A turn-on fluorescent Zn(ii) metal–organic framework sensor for quantitative anthrax biomarker detection

Abstract

2,6-Pyridine dicarboxylic acid (DPA) is considered one of the main anthrax biomarkers, and the detection of DPA is of great significance. This work presents a Zn(II)-based metal–organic framework (MOF) with the formula {[Zn₂(2,6-NBC)₂(vlpy)Zn(2,6-NBC)(vlpy)_0.5]·0.8(2,6-H₂NBC)·H₂O}_n (1) assembled from 2,6-naphthalenedicarboxylic acid (2,6-H₂NBC) and 4,4′-vinylenedipyridine (vlpy) for a photoluminescence sensor matrix for DPA detection. 1 features a 3D pillar–layer framework with nanopore sizes of ca.13.165 Å × 12.731 Å, 12.725 Å × 11.018 Å and 13.114 Å × 13.165 Å along the three directions, occupied by lattice water and disordered 2,6-H₂NBC molecules. The obtained 1 can be used as a turn-on fluorescence sensor for the detection of DPA with high selectivity, excellent sensitivity and recyclability. The luminescence of 1 demonstrates an obvious color change from blue to purplish blue as the DPA concentration rises. Furthermore, a linear correlation is presented between the fluorescence and a low DPA concentration of 0–0.3 mM, and the detection limit can reach as low as 128 nM, much lower than that of an infectious dose to a human of anthrax spores (60 μM). A fluorescence test paper is fabricated to detect DPA rapidly through color change. DFT calculations indicate the intermolecular photoinduced electron-transfer transition and hydrogen-bonding interaction between DPA molecules and the skeleton of 1 induces the “turn-on” fluorescence sensing of DPA behavior.