Article pubs.acs.org/IC
Cite This: Inorg. Chem. XXXX, XXX, XXX−XXX
Ln(III)-Functionalized Metal−Organic Frameworks Hybrid System: Luminescence Properties and Sensor for trans,trans-Muconic Acid as a Biomarker of Benzene Xiang-Long Qu§ and Bing Yan*,§ School of Chemical Science and Engineering, Tongji University, Siping Road 1239, Shanghai 200092, China
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ABSTRACT: By application of a straightforward postsynthetic modification strategy, a luminescent lanthanide-based MOFs hybrid material, Tb(III)@MOF-SO−3 , is first fabricated by loading Tb(III) ions into the pores of Zn-based MOF-SO3−. This hybrid system is constructed on notable and specific luminous sensitization of MOFSO−3 to Tb(III) ions. The further study shows that bi-metal-loaded Eu(III)/Tb(III)@MOF-SO−3 exhibits a Tb(III)-induced luminescence of Eu(III) ions, and the emissions of it all fall in the white region by altering the ratio of Eu(III)/Tb(III) ions and the excitation wavelengths. A kind of white-lighting thin film based on Eu(III)/Tb(III)@ MOF-SO−3 exhibits dazzling white light when excited at 295 nm (X = 0.338, Y = 0.323). Furthermore, the Tb(III)@MOF-SO−3 is first developed as a fluorescence sensor specifically toward biomarker of benzene, trans,trans-muconic acid (tt-MA), based on fluorescence quenching. This reusable sensor with high water tolerance and photostability displays excellent selectivity and sensitivity with a detection limit as low as 0.1 ppm, while being provided with the high antijamming of other urinary chemicals. These results make the sensor has the potential for the practical detection of tt-MA in a urine system. The possible quenching mechanisms are also investigated in detail.
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INTRODUCTION Benzene is one of the ubiquitous environmental pollutants and has been classified as a group I carcinogen by International Agency for Research on Cancer (IARC) and U.S. Environmental Protection Agency (EPA).1,2 Long-term environmental and occupational exposure to benzene could increase the risk of disease such as anemia, pancytopenia, aplasia, acute myeloid leukemia, and so on.3−7 Once exposed, benzene undergoes a complex metabolism pathway in the human body, converting benzene to certain metabolites.8 The American Conference of Governmental Industrial Hygienists (ACGIH) suggests that trans,trans-muconic acid (tt-MA) as a biological exposure index (BEI) is suitable urinary biomarker of benzene at high concentrations (above 1 ppm).9−12 Various test facilities have been applied to the determination of urinary tt-MA including gas chromatography (GC), high-performance liquid chromatography (HPLC), ultraviolet and visible spectrophotometry (UV−vis), and mass spectrometry (MS) detection.13−16 However, there are many difficulties in these techniques which are described with expensive instruments and raw stocks, complicated pretreatment, limited selectivity, and so on. Thus, an alternative method which is convenient, reusable, and high selective for the identification and quantification of tt-MA needs to be investigated urgently with the aim at the protection of human health. © XXXX American Chemical Society
Metal−organic frameworks (MOFs) are a class of highly porous and crystalline materials with intriguing architectures and wide potential applications in gas storage and separation,17−19 heterogeneous catalysis,20 magnetic,21 optic materials, and sensors.22−27 Among various fabricated MOFs, lanthanide-based MOFs (Ln-MOFs) usually exhibit unique photoluminescence properties originating from the 4f n electronic configuration such as large Stokes shifts, narrow feature emission, long luminescence lifetimes, and high quantum yields when sensitized by efficient “antenna effects” of ligand.22 Therefore, the synthesis of Ln-MOFs with outstanding fluorescent properties and permanent porosity become a desirable window for the preparation of Ln-MOFsbased sensors. To date, Ln-MOFs have proven successful in the detection of volatile organic compounds,28−31 small molecules,32−36 and ionic species37−43 as well as others.44−48 Nevertheless, Ln-MOFs-based sensors for biomarker tt-MA have never been investigated. In addition, given the element abundance, high coordination numbers, and variable nature of the Ln(III) sphere, the rational design and preparation of desired lanthanide MOFs remains a great challenge.25 Recently, postsynthetic modifications (PSM) of transition metal based MOFs can provide a solution by the introduction Received: April 4, 2018
