Zirconium-based metal-organic frameworks for fluorescent sensing

Multi-functional metal-organic frameworks for detection and removal of water pollutions.

Ratiometric fluorescent sensors can suppress the interference of factors unrelated to analysis due to their built-in self-calibration characteristics, which exhibit higher sensitivity and more obvious visual detection in the process of qualitative and quantitative analysis. Herein, we constructed a ratiometric fluorescence probe based on fluorescent/colorimetric dual-mode method for the determination of arginine by encapsulating rhodamine B in-situ into UiO-66-NH2 MOFs (UiO-66-NH2@RhB). The as-prepared probe showed dual-emission characteristics under a single excitation wavelength. The fluorescence intensity of UiO-66-NH2 was increased significantly by arginine, while the emission peak intensity of rhodamine B remained stable, resulting in a single-signal response with fixed reference. Furthermore, the practicality of the presented sensor was successfully validated by quantitative detection of arginine in human serum. More significantly, paper-based sensors for arginine detection were devised by using carboxymethyl cellulose modified filter papers. Under the irradiation of ultraviolet light, the paper-based sensors would produce obvious color variation from lightpink to bluish violet. This work provided a convenient and efficient method for on-site detection of arginine. 

A ratiometric fluorescent paper sensor based on dye-embedded MOF for high-sensitive detection of arginine.

MIL-101(FeII3,Mn) with dual-reaction center as Fenton-like catalyst for highly efficient peroxide activation and phenol degradation

Since the abuse of oxytetracycline (OTC) has brought serious environmental problems, it is of great practical significance to develop sensitive OTC fluorescent probes to quantify environmental OTC residues. Herein, the aluminum-based metal-organic framework MIL-53(Al) with microflower morphology and plentiful surface open aluminum sites (denoted as FMIL-53(Al)) was tailored via an acetic acid-assisted solvothermal method and subsequently exploited for ultrasensitive detection of OTC. Compared with conventional hydrothermally synthesized MIL-53(Al), FMIL-53(Al) possesses a larger specific surface with plentiful open aluminum sites, which can selectively coordinate with OTC to fix the molecular conformation. The coordinated OTC molecules undergo a transition from twisted-conformation to extended-conformation, accompanied by an increase in fluorescence quantum yield. As a fluorescent probe, the detection limit of FMIL-53(Al) for OTC is estimated as low as 0.94 nM. Finally, the FMIL-53(Al)-based probe can be applied for the detection of OTC in water samples of fish farm pond, and a portable test paper was successfully fabricated for on-site visual identification of OTC. This work not only demonstrates a novel morphology of MIL-53(Al) for OTC ultrasensitive sensing but also provides an example of morphological engineering to optimize the performance of MOF-based fluorescence sensors. • For the first time, FMIL-53(Al) with plentiful open aluminum sites on the surface was tailored via solvothermal method. • The open aluminum sites of FMIL-53(Al) readily capture OTC in extended conformation, enhancing the fluorescence of OTC. • FMIL-53(Al) can be used as one of the most sensitive non-aptamer fluorescent probes for OTC detection (LOD = 0.94 nM). 

Conformational fixation induced fluorescence turn-on of oxytetracycline coordinated on aluminum-based metal-organic frameworks for ultrasensitive sensing application

Herein, a dual-functional platform for simultaneous detection and removal of Nitrofurans (NFs), a class of widely used antibiotics, from aqueous solution is developed on the basis of water-stable luminescent UiO-Type Metal-Organic Frameworks (Zr-fcu-sti). Specifically, Zr-fcu-sti responds to NFs at parts per billion (ppb) levels based on the efficient luminescence quenching and is one of the most sensitive luminescent MOF-based sensing materials. The efficient luminescence quenching can be explained by a combined effect of the strong absorption of NFs at the excitation wavelength and the photo-induced electron transfer process from the ligand of Zr-fcu-sti to NFs. In addition, NFs can obviously cause the red shift of the probe's maximum emission, which can be used as an indicator for the qualitative detection of NFs, clearly distinguishing them from other types of antibiotics. Meanwhile, its suitable pore size, large surface areas and the widely distributed hydrogen bonding sites on pore surfaces endow the MOF with excellent uptake capacity toward NFs in aqueous environment. These results show that, as a water-stable dual-functional material with great application prospects, Zr-fcu-sti can achieve high-sensitivity fluorescence sensing and efficient adsorption of NFs from water.

Dual-functional UiO-type metal-organic frameworks for the sensitive sensing and effective removal of nitrofurans from water

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Dual-functional UiO-type metal-organic frameworks for the sensitive sensing and effective removal of nitrofurans from water