Search Results (271)

The widespread use of herbicides in agriculture results in their accumulation in the environment, which has a negative impact on non-target biota. One way to reduce environmental risks while maintaining the effectiveness of plant protection products is to apply supramolecular chemistry principles to agricultural practices. Although pillar[n]arenes are used in the production of sensors and antidotes for pesticides, their influence on the herbicidal properties and ecotoxicity of herbicides toward aquatic organisms and higher plants has hardly been studied. The effect of pillar[5]arenes on the herbicidal activity of 2,4-dichlorophenoxyacetic acid (2,4-D) and glyphosate (Glyp), as well as the ecotoxicity of the resulting binary systems toward Ceriodaphnia affinis and Paramecium caudatum, was assessed for the first time. The association constants of pillar[5]arenes with Glyp (logK_a = 3.92–4.06) were an order of magnitude higher than the corresponding values for 2,4-D (logK_a = 2.66–3.06) with the stoichiometry of 1:1. The formation of stable associates (143–177 nm) with negative zeta potential values (from −20.9 to −7.8 mV) was demonstrated for the pillar[5]arene/herbicide systems. Low phytotoxicity of pillar[5]arenes against Chlorella vulgaris was shown. The addition of pillar[5]arenes to 2,4-D reduced the wheat (Triticum aestivum L.) germination index by 4.5-fold compared to the pure herbicide. Forming associates between decamethoxypillar[5]arene and Glyp increased the LC₁₀ by more than twofold compared to the individual herbicide against Paramecium caudatum and Ceriodaphnia affinis. It was demonstrated that combining pillar[5]arenes with Glyp can reduce ecotoxicity while partially preserving or selectively modifying phytotoxicity. The results obtained in this study are encouraging for the development of materials and supramolecular systems that could boost agricultural efficiency while reducing its environmental impact. Full article

Hafnia (hafnium oxide) nanostructures, both unmodified and silica-modified with minor and major silica content, were synthesized using an adapted sol–gel method with D-L tartaric acid as an internal template. After thermal treatment, structural non-stoichiometry and light absorptive properties were identified in the resulting hafnium-based nanostructures, indicating their potential for various applications, including photocatalysis. The ability of these materials to photogenerate reactive oxygen species (ROS), namely superoxide anion radicals (•O₂₋) under simulated solar light (AM 1.5) and singlet oxygen (¹O₂) under visible light (λ > 390 nm), was evaluated and monitored by UV–Vis and photoluminescence spectroscopy. Functionalization of hafnium-based oxides with protoporphyrin IX was employed to enhance singlet oxygen photogeneration. The reactivity of the generated (¹O₂) was assessed by quenching of DL α-tocopherol photoluminescence under visible light irradiation. Photocatalytic experiments conducted under anaerobic conditions demonstrated the ability of the hafnia-based nanostructures to reduce 1,4-benzoquinone (BQ) to 1,4-hydroquinone (H₂Q). Furthermore, embedding the hafnia-based powders into polyvinyl alcohol hydrogels enabled the obtainment of photoactive coatings on glass substrates, for which their mechanical properties were evaluated using force–distance spectroscopy measurements. Morphological and structural characterization of the materials was performed using scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), atomic force microscopy (AFM), X-ray diffraction and fluorescence (XRD, XRF), X-ray photoelectron spectroscopy (XPS), N₂ adsorption–desorption measurements, UV–Vis spectroscopy, photoluminescence (PL) spectroscopy, and zeta potential measurements. These investigations revealed that adding silica induces significant modifications in the morphology, texture, and structure of the hafnia, thereby enhancing the functional properties of the resulting materials. Full article

