Search Results (1,413)

This study focuses on the exchange of mono- and divalent metal cations in FAU-type zeolite and their behavior in gas-phase CO₂ adsorption measurements and liquid-phase methylene blue (MB) adsorption in the absence of oxidizing agents under dark conditions. Firstly, zeolites exchanged with different cations were characterized by several techniques, such as XRD, SEM, XRF, XPS, and N₂ adsorption–desorption, to reveal the impact of the cations on the zeolite texture and structure. The adsorption studies revealed a positive effect of cation exchange on the adsorption capacity of the zeolite, particularly for silver-loaded FAU zeolite. In liquid-phase experiments, Ag-Y zeolite also demonstrated the highest MB removal, with a value of 79 mg/g. Kinetic studies highlighted that Ag-Y could reach the MB adsorption equilibrium within 1 h, with its highest rate of adsorption occurring during the first 5 min. In gas-phase adsorption studies, the highest CO₂ adsorption capacity was also achieved over Ag-Y, yielding 10.4 µmol/m² of CO₂ captured. Full article

In Gram-negative bacteria, lipopolysaccharides (LPSs, also known as endotoxin) can induce extensive immune responses that will enable victims to produce severe septic shock syndrome. Because of the high mortality of sepsis in the face of standard treatment, advance detoxification schemes are urgently needed in clinics. Herein, we described a supramolecular detoxification approach via direct host–guest complexation by a giant macrocycle. Cationic pentaphen[3]arene (CPP3) bearing multiple quaternary ammonium groups was screened as a candidate antidote. CPP3 exhibited robust binding affinity toward LPS with an association constant of (4.79 ± 0.29) × 10⁸ M⁻¹. Co-dosing with an equivalent amount of CPP3 has been demonstrated to decrease LPS-induced cytotoxicity on a cellular level through inhibiting ROS generation and proinflammatory cytokine expression. In vivo experiments have further proved that post-treatment by CPP3 could significantly improve the survival rate of LPS-poisoned mice from 0 to 100% over a period of 3 days, and inflammatory abnormalities and tissue damage were also alleviated. Full article

Graphene quantum dots (GQDs) obtained by microwave-induced pyrolysis of glutamic acid and triethylenetetramine (trien) are fairly stable, emissive, water-soluble, and positively charged nano-systems able to interact with negatively charged meso-tetrakis(4-sulfonatophenyl) porphyrin (TPPS₄). The stoichiometric control during the preparation affords a supramolecular adduct, GQDs@TPPS₄, that exhibits a double fluorescence emission from both the GQDs and the TPPS₄ fluorophores. These supramolecular aggregates have an overall negative charge that is responsible for the condensation of cations in the nearby aqueous layer, and a three-fold acceleration of the metalation rates of Cu²⁺ ions has been observed with respect to the parent porphyrin. Addition of various metal ions leads to some changes in the UV/Vis spectra and has a different impact on the fluorescence emission of GQDs and TPPS₄. The quenching efficiency of the TPPS₄ emission follows the order Cu²⁺ > Hg²⁺ > Cd²⁺ > Pb²⁺ ~ Zn²⁺ ~ Co²⁺ ~ Ni²⁺ > Mn²⁺ ~ Cr³⁺ >> Mg²⁺ ~ Ca²⁺ ~ Ba²⁺, and it has been related to literature data and to the sitting-atop mechanism that large transition metal ions (e.g., Hg²⁺ and Cd²⁺) exhibit in their interaction with the macrocyclic nitrogen atoms of the porphyrin, inducing distortion and accelerating the insertion of smaller metal ions, such as Zn²⁺. For the most relevant metal ions, emission quenching of the porphyrin evidences a linear behavior in the micromolar range, with the emission of the GQDs being moderately affected through a filter effect. Deliberate pollution of the samples with Zn²⁺ reveals the ability of the GQDs@TPPS₄ adduct to detect sensitively Cu²⁺, Hg^2+, and Cd²⁺ ions. Full article

