Search Results (358)

We report a defect-selective luminescence response in calcium-deficient hydroxyapatite (HAp) induced by electron and ion irradiation. Compacted HAp pellets prepared from hydrothermally grown nanofibers were investigated to analyze defect-related luminescence using photoluminescence (PL) and cathodoluminescence (CL) techniques, both before and after compaction. Low-energy electron beam irradiation (15 keV) produced a two-stage luminescent response, an initial enhancement arising from field-assisted activation of OH-channel vacancies (V_OH and V_OH + H_i), followed by an exponential decay attributed to defect annealing. Monochromatic transient CL measurements show that this rise–decay behavior is selective to the OH-related bands at 2.57 and 2.95 eV, whereas the 3.32 and 3.67 eV emissions exhibit only a monotonic exponential decay. The corresponding decay constants further indicate that the activated OH-channel vacancies anneal more rapidly than the other centers, consistent with their higher electron-capture probability and lower structural stability. In contrast, ${\mathrm{Ga}}^{+}$ ion irradiation (30 keV, 1.4 × 10⁻¹³ A/µm²) induced progressive monotonic luminescence quenching, primarily driven by selective annealing of oxygen vacancies in $\mathrm{P}{\mathrm{O}}_4^{3-}$ groups. These complementary pathways, electron-induced activation and ion-driven suppression, demonstrate that irradiation serves as a versatile tool for defect engineering in hydroxyapatite. Beyond providing fundamental insights into vacancy stability, these results open new routes for tailoring the optical, sensing, and bioimaging functionalities of HAp through controlled irradiation. Full article

Understanding the influence of solvent environments on the excited-state charge transfer process remains a fundamental question in molecular photophysics and photochemistry. While twisted intramolecular charge transfer (TICT) is crucial in determining fluorescence efficiency and photostability, the combined effects of solvent polarity and hydrogen bonding interactions are still elusive. Here, we employ steady-state and femtosecond transient absorption (fs-TA) spectroscopy with density functional theory (DFT) calculations to investigate the excited-state dynamics of 7-(diethylamino)coumarin-3-carboxylic acid (7-DCCA) in different solvents. Our findings reveal that in highly polar solvents with strong hydrogen-donating and hydrogen-accepting capabilities, 7-DCCA undergoes significant TICT formation, resulting in fluorescence quenching. Conversely, in environments with low polarity or weak hydrogen-bonding interactions, this transformation is largely suppressed. Quantitative correlation analysis utilizing the Kamlet–Taft and Catalán four-parameter models further elucidates the synergistic role of solvent polarity and specific hydrogen-bonding parameters in modulating the steady-state spectral behavior of 7-DCCA. This study provides microscopic insights into solvent–charge transfer interactions and establishes a general framework for enhancing the luminescence efficiency and structural robustness of organic optoelectronic materials through strategic solvent engineering. Full article

Translating the exceptional luminescent properties of AIEgens into efficient and practical sensing devices has long been a major challenge restricting their practical application. In this work, we demonstrate a novel strategy based on phase separation to fabricate stable, high-surface-area sensing films that address the fluorescence quenching typically associated with conventional nanospheres. Fluorescent polysiloxanes bearing tetraphenylphenyl (TPP) side groups were synthesized and processed into fibrous films via electrospinning. Leveraging the intrinsic incompatibility of the polymer, entropy-driven phase separation generated an “sea–island” morphology. This hierarchical structure significantly enlarged the specific surface area and facilitated analyte diffusion, thereby improving the accessibility of active sites. Molecular dynamics simulations not only predicted the formation of this architecture but also clarified the underlying entropy-driven mechanism. Overall, this work provides a solid foundation and conceptual framework for investigating how quantitative regulation of lumogenic unit density and spatial distribution governs sensing performance. Full article

