Search Results (564)

Y₂O₃ is widely used in IR windows and optoelectronics, but its vibrational and spectral properties under La³⁺ substitutions remain unclear. This work investigates xLa₂O₃-(1−x)Y₂O₃ with x = 0–0.2 via XRD, SEM, Raman, and IR spectroscopy to address the lack of comprehensive data on structure–property correlations. The solid solution (Y_1−xLa_x)₂O₃ with 0 ≤ x < 0.15 was determined. The cell parameter a increases from 10.6113(5) Å to 10.7116(1) Å as x increases from 0 to 0.15 according to the Rietveld refinements. Both the Raman spectra and infrared (IR) reflection spectra show that (Y_1−xLa_x)₂O₃ is a “one-mode” system, in which eight of the 22 theoretical first-order Raman modes and 12 of 16 theoretical IR modes for the (Y_1−xLa_x)₂O₃ are recognized. A local vibrational mode at approximately 680 cm⁻¹ is observed in the Raman spectra as x > 0. The Raman modes and IR modes of (Y_1−xLa_x)₂O₃ show red shift and obvious peak broadening as x increases, which is caused by the expansion of unit cell and local distortions of the crystal structure. As Y³⁺ is substituted by La³⁺, the extinction coefficient κ decreases significantly, which can lead to a lower IR absorption and should be beneficial for the IR window applications. Full article

New insecticides for indoor residual spraying (IRS) are being developed to manage resistance. Chlorfenapyr (Sylando^® 240SC), a pro-insecticide, is metabolized by active mosquitoes into the toxic metabolite tralopyril. This mode of action requires adapted “free flying” bioassays (because chlorfenapyr is converted to its toxic metabolite tralopyril when mosquitoes are metabolically active). A miniature-experimental hut (MEH) assay was developed within the Ifakara Ambient Chamber Test (I-ACT) with a rabbit as a host to measure residual efficacy under controlled conditions. Sylando^® 240SC was compared with SumiShield^® 50WG (clothianidin) for 12-month residual efficacy against malaria and arbovirus vectors. Residual activity was assessed on mud, wood and concrete with two huts per substrate treated with Sylando^® 240SC, one with SumiShield^® 50WG, and one with untreated control. Five replicates of 20 mosquitoes per strain (malaria vectors: pyrethroid-susceptible Anopheles gambiae and -resistant An. arabiensis and An. funestus; culicines Aedes aegypti and Culex quinquefasciatus) were exposed overnight at one-week post spraying and monthly thereafter. Multivariable mixed-effect logistic regression with binomial errors and log link function assessed non-inferiority with a 7% margin on mosquito mortality as the primary outcome for malaria vectors. Both products induced delayed mortality, with higher effects on malaria vectors than culicines. Across all substrates and malaria species combined over the full 12 months of observation, Sylando^® 240SC was non-inferior to SumiShield^® 50WG on mortality measured at 72 h (76% vs. 67%, OR = 0.86, 95% CI: 0.77–0.97) and 168 h (89% vs. 82%, OR = 0.74, 95% CI: 0.63–0.87). Sylando^® 240SC performed comparably to SumiShield^® 50WG, supporting its use as an IRS additional option. The new I-ACT mini-experimental-hut assay provides a practical tool for evaluating pro-insecticides. The importance of free-flight evaluation methods for pro-insecticides is discussed. Full article

Copper-based nanoparticles (Cu-based NPs) represent a major focus in nanomedicine due to their unique physicochemical properties and excellent biocompatibility. In this paper, we present an interdisciplinary study bridging engineering and biomedical sciences by employing a novel synthesis approach to produce highly stable and uniformly dispersed spherical copper nanoparticles (CuNPs), which were subsequently tested for their cytotoxic effects on SKBR3 and MSC human cells. The synthesis of CuNPs was performed in the presence of the complexing agent trisodium citrate (TSC), while starch was used for the chemical reduction step. Characterization of the Cu-based NPs via UV–Vis, FT-IR, Mie theory, DLS and SEM confirmed their nanoscale structure. The obtained CuNPs were subsequently assessed for their biological effects and cytotoxic responses induced in normal and SKBR3 cancer cell lines. The SKBR3 cell line showed a dose-dependent decrease in the cell index and a higher proportion of apoptotic cells compared to normal MSCs, with apoptosis representing the dominant mode of cell death. Although SKBR3 cells appeared to mount an antioxidant response against CuNP oxidative stress, the response was insufficient to counteract the apoptotic progression. In comparison, MSCs showed a greater resilience to CuNP-induced cellular stress. By promoting oxidative stress and disrupting the antioxidant defense system of cancer cells, CuNPs exhibit promising anti-cancer properties. Full article

