Search Results (136)

Degradable fluorescent sensors present a promising portable approach for heavy metal ion detection, aiming to prevent secondary environmental pollution. Additionally, the excessive intake of ferric ions (Fe³⁺), an essential trace element for human health, poses critical health risks that urgently require effective monitoring. In this study, we developed a thermally degradable fluorescent hydrogel sensor (Eu-CDs@DPPG) based on europium-doped carbon dots (Eu-CDs). The Eu-CDs, synthesized via a hydrothermal method, exhibited selective fluorescence quenching by Fe³⁺ through the inner filter effect (IFE). Embedding Eu-CDs into the hydrogel significantly enhanced their stability and dispersibility in aqueous environments, effectively resolving issues related to aggregation and matrix interference in traditional sensing methods. The developed sensor demonstrated a broad linear detection range (0–2.5 µM), an extremely low detection limit (1.25 nM), and rapid response (<40 s). Furthermore, a smartphone-assisted LAB color analysis allowed portable, visual quantification of Fe³⁺ with a practical LOD of 6.588 nM. Importantly, the hydrogel was thermally degradable at 80 °C, thus minimizing environmental impact. The sensor’s practical applicability was validated by accurately detecting Fe³⁺ in spinach and human urine samples, achieving recoveries of 98.7–108.0% with low relative standard deviations. This work provides an efficient, portable, and sustainable sensing platform that overcomes the limitations inherent in conventional analytical methods. Full article

Incorporation of lanthanide (Ln) and actinide (An) ions into the human body poses significant chemotoxic and radiotoxic risks, necessitating effective decorporation strategies. This study investigates the displacement of biologically relevant ligands from trivalent ions of europium, Eu(III), and curium, Cm(III), in artificial biofluids by various complexing agents, i.e., ethylenediaminetetraacetic acid (EDTA), ethylene glycol-bis(β-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA), diethylenetriaminepentaacetic acid (DTPA), and spermine-based hydroxypyridonate chelator 3,4,3-LI(1,2-HOPO) (HOPO). Utilizing a modified unified bioaccessibility method (UBM) to simulate gastrointestinal conditions, we conducted concentration-dependent displacement experiments at both room and body temperatures. Time-resolved laser-induced fluorescence spectroscopy (TRLFS) supported by ²H nuclear magnetic resonance (NMR) spectroscopy and thermodynamic modelling revealed the complexation efficacy of the agents under physiological conditions. Results demonstrate that high affinity, governed by complex stability constants and ligand pK_a values, is critical to overcome cation and anion competition and leads to effective decorporation. Additionally, there is evidence that cyclic ligands are inferior to linear ligands for this application. HOPO and DTPA exhibited superior displacement efficacy, particularly in the complete gastrointestinal tract simulation. This study highlights the utility of in vitro workflows for evaluating decorporation agents and emphasizes the need for ligands with optimal binding characteristics for enhanced chelation therapies. Full article

A diverse range of granitoids in the North Qilian Orogenic Belt (NQOB) offers valuable insights into the region’s tectonomagmatic evolution. In this study, we undertook a geochronological, mineralogical, geochemical, and zircon Hf isotopic analysis of granodiorites from the Yaogou area of the NQOB. Zircon U-Pb dating reveals that the Yaogou granodiorites formed during the Early–Middle Ordovician (473–460 Ma). The Yaogou granodiorites have high SiO₂ (63.3–71.1 wt.%), high Al₂O₃ (13.9–15.8 wt.%) contents, and low Zr (96–244 ppm), Nb (2.9–18 ppm), as well as low Ga/Al ratios (10,000 × Ga/Al ratios of 1.7–2.9) and FeO^T/MgO ratios (1.9–3.2), and are characterized by elevated concentrations of light rare earth elements and large-ion lithophile elements such as Rb, Th, and U, coupled with significant depletion in heavy rare earth elements and high-field-strength elements including Nb, Ta, and Ti. Additionally, the presence of negative europium anomalies further reflects geochemical signatures typical of I-type granitic rocks. The zircon grains from these rocks display negative ε_Hf(t) values (−14.6 to −10.7), with two-stage Hf model ages (T_DM2) from 2129 to 1907 Ma. These characteristics suggest that the magmatic source of the Yaogou granodiorites likely originated from the partial melting of Paleoproterozoic basement-derived crustal materials within a tectonic environment associated with subduction in the North Qilian Ocean. Integrating regional geological data, we suggest that during the Early Paleozoic, the North Qilian Oceanic slab underwent double subduction: initially southward, followed by a northward shift. Due to the deep northward subduction of the Qaidam continental crust and oceanic crust along the southern margin of the Qilian Orogenic Belt, the southward subduction of the North Qilian ocean was obstructed, triggering a reversal in subduction polarity. This reversal likely decelerated the southward subduction and initiated northward subduction, ultimately leading to the formation of the Yaogou granodiorites. These findings enhance our understanding of the complex tectonic processes that shaped the North Qilian Orogenic Belt during the Early Paleozoic, emphasizing the role of subduction dynamics and continental interactions in the region’s geological evolution. Full article

