Multifunctional fluorescent Eu-MOF probe for tetracycline antibiotics and dihydrogen phosphate sensing and visualizing latent fingerprints

Abstract

The contamination of tetracycline antibiotics and dihydrogen phosphate (H₂PO₄⁻) in food and the environment is one of the major concerns for human health. Herein, a water-stable carboxyl-functionalized europium metal–organic framework (Eu-MOF) was prepared and demonstrated, for the first time, as a dual-responsive fluorescent sensor of tetracycline antibiotics (oxytetracycline (OTC), tetracycline (TC), and doxycycline (DOX)) and H₂PO₄⁻ via fluorescent turn-on and turn-off, respectively. Eu-MOF presents a sensitive and selective detection of OTC with a rapid response time (1 min) and good anti-interference ability. The limits of detection (LODs) of 78 nm, 225 nm, and 201 nM were achieved for OTC, TC, and DOX, respectively. Coordination and hydrogen bonding led to energy and electron transfer from the TC to the MOF, contributing to the fluorescent enhancement mechanism. Moreover, Eu-MOF can effectively detect H₂PO₄⁻ via fluorescence turn-off with a LOD of 0.70 μM. The interactions between H₂PO₄⁻ and MOF interrupt the energy transfer from ligand to MOF, leading to fluorescence quenching. In addition, Eu-MOF was successfully applied to determine OTC and H₂PO₄⁻ in real samples, obtaining satisfactory recoveries and RSDs. More fascinating, Eu-MOF could be utilized to develop latent fingerprints on various surfaces, providing well-defined fluorescent fingerprint details in which the sweat pores can be seen with the naked eye.