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Organophosphorus pesticides (OPPs) such as parathion have extensive uses in agriculture and household applications. Chronic exposure to these pesticides can cause severe health and environmental issues. Therefore, a current ecological concern is associated with accumulating these noxious OPPs in food and water sources. In this work, a new Tb3+-doped Zn-LMOF (Zn-LMOF= (3D) {[Zn3(1,4 benzenedicarboxylate)3(EtOH)2]·(EtOH)0.6}∞) was synthesized by a solvent-free reaction between the Zn-LMOF and the salt TbCl3·6H2O using a high-speed ball milling. The Tb@Zn-LMOF was thoroughly characterized by multiple spectroscopic tools, including Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopy, and studied in-depth as a luminescent sensor for a series of pesticides (parathion, malathion, methalaxil, carbofuran, iprodione, captan and glyphosate) in aqueous methanol. The Tb@Zn-LMOF is a long-lived green-emitting compound with luminescence originated by an efficient antenna effect from the excited energy levels of Zn-LMOF toward the 5D state of Tb3+ ions, as it is displayed by its strong emission bands at 488, 545, 585, and 620 nm and a lifetime of 1.01 ms upon excitation at 290 nm. Additions of pesticides to a neutral methanolic dispersion of Tb@Zn-LMOF modified its green emission intensity with a pronounced selectivity toward parathion within the micromolar concentration range. The detection limit for parathion was calculated to be 3.04 ± 0.2 µM for Tb@Zn-LMOF. Based on 31P NMR and mass spectrometry studies, it is attributed to the release of lanthanide ions from Tb@Zn-LMOF with the simultaneous formation of a Tb3+-parathion complex.

Assuntos

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Terbium-doped YVO4 has been considered a nonluminescent solid since the first classic studies on rare-earth-doped phosphors in the 1960s. However, we demonstrate that defect engineering of YVO4:Tb3+ nanoparticles overcomes the metal-metal charge transfer (MMCT) process which is responsible for the quenching of the Tb3+ luminescence. Tetragonal (Y1-xTbx)VO4 nanoparticles obtained by colloidal precipitation showed expanded unit cells, high defect densities, and intimately mixed carbonates and hydroxides, which contribute to a shift of the MMCT states to higher energies. Consequently, we demonstrate unambiguously for the first time that Tb3+ luminescence can be excited by VO43- → Tb3+ energy transfer and by direct population of the 5D4 state in YVO4. We also discuss how thermal treatment removes these effects and shifts the quenching MMCT state to lower energies, thus highlighting the major consequences of defect density and microstructure in nanosized phosphors. Therefore, our findings ultimately show nanostructured YVO4:Tb3+ can be reclassified as a UV-excitable luminescent material.

RESUMO

This study reports the preparation of TiO2 and CeO2 doped with different quantities of terbium and discusses the influence of this dopant on the photocatalytic activity of the semiconductors, with respect to the degradation of methylene blue, under ultraviolet and solar radiations. The oxides obtained were characterized by X-ray diffraction, infrared vibrational spectroscopy, diffuse reflectance spectroscopy, scanning electron microscopy, and dispersive energy spectroscopy. The results indicate that the presence of the dopant in TiO2 favored the formation of the anatase crystalline phase to the detriment of rutile, increased the band gap energy, and decreased the size of the nanoparticles. Doping CeO2 with Tb resulted in a fluorite-type crystalline structure, reduced band gap, and smaller particle size. The photocatalytic activity decreases as the concentration of terbium increases regardless of the radiation source and nature of the oxide. Furthermore, a better performance was observed for all semiconductors excited by solar radiation in comparison to ultraviolet light. The samples of pure TiO2 and TiO2 doped with 0.5 and 1% terbium showed total removal of the dye after less than 120 min of reaction, while the samples of pure CeO2 and CeO2 doped with 0.5% terbium showed approximately 80% and 57% of dye removal after 120 min, suggesting that these materials can be promising for the treatment of industrial effluents.

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The synthesis of 1-benzyl-2-((2-Aminoethyl) amino)-5-oxopyrrolidine-3,4-diyl diacetate (boad), an oxopyrrolidine type ligand; designed to coordinate lanthanides (Eu3+ and Tb3+) to get luminescent material. The target complexes showed good photoluminescence properties, which indicate that this type of compound can be used as sensitizers having luminescence for the green (Tb3+) and red (Eu3+) emission. The obtained results revealed that sensitizer efficiency can be improved by adding ligands like acac (Eu(acac)3, which has also enhanced the luminescence quantum output and period for Eu3+ ions. The ground state geometries were developed by using density functional theory at B3LYP/6-31G** level. The charge transfer analysis and electronic properties were performed. The Europium and Terbium complexes formation with boad ligand was explored based on molecular electrostatic potential, MDC-q charges, and frontier molecular orbitals (FMOs) analysis.

RESUMO

In this paper, we present a combined experimental and theoretical study to disclose, the structure, electronic and optical properties of CaMoO 4 :xTb 3+ ( x = 1%, 2%, and 4%) microspheres. The microspheres were prepared by ultrasonic spray pyrolysis method and characterized by experimental and theoretical techniques. Theoretical calculations and XRD patterns indicate that these crystals have a scheelite-type tetragonal structure. The morphology of the CaMoO 4 :xTb 3+ ( x = 1%, 2% and 4% mol) samples were investigated from the FEG-SEM results and the formation of microspheres with a spherical shape were observed. The optical properties were investigated by UV-Vis and PL spectroscopy, as well as the chromaticity coordinates of these compounds. This also allowed us to understand the charge transfer process that happens in the singlet state and the excited states, generating the photoluminescence emissions of the Tb doping process in CaMoO 4 microspheres.

