Lanthanide Metal-organic Frameworks Research Articles

Multilevel Stimuli-Responsive Smart "Sandwich" Label with Physical Unclonable Functions Bionic Wrinkles and Space-Selective Fluorescence Patterns.

With the increasing popularity of the internet, it brings convenience to lives while also increases security risks. Physical Unclonable Functions (PUFs) can generate random, unclonable, and unique identifiers using their inherent physical characteristics, which have broad prospects in anti-counterfeiting. Herein, inspired by the irregular tree bark fissures and random skin wrinkles found in nature, a method for creating complex micro-wrinkles with unclonable random patterns is proposed by simply stretching hydrogels. The random texture information contained in the micro-wrinkles is digitized into binary codes using an adaptive threshold algorithm. Additionally, a novel "sandwich" label with a multilevel intelligent anti-counterfeiting system is proposed. The first-level involves photoluminescence encryption with adjustable luminescence within visible light range and modulated luminescence at different excitation wavelengths; the second-level includes strain-related mechanical encryption, and the third-level consists of highly random and unclonable micro-wrinkles. The certification difficulty increases as the anti-counterfeiting grade increases, thereby enhancing label security. Furthermore, space-selective doping of rare earth metal-organic framework (RE-MOF) fluorescent materials in hydrogels is achieved through the use of screen-printing technology. The concept of novel multilevel smart anti-counterfeiting PUF labels will further enhance current levels of counterfeiting prevention.

Luminescence Changeable CO2-Storage Cylinder: Triple-Stranded Helical Eu(III)/Tb(III) Fluorinated MOFs with Amide Linkers.

Triple-stranded helical lanthanide MOFs with CO2 adsorption properties were investigated. Lanthanide MOFs ([Eu0.1Tb0.9(hfa)3(dpa)]n) are composed of lanthanide luminophores (Eu(III) and/or Tb(III) ions), fluorinated antenna ligands (hfa: hexafluoroacetylacetonate), and polyamide-type linker ligands (dpa: 4-(diphenylphosphoryl)-N-(4-(diphenylphosphoryl)phenyl)benzamide). The cylindrical structure was characterized by single-crystal X-ray analysis, thermogravimetric analysis, and gas adsorption measurements. The inner surfaces of the cylindrical channels were covered with the fluorine atoms of the hfa ligands. The emission intensity ratio (IEu/ITb) in [Eu0.1Tb0.9(hfa)3(dpa)]n is affected by the CO2 gas adsorption behavior. The change in IEu/ITb value was caused by the intermolecular interactions between the CO2 gas molecules and the fluorinated ligands, resulting in an electronic structural change of the lowest triplet excited state in the photosensitized hfa ligands.

Regulating Ratiometric Fluorescence of Nanoporous Dual-Centered Lanthanide Metal–Organic Frameworks for Quantitative and Visual Detection of Anthrax Biomarkers

Regulating Ratiometric Fluorescence of Nanoporous Dual-Centered Lanthanide Metal–Organic Frameworks for Quantitative and Visual Detection of Anthrax Biomarkers

Epitaxial Growth of Multicolor Lanthanide MOFs by Ultrasound for Photonic Barcodes.

Epitaxially grown lanthanide metal-organic frameworks (Ln MOFs) exhibit multicolor and characteristic Ln emission with sharp emission bands, which are of great value in the field of information security and anti-counterfeiting. Epitaxial growth of Ln MOFs is generally achieved by solvothermal or hydrothermal methods, which suffer from challenges such as high reaction temperature and long growth time. Here, we report the fast epitaxial growth of multicolor lanthanide MOFs by an ultrasonic method at room temperature. The TbSmSQ shows a core-shell type structure with the Tb ion in the core and Sm in the shell within one crystal and exhibits the characteristic emission lines of Tb and Sm, respectively. The nonporous structure and large distance between lanthanide ions effectively avoid the influence of solvent vapor on the intensity and color of luminescence emission. Its application as photonic barcodes has been studied. This work demonstrates the feasibility of epitaxial growth of multicolor Ln MOFs by the ultrasonic method and its value for anti-counterfeiting and information security applications.