The chemical identity of oxygen species plays a decisive role in determining the optical stability of halide perovskite QD films. Here, real-time in situ spectroscopic monitoring, together with steady-state and time-resolved photoluminescence measurements, is utilized to differentiate the effects of molecular oxygen and plasma-activated oxygen species on CsPbBr₃ QD films. The films maintain nearly unchanged emission intensity, spectral profile, and carrier lifetimes when stored in vacuum or exposed to molecular O₂ even under UV illumination, demonstrating that neutral O₂ exhibits minimal reactivity toward the [PbBr₆]⁴⁻ framework. In contrast, oxygen plasma generates highly reactive atomic and ionic oxygen species that induce rapid and spatially heterogeneous photoluminescence quenching. This degradation is attributed to Br⁻ extraction, Br-vacancy formation, and subsequent Pb–O bond generation, which collectively introduce deep trap states and enhance nonradiative recombination. These findings clearly indicate that reactive oxygen species rather than molecular O₂ are the dominant driver of oxygen-induced luminescence degradation, providing mechanistic insight and offering processing guidelines for the reliable integration of perovskite nanomaterials in optoelectronic devices. Full article

The studied Ce_0.5Y_0.5−XTb_XF₃ (X = 0, 0.001, 0.002, 0.005, 0.01, and 0.05) nanoparticles were synthesized via the water-based co-precipitation method. All the samples demonstrated diameters in the 17–20 nm range and a hexagonal phase corresponding to the phase of CeF₃. Under 266 nm excitation (4f–5d absorption band of Ce³⁺), the luminescence spectrum shape was notably dependent on temperature. The integrated luminescence intensity ratio (LIR) of Ce³⁺ and Tb³⁺ (⁵D₄–⁷F₃) peaks was chosen as a temperature-dependent parameter. It was shown that the LIR functions linearly decay. The rate of decay decreases with the increase in Tb³⁺ concentration. This was explained by the fact that in the case of low Tb³⁺ concentrations, the spectral temperature dependence is mostly based on effective thermal quenching of Ce³⁺ luminescence. At higher Tb³⁺ concentrations, there is a higher probability of Ce³⁺ to Tb³⁺ energy transfer. Here, the efficiency of the temperature dependence of this process is lower, and the rate of LIR decay is lower as well. Full article

Mn⁴⁺-doped fluoride red phosphors are widely used in white LED lighting and display applications due to their excellent luminescent properties. However, their synthesis relies heavily on highly toxic aqueous hydrofluoric acid, which not only causes severe environmental and soil/water pollution but also makes it difficult to control the microstructure of the products due to the rapid reaction rate. In this study, low-melting-point NH₄HF₂ was used as the molten salt, with KMnO₄ and MnF₂ as manganese sources, to synthesize the red phosphor K₃AlF₆: Mn⁴⁺ via the molten salt method. After the reaction, impurities such as NH₄HF₂ were removed by washing with a dilute H₂O₂ solution. The microstructure, photoluminescence properties, thermal quenching behavior, and application in warm white light-emitting diodes (W-LEDs) of the K₃AlF₆: Mn⁴⁺ phosphors were investigated. The results indicate that the phosphors prepared by this method consist of a single pure phase. By adjusting the molten salt content, the morphology of the product can be transformed from nanoparticle-like to nanorod-like structures. All products exhibit the characteristic red emission of Mn⁴⁺ under blue and violet light excitation, with the optimally doped sample achieving an internal quantum efficiency (IQE) of 69% under blue light excitation. The combination of the obtained K₃AlF₆: Mn⁴⁺ with the yellow phosphor YAG enabled the fabrication of W-LEDs. These W-LEDs achieved a color rendering index (Ra) of 86.8, a luminous efficacy (LE) of 77 lm/W, and a correlated color temperature (CCT) of 3690 K, along with excellent color stability under operating conditions. Full article

