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

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.