A novel luminescent sensor based on Tb@UiO-66 for highly detecting Sm3+ and teflubenzuron
Graphical abstract
Introduction
Lanthanides (Lns), which is one of the most important branches of rare earth elements (REEs), have attracted considerable attention because of their applications in various fields, such as permanent magnets [1], luminescence [2,3], electric cars and smartphones [4,5], gas adsorption and separation [6], [7], [8], and lasers [9], etc. TbIII, DyIII and HoIII can be served as molecular coolers. EuIII-based and TbIII-based composites are the superior luminescent materials in the range of visible light. The main commercial application of SmIII is samarium-cobalt magnets, which have permanent magnetization second only to neodymium magnets. While, the increasing demands for LnIII salts are limited by the total amount in nature, which are insoluble in the presence of phosphate with the concentration of 10−13 M [10]. It is urgent to seek out environmentally friendly methods for detecting LnIII ions without separated from the system.
Pesticides [11], [12], [13], which are kinds of toxic organic compounds, have played a prominent role in increasing agricultural production and income, and have become one of the most effective measures to solve the problems of food and clothing for the world's 6 billion people. However, with the long-term use of pesticides, the pesticide residues in agricultural products exceed the international standard, which not only cause serious pollution to ecosystems, but also cause great harm to human health [14], [15], [16]. The negative impact caused by pesticide residues has aroused people's attention. Pesticide residues analyses methods are divided into three main categories according to their principles: chromatography, spectroscopy and biochemical measurement methods [17,18]. Chromatography method has the characteristics of excellent separation ability, good selectivity, and high sensitivity. While the disadvantages of chromatography method are long pretreatment time, interferences in the detection process and high costs. Chromatography method must be also combined with a highly selective detector. Spectroscopy method is fast, while the detection limit is relatively high. The principle of biochemical measurement method for detecting pesticides is to inhibit acetylcholinesterase (AChE) [19,20]. The biochemical measurement method has the advantages of low price and rapid detection, etc. However, the enzymes and antibodies served as sensors are easily affected by complex detection conditions. The scope of applications of biochemical measurement method is limited. Herein, exploiting a more convenient, fast, efficient and accurate approach to detect pesticides is strongly urgent priority.
So far, many techniques and materials for detecting cations and pesticides have been developed, such as biosensors [21], luminescent sensors [22], electrochemical sensors [23], porous materials [24], inductively coupled plasma mass spectroscopy (ICP-MS) and atomic adsorption spectrometry (AFS), etc. However, complicated sample preparation, sophisticated instruments, time-consuming and high cost have hindered the usage of these techniques. Chemosensors, such as luminescent sensors and electrochemical sensors, have developed rapidly due to the merits of sensitivity and selectivity of sensors [25]. Compared with electrochemical sensors, luminescent sensors cannot only eliminate the disadvantages of irregular shape and template leakage from electrochemical sensors, but also have high sensitivity and precision [26].
Metal–organic frameworks (MOFs), a class of crystal materials, are fabricated by metal ions or clusters and rigid or flexible organic ligands, which have been extensively applied in various fields, for instance, catalysis [27,28], adsorption [29,30], chemosensors [31,32], and electrochemistry [33,34], etc. While, the frameworks of most MOFs are unstable in the air due to the reversible coordination bonds, so that the potential applications of MOFs are limited to a certain degree [35], [36], [37]. Many efforts have been made to directly promote the stabilities of MOFs. One of the most remarkable examples is the synthesis of UiO-66, Zr6(μ3-O)4(μ3-OH)4(BDC)6 by Cavka et al [38], which exhibits the property of extremely hydrothermal stability. After that, many Zr-based metal–organic frameworks were reported and the potential applications were explored. The reason for the stabilities of Zr-MOFs is that zirconium ion has high charge density and bond polarization, and zirconium ion has strong electron affinity once it is bonded with the oxygen atoms coming from carboxylate [39]. The construction of luminescent sensors based on MOFs should be considered from the following points. Firstly, the frameworks of MOFs should be stable in different solvents, such as Zr-MOFs. Secondly, luminescent ligands with typical electron-rich properties combined with luminescent guest molecules should be selected to prepare luminescent sensors based on MOFs, which can eliminate the drawback of a single-emitting platform of the material with low recognition and stability. In addition, the preparation of dual-emitting platforms luminescent sensors based on MOFs also provides the possibility for the construction of visible luminescent probes. As luminescent sensors, lanthanide-based MOFs (LnMOFs) have stimulated the scientists’ attention due to the advantage of tuned luminescence properties [40]. Usually, the syntheses of LnIII luminescent sensors have been classified into two methods. One is that LnIII ions, as nodes, linked to the organic ligands directly and the other one is that LnIII ions were encapsulated into the channels or cages of MOFs [41]. On basis of the viewpoint, LnIII ions and Zr-MOFs may be integrated together to establish a new type of luminescent sensors, namely Ln@Zr-MOFs, which have the advantages of luminescent sensors based on MOFs mentioned above.
