Search Results (31)

AMn₇O₁₂ perovskites (with A = divalent elements) show complex structural and magnetic transitions including incommensurate orbital density waves and coupled/decoupled modulated spin helicity originating from charge-ordered Mn³⁺/Mn⁴⁺ cations with the 3:1 ratio at the B perovskite sites and unusual apically compressed Jahn–Teller distortions of MnO₆ octahedra. The same Mn³⁺:Mn⁴⁺ ratio can be achieved in RCuMn₆O₁₂ compositions, where R is a trivalent rare-earth cation. Therefore, the comparison in behavior of AMn₇O₁₂ and RCuMn₆O₁₂ is of interest. In this work, the A-site-ordered quadruple perovskite NdCuMn₆O₁₂ was prepared by a high-pressure high-temperature method. Its structural properties were investigated by synchrotron powder X-ray diffraction between 100 K and 350 K and laboratory powder X-ray diffraction between 5 K and 300 K. It shows a first-order structural phase transition from Im-3 symmetry (at high temperatures) to R-3 symmetry near 292 K. The structural transition is accompanied by charge (Mn³⁺/Mn⁴⁺) and unusual orbital (on the Jahn–Teller active Mn³⁺ cations located in MnO₆ octahedra) orders. However, no additional structural/orbital modulations were found at lower temperatures in comparison with AMn₇O₁₂. Magnetic properties were investigated by temperature- and field-dependent magnetization and specific heat measurements, where a ferrimagnetic transition was found near 120 K. In addition, low-temperature magnetic anomalies were observed near 20 K, probably originating from the Nd sublattice. Full article

DNA conformational transitions in aqueous environments are strongly influenced by electrostatic interactions with surrounding cations. This review/perspective article summarizes the experimental findings reported during the last decade on the competitive/cooperative effects of cations with different valencies on DNA conformational behavior. Recent experimental studies based on single DNA observations have shown that divalent cations, such as Mg(2+) and Ca(2+), can inhibit DNA compaction induced by the trivalent cation spermidine (SPD(3+)), revealing that the effects of coexisting cations are not simply additive. Such competitive behavior cannot be adequately explained within the conventional Debye–Hückel framework, which predicts always additive electrostatic screening contributions from cations of different valencies. To elucidate the underlying mechanism of competitive effects, a theoretical framework has been proposed by extending the framework of current counterion condensation theory, which incorporates changes in translational entropy arising from the ion-exchange process between monovalent counterions and divalent or trivalent cations interacting with DNA as a highly negatively charged polyelectrolyte. In the theoretical framework, the increase in translational entropy arises from the ion exchange process between monovalent counterions and trivalent cations in the absence of divalent cations, whereas the presence of divalent cations diminishes the entropic gain associated with this exchange. By interpreting the recent experimental findings through the aid of the development of theoretical modeling, this review/perspective article provides a coherent insight on how coexisting multiple cations regulate DNA conformation. Full article

Humus substances are an important part of stable soil organic matter, which is also influenced by the soil tillage system, particularly indirectly through the mechanisms of stabilisation. This study evaluated relationships within the humus substances–cations–soil texture system and differences between invasive and non-invasive tillage systems in four soils. The influence of exchangeable cations (K⁺, Na⁺, Ca²⁺, Mg²⁺, Fe³⁺, Al³⁺) and particle size distribution (sand, silt, clay) on quantity (humic and fulvic acids) and quality (ratio of HA/FA, degree of humification, colour coefficients) of humus substances was studied. In reduced tillage, the humus substances interacted mainly with iron and aluminium. Higher humus substance contents were associated with higher K⁺; the influence of Ca²⁺ was greater in coarse-grain soils (Haplic Chernozem, Eutric Regosol); and Al³⁺ was positively correlated with humic acids and negatively with fulvic acids. The statistical associations indicate that in conventional tillage, humus substances interacted mainly with Ca²⁺. Higher humic acid contents indicate an association pattern with higher Na⁺ contents; the relationship of Ca²⁺ appears more pronounced in fine-grained soils (Mollic Fluvisol, Haplic Luvisol); and Al³⁺ was positively correlated with fulvic acids and negatively with humic acids. The soil tillage system influenced the humus substances indirectly by a combination of factors—cation composition and soil texture in different ways. In reduced tillage, clay and silt were statistically associated with iron and aluminium; in conventional tillage, there were two branches: clay with divalent cations and silt with trivalent cations. The soil tillage system can modify the impact of carbonates on humus substances and thus indirectly change the character of transformation processes in the soil. Depth is very important in evaluating the influence of the soil tillage system. Full article

