Search Results (229)

This study investigates lignin as a renewable functional dye capable of simultaneously imparting coloration and multifunctional performance to cotton textiles, with particular emphasis on how chitosan polymorphs influence lignin-mediated silver nanoparticle (AgNP) systems. Cotton fabrics were pretreated with α- or β-chitosan crosslinked with glyoxal and subsequently dyed with lignin in the presence of silver ions to generate lignin-mediated AgNPs. Inductively coupled plasma optical emission spectrometry (ICP–OES) analysis showed that α-chitosan retained a higher silver content (40.7 mg/kg) than β-chitosan (14.7 mg/kg). Transmission electron microscopy (TEM) revealed that α-chitosan produced larger AgNPs (≈13.6 nm), whereas β-chitosan was associated with smaller measurable nanoparticles (≈4.3 nm). Despite lower silver loading, β-chitosan–modified fabrics exhibited higher antibacterial activity against Staphylococcus aureus (82.6%) than α-chitosan-modified fabrics (68.7%). These results suggest that antibacterial performance in lignin–silver coating systems may depend not only on silver loading, but also on the distribution and accessibility of active components within the coating layer. In addition, the coatings improved UV protection, tensile properties, and color strength. Overall, the findings demonstrate that chitosan polymorphism plays an important role in controlling nanoparticle characteristics and multifunctional performance in lignin-based textile systems. Full article

The Judd–Ofelt (J–O) intensity parameters and oscillator strengths are key to understanding the optical transition properties of rare-earth-doped glasses. However, the scarcity of experimental samples and the complex nonlinear relationship between composition and spectral properties pose significant challenges to accurate predictions. To address this, we propose a generalizable framework that integrates conditional generative adversarial network (cGAN)-based data augmentation with an attention-embedded artificial neural network (ANN)–support vector regression (SVR) hybrid model. The cGAN generates physically plausible virtual samples to enrich data distribution and enhance generalization in sparse compositional regions. The attention mechanism in the ANN identifies critical compositional features, which are then leveraged by SVR for robust regression of parameter trends. The framework demonstrates high predictive accuracy for Er³⁺-doped glasses, achieving R² values above 0.93 for Ω₂, Ω₄, and Ω₆, and exhibits strong generalization performance on independent Dy³⁺- and Nd³⁺-doped datasets without task-specific retraining, confirming its practical applicability across multiple rare-earth ions. The model maintains consistency across diverse glass host systems (tellurite, borate, phosphate, silicate/germanate, heavy-metal oxide), and the attention analysis reveals feature importance aligned with established glass chemistry principles. Demonstrated on Er³⁺, Dy³⁺, and Nd³⁺, with potential for a broader range of rare-earth ions through transfer learning and future dataset extensions, this approach offers a data-driven, physics-informed tool for the targeted design of rare-earth optical materials in next-generation optical sensors. Full article

Henosepilachna vigintioctopunctata is a major pest of solanaceous crops. Matrix metalloproteinase 2 (MMP2) is a zinc ion-dependent endopeptidase that plays a crucial role in the remodeling process of the extracellular matrix (ECM) within cells. However, the function of HvMMP2 in H. vigintioctopunctata remains unknown. In this study, we cloned and characterized the HvMMP2 gene in H. vigintioctopunctata and investigated its function using RNA interference (RNAi). HvMMP2 exists as two transcript variants that differ at the 5′ end. HvMMP2 is highly expressed in the prepupal stage, the pupal stage and the intestine. Silencing HvMMP2 expression in fourth-instar larvae led to approximately 54% mortality at the prepupal stage, with the remaining larvae dying after pupation. RNAi with HvMMP2 in third-instar larvae did not affect their development to the fourth instar, but caused mortality in the majority of larvae during the prepupal and pupal stages, and most of these pupae exhibited wing deformities. Examination of these stunted larvae by dissection showed that their fat bodies were abnormally shaped and that yellow uric acid crystals had accumulated in the Malpighian tubules. Collectively, our findings indicate that HvMMP2 plays a critical role in pupation and eclosion in H. vigintioctopunctata and support HvMMP2 as a potential molecular target for further RNAi-based control studies. Full article