Background: Upper-limb performance in handball depends on accurate shoulder sensorimotor control under high loads and fatigue. This study examined between-cohort differences associated with concentric versus eccentric exercise-induced fatigue in shoulder proprioception, kinesthesia, functional stability, and isometric force output in professional male handball players. Methods: This was a retrospective, quasi-experimental (non-randomized) between-cohort comparison of two previously collected cohorts who completed either a concentric (n = 46) or eccentric (n = 33) fatigue protocol, with pre- and post-fatigue assessments of joint repositioning sense (absolute angular error, AAE), threshold to detection of passive movement (TTDPM), Y Balance Test Upper Quarter (YBT-UQ), and the Athletic Shoulder (ASH) test. Results: Fatigue significantly increased AAE across all tested angles (Time: all p < 0.001), with a contraction-specific effect at end-range internal rotation (IR45°), where AAE increased more after concentric than eccentric fatigue (Time × Fatigue Type: p = 0.017; Δ = +1.34° (+61.8%) vs. +0.20° (+7.4%)). TTDPM increased after fatigue (p = 0.001) with no interaction (p = 0.968). YBT-UQ performance decreased after fatigue for all dominant-limb outcomes and for non-dominant inferolateral, superolateral, and composite scores (all p ≤ 0.018), but not for non-dominant anteromedial reach (p = 0.986); no Time × Fatigue Type interactions were detected for YBT-UQ outcomes (all p > 0.05). ASH force output decreased across all positions and both limbs (all p ≤ 0.002), with the dominant-limb Y position showing a greater decline following eccentric fatigue (Time × Fatigue Type: p = 0.030; e.g., ASH Y dominant Δ = −0.49 (−4.6%) vs. −1.43 N·kg⁻¹ (−13.3%)). Conclusions: Exercise-induced fatigue impairs shoulder sensorimotor function and upper-limb performance in handball. Contraction-mode differences were small and task-specific in this between-cohort comparison, emerging primarily at end-range proprioception and selected isometric strength positions. These findings may inform the design of training programs that emphasize fatigue-resistant sensorimotor control and end-range strength, while causal inferences regarding contraction mode are not warranted given the non-randomized design. Full article

This study investigates the rational design of a dinuclear zinc(II) coordination polymer, (C₃₆H₃₄Br₂N₈O₄S₂Zn₂), to explore how halogen substitution and ligand choice modulate structural architecture, contributing to the development of functional coordination polymers with tailored properties. The complex was synthesized from a bromo-substituted semicarbazone Schiff base ligand (L1) and a rigid bipyridine linker (L2) under solvothermal conditions, and its structure was elucidated using single-crystal X-ray diffraction (SCXRD), complemented by characterization via powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and infrared (IR) spectroscopy. Crystallographic analysis reveals that the complex crystallizes in the triclinic space group P-1, forming discrete dinuclear units where each Zn(II) center adopts a distorted square–pyramidal geometry; these units are extended into one-dimensional chains by bridging L2 ligands and further assembled into a three-dimensional supramolecular network through hydrogen-bonding interactions. PXRD confirms the high phase purity of the bulk material, TGA indicates notable thermal stability up to 130 °C, and IR spectroscopy validates the coordination modes and hydrogen-bonding network. This work elucidates the critical role of the bromo substituent and rigid ancillary ligands in modulating the solid-state structure of the zinc(II) complex. The revealed structure-directing principles provide a valuable reference for the rational design of functional coordination polymers. Full article