With increasingly stringent requirements for wear resistance and reliability of functional coatings for heavily loaded friction units, a relevant challenge in materials science is to establish the relationships between the parameters of reactive pulsed magnetron sputtering and the tribo-mechanical properties of TiN/CrN multilayer systems. In this study, TiN/CrN multilayer coatings were deposited by reactive pulsed magnetron sputtering using separate titanium and chromium targets. The effect of the nitrogen flow rate (0.20–0.36 L/h) during chromium sputtering on the structure, phase composition, and mechanical and tribological properties of the coatings was investigated at a fixed nitrogen flow rate of 0.08 L/h for titanium. SEM, EDS, and XRD showed that increasing the nitrogen flow rate leads to a non-monotonic change in coating thickness (2.0–2.6 µm), caused by the transition of the chromium target from the metallic to the poisoned sputtering mode. At low N₂ flow rates, a subnitride Cr₂N phase forms in the structure, whereas at the optimal flow rate of 0.32 L/h the coating consists of stable TiN, CrN, and (Cr_0.5Ti_0.5)N phases. The coating nanohardness was 20–23 GPa and the Young’s modulus was 250–300 GPa. The best tribological performance was achieved at a nitrogen flow rate of 0.32 L/h, coefficient of friction μ ≈ 0.5 and a minimum wear rate of 1 × 10⁻⁵ mm³/(m·N), which correlates with the highest H³/E² value. It is shown that independent control of the CrN layer stoichiometry using separate targets can affect the tribo-mechanical properties of the TiN/CrN multilayer system. Full article

Wollastonite-1A from Băița Bihor occurs in distal calcic skarns developed in the contact zone of a mainly granodioritic batholith, of Upper Cretaceous age, with Mesozoic limestones and dolostones. Wollastonite generally occurs in the inner part of metasomatic columns, in monomineralic skarns or associated with grossular and molybdenite-2H as ore mineral. The physical properties (i.e., refraction indices α = 1.616, β = 1.629, and γ = 1.631, 2V_α = 39° and density D_m = 2.922(3) g/cm³) are typical for a term close to the stoichiometry, which is confirmed by the chemical analysis. The chemical structural formula of the analyzed wollastonite-1A is (Ca_1.000Mg_0.002Mn_0.001Fe_0.001)(Al_0.004Ti_0.001Si_0.994)O₃, which closely approximates the ideal CaSiO₃. The Gladstone–Dale compatibility indices account for an excellent agreement between physical and chemical data. The mineral can be satisfactorily refined as triclinic, space group $P\overline{1}$, with R₁ = 0.0678 and cell parameters a = 7.9233(3) Å, b = 7.3203(3) Å, c = 7.0651(3) Å, α = 90.053(3)°, β = 95.208(3)°, γ = 103.384(3)°. Both the IR and Raman spectra principally reveal bands related to vibrations of bridged and non-bridged oxygens pertaining to SiO₄ structural tetrahedra. At Băița Bihor, wollastonite-1A is part of the prograde paragenesis, marked by a peak temperature of 550–600 °C. Full article

The effects of Fe non-stoichiometry on crystal structure, microstructural evolution, and thermoelectric transport properties were systematically investigated in bornite (Cu₅Fe_1+yS₄; −0.06 ≤ y ≤ 0.06) synthesized by mechanical alloying followed by hot pressing. X-ray diffraction analysis confirmed the formation of a single-phase orthorhombic bornite structure over the entire composition range. Anisotropic lattice distortion was observed with increasing Fe non-stoichiometry, manifested as contraction along the a-axis and expansion along the b- and c-axes, with a non-linear dependence on composition. Crystallite sizes estimated from Lorentzian peak fitting increased from 64.1 nm for the stoichiometric composition to 70.6–76.3 nm for Fe-deficient samples and 73.2–90.9 nm for Fe-excess samples. Hall-effect measurements revealed p-type semiconducting behavior for the stoichiometric composition, degenerate p-type transport with increased hole concentration under Fe-deficient conditions, and a transition to n-type behavior with reduced carrier mobility under Fe-excess conditions. While Fe-deficient samples retained high electrical conductivity and positive Seebeck coefficients, Fe-excess samples exhibited negative Seebeck coefficients at low temperatures with sign reversal at elevated temperatures. As a consequence, the power factor of Fe-deficient samples was enhanced by approximately 20–30% relative to the stoichiometric composition. In addition, the total thermal conductivity remained below 0.8 W·m⁻¹·K⁻¹ for all samples, and Fe non-stoichiometry effectively suppressed lattice thermal conductivity. Consequently, the Cu₅Fe_0.94S₄ composition achieved a maximum dimensionless figure of merit of ZT = 0.61 at 673 K, representing a performance enhancement of approximately 30–70% compared with the stoichiometric composition (ZT = 0.36 at 673 K and 0.47 at 723 K). Full article