The development of efficient scintillators emitting in the red and/or infrared spectral range represents an important scientific challenge, as such materials could find numerous practical applications. This work studies newly grown CsI:Yb,Sm and CsI:Eu,Sm single crystals demonstrating red and infrared luminescence. We measured luminescence spectra in the visible and near-IR range, excitation spectra across visible, UV, VUV, and X-ray ranges, Raman spectra, and thermoluminescence spectra. The results show that divalent europium and ytterbium ions can efficiently transfer excitation to samarium ions. The light output of the obtained crystals under X-ray excitation was roughly estimated from the X-ray luminescence spectra, with expected values of 37,000 photons/MeV for CsI:Yb,Sm and 40,000 photons/MeV for CsI:Eu,Sm. Full article

In this study, the photophysical properties of thin films of an Eu³⁺ dye, namely europium tetrakis(dibenzoylmethide) triethylammonium (EuD₄TEA), within deoxyribonucleic acid (DNA) biopolymer functionalized with hexadecyltrimethylammonium chloride (CTMA) were extensively investigated and compared with those of thin films of the same dye embedded in more conventional polymers, like poly(methyl methacrylate) and polycarbonate. The new materials obtained have good optical properties, as shown by their absorption and emission spectra. Remarkably, a large enhancement in photoluminescence was observed upon the interaction of EuD₄TEA with DNA-CTMA (2- and 17-fold increase in luminescence quantum yield with respect to PMMA and PC). Photophysical analyses suggest that the emission enhancement was mainly due to the increase in the sensitization efficiency (η_sens) from the ligands to the Eu³⁺ ion along with the suppression of the vibrational deactivation upon immobilization onto the DNA-CTMA matrix, as the concentration of the complex increased from 20 to 50%. These phenomena are primarily driven by the transformation of the Eu³⁺ micro-environments, which are created by the interactions between complex ligands and the DNA-CTMA matrix. Full article

This study investigates the synthesis and characterization of SiO₂-Gd₂O₃-Eu₂O₃ nanomaterials. The sol–gel method was employed using tetraethoxysilane (TEOS), gadolinium nitrate, and europium nitrate as precursors. The influence of rare earth oxide concentration on the hydrolysis kinetics and activation energy was evaluated. Additionally, the acid-base properties of the synthesized materials were examined using the Hammett indicator adsorption method. The results revealed that the addition of Gd₂O₃ and Eu₂O₃ oxides to the system accelerated the hydrolysis process and reduced the activation energy. The formation of a layered structure, consisting of a central Si(OH)₄ nucleus, a Si-O-Si polymer layer, and hydrated metal ion layers, was observed. The acid-base properties of the synthesized nanomaterials were influenced by the drying method and the composition of the system. The findings provide valuable insights into the synthesis and properties of SiO₂-Gd₂O₃-Eu₂O₃ nanomaterials, which have potential applications in various fields such as optoelectronics and catalysis. Full article

In this paper, the crystallization behavior of 52WO₃:22B₂O₃:26La₂O₃:0.5Eu₂O₃ glass has been investigated in detail by XRD and TEM analysis. The luminescent properties of the resulting glass-ceramics were also investigated. By XRD and TEM analysis, crystallization of β-La₂W₂O₉ and La₂WO₆ crystalline phases has been proved. Photoluminescent spectra showed increased emission in the resulting glass-ceramic samples compared to the parent glass sample due to higher asymmetry of Eu³⁺ ions in the obtained crystalline phases, where the active Eu³⁺ ions are incorporated. Also, in the glass-ceramics, the crystalline particles are embedded in the amorphous matrix and more of them are separated from each other which improves the light scattering intensity from the free interfaces of the nanocrystallites, resulting in the enhancement of the PL intensity. It was established that the optimum emission intensity is registered for glass-ceramic samples obtained after an 18 h heat treatment of the parent glass. After 21 h of glass crystallization, the amount of crystallite particles is high enough, and they are in close proximity to each other, and hence, the average distance between europium ions decreases, resulting in quenching of Eu³⁺ and a decrease in the emission intensity. Additionally, at 21 h of glass crystallization, formation of new crystalline phase—La₂WO₆ is established. A redistribution of Eu³⁺ ions in the different crystalline compounds is most likely taking place, which is also not favorable for the emission intensity. Full article