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DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry of Ln(III) ions into MOFs, which is able to efficiently sensitize the characteristic luminescence of Ln(III) ions and opens up a way to a new class of luminescence Ln-MOFs.24,26,27 When Ln(III) ions (mainly Eu(III) and Tb(III) ions) are introduced within a MOF host, they provide multiple luminescent centers in the hybrid systems that can emit at different positions in the visible region, which allows for luminescence tuning and whitelight integration for potential applications in lighting and displays.49−51 As prerequisites of Ln(III) incorporation, the MOFs selected must have high porosity and possess available functional groups that can withstand chemical transformations, and their crystalline structure must be stability after functionalization. These groups are commonly like carboxylic group,39,42,49,52,53 bidentate nitrogen sites,30,40,43 and so on. To the best of our knowledge, the PSM of MOFs containing uncoordinated sulfonate group has been rarely reported, though the sulfonate group has certain coordination ability to metal cations.54−58 Inspired by this, Zn-based MOF-SO−3 which has free sulfonate groups, high porosity, and stability as well as good luminescence property was chosen as a host framework57 to load Ln(III) ions for the purpose of sensitizing the Ln(III) luminescence. In this contribution, we present an alternative approach to prepare a highly luminescent Ln-based MOF by introducing Tb(III) ions in MOF-SO−3 to form Tb(III)@MOF-SO−3 which is based on notable and specific luminous sensitization of MOF-SO−3 to Tb(III) ions. The bi-metal-loaded Eu(III)/ Tb(III)@MOF-SO−3 exhibits a Tb(III)-induced luminescence of Eu(III) ions and the fluorescence emissions of this all locate in white region under various excitation wavelengths. A kind of white-lighting thin film is prepared based on this bimetal hybrid system and exhibits dazzling white light when excited at 295 nm. Moreover, the Tb(III)@MOF-SO−3 is first developed as a highly selective and sensitive fluorescence sensor toward biomarker tt-MA via fluorescence quenching. It is worth noting that the high fluorescence and structural stability in water, the low detection limit, and recyclability as well as high antidisturbance together give Tb(III)@MOF-SO−3 sensor the potential for the practical detection of tt-MA in urine systems. The possible quenching mechanisms are also investigated in detail. The design idea is illustrated in Scheme 1.
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Scheme 1. Schematic Illustration Showing the Design Principle of Tb(III)@MOF-SO−3 as a Luminescence Probe for tt-MA Which Is the Metabolite and Biomarker of Human Exposure to Benzenea
White-lighting thin film is prepared based on Tb(III)/Eu(III)@ MOF-SO−3 under excitation. a
UK) after the samples were decomposed with concentrated nitric acid. The X-ray photoelectron spectroscopy (XPS) profiles were recorded on a RBD upgraded PHI- 5000C ESCA system (PerkinElmer) with Mg Kα radiation (hυ = 1253.6 eV). The CIE (Commission International de I’Eclairage) color coordinates were calculated on the basis of the international CIE standards.60 Synthesis of {[Zn 3 (μ 3 -OH) 3 (2-stp)(bpy) 1.5 (H 2 O)](EtOH)(2H2O)}n (MOF-SO−3 ).57 In a typical synthesis procedure of MOFSO−3 with some modification, the reaction temperature was set at 80 °C. The ethanol solution (100 mL) containing Zn(NO3)2·6H2O (1.16 g) was added to H2O/ethanol (1:2) solution (150 mL) dissolved 2-sulfonylterephthalate (2-stp, 0.35 g), 4,4′-bipydine (bpy, 0.30 g), and NaOH (0.26 g) to give white powder precipitates. The reaction was then stirred for 1 day in a 80 °C oil bath and finally the resultant precipitates was filtrated, washed with ethanol, and dried at room temperature. Synthesis of Ln(III)@MOF-SO−3 . The newly prepared MOF-SO−3 sample (100 mg) was ground and then immersed into a vial of 20 mL Ln(NO3)3 aqueous solutions (Ln = Tb, Eu, Sm, and Dy; 10−3 mol· L−1). After stirring at room temperature for 12 h, the products were filtrated and washed with water several times out of residual rare earth salt, followed by drying under a vacuum at 100 °C for 12 h in order to remove solvents in pores. Finally, Ln(III)@MOF-SO−3 was obtained with high yield (95% based on MOF-SO−3 ). The synthesis method of Eu(III)/Tb(III)@MOF-SO−3 was similar to that of Ln(III)@MOFSO−3 except for the Eu(III)/Tb(III) concentration of 10−3/10−3 mol· L−1 or 2.5 × 10−3/10−3 mol·L−1. Luminescence Sensing Experiments. As for the experiments of sensing urine chemicals, finely ground sample (2.5 mg) of Tb(III)@ MOF-SO−3 was straightly dispersed into the aqueous solutions (3 mL, 10 mM) of different urine chemicals including creatine, creatinine (Cre), KCl, NaCl, NH4Cl, urea, glucose (Glu), Na2SO4, and tt-MA, treated