The global atmospheric concentration of carbon dioxide (CO₂) has exceeded 420 ppm. Adsorption-based carbon capture technologies, offer energy-efficient, sustainable solutions. Relying on classical adsorption models like Langmuir to predict CO₂ uptake presents limitations due to the need for case-specific parameter fitting. To address this, the present study introduces a universal machine learning (ML) framework using multiple algorithms—Generalized Linear Model (GLM), Feed-forward Multilayer Perceptron (DL), Decision Tree (DT), Random Forest (RF), Support Vector Machine (SVM), and Gradient Boosted Trees (GBT)—to reliably predict CO₂ adsorption capacities across diverse zeolite structures and conditions. By compiling over 5700 experimentally measured adsorption data points from 71 independent studies, this approach systematically incorporates critical factors including pore size, Si/Al ratio, cation type, temperature, and pressure. Rigorous Cross-Validation confirmed superior performance of the GBT model (R² = 0.936, RMSE = 0.806 mmol/g), outperforming other ML models and providing comparable performance with classical Langmuir model predictions without separate parameter calibration. Feature importance analysis identified pressure, Si/Al ratio, and cation type as dominant influences on adsorption performance. Overall, this ML-driven methodology demonstrates substantial promise for accelerating material discovery, optimization, and practical deployment of zeolite-based CO₂ capture technologies. Full article

Novel high-entropy perovskite oxide powders were synthesized using a sol-gel process. The B-site contained five cations: chromium, cobalt, iron, manganese, and nickel. The B-site cations were present on an equiatomic basis. The A-site cation was lanthanum, with calcium doping. The amount of A-site doping varied from 0 to 30 at%, yielding a composition of La_1−xCa_x(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O_3−δ. The resulting perovskite powders were pressurelessly sintered in air at 1400 °C for 2 h. Sintered densities were measured, and the grain structure was imaged via scanning electron microscopy to investigate the effect of doping. Samples were cut and polished, and their resistance was measured at varying temperatures in air to obtain the electrical conductivity and the mechanism that governs it. Plots of electrical conductivity as a function of composition and temperature indicate that the increased configurational entropy of the perovskite materials has a demonstrable effect. Full article

Enhanced weathering of silicate rocks in agriculture is an option for atmospheric CO₂ removal and fertility improvement. The objective of our work is to characterise some of the agricultural consequences of a basaltic powder amendment on soil-crop systems. Two doses of basalt (80 and 160 t ha⁻¹) were applied to two types of slightly acid soils (sandy or silty clayey), derived from long-term trials at Bordeaux (INRAE, France) and Rothamsted Research (England), respectively. For each soil, half of the pots were planted with ryegrass; the other half were left bare. Thus, the experiment had twelve treatments with four replications per treatment. Soil pH increased with the addition of basalt (+0.8 unit), with a 5% equivalence of that of reactive chalk. The basalt contained macro- and micronutrients. Some cations extractable in the basalt before being mixed to the soil became more extractable with increased weathering, independent of plant cover. Plant uptake generally increased for macronutrients and decreased for micronutrients, due to increased stock (macro) and reduced availability (micronutrients and P), related to pH increases. K supplied in the basalt was responsible for a significant increase in plant yield on the sandy soil, linked to an average basalt K utilisation efficiency of 33%. Our general conclusion is that rock dust applications have to be re-evaluated at each site with differing soil characteristics. Full article

Ceria is an important redox catalyst due to the facile Ce³⁺/Ce⁴⁺ switching at its surface. Therefore, in situ determination of the oxidation state of surface cerium cations is of significant interest. Infrared spectroscopy of probe molecules such as CO holds great potential for this purpose. However, the ability of CO to reduce Ce⁴⁺ cations is an important drawback as it alters the initial cerium speciation. Dinitrogen (N₂), due to its chemical inertness, presents an attractive alternative. We recently demonstrated that low-temperature ¹⁵N₂ adsorption on stoichiometric ceria leads to the formation of complexes with Ce⁴⁺ cations on the (110) and (100) planes (bands at 2257 and 2252 cm⁻¹, respectively), while the (111) plane is inert. Here, we report results on the low-temperature ¹⁵N₂ adsorption on reduced ceria nanoshapes (cubes, polyhedra, and rods). A main band at 2255 cm⁻¹, with a weak shoulder at 2254 cm⁻¹, was observed. We attributed these bands to ¹⁵N₂ adsorbed on Ce³⁺ sites located on edges and corners as well as on {100} facets. In conclusion, ¹⁵N₂ adsorbs on the most acidic surface Ce³⁺ sites and enables their distinction from Ce⁴⁺ cations. Full article

