Ln(III)-Functionalized Metal–Organic Frameworks Hybrid System: Luminescence Properties and Sensor for trans,trans-Muconic Acid as a Biomarker of Benzene

Abstract

By application of a straightforward postsynthetic modification strategy, a luminescent lanthanide-based MOFs hybrid material, Tb(III)@MOF-SO, is first fabricated by loading Tb(III) ions into the pores of Zn-based MOF-SO. This hybrid system is constructed on notable and specific luminous sensitization of MOF-SO to Tb(III) ions. The further study shows that bi-metal-loaded Eu(III)/Tb(III)@MOF-SO 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 exhibits dazzling white light when excited at 295 nm ( X = 0.338, Y = 0.323). Furthermore, the Tb(III)@MOF-SO 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.

SURMOF Devices Based on Heteroepitaxial Architectures with White‐Light Emission and Luminescent Thermal‐Dependent Performance

“…In recent years, a large number of luminescent MOFs have been reported for this purpose. [ 5,13–24 ] Moreover, for uses in nanotechnology, it is mandatory that MOFs are anchored on solid substrates, being particularly evident in the case of optoelectronic applications. [ 25,26 ] According to specialized reviews such as those from Wöll group, [ 27 ] it is distinguishable the surface‐supported metal–organic frameworks (SURMOFs) devices, fabricated using layer‐by‐layer (LbL) methodologies, where the orientation and film thickness can be well‐controlled.…”

“…[ 32 ] For example, by a rational combination of the blue, red, and green emission colors white‐light emission was achieved with Ln 3+ intercalated into the pore system, for example, the MOFs [ 24,33 ] Eu 3+ ,Tb 3+ @ZJU‐1 or Eu/Tb@IFP‐1 and IFP‐6 with CIE coordinates close to ideal white light, [ 24,33 ] among others. [ 15,17 ] Also, another strategy to produce SSWL devices is the incorporation of lanthanide‐coordination compounds into HKUST‐1 films. [ 34 ]…”

“…In the literature, luminescent MOFs play an important role for white‐light emission with a significant number of examples of white‐light emitters for powdered/bulk MOFs that exhibit emission of white light or close to the white point (for more information, see Table S1, Supporting Information). [ 13–24 ] However the implementation of thin films and eventually SURMOFs is scarcely reported.…”

Different Analytical Techniques, Pretreatment Methods and Adsorbent Materials for the Determination of Trans, Trans-Muconic Acid in Urine Samples

“…Trans, trans-muconic acid (tt-MA) and S-phenylmercapturic acid (S-PMA) are the most commonly used urinary biomarkers associated with benzene exposure in humans to be detected from urine or blood [7][8][9]. The American Conference of Governmental Industrial Hygienists (ACGIH) has recommended tt-MA as a biological exposure index (BEI) which is suitable urinary biomarker of benzene at high concentrations (above 1 ppm) [1,[10][11][12]. It appears that tt-MA is a more specific biomarker than other metabolites at high levels of benzene exposure.…”

Novel Composites of Graphitic‐phase Nitrogen Carbon/Lanthanide Coordination Polymers as White Light‐emitting Phosphor

“…Among these materials, lanthanide coordination polymers are excellent candidates for designing multi‐color luminescent materials due to their unique, plentiful, and efficient emission of different colors . Up to now, reports of while‐light emission from lanthanide metal organic frameworks share some common strategies: (i) three‐component approach, which is based on isomorphous solid solution‐type mix‐Ln‐CPs, such as in blue emission La 3+ /Gd 3+ ‐coordinated ligand codoped with the red and green emissions of Eu 3+ and Tb 3+ by fine‐tuning the Ln 3+ ions molar ratios;, (ii) two‐component approach, in which two distinct Ln 3+ ions coexist in a single phase of the white‐light emitting materials , . For example, in Eu 3+ ‐doped Gd 3+ isostructural CPs color‐tunable luminescence and white‐light emission are realized by varying the excitation wavelength; (iii) mono‐ or homometallic lanthanide complexes, which usually comprise a single Ln 3+ ions with multiple emitting peaks, or, wisely, by the delicate design of homolanthanide complexes incorporating appropriate organic ligands or dyes for compensating emitting light …”