The pure and xDy³⁺-doped SrMoO₄ series (x = 0.5, 1.0, 1.5 and 2.0 at.%) were synthesized using a direct mechanochemical route. We found that a milling speed of 850 rpm and a milling time of 30 min result in a complete chemical reaction at different concentrations of dopant ions. The phase formation, structural units, and optical properties of the obtained samples were investigated by XRD, IR, UV-Vis and PL analyses. It has been established that Dy₂O₃ mainly influences the lattice parameters, unit cell volumes, crystallite sizes, and microstrains. The symmetry of MoO₄ groups was investigated using IR spectroscopy, and it showed that pure and Dy³⁺-doped SrMoO₄ samples are built up of deformed structural units. The calculated optical band gap of the obtained crystal phases decreases with increasing concentrations of Dy³⁺ ions. The host SrMoO₄ matrix shows broad blue emission centered at 430 nm under an excitation wavelength of 230 nm. All doped samples display a strong yellow emission at 570 nm, belonging to the ⁴F_9/2 → ⁶H_13/2 transition of Dy³⁺ ions. The highest luminescence intensity was observed when the concentration of the Dy³⁺ ion was 0.5 at.%. The mechanism of concentration quenching was mainly caused by the electric dipole–dipole interaction. The calculated CIE chromaticity coordinates of the doped samples fall in the yellow range. This study demonstrates that mechanochemical treatment is an appropriate route for the fast preparation of yellow phosphors. Full article

As critical rare earth elements (REEs), the industrial demand for neodymium (Nd) and dysprosium (Dy) increases rapidly due to their specific physical and chemical properties. Recycling these REEs from secondary resources such as spent NdFeB magnetic materials is an efficient approach for sustainable production. However, the separation of neodymium and dysprosium in aqueous solutions is an arduous task because of their close chemical properties. Recovering and purifying neodymium and dysprosium from a simulated leaching solution of spent NdFeB magnets were conducted by employing selective ion exchange resins. It was found that Purolite S950 PLUS resin functionalized with aminophosphonic groups demonstrated selective adsorption toward Nd³⁺ and Dy³⁺ while maintaining low affinity for Fe(II) at low pH (i.e., 0.65), which could realize efficient iron removal from the solution. Purolite MTX7010 resin impregnated with di-(2-ethylhexyl) phosphoric acid (D2EHPA) had a strong adsorption preference for Dy³⁺ over Nd³⁺, which is highly suitable for Dy separation from their mixed solutions under optimized conditions. By employing a multistage adsorption–elution process analogous to distillation, a prospective purity of 98.51% for Dy and a purity over 99.90% for Nd were realized with high metal recoveries from the synthetic leaching solution of spent NdFeB magnets. This research demonstrates that recovery and purification of single REEs from leaching solutions containing mixed REEs and other metals can be achieved with selective resin adsorption processes analogous to distillation despite large concentration differences in the metals in the solutions, which presents a new approach. Full article

The inevitable toxicity and bioaccumulation of rare earth elements (REEs) have posed potential pollution risks to the environment. In this study, two major clay minerals from weathered ion-adsorption rare earth deposits—tubular halloysite and platy kaolinite—were used as research objects, and a series of batch adsorption experiments were conducted on light rare earth elements (La, Eu) and heavy rare earth elements (Y, Dy) at different concentrations, aiming to clarify the adsorption mechanisms of rare earth ions onto clay minerals. The results showed that under the same conditions, the adsorption capacity of halloysite was higher than that of kaolinite. The unit adsorption capacity of both kaolinite and halloysite for REEs increased with rising pH. The adsorption processes of REEs onto kaolinite and halloysite were better fitted by the pseudo-second-order kinetic model and the Langmuir model, indicating that the adsorption was a homogeneous process dominated by chemisorption, with a fast adsorption rate that was basically completed within the first 5 min. The 1/n values fitted by the Freundlich model were all between 0 and 1, suggesting that the adsorption reaction was favorable. Rare earth ions were adsorbed onto halloysite and kaolinite through outer-sphere complexation (electrostatic attraction) and inner-sphere complexation. Full article

