Rapid and Reusable Amino Acid–Derived MOFs for the Removal of Estrogenic Hormones From Real Water Matrices

ABSTRACT

Estrogenic hormones are potent endocrine‐disrupting contaminants that are inefficiently removed by conventional wastewater treatment processes. Herein, we evaluate a family of isoreticular amino‐acid–derived metal–organic frameworks (MOFs), including multivariate variants, for the simultaneous capture of estrone (E1), 17β‐estradiol (E2), estriol (E3), and 17α‐ethinylestradiol (EE2) from water. Using a solid‐phase extraction configuration, a leucine‐based oxamidato MOF emerges as a highly efficient sorbent, achieving >90%–95% removal of all four hormones within 30 s in a single loading step, representing one of the fastest simultaneous estrogen capture systems reported to date under SPE conditions. This material exhibits exceptional regenerability, enabling near‐quantitative desorption under mild conditions with minimal solvent consumption (1 mL methanol), and stable performance over at least ten reuse cycles. Notably, comparable capture efficiencies are maintained in real river‐water samples, demonstrating robustness toward complex aqueous matrices. The crystal structure of a host–guest aggregate confirms estrogen encapsulation within the flexible framework, providing direct structural insight into the origin of the high capture efficiency. These results identify amino‐acid–based MOFs as a highly competitive platform for rapid, regenerable, and selective estrogen capture, combining excellent performance with valuable structural insight into host–guest interactions.