Search Results (133)

Constructing heterojunctions can combine the superior performance of different two-dimensional (2D) materials and eliminate the drawbacks of a single material, and modulating heterojunctions can enhance the capability and extend the application field. Here, we investigate the physical properties of the heterojunctions formed by the contact of different atom planes of Janus MoSSe (JMoSSe) and graphene (Gr), and regulate the Schottky barrier of the Gr/JMoSSe heterojunction by the number of layers and the electric field. Due to the difference in atomic electronegativity and surface work function (WF), the Gr/JSMoSe heterojunction formed by the contact of S atoms with Gr exhibits an n-type Schottky barrier, whereas the Gr/JSeMoS heterojunction formed by the contact of the Se atoms with Gr reveals a p-type Schottky barrier. Increasing the number of layers of JMoSSe allows the Gr/JMoSSe heterojunction to achieve the transition from Schottky contact to Ohmic contact. Moreover, under the control of an external electric field, the Gr/JMoSSe heterojunction can realize the transition among n-type Schottky barrier, p-type Schottky barrier, and Ohmic contact. The physical mechanism of the layer number and electric field modulation effect is analyzed in detail by the change in the interface electron charge transfer. Our results will contribute to the design and application of nanoelectronics and optoelectronic devices based on Gr/JMoSSe heterojunctions in the future. Full article

This research aimed to co-produce CQDs and hydrochar from natural sources to improve the photocatalytic properties of TiO₂. Juice extract from Citrus lemon fruits from south-eastern Spain was used as the carbon precursor. The synthesis strategy of the CQDs and hydrochar (Hc) was divided into different stages aimed at figuring out the role of the temperature (180, 220, 250 °C), the addition of TiO₂ nanoparticles, and the presence of N-/P-donor compounds (ethylenediamine and orto-phosphoric acid) in the photocatalytic properties of final composites. The results revealed that at 250 °C, using agro-carbon materials as Hc, and the addition of N-donor compounds, improved the photocatalytic activity and photodegradation rate of TiO₂ over methyl orange (MO) under blue light by 1000% and 2700%, respectively, with the parallel reduction of TiO₂ bandgap from 3.5 eV (Uv light) to 3.00 eV (visible light). These results are related to the ability of the carbon materials (electronegative) to enhance the formation of a Ti³⁺-active state. This study provides a landscape for a one-step method for the production of agro-carbon/TiO₂ photocatalysts with high activity under visible light as an efficient and sustainable strategy for applications such as energy generation and water purification under sunlight. Full article

The subcellular partitioning of trace elements (TEs) may depend on their binding preferences, although few field data are available from mining-impacted areas. Northern pike and lake whitefish were collected from different aquatic systems located in the Yellowknife mining area (Northwest Territories, Canada) to examine the subcellular partitioning of TEs in liver cells. Elements belonging to metal classes based on binding affinities were considered: A (Ce, La), borderline (As, Pb), and class B (Ag, Cd). Measurements in the metal-detoxified fractions (granule-like structures and heat-stable proteins and peptides) and in the putative metal-sensitive fractions (heat-denatured proteins, mitochondria and microsomes, and lysosomes) revealed marked differences among metal classes. In both fish species, Cd and Ag accumulated more as detoxified forms (higher than 50%, likely bound to metallothionein-like proteins) than La and Ce (not more than 20%). The two borderline TEs (As and Pb) showed an intermediate behavior between classes A and B. Similar proportions were found in the “sensitive” subcellular fractions for all TEs, where quantitative ion character-activity relationships (QICARs) indicated the covalent index and electronegativity as predictors of the TE contribution in this compartment. This study supports the use of classes of metals to predict the toxicological risk of data-poor metals in mining areas. Full article

In the N$\nu$DEx collaboration, a high-pressure gas TPC is being developed to search for the neutrinoless double beta decay. The use of electronegative ⁸²SeF₆ gas mandates an ion-TPC. The reconstruction of the z coordinate is to be realized by exploiting the feature of multiple species of charge carriers. As the initial stage of the development, we studied the properties of the ${\mathrm{SF}}_6$ gas, which is non-toxic and has a similar molecular structure to ${\mathrm{SeF}}_6$. In the paper, we present the measurement of drift velocities and mobilities of the majority and minority negative charge carriers found in ${\mathrm{SF}}_6$ at a pressure of 750 Torr, slightly higher than the local atmospheric pressure. The reduced fields range between 3.0 and 5.5 Td. This was performed using a laser beam to ionize the gas inside a small TPC, with a drift length of 3.7 cm. A customized charge-sensitive amplifier was developed to read out the anode signals induced by the slowly drifting ions. The closure test of the reconstruction of the z coordinate using the difference in the velocities of the two carriers was also demonstrated. Full article