by ultrasonication for approximately 20 min, and then aged for 12 h for the formation of stable suspensions. The luminescence spectra of these suspensions were measured after sonicating for 3 min. Preparation of Eu(III)/Tb(III)@MOF-SO3− Thin Film. The mixture of Eu(III)/Tb(III)@MOF-SO−3 , ethyl methacrylate (EMA), and tetramethyleneoxide (THF) was stirred evenly, followed by adding benzoperoxide (BPO) as an initiator. Through 65 °C reflux, cooling, and vacuum rotary drying, the resulting colloid product was directly spin-coated on the surface of the precleaned quartz glass (1 cm × 1 cm), and finally, the thin films based on Eu(III)/Tb(III)@ MOF-SO−3 can be obtained. Preparation of Test Paper Based on Tb(III)@MOF-SO−3 . The filter paper was cut into strips (1 cm × 2.5 cm) that were dipped in
MATERIALS AND METHODS
Materials and Instruments. Ln(NO3)3·6H2O (Ln = Tb, Eu, Sm, Dy) was prepared by dissolving the Ln2O3 into excess hydrogen nitrate with continuous stirring, followed by evaporation and crystallization for several times. All the other reagents and solvents were purchased commercially. The powder X-ray diffraction (PXRD) patterns were recorded with a Bruker D8 Advance diffractometer. UV−vis absorption spectra were carried on Agilent 8453 spectrometer. The excitation and emission spectra of the solid or liquid samples were obtained on an Edinburgh FLS920 spectrophotometer with a 450 W xenon lamp as an excitation source. Luminescence lifetime measurements were carried out on an Edinburgh FLS920 phosphorimeter using a microsecond lamp (100 mW). The emission quantum yields (QY) were measured with a Fluorolog-3 (HORIBA company) quantum yield measurement system with a 450 W Xe lamp coupled to a monochromator for wavelength discrimination, an integrating sphere as sample chamber, and an R928P analyzer for signal detection. Fourier transform infrared spectra (FTIR) were measured within KBr slices in the range of 4000−400 cm−1 using a Nexus 912 AO446 infrared spectrum radiometer. The quantitative analysis of Zn(II) and Ln(III) ions in the materials was performed on an X7 Series inductively coupled plasma mass spectrometer (ICP-MS) (Thermo Elemental, Cheshire, B
DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry the suspension of Tb(III)@MOF-SO−3 (1 mg/mL) in ethanol and then left to dry at room temperature. To determine tt-MA, the strips were immersed into different concentrations of tt-MA aqueous solutions for 4 min and then exposed to air for drying.
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centered luminescence emission.22 The emission spectrum of MOF-SO−3 in the solid state displays blue emission with a broad band around 408 nm (excitation wavelength (λex) at 305 nm), which comes from the intraligand π*−π transition of the ligands. The solid-state excitation and emission spectra of MOF-SO−3 are similar to those of the 2-stp ligand except for some blueshift of the wavelength (Figure S4a,b), which can be attributed to the coordination and deprotonation of the Zn(II) cations to 2-stp ligands. The luminescence of MOF-SO−3 is stronger than that of free ligands, which is due to the coordination effect.59 In recent years, outstanding luminescent materials designed by encapsulating lanthanide cations within the porous MOFs are of interest in photoluminescence properties.26,27 The MOF-SO−3 framework containing free pendent twigs and electron-rich π-systems that exhibit a good ligand-centered luminescence can be regarded as an ideal substrate to postsynthetically functionalize Ln(III) ions in order to sensitize the luminescence of Ln(III) ions. Thus, we react MOF-SO−3 powder with Ln(NO3)3 (Ln(III) = Tb(III), Eu(III), Sm(III), Dy(III)) salt in aqueous solution containing Ln(III) ions (10−3 mol·L−1) to yield Ln(III)@MOF-SO3− hybrid systems, of which the PXRD patterns (Figure S5) are almost matched with the PXRD pattern of the simulated and as-synthesized MOF-SO−3 , denoting that MOF-SO−3 framework remains unchanged after reaction. The emission spectra of Ln(III)@MOF-SO−3 in the solid state are initially measured at room temperature. As shown in Figure 1, the single Tb(III)
RESULTS AND DISCUSSION