A 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (^tBuN4) for supporting nitrene transfer to olefins. The known [(^tBuN4)M^II(MeCN)₂]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(MeCN)]⁺ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold. Full article

Enhanced oil recovery (EOR) via CO₂ flooding is a promising strategy for improving hydrocarbon recovery and carbon sequestration, yet the influence of pH on solid–liquid interfacial interactions in quartz-dominated reservoirs remains poorly understood. This study employs molecular dynamics (MD) simulations to investigate the pH-dependent adsorption behavior of crude oil components on quartz surfaces and its impact on CO₂ displacement mechanisms. Three quartz surface models with varying ionization degrees (0%, 9%, 18%, corresponding to pH 2–4, 5–7, and 7–9) were constructed to simulate different pH environments. The MD results reveal that aromatic hydrocarbons exhibit significantly stronger adsorption on quartz surfaces at high pH, with their maximum adsorption peak increasing from 398 kg/m³ (pH 2–4) to 778 kg/m³ (pH 7–9), while their alkane adsorption peaks decrease from 764 kg/m³ to 460 kg/m³. This pH-dependent behavior is attributed to enhanced cation–π interactions that are facilitated by Na⁺ ion aggregation on negatively charged quartz surfaces at high pH, which form stable tetrahedral configurations with aromatic molecules and surface oxygen ions. During CO₂ displacement, an adsorption–stripping–displacement mechanism was observed: CO₂ first forms an adsorption layer on the quartz surface, then penetrates the oil phase to induce the detachment of crude oil components, which are subsequently displaced by pressure. Although high pH enhances the Na⁺-mediated weakening of oil-surface interactions, which leads to a 37% higher diffusion coefficient (8.5 × 10⁻⁵ cm²/s vs. 6.2 × 10⁻⁵ cm²/s at low pH), the tighter packing of aromatic molecules at high pH slows down the displacement rate. This study provides molecular-level insights into pH-regulated adsorption and CO₂ displacement processes, highlighting the critical role of the surface charge and cation–π interactions in optimizing CO₂-EOR strategies for quartz-rich reservoirs. Full article

Reclaimed fields have a low soil fertility and low productivity compared to conventional arable land, necessitating research on productivity enhancement. The rice–frog co-culture model is an ecologically intensive practice that combines biodiversity objectives with agricultural production needs, offering high ecological and economic value. However, there is a lack of research on this model that has focused on factors other than soil nutrient levels. The present study evaluated the rice–frog co-culture model in a reclaimed paddy field across three experimental plots with varying frog stocking densities: a rice monoculture (CG), low-density co-culture (LRF), and high-density co-culture (HRF). We investigated the effects of the frog density on greenhouse gas emissions throughout the rice growth. The rice–frog co-culture model significantly reduced methane (CH₄) emissions, with fluxes highest in the CG plot, followed by the LRF and then HRF plots. This reduction was achieved by altering the soil pH, the cation exchange capacity, the mcrA gene abundance, and the mcrA/pmoA gene abundance ratio. However, there was a contrasting nitrous oxide (N₂O) emission pattern. The co-culture model actually increased N₂O emissions, with fluxes being highest in the HRF plots, followed by the LRF and then CG plots. The correlation analysis identified the soil nosZ gene abundance, redox potential, urease activity, nirS gene abundance, and ratio of the combined nirK and nirS abundance to the nosZ abundance as key factors associated with N₂O emissions. While the co-cultivation model increased N₂O emissions, it also significantly reduced CH₄ emissions. Overall, the rice–frog co-culture model, especially at a high density, offers a favorable sustainable agricultural production model. Full article