An ultrasensitive and visual ratio fluorescence sensing platform for tannic acid in water based on boric acid functionalized lanthanide MOF

Tannic acid (TA) is a natural polyphenol that is widely used as a preservative and antioxidant in foods, beverages, health products and pharmaceuticals. In this study, a novel Eu-MOF skeleton was prepared using a simple solvothermal strategy and used as a ratio-metric fluorescence sensor for the ultra-sensitive detection of TA. The constructed Eu-MOF has excellent fluorescence properties and high stability in the aqueous phase. With the introduction of TA, a special covalent structure is formed between the o-diphenol group of TA and the boric acid hydroxyl group in ligand of the MOF, resulting in a gradual decrease in the red emission of Eu-MOF at 614 nm and a basically invariable blue emission at 420 nm. As the concentration of TA increased, the color of the system also changes from red to blue, thus achieving rapid and sensitive detection with a low limit of detection (LOD) of 75.6 nM through a ratiometric fluorescence strategy. What is more, Eu-MOF fluorescent probe combined with smart phone color detector is used to visually detect TA. The propose method is successfully applied in the target analysis in tea and beverage samples and the recovery is 95.6∼110.0 %, which is proved to be an effective strategy for the food safety and healthy monitoring.

Regulating Energy Transfer Pathways to Construct Multicolor Luminescent Lanthanide Metal–Organic Frameworks and Their Multiorder Anticounterfeiting Barcodes and Antibiotic Sensing

Regulating Energy Transfer Pathways to Construct Multicolor Luminescent Lanthanide Metal–Organic Frameworks and Their Multiorder Anticounterfeiting Barcodes and Antibiotic Sensing

A smartphone-integrated bimetallic ratiometric fluorescent probe for specific visual detection of tetracycline antibiotics in food samples and latent fingerprinting

Designing and preparing highly sensitive and accurate fluorescent chemosensors for monitoring tetracycline antibiotics remains a challenge. Herein, a fluorescent chemosensor based on lanthanide metal-organic frameworks (Ln-MOFs) is proposed to realize high-precision monitoring by adjusting the ratio of lanthanide ions. Ln-MOFs with good aqueous stability were prepared by a solvothermal method using Eu3+, Tb3+ and the ligand 4,4′,4″-s-triazine-2,4,6-triyltribenzoic acid (H3TATB) in DMF/NMP/H2O. The Ln-MOFs could recognize oxytetracycline (OTC) and doxycycline (DOX), and the detection limits of OTC and DOX were as low as 8.6 and 4.8 nM, respectively. In particular, Eu(1.4 μM)-Tb-MOF sensors were used for visual detection of OTC and DOX in combination with smartphones with detection lines as low as 9.8 nM and 14.2 nM, respectively. Meanwhile, Eu-MOF, Tb-MOF and Eu(1.4 μM)-Tb-MOF can be used for latent fingerprint (LFP) visualization, demonstrating their potential applications in the field of criminal case investigation. The developed probes were successfully applied to determining OTC and DOX in milk, beef and pork with recoveries ranging from 92.0 % to 109.63 % and relative standard deviations (RSDs) ranging from 1.83 % to 4.56 %. Eu(1.4 μM)-Tb-MOF is believed to utilize its lanthanide metal ion coordination and photoinduced electron transfer (PET) mechanism to achieve highly selective and accurate OTC and DOX detection, which is supported by experimental and density functional theory (DFT) calculations.

In-situ preparation of lanthanide luminescent MOF hydrogel for aldehyde detection☆

Metal-organic frameworks (MOFs) usually exist in the state of powder or crystal. When they are exposed to hydrophilic solvents, their structure will change and become unstable. Therefore, it is a challenge to construct MOF materials with tunable mechanical properties. Herein, we report in-situ growth lanthanide metal-organic framework (LnMOF) in sodium alginate (SA) and polyvinyl alcohol (PVA) hydrogel matrix. The prepared composite hydrogel not only displays characteristic lanthanide narrow-band emission under ultraviolet light, but also demonstrates excellent mechanical properties. The addition of LnMOF significantly enhances the compressive strength of the hydrogel (from 0.75 to 7.32 MPa). Furthermore, the composite hydrogel shows highly selective recognition of glutaraldehyde and gaseous formaldehyde at room temperature. The detection limits (LOD) of SP-EuMOF for glutaraldehyde and formaldehyde are 0.27 and 0.22 ppm, respectively. Based on these results, the LnMOF composite hydrogel is deemed to have significant potential as a fluorescent sensor for both glutaraldehyde and formaldehyde detection.