The relative position of the oxime group within pharmaceutically relevant pyridinium oximes is a pivotal factor that governs their intrinsic physicochemical properties and their biological reactivity. However, studies providing in-depth, molecular-level insight into these structure–reactivity relationships are still limited. In this work, we present an integrated experimental and computational study of N-methylpyridinium-2-aldoxime chloride (PAM2-Cl), N-methylpyridinium-3-aldoxime iodide (PAM3-I), and N-methylpyridinium-4-aldoxime iodide (PAM4-I), aimed at elucidating discrete differences in their ionization behavior, electronic structure, σ-donor properties, and nucleophilicity. The crystal structure of PAM3-I was determined by X-ray diffraction. Comparative structural and spectroscopic (UV–Vis, NMR, IR) analyses elucidated the structural and electronic effects arising from the position of the oxime group. Kinetic studies of substitution reactions with aquapentacyanoferrate(II) in aqueous solution enabled the determination of pentacyano(PAM)ferrate(II) formation and dissociation rate constants, coordination modes, pK_a values of the coordinated ligands, complex stability constants, and σ-donating capabilities. The DFT-based analysis of atomic charge distribution transcended experimental limitations, offering a new perspective on electronic structure-related properties. This study presents the first side-by-side, internally consistent structure–reactivity map across PAM2, PAM3, and PAM4 isomers that triangulates crystallography, UV–Vis-derived pK_a values, substitution kinetics, and DFT descriptors in a single framework. Full article

In order to solve the problems of insufficient medical image feature extraction, high classification accuracy, and computational complexity in automatic diagnosis of skin lesions in the edge computing environment, this paper proposes a real-time pseudo-multimodal low-delay diagnosis framework, SCGViT, based on a vision transformer. The framework is constructed around three functional objectives: mitigating data imbalance through generative modeling, capturing diverse representations via multi-dimensional perception, and optimizing feature fusion through adaptive refinement. Firstly, using Class-Conditioned Generative Adversarial Networks (CGANs) simulates manifolds of minority class samples in latent space, achieving preliminary balance of data distribution. Secondly, a branch feature-extraction path is constructed to simulate inversion (INV) and infrared (IR) modes in the original visual primary color mode (RGB), in order to achieve multi-dimensional perception. Finally, a cross-attention mechanism is combined for cross-branch feature aggregation, and a channel-attention mechanism (squeeze and excitation) is embedded for secondary refinement of the mixed global local features to enhance the representation ability of key pathological regions by integrating complementary structural and contrast information. The experimental results on the HAM10000 dataset showed that the F1 score reached 0.973, the inference speed reached 304.439 FPS, the parameter count was only 0.524 M, and the computational complexity was only 0.866 G FLOPs, achieving a balance between high accuracy and light weight. Full article

To address the reduction in energy efficiency caused by severe signal attenuation during long-distance transmission in cognitive radio networks, this paper constructs an IRS-assisted and energy-constrained relay cognitive radio resource allocation model operating in the underlay mode. By introducing controllable reflective paths, the model enhances link quality and improves energy utilization efficiency. Our objective is to maximize the energy efficiency of secondary users while satisfying the interference constraints imposed on the primary user. To effectively solve the highly non-convex and high-dimensional optimization problem, we propose a Chaotic Spider Wasp Optimization algorithm. The algorithm employs chaotic mapping to initialize the population and enhance population diversity, and incorporates a dynamic trade-off factor to achieve an adaptive balance between hunting and nesting behaviors, thereby improving global search capability and avoiding premature convergence. In addition, the Jain fairness index is introduced to enforce fairness in the power allocation among secondary users. Simulation results demonstrate that the proposed model and optimization method significantly improve system energy efficiency and the stability of communication quality. Full article

