Illuminating tetracycline: The role of metal coordination in fluorescence emission and its optical detection potential

Rapid on-site detection of antibiotics such as tetracycline (TC) is crucial for understanding their elusive environmental fate. Fluorescence-based strategies are promising owing to their sensitivity and ease of use. This study demonstrates that Al³⁺–TC coordination significantly enhances the intrinsic fluorescence of TC at excitation/emission wavelengths of 395/490 and 270/490 nm. The fluorescence emission intensity is proportional to the TC concentration between 0.005 and 7.5 μmol/L TC, which increases the detection sensitivity by 40 times compared with the commonly used absorption signals. Density functional theory calculations, when combined with the independent gradient model, indicate that the six-membered chelate ring in the octahedral Al³⁺–TC complex restricts molecular motion, along with two intramolecular hydrogen bonds formed between TC and water ligands. These factors lead to a narrowing of the energy gap between the highest occupied and lowest unoccupied molecular orbitals upon complexation with Al³⁺. Consequently, the enhanced molecular rigidity and facilitated electron transfer result in a significant increase in the fluorescence quantum yield. This captivating fluorescence response significantly enhances the proficiency of optical signals in detecting TC, thereby enriching future environmental monitoring systems with greater diversity and adaptability.