The aim of this study is to investigate the effect of hydrogen bonds in natural cellulose on luminescent properties, specifically focusing on controlling optical characteristics by tuning hydrogen bond interactions through the incorporation of light scattering from gold nanoparticles (AuNPs). The results from gold nanoparticles are that all samples exhibited strong plasmonic scattering within the 350–800 nm range, albeit with varying intensities. This study demonstrates that cellulose combined with AuNPs is highly effective for light scattering applications due to the reflective properties of cellulose and the surface plasmon resonance (SPR) effects of AuNPs. The enhancement of the autofluorescence signal increased about 2X relative to the Agave-AuNP sample and 67% higher than pure agave cellulose autofluorescence. Moreover, a quenching effect was observed in the mixture of cellulose, C₉H₂₃NO₃Si, (APTES) and AuNPs attributed to hydrogen bond interactions, which diminished the light scattering properties. To understand the autofluorescence properties of cellulose and its interaction with metal nanoparticles, these composite materials are promising candidates for novel applications in bioimaging, sensing, and optoelectronic devices. Full article

Thermal stability is a crucial factor in evaluating phosphors and determining whether they can be utilized in white light emitting diodes (w-LEDs). In this work, a series of Sr₆LuAl(BO₃)₆: Dy³⁺ (SLAB:Dy³⁺) phosphors was synthesized via high-temperature solid-state reaction. The synthesized SLAB:Dy³⁺ phosphor exhibits narrow-band emission in the range of 450–700 nm under 348 nm UV excitation. The strongest emission peak is located at 577 nm and is primarily due to ⁴F_9/2-⁶H_13/2 electron transitions. The optimal doping concentration of Dy³⁺ in the synthesized phosphor was 15 mol%. The integrated emission intensity of the synthesized phosphor at 480 k is 97.84% of that at 300 k, with excellent thermal stability. The activation energy E_g = 0.62 eV. Meanwhile, the Commission International de l’Eclairage (CIE) coordinates of the prepared w-LEDs were (0.309,0.363) with a correlated color temperature (CCT) of 6497 K. Preliminary experimental findings suggest that SLAB:Dy³⁺ phosphors hold promise for utilization in w-LEDs applications. Full article

In recent years, cadmium sulfide (CdS) has been widely investigated due to its excellent photocatalytic performance. However, its practical application in pollutant treatment is limited by its narrow photoresponse range and susceptibility to photocorrosion. Herein, we design a unique four-layer core–shell structure NaYF₄:Yb³⁺,Er³⁺@NaYF₄@CdS@Au (CSNPs@CdS@Au), with an inert NaYF₄ shell coating on NaYF₄:Yb³⁺,Er³⁺ (CNPs) to form NaYF₄:Yb³⁺,Er³⁺@NaYF₄ (CSNPs) and CdS depositing on CSNPs (CSNPs@CdS); Au nanoparticles are loaded on CdS (CSNPs@CdS@Au). Compared with CdS (9.81%), CSNPs (5.0%), CSNPs/CdS (6.9%), and CSNPs@CdS (81.0%), CSNPs@CdS@Au degrades 97.7% Rhodamine B (RhB) within 15 min, exhibiting superior photocatalytic performance, attributable to two key factors: (1) the NaYF₄ inert shell encapsulation amplifies upconversion (UC) luminescence intensity by suppressing surface quenching; and (2) the electron transfer between Au nanoparticles and CdS effectively promotes spatial separation of photogenerated charge carriers and increases reactive active sites. Additionally, after five degradation cycles, CSNPs@CdS@Au still maintains a 93.25% degradation rate for RhB, confirming its excellent stability. This remarkable stability is attributed to the uniquely designed multilayer core–shell architecture, which significantly enhances structural integrity through physical isolation effects. This study establishes a material preparation strategy for efficient photocatalytic pollutant degradation. Full article

