In Situ Fabrication of Photoluminescent Hydrogen-Bonded Organic Framework-Functionalized Ca (II) Hydrogel Film for the Tetracyclines Visual Sensor and Information Security

A facilely in situ fabricated hydrogen-bonded organic framework (HOF) hydrogel film with perfect photoluminescent performance was designed for visual sensing of tetracycline antibiotics (TCs) and information security. Luminescent HOF (MA-IPA) was combined with sodium alginate (SA) through hydrogen bonding actions and electrostatic interactions, then cross-linked with Ca²⁺ ions to form HOF hydrogel film (Ca@MA-IPA@SA). The HOF hydrogel film exhibited exceptional mechanical robustness along with stable blue fluorescence and ultralong green phosphorescence. After exposure to TCs, Ca²⁺ was combined with TCs to generate a new green fluorescence exciplex (TC-Ca²⁺) in hydrogel films. Due to fluorescence resonance energy transfer, the fluorescence of MA-IPA was quenched, and the fluorescent color of the HOF hydrogel film was changed from blue to green. This dichromatic fluorescent response is convenient for the visual and rapid detection of TCs. The detection limits of tetracycline (TC), oxytetracycline (OTC), and chlortetracycline (CTC) were 5.1, 7.7, and 32.7 ng mL^-1, respectively. Importantly, this hydrogel sensing platform was free of tedious operation and enabled the ultrasensitive and selective detection of TCs within 6 min. It has been successfully applied to TC detection in pork and milk samples. Based on the stable photoluminescence performance of HOF hydrogel films and fluorescent-responsive properties to TCs, two types of anticounterfeiting arrays were fabricated for information encryption and decryption. This work provides a novel approach for on-site detection of TCs and offers valuable insights into information security.