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A luminescent terbium metal-organic framework for highly sensitive and selective detection of uric acid in aqueous media
摘要： As the final product of purine metabolism, uric acid (UA) existing in urine and serum plays an important role in the body's metabolism, immunity and other functions. However, it is still difficult to sense UA in practice. Herein, a new terbium metal–organic framework (Me2NH2)2[Tb2(L)2]·(H2O)6 (ZJU-158-Tb, ZJU=Zhejiang University, L= 1-(3,5-dicarboxylatobenzyl)-3,5-pyrazole dicarboxylic acid )for luminescent sensing of UA was designed and synthesized. It exhibits highly sensitive and selective detection to UA in aqueous solutions with a quite low detection limit of 7 nM by a luminescence turn-down phenomenon. Furthermore, the practical test papers made by ZJU-158-Tb possess fast monitoring ability for abnormal UA levels in artificial urine and serum through distinct color change, which could be even distinguished by the naked eye.
关键词： uric acid,Metal-organic frameworks,test paper.,fluorescence sensor
更新于2025-09-19 17:15:36
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8-Hydroxyquinolinate-Based Metal–Organic Frameworks: Synthesis, Tunable Luminescent Properties, and Highly Sensitive Detection of Small Molecules and Metal Ions
摘要： Five new metal?organic frameworks, [Zn2L2]·2DMF·2MeOH (1), [Zn2L2(py)2] (2), [Cd2L2]·Diox·MeOH·6H2O (3), [Mn2L2]·2DMF·2MeOH (4), and [Co2L2]·2DMF·4H2O (5), were assembled by using a novel 8-hydroxyquinolinate derivative H2L with different metal ions. Complex 1 features a 3D porous network consisting of meso-helical chains (P + M) built from metal?ligand coordination bonds. The adjacent dinuclear ZnII building blocks in 2 are connected together to generate a 2D grid network. In complex 3, each binuclear motif is bound to four ZnII ions to produce a 2D layer structure that stacks into a 3D porous structure. The framework of complex 4 is isostructural to 5, featuring a 21 helical chain built from [M2L2] units (M = Mn or Co). The adjacent meso-helices associated in parallel are interconnected by the phenolate μ2-O atoms of H2L to give rise to a 2D network. Distinct solid-state luminescence properties of 1?3 were observed, arising from their different metal nodes and frameworks. In particular, complex 1 exhibited excellent stability in both common organic solvents and H2O, thus facilitating its utility as a chemical sensor. Remarkably, luminescent 1 showed highly sensitive detection for nitroaromatic molecules in methanol and Fe3+ ion in H2O even in the presence of other interfering metal cations.
关键词： metal-organic frameworks,nitroaromatic compounds,Fe3+ ion,sensing,water stability,luminescence
更新于2025-09-19 17:15:36
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Post-Synthetic Ligand Exchange of Metal Organic Framework for Photodynamic Therapy
摘要： Attributed to the large pore size and excellent stability, the metal organic framework (MOF) NU-1000, which is formed by the coordination of Zr cluster and 1,3,6,8-tetrakis(p-benzoicacid)pyrene (H4TBAPy) ligand, has been widely studied in the catalysis research field, however, only a few reports about the biomedical application of NU-1000 could be found in the open literature. In this study, a functional ligand, tetrakis(4-carboxyphenyl)porphyrin (TCPP) was introduced into NU-1000 via post-synthetic ligand exchange method, and the resultant mixed ligand MOF possesses excellent photodynamic effect. Finally, in vitro and in vivo assessment about the antitumor efficacy was investigated for the first time. It demonstrates the feasibility of TCPP substituted NU-1000 to be used for photodynamic therapy, and also provides an alternative approach to enrich the function of MOF for various applications via post-synthetic method.
关键词： Metal Organic Frameworks,ligand exchange,NU-1000,photodynamic therapy,post-synthetic modification
更新于2025-09-19 17:15:36
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ZnO Nanosheets Abundant in Oxygen Vacancies Derived from Metal-Organic Frameworks for ppb-Level Gas Sensing
摘要： Surmounting the inhomogeniety issue of gas sensors and realizing their reproducible ppb-level gas sensing are highly desirable for widespread deployments of sensors to build networks in applications of industrial safety and indoor/outdoor air quality monitoring. Herein, a strategy is proposed to substantially improve the surface homogeneity of sensing materials and gas sensing performance via chip-level pyrolysis of as-grown ZIF-L (ZIF stands for zeolitic imidazolate framework) films to porous and hierarchical zinc oxide (ZnO) nanosheets. A novel approach to generate adjustable oxygen vacancies is demonstrated, through which the electronic structure of sensing materials can be fine-tuned. Their presence is thoroughly verified by various techniques. The sensing results demonstrate that the resultant oxygen vacancy-abundant ZnO nanosheets exhibit significantly enhanced sensitivity and shortened response time toward ppb-level carbon monoxide (CO) and volatile organic compounds encompassing 1,3-butadiene, toluene, and tetrachloroethylene, which can be ascribed to several reasons including unpaired electrons, consequent bandgap narrowing, increased specific surface area, and hierarchical micro–mesoporous structures. This facile approach sheds light on the rational design of sensing materials via defect engineering, and can facilitate the mass production, commercialization, and large-scale deployments of sensors with controllable morphology and superior sensing performance targeted for ultratrace gas detection.