Understanding how solvents influence the luminescence behavior of Cu(I) complexes is crucial for designing advanced optical sensors. This study reports the synthesis, structures and photophysical investigation of an 8-hydroxyquinoline-functionalized 1H-imidazo[4,5-f][1,10]phenanthroline ligand, ipqH₂, and its four Cu(I) complexes with diphosphine co-ligands. Photoluminescence studies demonstrated distinct solvent-dependent excited-state mechanisms. In DMSO/alcohol mixtures, free ipqH₂ exhibited excited-state proton transfer (ESPT) and enol-keto tautomerization, producing dual emission at about 447 and 560 nm, while the complexes resisted ESPT due to hydrogen bond blocking by PF₆⁻ anions and Cu(I) coordination. In DMSO/H₂O, aggregation-caused quenching (ACQ) and high-energy O–H vibrational quenching dominated, but complexes 1 and 2 showed a significant red-shifted emission (569–574 nm) with high water content due to solvent-stabilized intra-ligand charge transfer and metal-to-ligand charge transfer ((IL+ML)CT) states. In DMSO/DMF, hydrogen bond competition and solvation-shell reorganization led to distinct responses: complexes 1 and 3, with flexible bis[(2-diphenylphosphino)phenyl]ether (POP) ligands, displayed peak splitting and (IL + ML)CT redshift emission (501 ⟶ 530 nm), whereas complexes 2 and 4, with rigid 9,9-dimethyl-4,5-bis(diphenylphosphino)-9H-xanthene (xantphos), showed weaker responses. The flexibility of the diphosphine ligand dictated DMF sensitivity, while the coordination, the hydrogen bonds between PF₆⁻ anions and ipqH₂, and water solubility governed the alcohol/water responses. This work elucidates the multifaceted solvent-responsive mechanisms in Cu(I) complexes, facilitating the design of solvent-discriminative luminescent sensors. Full article

Iron detection is of growing importance in the critical minerals sector, where unwanted iron ions are typically removed during the processing of target critical metals. The ideal sensor should utilize inexpensive, scalable materials along with a low-cost, robust, and easy-to-use analysis platform. Here, we demonstrate a simple acid–base synthesis of luminescent iron-responsive carbon dots by reacting ethanolamine, phosphoric acid, and m-phenylenediamine. The carbon dots exhibit selective, iron-specific emission quenching, with the ability to detect part-per-billion levels of iron ions even in 0.1 M HCl. After benchmarking the purified materials using a commercial spectrometer, a “low-cost” process is demonstrated in which carbon dots with minimal purification are coupled with a portable fiber-optic spectrometer for analyzing iron content. Carbon dot-coated paper strips are also evaluated as another convenient platform for iron analysis. Taken together, the sensing material and platforms demonstrated here are well-suited for detecting trace quantities of iron in environmentally relevant conditions, with potential applications in tracking iron removal processes during critical mineral production as one exciting area of interest. Full article

Metal–organic compounds, and especially those containing well-known antioxidant natural flavonoids (Chrysin, Chr) and metal ions (Ti(IV)), attract keen interest for their potential biological activity nutritionally and pharmacologically. To that end, chemical reactivity profiling in binary/ternary systems was investigated synthetically, revealing unique structural correlations between mononuclear (Ti(IV)-Chr) and tetranuclear assemblies (Ti(IV)-Chr-phen). Chemical profiling involved physicochemical characterization through elemental analysis, FT-IR, UV–Visible, 1D-2D NMR, ESI-MS spectrometry, solid-state luminescence, and X-ray crystallography, with theoretical work on intra(inter)molecular interactions of 3D assemblies pursued through Hirshfeld analysis and BVS calculations. An in-depth study of their chemical reactivity shed light onto specific structural properties in the solid-state and in solution, while concurrently exemplifying quenching behavior due to their distinct flavonoid pattern. In the framework of biological activity, the materials were investigated for their antibacterial properties toward Gram(−)-E. coli and Gram(+)-S. aureus, exhibiting an enhanced effect compared to the free ligand and metal ion. Further investigation of BSA denaturation revealed strong anti-inflammatory properties compared to Chr and Diclofenac, an anti-inflammatory agent. Finally, in vitro studies using physiological and cancer cell lines, including breast (MCF10A, MCF7) and lung tissues (MRC-5, A549), formulated a structure–tissue relation reactivity profile, thus justifying their potential as future metallodrugs. Full article