Traditional chemical hair dyes are associated with potential health risks, while botanical alternatives are often hampered by poor stability and limited color longevity. In this study, discarded squid ink was used to prepare bionic hair colorants of high performance. By synergizing ultrasound disruption with enzymatic hydrolysis, the crude ink aggregates were transformed into highly uniform squid ink melanin nanoparticles (SIMNPs) with size and zeta potential of ~174 nm and −37.5 mV, respectively. This effectively improved the solubility but reduced the steric limitation of natural melanin. To overcome the weak affinity between melanin and human hair, a biomimetic interface where Fe(III) ions act as supramolecular bridges was further engineered to stably bind the SIMNPs to hair keratin. Under optimized conditions (pH 8.0, 45 °C, and 80 min), the dyed hair achieved a natural deep black with a total color difference (ΔE*) of 68.79 ± 0.29, which was maintained at 63.19 ± 0.27 even after 13 consecutive water washing cycles. Unlike destructive oxidative dyes, this SIMNP dyeing system assisted by coordination-driven assembly preserved the native α-helical architecture and disulfide bond networks of hair keratin. Furthermore, the deposited SIMNP layer effectively protected hair fibers from ultraviolet (UV) damage due to its powerful UV-shielding capacity. Crucially, in vitro and in vivo evaluations confirmed the exceptional biosafety of this formulation, demonstrating robust cellular tolerance and absence of murine skin irritation. The work demonstrates a green, low-damage paradigm for the development of bio-based hair colorants of high performance and presents a promising pathway for the high-value utilization of marine by-products. Full article

To promote the application of natural dyes in eco-textiles and develop multifunctional silk fabrics, this study optimized the extraction of functional pigments from rhubarb and investigated their dyeing performance and functional properties on silk. The optimal extraction conditions were determined as pH 11, 80 °C, 50 min, with three extraction stages. The optimized direct dyeing parameters for silk fabrics were: dye bath pH value of 7, bath ratio of 1:40, dye solution concentration of 5%, and dyeing at 80 °C for 60 min. Post-dyeing metal ion mordanting significantly regulated the hue and dyeing depth of fabrics, with ferrous sulfate mordanting demonstrating the most ideal effect, enabling fabrics to exhibit deep gray coloration and a substantial increase in K/S value. The dyed silk exhibited significantly enhanced Ultraviolet (UV) protection (UPF 18.72 for direct dyeing, reaching 29.80 after Fe²⁺ mordanting) and antibacterial activity (inhibition rates of 69.26% and 77.49% against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), respectively, exceeding 95% after Fe²⁺ treatment). This work demonstrates that rhubarb dyeing can produce functional silk with excellent UV-blocking and antibacterial properties, supporting its potential in ecological textiles. Full article

A novel catalyst, Tm₂FeSbO₇, was synthesized by employing the solid-phase high-temperature sintering method, and, for the first time, it was utilized to create a Z-type heterojunction with BiYO₃. A direct Z-scheme Tm₂FeSbO₇/BiYO₃ heterojunction photocatalyst (TBHP) was successfully produced by employing the ball-milling technique. X-ray diffraction analysis results indicated that Tm₂FeSbO₇ crystallized in a cubic pyrochlorestructure which owned the Fd-3m space group, with a unit cell parameter of 10.1769 Å, whereas BiYO₃ displayed a fluorite structure in the Fm-3m space group, with a unit cell parameter of 5.4222 Å. The Mossbauer spectrum of Tm₂FeSbO₇ showed that Fe³⁺ ions might locate at octahedral sites. The measured bandgap widths for the TBHP, Tm₂FeSbO_7, and BiYO₃ were 2.14 eV, 2.21 eV, and 2.30 eV, respectively. Multiple experimental results demonstrated that the TBHP exhibited a higher valence band ionization potential, a narrower band gap width, and a higher removal efficiency of the sulfamethoxazole (SMX) compared with the Dy₂TmSbO₇/BiHoO₃ heterojunction photocatalyst. Under visible-light irradiation (VISLI) of 115 min, the TBHP showcased exceptional photocatalytic elimination performance; therefore, the elimination rate of the SMX and the total organic carbon (TOC) mineralization rate reached 99.51% and 98.10%, respectively. In contrast to single-component Tm₂FeSbO₇, BiYO_3, or conventional nitrogen-doped titanium dioxide (N-TiO₂) catalyst, the TBHP exhibited removal efficiency enhancement for degrading the SMX by 1.17 times, 1.31 times, or 4.06 times. Simultaneously, the matching mineralization rate for removing the TOC density by employing the TBHP was 1.20 times, 1.34 times, or 4.73 times higher than that by employing Tm₂FeSbO₇, BiYO₃, or conventional N-TiO₂. Above experimental results indicated that the mineralization efficiency for removing TOC density by employing the TBHP was higher than that by employing Tm₂FeSbO₇, BiYO₃, or N-TiO₂. Radicals trapping experiments and the electron paramagnetic resonance spectroscopy results revealed that hydroxyl radicals, superoxide anions, and photoinduced holes were the primary active species during the catalytic elimination course of the SMX by employing the TBHP under VISLI. The results demonstrated that the direct Z-scheme TBHP, which was developed in this study, exhibited the maximal removal efficiency for degrading the SMX in contrast to Tm₂FeSbO₇, BiYO₃, or N-TiO₂. Additionally, the possible elimination routes and elimination mechanisms of the SMX were proposed. Therefore, an important scientific foundation for developing high-performance heterojunction catalysts was established. Full article

