Search

Developing facile methods to modulate the structure and performance of photocatalysts plays a pivotal role in the potential large-scale application of photocatalytic hydrogen production. Herein, a series of uniformly sized and highly dispersed copper-doped cadmium sulfide (CdS) nanoparticles (NPs) were successfully synthesized through a facile cation exchange strategy. The resulting Cu-doped CdS samples exhibited a remarkable photocatalytic hydrogen production rate of 2459.3 μ mol·h−1g−1, nearly 11 times that of pure CdS. The introduction of Cu+ ions effectively reduced the band gap, leading to enhanced light absorption, as well as improved charge carrier separation and transfer efficiency. Meanwhile, the theoretical investigation further confirmed that Cu+ doping substantially decreased the free energy of hydrogen adsorption and provided more suitable active sites, thereby promoting the photocatalytic hydrogen production activity on CdS NPs. This work provides compelling evidence for the exploration of novel transition metal-doped photocatalysts for hydrogen production using the cation exchange method. [Display omitted] • Controllable Cu-doped CdS was prepared via cation-exchange approach. • Cu doping induced extended light absorption and accelerated charge separation. • HER was promoted by reduced free energy of hydrogen adsorption via Cu doping. • Photocatalytic hydrogen production of CdS was enhanced by 11 times. [ABSTRACT FROM AUTHOR]

Therapeutic antibodies play an important role in the public healthcare system to treat patients with a variety of diseases. Protein characterization using an array of analytical tools provides in-depth information for drug quality, safety, efficacy, and the further understanding of the molecule. A therapeutic antibody candidate MAB1 exhibits unique binding properties to both cation and anion exchange columns at neutral pH. This uniqueness disrupts standard purification processes and necessitates adjustments in manufacturing. This study identifies that the charge heterogeneity of MAB1 is primarily due to the N-terminal cyclization of glutamine to pyroglutamine and, to a lesser extent, succinimide intermediate, deamidation, and C-terminal lysine. Using three approaches, i.e., deferential chemical labeling, H/D exchange, and molecular modeling, the binding to anion exchange resins is attributed to negatively charged patches on the antibody's surface, involving specific carboxylic acid residues. The methodologies shown here can be extended to study protein binding orientation in column chromatography. [ABSTRACT FROM AUTHOR]

Lead halide perovskites have been explored ardently in the past decade owing to their excellent photophysical properties. High‐temperature cation exchange reactions have been employed to improve the stability and performance in perovskite lattice, but lacks control over size, shape, and stoichiometry. Herein, the solution phase interaction of cesium lead bromide (CsPbBr3) nanocrystals with monovalent and bivalent copper ions, under ambient conditions is systematically investigated. The introduction of Cu1+ explicitly initiates a one‐dimensional growth with a distinct phase transition, that is from cubic to orthorhombic, while Cu2+ induces a partial exchange with Pb2+ with no phase change. DFT calculations suggest that Cu1+ induces structural distortion via Cs1+ substitution, altering the Goldschmidt tolerance factor and perovskite octahedral tilting, leading to the phase transition. Additionally, the oleic acid/amine ligands used to stabilize the nanocrystals, are preferentially etched away to form complexes with Cu1+, initializing an oriented growth of the nanocubes to nanorods. A mechanistic investigation of the evolution of the nanorods gave insights on tuning the tolerance factor via room temperature modifications and cation exchanges in perovskites for anisotropy and morphology tuning. This effortlessly obtained perovskite nanorods with Cu1+ could find effective applications in optoelectronics, and as novel photocatalysts. [ABSTRACT FROM AUTHOR]

Phase control over cation exchange (CE) reactions has emerged as an important approach for the synthesis of nanomaterials (NMs), enabling precise determination of their reactivity and properties. Although factors such as crystal structure and morphology have been studied for the phase engineering of CE reactions in NMs, there remains a lack of systematic investigation to reveal the impact for the factors in heterogeneous materials. Herein, we report a molybdenum disulfide induced phase control method for synthesizing multidimensional Co3S4‐MoS2 heteronanostructures (HNs) via cation exchange. MoS2 in parent Cu1.94S‐MoS2 HNs are proved to affect the thermodynamics and kinetics of CE reactions, and facilitate the formation of Co3S4‐MoS2 HNs with controlled phase. This MoS2 induced phase control method can be extended to other parent HNs with multiple dimensions, which shows its diversity. Further, theoretical calculations demonstrate that Co3S4 (111)/MoS2 (001) exhibits a higher adhesion work, providing further evidence that MoS2 enables phase control in the HNs CE reactions, inducing the generation of novel Co3S4‐MoS2 HNs. As a proof‐of‐concept application for crystal phase‐ and dimensionality‐dependent of cobalt sulfide based HNs, the obtained Co3S4‐MoS2 heteronanoplates (HNPls) show remarkable performance in hydrogen evolution reactions (HER) under alkaline media. This synthetic methodology provides a unique design strategy to control the crystal structure and fills the gap in the study of heterogeneous materials on CE reaction over phase engineering that are otherwise inaccessible. [ABSTRACT FROM AUTHOR]