The sodium–galactose cotransporter from Vibrio parahaemolyticus (vSGLT) was first cloned and functionally characterized by the laboratory of Ernest M. Wright in 2000, establishing a one-to-one Na⁺:sugar coupling stoichiometry and pioneering a bacterial model for human SGLTs. Here, we revisit vSGLT using solid-supported membrane electrophysiology on the Nanion SURFE²R N1, providing a modern, non-radioactive kinetic analysis of Na⁺-coupled sugar transport. Rapid transient currents were observed upon substrate application to proteoliposomes containing purified vSGLT. D-galactose elicited the largest Na⁺-dependent responses, followed by D-glucose and D-fucose, while no transport was observed in K⁺-based solutions. Apparent kinetic parameters recapitulate the overall trends observed in the original radiolabeled uptake assays, with K_m(Na⁺) ≈ 18 mM and K_m(gal) ≈ 9.8 mM. These findings validate the SURFE²R N1 SSM system as a quantitative, label-free method for Na⁺ symport characterization and demonstrate that vSGLT retains its canonical substrate selectivity and stoichiometry. Full article

The potential of La_0.2Sr_0.8MnO₃ (LSM28) perovskite oxide for thermochemical energy storage (TCES) is assessed by analyzing its thermochemical performance. The TCES capacity of LSM28 was measured using a non-stoichiometric and van’t Hoff analysis at various reduction temperatures ( T r e d ) and oxygen partial pressures ( P O 2 ). O₂ release and the associated non-stoichiometry (δ) increase with T r e d and decrease with P O 2 , according to the results, reaching a maximum δ of 0.101 at 1473 K and 0.0001 atm. The van’t Hoff research also showed that LSM28’s TCES capacity fluctuates greatly with δ, peaking at 37.1 kJ/kg under ideal circumstances. Full article

This review systematizes data on the phase composition and key properties of compounds in the W–B system, including thermodynamic stability, crystal structure, and hardness. The current understanding of the binary W–B phase diagram and the stability of individual borides is discussed, alongside the influence of defects and non-stoichiometry on their properties. The main methods for synthesizing these materials and producing coatings based on them are summarized. Potential applications of tungsten borides are highlighted, particularly for high-temperature environments, cutting tools, and protective and functional coatings. Finally, key directions for future research are outlined, focusing on the refinement of phase equilibria, the scaling of production methods, and the development of W–B-based materials with tailored performance characteristics. Full article

In forest ecosystems, rhizodeposition can lead to significant differences in the availability of soil carbon (C), nitrogen (N), and phosphorus (P) between rhizosphere and bulk soils. Soil stoichiometry affects microbial and enzyme nutrient content and determines the abundance and composition of microbes and thus regulates microbial carbon use efficiency (CUE). However, how soil stoichiometry—particularly its variation between the rhizosphere and bulk soil—regulates microbial CUE by shaping microbial biomass, extracellular enzyme stoichiometry, and community composition remains insufficiently quantified. Here, through the C:N, C:P, and N:P ratios for available soil nutrients, microbial biomass, and extracellular enzyme activities—(β-1,4-glucosidase (BG), β-1,4-N-acetylglucosaminodase (NAG), leucine aminopeptidase (LAP), and acid phosphatase (ACP))—and the composition and activity of microbial communities (based on sequencing of bacterial 16S rRNA and fungal ITS genes) in the rhizosphere and bulk soils of five temperate forest ecosystems in northeastern China, we aimed to unravel their integrated effects on microbial CUE. Results indicated that soil C, N, and P and their stoichiometry, microbial community composition, and microbial CUE were significantly different between rhizosphere and bulk soils among all tree species. The disproportionate variation in soil nutrient pools between the rhizosphere and non-rhizosphere regions has led to a stoichiometric imbalance. There was higher microbial CUE in the rhizosphere soil than that in the bulk soil among all tree species. However, the effect pathways of tree species on microbial CUE in the rhizosphere and bulk soils differed. The structural equation model (SEM) further suggested that tree species affected microbial CUE through distinct pathways in different soil compartments. In the rhizosphere, the effect was directly driven by available nutrient stoichiometry. In bulk soil, it was jointly mediated by both available nutrients and microbial biomass stoichiometry. These findings demonstrate that root rhizodeposition shapes microbial carbon cycling by altering soil stoichiometric imbalances, which can strengthen the current understanding of plant–microbe–soil interactions in temperate forests. Full article