关键词： metal-organic frameworks,oxygen vacancies,ppb-level gas sensing,defect engineering,ZnO nanosheets
更新于2025-09-19 17:15:36
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Four Co( <scp>ii</scp> ) coordination polymers based on 4,4′-(1 <i>H</i> -1,2,4-triazol-1-yl)methylenebis(benzoic acid): syntheses, structural diversity, magnetic properties, dye adsorption and photocatalytic properties
摘要： Four Co(II) coordination polymers based on 4,4′-(1H-1,2,4-triazol-1-yl)methylenebis(benzoic acid) (H2tmlb), namely: {[Co4(tmlb)4(H2O)]·2CH3CN·4H2O}n (1), {[Co(tmlb)(bbibp)]·1.5CH3OH·2H2O}n (2), {[Co2(tmlb)2(bimmb)]·6CH3CH2OH·4H2O}n (3), and {[Co(tmlb)(bibp)(H2O)]·DMA}n (4) (bbibp = 4,4′-bis(benzoimidazo-1-yl)biphenyl, bimmb = 1,4-bis(imidazol-1-ylmethyl)benzene, bibp = 4,4′-bis(imidazolyl)biphenyl), have been synthesized under solvothermal conditions. Four Co complexes have been characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction, thermogravimetric (TG) analysis and powder X-ray diffraction (PXRD). The single-crystal X-ray diffraction analysis reveals that complex 1 shows a two-fold interpenetrating (3,6,6)-connected framework with a Schl?fli symbol of (4·62)2(42·610·83) topology; complex 2 shows a two-fold interpenetrating uninodal 4-connected cds topology with a point symbol of (65·8); complex 3 shows a 2D → 3D supramolecular structure through weak interactions; complex 4 shows a (3,4,6)-connected network with a point symbol of (4·62)2(42·64·93·106)(64·9·10) topology. Furthermore, the variable temperature magnetic susceptibilities of complexes 1–4 have been discussed. Complex 4 can selectively adsorb sulfate-containing dyes by Lewis acid–base interactions. And the four complexes all exhibit excellent photocatalytic capability in degradation of MB/MV.
关键词： Structural diversity,Coordination polymers,Photocatalytic properties,Metal–organic frameworks,Dye adsorption,Magnetic properties
更新于2025-09-19 17:15:36
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Ultrafast Laser Manufacture of Stable, Efficient Ultrafine Noble Metal Catalysts Mediated with MOF Derived High Density Defective Metal Oxides
摘要： Supported metal nanoparticles (MNPs) undergo severe aggregation, especially when the interaction between MNPs and their supports are limited and weak where their performance deteriorates dramatically. This becomes more severe when catalysts are operated under high temperature. Here, it is reported that MNPs including Pt, Au, Rh, and Ru, with sub-2 nm size can be stabilized on densely packed defective CeO2 nanoparticles with sub-5 nm size via strong coupling by direct laser conversion of corresponding metal ions encapsulated cerous metal–organic frameworks (Ce-MOFs). Ce-MOF serves as an ideal dispersion precursor to uniformly encapsulate noble metal ions in their orderly arranged pores. Ultrafast laser vaporization and cooling forms uniform, ultra-small, well-mixed, and exceptionally dense nanoparticles of metal and metal oxide concurrently. The laser-induced ultrafast reaction (within tens of nanoseconds) facilitates the precipitation of CeO2 nanoparticles with abundant surficial defects. Due to the well-mixed ultrasmall Pt and CeO2 components with strong coupling, this catalyst exhibits exceptionally high stability and activity both at low and high temperatures (170–1100 °C) for CO oxidation in long-term operation, significantly exceeding catalysts prepared by traditional methods. The scalable feature of laser and huge MOF family make it a versatile method for the production of MNP-based nanocomposites in wide applications.
