A smartphone-integrated bimetallic ratiometric fluorescent probe for specific visual detection of tetracycline antibiotics in food samples and latent fingerprinting

Designing and preparing highly sensitive and accurate fluorescent chemosensors for monitoring tetracycline antibiotics remains a challenge. Herein, a fluorescent chemosensor based on lanthanide metal-organic frameworks (Ln-MOFs) is proposed to realize high-precision monitoring by adjusting the ratio of lanthanide ions. Ln-MOFs with good aqueous stability were prepared by a solvothermal method using Eu³⁺, Tb³⁺ and the ligand 4,4',4″-s-triazine-2,4,6-triyltribenzoic acid (H₃TATB) in DMF/NMP/H₂O. The Ln-MOFs could recognize oxytetracycline (OTC) and doxycycline (DOX), and the detection limits of OTC and DOX were as low as 8.6 and 4.8 nM, respectively. In particular, Eu_{(1.4 μM)}-Tb-MOF sensors were used for visual detection of OTC and DOX in combination with smartphones with detection lines as low as 9.8 nM and 14.2 nM, respectively. Meanwhile, Eu-MOF, Tb-MOF and Eu_{(1.4 μM)}-Tb-MOF can be used for latent fingerprint (LFP) visualization, demonstrating their potential applications in the field of criminal case investigation. The developed probes were successfully applied to determining OTC and DOX in milk, beef and pork with recoveries ranging from 92.0 % to 109.63 % and relative standard deviations (RSDs) ranging from 1.83 % to 4.56 %. Eu_{(1.4 μM)}-Tb-MOF is believed to utilize its lanthanide metal ion coordination and photoinduced electron transfer (PET) mechanism to achieve highly selective and accurate OTC and DOX detection, which is supported by experimental and density functional theory (DFT) calculations.