Precise control over the composition of heterostructure nanocrystals and their self-assembly is an emerging research interest. Superstructures of this type are typically enhanced in terms of their collective functionalities. Herein, we developed a practical yet simple approach to synthesize and self-assemble Cu2–xS/CuYS (Y = In, Sb, and Sn) heterostructured nanorods (NRs) into their vertically standing up assemblies. First NRs come together via depletion–attraction forces, and then partial cation exchange between Cu31S16 NRs and the injected cationic precursor taken in stoichiometric amounts dissolved in trioctylphosphine and oleylamine (Olam) results in heterostructured NRs possessing compositions of Cu2–xS/CuYS (Y = In, Sb, and Sn). The chemical composition changes lead to surface chemistry modifications as the injected guest cationic part of the NR is either naked or covered with Olam which is quite easy to strip-off from the NC surface at high temperature, resulting in a 2D sheetlike structure of heterostructured vertically oriented NRs in solution. The route to obtaining long-range heterostructured assembled NRs is studied and characterized systematically. This work presents a detailed mechanistic insight into the cation exchange-induced self-assembly of heterostructured NRs, where the particles are coupled, which is of growing importance as a synthesis tool. The complex nanostructures synthesized in the present work may benefit solution-processed optoelectronic applications. [ABSTRACT FROM AUTHOR]

Metal chalcogenide nanocrystals with variable composition and shape can conveniently be produced using cation exchange synthesis; however, the presence of cation‐containing ligands inherited from the starting material often results in contamination of the final product. To address this issue, a two‐step ligand replacement strategy is developed to fabricate CuInSe2/CuInS2 nanorods from CdSe/CdS nanorods via removal of Cd‐phosphonates from an intermediate Cu2‐xSe/Cu2‐xS phase used in the cation exchange conversion. This synthetic approach furnishes CuInSe2/CuInS2 nanorods with cadmium content below 1 at.%, and high photoluminescence quantum yields reaching 40% in the near‐infrared spectral range. Transient absorption studies reveal that the band alignment in the CuInSe2/CuInS2 heterostructure features a quasi‐type II character, with an electron localized in the core and a hole wavefunction spread over the entire nanorod. The efficient passivation of the core and the reduced Cd content leads to excitonic emission with full width at half maximum down to 110 meV, superimposed with a broad emission band from copper‐induced defects. Field‐effect transistors based on cadmium‐free CuInSe2/CuInS2 nanorods show two orders of magnitude lower noise current density compared with the cadmium‐rich devices. The responsivity and specific detectivity of these devices reach 230 mA W−1 and 108 Jones, respectively, under near‐infrared excitation at room temperature. [ABSTRACT FROM AUTHOR]

Considering groundwater from the aquifers overlying the bedrock is an important water source for drinking purposes. As such, the investigation of its property is essential. Based on the spatial structure of aquifers in the study area, the aquifers in the Cenozoic strata are divided into three groups. The multivariate statistical approaches are employed to identify the hydrogeochemical processes and hydro-chemical types, and hydrogeochemical inverse modeling is applied to further validate and elucidate the hydrogeochemical process and water–rock interaction. The results are as follows: (1) The hydro-chemical type of the upper aquifer is dominated by the K + Na-HCO3 type, while others have similar water quality types, which are dominated by the K + Na-Cl type and the K + Na-SO4 type. (2) The saturation index of anhydrite, gypsum, halite, and CO2(g) is below zero in three aquifers, indicating that they are unsaturated. While aragonite, calcite, and dolomite in the middle aquifer remain in the unsaturated–saturated state. (3) The cation exchange process accelerating the reduction of Ca2+ concentration and the increase of SO42− concentration occurs in three aquifers, and the dissolution of calcite and dolomite minerals occurs in most cases. This study supports the fundamental evidence for the hydrogeochemical processes and water resource utilization and has a certain practical significance. HIGHLIGHTS Hydrogeochemical characteristics of the Cenozoic aquifers are investigated.; Relationship between ions reveals the hydrogeochemical processes and water–rock interaction.; Cation exchange process accelerates the reduction of Ca2+ concentration and the increase of SO42+ concentration.; A hydro-chemical boundary is identified.; Reverse simulation and cluster analysis further validate the water–rock interaction processes.;