The complexes cis-[Ru(dmbpy)₂Cl(bpy)](PF₆) (Rubpy) and cis-[Ru(dmbpy)₂Cl(bpe)](PF₆) (Rubpe) (dmbpy = 4,4′-Dimethyl-2,2′-dipyridyl, bpy= 4,4′-dipyridyl and bpe = 1,2-bis(4-pyridyl)ethane) were synthesized and spectroelectrochemically characterized. Both Ru(II) complexes exhibited absorption bands assigned to intraligand and metal-to-ligand charge transfer (MLCT) transitions, and their spectral stability in PBS buffer (pH 7.4) supports their suitability for biological studies involving biomolecules or living cells. Fluorescence quenching assays revealed strong interactions with bovine serum albumin (BSA), with binding constants (K_b) values were 2.89 × 10⁵ M⁻¹ for Rubpy and 1.97 × 10⁵ M⁻¹ for Rubpe, and a stoichiometry of one binding site per albumin molecule. DNA-binding studies demonstrated non-covalent interactions with ss-DNA, evidenced by a hyperchromic effect in the MLCT bands, suggesting a partial intercalation or groove-binding mechanism. Cellular uptake assays indicated moderate incorporation of both complexes in tumor cells, with uptake levels of 52% (Rubpy) and 47% (Rubpe) in HeLa cells, and 42% (Rubpy) and 32% (Rubpe) in MDA-MB-231 cells. Despite the similar uptake profiles, cytotoxicity assays showed that Rubpe is approximately 2.4 times more potent than Rubpy, with IC₅₀ values of 9 μM (HeLa) and 12 μM (MDA-MB-231), compared to 22 μM and 29 μM for Rubpy, respectively. These results highlight the relevance of these Ru(II) complexes as molecular platforms for exploring structure–activity relationships in anticancer agents. Full article

Rapid removal of chemically diverse organic pollutants remains a major challenge in aqueous decontamination. In this study, atmosphere-controlled defect engineering was used to activate anatase TiO₂ as a rapid adsorbent operating on the minute scale, exhibiting low charge selectivity under the investigated conditions. A reduced black TiO₂ (B–TiO₂), produced by inert annealing, achieved ≈100% removal of cationic methylene blue within ~6 min and ≈91% uptake of anionic methyl orange within ~3 min, whereas pristine and air-annealed TiO₂ showed only marginal adsorption under identical conditions. Correlative structural and surface-sensitive analyses indicated that this behaviour was associated with a chemically activated near-surface region enriched in reduced titanium contributions, defect-associated or non-lattice oxygen environments and a locally perturbed anatase framework, together with finely dispersed carbon-related motifs integrated within the oxide matrix. Adsorption kinetics were described, within experimental resolution, by pseudo-second-order fitting, while intraparticle diffusion analysis supported sequential regimes initiated by rapid interfacial attachment. Equilibrium analysis yielded apparent maximum capacities of 6.116 mg g⁻¹ for methylene blue and 2.950 mg g⁻¹ for methyl orange, reflecting adsorption governed by surface heterogeneity for cationic species and an apparent saturation-type response for anionic uptake. Overall, controlled surface non-stoichiometry emerges as a viable strategy to enhance adsorption kinetics in TiO₂, providing a transferable design framework for developing oxide-based adsorbents for sustainable water-treatment applications. Full article

This study aimed to explore the effect of doubled CO₂ concentration (d[CO₂]) on the modulation of root morphological structure, leaf potassium (K)/sodium (Na) ratio, and nutrient stoichiometry, as well as water use efficiency (WUE) of a C₄ maize (Zea mays L.) in response to soil drought and salinity. C₄ maize was grown in two atmospheric CO₂ concentrations of 400 and 800 ppm (a[CO₂] and d[CO₂]), subjected to two soil water regimes (well-watered and drought stress) and two soil salinity levels (0 and 100 mM NaCl pot⁻¹ (non-salt and salt stress)). The results indicated that soil drought increased maize root tissue density and specific root length. Both d[CO₂] and salt stress reduced leaf phosphorus (P) and K concentrations; conversely, drought stress enhanced leaf nitrogen (N) and K concentrations. The lower specific leaf area, but greater specific leaf N and N/K under soil drought, was amplified by salt stress. In contrast, d[CO₂] promoted leaf carbon (C)/N and C/K. Notably, d[CO₂] combined with soil drought enhanced leaf K/Na under salt stress. Moreover, d[CO₂] ameliorated the adverse impacts of soil drought and salinity on root morphology in terms of enlarged root length and root surface area, contributing to superior leaf C, N, and K use efficiency and consequently improved C₄ maize plant dry mass and WUE. These findings would provide essential knowledge to elevate salt tolerance and achieve optimal nutrient homeostasis and WUE in C₄ maize, adapting to future drier and more saline soils under a CO₂-enriched scenario. Full article