The Cambrian period marks a crucial phase in the initial subduction of the Proto-Tethys Ocean beneath the East Kunlun Orogen. Studying the I-type granites and mafic–ultramafic rocks formed during this period can provide valuable insights into the early Paleozoic tectonic evolution of the region. This paper incorporates petrology, LA-ICP-MS zircon U-Pb geochronology, and whole-rock major and trace element data obtained from the Kekesha intrusion in the eastern section of the East Kunlun Orogen. The formation age, petrogenesis, and magmatic source region of the intrusion are revealed, and the early tectonic evolution process of the subduction of the Proto-Tethys Ocean is discussed. The Kekesha intrusion includes four main rock types: gabbro, gabbro diorite, quartz diorite, and granodiorite. The zircon U-Pb ages are 515.7 ± 7.4 Ma for gabbro, 508.9 ± 9.8 Ma for gabbro diorite, 499.6 ± 4.0 Ma for quartz diorite, and 502.3 ± 9.3 Ma and 501.6 ± 6.2 Ma for granodiorite, respectively, indicating that they were formed in the Middle Cambrian. The geochemical results indicate that the gabbro belongs to the high-Al calc-alkaline basalt series, the gabbro diorite belongs to the medium-high-K calc-alkaline basalt series, the quartz diorite belongs to the quasi-aluminous medium-high-K calc-alkaline I-type granite series, and the granodiorite belongs to the weakly peraluminous calc-alkaline I-type granite series, all of which belong to the medium-high-K calc-alkaline series that have undergone varying degrees of differentiation and contamination. Gabbro and gabbro diorite exhibit significant enrichment in light rare earth elements (LREEs), depletion in heavy rare earth elements (HREEs), and an enhanced negative anomaly in Eu (Europium). Compared to gabbro and gabbro diorite, quartz diorite and granodiorite exhibit more pronounced enrichment in LREEs, more significant depletion in HREEs, and an enhanced negative anomaly in Eu. All four rock types are enriched in large-ion lithophile elements (LILEs) such as Cs, Rb, Th, Ba, and U, and are depleted in high-field-strength elements (HFSEs) such as Nb, Ta, and Ti. This indicates that these rocks originated from the same or similar mixed mantle source regions, and that they are formed in the island-arc tectonic environment. This paper suggests that the gabbro and gabbro diorite are mainly derived from the basic magma formed by partial melting of the lithospheric mantle metasomatized by subducted slab melt in the oceanic crust subduction zone and mixed with a small amount of asthenosphere mantle material. Quartz diorite results from the crystal fractionation of basic magma and experiences crustal contamination during magmatic evolution. Granodiorite forms through the crystal fractionation of basic magma, mixed with partial melting products from quartz diorite. While the lithology of the intrusions differs, their geochemical characteristics suggest they share the same tectonic environment. Together, they record the geological processes associated with island-arc formation in the East Kunlun region, driven by the northward subduction of the Proto-Tethys Ocean during the Early Paleozoic. Based on regional tectonic evolution, it is proposed that the Proto-Tethys Ocean began subducting northward beneath the East Kunlun block from the Middle Cambrian. The Kekesha intrusion formed between 516 and 500 Ma, marking the early stages of Proto-Tethys Ocean crust subduction. Full article

Using the solid-state reaction technique, varied Y₂SiO₅ phosphors activated by europium (Eu³⁺) ions at varied concentrations were made at calcination temperatures of 1000 °C and 1250 °C during sintering in an air environment. The XRD technique identified the monoclinic structure, and the FTIR technique was used to analyze the generated phosphors. Photoluminescence emission and excitation patterns were measured using varying concentrations of Eu³⁺ ions. The optimal strength was observed at a 2.0 mol% concentration. Emission peaks were detected at 582 nm and 589 nm for the ⁵D₀→⁷F₁ transition and at 601 nm, 613 nm, and 632 nm for the ⁵D₀→⁷F₂ transition under 263 nm excitation. Because Eu³⁺ is naturally bright, these emission peaks show how ions change from one excited state to another. This makes them useful for making phosphors that emit red light for use in optoelectronics and flexible displays. Based on the computed (1931 CIE) chromaticity coordinates for the photoluminescence emission spectra, it was determined that the produced phosphor may be used in light-emitting diodes. The TL glow curve was examined for various doping ion concentrations and durations of UV exposure levels, revealing a broad peak at 183 °C. Using computerized glow curve deconvolution (CGCD), we calculated the kinetic parameters. Full article