Metal cations are often used to regulate montmorillonite, but the mechanism is still unclear. In this paper, the regulation of different cations in montmorillonite was studied, and it was found that the regulation of different cations had significant effects on the structure of montmorillonite. Firstly, the viscosity is negatively correlated with particle size, and the order of particle size is trivalent > divalent > monovalent cation. Secondly, the swelling capacity is positively correlated with the absolute value of zeta potential, and the order of the zeta potential is monovalent > trivalent > divalent cation. Thirdly, the smaller hydrated ion radius and static electricity of monovalent cations significantly reduce the layer spacing. Meanwhile, isomorphism displacement results in a significant increase in the proportion of cis-vacant configuration due to changing the electronegativity of the octahedron. The comprehensive performance is that the particle size is significantly reduced and the absolute value of zeta potential is significantly increased. It is easy to peel off and expand in water to form a uniform and stable colloidal substance, which has the best gel performance. The research results can provide theoretical support for the regulation of montmorillonite structure and gel properties by different valence metal cations. Full article

Doping lithium cobalt oxide (LiCoO₂) cathode materials is an effective strategy for mitigating the detrimental phase transitions that occur at high voltages. A deep understanding of the relationships between cycle capacity and the design elements of doped LiCoO₂ is critical for overcoming the existing research limitations. The key lies in constructing a robust and interpretable mapping model between data and performance. In this study, we analyze the correlations between the features and cycle capacity of 158 different element-doped LiCoO₂ systems by using five advanced machine learning algorithms. First, we conducted a feature election to reduce model overfitting through a combined approach of mechanistic analysis and Pearson correlation analysis. Second, the experimental results revealed that RF and XGBoost are the two best-performing models for data fitting. Specifically, the RF and XGBoost models have the highest fitting performance for IC and EC prediction, with R² values of 0.8882 and 0.8318, respectively. Experiments focusing on ion electronegativity design verified the effectiveness of the optimal combined model. We demonstrate the benefits of machine learning models in uncovering the core elements of complex doped LiCoO₂ formulation design. Furthermore, these combined models can be employed to search for materials with superior electrochemical performance and processing conditions. In the future, we aim to develop more accurate and efficient machine learning algorithms to explore the microscopic mechanisms affecting doped layered oxide cathode material design, thereby establishing new paradigms for the research of high-performance cathode materials for lithium batteries. Full article

In this study, Ti-6Al-4V (TC4) powder was uniformly mixed with B₄C and TiC, respectively. Subsequently, the dielectric properties of the B₄C/TC4 and TiC/TC4 composite powders were measured. Meanwhile, XPS analysis was used to deeply analyze different atoms in these samples to obtain the electron binding energy data of each atom. The experimental results show that even when there is no phase structure transformation between B₄C, TiC, and TC4, the dielectric coefficient of the composite powder and the electron binding energy values of various elements still exhibit significant changes. When the mass ratio of B₄C or TiC to TC4 reaches 1:30, the dielectric constant of the composite powder is significantly increased from 5 (the original TC4) to about 11 and 15, respectively. At the same time, the electron binding energy of the Ti element in TC4 also reaches the maximum value. In addition, due to the difference in electronegativity between B₄C and TiC, during the process of compounding with TC4, the incorporation contents and the occurrence frequencies of abnormal dispersion phenomena are different. Specifically, when the ratio of B₄C to TC4 is 1:30, abnormal dispersion occurs at a frequency of 9.5 GHz; however, when the ratio of TiC to TC4 is 1:20, the composite coating shows an abnormal dispersion phenomenon at 8.5 GHz. Full article

In this study, the novel composite materials of activated carbon (AC) and persulfate (PS) doped by nitrogen (N) and sulfur (S) were successfully synthesized through one-step mechanical ball milling. Different from the previous liquid-phase activation process of PS, the direct in situ solid-phase activation of PS was achieved through the newly generated chemical bonds between AC and PS. The increased crystal surface exposure and highly electronegative atoms provided more reactive sites for the modified composites, enabling them to extract electrons from the pollutant. Compared to S doping, the N-doped composite exhibited a higher oxidative degradation ability, with a removal rate of 93.6% for tetracycline (TC, 40 mg/L) within 40 min. The interactions between AC and PS that occur in the interior of the composite avoid the limitations of mass transfer between the solid–liquid interface, thus expanding the pH application range of the catalytic reaction and minimizing the interference of other components in the solution. The synergistic effect between active oxygen species and electron transfer is the main mechanism for promoting pollutant degradation. This research puts forward a new insight into the activation approach of PS and proposes a feasible method for the advanced treatment of TC wastewater. Full article