The synthesis of the accurate composition and morphological/structural design of multielement semiconductor materials is considered an effective strategy for obtaining high-performance hybrid photocatalysts. Herein, sulfur vacancy (Vs)-bearing In2S3/CuInS2 microflower heterojunctions (denoted Vs-In2S3/CuInS2) were formed in situ using In2S3 microsphere template-directed synthesis and a metal ion exchange-mediated growth strategy. Photocatalysts with flower-like microspheres can be obtained using hydrothermally synthesized In2S3 microspheres as a template, followed by Ostwald ripening growth during the metal cation exchange of Cu+ and In3+. The optimal heterostructured Vs-In2S3/CuInS2 microflowers exhibited CO and CH4 evolution rates of 80.3 and 11.8 μmol g−1 h−1, respectively, under visible-light irradiation; these values are approximately 4 and 6.8 times higher than those reported for pristine In2S3, respectively. The enhanced photocatalytic performance of the Vs-In2S3/CuInS2 catalysts could be attributed to the synergistic effects of the following factors: (i) the constructed heterojunctions accelerate charge-carrier separation; (ii) the flower-like microspheres exhibit highly uniform morphologies and compositions, which enhance electron transport and light harvesting; and (iii) the vs. may trap excited electrons and, thus, inhibit charge-carrier recombination. This study not only confirms the feasibility of the design of heterostructures on demand, but also presents a simple and efficient strategy to engineer metal sulfide photocatalysts with enhanced photocatalytic performance. [ABSTRACT FROM AUTHOR]

Lepidocrocite-type layered sodium titanate (NaxH2−xTi2O5) is widely used in environmental remediation because of its large specific surface area, formed by anisotropic crystal growth, and its ability to store and exchange cations between layers. Additionally, peroxo-titanate nanotubes (PTNTs), which are tubular titanates with peroxy groups, exhibit visible-light absorption capabilities, rendering them suitable for photocatalytic applications under visible light irradiation. However, because of cation exchange reactions, the Na+ concentration and pH of the solution can fluctuate under aqueous conditions, affecting the photocatalytic performance of the PTNTs. Herein, we evaluated the impact of cation exchange reactions on the photocatalytic degradation of Rhodamine B (Rh B) by PTNTs at controlled Na+ ratios. The observed pH of Rh B solutions increases due to the cation exchange reaction with Na+ and H3O+, leading to the formation of zwitter-ionic Rh B molecules, eventually weakening their adsorption and photodegradation performance. Moreover, the results indicate that inhibiting the pH increase of the Rh B solution can prevent the weakening of both the adsorption and photodegradation performance of PTNTs. This study highlights the significance of regulating the sodium ion content in layered titanate materials, emphasizing their importance in optimizing these materials' photocatalytic efficacy for environmental purification applications. [ABSTRACT FROM AUTHOR]

The concentration of heavy metals in soil layers has increased due to the rapid development of the industry. Lead and zinc are two frequent heavy metal contaminants in soil. This paper aims to study the effect of these types of contaminants on different fines, including kaolinite, bentonite, and zeolite mixed with sand. First, mixtures of sand and kaolinite, bentonite, and zeolite were prepared, then they were contaminated by two contaminants of lead and zinc nitrates, separately. Consolidated undrained triaxial tests, Soil Conservation Service (SCS) double hydrometer tests, scanning electron microscope (SEM), Atterberg limits, and pH determination tests were conducted on the soil samples to investigate the changes in the strength and microstructure in the presence of heavy metals. In general, triaxial test results showed that various parameters influence the strength results of these heavy metal-contaminated sandy soil samples such as type, percentage, and structure of the fine portion, type, and concentration of contaminants, bonding mechanism of fine grains, and ion exchange capacity. For instance, in the presence of kaolinite (and kaolinite-zeolite mixtures), contamination with lead decreased the strength of soil samples, but in the soil mixtures containing bentonite (and bentonite-kaolinite mixtures), an opposite trend was seen. The plasticity index of mixtures containing kaolinite and zeolite increased in the presence of heavy metal contaminants, but it decreased when the fine portion of the soil was bentonite. Heavy metal contaminants decreased the pH of all soil mixtures and made them to be acidic. The results of the SCS double hydrometer test and SEM indicated that contaminated kaolinite and zeolite soil mixtures have a dispersed structure, while bentonite soil mixtures are not dispersive. [ABSTRACT FROM AUTHOR]

