Eu-MOF-based highly sensitive and selective luminescence probe for trace, in situ and visual detection of flunitrazepam.

Flunitrazepam, as an emerging new psychoactive substance classified as a third-generation drug that is more harmful and camouflaged, is gradually proliferating globally. Maliciously used as a criminal tool in homicide and rape cases, it has already caused serious harm to public safety and social stability. Owing to its special molecular structure, low concentration level and rapid metabolic process in the human body, accurate detection of flunitrazepam remains a major challenge, especially for real sample and on-site detection. In this paper, a lanthanide MOF (Eu-MOF) based on bi-ligand was constructed as a luminescence probe and used for the first time to detect trace amounts of flunitrazepam. The 'antenna effect' promotes strong luminescence of Eu-MOF, while the lower LUMO orbital energy level of flunitrazepam allows it to accept electrons from the electron donor leading to quenching of Eu-MOF luminescence. The probe has a high sensitivity and can detect flunitrazepam in the range of 0-800 µM with a detection limit as low as 73 nM. Moreover, flunitrazepam was detected in urine from real samples as well as in a variety of beverages to further validate its accuracy and practicality. The reported Eu-MOF represents one of the pioneering luminescence probes for the detection of flunitrazepam, which offers great promise for the on-site or on-line analysis of flunitrazepam.

Synthesis of highly sensitive and multi-response Eu-MOF, fluorescence sensing properties and anti-counterfeiting applications.

A new Europium metal-organic framework (Eu-MOF), namely [Eu(dpa) (H2O)]·0.5(bpy)·4H2O}n (H4dpa = 5-(3,4-dicarboxyphenoxy) isophenic acid, bpy = protonated 4,4'-bipyridine) was synthesized and structurally characterized by elemental analyses, infrared spectroscopy, and X-ray single-crystal diffraction analyses. Eu-MOF shows a three-dimensional network structure based on EuIII ions and (dpa)4- ligands via µ4: η1, η2, η2, η2 coordination mode. Fluorescence analysis shows that Eu-MOF has excellent fluorescence sensing characteristics, which can efficiently and sensitively detect various pollutants in water: the limit of detection (LOD) of ratiometric fluorescence detection of ANI in water was 42.9 nM, which was better than the single-peak detection limit. In addition, the peak detection limits of Eu-MOF for Flu, ORN and NB were 120 nM, 27 nM and 94 nM, respectively. In addition, XPS, LUMO orbital energy level, fluorescence lifetime, ultraviolet absorption and other principles are used to explore the mechanism of fluorescence quenching. Surprisingly, Eu-MOF not only has excellent anti- counterfeiting ability and stability, can be used as anti-counterfeiting material in life, but also has good selectivity to Flu. Eu-MOF has obvious fluorescence quenching effect on Flu on paper under ultraviolet light, which can be used for rapid in situ imaging test paper of pesticide residues.

Dual-ligand lanthanide metal-organic framework based ratiometric fluorescent platform for visual monitoring of aminoglycoside residues in food samples.

Herein, a dual-emission Eu metal-organic framework (Eu-MOF) is prepared and used as the ratiometric fluorescence probe for ultrasensitive detection of aminoglycoside antibiotics (AGs). Due to the strong hydrogen bond interactions between AGs and Eu-MOF, the blue emission is enhanced while the red emission has little fluctuation in Eu-MOF with the addition of AGs, thus a good linear relationship with the logarithm of AGs concentrations from 0.001 to 100 µg/mL can be established for quantitative analysis. Good sensitivity with the detection limit of 0.33 ng/mL for apramycin, 0.32 ng/mL for amikacin and 0.30 ng/mL for kanamycin is achieved. The proposed assay demonstrates good selectivity and applicability for determination of AGs in real milk and honey samples. The Eu-MOF materials are further fabricated as fluorescent test papers for facile visual detection. The as-established ratio fluorescence platform offers a portable and economical way for rapid monitoring AGs residues in complex food samples.