Aqueous electrochromic systems based on tungsten oxide (WO₃) have attracted increasing attention because of their high ionic conductivity, low cost, and improved safety compared with organic systems. However, the role of electrolyte pH in regulating the electrochromic behavior of hydrated WO₃ films remains insufficiently understood, particularly across cation systems with different valences. In this work, amorphous WO₃·2H₂O films were electrodeposited on ITO substrates and systematically evaluated in LiCl and ZnCl₂ aqueous electrolytes with different pH values, with acidic AlCl₃ used as a supplementary trivalent system. The results reveal pronounced pH-dependent electrochromic behavior in both the monovalent and divalent systems. In LiCl, acidic conditions, especially pH 2.0, gave the best overall performance, including high optical modulation and improved cycling stability, while the dominant pseudocapacitive charge-storage behavior was largely preserved. In ZnCl₂, films tested at pH 1.5–2.0 showed significantly better electrochromic performance than those at higher pH values, indicating a much stronger kinetic sensitivity to pH. Combined experimental and first-principles results show that electrolyte pH influences not only proton availability, but also the cation-dependent interfacial charge-compensation environment in hydrated WO₃ films. Full article

Wastewater contains dyes originating from textile industries, and above a certain concentration, they can become dangerous due to their high toxicity. Divalent and trivalent metal coagulants, usually aluminum- or iron-based, have been studied worldwide. However, tetravalent coagulants, such as tin chloride, have not yet been extensively studied for application in wastewater treatment. Therefore, in this study, three types of coagulants were examined: SnCl₄, Cs, and a hybrid composite (CS@Sn) in two different mass ratios, abbreviated hereafter as CS@Sn_5% and CS@Sn_50%. The formation of the suggested CS@Sn hybrid coagulants was confirmed by applying SEM, XRD, and FTIR techniques. The results showed that the optimum conditions for RB5 removal was the addition of 20 mg Sn/L SnCl₄ (97.8%) and 50 mg Sn/L of CS@Sn_50% (64.8%) at pH 3.0. In addition, SnCl₄ was found to be an effective coagulant for all the examined anionic dyes, but it was not as effective for cationic dyes. Moreover, the coagulants were then tested in two mixed-dye solutions, both anionic dyes (RB5/RR120) and anionic/cationic (RB5/MV), resulting in a synergistic effect in the first one and a competitive effect in the secon. Finally, the proposed coagulants were successfully tested on real wastewater samples from an untreated textile dyeing industry. Therefore, the coagulants presented in this work for the removal of several dyes are also capable of being used for wastewater treatment. Full article

Spinel ferrites have emerged as fascinating materials, not just for their diverse functionalities, but for the dynamic structural transformations they undergo under varying conditions. These phase transitions, often subtle yet deeply influential, play a pivotal role in tuning their electronic, magnetic, and vibrational properties. At the heart of this complexity lies the versatile arrangement of divalent and trivalent cations between the tetrahedral (A) and octahedral (B) sites, giving rise to a rich spectrum of magnetic interactions, charge dynamics, and lattice responses. This intricate cation interplay makes spinel ferrites a playground for exploring structure–property relationships in advanced functional materials. In this study, we investigated the structural, vibrational, and magnetic properties of Cd ferrite using advanced hybrid functionals (B3LYP, HSE06, and PBE0). Our calculations reveal that the normal spinel phase is the most stable configuration, with minimal energy differences between spin arrangements (~0.005–0.008 eV) and slightly larger differences when including zero-point energy (~0.023 eV). All the investigated structures exhibit a semiconducting nature, with band gaps varying depending on the spin arrangements. The IR and Raman spectra highlight the influence of spin ordering on vibrational modes. The simulations of the Raman spectra demonstrate that both the frequencies and intensities of the Raman peaks strongly depend on the magnetic ordering. The present theoretical study offers a consistent framework for assigning vibrational modes, which may help resolve ambiguities and contribute to a deeper understanding of the vibrational properties of Cd ferrite. These findings provide a robust foundation for further experimental and computational exploration of this material. 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