High sensitivity distinguishing detection of fluoroquinolones with a cage-based lanthanide metal-organic framework in food

Sensitive and selective detection of fluoroquinolones, especially from different sources, is challenging. This study reported an uncommon three-cage lanthanide metal-organic framework (1-Eu) with a Eu3+ cluster as its structural primitive using a C2-symmetric 5,5-(Pyrazine-2,6-diyl) diisophthalic acid ligand. The 1-Eu probe effectively detected four fluoroquinolones through distinct color changes and spectral emission bands, demonstrating excellent performance with low detection limits: moxifloxacin (LOD: 9.3 nM), danofloxacin (LOD: 33.7 nM), gatifloxacin (LOD: 67.9 nM), and ofloxacin (LOD: 238.6 nM). Mechanistic studies revealed that internal filtration and photoinduced electron transfer (a-PET) effects were key factors. Furthermore, 1-Eu was successfully used to detect fluoroquinolones in food samples. Additionally, portable paper-based sensors were developed to quickly semi-quantify analyte concentrations using a smartphone color recognition app, underscoring the practical potential of this probe. This study introduces a novel methodology for the identification and detection of fluoroquinolones to enhance food safety.

A mixed Ce/Eu metal-organic framework for ratiometric detection of Al3+ ion.

As a heavy metal ion, excessive aluminum ions pose a serious threat to human health and the ecological environment. Developing a simple, efficient, and fast detection method to detect the content of aluminum ions is of great significance, especially for ensuring human health and ecological safety. Herein, the mixed rare earth metal-organic framework (Ce0.74Eu0.26TPTC and Ce0.62Eu0.38TPTC) were prepared based on simple ligand 1,1':4',1″-Terphenyl-2',4,4″,5'-tetracarboxylic acid (H4TPTC). The Ce0.74Eu0.26TPTC and Ce0.62Eu0.38TPTC have dual luminescence centers, which can be used as ratio fluorescent probes to detect Al3+ ions, making the detection results more accurate and reliable. Therefore, this work can promote the further development of rare earth-based MOFs in the detection of heavy metal ions.

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.

Synergic effect between La-MOF and MXene: Revolutionizing TPU with improved mechanical strength and fire safety

Two-dimensional MXene nanosheets with lamellar structure and high specific surface area are considered promising flame retardants for polymers. However, MXene easily accumulates in polymer materials, resulting in the impairment of their mechanical properties. Metal-organic frameworks (MOFs) not only address this issue effectively but also improve compatibility with polymer materials due to their organic components. In this work, lanthanide rare-earth MOF (La-MOF) were successfully grown in-situ on the MXene surface to prepare hybrid flame retardants (La-MOF@MXene), then added to thermoplastic polyurethane (TPU). The La-MOF suppressed the accumulation of MXene in TPU, and the synergistic effect between them improved the fire safety and mechanical strength of TPU composites. The peak heat release rate of the TPU composites with the addition of 3 wt% La-MOF@MXene was 473.3 kW/m2, which represented a 49.4 % decrease compared to that of pure TPU. Besides, due to the synergic properties of MXene and La-MOF, La-MOF@MXene further reduced total smoke, CO2, and CO of TPU composites in fires. Moreover, with the addition of 3.0 wt% La-MOF@MXene, the tensile strength and elongation at break of TPU composites dramatically improved to 42.4 MPa and 686 %, respectively. Therefore, this study provides a novel paradigm for preparing hybrid flame retardants that can improve the fire safety and mechanical properties of TPU composites, exhibiting broad application prospects.

Lanthanide MOF-based luminescent sensor array for detection and identification of contaminants in water and biomarkers

In today's society, heavy metal ions and antibiotic contaminants have caused great harm to water systems and human health. In this study, six isostructural lanthanide metal-organic frameworks [Ln(H3imda)2(TPA)(H2O)2](Tb for CUST-881, Eu for CUST-882, Dy for CUST-883, Er for CUST-884, Nd for CUST-885, Sm for CUST-886) were constructed by selecting terephthalic acid (TPA) and 4,5-Imidazoledicarboxylic acid (H3imda) and lanthanide metal ions via solvethermal method. Among them, CUST-881 and CUST-882 can selectively detect Fe3+, Cr2O72−, CrO42, and ceftriaxone sodium (CRO) in water systems and uric acid in urine. CUST-881 shows very low detection limits for these five substances. Furthermore, Principal Component Analysis (PCA) was used to distinguish Fe3+, Cr2O72−, CrO42−, and CRO in water. To our knowledge, this is the first time that they have been able to be simultaneously distinguished. In addition, the possible sensing mechanism was studied through UV–visible spectroscopy, Infrared spectroscopy, and PXRD analysis. Furthermore, the probe also showed satisfactory repeatability and recovery when applied to UA samples that simulated urine. Based on the above results, lanthanide metal-organic frameworks have great potential for practical monitoring of contaminants in water environments.

Reaction Time Induced a Two-Step Dissolution and Recrystallization Structural Transformation with Three Eu Metal-Organic Frameworks: Crystal Structures and Multiresponsive Fluorescence Detection.

