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Water-Stable Metal–Organic Frameworks with Selective Sensing on Fe <sup>3+</sup> and Nitroaromatic Explosives, and Stimuli-Responsive Luminescence on Lanthanide Encapsulation
摘要： Three water-stable luminescent MOFs [Zn4(bptc)2(NMP)3(DMF)(H2O)2]n (1-a), [Cd4(bptc)2(NMP)3(DMF)2(H2O)1]n (1-b), and {[Zn2(bptc)(DMA)(H2O)2]·(DMA)2·H2O}n (2), possessing similar chemical components (M2:L1:Sol3) and topology structures, were synthesized by solvents control. Their excellent sensing on iron(III) cation and nitroaromatic explosives (NACs) with great selectivity, sensitivity and a high Ksv (4.54 × 10^4 for 1-b on PNP) were observed by quenching effects. Furthermore, Zn-MOFs exhibit interesting stimuli-responsive luminescence enhancement after the encapsulation of a series of IIIB cations stimulated different luminescent emitting and intensity enhancement through host–guest processes of the pores in MOFs, especially for two distinct responses of Zn-MOF on a Tb3+ cation.
关键词： stimuli-responsive,nitroaromatic explosives,luminescent,water-stable,lanthanide encapsulation,iron(III),metal-organic frameworks,sensing
更新于2025-09-23 15:23:52
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Highly Selective Photocatalytic Reduction of o-Dinitrobenzene to o-Phenylenediamine over Non-Metal-Doped TiO2 under Simulated Solar Light Irradiation
摘要： Photocatalytic reduction and hydrogenation reaction of o-dinitrobenzene in the presence of oxalic acid over anatase-brookite biphasic TiO2 and non-metal-doped anatase-brookite biphasic TiO2 photocatalysts under solar simulated light was investigated. Compared with commercial P25 TiO2, the prepared un-doped and doped anatase-brookite biphasic TiO2 exhibited a high selectivity towards the formation of o-nitroaniline (85.5%) and o-phenylenediamine ~97%, respectively. The doped anatase-brookite biphasic TiO2 has promoted photocatalytic reduction of the two-nitro groups of o-dinitrobenzene to the corresponding o-phenylenediamine with very high yield ~97%. Electron paramagnetic resonance analysis, Transient Absorption Spectroscopy (TAS) and Photoluminescence analysis (PL) were performed to determine the distribution of defects and the fluorescence lifetime of the charge carriers for un-doped and doped photocatalysts. The superiority of the doped TiO2 photocatalysts is accredited to the creation of new dopants (C, N, and S) as hole traps, the formation of long-lived Ti3+ defects which leads to an increase in the fluorescence lifetime of the formed charge carriers. The schematic diagram of the photocatalytic reduction of o-dinitrobenzene using the doped TiO2 under solar light was also illustrated in detail.
关键词： selectivity,photocatalysis,non-metal-doped TiO2,nitroaromatic compounds,reduction
更新于2025-09-23 15:22:29
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Synthesis of eight isostructural 2D lanthanide coordination polymers assembled by rigid furan-2,5-dicarboxylic acid and flexible adipic acid as linkers and exploration of luminescent Eu/Tb polymers as efficient and sensitive sensors for nitroaromatic compounds
摘要： Detection of hazardous chemicals is crucial for a healthy and safe environment as well as for the well-being of humans. A confluence of chemistry and engineering continues to improve the sensitivity and selectivity for several classes of harmful chemicals with the promise of cheap and portable sensing. Herein, following the function-oriented research strategy, eight novel lanthanide coordination polymers (Ln-CPs) have been successfully assembled with the framework composition [Ln(2,5-FDC)0.5(Adip)(H2O)2] (Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6), Ho (7), Er (8), 2,5-FDC2? = furan-2,5-dicarboxylate, Adip2? = Adipate) under solvothermal synthesis conditions. The structural analysis indicates that all the eight CPs have the same structural features. All compounds crystallize in the orthorhombic crystal system (space group Pnma) with point symbol {33·44·53} and consist of 2D cem topological type. The linkers 2,5-FDC2? and Adip2? exhibit μ2-κ4,Z1:Z1:Z1:Z1 and μ3-κ5,Z2:Z1:Z1:Z1 coordination modes respectively. The as-synthesized polymers were characterized by powder X-ray crystallography, infrared spectroscopy, thermogravimetric analysis, and photoluminescence studies. CP-3 and CP-5 are promising luminescent lanthanide coordination polymers (Ln-CPs) and function as efficient sensors for the detection of nitroaromatic compounds at the ppm level in mix N,N′-dimethyl formamide-aqueous medium via the luminescence quenching mechanism.