Background/Objectives: Pyrazole carboxamides are widely used as adaptable medicinal-chemistry scaffolds and have been explored as cholinesterase (ChE) inhibitor chemotypes. In this work, we prepared a new series of 4-arylazo-3,5-diamino-N-tosyl-1H-pyrazole-1-carboxamides 5(a–m) and evaluated their inhibitory activity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE), supported by structure-based computational analyses. Methods: Thirteen derivatives 5(a–m) were synthesized, fully characterized with analytical techniques (FT-IR, H NMR, and C NMR), and tested in vitro against AChE and BChE, with tacrine (THA) used as the reference inhibitor. Docking calculations were used to examine plausible binding modes. The top-ranked complexes (7XN1–5e and 4BDS–5i) were further examined by 100 ns explicit-solvent molecular dynamics (MD) simulations in Cresset Flare, followed by RMSD/RMSF analysis and contact-persistence profiling. Predicted ADME/Tox. properties were also assessed to identify potential developability issues. Results: The series showed strong ChE inhibition, and several compounds were more potent than THA. Compound 5e (4-nitro) was the most active AChE inhibitor (K_I = 20.86 ± 1.61 nM) compared with THA (K_I = 164.40 ± 20.84 nM). For BChE, the K_I values ranged from 31.21 to 87.07 nM and exceeded the reference compound’s activity. MD trajectories supported stable binding in both systems (10–100 ns mean backbone RMSD: 2.21 ± 0.17 Å for 7XN1–5e; 1.89 ± 0.11 Å for 4BDS–5i). Most fluctuations were confined to flexible regions, while key contacts remained in place, consistent with the docking models. ADME/Tox. predictions suggested moderate lipophilicity but generally low aqueous solubility; all compounds were predicted as non-BBB permeant, and selected liabilities were flagged (e.g., carcinogenicity for 5e/5g/5h/5i; nephrotoxicity for 5f/5g). Conclusions: The 4-arylazo-3,5-diamino-N-tosyl-1H-pyrazole-1-carboxamide scaffold delivers low-nanomolar ChE inhibition, with docking and MD supporting stable binding modes. Future optimization should prioritize solubility improvement and mitigation of predicted toxicities and metabolic liabilities, especially given the predicted lack of BBB permeability for CNS-directed applications. Full article

The six platinum group elements (PGE) are among the rarest elements in the upper continental crust of the earth. Higher values of PGE have been detected in the upper mantle and in chondrite meteorites. The PGE are siderophile and chalcophile elements and are divided into the following: (1) the Ir subgroup (IPGE) = Os, Ir, and Ru and (2) the Pd subgroup (PPGE) = Rh, Pt, and Pd. The IPGE are more refractory and less chalcophile than the PPGE. High concentrations of PGE led, in rare cases, to the formation of mineral deposits. The PGE are carried in discrete phases, the platinum group minerals (PGM), and are included as trace elements into the structure of base metal sulphides (BM), such as pentlandite, chalcopyrite, pyrite, and pyrrhotite. Similarly to PGE, the PGM are also divided into two main groups, i.e., IPGM composed of Os, Ir, and Ru and PPGM containing Rh, Pt, and Pd. The PGM occur both in mafic and ultramafic rocks and are mainly hosted in stratiform reefs, sulphide-rich lenses, and placer deposits. Presently, there are only 169 valid PGM that represent about 2.7% of all 6176 minerals discovered so far. However, 496 PGM are listed among the valid species that have not yet been officially accepted, while a further 641 are considered as invalid or discredited species. The main reason for the incomplete characterization of PGM resides in their mode of occurrence, i.e., as grains in composite aggregates of a few microns in size, which makes it difficult to determine their crystallography. Among the PGM officially accepted by the IMA, only 13 (8%) were discovered before 1958, the year when the IMA was established. The highest number of PGM was discovered between 1970 and 1979, and 99 PGM have been accepted from 1980 until now. Of the 169 PGM accepted by the IMA, 44% are named in honour of a person, typically a scientist or geologist, and 31% are named after their discovery localities. The nomenclature of 25% of the PGM is based on their chemical composition and/or their physical properties. PGM have been discovered in 25 countries throughout the world, with 64 from Russia, 17 from Canada and South Africa (each), 15 from China, 12 from the USA, 8 from Brazil, 6 from Japan, 5 from Congo, 3 from Finland and Germany (each), 2 from the Dominican Republic, Greenland, Malaysia, and Papua New Guinea each, and only 1 from Argentine, Australia, Bulgaria, Colombia, Czech Republic, England, Ethiopia, Guyana, Mexico, Serbia, and Tanzania each. Most PGM phases contain Pd (82 phases, 48% of all accepted PGM), followed, in decreasing order of abundances, by those of Pt 35 phases (21%), Rh 23 phases (14%), Ir 18 phases (11%), Ru 7 phases (4%), and Os 4 phases (2%). The six PGE forming the PGM are bonded to other elements such as Fe, Ni, Cu, S, As, Te, Bi, Sb, Se, Sn, Hg, Ag, Zn, Si, Pb, Ge, In, Mo, and O. Thirty-two percent of the 169 valid PGM crystallize in the cubic system, 17% are orthorhombic, 16% hexagonal, 14% tetragonal, 11% trigonal, 3% monoclinic, and only 1% triclinic. Some PGM are members of a solid-solution series, which may be complete or contain a miscibility gap, providing information concerning the chemical and physical environment in which the mineral was formed. The refractory IPGM precipitate principally in primitive, high-temperature, mantle-hosted rocks such as podiform and layered chromitites. Being more chalcophile, PPGE are preferentially collected and concentrated in an immiscible sulphide liquid, and, under appropriate conditions, the PPGM can precipitate in a thermal range of about 900–300 °C in the presence of fluids and a progressive increase of oxygen fugacity (fO₂). Thus, a great number of Pt and Pd minerals have been described in Ni-Cu sulphide deposits. Two main genetic models have been proposed for the formation of PGM nuggets: (1) Detrital PGM represent magmatic grains that were mechanically liberated from their primary source by weathering and erosion with or without minor alteration processes, and (2) PGM reprecipitated in the supergene environment through a complex process that comprises solubility, the leaching of PGE from the primary PGM, and variation in Eh-pH and microbial activity. These two models do not exclude each other, and alluvial deposits may contain contributions from both processes. Full article