Under solvothermal conditions, three 3D lanthanide metal-organic frameworks (Ln-MOFs): [Eu(H2DHTA)1.5(DMF)2]·DMF (1), [Eu(H2DHTA)0.5(DHTA)0.5(DMF)(H2O)]·2H2O (2), and Eu(HCOO)3 (3) (H4DHTA = 2,5-dihydroxyterephthalic acid) have been synthesized by different reaction times. Interestingly, induced by reaction time, compounds 1-3 underwent a two-step dissolution and recrystallization structural transformation (DRST) reaction. Investigations on the DRST processes were carried out, and the transformation pathway was deduced, which was verified by XRD analyses. Notably, compound 2 demonstrates pronounced luminescence as well as high stability in water and other organic solvents. The fluorescent detection of furan antibiotics can serve as turn-off effects, and glutamic acid (Glu), aspartic acid (Asp), and riboflavin (VB2) can serve as the turn-on effect. To explain the enhancing and quenching mechanisms, XRD, UV-visible absorption spectroscopy, electrochemistry, IR spectra, theoretical calculation, fluorescence lifetimes, and XPS were discussed. Additionally, MOF-coated test strips were utilized to detect these analytes, exhibiting excellent agreement with fluorescence spectroscopy. This work provides an example for more effective designs to employ Ln-MOFs as multiresponsive fluorescent sensors for detection of environmental pollutants in aqueous solution.

On-site visual sensing of antibiotics in food by new fluorescent lanthanide metal–organic frameworks

In recent years, foods that contaminated by the antibiotics is a serious threat to human health, so, the on-site visual detection of antibiotics in food is crucial. In this work, two new two-dimensional lanthanide metal–organic frameworks (2D LnMOFs) are synthesized by mild hydrothermal method and detailly characterized by single crystal structure analysis, photophysics, thermal gravimetric analysis (TGA), powder X-ray diffraction (PXRD), FT-IR spectra. Results show the two LnMOFs has high thermo-stability, strong acid and alkaline resistance. Further studies reveal that TbMOF is a highly sensitive and selective fluorescent probe for the antibiotics of enrofloxacin (Enr) and ciprofloxacin (Cip), with a very short response time of 15 s. The limits of detection (LODs) for Enr and Cip are very low values of 190 and 70 nM, respectively, based on the method of 3σ/K, which is lower than the national food safety standard (GB 31650–2019). In addition, portable test paper based on TbMOF is fabricated, which realized the visible and on-site detection of Enr and Cip in the real samples of egg and milk.

Lanthanide metal-organic framework functionalized with 10-hydroxybenzo[h]quinoline for ratiometric sensing to real-time determine monophenolase activity through indicator displacement assay

Tyrosinase monophenolase activity plays a crucial role in various biological processes and industrial applications, making the development of continuous monophenolase assays highly significant. In this study, ratiometric fluorescence sensing using a dual-emission sensor was established to determine monophenolase activity in real-time by integrating indicator displacement assay with lanthanide metal-organic frameworks (MOFs). Europium MOFs functionalized with 10-hydroxybenzo[h]quinoline (HBQ) were fabricated by conjugating an HBQ guest fluorophore to the 3,5-dicarboxyphenylboronic acid (DBA) ligand using a solvothermal method. The conjugated HBQ served as an optical indicator at 510 nm with large Stokes shift, whereas the Eu-MOFs acted as a fluorescent internal standard at 616 nm for dual emission. DBA acts as an antenna ligand and provides a competitive receptor site for L-3,4-dihydroxyphenlalanine (L-DOPA) and HBQ. L-DOPA competitively binds to DBA owing to its higher affinity and displaces the conjugated HBQ, resulting in the quenching of HBQ and Eu-MOFs fluorescence. A linear change in the dual-emission intensity ratio was observed as a ratiometric response towards L-DOPA. The sensor quantified L-DOPA with a detection limit of 0.13 μM. Monophenolase activity was correlated with the real-time change in the ratiometric signal using L-DOPA as the product of the enzymatic reaction. A progression curve for the formation of L-DOPA was constructed to calculate the initial rate, yielding a low detection limit for monophenolase activity of 0.15 U·mL−1. The method has been successfully applied to real samples, kinetic studies, and high-throughput screening of inhibitors. This sensing platform opens a new avenue for determining tyrosinase activity.

Synthesis and Characterization of Highly Fluorinated Hydrophobic Rare-Earth Metal-Organic Frameworks (MOFs).