The co-occurrence of microplastics (MPs) and antibiotics as emerging contaminants demonstrates significant ecological perturbations in soil matrices. Of particular scientific interest is the potential for MPs to mediate the environmental fate and transport dynamics of co-existing antibiotics. This study investigated MP-mediated ciprofloxacin (CIP) adsorption in lateritic soils. Batch experiments with polyethylene (PE), polypropylene (PP), and poly (ethylene-terephthalate) (PET) revealed soil components dominated CIP retention, while 10% (w/w) MPs reduced soil adsorption capacity by ≥10.8%, with inhibition intensity following PET > PE > PP. Adsorption thermodynamics exhibited significant pH dependence, achieving maximum sorption efficiency at pH 5.0 (± 0.2), which was approximately 83%. Competitive adsorption analysis demonstrated inverse proportionality between ionic strength and CIP retention, with trivalent cations exhibiting superior competitive displacement capacity compared to mono- and divalent counterparts. Isothermal modeling revealed multilayer adsorption mechanisms governed by hybrid chemisorption/physisorption processes in both soil and MP substrates. Spectroscopic characterization suggested differential adsorption pathways: MP-CIP interactions were primarily mediated through hydrophobic partitioning and π-π electron coupling, while soil–MP composite systems exhibited dominant cation exchange capacity and surface complexation mechanisms. Notably, electrostatic attraction/repulsion forces modulated adsorption efficiency across all experimental conditions, particularly under varying pH regimes. This work advances understanding of co-contaminant dynamics in soil ecosystems, informing risk assessment frameworks. Full article

While there is enormous interest in studying oxide perovskites with stoichiometries based upon or derived from ABO₃, including oxygen-deficient compositions and organometallics, other closely related topologies have been overlooked. Hydroxyperovskites are such a group. Their structures are perovskite-like octahedral frameworks with vacant cavity A sites, and all oxygen atoms form hydroxyl groups. There are fifteen naturally occurring hydroxyperovskites and numerous synthetic analogues. There are two stoichiometries: BB′(OH)₆ and B(OH)₃. The former consist of alternating divalent and tetravalent cations (B = Mg, Ca, Mn²⁺, Fe²⁺, Co²⁺, Cu²⁺, Zn; B′ = Sn, Ge). B(OH)₃ structures have only trivalent cations (Al, Fe³⁺, Ga). The properties and behavior of solid solutions in hydroxyperovskites are largely unexplored. This article summarizes our current knowledge of the crystallography and crystal chemistry of hydroxyperovskites and suggests productive areas of research in relation to their potential as functional materials. It should be evident that much of the findings remains to be discovered. Full article

Background/Objectives: Posaconazole is an antifungal agent from triazoles with variable bioavailability. To avoid its irregular absorption caused by gastric conditions and ensure more repeatable pharmacokinetic enabling the maximization of its absorption regardless of food intake without the need to administer multiple doses, can be provided by the technology of enteric drug preparations. The cross-linking of polysaccharide polymers with divalent and trivalent cations enables multi-unit formulations to be obtained that prevent drug absorption in the stomach. Microcapsules, as an example of multi-unit drug dosage forms, provide more predictable gastric emptying, depending on nutritional status, and spread extensively throughout the gastrointestinal tract. Methods: Therefore, the utilization of zinc acetate for the cross-linking of the alginate and pectin mixture was evaluated. The obtained formulations were evaluated for the impact of cross-linking process and pectin’s presence on their pharmaceutical, mucoadhesive, physicochemical and antifungal properties. Results: It was shown that cross-linked microcapsules by zinc acetate provided delayed posaconazole release. Additionally, the cross-linking process with Zn²⁺ ions significantly enhanced antifungal activity against the analyzed Candida strains. It was observed that pectin content in the formulation enhanced the swelling ability in an intestinal condition and increased the mucoadhesive properties of drug-loaded formulations to the intestinal mucosa. Full article