Detailed analysis covered the optical and structural properties of Eu³⁺-doped NaY₉Si₆O₂₆ oxyapatite phosphors, which were obtained via hydrothermal synthesis. X-ray diffraction patterns of NaY₉Si₆O₂₆:xEu³⁺ (x = 0, 1, 5, 7, 10 mol% Eu³⁺) samples proved a single-phase hexagonal structure (P63/m (176) space group). Differential thermal analysis showed an exothermic peak at 995 °C attributed to the amorphous to crystalline transformation of NaY₉Si₆O₂₆. Electron microscopy showed agglomerates composed of round-shaped nanoparticles ~53 nm in size. Room temperature photoluminescent emission spectra consisted of emission bands in the visible spectral region corresponding to ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) f-f transitions of Eu³⁺. Lifetime measurements showed that the Eu³⁺ concentration had no substantial effect on the rather long ⁵D₀-level lifetime. The Eu³⁺ energy levels in the structure were determined using room-temperature excitation/emission spectra. Using the ⁷F₁ manifold, the Nv-crystal field strength parameter was calculated to be 1442.65 cm⁻¹. Structural, electronic, and optical properties were calculated to determine the band gap value, density of states, and index of refraction. The calculated direct band gap value was 4.665 eV (local density approximation) and 3.765 eV (general gradient approximation). Finally, the complete Judd–Ofelt analysis performed on all samples confirmed the experimental findings. Full article

This study conducted adsorption experiments using Europium (Eu(III)) on geological materials collected from Taiwan. Batch tests on argillite, basalt, granite, and biotite showed that argillite and basalt exhibited strong adsorption reactions with Eu. X-ray diffraction (XRD) analysis also clearly indicated differences before and after adsorption. By combining X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), and wavelet transform (WT) analyses, we observed that the Fe₂O₃ content significantly affects the Eu-Fe distance in the inner-sphere layer during the Eu adsorption process. The wavelet transform analysis for two-dimensional information helps differentiate two distances of Eu-O, which are difficult to analyze, with hydrated outer-sphere Eu-O distances ranging from 2.42 to 2.52 Å and inner-sphere Eu-O distances from 2.27 to 2.32 Å. The EXAFS results for Fe₂O₃ and SiO₂ in argillite and basalt reveal different adsorption mechanisms. Fe₂O₃ exhibits inner-sphere surface complexation in the order of basalt, argillite, and granite, while SiO₂ forms outer-sphere ion exchange with basalt and argillite. Wavelet transform analysis also highlights the differences among these materials. Full article

New heterometallic antenna terephthalate MOFs, namely, (Eu_xM_1−x)₂bdc₃·4H₂O (M = Y, La, Gd) (x = 0.001–1), were synthesized by a one-step method from aqueous solutions. The resulting compounds are isomorphic to each other; the crystalline phase corresponds to Ln₂bdc₃∙4H₂O. Upon 300 nm excitation to the singlet excited state of terephthalate ions, all compounds exhibit a bright red emission corresponding to the of ⁵D₀–⁷F_J (J = 0–4) f-f transitions of Eu³⁺ ions. The Eu(III) concentration dependence of the photophysical properties was carefully studied. We revealed that Gd-doping results in photoluminescence enhancement due to the heavy atom effect. To quantitatively compare the antenna effect among different compounds, we proposed the new approach, where the quantum yield of the ⁵D₀ formation is used to characterize the efficiency of energy transfer from the ligand antenna to the Eu³⁺ emitter. Full article

In this paper, the crystallization behavior of 50ZnO:47B₂O₃:3Nb₂O₃:0.5Eu₂O₃ (G-0 h) glass has been investigated in detail by DSC, XRD and TEM analysis. The luminescent properties of the resulting glass-ceramics were also investigated. By XRD and TEM analysis, crystallization of several crystalline phases has been proved (α-Zn₃B₂O₆, β-Zn₃B₂O₆ and ZnNb₂O₆). By calculating crystal parameters, it was found that europium ions are successfully incorporated in the β-Zn₃B₂O₆. Photo-luminescent spectra showed increased emission in the resulting glass-ceramic samples compared to the parent glass sample due to higher asymmetry of Eu³⁺ ions in the obtained crystalline phases. It was established that the optimum emission intensity is registered for glass-ceramic samples obtained after 25 h heat treatment of the parent glass. Full article

