Dual-emissive europium doped UiO-66-based ratiometric light-up biosensor for highly sensitive detection of histidinemia biomarker

Lanthanide metal-organic frameworks (Ln-MOFs) are a kind of emerging crystalline porous materials with high fluorescence and easy-to-tunable properties, making them ideal for sensing applications. However, current Ln-MOFs based fluorescent probes are primarily single-emissive or fluorescence-quenched, which greatly limited the detection performances such as sensitivity, accuracy and repeatability, thereby hindering their applications in efficient target monitoring and related disease diagnosis. To address these issues, the reasonable design of Ln-MOFs equipped with dual fluorescence emissions and light-up mode is urgently needed for a high-performance biosensor. A dual-emissive europium doped UiO-66 (Eu@UiO-66-NH2-PMA)-based ratiometric fluorescent biosensing platform was constructed for highly sensitive and selective detection of the histidinemia biomarker-histidine (His). Eu@UiO-66-NH2-PMA (pyromellitic acid abbreviated as PMA) was synthesized utilizing a post-synthetic modification method via coordination interactions between the free –COOH of UiO-66-NH2-PMA and Eu3+, which exhibited characteristic peaks of broad ligand emission and sharp Eu3+ emissions simultaneously. Considering that Cu2+ had the excellent fluorescence quenching ability toward Eu3+ and superior affinity with His, it was deliberately introduced into the Eu@UiO-66-NH2-PMA, acting as active sites for target His responsiveness. The Eu@UiO-66-NH2-PMA/Cu2+/His ternary competition system demonstrated a low detection limit of 74 nM, excellent selectivity and good anti-interference capability that allowed for sensitive analysis of His levels in milk and human serum samples. Attributing to the superior luminescent properties, good stability and self-calibration capability of Eu@UiO-66-NH2-PMA, the developed ratiometric light-up sensing platform enabled sensitive, selective and credible analysis of His in complex practical samples, which might provide an available tool for food nutrition guideline and diagnostic applications of His related diseases.