A novel strategy for the synthesis of samarium/europium-metal organic frameworks, and their utilization for detection of Cr3+, Pb2+, and acetone as a luminescent sensor with superior selectivity and sensitivity properties.

With outstanding detection selectivity and sensitivity characteristics, samarium/europium-metal organic frameworks (Sm/Eu-MOF) is capable of functioning as a versatile light-emitting sensor particularly for detecting acetone, Cr3+, and Pb2+ in aqueous environment. While considering maximum detectable concentrations of 0.85 µM, 0.46 µM, and 1.04 µM, respectively, competitive energy interactions for acetone, absorption of energy for Cr3+, and substitution of ions for Pb2+ are the elucidated mechanisms of detecting these substances by Sm/Eu-MOF. Successful formulation and synthesis of a core-shell structured Sm/Eu-MOF, which has endurance to acid/alkali conditions and hydration/heat-stability, can be accomplished by utilizing Samarium and Europium nitrate ions, terephthalic acid, and 2, 5-furandicarboxylic acid. The recovery rate of acetone, Cr3+, and Pb2+ detection from real samples were 95.0-101.0 %, 99.8-101.0 %, and 99.9-104.0 %, respectively.

A Eu-MOF-Based Fluorescent Sensing Probe for the Detection of Tryptophan and Cu2+ in Aqueous Solutions.

Abnormal tryptophan (Trp) metabolism can be used as an important indicator of chronic hepatitis, paranoia, Parkinson's disease and other diseases. Deficiency or excessive accumulation of Cu2+ can cause diseases such as Wilson's disease and Alzheimer's disease. Eu-based metal-organic framework (Eu-MOF) was successfully prepared for fluorescence sensing of Trp and Cu2+ in an aqueous solution (pH = 7.4). Eu-MOF showed high selectivity and sensitivity for Trp and Cu2+ with detection limits of 0.22 µM and 0.09 µM and Ksv of 6.17 × 103 M- 1 and 2.37 × 104 M- 1 respectively. Trp and Cu2+ had overlapped UV absorption spectra with that of Eu-MOF and competed for the excitation light source. Trp also attenuated the antennae effect of organic ligands on Eu-MOF, thus quenching the red fluorescence of Eu-MOF. This study provides insights into the application of MOFs in bioanalysis and diagnostics.

Ratiometric fluorescence sensor based on europium-organic frameworks for selective and quantitative detection of cerium ions.

BACKGROUND: Due to the unavoidable use of cerium in daily life, the accumulation of cerium in the environment increases health risks for humans. Therefore, it is crucial to develop a chemical sensing technology for the rapid, sensitive, and selective detection of cerium ions. RESULTS: In this research work, a novel two-dimensional chain structure of a europium-based metal organic framework (Eu-MOF) [Eu2(tcpa)(Htcpa)2] was synthesized by using 3,4,5,6-tetrachloro-1,2-benzenedicarboxylic acid (H2TCPA) as the ligand and europium nitrate as the metal source. The results of powder X-ray diffraction and thermogravimetric analysis show that the synthesized Eu-MOF has excellent chemical and thermal stability. When the Eu-MOF suspension was excited by ultraviolet light at 292 nm, four fluorescence emissions were observed at 420, 595, 620 and 705 nm. It was particularly interesting that when cerium ions (Ce3+/Ce4+) were added to the Eu-MOF suspension, the fluorescence intensity at 420 nm was enhanced, while the fluorescence at 620 nm was quenched. On this basis, a ratiometric fluorescent sensor for detecting cerium ions was constructed, which has a good linear relationship in the range of 0.05-15 µM and a detection limit of 16 nM. The plausible mechanism of the change in the fluorescence characteristics of Eu-MOF caused by cerium ions was discussed in detail. Through the study of fluorescence lifetime and ultraviolet absorption, it was proven that the mechanism of Ce3+-quenching Eu-MOF fluorescence is the inner filter effect. Photoinduced electron transfer and internal filtering effects lead to fluorescence quenching at 620 nm, while redox reactions lead to fluorescence enhancement of the ligand at 420 nm. SIGNIFICANCE: The proposed ratiometric fluorescence sensor was successfully employed for the detection of cerium ions in real water samples, confirming that it can be used as an alternative method for the detection of Ce3+ and Ce4+ in environmental samples.