A comprehensive understanding of the hydrochemical evolution and spatial patterns of shallow groundwater systems is essential for water resource management and wetland ecological restoration. The Baiyangdian Wetland is one of the most concerning areas because of the development of the Xiong'an New Area. The spatial characteristics of groundwater hydrochemistry and potential controlling factors associated with hydrochemical evolution remain unclear. In this study, hydrogeochemistry together with the hierarchical cluster analysis were used to elucidate the hydrochemical processes and hydrological zoning patterns of shallow groundwater systems in the Baiyangdian Wetland, North China Plain. The results showed that hydrochemical compositions of shallow groundwater had considerable spatial variations, which was closely related to the inflow rivers hydrochemistry and the dynamics of groundwater–surface water interactions. A significant increase in SO42− concentration occurring at the cone of the depression was related to extensive pumping caused by anthropogenic activities. Anthropogenic activities were also a major factor controlling the spatial distribution patterns of shallow groundwater hydrochemistry. Ca2+, Mg2+, and SO42− in the wetland and shallow groundwater were primarily derived from carbonate and gypsum dissolution, while Na+ and Cl− originated from halite and silicate dissolution. Rock weathering predominated the geochemical evolution of shallow groundwater in conjunction with carbonate precipitation and cation exchange. The hydrochemistry of the shallow groundwater system presented distinct spatial zonation patterns that were classified into four clusters corresponding to seven subzones. In Zones I–IV, water‐rock interaction was the dominant factor controlling shallow groundwater chemistry, which was driven by the positive groundwater–surface water exchange. The coupled effects of anthropogenic activities and river infiltration and mixing caused the high levels of dissolved components in Zones V–VII. This study contributes to have a better understanding of the water cycle and hydraulic connections among different bodies, and will benefit the rational evaluation of hydrochemical evolution and wetland ecological restoration in the Baiyangdian Wetland. [ABSTRACT FROM AUTHOR]

The amendment of agricultural soils by crushed silicate minerals has been proposed to enhance weathering rates and facilitate carbon dioxide (CO2) removal from the atmosphere. Laboratory dissolution experiments typically provide weathering rates that are significantly higher than those observed under natural conditions, while field studies are limited in the nature of data they can collect. This study uses an experimental setup that aims to emulate natural field conditions in a controlled setting using soil cores retrieved from UK cropland amended with crushed olivine at 32°C. Results are compared to enhanced weathering experiments run at 4°C and 19°C under otherwise identical conditions. The data reveal temperature-dependent variations in the behaviour of different elements, most importantly Mg and Si, with silicon being retained at moderate temperatures and magnesium being retained at higher temperatures. These patterns are most likely due to different retention mechanisms, notably Si reprecipitation (e.g. as cation-depleted Si-enriched mineral surface coatings) and cation exchange (affecting Mg, but to a lesser degree Si), such that the influence of cation exchange should be accounted for when interpreting enhanced weathering field data. We therefore recommend that estimates of carbon sequestration should not be based on the behaviour of individual elements. A temperature effect on the weathering rate of olivine added to soil columns is observed with the weathering rate being higher at 32°C than at 19°C and 4°C, and significantly lower than laboratory experiment-derived weathering rates. This further emphasises the need for enhanced weathering field trials, as simple laboratory-derived rates cannot be used to assess the feasibility of enhanced weathering measures. The carbon dioxide capture potential at 32°C is conservatively estimated at ~115 t CO2 km-2 yr-1 assuming an olivine amendment rate of 12.7 kg m-2. Our data suggests that soil accumulation of heavy metals like Cu and Cr at high temperatures (hence high weathering rates) is nondangerous, however, Ni concentrations in the effluent solution are close to EU guidelines while Cr and Cu are considerably lower than guidelines. All of these conclusions have implications for the application of enhanced weathering for carbon dioxide removal from the atmosphere. [ABSTRACT FROM AUTHOR]

A geosynthetic clay liner (GCL) was exhumed from a composite liner (geomembrane over GCL containing granular sodium bentonite) in the base of a landfill cell after 12 years of atmospheric exposure. The GCL was altered appreciably during exposure, despite being overlain by a geomembrane. Water content, hydration, and bentonite erosion varied considerably along the slope. GCL samples from the top of the slope were dry, with visible bentonite granules comparable to those in a virgin GCL as if the bentonite had not hydrated. No substantial change in exchange complex or swell index (SI) occurred in samples from the top of the slope, and hydraulic conductivity of these samples to water was low (≈10−11 m/s). GCL samples from the toe of the slope varied considerably, from moist and soft to dry and cracked, but all had undergone hydration, and had low SI, a small mole fraction of monovalent cations in the exchange complex, and high hydraulic conductivity (10−8 m/s or higher). Bentonite in GCL samples from midslope had a cracked structure commonly observed in GCLs that have undergone wet–dry cycling. Midslope GCLs typically had hydraulic conductivity greater than 10−7 m/s. A sample from the top of the slope from a location near a GCL panel separation was comparable to other samples from the top of the slope. GCL samples from the anchor trench differed considerably, being very permeable or having low hydraulic conductivity. Hydraulic conductivity was strongly correlated with SI; GCL samples with SI<15 mL/2 g were highly permeable, and those with SI>15 mL/2 g were comparable to a virgin GCL. The variation in SI was related directly to replacement of sodium by calcium in the exchange complex of the bentonite. Hydraulic conductivity also was affected by the thinning of the GCL. [ABSTRACT FROM AUTHOR]