关键词： furan-2,5-dicarboxylic acid,lanthanide coordination polymers,adipic acid,luminescent sensors,nitroaromatic compounds
更新于2025-09-23 15:21:01
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A water-stable Eu <sup>III</sup> -based MOF as a dual-emission luminescent sensor for discriminative detection of nitroaromatic pollutants
摘要： A water-stable EuIII-based metal–organic framework (MOF) with dual-emission luminescence behavior, namely {[Eu4(INO)5(μ3-OH)2Cl4(H2O)]·(NO3)·(H2O)5}n (Eu-MOF; HINO = isonicotinic acid N-oxide), was successfully constructed by the solvothermal reaction of Eu3+ ions with the organic ligand HINO. The cationic 3D framework contains microporous channels with accessible Lewis-base sites and NO3? ions as balanced anions, which all contribute to the selective detection of multifarious analytes. This MOF shows ratiometric detection of acetone, Cr2O72? ions, and nitroaromatic compounds (NACs). In particular, it shows great recognition of four NACs in water, representing the first LnIII-MOF which can display distinguishing fluorescence phenomena on NACs rather than relying on the quenching effect. Furthermore, this is also the first example of a MOF-sensor for detecting these explosives discriminatively by ratiometric methods. Additionally, the mechanisms for luminescent responses towards different analytes have been discussed in detail.
关键词： luminescent sensor,dual-emission,ratiometric detection,EuIII-based MOF,nitroaromatic pollutants,water-stable
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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[IEEE 2019 Conference on Lasers and Electro-Optics Europe & European Quantum Electronics Conference (CLEO/Europe-EQEC) - Munich, Germany (2019.6.23-2019.6.27)] 2019 Conference on Lasers and Electro-Optics Europe & European Quantum Electronics Conference (CLEO/Europe-EQEC) - Fluorescence-Based Sensors and Preconcentration Techniques for Buried Explosives Detection
摘要： Trace detection of explosives is an important challenge in both humanitarian landmine clearance and in homeland security scenarios. The ability to detect the presence of explosives across an area of interest would be of particular use in technical surveys of suspected minefields. In this paper we present the development and application of fluorescence-based trace-explosives sensors based on organic semiconductor thin films. We show that these can be used to detect nano-gram level quantities of nitroaromatic (TNT-like) molecules, and combine them for the first time with a novel preconcentration approach to detect buried explosives. Initial field trials on a test minefield will also be presented, in which the sensors are used to detect trace explosives collected by colonies of foraging honeybees.
关键词： fluorescence-based sensors,nitroaromatic molecules,buried explosives detection,organic semiconductor thin films,preconcentration techniques
更新于2025-09-12 10:27:22
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Probing the Aggregation and Signaling Behavior of Some Twisted 9,9′-Bianthryl Derivatives: Observation of Aggregation-Induced Blue-Shifted Emission
摘要： With an aim to understand the photophysical behavior of twisted organic fluorescent molecules in their aggregated state, two twisted biaryl molecules, namely, 9,9′-bianthryl and 10,10′-dicyano-9,9′-bianthryl, have been synthesized and characterized by conventional spectroscopic methods. To understand the role of C?C bond twisting on the photophysical response of biaryl aggregates, monoaryl counterparts (anthracene and 9-anthracenecarbonitrile) of the biaryl systems are also investigated. Photophysical behaviors of these systems along with their monoaryl counterpart are investigated in both solution and aggregated state. Investigations reveal that fluorescence spectra of the biaryl compounds show blue-shifted emission upon aggregation. Interestingly, no blue shift of the emission has been observed for monoaryl aggregates. Photophysical data of biaryl systems compared to monoaryl unit reveal that change in geometry, during self-assembly process, disfavors the formation of charge-transfer state, which eventually causes blue shift in the emission upon aggregation. In addition to this, potential of these systems toward signaling of nitroaromatic explosive has also been explored. Among all of the nitroaromatics, the highest fluorescence quenching is observed for nitrophenols (say picric acid (PA)). The investigation also reveals that compared to monoaryl systems, biaryl systems are more responsive to fluorescence quenching by nitroaromatics. Perrin’s model of quenching sphere action has been attributed to nitrophenol (PA) selective signaling behavior of biaryl systems.