Lanthanide Metal-Organic Framework Isomers with Novel Water-Boosting Lanthanide Luminescence Behaviors.

Lanthanide metal-organic frameworks (Ln-MOFs) with exceptional optical performance and structural diversity offer a unique platform for the development of luminescent materials. However, Ln-MOFs often suffer from luminescence quenching by high-vibrating oscillators, especially in aqueous solution. Thus, multiple strategies have been adopted to improve the luminescence of Ln3+. Anomalous research about water-induced lanthanide luminescence enhancement of Ln-MOFs is in the primary stage. Here, two Eu-based metal-organic framework (Eu-MOF) isomers named QXBA-Eu-1 and QXBA-Eu-2 were constructed by using the same ligand under different solvent thermal conditions, which exhibited distinctive water- and methanol-boosting emission behaviors. As for QXBA-Eu-1, water and methanol molecules replaced the free N,N-dimethylacetamide (DMA) molecules in the framework, repressed the rotation or libration suppression of the QXBA linker, and formed hydrogen bonds with the coordinated water molecules, which suppressed the O-H high-energy vibrations, reduced nonradiative transitions, stabilized the T1 state, and facilitated the intersystem crossing (ISC) process. For QXBA-Eu-2, water molecules tended to replace the coordinated DMA ligands, which altered the S1 and T1 energy levels of the ligand and facilitated the ligand-to-metal energy transfer (LMET) process and strengthened the luminescence of Eu3+. Importantly, free solvent molecules and the hydroxylation of Eu3+ centers also restrained the rotation or libration of the QXBA linker, by which the nonradiative transition was further inhibited and the lanthanide luminescence enhanced. Thus, this work not only opened an unprecedented path to enhance lanthanide luminescence in aqueous solution but also expanded its application scope.

Europium-based metal-organic framework with acid-base buffer structure as electrochemiluminescence luminophore for hyperstatic trenbolone trace monitoring under wide pH range.

The wide and even whole pH range electrochemiluminescence (ECL) is attractive for steroid estrogens detection under harsh conditions (such as strong acid and alkali). Herein, we presented an efficient europium-based metal-organic framework (Eu-MOF) as ECL luminophore, which has been synthesized via the specific 2, 4-bis(3, 5-dicarboxyphenylamino)-6-oltriazine (H4BDPO) ligand with acid-base buffering effect. The functional groups with weak acid and base endowed the H4BDPO with eight ionogenic group states, thereout different total charges of H4BDPO were derived, thus high and steady ECL signals of Eu-MOF were acquired under different environments with pH = 1.0-14.0. Most notably, combined with the means of UV-vis, fluorescence spectra, cyclic voltammetry (CV) and density functional theory (DFT) calculations, the Eu-MOF has been explored different luminescence mechanisms with variational total charges. The constructed ECL biosensor based on the Eu-MOF realized sensitive detection of trenbolone under wide pH range (In order to maintain the biological activity of antigen and antibody, the studied pH value is 5-8.5), in which the limits of detection were 3.95 fg/mL (pH = 5.0), 2.36 fg/mL (pH = 7.4) and 5.48 fg/mL (pH = 8.5) respectively. This work provides a considerable method to realize efficient trace detection of steroid estrogens under the wide or even whole pH conditions.

Carbon-dots-referenced metal-organic frameworks for chemical sensing of tumor/mood biomarker 5-hydroxyindoleacetic acid in human urine: Covalent grafting blue-emitting carbon dots onto red-emitting MOF.