Understanding the adsorption mechanism is essential for developing efficient technologies to capture carbon dioxide from industrial flue gases. In this work, laboratory measurements, density functional theory calculations, and molecular dynamics simulations were employed to study CO₂ adsorption and diffusion behavior in LTA-type zeolites. The CO₂ adsorption isotherms measured in zeolite 5A are best described by the Toth model. Thermodynamic analysis indicates that the adsorption process is spontaneous and exothermic, with an enthalpy change of −44.04 kJ/mol, an entropy change of −115.23 J/(mol·K), and Gibbs free energy values ranging from −9.68 to −1.03 kJ/mol over the temperature range of 298–373 K. The isosteric heat of CO₂ adsorption decreases from 40.35 to 21.75 kJ/mol with increasing coverage, reflecting heterogeneous interactions at Ca²⁺ and Na⁺ sites. The adsorption kinetics follow a pseudo-first-order model, with an activation energy of 2.24 kJ/mol, confirming a physisorption mechanism. The intraparticle diffusion model indicates that internal diffusion is the rate-limiting step, supported by a significant reduction in the diffusion rate. The DFT calculations demonstrated that CO₂ exhibited a −35 kJ/mol more negative adsorption energy in zeolite 5A than in zeolite ITQ-29, attributable to strong interactions with Ca²⁺/Na⁺ cations in 5A that were absent in the pure silica ITQ-29 framework. The molecular dynamics simulations based on molecular force fields indicate that CO₂ diffuses more rapidly in ITQ-29, with a diffusion coefficient measuring 2.54 × 10⁻⁹ m²/s at 298 K, whereas it was 1.02 × 10⁻⁹ m²/s in zeolite 5A under identical conditions. The activation energy for molecular diffusion reaches 5.54 kJ/mol in zeolite 5A, exceeding the 4.12 kJ/mol value in ITQ-29 by 33%, which accounts for the slower diffusion kinetics in zeolite 5A. There is good agreement between experimental measurements and molecular simulation results for zeolite 5A across the studied temperature and pressure ranges. This confirms the accuracy and reliability of the selected simulation parameters and allows for the study of zeolite ITQ under similar simulation conditions. This research provides insights into CO₂ adsorption energetics and diffusion within LTA-type zeolite frameworks, supporting the rational design of high-performance adsorbents for industrial gas separation. Full article

Soil degradation and declining fertility threaten sustainable agriculture and crop productivity. This study evaluates the effects of CFMI-8, a co-fermented microbial inoculant comprising eight bacterial strains selected through genomic and metabolic modeling, on soil health, nutrient availability, and corn performance. Conducted in a randomized complete block design at Findlay Farm, Wisconsin, the field trial assessed soil biological activity, nutrient cycling, and crop yield responses to CFMI-8 treatment. Treated soils exhibited significant increases in microbial organic carbon (+224.1%) and CO₂ respiration (+167.1%), indicating enhanced microbial activity and organic matter decomposition. Improvements in nitrate nitrogen (+20.2%), cation exchange capacity (+23.1%), and potassium (+27.3%) were also observed. Corn yield increased by 28.6%, with corresponding gains in silage yield (+9.6%) and nutritional quality. Leaf micronutrient concentrations, particularly iron, manganese, boron, and zinc, were significantly higher in treated plants. Correlation and Random Forest analyses identified microbial activity and nitrogen availability as key predictors of yield and nutrient uptake. These results demonstrate CFMI-8’s potential to enhance soil fertility, promote nutrient cycling, and improve crop productivity under field conditions. The findings support microbial inoculants as viable tools for regenerative agriculture and emphasize the need for long-term studies to assess sustainability impacts. Full article

