Fluorescence and Colorimetric Dual-Mode Ratiometric Sensor Based on Zr-Tetraphenylporphyrin Tetrasulfonic Acid Hydrate Metal-Organic Frameworks for Visual Detection of Copper Ions.

As a special heavy metal ion, copper ions (Cu) play an indispensable role in the fields of environmental protection and safety. Their excessive intake not only easily leads to diseases but also affects human health. Therefore, it is particularly important to construct a facile, effective, and highly selective Cu probe. Herein, a novel Zr-tetraphenylporphyrin tetrasulfonic acid hydrate (TPPS) metal-organic framework (ZTM) was fabricated using TPPS as the ligand and exhibited strong red fluorescence with a high quantum yield of 12.22%. In addition, we designed a ratiometric fluorescent probe by introducing green fluorescein isothiocyanate (FITC), which was not subject to environmental interference and had high accuracy. When exposed to different amounts of Cu, the fluorescence emission at 667 nm from ZTMs is remarkably quenched, while that at 515 nm from FITC is enhanced, accompanied by a change in the solutions' fluorescence color from red to green under a UV lamp. Besides, the ZTMs solutions display an excellent ratiometric colorimetric response for Cu and produce an obvious color change (from green to colorless) that is visible to the naked eye. The fabricated ZTMs@FITC fluorescent probe exhibits distinguished performance for Cu detection with linear ranges of 0.1 to 5 μM and 5 to 50 μM, as well as a low detection limit of 5.61 nM. Moreover, a colorimetric sensor based on ZTMs exhibits a good linear range from 0.1 to 20 μM for Cu with the detection limit of 4.96 nM. Furthermore, the dual-signal ratiometric sensor has significant specificity for Cu and is successfully applied for monitoring Cu in water samples, which proves its practical application value in the environment and biological systems.