Vehicle exhaust gases remain one of the key sources of atmospheric air pollution and pose a serious threat to ecosystems and public health. This study presents an experimental investigation into reducing the toxicity of gasoline internal combustion engine exhaust using ultrasonic waves and infrared (IR) laser exposure. An original hybrid system integrating an ultrasonic emitter and an IR laser module was developed. Four operating modes were examined: no treatment, ultrasound only, laser only, and combined ultrasound–laser treatment. The concentrations of CH, CO, CO₂, and O₂, as well as exhaust gas temperature, were measured at idle and under operating engine speeds. The experimental results show that ultrasound provides a substantial reduction in CO concentration (up to 40%), while IR laser exposure effectively decreases unburned hydrocarbons CH (by 35–40%). The combined treatment produces a synergistic effect, reducing CH and CO by 38% and 43%, respectively, while increasing the CO₂ fraction and decreasing O₂ content, indicating more complete post-oxidation of combustion products. The underlying physical mechanisms responsible for the purification were identified as acoustic coagulation of particulates, oxidation, and photodissociation of harmful molecules. The findings support the hypothesis that combined ultrasonic and laser treatment can enhance real-time exhaust gas purification efficiency. It is demonstrated that physical treatment of the gas phase not only lowers the persistence of by-products but also promotes more complete oxidation processes within the flow. Full article

The objective of this research is to develop environmentally friendly, risk-free and effective adsorbent composite beads that remove Cu(II) ions from aqueous solutions using cost-effective biopolymers (Carboxymethylcellulose (CMC) and sodium alginate (AL)). The synthesized hydrogel beads (AL@CMC) were dried using two drying modes, namely air-drying and freeze-drying, and characterized using scanning electron microscopy (SEM), Fourier Transform Infrared Spectroscopy (FT-IR), and Brunauer–Emmett–Teller (BET) analysis. The study investigated factors such as pH, adsorbent dosage, reaction time, Cu(II) ions concentration, and temperature to elucidate the adsorption mechanisms involved in removing copper ions. The results indicated that the hydrogel exhibited a maximum adsorption capacity of 99.05 mg·g⁻¹, which is highly competitive compared to previous studies; the AL@CMC beads prepared in this work show a significantly higher adsorption capacity, improved stability due to the interpenetrated biopolymer network, and a clear enhancement from freeze-drying, which greatly increases porosity and active surface area. In addition, the pseudo-second-order nonlinear kinetic model best described the experimental data, implying the chemical nature of the adsorption process. Furthermore, the thermodynamic studies revealed that the adsorption process was endothermic, spontaneous, and homogenous. A Monte Carlo simulation model was utilized to ensure compatibility with the adsorption mechanism, in order to delve deeper into the intricacies of the adsorption process and gain a more comprehensive understanding of its underlying mechanisms and behavior. In conclusion, the prepared hydrogel beads proved to be an effective adsorbent for efficiently removing copper ions, making them a promising solution for addressing Cu(II) ion pollution. Full article