In this study, 3-chlorothiophene-2-carboxylic acid (HL) was used as a main ligand to successfully synthesize four novel complexes: [Cu(L)₂(Py)₂(OH₂)₂] (1), [Co(L)₂(Py)₂(OH₂)₂] (2) (Py = pyridine), [{Ni(L)₂(OH₂)₄}₂{Ni(L)(OH₂)₅}]L•5H₂O (3), and [{Co(L)₂(OH₂)₄}₂{Co(L)(OH₂)₅}]L•5H₂O (4). All four compounds were identified by elemental analysis and ESI mass spectrometry, and subsequently characterized by IR spectroscopy, UV-visible diffuse reflectance spectroscopy, electron paramagnetic resonance spectroscopy, thermogravimetric analysis, single-crystal X-ray crystallography, and cyclic voltammetry. X-ray analyses revealed that complexes 1 and 2 exhibit a centrosymmetric pseudo-octahedral coordination geometry; the copper (II) and cobalt (II) metal ions, respectively, are located at the crystallographic center of inversion. The coordination sphere of the copper (II) complex is axially elongated in accordance with the Jahn–Teller effect. Intriguingly, for charge neutrality, compounds 3 and 4 crystallized as three independent mononuclear octahedrally coordinated metal centers, which are two $\left[\mathrm{M}{\mathrm{L}}_2{\left({\mathrm{O}\mathrm{H}}_2\right)}_4\right]$ complex molecules and one ${\left[\mathrm{M}\mathrm{L}{\left({\mathrm{O}\mathrm{H}}_2\right)}_5\right]}^{+}$ complex cation (M = ${\mathrm{N}\mathrm{i}}^{\mathrm{I}\mathrm{I}}$ and ${\mathrm{C}\mathrm{o}}^{\mathrm{I}\mathrm{I}}$, respectively), with the ligand anion ${\mathrm{L}}^{-}$ serving as the counter ion. The anticancer activities of these complexes were systematically assessed on human leukemia K562 cells, lung cancer A549 cells, liver cancer HepG2 cells, breast cancer MDA-MB-231 cells, and colon cancer SW480 cells. Among them, complex 4 shows significant inhibitory effects on leukemia K562 cells and colon cancer SW480 cells. Full article

Because of their potential “smart” applications, multifunctional stimuli-responsive polymers are gaining increasing scientific interest. The present work explores the possibility of developing such materials based on the hydrolytically stable N-3-dimethylamino propyl methacrylamide), DMAPMA. To this end, the properties in aqueous solution of the homopolymer PDMAPMA and copolymers P(DMAPMA-co-MMA_x) of DMAPMA with the hydrophobic monomer methyl methacrylate, MMA, were explored. Two copolymers were prepared with a molar content x = 20% and 35%, as determined by Proton Nuclear Magnetic Resonance (¹H NMR). Turbidimetry studies revealed that, in contrast to the homopolymer exhibiting a lower critical solution temperature (LCST) behavior only at pH 14 in the absence of salt, the LCST of the copolymers covers a wider pH range (pH > 8.5) and can be tuned within the whole temperature range studied (from room temperature up to ~70 °C) through the use of salt. The copolymers self-assemble in water above a critical aggregation Concentration (CAC), as determined by Nile Red probing, and form nanostructures with a size of ~15 nm (for P(DMAPMA-co-MMA₃₅)), as revealed by transmission electron microscopy (TEM) and dynamic light scattering (DLS). The combination of turbidimetry with ¹H NMR and automatic total organic carbon/total nitrogen (TOC/TN) results revealed the potential of the copolymers as visual CO₂ sensors. Finally, the alkylation of the copolymers with dodecyl groups lead to cationic amphiphilic materials with an order of magnitude lower CAC (as compared to the unmodified precursor), effectively stabilized in water as larger aggregates (~200 nm) over a wide temperature range, due to their increased ζ potential (+15 mV). Such alkylated products show promising biocidal properties against microorganisms such as Escherichia coli and Staphylococcus aureus. Full article

This study addresses the efficiency and cost challenges of hydrogen evolution reaction (HER) catalysts in the context of carbon neutrality strategies by employing a synergistic approach that combines cation vacancy anchoring and transition metal doping on two-dimensional (2D) MXenes. Using an in situ LiF/HCl etching process, the aluminum layers in Ti₃AlC₂ were precisely removed, resulting in a few-layer Ti₃C₂T_x MXene with an increased interlayer spacing of 12.3 Å. Doping with the transition metals Fe, Co, Ni, and Cu demonstrated that Fe@Ti₃C₂ provided the optimal HER performance, characterized by an overpotential (η₁₀) of 81 mV at 10 mA cm⁻², a low Tafel slope of 33.03 mV dec⁻¹, and the lowest charge transfer resistance (R_ct = 5.6 Ω cm²). Mechanistic investigations revealed that Fe’s 3d⁶ electrons induce an upward shift in the d-band center of MXene, improving hydrogen adsorption free energy and reducing lattice distortion. This research lays a solid foundation for the design of non-precious metal catalysts using MXenes and highlights future avenues in bimetallic synergy and scalability. Full article