The newly discovered Erdaodianzi gold deposit in southern Jilin Province, Northeast China, is located in the eastern segment of the northern margin of the North China Craton (NCC). It is a large-scale gold deposit with reserves of 38.4 tons of gold. Gold mineralization in the ore district primarily occurs in gold-bearing quartz–sulfide veins. The gold ore occurs mainly as vein, veinlet, crumby, and disseminated structures. The hydrothermal process can be divided into three stages: stage I, characterized by quartz, arsenopyrite, and pyrite; stage II, featuring quartz, arsenopyrite, pyrite, pyrrhotite, chalcopyrite, sphalerite, and native gold; and stage III, consisting of quartz, pyrite, sphalerite, galena, electrum (a naturally occurring Au–Ag alloy), and calcite. Electrum and native gold primarily occur within the fissures of the polymetallic sulfides. To determine the enrichment mechanism of the Au element and the genetic types of ore deposits in the Erdaodianzi deposit, sourcing in situ trace element data, element mapping and sulfur isotope analysis were carried out on sphalerites from different stages using LA-ICP-MS. Minor invisible gold, in the form of Au–Ag alloy inclusions, is present within sphalerites, as revealed by time-resolved depth profiles. The LA-ICP-MS trace element data and mapping results indicate that trivalent or quadrivalent cations, such as Sb³⁺ and Te⁴⁺, exhibit a strong correlation with Au. This correlation can be explained by a coupled substitution mechanism, where these cations (Sb³⁺ and Te⁴⁺) replace zinc ions within the mineral structure, resulting in a strong association with Au. Similarly, the element Pb exhibits a close relationship with Au, which can be attributed to the incorporation of tetravalent cations like Te⁴⁺ into the mineral structure. The positive correlation between Hg and Au can be attributed to the formation of vacancies and defects within sphalerite, caused by the aforementioned coupled substitution mechanism. A slight positive relationship between Au and other divalent cations, including Fe²⁺, Mn²⁺, and Cd²⁺, may result from these cations simply replacing Zn within the sphalerite lattice. The crystallization temperatures of the sphalerite, calculated via the Fe/Zn ratio, range from 238 °C to 320 °C. The δ³⁴S values are divided into two intervals: one ranging from −1.99 to −1.12‰ and the other varying from 10.96 to 11.48‰. The sulfur isotopic analysis revealed that the ore-forming materials originated from magmatic rock, with some incorporation of metamorphic rock. Comparative studies of the Erdaodianzi gold deposit and other gold deposits in the Jiapigou–Haigou gold belt have confirmed that they are all mesothermal magmatic–hydrothermal lode gold deposits formed at the subduction of the Paleo-Pacific Plate beneath the Eurasian Plate during the Middle Jurassic. The Jiapigou–Haigou gold belt extends northwest to the Huadian area of Jilin province. This suggests potential for research on gold mineralization in the northwest of the belt and indicates a new direction for further gold prospecting in the region. Full article

We present magnesium alginate as an aqueous polymer electrolyte for use in magnesium batteries. Alginates are polysaccharides extracted from algae, which form hydrogel materials upon interaction with divalent and trivalent cations. They are renewable, non-toxic, biocompatible materials that are widely used in the food and pharmaceutical industries. Mg²⁺ is weakly bound to an alginate polymer, which results in a hydrogel-like material that contains mobile magnesium ions. We propose that this is the ideal situation for an electrolyte that behaves in a similar way as a ‘water-in-salt’ system. Magnesium alginate was successfully synthesized and characterized by FTIR, XRD, and PDF. Ionic conductivity was measured with EIS measurements; a 2 wt% magnesium electrolyte shows a conductivity of 1.8 mS/cm. During conductivity experiments, we noticed the formation of a black layer on magnesium electrodes, which can improve the ionic conductivity between the electrodes. We carefully characterized this layer with XPS and saw that it mainly consists of alginate derivatives. Full article

The solids in sewage sludge are primarily composed of organic matter and offer new possibilities for sustainable sludge management, if considered as a stable biomass source in terms of quantity and quality. Reducing the volume of sludge with an extremely high moisture content is challenging, and enhanced dewatering through mechanical treatment is crucial from an environmental and sustainability perspective because it alleviates the reliance on thermal treatment. This study employed ultrasonication to enhance the dewatering efficiency of activated sludge. The disruption of sludge induced by ultrasonication notably facilitated the elimination of intracellular water during mechanical expression. Additionally, the ultrasonicated sludge was verified to be re-flocculated by introducing inorganic electrolytes such as Ca²⁺ (divalent cations), Al³⁺ (trivalent cations), and polyferric sulfate. Conversely, no re-flocculation of disrupted sludge was observed upon applying organic polymer flocculant. Under optimized conditions, the sludge re-flocculation progressed to form large flocs, leading to a decreased suspended solids (SS) value from 1423 to 73 mg/L and reduction in capillary suction time (CST) from over 2000 to 18 s. Following pretreatment, the moisture content of the mechanically expressed cake at 500 kPa decreased significantly from 76 wt% (untreated sludge) to less than 60 wt% (treated sludge) due to the elimination of intracellular water. Full article