In this work, 1,4-dicarboxybenzene (H2BDC) and ZrCl4 were utilized to synthesize UiO-66. Next, TbIII ions were encapsulated into the tetrahedral and octahedral cages of UiO-66, namely Tb@UiO-66, which can be served as a multifunctional luminescent sensor for highly detecting cations and pesticides, especially for Sm3+ and teflubenzuron. A series of approaches were utilized to characterize Tb@UiO-66, for instance, inductively coupled plasma (ICP), thermogravimetric analyses (TGA), infrared radiation (IR) and powder X-ray diffraction (PXRD). Tb@UiO-66 showed the luminescence enhancements phenomena for the detection of Sm3+ and teflubenzuron observed by the naked eyes under the UV light at 365 nm. Meanwhile, Tb@UiO-66 exhibited superior recyclability and low LODs for detecting Sm3+ and teflubenzuron. Tb@UiO-66 could also be used to detect teflubenzuron in real water samples. The mechanisms for detecting Sm3+ and teflubenzuron were investigated.
Section snippets
Materials and physical measurements
1,4-dicarboxybenzene (H2BDC) and Zirconium(IV) chloride (ZrCl4, 99.5%) were obtained from Alfa. Tb(NO3)3·6H2O, CrCl3, KCl, FeCl3, AlCl3, BaCl2, NaCl, CoCl2, PbCl2, ZnCl2, AgNO3, MgCl2, SnCl2, FeCl2, NiCl2, CuCl, MnCl2, CdCl2, HgCl2, SmCl3, InCl3, GaCl3 and BiCl3 were purchased from Sigma Aldrich. Thiamethoxam, etoxazole, teflubenzuron, isoxaflutole, acetamiprid, carbaryl, rotenone, fluroxypyr, carbendazim, nitenpyram and cypermethrin were also purchased from Sigma Aldrich. N,N’
Characterization of UiO-66 and Tb@UiO-66
UiO-66 was constructed by a mixture of ZrCl4 and H2BDC in acetic acid/DMF solutions. UiO-66 is colorless and crystallizes in the cubic system, where the space group is Fm-3m. In Fig. 1, the unit of UiO-66 consists [Zr6O4(OH)4] clusters and 12 H2BDC ligands. The pore structure of UiO-66 consisted of a regular octahedral cage of ca. 1.1 nm and a regular tetrahedral cage of ca. 0.8 nm connected by a 0.6 nm triangular. When the degassed UiO-66 was immersed in methanol solution containing Tb(NO3)3·6H
Conclusions
In summary, Tb@UiO-66 was successfully fabricated on basis of the exchange of guest molecules, where Tb3+ ions were encapsulated into the cages of UiO-66, and Tb@UiO-66 could act as an outstanding chemosensor for the detection of cations and pesticides, especially for Sm3+ and teflubenzuron. Tb@UiO-66 displayed high thermal stability, good selectivity and excellent recyclability for sensing small-molecules. The LODs of Tb@UiO-66 for detecting Sm3+ and teflubenzuron were 0.09 μM and 0.21 μM,
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgments
Thank for the National Natural Science Foundation of China (No. 51903032), Natural Science Foundation of Heilongjiang Province (No. LH2019B002), Postdoctoral Science Foundation of Heilongjiang Province (No. LBH-Z19045), the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province, China (No. UNPYSCT-2020111) and the “Young Talents” Project of Northeast Agricultural University of Heilongjiang Province (No. 18QC64) for this work.