Starting from poly(4-vinylpyridine) ((P4VP)_n), poly(2-vinylpyridine) ((P2VP)_n), and [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀ block copolymers, a series of metal-containing homopolymers, (P4VP)_n⊕MX_m, (P2VP)_n⊕MX_m, and [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m MX_m = PtCl₂, ZnCl₂, and Eu(NO₃)₃, have been successfully prepared by using a direct and simple solution methodology. Solid-state pyrolysis of the prepared metal-containing polymeric precursors led to the formation of a variety of different metallic and metal oxide nanoparticles (Pt, ZnO, Eu₂O₃, and EuPO₄) depending on the composition and nature of the polymeric template precursor. Thus, whereas Eu₂O₃ nanostructures were obtained from europium-containing homopolymers ((P4VP)_n⊕MX_m and (P2VP)_n⊕MX_m), EuPO₄ nanostructures were achieved using phosphorus-containing block copolymer precursors, [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m with MX_m = Eu(NO₃)₃. Importantly, and although both Eu₂O₃ and EuPO₄ nanostructures exhibited a strong luminescence emission, these were strongly influenced by the nature and composition of the macromolecular metal-containing polymer template. Thus, for P2VP europium-containing homopolymers ((P4VP)_n⊕MX_m and (P2VP)_n⊕MX_m), the highest emission intensity corresponded to the lowest-molecular-weight homopolymer template, [P4VP(Eu(NO₃)₃]₆₀₀₀, whereas the opposite behavior was observed when block copolymer precursors, [N=P(O₂CH₂CF₃)]_m-b-P2VP₂₀]⊕MX_m MX_m= Eu(NO₃)₃, were used (highest emission intensity corresponded to [N=P(O₂CH₂CF₃)]₁₀₀-b-[P2VP(Eu(NO₃)₃)_x]₂₀). The intensity ratio of the emission transitions: ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁, suggested a different symmetry around the Eu³⁺ ions depending on the nature of the polymeric precursor, which also influenced the sizes of the prepared Pt°, ZnO, Eu₂O₃, and EuPO₄ nanostructures. Full article

The layered orthorhombic quaternary tellurides EuRECuTe₃ (RE = Ho, Tm, Sc) with Cmcm symmetry were first synthesized. Single crystals of the compounds up to 500 μm in size were obtained by the halide-flux method at 1120 K from elements taken in a ratio of Eu/RE/Cu/Te = 1:1:1:3. In the series of compounds, the changes in lattice parameters were in the ranges a = 4.3129(3)–4.2341(3) Å, b = 14.3150(9)–14.1562(9) Å, c = 11.2312(7)–10.8698(7) Å, V = 693.40(8)–651.52(7) ų. In the structures, the cations Eu²⁺, RE³⁺ (RE = Ho, Tm, Sc), and Cu⁺ occupied independent crystallographic positions. The structures were built with distorted copper tetrahedra forming infinite chains [CuTe₄]⁷⁻ and octahedra [RETe₆]⁹⁻ forming two-dimensional layers along the a-axis. These coordination polyhedra formed parallel two-dimensional layers ${}_{\infty }{}^2\left\{{\left[\mathrm{C}\mathrm{u}RE{\mathrm{T}\mathrm{e}}_3\right]}^{2-}\right\}$. Between the layers, along the a-axis, chains of europium trigonal prisms [EuTe₆]¹⁰⁻ were located. Regularities in the variation of structural parameters and the degree of distortion of coordination polyhedra depending on the ionic radius of the rare-earth metal in the compounds EuRECuCh₃ (RE = Ho, Er, Tm, Lu, Sc; Ch = S, Se, Te) were established. It is shown that with a decrease in the ionic radius r_i(RE³⁺) in the compounds EuRECuTe₃, the unit-cell volume, bond length d(RE–Te), distortion degree [CuTe₄]⁷⁻, and crystallographic compression of layers [RECuTe₃]²⁻ decreased. The distortion degree of tetrahedral polyhedra [CuCh₄]⁷⁻, as well as the structural parameters in europium rare-earth copper tellurides EuRECuTe₃, were higher than in isostructural quaternary chalcogenides. Ab initio calculations of the crystalline structure, phonon spectrum, and elastic properties of compounds EuRECuTe₃ (RE = Ho, Tm, and Sc) ere conducted. The types and wave numbers of fundamental modes were determined, and the involvement of ions in IR and Raman modes was assessed. The calculated data of the crystal structure correlated well with the experimental results. Full article