The contamination of water bodies by polycyclic aromatic hydrocarbons (PAHs) poses a significant concern for the ecological systems, along with public health. Magnetic adsorption stands out as a green and practical solution for treating polluted water. To make the process more efficient and economical, it is important to create materials that not only absorb contaminants effectively but also allow for easy recovery and reuse. This study proposes a simple yet effective method for coating Fe₃O₄ nanoparticles with hydroxypropyl-β-cyclodextrin polymer (HP-β-CDCP). The physicochemical properties of the synthesized sorbent were characterized using a transmission electron microscope (TEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and Vibrating Sample Magnetometer (VSM) analysis. The adsorption performance of HP-β-CDCP/Fe₃O₄ nanoparticles was well-described by the pseudo-second-order kinetic model, thermodynamic analysis, and the Freundlich isotherm model, indicating multiple interaction mechanisms with PAHs, such as π–π interactions, hydrogen bonding, and van der Waals forces. Using HP-β-CDCP/Fe₃O₄ nanoparticles as the adsorbent, the purification rates for the fifteen representative PAHs were achieved within the range of 33.9–93.1%, compared to 15.3–64.8% of the unmodified Fe₃O₄ nanoparticles. The adsorption of all studied PAHs onto HP-β-CDCP/Fe₃O₄ nanocomposites was governed by pH, time, and temperature. Equilibrium in the uptake mechanism was obtained within 15 min, with the largest adsorption capacities for PAHs in competitive adsorption mode being 6.46–19.0 mg·g⁻¹ at 20 °C, pH 7.0. This study points to the practical value of incorporating cyclodextrins into tailored polymer frameworks for improving the removal of PAHs from polluted water. Full article

The vibrational properties of the chiral sulfoxide methyl-p-tolyl-sulfoxide (Metoso) were investigated by infrared and Raman spectroscopy in the solid, liquid and aqueous solution phases, for both the enantiopure compounds and their racemic mixture. Experimental data were complemented by DFT calculations on the isolated enantiomer and on the two RR and RS dimeric conformers to support spectral interpretation and mode assignment. The IR and Raman spectra of the crystalline enantiomer and racemic mixture are similar, indicating comparable molecular organization and intermolecular interactions in the solid state. Upon melting, band broadening and frequency shifts are observed, consistent with molecular disorder and the breaking of weak intramolecular interactions, accompanied by changes in the S-O, S-CH₃ and C-H stretching frequencies. In aqueous solution, further broadening and opposite shifts in these bands reflect the formation of Metoso-H₂O complexes through hydrogen bonds. Theoretical spectra reproduce the observed trends and confirm that either solvent or phase transitions control the balance between intra- and intermolecular interactions thus influencing the vibrational degrees of freedom of the model chiral sulfoxide. Full article

To address the challenges posed by increased power consumption in traditional active relays and the difficulties associated with countering channel fading for Intelligent Reflecting Surfaces (IRSs), we propose a dual-mode relay (DMR). This relay can dynamically switch between two operational modes: active relaying and passive IRS reflection. The DMR allows its units (DMRUs) to select their operational modes based on channel conditions. This capability enables the transmission of composite-mode signals, which consist of both active relaying components and IRS-reflected components. This dynamic switching enhances adaptation to the wireless environment. Furthermore, under the constraint of limited transmit power, we introduce a DMR-based Adaptive Transmission (DMRAT) method. This approach explores all possible DMR operational modes and employs the Alternating Optimization (AO) algorithm in each mode to jointly optimize the beamforming matrices of both the transmitter and the DMR, along with the reflection coefficient matrix of the IRS. Consequently, this maximizes the data transmission rate for the target communication pair. The optimal DMR mode can then be determined based on the optimized data rate for the target communication across various operational modes. Simulation results demonstrate that the proposed method significantly enhances the data transmission rate for the target communication pair. Full article