Lead borophosphate zinc barium glass systems doped with different concentrations of Dy₂O₃ (0.5–2.0 mol%) were fabricated using the traditional melt-quenching method. The non-crystalline nature of the synthesized glass samples was verified through X-ray diffraction (XRD) analysis, which exhibited the characteristic absence of sharp diffraction peaks. Morphological, structural, and vibrational properties were analyzed using scanning electron microscopy (SEM) and Fourier infrared transmission (FTIR) spectroscopy. Optical absorption, emission, and decay lifetime observations were recorded to evaluate the luminescence behavior of Dy³⁺ ions. Judd–Ofelt parameters (Ω₂, Ω₄, and Ω₆) were evaluated from the optical absorption spectra of all the prepared glass samples. The emission spectra revealed three dominant transitions in the visible region corresponding to the ⁴F_9/2 ⟶ ⁶H_15/2 (blue ~ 484 nm), ⁴F_9/2 ⟶ ⁶H_13/2 (yellow ~ 574 nm), and ⁴F_9/2 ⟶ ⁶H_11/2 (~663 nm) transitions. Radiative characteristics, including radiative transition probability (A_R), radiative lifetime (τ_R), and branching ratio (β_R), were calculated from the emission spectra. Among the investigated compositions, the host glass embedded with 1.0 mol% Dy₂O₃ demonstrated the maximum emission intensity was observed along with superior quantum efficiency (η = 91.68%). The chromaticity coordinates for this composition (x = 0.33, y = 0.41) are positioned close to the white-light region in the CIE 1931 chromaticity diagram. These findings suggest that incorporating 1.0 mol% of Dy₂O₃ yields the highest luminescence efficiency, making the present glass system a promising candidate for white-light-emitting and photonic device applications. Full article

Addressing the need for efficient separation of critical elements from NdFeB magnets, this study introduces, for the first time, a D001 cation exchange resin for the selective separation Co(II) from Nd(III) and Dy(III). At pH 5, the resin adsorbs Nd and Dy with high capacities (97.57 and 86.38 mg/g, respectively) and efficiencies (over 98%), but shows low affinity for Co (26.6% efficiency). The resin exhibits excellent stability across a wide pH range of 2–7 and maintains high adsorption performance over five consecutive cycles. The process follows pseudo-second-order kinetics and the Langmuir model. Co(II) is effectively desorbed with high purity (>99%) using 2.5 M H₂SO₄. Characterization confirms that adsorption occurs via ion exchange on –SO₃Na groups. This method successfully separates Co, providing a high-purity stream for further rare earth purification and demonstrating strong industrial potential. Full article

A new solvent extraction system for the removal of 4f ions (Ln³⁺) from water by use of chelating ligands (HLn, n = 5, 6, 7, and 8) composed of heterocyclic receptors and one β-dicarbonyl fragment is reported. The covalent attachment of a β-dicarbonyl unit to a saturated N-heterocycle with variable ring size resulted in a cooperative interaction within the receptor for Ln³⁺ transfer, which remarkably enhanced the efficiency of the process. The intramolecular cooperative effect was observed only in the ionic liquid (IL) solvent system, providing a several-fold increase in extraction performance for Ln³⁺ ions (La, Nd, Eu and Dy) over chloroform. Thus, it is not possible to confirm that an identical reaction mechanism operated in both liquid systems: IL or CHCl₃. The existence of neutral chelates of the type LnL₃ or anionic lanthanoid complexes [LnL₄⁻] in an ionic medium during the solvent extraction process applying various solvent systems has been established hitherto. Consequently, the Ln³⁺ ion was held by HLn molecules more rigidly in an IL medium ([C₁C_nim⁺]/[C₁C₄pyr⁺]/[C₁C₄pip⁺][Tf₂N⁻], n = 4, 6, 8, 10) than in chloroform, representing an important factor dominating the magnitude of the intramolecular cooperative effect of the chelating ligands for Ln³⁺ ions. The effect of the diluent’s chemical nature on the metal extraction and separation has been studied and discussed thoroughly. Furthermore, competitive solvent extraction and separation studies with various s-, p-, d-, and f-ions of the periodic table revealed that the magnitude of the intramolecular cooperative effect depends on the suitability between the metal ion size and the cavity size or flexibility of the HLn compounds. In addition, the solvent extraction process of 12 refractory metals and 8 platinum group metals with the synthesized chelating extractants is also investigated in different organic liquid media. Full article