Characterizations of MOF-SO−3 and Tb(III)@MOF-SO−3 . The pristine framework MOF-SO−3 was prepared as previous report.57 For the as-synthesized MOF-SO−3 , the PXRD profiles of the experimental and simulated patterns are consistent with each other according to single crystal structure (Figure S1) which demonstrates the successful preparation of MOF-SO−3 with high phase purity. The structure of MOF-SO−3 crystallizes in the orthorhombic space group Pnma and features a pillaredlayer type 3D porous framework with the 1D channel that has undulated surface. The 1D channel is formed with the smallest cross section of 4.6 × 4.6 Å2 and occupied with guest water and EtOH molecules. The metal-free sulfonate groups of 2-stp ligands are directed into the rectangular pores, which provide free Lewis basic sites for the coordination of metal cations. Attributed to the orderly pendent twigs on the pore walls and the permanent porosity, MOF-SO−3 as an ideal host can be readily postfunctionalized with Ln(NO3)3 aqueous solution by a straightforward acid−base reaction. Therefore, Tb(III)@ MOF-SO−3 hybrid system was obtained by reacting MOF-SO−3 sample with nitrate salts of Tb(III) in water. X-ray photoelectron spectroscopy (XPS) characterization of MOF-SO−3 and Tb(III)@MOF-SO−3 were applied in order to validate the coordination effect between the sulfonate groups on MOFSO−3 and Tb(III) ions. As demonstrated in the full XPS profiles, (Figure S2a), the peaks at the ranges of 1007−1070 eV and 1220−1292 eV pertaining to Zn 2p and Tb 3d manifest the existence of Zn(II) and Tb(III) ions in the Tb(III)@ MOF-SO−3 . The XPS profiles of O 1s and Tb 3d are enlarged in Figure S2b,c. The O 1s peaks at 529.3 eV in MOF-SO−3 shifts to 529.4 eV after incorporating Tb(III) ions, which is a minor change that may be due to the smaller proportion of oxygen atoms of sulfonate groups than carboxyl groups. There are two emerging Tb 3d signals of Tb(III)@MOF-SO3− peaking at about 1240.2 and 1275.1 eV which are both lower than those of the Tb(NO3)3·6H2O (1239.5 and 1274.5 eV). These changes of the binding energy can demonstrate the effect of coordination bonds between Tb(III) ions and free sulfonate group on 2-stp ligands. In addition, the observably weakened IR absorption of the free sulfonate groups at about 1190 cm−1 in MOF-SO−3 after the incorporation of Tb(III), Eu(III) Sm(III), and Dy(III) ions into framework demonstrates the coordination interaction between free sulfonate groups and the loaded metal cations (Figure S3), and the remaining absorption band of free sulfonate groups implies the possibility of multimetal loaded. The loading amount of Ln(III) ions on MOF-SO3− were measured by ICP-MS analysis, and the molar ratios of Zn(II) and Ln(III) ions are listed in Table S1, clearly showing the successful loading of Ln(III) ions. As shown in Figure S4a, the excitation maximum of MOF-SO−3 shows a significant blue-shift from 305 to 291 nm after incorporating Tb(III) and Eu(III) ions, which also indicates the coordination effect between the metal cations and free sulfonate groups of MOF-SO−3 . Luminescent Property. The fluorescent spectra of MOFSO−3 and the free ligands in the solid state are first recorded at room temperature. Such complexes containing Zn(II) nodes that have d10 configurations generally exhibit excellent ligand-
Figure 1. Solid-state emission spectra of Ln(III)@MOF-SO 3− (Ln(III) = Eu(III), Tb(III), Sm(III), Dy(III)) (λex = 291 nm). Inset: CIE chromaticity diagram (A: Tb(III)@MOF-SO−3 , B: Eu(III) @MOF-SO−3 , C: MOF-SO−3 ).
and Eu(III)-loaded MOF-SO−3 show obvious emissions of the Tb(III) and Eu(III) ions, while there are hardly corresponding Ln(III) fluorescence emissions observed for Sm(III) and Dy(III)-loaded MOF-SO3−. This indicates that the open framework MOF-SO−3 is not able to sensitize Sm(III) and Dy(III) ions. When excited at the wavelength of 291 nm, a series of narrow emission peaks appear at 490, 544, 586, and 622 nm for Tb(III)@MOF-SO−3 are clearly observed. This can be ascribed to the characteristic 5D4 → 7FJ (J = 6−3) transitions of Tb(III) and the most intense transition exhibited by 5D4 → 7F5 transition (at 544 nm) located in the green region with a CIE coordinate of (0.258, 0.3392). The lifetime value of typical 5D4 Tb(III) emission at 544 nm is 1.035 ms from its luminescent decay pattern by fitting the data with a biexponential curve (Figure S7b). In the excitation spectrum of C
DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry Eu(III)@MOF-SO−3 , a sharp line is observed at 396 nm corresponding to the 7F0 → 5L6 transition of Eu(III) ions (Figure S4a). Compared with the luminescence of Tb(III)@ MOF-SO−3 , the inconspicuous emissions at 590 and 613 nm for Eu(III)@MOF-SO−3 originate from magnetic-dipole (5D0 → 7F1) and electric-dipole (5D0 → 7F2) transitions of Eu(III) ions. This indicates the lower sensitization of Eu(III) ions in Eu(III)@MOF-SO−3 and achieving a CIE coordinate of (0.249, 0.113) which is close to the (0.171, 0.100) coordinate of MOF-SO−3 in the blue region. The emission decay curve of typical 5D0 Eu(III) monitored at 5D0 → 7F2 for Eu(III)@ MOF-SO−3 displays a biexponential behavior yielding a lifetime value of 0.362 ms. (Figure S7a) The quantum yield (QY) of Tb(III)@MOF-SO−3 