Zn-Al-Mg-Si coatings are an excellent alternative to conventional hot-dip galvanizing coatings. Their high corrosion resistance in corrosive environments containing chlorides and CO₂ is well recognized. But sulfur dioxide is also an important stimulator of corrosion in the atmospheric environment. This article presents the results of microstructure (SEM/EDS/XRD) and corrosion behavior tests of Zn-Al-Mg-Si coatings obtained by a double hot-dip method on HSLA steel. The corrosion resistance of the coatings was determined in the sulfur dioxide test with general condensation of moisture (EN ISO 6988). In the corrosion test, Zn-Al-Mg-Si coatings showed twofold smaller weight loss compared to conventional hot-dip zinc coatings. It was found that the corrosion behavior of coatings was influenced by the structural components revealed in the outer layer: Al-rich dendritic and interdendritic areas with Zn/MgZn₂ eutectic, MgZn₂ intermetallic and Si precipitates and their electrochemical nature. The increase in corrosion resistance was caused by the formation of beneficial corrosion products: layered double hydroxides (LDHs) based on divalent Mg²⁺ and Zn²⁺ cations, trivalent Al³⁺ cations and SO₄²⁻ anions, and zinc hydroxysulfate—Zn₄SO₄(OH)₆∙5H₂O. The presence of Si precipitates could cause pitting corrosion of coatings. Full article

Demantoid is the green variety of andradite [Ca₃Fe₂(SiO₄)₃], an exceptionally rare and precious gemstone worldwide. In recent years, a small amount of gem-quality demantoid has been found in Pakistan. This research focuses on nine demantoids sourced from Muslim Bagh, Baluchistan, Pakistan, presenting a comprehensive analysis of the spectral characteristics and inclusions of Pakistani demantoid using classical gemological methods, energy dispersive X-ray fluorescence (EDXRF) chemical analyses, Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, and ultraviolet and visible (UV-vis) spectroscopy. The results show that the content of Cr and V in most samples is lower than the detection line of EDXRF, with only one sample containing a Cr₂O₃ content of 0.032%. The extremely low Cr content sets Pakistani demantoid apart from demantoid of the serpentinite type found in other regions. Notably, the UV-vis spectrum reveals characteristic absorption at 443 nm due to Fe³⁺, while a further contribution from Cr³⁺ would be highly likely, and weak absorption at 550 nm caused by Fe³⁺. This suggests that iron (Fe) is the primary chromogenic element of Pakistani demantoid, but the role of Cr³⁺ cannot be ignored. The FTIR spectrum of Pakistani demantoid displays the absorption peaks associated with [SiO₄]⁴⁻ groups at 937 cm⁻¹, 848 cm⁻¹, and 817 cm⁻¹, while the absorption peaks resulting from trivalent cations appear at 481 cm⁻¹ and 442 cm⁻¹, which are the characteristic FTIR spectra of demantoid. Raman spectroscopy further reveals absorption peaks are displayed near 994 cm⁻¹, 843 cm⁻¹, 818 cm⁻¹, associated with (Si–O)_Str vibrations (Si–O stretching vibration), and absorption peaks are displayed near 350 cm⁻¹ and 310 cm⁻¹, related to the rotation of SiO₄–R(SiO₄)⁴⁻, and the peaks near 514 cm⁻¹ and 494 cm⁻¹ are related to (Si–O)_bend vibrations (Si–O bending vibration). Additionally, related absorption peaks near 168 cm⁻¹ are attributed to the translation of SiO₄–T(SiO₄)⁴⁻, and absorption peaks near 234 cm⁻¹ are associated with the translation of X²⁺–T(X²⁺) (X²⁺ represents divalent ions). The common dark opaque inclusions found in Pakistani demantoid consist of a combination of magnetite and hematite. Additionally, some samples of Pakistani demantoid display inclusions of calcite. This unique combination of inclusions differentiates Pakistani demantoid from demantoids sourced from other regions. It signifies that Pakistani demantoid has a distinctive geological origin resulting from the interplay of serpentinization and skarnization processes. This geological formation distinguishes it from demantoids solely hosted in serpentinite or skarn environments in other origins. The identification of these characteristics holds significant importance for accurately determining the origin of Pakistani demantoid. Full article