This work found that rectorite (REC) has a good adsorption effect on cationic pollutants such as ciprofloxacin (CIP), with a maximum adsorption capacity of 79.73 mg/g for CIP. The zeta potential analysis showed that the electronegativity of the REC surface would be weakened after CIP adsorption under acidic conditions. Through adsorption kinetics, isotherm study, XRD, FTIR, and other characterizations, the phenomenon of reduced negative charge on the surface of REC adsorbed with CIP under acidic conditions was explained. Based on the Langmuir and Temkin models, the adsorption process of CIP on REC is a spontaneous endothermic adsorption process. The adsorption kinetics can be better described using a pseudo-second-order model, indicating that the adsorption rate is mainly controlled by chemical adsorption. The characterization further proved that REC adsorbed ciprofloxacin mainly through hydrogen bonding, cation exchange, and electrostatic gravitational interaction. CIP, as an emerging contaminant discharged into the water environment, will be harmful to the ecological environment and human health. Therefore, the utilization of REC for the removal of CIP from an aqueous solution has potential prospects. [ABSTRACT FROM AUTHOR]

Salt stress seriously hinders the normal growth of plant seedling roots. Magnesium, as one of the essential medium elements for plant growth, can effectively alleviate the damage of salt stress to plant roots, but the key genes involved and their mechanism are still unclear. The purpose of this study was to explore the related molecular mechanism of exogenous magnesium regulating cation homeostasis in peanut seedlings under salt stress. Firstly, according to plant physiology experiments, it was found that exogenous magnesium treatment significantly improved the tolerance of peanut seedlings to salt stress. After that, the transcriptome data were integrated, and further gene expression analysis showed that the expression of genes such as CNGC1, NCLs, and NHX7 was regulated under exogenous magnesium treatment, which effectively reduced the accumulation of sodium ions in cells. At the same time, exogenous magnesium also regulates the expression of genes such as ACAs and POTs and maintains the homeostasis of calcium and potassium ions in cells. These results reveal the molecular mechanism of exogenous magnesium regulating the cation homeostasis of peanut seedlings under salt stress, which provides an important reference for further revealing the key genes of salt tolerance in plants. [ABSTRACT FROM AUTHOR]

Interactions at the oil/brine/rock interfaces play a pivotal role in the mobility of crude oil within reservoir matrices. Unraveling the microscopic mechanisms of these interactions is crucial for ion-engineered water flooding in secondary and tertiary oil recovery. In this study, the occurrence and transport behavior of crude oil in kaolinite nanopores covered with thin brine films was investigated by molecular dynamics simulation. There is an apparent interface layered phenomenon for the liquid molecules in slit pores and the polar oil components primarily concentrate at the oil/brine interfacial region and form various binding connections with ions. The interfacial interactions between the polar oil components and brine ions exhibit an inhibitory effect on the transport of crude oil through nanopores. The interaction mechanism between acetic acid molecules and hydrated ions was elucidated by interaction modes and interaction intensity, which was proved to illustrate the flow difference in different brine film systems. Moreover, a strategy of exchanging the binding sites of divalent cations with acetic acid molecules by monovalent cations with a higher concentration was proposed. The cation exchange scheme was further validated, demonstrating an enhancement in the oil mobility within nanopores. These findings deepen our understanding of oil/brine/rock interfacial interactions and provide a significant molecular perspective on ion-engineered water flooding for enhanced oil recovery. [ABSTRACT FROM AUTHOR]