5-HIAA (5-hydroxyindoleacetic acid) is a metabolite for 5-hydroxytryptamine which is excreted in urine and reflects human homeostatic sate. Thus, its monitoring is of great important for clinical diagnosis. In this work, blue-emitting carbon dots (BCD) were firstly synthesize and then covalently grafted onto red-emitting MOF (EuBTC), resulting in a composite sensing platform (BCD@EuBTC) with two emission bands (blue emission peaking at 441 nm and red emission peaking at 616 nm). This composite structure was characterized by means of XRD, IR, TGA, N2 adsorption/desorption, and SEM/TEM. It was found that BCD was grafted on EuBTC surface, not loaded in its micropores, with doping level of 5.02 wt%. 5-HIAA replaced and released the BCD in BCD@EuBTC. The released BCD showed strong blue emission. In the meanwhile, EuBTC red emission was quenched by 5-HIAA thermal relaxation. As a consequence, a ratiometric sensing signal was observed for 5-HIAA. A linear working calibration curve was fitted as F/F0 = 0.588 + 1.598*[5-HIAA], R2 = 0.999, with detection of limit (LOD) determined as 0.3 µM, working region of 0.3-70 µM, and good selectivity. The practical sensing performance of BCD@EuBTC for 5-HIAA in human urine was confirmed, with recovery of 103%.

Controllable Enhanced Ru(bpy)32+ Electrochemiluminescence Detection Systems Based on Eu@MOF253@AuNPs/GCE for the Sensitive Detection of Carbaryl in Food.

In this study, an electrochemiluminescence detection system for the sensitive detection of carbaryl was constructed based on the dual identification of Eu@MOF253, which has a recognition effect on carbaryl, and the electrochemiluminescence system of Ru(bpy)32+/S2O82-, which can react with carbaryl in a redox reaction. This method not only overcame the weakness of the electrochemiluminescence instability of the Ru(bpy)32+/S2O82- system but also changed the sensitivity of the sensing detection system to the target by adjusting the concentration of Ru(bpy)32+ and then proposed a detection strategy with a controllable detection range. After analyzing the electrochemiluminescence signal change mechanism of this system and optimizing the detection conditions, it was concluded that the strategy has good linear detection of carbaryl in the range of 1-1000 and 0.02-0.3 µg L-1, and the detection limits were 0.058 and 0.014 µg L-1. Finally, the strategy was also successfully applied to the detection of actual samples.

Rational design of dual-ligand Eu-MOF for ratiometric fluorescence sensing Cu2+ ions in human serum to diagnose Wilson's disease.

Copper levels in body fluids provide an important reference for the diagnosis of Wilson's disease, which associated with blood abnormalities, kidney and cardiovascular disease, and neuropathy. Metal-organic frameworks (MOF) can easily realize dual-emission from single excitation as ratiometric fluorescence sensing and visible detection platform with the intensity ratio of two emissions for simple, rapid, sensitive, and specific analysis of biological samples. Here, we rationally designed a dual-emission Eu-MOF with dual-ligand strategy, denoted as Eu-DATA/BDC. While terephthalic acid (H2BDC) was selected to sensitize Eu3+ ions for the antenna effect emission, 2,5-diaminoterephthalic acid (H2DATA) maintained its own emission and was used to identify Cu2+ ions. Thus, dual-emission from Eu-DATA/BDC and specific recognition of Cu2+ ions were realized for ratiometric sensing of Cu2+ ions. A wide linear concentration range (1-40 µM), low detection limit (0.15 µM), and fast response (less than 10 s) were realized. The color change also achieved the visible detection by naked eye. Copper levels were tested with human serum samples and compared to the ICP-OES results, confirmed the potential of Eu-DATA/BDC probe in the diagnosis of Wilson's disease. The response mechanism to Cu2+ ions was proposed as electron transfer between host and guest for fluorescence quenching. Thus, dual-ligand is a simple and efficient strategy to prepared dual-emission Eu-MOF for the ratiometric sensing and visible detection.