is about 20.12% which is higher than 10.32% of Eu(III)@MOF-SO−3 , further indicating the excellent sensitization of MOF-SO−3 to Tb(III) ions. It is worth noting that the ligands-based luminescence intensities of MOF-SO−3 at 408 nm are apparently reduced in the solid-state emission spectra of the single Tb(III) and Eu(III)-loaded MOF-SO−3 , while the characteristic emission intensities of Tb(III) and Eu(III) are enhanced, especially Tb(III) ions. As we know, the f−f transitions of Ln(III) ions with a low molar absorptivity are forbidden by parity (Laporte) selection rules, which is responsible for weak absorbance and faint luminescence. However, organic fluorophores can efficiently transfers energy absorbed to Ln(III) excited levels to trigger the characteristic fluorescence of Ln(III) emitters, which is known as the “antenna effect”.22 On the basis of outstanding luminescence performance of Tb(III)@MOF-SO−3 , the Tb(III)-induced luminescence of other Ln(III)@MOF-SO−3 system is further investigated. After introducing Eu(III) ions into Tb(III)@ MOF-SO−3 , bi-metal-loaded Tb(III)/Eu(III)@MOF-SO−3 system is prepared by reacting MOF-SO−3 with aqueous solution containing Tb(III) and Eu(III) ions of 10−3/10−3 mol·L−1, and the PXRD pattern of this system is basically consistent with that of MOF-SO−3 , indicating the structural integrity (Figure S5). An obvious increase of typical Eu(III) emissions in Tb(III)/Eu(III)@MOF-SO−3 are observed at the maximum excitation wavelength of 291 nm (Figure S6). The lifetime value of the typical Eu(III) emission at 614 nm is 0.392 ms higher than 0.363 ms of Eu(III)@MOF-SO−3 ; furthermore, the lifetime value of Tb(III) at 544 nm is 1.006 ms lower than 1.035 ms of Tb(III)@MOF-SO−3 (Figure S7c,d). These results demonstrate exclusively a Tb(III)-induced Eu(III) luminescence based on the energy transfers from Tb(III) to Eu(III) center, as observed in several Eu(III) and Tb(III) cosystems.61−63 With consideration of the green and red emission features of Tb(III) and Eu(III) ion, as well as the blue emission feature of the MOF-SO−3 , we further investigate the luminescence color tuning of bilanthanum ion loaded MOF-SO−3 by adjusting the amount of metals doped and changing the excitation wavelengths. The Tb(III)/Eu(III)@MOF-SO3− system is successfully prepared through reacting MOF-SO3− with aqueous solution containing Tb(III) and Eu(III) ions of 2.5 × 10−3/10−3 mol·L−1. According to the excitation spectrum of this Tb(III)/Eu(III)@MOF-SO−3 system, when the absorption wavelengths are changed from 265 to 295 nm, we can clearly find that the luminescence intensities of typical Tb(III) and Eu(III) ions emissions and the ligand-centered emission change under different excitation wavelengths (Figure 2, points a−g). Nevertheless, the corresponding CIE coordinates are calculated to change from (0.373, 0.369) to (0.301, 0.264),
Figure 2. Solid-state emission spectra of Tb(III)/Eu(III)@MOF-SO−3 with different excitation wavelengths: (a) 265 nm, (b) 270 nm, (c) 275 nm, (d) 280 nm, (e) 285 nm, (f) 291 nm, (g) 295 nm. Inset: CIE chromaticity diagram and the solid-state excitation spectrum.
which are all located in white region. Specifically, when Tb(III)/Eu(III)@MOF-SO−3 is excited at 275, 280, and 285 nm, the chromaticity coordinates at (0.339, 0.330), (0.337,0.326), and (0.334, 0.316) are very close to those of standard white light (0.333, 0.333) according to the 1931 CIE coordinate diagram, which all have high color rendering index (CRI) of about 85 and QY values of 8.86, 9.06, and 10.12%, respectively (Table S2). Keeping the positive results of the Tb(III)/Eu(III)@MOF-SO−3 in hand, we then explore the possibility of application in small device like thin films with this hybrid system. Organic polymeric monomer of ethyl methacrylate (EMA) is commonly selected for the preparation of thin films because of its low absorption in the UV region.64 The Tb(III)/Eu(III)@MOF-SO−3 -based thin film is successfully prepared according to literature reports.50,51 The thin film is strikingly transparent, and its surface is smooth and continuous (Figure 3 inset). When the excitation wavelengths are in the range of 275−300 nm, the emission spectra of this
Figure 3. Emission spectra of Tb(III)/Eu(III)@MOF-SO−3 thin film with different excitation wavelength: (a) 275 nm, (b) 280 nm, (c) 285 nm, (d) 291 nm, (e) 295 nm, (f) 300 nm. Inset: CIE chromaticity diagram, the excitation spectrum of thin film and images under excitation wavelengths. D
DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
Figure 4. PXRD patterns and solid-state emissions of Tb(III)@MOF-SO−3 and Tb(III)@MOF-SO−3 collected from water with different pH values and prolonged immersion in water.