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Mesoporous silica nanoparticles prepared by organic template-driven synthesis have been successfully explored as carriers of the drug-derivate green luminescent complex of terbium (III) with the nonsteroidal anti-inflammatory drug ketoprofen. The terbium (III) complex was synthesized by reacting ketoprofen sodium salt with terbium (III) chloride, which was further adsorbed onto the surface of mesoporous nanoparticles with a mean particle size of 47 ± 4 nm and pore size of 11 nm. The incorporation of the complex into mesoporous silica nanoparticles was tracked by the decrease in the surface area and pore size of the nanoparticles, and successfully demonstrated by substantial changes in the adsorption isotherms and thermal and vibrational spectroscopy results. The cytotoxicity assay and confocal microscopy have shown that the novel luminescent nanohybrid presents high cell viability and the characteristic terbium (III) emission can be assessed through two-photon excitation, which paves the way for bioimaging applications in nanomedicine.

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Chemisorption of Eu3+ and Tb3+ on SBA-15 functionalized with succinic groups has been studied by in situ steady-state fluorescence measurements. The enhancement of the emission sensitive bands indicates that both ions adsorb forming inner-sphere surface complexes. Adsorption is a fast process that attains equilibrium in about 5min. The variation of the peaks maxima (I592 and I616, for europium, and I490 and I545, for terbium) with the total ion concentration is accounted for by the sum of the contributions due to the adsorbed and free ions. The former contribution is langmuirian. At pH 4.5, the respective adsorption constants are 5×105 and 3×105M-1, and the maximum adsorption capacities are 5.10×10-4 and 5.23×10-4molg-1. The mismatch between the latter values and the number of attached carboxylic groups is discussed. Comparison with other functionalized mesoporous silicas indicates that the anchored succinic groups are very efficient for removing lanthanide ions from aqueous solutions.

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Persistent luminescence materials Lu2O3:R(3+),M (Pr,Hf(IV); Eu; or Tb,Ca(2+)) were successfully and rapidly (22 min) prepared by microwave-assisted solid-state synthesis (MASS) using a carbon microwave susceptor and H3BO3 as flux. Reaction times are reduced by up to 93% over previous synthetic methods, without special gases application and using a domestic microwave oven. All materials prepared with H3BO3 flux exhibit LuBO3 impurities that were quantified by Rietveld refinement from synchrotron radiation X-ray powder diffraction patterns. The flux does not considerably affect the crystalline structure of the C-Lu2O3, however. Scanning electron micrographs suggest low surface area when H3BO3 flux is used in the materials' synthesis, decreasing the amount of surface hydroxyl groups in Lu2O3 and improving the luminescence intensity of the phosphors. The carbon used as the susceptor generates CO gas, leading to complete reduction of Tb(IV) to Tb(3+) and partial conversion of Pr(IV) to Pr(3+) present in the Tb4O7 and Pr6O11 precursors, as indicated by X-ray absorption near-edge structure data. Persistent luminescence spectra of the materials show the red/near-IR, reddish orange, and green emission colors assigned to the 4f(n) → 4f(n) transitions characteristics of Pr(3+), Eu(3+), and Tb(3+) ions, respectively. Differences between the UV-excited and persistent luminescence spectra can be explained by the preferential persistent luminescence emission of R(3+) ion in the S6 site rather than R(3+) in the C2 site. In addition, inclusion of Hf(IV) and Ca(2+) codopants in the Lu2O3 host increases the emission intensity and duration of persistent luminescence due to generation of traps caused by charge compensation in the lattice. Photonic materials prepared by MASS with H3BO3 flux show higher persistent luminescence performance than those prepared by the ceramic method or MASS without flux. Color tuning of persistent luminescence in Lu2O3:R(3+),M provides potential applications in bioimaging as well as in solar cell sensitizers.

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The reaction of terbium(III) nitrate penta-hydrate in aceto-nitrile with N,N'-bis-(2-hy-droxy-benz-yl)-N,N'-bis-(pyridin-2-ylmeth-yl)ethyl-enedi-amine (H2bbpen), previously deprotonated with tri-ethyl-amine, produced the mononuclear compound [N,N'-bis-(2-oxidobenzyl-κO)-N,N'-bis-(pyridin-2-ylmethyl-κN)ethylenedi-amine-κ(2) N,N'](nitrato-κ(2) O,O')terbium(III), [Tb(C28H28N4O2)(NO3)]. The mol-ecule lies on a twofold rotation axis and the Tb(III) ion is eight-coordinate with a slightly distorted dodeca-hedral coordination geometry. In the symmetry-unique part of the mol-ecule, the pyridine and benzene rings are both essentially planar and form a dihedral angle of 61.42 (7)°. In the mol-ecular structure, the N4O4 coordination environment is defined by the hexa-dentate bbpen ligand and the bidentate nitrate anion. In the crystal, a weak C-H⋯O hydrogen bond links mol-ecules into a two-dimensional network parallel to (001).