A turn-off Eu-MOF@Fe2+ sensor for the selective and sensitive fluorescence detection of bromate in wheat flour.

A new europium metal-organic framework (Eu-MOF) was prepared by simple hydrothermal method. The product exhibited intense red fluorescence, long fluorescence lifetime (0.454 ms) and excellent fluorescence stability. The fluorescence titration result showed that Fe3+ could completely quench the fluorescence of Eu-MOF, while the fluorescence quenching effect of Fe2+ or bromate was negligible. Considering the strong oxidizing property of bromate, a "turn off" Eu-MOF@Fe2+ sensor toward bromate was designed by generating Fe3+ due to the redox reaction. The results showed that the sensor displayed a wide linear range (0-0.2 mM), high sensitivity (LOD = 3.7 × 10-6 mol/L), good selectivity and resistant to possible interferences in real four sample. Furthermore, the detection mechanism was investigated by PXRD, XPS and UV-Vis methods. More importantly, the Eu-MOF@Fe2+ sensor was further applied to detect bromate in wheat flour with satisfactory recovery (95.30%-104.38%) and accuracy (RSD < 2.85%). These results suggest that Eu-MOF@Fe2+ can be used as a potential sensor to detect bromate in food industry.

Synergistic Effects of Eu-MOF on Perovskite Solar Cells with Improved Stability.

Enhancing device lifetime is one of the essential challenges in perovskite solar cells. The ultrathin Eu-MOF layer is introduced at the interface between the electron-transport layer and the perovskite absorber to improve the device stability. Both Eu ions and organic ligands in the MOF can reduce the defect concentration and improve carrier transport. Moreover, due to the Förster resonance energy transfer effect, Eu-MOF in perovskite films can improve light utilization and reduce the decomposition under ultraviolet light. Meanwhile, Eu-MOF also turns tensile strain to compressive strain in the perovskite films. As a result, the corresponding devices achieve a champion power conversion efficiency (PCE) of 22.16%. In addition, the devices retain 96% of their original PCE after 2000 h under the relative humidity of 30% and 91% of their original PCE after 1200 h after continuous 85 °C aging condition in N2 .

A Facile One-Pot Approach to the Synthesis of Gd-Eu Based Metal-Organic Frameworks and Applications to Sensing of Fe3+ and Cr2O72- Ions.

Gadolinium metal-organic frameworks (Gd-MOFs) and Eu-doped Gd-MOFs have been synthesized through a one-pot green approach using commercially available reagents. The 1,4-benzenedicarboxylic acid (H2-BDC) and 2,6-naphthalenedicarboxylic acid (H2-NDC) were chosen as ditopic organic linkers to build the 3D structure of the network. The Gd-MOFs were characterized using powder X-ray diffraction (XRD), FT-IR spectroscopy, field emission scanning electron microscopy (FE-SEM) and N2 adsorption-desorption analysis. The Gd-MOF structures were attributed comparing the XRD patterns, supported by the FT-IR spectra, with data reported in the literature for Ln-MOFs of similar lanthanide ionic radius. FE-SEM characterization points to the effect of the duration of the synthesis to a more crystalline and organized structure, with grain dimensions increasing upon increasing reaction time. The total surface area of the MOFs has been determined from the application of the Brunauer-Emmett-Teller method. The study allowed us to correlate the processing conditions and ditopic linker dimension to the network surface area. Both Gd-MOF and Eu-doped Gd-MOF have been tested for sensing of the inorganic ions such as Fe3+ and Cr2O72-.

A novel ultrasonic reverse micelle-assisted electrospun efficient route for Eu-MOF and Eu-MOF/CA composite nanofibers: a high performance photocatalytic treatment for removal of BG pollutant.