Montmorillonite (Mt) is a ubiquitous swelling clay mineral and major component of soft rocks, sediments, and soils with an inherent capability to sorb metal cations. This unique feature renders Mt important for the enrichment and mobilization of environmentally important metal cations, retardation of heavy metals and radionuclide ions, the evolution of clay mineral itself, soils and sediments, and other geological processes. Understanding the interfacial interactions of Mt with metal cations at the molecular level is of fundamental importance in all these processes, but still remains elusive, due to the chemical and structural complexity of Mt surfaces and the diverse chemistries of metal cations. In this Review, we aim to provide the reader with a comprehensive overview of the adsorption modes of metal cations on basal and edge surfaces of Mt, local chemical environments of the cation binding sites, the driving forces for metal sorption, and factors influencing the dynamics of cation uptake onto Mt surfaces. Various surface complexation models [i.e., nonelectrostatic model (NEM), constant capacitance model (CCM), diffuse layer model (DLM), and triple-layer model (TLM)], advanced spectroscopic techniques (i.e., NEM, CCM, DLM, and TLM), and atomistic simulation methods (i.e., MD, DFT, and FPMD) have been used in conjunction with macroscopic adsorption experiments to gain detailed insights into the interfacial interactions of metal cations on Mt. Mt adsorbs metal cations via three independent pathways: (1) cation exchange; (2) surface complexation; and (3) nucleation and surface precipitation. The principal driving force for cation exchange is electrostatic interaction, while chemical bonding governs the two other mechanisms that depend on the basal and edge surface properties of Mt. The siloxane cavities on the tetrahedral basal plane exhibit the strongest adsorption sites for cation exchange and are greatly affected by the the degree of Al3+/Si4+ tetrahedral substitutions. At the amphoteric edge surfaces bearing hydroxyl groups, metal cations could form mono/multidentate surface complexes on Mt [010] and [110] edges. Ionic strength, pH, the presence of competing cations, temperature, and layer charge have been shown to affect the adsorption mechanisms and quantity of adsorbed cations. The updated information on the interfacial interactions of metal cations with Mt basal and edge surfaces presented in this review provides an improved understanding of the enrichment of metals, formation of metal ores, and natural biogeochemical cycles, as well as may promote technological and engineering applications of this important clay mineral in environmental remediation, geological repository, petroleum exploration and extraction, and extraterrestrial research. [ABSTRACT FROM AUTHOR]

It is investigated to identify the controlling processes for chemical compositions of unconfined groundwater along mainly eastward flowpaths on Musashino Uplands, located in Tokyo Metropolitan. Along the flowpaths, Ca2+ concentrations decreased, while Mg2+ and Na+ concentrations increased. Considering the facts that the observed changes along the paths occurred without a remarkable increase of TDS (total dissolved solid) values and that saturation index for calcite (SIc) of the groundwater samples indicated they were mostly under unsaturated conditions, the changes would be attributed to cation exchange reactions. This idea is concordant well with two previsous reports; one is for exchangeable cation compositions extracted from Kanto Loam and the other is for long-term monitoring of groundwater chemical compositions. Moreover, decrease of NO3- concentrations and increase of SO42- concentrations occured in special wards, the eastern part of Tokyo, These occurences can be caused by denitrification under anoxic conditions associated with higher covering area and by oxidation of sulfide involved in marine clays. Such an oxidation is likely induced by local percolation of precipitation and/or leakage from water supply pipes accompanied with dissolved O2. By using previous reports for the unconfined groundwater sources and aquifer parameters in Musashino Uplands, it is evaluated that percentage of the both of leakage and precipitation components is approximately 16% and the remaining is for groundwater advection component from upstream of special wards. In this evaluation, such a low percentage of oxic water components is accordant with regards to the occurrence capability for anoxic conditions in special wards. [ABSTRACT FROM AUTHOR]

To trace Critical Zone processes and to quantify Li fluxes from one Critical Zone compartment into another, we investigated the Li concentration and isotopic composition (δ7Li) of time-series water samples (including subsurface flow, groundwater and creek water), vegetation, bedrock (including separated minerals from bedrock), and regolith (including exchangeable fraction and clay-sized fraction of regolith) in a temperate forested headwater catchment in the Black Forest, Conventwald, Germany. Our estimation of the Li budget shows that atmospheric deposition and biological processes played minor roles in the Li cycle relative to chemical weathering. All water samples (δ 7Li value of 6.5 to 20.4 ‰) were enriched in 7Li compared to bedrock (-1.3 ‰) and regolith (∼-1.7 ‰), but δ7Li differed between water pathways: δ7Li variations in subsurface flow, creek water and groundwater were controlled by conservative mixing, exchangeable pool buffering and Li incorporation/adsorption, respectively. Fractionated heavy Li isotopes in water samples resulted from the formation of secondary solids which preferentially incorporated 6Li, with the separated clay-sized fraction of the regolith exhibiting more negative δ7Li values (-5.4 to −3.5 ‰) than the bulk regolith (∼-1.7 ‰). However, Li in secondary solids only accounted for 8 ± 6 % of the total Li hosted in bulk regolith, and consequently δ7Li in soil did not differ significantly from δ 7Li in bedrock. This is unexpected considering water is continuously removing 7Li in preference over 6Li from regolith. Mass balance calculations applied at the catchment scale point to an irreconcilable imbalance with our data. On one hand, the regolith's δ7Li values are not negative enough to balance the 7Li export by river water, and on the other hand Li in the riverine dissolved load only accounts for ∼ 30 % of the Li solubilized from regolith. Therefore, we suggest that there might be a "hidden export pathway" for Li at our site, possibly subsurface removal of fine particles enriched in 6Li. In light of increasingly frequent observations of such isotopic imbalances in the Critical Zone this phenomenon deserves increased attention. [ABSTRACT FROM AUTHOR]