关键词： noble metal catalysts,lasers,metal oxides,defects,metal–organic frameworks
更新于2025-09-19 17:13:59
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Nanoscale lighta??matter interactions in metala??organic frameworks cladding optical fibers
摘要： The utilization of refractive index (RI) change due to guest–host interactions between the guest volatile organic compound vapor and porous metal–organic frameworks (vapor–MOF interactions) is promising in photonic vapor sensors. Therefore, the study of light–matter interactions in nanoporous metal–organic frameworks (MOFs) is fundamental and essential for MOF-based photonic devices. In this work, the manipulation of light in MOFs to investigate the vapor–MOF interactions by using optical fiber devices is demonstrated. The vapor–MOF interactions and the light–vapor interactions (light in MOFs to sense the RI changes resulting from the vapor–MOF interactions) are investigated. The cladding mode is excited by a long-period fiber grating (LPFG) for evanescent field sensing in a ZIF-8 sensitive coating. The experimental results combining quantum chemical calculations and optical simulations reveal the relationships between the microscopic energy of vapor desorption, RI changes and evanescent field enhancement in ZIF-8 during the vapor–MOF interactions. With exceptionally large RI changes, the evanescent field of cladding mode in ZIF-8 is greatly enhanced to sense the vapor–MOF interactions. As a proof-of-concept, a LPFG sensor with ZIF-8 coating showed a high sensitivity of 1.33 pm ppm?1 in the linear range from 9.8 ppm to 540 ppm for the sensing of ethanol vapor. The investigation of light–matter interactions in ZIF-8 provides a useful guideline for the design and fabrication of MOF-based optical waveguide/fiber sensors.
关键词： Nanoscale,metal–organic frameworks,light–matter interactions,vapor sensing,optical fibers
更新于2025-09-19 17:13:59
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A stable nanoscaled Zr-MOF for the detection of toxic mycotoxin through a pH-modulated ratiometric luminescent switch
摘要： A stable nanoscaled single-excitation ratiometric luminescent pH sensor (MPDB-PCN) over a broad pH range from 2.5 to 8.6 is fabricated through post-synthetic modification of PCN-224 with naphthalimide-derived molecules. Due to the rapid, sensitive and linear response to pH, MPDB-PCN is capable of detecting 3-nitropropionic acid (3-NPA), an acid neurotoxin in food safety, with a low detection limit of 15 μM in sugarcane juice.
关键词： Luminescent metal-organic frameworks,food safety,pH sensor,3-nitropropionic acid
更新于2025-09-19 17:13:59
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Self-Assembly of Hybrid Oxidant POM@Cu-BTC for Enhanced Efficiency and Long-Term Stability of Perovskite Solar Cells
摘要： The controllable oxidation of Spiro-OMeTAD and improving stability of hole transport materials (HTMs) layer are crucial for good performance and stability of perovskite solar cells (PSCs). Herein, we report a hybrid polyoxometalate@metal-organic framework (POM@MOF) material – [Cu2(BTC)4/3(H2O)2]6[H3PMo12O40]2 or POM@Cu-BTC – for oxidation of Spiro-OMeTAD with Li-TFSI and TBP. When POM@Cu-BTC is introduced to the HTM layer as dopant, the PSCs achieve a superior fill factor of 0.80 and enhanced power conversion efficiency 21.44%, as well as improved long-term stability in an ambient atmosphere without encapsulation. The enhanced performance is attributed to the oxidation activity of POM anions and solid-state nanoparticles. Therefore, this research presents a facile way by using hybrid porous materials to accelerate oxidation of Spiro-OMeTAD, further improving the efficiency and stability of PSCs.
关键词： metal-organic frameworks,oxidation,polyoxometalate,stability,PSCs
更新于2025-09-19 17:13:59
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Metal–Organic Framework‐Derived N‐Rich Porous Carbon as an Auxiliary Additive of Hole Transport Layers for Highly Efficient and Long‐Term Stable Perovskite Solar Cells
摘要： As the standard bidopants of hole transport layers (HTLs) in perovskite solar cells (PSCs), bis(tri?uoromethane)sulfonimide lithium salt (Li-TFSI) and 4-tert-butylpyridine not only induce adverse in?uence on the quality of thin ?lms, but also seriously impair the long-term stability of devices. Herein, a metal–organic framework-derived 2D graphitic N-rich porous carbon (NPC) is ?rst introduced into the HTLs as an effective auxiliary additive. The introduction of NPC signi?cantly reduces the aggregation of lithium salts and the formation of HTL defects, optimizing ?lm quality for rapid hole extraction and migration. Furthermore, inherent porosity and hydrophobicity of NPCs are extremely bene?cial to restrict the permeation of Li ions and anode metals, and prevent the moisture from eroding the HTLs and perovskite layers, enhancing the stability of PSCs. As expected, the PSCs with NPC realize a satisfactory ?ll factor of 0.76 and power conversion ef?ciency (PCE) of 18.51%, apparently higher than that of pristine devices (0.70% and 16.47%). In addition, over 85% of the initial PCE for optimized PSCs is maintained after 720 h of exposure to air. Obviously, an innovative strategy for highly ef?cient and long-term stable PSC devices is provided.
关键词： metal–organic frameworks,perovskite solar cells,auxiliary additives,hole transport layers,N-rich porous carbons
更新于2025-09-19 17:13:59