References (64)
- et al.
Commensurate adsorption of hydrocarbons and alcohols in microporous metal organic frameworks
Chem Rev
(2012) - et al.
Design, synthesis, herbicidal activity and CoMFA of novel aryl-formyl piperidinone HPPD inhibitors
Pestic Biochem Physiol
(2021) - et al.
Cobalt (II) complex as a fluorescent sensing platform for the selective and sensitive detection of triketone HPPD inhibitors
J Hazard Mater
(2021) - et al.
Exposure to pesticides and the associated human health effects
Sci Total Environ
(2017) - et al.
Seasonal variation in accumulation of persistent organic pollutants in an Arctic marine benthic food web
Sci Total Environ
(2016) - et al.
Organochlorine chemicals in seafood: occurrence and health concerns
Food Chem Toxicol
(2002) - et al.
Development of a direct competitive enzyme-linked immunosorbent assay for parathion residue in food samples
Anal Biochem
(2009) - et al.
Recent advancements in sensing techniques based on functional materials for organophosphate pesticides
Biosens Bioelectron
(2015) - et al.
A simple electrochemical biosensor based on AuNPs/MPS/Au electrode sensing layer for monitoring carbamate pesticides in real samples
J Hazard Mater
(2016) - et al.
Rare-earth post-modified Zn-based coordination polymer microspheres: T Simple room-temperature preparation, fluorescent performances and application for detection of tryptophane
Sens Actuators B: Chem
(2019)
Porous zeolite imidazole framework-wrapped urchin-like Au-Ag nanocrystals for SERS detection of trace hexachlorocyclohexane pesticides via efficient enrichment
J Hazard Mater
Two luminescent dye@MOFs systems as dual-emitting platforms for efficient pesticides detection
J Hazard Mater
Highly efficient hydrogenation of biomass oxygenates to alcohol products on MOF composite catalysts
J Taiwan Inst Chem Eng
Water stable metal-organic framework as adsorbent from aqueous solution: A mini-review
J Taiwan Inst Chem Eng
A cationic metal-organic framework for dye adsorption and separation based on column-chromatography
J Mol Liq
Graphene-based magnetic metal organic framework nanocomposite for sensitive colorimetric detection and facile degradation of phenol
J Taiwan Inst Chem Eng
A metal–organic framework derived PtCo/C electrocatalyst for ethanol electro-oxidation
J Taiwan Inst Chem Eng
Eu(III) functionalized Zr-based metal-organic framework as excellent fluorescent probe for Cd2+ detection in aqueous environment
Sens Actuators B: Chem
Dual-emitting fluorescence of Eu/Zr-MOF for ratiometric sensing formaldehyde
Sens Actuators B: Chem
Highly selective colorimetric and electrochemical sensing of iron (III) using Nile red functionalized graphene film
Biosens Bioelectron
5-Bromo-1H-indol based flexible molecular receptor possessing spectroscopic characteristics for detection of Sm(III) and Dy(III) ions
Inorg Chim Acta
Hybridization of Metal-Organic Frameworks with attapulgite for magnetic solid phase extraction and determination of benzoylurea insecticides in environmental water samples
Microchem J
Lanthanide single-molecule magnets
Chem Rev
Lanthanide-based luminescent hybrid materials
Chem Rev
Luminescent functional metal–organic frameworks
Chem Rev
Rare earth elements: critical resources for high technology; U.S. Geological Survey Fact Sheet 087-02; U.S. Geological Survey
Rare-earth recovery: U.S. efforts to extract valuable elements from coal waste surge
Chem Eng News
Hydrogen storage in metal–organic frameworks
Chem Rev
Self-assembly versus stepwise synthesis: heterometal–organic frameworks based on metalloligands with tunable luminescence properties
Chem Eur J
Organic lasers: recent developments on materials, device geometries, and fabrication techniques
Chem Rev
Solubility products of the trivalent rare-earth phosphates
J Chem Eng Data
Design, synthesis and SAR of novel 1,3-disubstituted imidazolidine or hexahydropyrimidine derivatives as herbicide safeners
J Agric Food Chem
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