Fabrication of a bifunctional fluorescent chiral composite based on magnetic Fe3O4/chiral carbon dots@hierarchical porous metal-organic framework

Considering the selective pharmacological activity and ecotoxicity of chiral drugs, the development of chiral materials with the dual functions of enantiomeric recognition and adsorption is of great significance. Herein, a novel bifunctional chiral composite (Fe3O4/CCDs@HP-ZIF-8) which does not contain expensive and rare fluorescent chiral ligands or metal ions, was constructed for the first time by encapsulating chiral carbon dots (CCDs) and magnetic Fe3O4 nanoparticles into hierarchical porous metal-organic frameworks (HP-MOFs). Fe3O4/CCDs@HP-ZIF-8, which integrates fluorescent chiral property, magnetism, and hierarchical porosity, shows enormous potential in enantiomeric recognition and adsorption. Fluorescence detection results demonstrate that Fe3O4/CCDs@HP-ZIF-8 presents different fluorescence quenching for naproxen enantiomers. The limits of detection are determined to be 0.05 μM for S-naproxen (S-Nap) and 0.30 μM for R-naproxen (R-Nap), respectively. Furthermore, the isothermal, kinetic, and thermodynamic adsorption behaviors of Fe3O4/CCDs@HP-ZIF-8 to naproxen enantiomers were systematically studied. Due to its hierarchical porosity, the composite exhibits higher adsorption capacity to naproxen enantiomers compared to the non-hierarchical porous composite. Studies of enantiomeric recognition and adsorption mechanisms affirm that the synergistic effect of multiple mechanisms exists between Fe3O4/CCDs@HP-ZIF-8 and naproxen enantiomers. Finally, the satisfactory recoveries and relative standard deviations in the actual sample assays demonstrate the practicality of Fe3O4/CCDs@HP-ZIF-8 for S-Nap detection. This non-destructive functionalization method creates an innovative pathway for developing advanced multifunctional chiral materials, holding great promise for enantiomeric recognition and adsorption.