Figure 5. Emission spectra of Tb(III)@MOF-SO−3 in different aqueous solutions of common ingredients in urine (a); emission intensities (b) of the main peak at 544 nm assigned to5D4 → 7F5 transition of Tb(III) (λex = 291 nm).
means of fluorescence sensing can be a convenient and effective way of monitoring benzene exposure and realizing the protection of human health. The remarkable luminescence properties of Tb(III)@MOF-SO−3 , including highly intense emission, high quantum yield, and long emission lifetime, prompt us to examine whether this hybrid system possesses the potential for sensing tt-MA. tt-MA as biomarker of the benzene metabolic process is usually found in urine, mainly in water. Therefore, it is essential for Tb(III)@MOF-SO−3 to investigate the stability in water so as to confirm whether Tb(III)@MOFSO−3 can be regarded as a candidate for sensing tt-MA in urine. The Tb(III)@MOF-SO−3 sample was immersed in water for several days’ storage. Then, the solid sample was collected, and PXRD measurement was carried out. Almost no obvious changes of the PXRD pattern can be observed compared with the PXRD pattern of as-synthesized MOF-SO−3 , and the solid emission intensity of Tb(III)@MOF-SO−3 at 544 nm is
thin film are similar to that of solid Tb(III)/Eu(III)@MOFSO3− (Figure 3, points a−f). The corresponding CIE coordinates change from (0.347,0.364) to (0.310, 0.269) which also fall within the white region with high CRI value, indicating that the quartz glass matrix has little effect on luminescence of Tb(III)/Eu(III)@MOF-SO3− thin film. Notably, under different excitation wavelengths, the Tb(III)/ Eu(III)@MOF-SO−3 thin film can emit dizzying white light in the dark environment (Figure 3 inset). When the excitation wavelengths is excited at 295 nm, the chromaticity coordinate at (0.338,0.323) is very close to the standard white light (0.333, 0.333) with CRI value of 86 and QY value of 10.03% (Figure 3 point e, Table S2). Sensing Performance for tt-MA. Urinary tt-MA usually as a benzene metabolite is widely used as a biological biomarker of environmental and occupational exposure to this xenobiotic.3−7 The measurement of urinary tt-MA by E
DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
lifetime of Tb(III) ions (Figure S9, Table S3), which suggests the specific interaction between the Tb(III) ions and the ttMA. These show that the quenching effect of tt-MA on the characteristic emission of Tb(III) ions in aqueous suspensions of Tb(III)@MOF-SO−3 is not influenced by the coexisting components, further confirming that Tb(III)@MOF-SO−3 is a highly selective sensor for tt-MA in aqueous media. In order to evaluate the response sensitivity of Tb(III)@ MOF-SO−3 to tt-MA, the concentration of tt-MA toward the quenching effect on luminescence of Tb(III)@MOF-SO3− aqueous suspensions is further investigated. As a result of the high energy O−H oscillators of the water molecule that significantly quench the metal excited states nonradiatively,65 there exists difference between the fluorescence emission of Tb(III)@MOF-SO−3 aqueous suspensions and its solid-state sample. This is mainly manifested as the relative intensity of luminescence between ligands-based emission and typical Tb(III) emission at 408 and 544 nm changing obviously in both phases. The lifetime value of Tb(III) emission at 544 nm in the aqueous suspensions of Tb(III)@MOF-SO−3 is 0.985 ms that is lower than 1.035 ms of solid Tb(III)@MOF-SO−3 sample, which shows that the “antenna effect” of ligands is suppressed in aqueous environment. As shown in Figure 7a, gradual decreases of the fluorescence emissions of ligandsbased and typical Tb(III) ions are observed in Tb(III)@MOFSO−3 aqueous suspensions as the tt-MA concentration increases from 0 to 200 μg·mL−1. When the concentration of tt-MA is 5 μg·mL−1, nearly half the intensity of typical Tb(III) emission at 544 nm is quenched with the quenching efficiency of 49%. (The quenching efficiency (QE) is defined by (I0 − I)/I0 × 100%,63 where I0 and I are the luminescence intensities of Tb(III) ions before and after the addition of tt-MA, respectively.) When the tt-MA concentration is 100 μg·mL−1, the QE value of typical Tb(III) emission is up to 92%, though the blue emission band of ligands-based can still be observed. However, there are almost no conspicuous emissions of the