Novel "Turn-On" Fluorescent Probe for Highly Selectively Sensing Fluoride in Aqueous Solution Based on Tb3+-Functionalized Metal-Organic Frameworks.
03 Oct 2018-Vol. 3, Iss: 10, pp 12513-12519
TL;DR: The Tb3+@Zr-MOF is developed as a novel “turn-on” fluorescent probe to detect fluoride ions in aqueous solution and exhibits excellent selectivity, high stability, low detection limits, and good anti-interference for sensitizing fluoride ions.
Abstract: A Zr-based metal-organic framework (Zr-MOF) which has free carbonyl groups is synthesized successfully through mix-ligand strategy. Subsequently, Tb3+ is encapsulated into a Zr-MOF by postcoordinated modification. The Tb3+@Zr-MOF exhibits the characteristic emission of Tb3+ because of efficient sensitization through antenna effects. The Tb3+@Zr-MOF is further developed as a novel "turn-on" fluorescent probe to detect fluoride ions in aqueous solution. The results show that Tb3+@Zr-MOF exhibits excellent selectivity, high stability, low detection limits, and good anti-interference for sensitizing fluoride ions. In addition, the possible sensing mechanism that the induced luminescence properties may be attributed to Lewis acid-base interactions is discussed.
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TL;DR: The metal-organic frameworks (MOFs) have been used as excellent platforms for designing luminescent sensors as mentioned in this paper, which can be generated from the building ligands, emissive metal ions, guest ions, or molecules used to construct them as well as from their catalytic activities.
Abstract: Metal–organic frameworks (MOFs), with diverse framework architectures, have evolved as next-generation utility multifunctional hybrid materials. One of the key features of MOFs is their luminescence properties, which can be generated from the building ligands, emissive metal ions, guest ions, or molecules used to construct them as well as from their catalytic activities. MOFs with luminescent properties have been used as excellent platforms for designing luminescent sensors. Their chemically tailorable framework with specific host–guest interactions plays an important role in selectively sensing metal ions, small organic molecules, and biomolecules. This review intends to summarize the recent advances in the construction of MOF-based sensors for chemical sensing and biosensing. Specially, we focus on the fabrication strategies of MOF-based luminescent sensors, and summarize their sensing mechanisms in detail. Also, the major challenges and constraints for this research field are discussed.
241 citations
TL;DR: In this paper, the authors reviewed the encapsulation of various luminescent guests such as lanthanide ions, dyes, quantum dots, and luminescence complexes in metal-organic frameworks to construct luminous sensors with single- or double-emission centers.
Abstract: Metal-organic frameworks (MOFs), which are a class of coordination polymers constructed by metal ions or clusters with organic ligands, have emerged as exciting inorganic-organic hybrid materials with the superiorities of inherent crystallinity, adjustable pore size, clear structure, and high degree of functionalization The MOFs have attracted much attention to develop good luminescent functional materials due to their inherent luminescent centers of both inorganic and organic photonic units Furthermore, the pores within MOFs can also be used to encapsulate a large number of luminescent guest species, which provides a broader luminescent property for MOF materials MOFs possess the incomparable multifunctional advantages of inorganic and organic luminescent materials A large number of luminescent MOFs (LMOFs) have been synthesized for applications in sensing, white-light-emitting diodes (LED), photocatalysis, biomedicine, etc This paper reviews the encapsulation of various luminescent guests such as lanthanide ions, dyes, quantum dots, and luminescent complexes in metal-organic frameworks to construct luminous sensors with single- or double-emission centers, as well as the research progress of these sensors in chemical sensing Finally, the challenges in these fields were outlined and the prospects for future development were put forward
137 citations
TL;DR: This comprehensive review systematically summarizes the luminescence response mode and chemical sensing mechanism for lanthanide-functionalized MOF hybrids (abbreviated as LnFMOFH).