Tuning a material's hydrophobicity is desirable in several industrial applications, such as hydrocarbon storage, separation, selective CO2 capture, oil spill cleanup, and water purification. The introduction of fluorine into rare-earth (RE) metal-organic frameworks (MOFs) can make them hydrophobic. In this work, the linker bis(trifluoromethyl)terephthalic acid (TTA) was used to make highly fluorinated MOFs. The reaction of the TTA and RE3+ (RE: Y, Gd, or Eu) ions resulted in the primitive cubic structure (pcu) exhibiting RE dimer nodes (RE-TTA-pcu). The crystal structure of the RE-TTA-pcu was obtained. The use of the 2-fluorobenzoic acid in the synthesis resulted in fluorinated hexaclusters in the face-centered cubic (fcu) framework (RE-TTA-fcu), analogous to the UiO-66 MOF. The RE-TTA-fcu has fluorine on the linker as well as in the cluster. The MOFs were characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, and contact angle measurements.

A rapid and accurate fluorescent sensor array based on lanthanide metal-organic framework for identification and determination of perfluorinated compounds

Perfluorinated compounds (PFCs), as an important class of environmental pollutants, have chemical and structural similarities that make their detection a great technical challenge. This study synthesized three species of metal-organic frameworks (MOFs) using different lanthanide metal ions or organic ligands, which were integrated into a fluorescent sensor array. This innovative approach offers a straightforward, rapid, and precise detection strategy for PFCs. Different ionization properties and fluorinated hydrophobic tails of PFCs lead to different electrostatic attraction and hydrophobic effects between PFCs and sensing elements, which become the basis for differential sensing. Furthermore, the fluorescence signal is more convenient to collect, making the sensor array simple to complete the identification. Combined with pattern recognition methods, the array successfully identified seven kinds of PFCs and mixtures with a classification accuracy of 100 % and a detection limit as low as 51 nM. Finally, the utility of the sensor array in river water sample analysis was verified. The strategy provides an effective method for identifying and determining PFCs and offers new opportunities for developing sensor arrays based on lanthanide MOFs.

A novel Y/Eu co-doped Ln-MOF for ratiometric luminescent thermometer of high sensitivity

Lanthanide metal-organic frameworks (Ln-MOFs) co-doped by mixed lanthanide ions is a preeminent candidate for ratiometric luminescence thermometers. In recent years, there are few studies on the synthesis of such MOFs by introducing Ln3+ ions of no luminescent properties such as Y3+. Herein, a novel Y/Eu co-doped Ln-MOF (Y0.95Eu0.05NDPA, H4NDPA = 5,5′-naphthalene-1,4-diyl-diisophthalic acid) was synthesized via solvothermal methods, which showed good phase purity and thermal stability. Compared with EuNDPA, the Y3+ ions in Y0.95Eu0.05NDPA dilute the molar concentration of Eu3+, causing the emerge of ligand emission band. The luminescence intensity ratio of organic ligands and Eu3+ owns a good exponential dependence on temperature variation. As investigated, Y0.95Eu0.05NDPA owns the merits including a wide temperature sensing range (303–423 K), high relative sensitivity (3.04 %·K-1 at 423 K), good spectral repeatability (>92 %) and distinct emission color change from red to blue. This novel Y0.95Eu0.05NDPA ratiometric thermometer is expected to promote the application and development of dual-emission MOF materials in the field of microelectronic temperature measurement.

Heterogeneous Acetalization of Benzaldehyde over Lanthanide Oxalate Metal-Organic Frameworks.

Lanthanides (Ln) from the f-blocks of the periodic table have gained significant interest due to their unique characteristics, including magnetism, photoluminescence, and catalysis. In this study, a series of lanthanide metal-organic frameworks [Ln-MOFs, Ln = Eu(III), Tb(III), Nd(III), Er(III), Ho(III), Gd(III), Pr(III), and Dy(III)] were constructed based on oxalic acid and lanthanide metals as the building blocks. These MOFs were comprehensively characterized using various analytical and spectroscopic techniques, including powder X-ray diffraction, Fourier-transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, nitrogen adsorption-desorption, and Raman spectroscopy. The magnetic properties of the investigated materials were examined, revealing both antiferromagnetic and ferromagnetic interactions within the Ln-Ox MOFs. The catalytic activities of Ln-Ox MOFs were evaluated through the heterogeneous acetalization of benzaldehyde with methanol. Reaction yields by the reported catalysts varied up to 90% depending on the MOF's metal center, and the product was confirmed by gas chromatography-mass spectrometry. Recycling experiments have confirmed the stable regeneration of Ln-Ox MOFs in which the product yields remained the same over four consecutive cycles. The hydrothermal synthesis of these MOFs paves the way for a diverse array of materials showcasing unique lanthanide properties, making them suitable for various applications.