Three Schiff base fluorescent probes 3a–3c with N-heterocyclic structure were designed and synthesized by using the reaction of 4-diethylaminosalicylaldehyde with different N-heterocyclic amines, such as 2-aminobenzimidazole, 2-aminobenzothiazole, and 2-amino-6-methylpyridine. Compound 3a exhibited excellent selectivity towards Hg²⁺, with a detection limit of 3.21 × 10⁻⁷ M and a response time of only 30 s. It could be used as a fluorescent probe for detecting Hg²⁺. Meanwhile, compounds 3b and 3c exhibited excellent selectivity towards Zn²⁺, with detection limits of 1.61 × 10⁻⁷ M and 2.03 × 10⁻⁷ M, respectively, and response times of only 30 s. They could serve as fluorescent probes for detecting Zn²⁺. Using probe 3a for Hg²⁺ as an example, the detecting mechanism was further elucidated through ¹H NMR, ESI-MS testing, and DFT calculation analysis. For compound 3a, the coordination stoichiometry between compound 3a and Hg²⁺ was verified to be 1:1 through a Job’s plot. After coordination with Hg²⁺, the molecular rigidity of compound 3a was enhanced, which inhibited the non-radiative decay process and led to the closure of the excited-state intramolecular proton transfer (ESIPT) effect. At the same time, the fluorescence intensity was significantly increased through the chelation-enhanced fluorescence (CHEF) mechanism, which was confirmed by density functional theory (DFT) calculations. In addition, compounds 3a–3c were successfully applied in practical water samples and test strips for the detection of Hg²⁺/Zn²⁺. Full article

The transition to the 4th Industrial Revolution (4IR) in the electroplating industry necessitates intelligent, real-time monitoring systems to replace traditional, time-consuming offline analysis. In this study, we developed a cost-effective, automated measurement system for hexavalent chromium (Cr(VI)) in plating wastewater using an Arduino-based RGB sensor. Unlike conventional single-variable approaches, we conducted a comprehensive feature sensitivity analysis on multi-sensor data (including pH, ORP, and EC). While electrochemical sensors were found to be susceptible to pH interference, the analysis identified that the Red and Green optical channels are the most critical indicators due to the distinct chromatic characteristics of Cr(VI). Specifically, the combination of these two channels effectively functions as a dual-variable sensing mechanism, compensating for potential interferences. To optimize prediction accuracy, a systematic machine learning strategy was employed. While the Convolutional Neural Network (CNN) achieved the highest classification accuracy of 89% for initial screening, a polynomial regression algorithm was ultimately implemented to model the non-linear relationship between sensor outputs and concentration. The derived regression model achieved an excellent determination coefficient (R² = 0.997), effectively compensating for optical saturation effects at high concentrations. Furthermore, by integrating this sensing model with the chemical stoichiometry of the reduction process, the proposed system enables the precise, automated dosing of reducing agents. This capability facilitates the establishment of a “Digital Twin” for wastewater treatment, offering a practical ICT (Information and Communication Technology)-based solution for autonomous process control and strict environmental compliance. Full article

ABO₃ perovskite oxides are a versatile class of materials whose surfaces and interfaces play essential roles in sustainable energy technologies, including catalysis, solid oxide fuel and electrolysis cells, thermoelectrics, and energy-relevant oxide electronics. The interplay between point defects and surface reconstructions strongly affects interfacial stability, charge transport, and catalytic activity under operating conditions. This review summarizes recent progress in understanding how oxygen vacancies, cation nonstoichiometry, and electronic defects couple to atomic-scale surface rearrangements in representative perovskite systems. We first revisit Tasker’s classification of ionic surfaces and clarify how defect chemistry provides compensation mechanisms that stabilize otherwise polar or metastable terminations. We then discuss experimental and theoretical insights into defect-mediated reconstructions on perovskite surfaces and how they influence the performance of energy conversion devices. Finally, we conclude with a perspective on design strategies that leverage defect engineering and surface control to enhance functionality in energy applications, aiming to connect fundamental surface science with practical materials solutions for the transition to sustainable energy. Full article