The search for efficient, environmentally friendly adsorbents is critical for purifying dye wastewater. In this study, we produced a first-of-its-kind effective biomimetic amorphous calcium carbonate (BACC) using bacterial processes and evaluated its capacity to adsorb a hazardous organic cationic dye—methylene blue (MB). BACC can adsorb a maximum of 494.86 mg/g of MB, and this excellent adsorption performance was maintained during different solution temperature (10–55 °C) and broad pH (3–12) conditions. The favorable adsorption characteristics of BACC can be attributable to its hydrophobic property, porosity, electronegativity, and perfect dispersity in aqueous solution. During adsorption, MB can form Cl-Ca, S-O, N-Ca, and H-bonds on the surface of BACC. Since BACC has excellent resistance to adsorption interference in different water bodies and in real dye wastewater, and can also be effectively recycled six times, our study is an important step forward in dye wastewater treatment applications. Full article

The series of iridium(III) complexes, [Ir(ppy)₂(RCOCHCOR′)], with R = CH₃ and R′ = CH₃ (1), Rc (2), and Fc (3), as well as R = Rc and R′ = Rc (4) or Fc (5), and R = R′ = Fc (6), ppy = 2-phenylpyridinyl, Fc = Fe^II(η⁵–C₅H₄)(η⁵–C₅H₅), and Rc = Ru^II(η⁵–C₅H₄)(η⁵–C₅H₅), has been investigated by single-crystal X-ray crystallography and X-ray photoelectron spectroscopy (XPS) supplemented by DFT calculations. Here, in the range of 3.74 ≤ Σχ_R ≤ 4.68, for Ir 4f, Ru 3d and 3p and N 1s orbitals, binding energies unexpectedly decreased with increasing Σχ_R (Σχ_R = the sum of Gordy group electronegativities of the R groups on β-diketonato ligands = a measure of electron density on atoms), while in Fe 2p orbitals, XPS binding energy, as expected, increased with increasing Σχ_R. Which trend direction prevails is a function of main quantum level, n = 1, 2, 3…, sub-quantum level (s, p, d, and f), initial state energies, and final state relaxation energies, and it may differ from compound series to compound series. Relations between DFT-calculated orbital energies and Σχ_R followed opposite trend directions than binding energy/Σχ_R trends. X-ray-induced decomposition of compounds was observed. The results confirmed good communication between molecular fragments. Lower binding energies of both the Ir 4f_7/2 and N 1s photoelectron lines are associated with shorter Ir-N bond lengths. Cytotoxic tests showed that 1 (IC₅₀ = 25.1 μM) and 3 (IC₅₀ = 37.8 μM) are less cytotoxic against HeLa cells than cisplatin (IC₅₀ = 1.1 μM), but more cytotoxic than the free β-diketone FcCOCH₂COCH₃ (IC₅₀ = 66.6 μM). Full article

Plastics are vital for society, but their usage has grown exponentially and contributes to the growth of pollution worldwide. The World Health Organization, WHO, already reported that microplastics (MPs) are found everywhere, in waste and fresh water, and in the air and soil. Regarding water effluents, waste-water treatment plants only minimize the problem, trapping only larger size particles. In contrast, smaller ones remain in oxidation ponds or sewage sludges, or are even released to aquifers environment. Classic procedures for MPs detection are still quite laborious, and are usually conducted off-line, involving several steps and expensive equipment. Electrical Impedance Spectroscopy, EIS, is a technique that allows the analysis of a system’s electrical response, yielding helpful information about its domain-dependent on physical-chemical properties. Due to the superficial electronegativity of MPs’ particles, EIS may allow to attain the purpose of the present work: to provide a fast and reliable method to detect/estimate MPs’ concentration in water effluents. Among the most common microplastics are Polyethylene, PE, and Polyvinyl Chloride, PVC. Using the developed setup and experimental data collection methodology, the authors could differentiate between MPs’ suspensions containing the same concentration of the different evaluated MPs, PVC and PE, and assess PVC concentration variation, in the interval between 0.03 to 0.5 g (w/w), with an error, estimated based on the obtained impedance modulus, around or below 3% for the entire stimulus signal frequency range (from 100 Hz to 40 MHz) for the PVC particles. Full article