Considering the novel applications of metal organic frameworks (MOFs) in photocatalytic fields, in this study, new nanostructures of Eu-MOF have been synthesized using effective, facile, cost-effective, and fast reverse micelle (RM) as well as ultrasound assisted reverse micelle (UARM) methods under the optimal conditions. In order to improve the properties, these nanostructures were extended in the form of fibrous networks. To find nanostructure with distinctive features, thermogravimetric analysis, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, X-ray diffraction, and N2 adsorption/desorption analysis were applied. The results revealed that the samples synthesized by UARM method had a crystallite size of 27.5 nm and thermal stability of 252 °C. Therefore, the UARM Eu-MOF sample was selected as the desirable sample. Also, its application was studied as a novel nanophotocatalyst with the ideal properties in the field of brilliant green dye removal. The photocatalytic results indicated the influence of initial dye concentration, pH, photocatalyst dosage, and contact time parameters on the photocatalytic properties with an efficiency of 99.80%. This study provides a new strategy for developing desirable methods, extended structures, and the photocatalytic applications of these products.

Eu3+@metal-organic frameworks encapsulating carbon dots as ratiometric fluorescent probes for rapid recognition of anthrax spore biomarker.

Anthrax spores pose a serious threat to human well-being and life, so it is highly desirable to develop a rapid, sensitive, and selective quantitative assay of calcium pyridine dicarboxylate (CaDPA) as a biomarker of anthrax spores. Herein, carbon dots (CDs) chelated Eu3+@metal-organic framework (Eu-MOFs) as dual-emissive ratiometric fluorescent (RF) probe was successfully fabricated by a simple one-pot in situ selective self-assembly synthetic strategy. The developed RF probe has an effective self-calibration function, which performs a highly sensitive and selective recognition of CaDPA in water and human serum sample. The blue-emitting CDs was employed as an effective fluorescence reference, while the Eu-MOFs exhibited enhanced red fluorescence signal through the coordination interaction with CaDPA chromophore. The sensing mechanism is attributed to that CaDPA can sensitize Eu3+ intrinsic luminescence due to the energy transfer from CaDPA to Eu3+. What's more interesting is that with the continuous drop of CaDPA, the emission color of CDs@Eu-MOF changes from blue to red. The results revealed that CDs@Eu-MOFs RF probe can detect CaDPA effectively in the range of 8-170 µg/L with good linear relationship, and exhibited a remarkable selectivity for CaDPA. More interestingly, a paper-based probe has also been devised for on-site detection of CaDPA. In addition, CaDPA is used as input signal to construct an IHIBITION logic gate device which performs the "off-on" mode. The constructed CDs@Eu-MOF probe can achieve exceptionally rapid, highly sensitive and selective detection of CaDPA, which can further expand the application prospects in environmental and biological analysis.

A ratiometric fluorescence platform based on boric-acid-functional Eu-MOF for sensitive detection of H2O2 and glucose.

A Eu-metal organic framework (Eu-MOF) probe with dual-emission was reported for the ratiometric fluorescence detection of H2O2 and glucose. Because of the special nucleophilic reaction between boric group and H2O2, Eu3+ and 5-boronobenzene-1,3-dicarboxylic acid (BBDC) were selected to synthesize the functional MOF probe via a simple one-pot solvothermal method. The Eu-MOF shows dual-emission at 370 and 623 nm with the single excitation at 270 nm due to the energy transfer efficiency change for antenna effect procedure. After addition of H2O2, the red emission of Eu-MOF weakened and the blue emission enhances immediately under 270 nm irradiation, so the ratiometric fluorescence detection is established. Moreover, the obvious color change for visual measuring of H2O2 and glucose is illustrated to reveal the merit of Eu-MOF probe. The proposed method was demonstrated to be highly sensitive and selective for H2O2 and glucose, with the low detection limits of 0.0335 and 0.0643 µM, respectively. The established boric-acid-functional Eu-MOF sensing platform was proved as the powerful probe for H2O2 and the metabolites involved in H2O2-generating reaction.