Hollow dendritic Na₄La₂(CO₃)₅ crystals doped with Sm³⁺ ions were synthesized with sodium carbonate using a hydrothermal method. The unique lifetime of Sm³⁺ enables the optical measurement of luminescent ion content. The X-ray diffraction spectrum indicates that the nanocrystals maintain structural stability with a hexagonal arrangement, even when the concentration of Sm³⁺ reaches 50 at.%. As the concentration of Sm³⁺ increases, the emission intensity of Na₄(La_1−xSm_x)₂(CO₃)₅ first rises and then falls. The maximum emission intensity of the fluorescent powder occurs at a Sm³⁺ concentration of 0.04. Beyond this concentration, concentration quenching takes place, primarily due to electric dipole–dipole interactions. Using an excitation wavelength of 404 nm and monitoring at 596 nm, the fluorescence lifetime of Na₄(La_1−xSm_x)₂(CO₃)₅ shows a strong dependence on Sm³⁺ concentration, which can be described by a precise equation. Over the range of Sm³⁺ concentrations from 0.005 to 1, the lifetime decreases from 3.126 ms to 0.023 ms. Therefore, optical monitoring of fluorescent powders is crucial for confirming the composition of coatings used in applications such as solid-state lighting and anti-counterfeiting, by utilizing the relationship between lifetime and doping concentration. Full article

Lanthanide hydrogen-bonded organic frameworks (Ln-HOFs) integrating luminescent and proton-conductive properties hold significant promise for multifunctional sensing and energy applications, yet their development remains challenging due to the difficulty of balancing structural stability and functional diversity. In this context, this study successfully synthesized a novel neodymium(III)-based hydrogen-bonded framework material, formulated as {Nd(H₂O)₃(4-CPCA)[H(4-CPCA)]∙H₂O}ₙ (SNUT-15), via hydrothermal assembly using 1-(4-carboxyphenyl)-4-oxo-1,4-dihydropyridazine-3-carboxylic acid (H₂(4-CPCA)) as the ligand. Single-crystal X-ray diffraction analysis revealed a rare two-dimensional hydrogen-bonded bilayer structure stabilized by π-π stacking interactions and intermolecular hydrogen bonds. Hirshfeld surface analysis further corroborated the structural characteristics of this material. Moreover, leveraging the superior luminescent properties of lanthanide elements, this crystalline material exhibits dual functionality: selective fluorescence quenching toward Fe³⁺, La³⁺, and Mn²⁺ (with detection limits of 1.74 × 10⁻⁴, 1.88 × 10⁻⁴, and 3.57 × 10⁻⁴ mol·L⁻¹, respectively), as well as excellent proton conductivity reaching 7.92 × 10⁻³ S cm⁻¹ under conditions of 98% relative humidity and 353 K (80 °C). As a multifunctional neodymium(III)-based HOF material, SNUT-15 demonstrates its potential for applications in environmental monitoring and solid-state electrolytes, providing valuable insights into the rational design of lanthanide-containing frameworks. Full article

Three fluorophenyl-substituted cyclometalated Ir(III) complexes (Ir1–Ir3) have been synthesized by changing the position of the fluorine atom. All complexes exhibit distinct aggregation-induced phosphorescence emission (AIPE) characteristics in CH₃CN/H₂O and demonstrate satisfactory detection performance for 2,4,6-trinitrophenols (TNPs) with limits of detection of 124 nM, 101 nM, and 127 nM, respectively. In addition, Ir1–Ir3 possess excellent selectivity and anti-interference capability for TNP detection, showing outstanding performance even in different common water samples. The ultraviolet–visible absorption spectra and luminescence lifetimes of the complexes show that their quenching processes include both a static process and dynamic process, and the detection mechanism may be assigned to a combination of photo-induced electron transfer and an inner-filter effect. Full article