Dual-mode Tb-cyclophosphazene-MOF sensors for on-site discrimination and quantification of structurally similar flunoquinolone antibiotics in aquatic organisms via smartphone platform
Abstract
We have successfully synthesized two novel terbium-cyclophosphazene MOFs (Tb-Cpz-MOFs) featuring dual-response functionality for the first simultaneous discrimination and quantification of structurally similar third- and fourth-generation fluoroquinolone antibiotics (norfloxacin, Nor: ratiometric response; moxifloxacin, Moxi: quenching response). The two Tb-Cpz-MOFs were constructed from structurally distinct cyclophosphazene-based ligands to form a two-dimensional supramolecular network and a three-dimensional framework structure, respectively. Remarkably, the Tb-Cpz-MOFs demonstrate exceptional analytical performance, achieving detection limits of 34 nM (Nor) and 9 nM (Moxi) in spiked shrimp samples, with excellent recovery rates (96.2-105 % for Nor; 95.2-107 % for Moxi). Detailed mechanistic studies combining fluorescence spectra, UV-vis absorption, theory calculations by Vienna ab initio simulation package (VASP), and XPS analysis revealed that the ratiometric response to Nor arose from its ability to capture ligand-to-Tb3+ energy transfer, while Moxi induced fluorescence quenching through competitive light absorption with MOFs. Notably, we engineered Tb-Cpz-MOFs into field-deployable PVA films integrated with smartphone colorimetry to achieve rapid visualization of dual functional detection capabilities and on-site semi quantitative analysis. This work not only provides a reliable solution for monitoring antibiotic contamination in aquatic organisms but also establishes…
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