Dual-Ligand Near-Infrared Luminescent Lanthanide-Based Metal-Organic Framework Coupled with In Vivo Microdialysis for Highly Sensitive Ratiometric Detection of Zn 2+ in a Mouse Model of Alzheimer's Disease.

Zinc, which is the second most abundant trace element in the human central nervous system, is closely associated with Alzheimer's disease (AD). However, attempts to develop highly sensitive and selective sensing systems for Zn 2+ in the brain have not been successful. Here, we used a one-step solvothermal method to design and prepare a metal-organic framework (MOF) containing the dual ligands, terephthalic acid (H 2 BDC) and 2,2':6',2″-terpyridine (TPY), with Eu 3+ as a metal node. This MOF is denoted as Eu-MOF/BDC-TPY. Adjustment of the size and morphology of Eu-MOF/BDC-TPY allowed the dual ligands to produce multiple luminescence peaks, which could be interpreted via ratiometric fluorescence to detect Zn 2+ using the ratio of Eu 3+ -based emission, as the internal reference, and ligand-based emission, as the indicator. Thus, Eu-MOF/BDC-TPY not only displayed higher selectivity than other metal cations but also offered a highly accurate, sensitive, wide linear, color change-based technique for detecting Zn 2+ at concentrations ranging from 1 nM to 2 μM, with a low limit of detection (0.08 nM). Moreover, Eu-MOF/BDC-TPY maintained structural stability and displayed a fluorescence intensity of at least 95.4% following storage in water for 6 months. More importantly, Eu-MOF/BDC-TPY sensed the presence of Zn 2+ markedly rapidly (within 5 s), which was very useful in practical application. Furthermore, the results of our ratiometric luminescent method-based analysis of Zn 2+ in AD mouse brains were consistent with those obtained using inductively coupled plasma mass spectrometry.