关键词： aggregation-induced blue-shifted emission,twisted biaryl molecules,fluorescence quenching,photophysical behavior,nitroaromatic explosives
更新于2025-09-09 09:28:46
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Four new luminescent-organic frameworks exhibiting highly sensing of nitroaromatics: an experimental and computational insight
摘要： Four new metal–organic frameworks (MOFs) namely {[Cd(L)(bpp)]·H2O}n (1), {[Zn(L)(bpp)]·H2O}n (2), {[Cd(L)(bpz)]·H2O}n (3), [Zn(L)(bib)(H2O)]n (4), (H2L = 1,4-bis(4-carboxylbenzyl)piperazine acid; bpp =1,3-bis(4-pyridyl)propane; bpz = 3,3′,5,5′-tetramethyl-4,4′-bipyrazole, bib = 1,4-bis(imidazol-1-yl)butane)) have been designed, synthesized and characterized. The MOFs 1 and 2 are isostructural and possess 4-connected dia topology with rare 8-fold interpenetrating network. In 3, the dianionic ligand L and bpz ligands link binuclear Cd(II) centres to generate a 2D layer framework with a double stranded chain. While in 4, the Zn(II) centres are bridged by L and bib ligands to furnish a 2D framework, which further generates a 3D supramolecular structure through the hydrogen bonding interactions formed between coordinated water molecules and carboxylate groups. The MOF 1 have been utilized as a possible luminescent sensor to detect nitroaromatic compounds (NACs). The results indicates that 1 showed good sensitivity towards p-nitrophenol (PNP) in comparison to other NACs by the decline in its luminescent intensity. The detection limit for PNP was found to be extremely low(1.27 ppm in solution) which represents one of the most efficient MOF-based sensors for PNP. The most plausible mechanism associated with sensing have been explained with the aid of theoretical calculations which indicated that a simultaneous electron/energy transfer phenomenon operating between 1 and NACs contributes toward the decline in the luminescence intensity
关键词： Nitroaromatic,Luminescence sensor,MOFs,Theoretical calculation
更新于2025-09-04 15:30:14
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Water-dispersed fluorescent silicon nanodots as probes for fluorometric determination of picric acid via energy transfer
摘要： Water-dispersed fluorescent silicon nanodots (SiNDs) were synthesized by a one-pot hydrothermal method starting from tetraethyl orthosilicate (TEOS) as silicon source and trisodium citrate as reducing reagent. The method is simple and convenient. The SiNDs, with excitation/emission peaks at 347/440 nm and with fluorescence quantum yield of 18% are shown to be viable fluorescent probes for picric acid (PA). The SiNDs strongly bind PA, and their blue fluorescence is quenched. The distance between the donor and acceptor (R0 value) is calculated from fluorescence data to be 2.1 nm. A fluorometric method was worked out that has a linear response in the 8 nM to 50 μM PA concentration range and a 0.92 nM limit of detection. The method has a fast response (2 min) and is well selective over other nitroaromatic compounds and metal ions. The average recoveries from spiked lake water samples ranged between 98.4 and 100.8%.
关键词： Nitroaromatic compounds,Picric acid (PA),Fluorometric determination,Tetraethyl orthosilicate (TEOS),Hydrothermal strategy
更新于2025-09-04 15:30:14