both detected when the tt-MA concentration is 200 μg·mL−1. Interestingly, under irradiation with a UV lamp, Tb(III)@ MOF-SO−3 test papers show visible luminous variation from light green to nattier blue after soaking in various concentrations of tt-MA aqueous solutions (from 0 to 100 μg·mL−1) (Figure 7b). This is in accord with the luminescence changes of Tb(III)@MOF-SO−3 aqueous suspensions under different concentrations of tt-MA. These also demonstrate the good response sensitivity of Tb(III) ions to tt-MA, realizing visible detection of tt-MA in aqueous solution. The relationship curve of the quenching effect (I0/I) and tt-MA content is nonlinear within the full range concentrations of tt-MA, which cannot be fitted well by the Stern−Volmer equation,37 I0/I = 1 + Ksv × [M] (Ksv is the quenching constant and [M] is the mass concentration of tt-MA). However, in the range of low concentrations of tt-MA from 0 to 20 μg·mL−1, the S−V equation shows a certain linear relationship (R2 = 0.97) and yields a linear curve by which Ksv can be calculated as 0.27932 mL·μg−1 (Figure 7c). The limit of detection (LOD) is estimated to be 0.1 μg·mL−1 (ppm) according to 3σ/k (σ: standard error; k: slope),39,40 which indicates that Tb(III)@ MOF-SO3− can be an effective luminescent sensor for quantifiably probing tt-MA when the tt-MA content is less than 20 μg·mL−1 in aqueous media. To test the response rate of Tb(III)@MOF-SO−3 as a tt-MA sensor, the real-time sensing of tt-MA in aqueous media was implemented. The timedependence of emission spectra and intensities of typical
maintained at a high level compared to the initial value, which shows the high water tolerance and photostability of Tb(III)@ MOF-SO−3 . Moreover, Tb(III)@MOF-SO−3 also exhibits good pH-independent luminescence stability and structure stability according to the urine pH range of 4−10 (Figure 4). These results demonstrate that the Tb(III)@MOF-SO−3 can be used for sensing experiences in urine environment. Thus, the Tb(III)@MOF-SO−3 sample was first immersed in different aqueous solutions of common ingredients in urine (10−2 mol· L−1) including creatine, creatinine (Cre), urea, uric acid (UA), tt-MA, Na+, K+, NH4+, Cl−, SO42−, and glucose (Glu) to form stable suspensions by ultrasonication and aging for 12 h. The PXRD patterns of Tb(III)@MOF-SO−3 collected from aqueous solutions of these chemicals match well with the PXRD pattern of the as-synthesized MOF-SO−3 , demonstrating its good structure stability after immersing treatment (Figure S8). The emission spectra of the Tb(III)@MOF-SO−3 aqueous suspensions containing different urine chemicals are investigated and compared at an excitation wavelength of 291 nm. The results clearly show that the fluorescence emission of Tb(III)@MOFSO−3 suspension is totally quenched only by tt-MA (Figure 5a). Notably, the emission intensity of Tb(III) ions at 544 nm in aqueous suspension of Tb(III)@MOF-SO−3 /tt-MA contrasts sharply with that in aqueous suspension of Tb(III)@MOFSO−3 /other urine chemicals (Figure 5b), indicating Tb(III)@ MOF-SO−3 can serve as a sensor for selective recognition of ttMA in aqueous media. The competition experiments are also carried out to investigate the antidisturbance of the Tb(III)@ MOF-SO−3 sensor. As shown in Figure 6, when extra tt-MA is
Figure 6. Emission intensities of Tb(III)@MOF-SO−3 at 544 nm (5D4 → 7F5 Tb(III)) upon the addition of tt-MA (10 mM) in the presence of a background concentration of various urine chemicals (10 mM) in aqueous solution (λex = 291 nm).
added to the Tb(III)@MOF-SO3− aqueous suspensions containing other urine chemicals, the fluorescence emissions of these suspensions are almost entirely quenched, results similar to that with suspensions containing tt-MA only. Moreover, the fluorescence lifetime of 5D4 Tb(III) emission at 544 nm is greatly reduced from 0.985 to 0.539 ms, and other urine chemicals have no significant effects on the emission F
DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry
Figure 7. (a) Emission spectra of Tb(III)@MOF-SO−3 dispersed in aqueous solutions with different concentrations of tt-MA (λex = 291 nm). (b) Optical images of test paper under 254 nm UV light irradiation after immersing into aqueous solutions with different concentrations of tt-MA. (c) S−V curve of I0/I − 1 versus concentration of tt-MA.
