prepared by surface initiated atom transfer radical polymerization (si-ATRP). By using one-step swelling and polymerization method, the monodispersed macroporous poly(glycidyl methacrylate) (PGMA) particles were synthesized and used as supporting matrix for preparing surface MIP particles (PGMA@MIP). Thanks to the inner and outer surface-located binding cavities and the macroporous structure, the PGMA@MIPs revealed desirable efficiency for template removal and mass transfer, and thus excellent accessibility and affinity toward template 2,4-D. Moreover, PGMA@MIPs exhibited much higher selectivity toward 2,4-D than PGMA@NIPs. PGMA@MIP particles were directly used to selectively enrich 2,4-D from tap water and the recoveries of 2,4-D were obtained as 90.0–93.4% with relative standard division of 3.1–3.4% (n = 3). The macroporous PGMA@MIPs also possessed steady and excellent reusable performance for 2,4-D in four extraction/stripping cycles. This novel macroporous core–shell imprinted material may become a powerful tool for rapid and efficient enrichment and separation of target compounds from the complicated samples.