The interaction between different types of substituents in dicarbollide ligands and their influence on the stabilization of various rotational conformers (rotamers) of transition metal bis(dicarbollide) complexes [3,3′-M(1,2-C₂B₉H₁₁)₂]⁻ are considered. It has been shown that the formation of intramolecular CH···X hydrogen bonds between dicarbollide ligands is determined by the size of the proton acceptor atom X rather than its electronegativity. Due to the stabilization of rotamers with different dipole moments, intramolecular hydrogen bonds between ligands in transition metal bis(dicarbollide) complexes can have a significant impact on the biological properties of their derivatives. In the presence of external complexing metals, weak intramolecular CH···X hydrogen bonds can be broken to form stronger X—>M donor-acceptor bonds. This process is accompanied by the mutual rotation of dicarbollide ligands and can be used in sensors and molecular switches based on transition metal bis(dicarbollide) complexes. Full article

The ability of thermoresponsive polymers to respond to temperature with a reversible conformational change makes them promising ‘smart’ materials for solutions in medical and biotechnological applications. In this work, two such polymers and structural isomers were studied: poly(N-isopropyl acrylamide) (PNiPAm) and poly(2-isopropyl-2-oxazoline) (PiPOx). We compare the critical solution temperatures (CST) of these polymers in D₂O and H₂O in the presence of Hofmeister series salts, as results obtained under these different solvent conditions are often compared. D₂O has a higher dipole moment and electronegativity than H₂O, which could significantly alter the CST transition. We used two complementary methods to measure the CST, dynamic light scattering (DLS) and differential scanning calorimetry (DSC) and found that the CST decreased significantly in D₂O compared to H₂O. In the presence of highly concentrated kosmotropes, the CST of both polymers decreased in both solvents. The influence of the kosmotropic anions was smaller than the water isotope effect at low ionic strengths but considerably higher at physiological ionic strengths. However, the Hofmeister anion effect was quantitatively different in H₂O than in D₂O, with the largest relative differences observed for Cl⁻, where the CSTs in D₂O decreased more than in H₂O measured by DLS but less by DSC. PiPOx was more sensitive than PNiPAm to the presence of chaotropes. It exhibited much higher transition enthalpies and multistep transitions, especially in aqueous solutions. Our results highlight that measurements of thermoresponsive polymer properties in D₂O cannot be compared directly or quantitatively to application conditions or even measurements performed in H₂O. Full article

The need to solvate and encapsulate hydro-sensitive molecules drives noticeable trends in the applications of cyclodextrins in the pharmaceutical industry, in foods, polymers, materials, and in agricultural science. Among them, β-cyclodextrin is one of the most used for the entrapment of phenolic acid compounds to mask the bitterness of wheat bran. In this regard, there is still a need for good data and especially for a robust predictive model that assesses the bitterness masking capabilities of β-cyclodextrin for various phenolic compounds. This study uses a dataset of 20 phenolic acids docked into the β-cyclodextrin cavity to generate three different binding constants. The data from the docking study were combined with topological, topographical, and quantum-chemical features from the ligands in a machine learning-based structure–activity relationship study. Three different models for each binding constant were computed using a combination of the genetic algorithm (GA) and multiple linear regression (MLR) approaches. The developed ML/QSAR models showed a very good performance, with high predictive ability and correlation coefficients of 0.969 and 0.984 for the training and test sets, respectively. The models revealed several factors responsible for binding with cyclodextrin, showing positive contributions toward the binding affinity values, including such features as the presence of six-membered rings in the molecule, branching, electronegativity values, and polar surface area. Full article

The aim of this study was a systematic analysis of the influence of anions (chloride and sulfate) on the electrochemical behavior of the Co-Sn system during codeposition from gluconate baths. The pH-dependent multiple equilibria in cobalt–tin baths were calculated using stability constants. The codeposition of the metals was characterized thermodynamically considering the formation of various Co_xSn_y intermetallic phases. The alloys obtained at different potentials were characterized in terms of their elemental (EDS and anodic stripping) and phase compositions (XRD), the development of preferred orientation planes (texture coefficients), surface morphology (SEM), and wettability (water; diiodomethane; surface energy). The mass of the deposits and cathodic current efficiencies were strongly dependent on both the deposition potential and the bath composition. The morphology and composition of the alloys were mainly dependent on the deposition potential, while the effect of the anions was less emphasized. Two-phase alloys were produced at potentials −0.9 V (Ag/AgCl) and lower, and they consisted of a mixture of tetragonal tin and an uncommon tetragonal CoSn phase. The preferential orientation planes of tin grains were dependent on the cobalt incorporation into the deposits and anion type in the bath, while the latter did not affect the preferential orientation plane of the CoSn phase. The surface wettability of the alloys displayed hydrophobicity and oleophilicity originating from the hierarchical porous surface topography rather than the elemental or phase composition. The codeposition of the metals occurs within the progressive nucleation model, but at more electronegative potentials and in the presence of sulfate ions, a transition from progressive to instantaneous nucleation can be possible. This correlated well with the partial polarization curves of the alloy deposition and the texture of the tin phase. Full article