Abstract: The luminescence response application in chemical sensing by metal–organic frameworks (MOFs) and their hybrid materials has been reported extensively in recent years. However, the reviews on this topic are mainly focused on the sensing materials (MOFs and their functionalized hybrid materials) and analytes (all types of species). In this comprehensive review, the luminescence response mode and chemical sensing mechanism for lanthanide-functionalized MOF hybrids (abbreviated as LnFMOFH) are systematically summarized. Specifically, ten sections are subdivided, and importantly involve three main topics. Firstly, LnFMOFH and the luminescence responsive chemical sensing for these hybrids are introduced. Secondly, three single luminescence response modes, including “Turn-Off”, “Turn-On” “Turn–Off–On” and dual mode, as ratiometric luminescence (RL) for chemical sensing in LnFMOFH materials are summarized. Thirdly, some types of chemical sensing mechanisms observed in LnFMOFH materials are outlined, which involve the ligand–metal energy transfer (LMET) for the luminescence response in chemical sensing of enhanced or weakened analytes; the fluorescence (Forster) resonance energy transfer (FRET) and photo-induced electronic transfer (PET) mechanism depending on the energy match between the probe and analyte; and some special chemical interactions for their luminescence response upon chemical sensing, such as hydrogen bonding interaction, coordination interaction and other reactions. Finally, the conclusion and prospects are given for this topic. It needs to be noted that pure lanthanide MOFs (lanthanide ions as the framework metal, including mixed lanthanide MOFs) are not the topic of this review and are only mentioned for background knowledge. Herein, LnFMOFH materials in which the lanthanide ions behave only as photoactive species to functionalize MOF units via post-synthetic modification (PSM) by researchers are the emphasis of this review.
131 citations
TL;DR: A brief overview of the recent developments of MOFs as "turn-on" sensors for a wide range of analytes (viz.
Abstract: Metal-organic frameworks (MOFs) have evolved as an exciting class of materials in the domain of porous materials. The unique features of these materials arise from the combined properties of metal ions/clusters and organic struts which form the building blocks of these fascinating architectures. Among other multifarious applications, MOFs have shown tremendous applications as sensory materials for a wide variety of species. The signal transduction induced mechanism in these confined nanospaces generate optical output in response to a particular analyte which can be detected by wide variety of detection techniques. Fluorometric methods of sensing is one of widely studied method over past few decades. MOF-based fluorometric detection is a key research theme developed over the past few years. In this review, we give a brief overview of the recent developments of MOFs as "turn-on" sensors for a wide range of analytes (viz. cations, anions, volatile organic compounds (VOCs), etc.).
117 citations
TL;DR: A new dual-signal probe based on the boric acid (BA) functionalized Lanthanide metal-organic framework (BA-Eu-MOF) was developed for the detection of Hg2+ and CH3Hg+ ions for the first time and showed excellent characteristics for simultaneous detection.
Abstract: Mercury detection remains an important task because of its high toxicity. Herein a new dual-signal probe based on a boric acid (BA)-functionalized lanthanide metal-organic framework (BA-Eu-MOF) was developed for the detection of Hg2+ and CH3Hg+ ions for the first time. The BA-Eu-MOF was synthesized by coordination of Eu3+ with 5-boronobezene-1, 3-dicarboxylic acid (5-bop) through a one-pot method. The 5-bop ligand not only acted as the "antenna" to sensitize the luminescence of Eu3+ but also provided reaction sites for Hg2+ and CH3Hg+. Owing to the electron-withdrawing effect of the BA group, the "antenna" effect of the ligand was passivating and the BA-Eu-MOF showed weak red emission in water. Upon addition of Hg2+ or CH3Hg+ into the system, a transmetalation reaction took place, i.e., BA groups were replaced by Hg2+ or CH3Hg+; therefore, the "antenna" effect of the ligand was triggered, leading to the enhancement of red emission. As Hg2+ or CH3Hg+ concentration increased, the red emission was gradually enhanced, and the color change was also observed with the naked eye under 365 nm ultraviolet light. Owing to the porous characteristics and the surface effect of the MOF, as well as the unique transmetalation reaction between the BA group and Hg2+ or CH3Hg+, the developed nanoprobe showed excellent characteristics for simultaneous detection of Hg2+ and CH3Hg+, such as simple preparation, convenient operation, "turn-on" signal output, high sensitivity, and selectivity. The unique features of the BA-Eu-MOF make it an attractive probe for monitoring Hg2+ and CH3Hg+.
116 citations
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