Ningnanmycin is a widely used antibiotic in agricultural production that effectively controls fungal and viral diseases in tea trees and chrysanthemums. The polarity characteristic of ningnanmycin has posed limitations on the development of robust detection methods, thereby hindering effective monitoring and control measures. By combining cation exchange solid phase extraction (SPE) with hydrophilic interaction chromatography tandem mass spectrometry (HILIC-MS/MS), we have effectively tackled the issue pertaining to the separation and retention of ningnanmycin. The average recoveries of ningnanmycin in green tea, black tea, and chrysanthemum were 77.3–82.0%, 80.1–81.5%, and 74.0–80.0%, respectively. The intraday and interday relative standard deviations (RSDs) were below and equal to 7.7%. Good linearity was observed in the concentration range of 1–1000 μg/L (R2 > 0.998). The limits of detection (LODs) ranged from 1.1 μg/kg to 7.1 μg/kg, and the limits of quantification (LOQs) ranged from 3.6 μg/kg to 23.7 μg/kg for ningnanmycin. These results indicate the good accuracy, repeatability, reproducibility, and sensitivity of the method. It is suitable for detecting ningnanmycin in tea and chrysanthemum. [ABSTRACT FROM AUTHOR]

Bicarbonate ions (HCO3−) are abundant in karst water with poor lead (Pb) utilization and biodegradation. This study aimed to investigate the mechanism of HCO3− on the Pb removal efficiency and uptake ability of Pontederia crassipes (a widespread hydrophyte in the karst area) from karst water. The Pb concentration, Pontederia crassipes morphology, and functional group were detected. As the HCO3− molarity in karst water increased (3, 4, and 5 mmol/L), the removal of Pb increased (85.31%, 93.28%, and 95.16%), whereas the bioconcentration amount of Pb decreased (573, 501, and 301 mg/kg), mainly due to the insoluble PbCO3 and Pb (OH)2. The Pb bioconcentration factor was the highest (15,564) at 4 mmol/L HCO3− due to the maximum strength of cation exchange and cell wall protein C=O. High HCO3− molarities changed the variety of positive ions of cation exchange (HCO3− ≤ 4 mmol/L: Na, K, and Mg; HCO3− > 4 mmol/L: Mg and K), and relieved the breaking of roots, stomatal closure, and vascular system shrinking. Moreover, high HCO3− molarities diminished the C≡C oxidation, enlarged the displacement of SO42− and C-O, and stimulated the methyl transfer reaction and the bonding between -CH3 and Pb. [ABSTRACT FROM AUTHOR]

Owing to the absence of organic cations, all‐inorganic perovskite exhibits superior thermal and irradiation stability compared to organic‐inorganic perovskite. However, it is difficult for the traditional solution method to produce pinhole‐free and phase‐pure all‐inorganic perovskite films, which hinders its application. Here, a method of in situ A‐site cation exchange to synthesize CsPbBr3 films is introduced. The MAPbBr3 films are treated with CsAc solution to initiate cation exchange, where the intermediate product MAAc plays a crucial role in guiding grain growth during evaporation, resulting in the production of pinhole‐free and phase‐pure CsPbBr3 films. The self‐powered photodetector, based on compact and pinhole‐free CsPbBr3 film, exhibits excellent performance with an LDR of 126.7 dB, a detectivity of 1.1 × 1013 Jones, and a rise/decay time of 2.9/25.1 µs. Furthermore, the photodetector maintains over 90% of its original performance after a 2500 s irradiation test and a 30‐day air exposure test. Benefiting from the exceptional device performance and stability, the photodetector proves to be a valuable component in the laser eavesdropping system. [ABSTRACT FROM AUTHOR]