Precise control over defect structures is essential for tuning the functional properties of lithium niobate (LiNbO₃) crystals. Although the threshold effect of Hf⁴⁺ doping is well recognized, its underlying atomic-scale mechanism, especially in systems co-doped with luminescent rare earth ions, remains unclear. In this study, we combine experimental and theoretical approaches to elucidate the Hf⁴⁺ concentration-driven threshold behavior in Dy: LiNbO₃ crystals. A series of crystals with Hf⁴⁺ concentrations of 2, 4, 6, and 8 mol% were grown using the Czochralski method. Characterization through XRD and IR spectroscopy identified a threshold near 4 mol%, evidenced by an inflection in lattice constants and a pronounced blue shift of the OH⁻ absorption peak. UV–Vis–NIR absorption spectra revealed a systematic enhancement of Dy³⁺f–f transition intensities, linking the global defect structure to the local crystal field of the optical activator. First-principles calculations showed that Hf⁴⁺ ions preferentially occupy Li sites, repairing antisite Nb defects ($\mathrm{N}{\mathrm{b}}_{\mathrm{Li}}^{4+}$) below the threshold, and incorporate into Nb sites beyond it, inducing structural reorganization. Electron Localization Function analysis visualized strengthened Hf-O covalent bonding in the post-threshold regime. This work establishes a complete atomic-scale picture connecting dopant site preference, chemical bonding, and macroscopic properties, providing a foundational framework for the rational design of advanced LiNbO₃-based materials. Full article

Doping lead-free halide perovskite nanocrystals with trivalent lanthanide ions has emerged as a promising strategy for engineering their optical properties in various photonic applications. Here, we report the design and synthesis of a series of lead-free double halide perovskite (Cs₂Na(In/Y/Gd)Cl₆) nanocrystals co-doped with a pair of different lanthanides (e.g., Tb³⁺, Dy³⁺, and Eu³⁺) as emission centers, and ns² ions (Sb³⁺ or Bi³⁺) as sensitizers. The tunability of the delayed photoluminescence spectral density was achieved through the selective excitation of lanthanide dopants either via ligand-to-metal charge transfer (e.g., Eu³⁺) or via ns² ion s-p transitions (e.g., Dy³⁺ or Tb³⁺). The intensities of the narrow lanthanide f-f emission bands can, therefore, be tuned by modulating the excitation wavelength and/or dopant ratio, allowing for the accurate engineering of the emission color coordinates and spectral density. We also demonstrated time-resolved tuning of the photoluminescence spectral density for the investigated nanocrystal host lattices co-doped with transition-metal (Mn²⁺) and lanthanide ions, owing to a large difference between the decay dynamics for Mn²⁺ d-d and lanthanide f-f transitions. The rational co-doping of double halide perovskite nanocrystals reported in this work provides a new strategy for generating pre-designed multilevel luminescent signatures for protection against counterfeiting. Full article

Ionomers are promising materials because ionic interactions and their reversible clustering provide sensitivity to stimuli and facilitate energy dissipation, polymer miscibility, and ion transport. The existence of a wide variety of interacting ionic groups and their associated macromolecular structures provides the basis for considering the supramolecular organization of ionic polymeric materials as a factor determining the emergence of specific properties. The main structural elements of ionomers are ionic clusters, and the properties of ionomers are determined by their sizes and size distribution. Ionomers are attractive for use in composites, actuators, coatings, dyed textiles, adhesives, shape-memory and self-healing materials, water purification membranes, and ion-exchange membranes for fuel cells and batteries. This paper presents a review of the macromolecular structure and supramolecular organization of ionomers and their properties, depending on the basis of their ionic functionalization. The ionic functions of ionomers are determined primarily by the type of ion (cations or anions) that serves as the basis for their functionalization. Ionomers containing both anionic and cationic pendant ions are considered, with attention given to the influence of the nature of the counterions used on the properties of ionomers. Full article