A Water-Stable Tb-MOF As a Rapid, Accurate, and Highly Sensitive Ratiometric Luminescent Sensor for the Discriminative Sensing of Antibiotics and D₂O in H₂O

Abstract

The design and development of self-calibrating ratiometric luminescent sensors for the fast, accurate, and sensitive discrimination and determination of pollutants in wastewater is highly desirable for public and environmental health. Herein, a 3D porous Tb(III)-based metal−organic framework (MOF), {[Tb-(HL)(H 2 O) 2 ]•x(solv)} n (1), was facilely synthesized using a ureafunctionalized tetracarboxylate ligand, 5,5′-(((1,4-phenylenebis-(azanediyl))bis(carbonyl))bis(azanediyl))diisophthalic acid (H 4 L). The activated framework showed a good water stability in both aqueous solutions at a wide pH range of 2−14 and simulated antibiotic wastewaters. Interestingly, this Tb-MOF exhibited dual luminescence owing to the partial energy transfer from the antenna H 4 L to Tb 3+ . More importantly, activated 1 (1a) that was dispersed in water showed a fast, accurate, and highly sensitive discrimination ability toward antibiotics with a good recyclability, discriminating three different classes of antibiotics from each other via the quenching or enhancement of the luminescence and tuning the emission intensity ratio between the H 4 L ligand and the Tb 3+ center for the first time. Simultaneously, 1a is a ratiometric luminescent sensor for the rapid, accurate, and quantitative discrimination of D 2 O from H 2 O. Furthermore, this complex was successfully used for the effective determination of antibiotics and D 2 O in real water samples. This work indicates that 1a represents the first ever MOF material for the discriminative sensing of antibiotics and D 2 O in H 2 O and promotes the practical application of Ln-MOF-based ratiometric luminescent sensors in monitoring water quality and avoiding any major leak situation.

Fabrication of a Stable Europium-Based Luminescent Sensor for Fast Detection of Urinary 1-Hydroxypyrene Constructed from a Tetracarboxylate Ligand

“…In fact, considerable efforts have been dedicated to seeking simple and effective methods on detecting urinary 1-HP for the past few years. Benefitting from the fascinating fluorescent capabilities such as characteristic and strong emission peaks, long lifetimes, high quantum yields, and large Stokes shift, − metal–organic frameworks constructed from lanthanide (Ln-MOFs), especially Eu-centered and Tb-centered MOFs featuring the typical red or green luminescence of Eu­(III) and Tb­(III), have been successfully explored and widely applied in chemical sensors, covering metal ions, − anions, − organic molecules, − antibiotics, − temperature variation, and luminescent devices. − Yan’s group reported a luminescent Eu-doped Ga-MOF applied as a fast-responsive, highly sensitive, and selective sensor for detecting 1-HP . Liu and coworkers developed an Eu 3+ -incorporated Zn-MOF considered as a potential ratiometric luminescent probe for 1-HP .…”

Soft Metal–Organic Frameworks Based on {Na@Ln6} as a Secondary Building Unit Featuring a Magnetocaloric Effect and Fluorescent Sensing for Cyclohexane and Fe3+

“…The unique 4f n electronic arrangements of Ln 3+ ions result in the rich electronic energy spectrum transition, which gives them unique luminescent properties, such as red-emitting Eu 3+ , − green-emitting Tb 3+ /Er 3+ , − and near-infrared-emitting Nd 3+ /Yb 3+ . − Ln-MOFs are considered to be a potential fluorescent probe and colorful tunable luminescent materials due to their long lifetime, high quantum yield, large Stokes shift, and strong emission spectrum. − In particular, Eu/Tb-MOFs have been widely used in the detection of cations and anions, small-molecule recognition, and the exploration of temperature-sensitive properties. − With the development of industrialization, heavy metal ion pollution and organic waste have become increasingly serious. With the needs of environmental detection and health science, the rapid and effective identification of trace metal ions is an urgently needed molecular technology.…”

Impact of Zr6 Node in a Metal–Organic Framework for Adsorptive Removal of Antibiotics from Water

“…Due to such limitations, the race for new methods to remove antibiotics has begun to find ideal adsorptive materials with high surface areas. − A versatile platform for the removal of antibiotics is particularly desirable. A new class of porous materials, metal–organic frameworks (MOFs) composed of metal nodes and organic linkers, can be an ideal material platform because virtually limitless combination of metal nodes and organic linkers has facilitated the production of more than 80,000 MOF entries. − Since the ultimate purpose is to eliminate antibiotics remaining in water through MOFs, it is very essential and should not be overlooked to consider stable MOFs that do not collapse in the water and chemical environments. − Zr-based MOFs are particularly attractive due to the presence of high-valent transition metals and carboxylate ligands, presenting good water stability.…”