experiment of sensing tt-MA was carried out with the similar method, in a simulated urine system containing creatine (Cre), urea (UA), Na+, K+, NH4+, Cl−, SO42−, and Glu. The luminescence spectra of Tb(III)@MOF-SO−3 show a similar result as the concentration of tt-MA increases (Figure S11) and when the tt-MA is increased to 90 μg·mL−1, the emission intensity of typical Tb(III) ions is largely quenched with the QE value of 89%, which further indicates the extremely high antidisturbance of Tb(III)@MOF-SO−3 even in the multicomponent simulated urine. These results suggest that the fabricated Tb(III)@MOF-SO−3 can serve as an excellent candidate for practical detection of biomarker tt-MA in urine systems. Sensing Mechanisms. The possible mechanisms for the quenching effects of tt-MA on luminescence of Tb(III)@ MOF-SO−3 are further investigated. The PXRD pattern (Figure S8) of Tb(III)@MOF-SO−3 collected from tt-MA aqueous solution is very similar to that of MOF-SO−3 , which not only indicates the structure stability of Tb(III)@MOF-SO−3 but also automatically excludes possibility of fluorescence quenching based on structural reorganization and collapse. Both the depressed emission lifetime of Tb(III) ions and the variation of intensity ratio I(5D4 → 7F6)/I(5D4 → 7F5) for Tb(III) ions in aqueous suspension of Tb(III)@MOF-SO−3 /tt-MA (Figure S13, Table S3) demonstrate the weak coordination interaction between tt-MA sites and Tb(III) ions; therefore, the luminescence of Tb(III) ions is reduced by the vibrations of tt-MA molecules.66,67 The UV−vis absorption spectrum for the tt-MA aqueous solution shows strong absorption from 230 to 285 nm, which is largely overlapped by the absorption band of MOF-SO−3 and Tb(III)@MOF-SO−3 . When adding tt-MA into the aqueous suspensions of MOF-SO−3 and Tb(III)@MOFSO−3 , the absorption spectra of both show a marked decrease (Figure S14a). These demonstrate that the competitive absorption24 and the inefficient ligand-to-Tb(III) energy
Tb(III) ions at 544 nm are shown in Figure S10a,b. The luminescence intensity of Tb(III) ions is significantly reduced within 30 s with a QE of nearly 50% after addition of tt-MA (80 μg·mL−1). However, the luminescence quenching reached a constant with a QE of more than 75% in 10 min. This demonstrates the fast luminescence response of the sensor to tt-MA. Regeneration experiences show that the Tb(III)@ MOF-SO−3 can be a recyclable sensor to recognize tt-MA in aqueous solution after collecting by simple filter and multiple washing with distilled water. As shown in Figure 8, the luminescence intensity of Tb(III) ions can basically recover as before through removal of tt-MA, and Tb(III)@MOF-SO−3 still exhibits the quenching effect toward tt-MA as well as the structural stability after four cycles (Figure S11). The
Figure 8. Luminescence intensity of Tb(III)@MOF-SO−3 at 544 nm after four recyclable experiments of sensing for tt-MA in aqueous solution. (λex = 291 nm). G
DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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Inorganic Chemistry transfer can quench the fluorescence of the ligands-based emission and typical Tb(III) ions emissions in aqueous suspension of Tb(III)@MOF-SO−3 /tt-MA. Moreover, we also found that the fluorescence of ligands-based emissions in Tb(III)@MOF-SO−3 aqueous suspensions are no apparent wavelength-shift except that the luminescence intensities gradually decrease as the concentration of tt-MA increases, (Figure S14c) which can rule out the possibility of static quenching that is based on the formation of nonemissive intermediates.35,37,68 In other words, the mechanism of dynamic quenching based on collision between the excitedstated Tb(III)@MOF-SO3− and tt-MA can mainly be responsible for the quenching effect of tt-MA on the luminescence of Tb(III) ions in Tb(III)@MOF-SO−3 aqueous suspensions, as proved by that the fluorescence lifetime of Tb(III) ions gradually decreases when the concentration of ttMA increases. Moreover, a certain linear relationship (R2 = 0.97) between the lifetime value of Tb(III) ions and the concentration of tt-MA is obtained (Figure S14b). In addition, the luminescence intensity of typical Tb(III) ions at 544 nm steeply declines when the concentration of tt-MA increases from 0 to 20 μg·mL−1 and there is a linear curve (R2 = 0.97) between the luminescence intensity of Tb(III) ions and the concentration of tt-MA. However, when the tt-MA content is above 20 μg·mL−1, this curve deviates from the straight line and gradually slows down reaching quenching saturation, (Figure S14d) which can be result from that the diffusion from tt-MA to host is suppressed under the high concentration.35
Author Contributions §
X.-L.Q. and B.Y. contributed equally to this work.
Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (21571142) and the Developing Science Funds of Tongji University.
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CONCLUSION In summary, new luminescent lanthanide-based MOFs hybrid systems are first fabricated using a straightforward postsynthetic modification strategy to incorporate Ln(III) ions into the pores of MOF-SO−3 . The notable and specific luminous sensitization of MOF-SO−3 to Tb(III) ions constitutes the basis of the design and construction of Tb(III)@MOF-SO−3 hybrid system. The Eu(III)/Tb(III) loaded MOF-SO−3 exhibits a Tb(III)-induced luminescence of Eu(III) ions and realizes the white-lighting tuning. A kind of white-lighting thin film prepared on the bimetal hybrid system exhibits dazzling white light. Moreover, Tb(III)@MOF-SO−3 shows not only strongly selective quenching effect on the biomarker tt-MA but also excellent sensitivity (LOD = 0.1 ppm), high antijamming, as well as recyclability. Such properties make the prepared Tb(III)@MOF-SO−3 an effective sensor toward the biomarker tt-MA of benzene and open up a new approach for practical detection of tt-MA in urine systems.
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ASSOCIATED CONTENT
* Supporting Information S
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.8b00912. Structure representation; IR spectra; XPS spectra; ICP data; PXRD patterns; and other luminescence data (PDF)
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected]. ORCID
Bing Yan: 0000-0002-0216-9454 H
DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
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DOI: 10.1021/acs.inorgchem.8b00912 Inorg. Chem. XXXX, XXX, XXX−XXX