Thick‐shell colloidal quantum dots (QDs) are promising building blocks for solar technologies due to their size/composition/shape‐tunable properties. However, most well‐performed thick‐shell QDs suffer from frequent use of toxic metal elements including Pb and Cd, and inadequate light absorption in the visible and near‐infrared (NIR) region due to the wide bandgap of the shell. In this work, eco‐friendly AgInSe2/AgInS2 core/shell QDs, which are optically active in the NIR region and are suitable candidates to fabricate devices for solar energy conversion, are developed. Direct synthesis suffers from simultaneously controlling the reactivity of multiple precursors, instead, a template‐assisted cation exchange method is used. By modulating the monolayer growth of template QDs, gradient AgInSeS shell layers are incorporated into AgInSe2/AgInS2 QDs. The resulting AgInSe2/AgInSeS/AgInS2 exhibits better charge transfer than AgInSe2/AgInS2 due to their favorable electronic band alignment, as predicted by first‐principle calculations and confirmed by transient fluorescence spectroscopy. The photoelectrochemical cells fabricated with AgInSe2/AgInSeS/AgInS2 QDs present ≈1.5‐fold higher current density and better stability compared to AgInSe2/AgInS2. The findings define a promising approach toward multinary QDs and pave the way for engineering the QDs' electronic band structures for solar‐energy conversion. [ABSTRACT FROM AUTHOR]

The western U.S. is experiencing shifts in recharge due to climate change, and it is currently unclear how hydrologic shifts will impact geochemical weathering and stream concentration–discharge (C–Q) patterns. Hydrologists often use C–Q analyses to assess feedbacks between stream discharge and geochemistry, given abundant stream discharge and chemistry data. Chemostasis is commonly observed, indicating that geochemical controls, rather than changes in discharge, are shaping stream C–Q patterns. However, few C–Q studies investigate how geochemical reactions evolve along groundwater flowpaths before groundwater contributes to streamflow, resulting in potential omission of important C–Q controls such as coupled mineral dissolution and clay precipitation and subsequent cation exchange. Here, we use field observations—including groundwater age, stream discharge, and stream and groundwater chemistry—to analyse C–Q relations in the Manitou Experimental Forest in the Colorado Front Range, USA, a site where chemostasis is observed. We combine field data with laboratory analyses of whole rock and clay x‐ray diffraction and soil cation‐extraction experiments to investigate the role that clays play in influencing stream chemistry. We use Geochemist's Workbench to identify geochemical reactions driving stream chemistry and subsequently suggest how climate change will impact stream C–Q trends. We show that as groundwater age increases, C–Q slope and stream solute response are not impacted. Instead, primary mineral dissolution and subsequent clay precipitation drive strong chemostasis for silica and aluminium and enable cation exchange that buffers calcium and magnesium concentrations, leading to weak chemostatic behaviour for divalent cations. The influence of clays on stream C–Q highlights the importance of delineating geochemical controls along flowpaths, as upgradient mineral dissolution and clay precipitation enable downgradient cation exchange. Our results suggest that geochemical reactions will not be impacted by future decreasing flows, and thus where chemostasis currently exists, it will continue to persist despite changes in recharge. [ABSTRACT FROM AUTHOR]

Mullite-type AMn2O5 materials represent a group of promising candidates to substitute noble metal catalysts for the catalytic removal of volatile organic compounds (VOCs). When applied to catalytic oxidation of aromatic hydrocarbons such as toluene, AMn2O5 exhibits undesirable performance due to its poor intrinsic activity of oxygen species, leading to a light-off temperature above 250 °C. In this work, we have developed a synthesis route combining a two-step calcination and cation-exchange process to prepare a nanoporous CeO2-decorated Cu-SmMn2O5 composite mullite oxide catalyst applied in toluene oxidation. The best performing sample reached 90% toluene conversion at 190 °C, surpassing other transition metal oxide catalysts. Comprehensive characterizations reveal that Cu ion doping into the crystal lattice of the mullite phase is achieved via the cation-exchange process. In this catalyst design, surface CeO2 decoration and Cu doping promote the reduction ability and improve oxygen species activity to accelerate toluene oxidation. Overall, this work provides a strategy to prepare composite mullite oxide catalysts with high performance in the removal of VOCs, broadening the industrial application prospects of mullite-type materials. [ABSTRACT FROM AUTHOR]

The synthesis of the accurate composition and morphological/structural design of multielement semiconductor materials is considered an effective strategy for obtaining high-performance hybrid photocatalysts. Herein, sulfur vacancy (Vs)-bearing In2S3/CuInS2 microflower heterojunctions (denoted Vs-In2S3/CuInS2) were formed in situ using In2S3 microsphere template-directed synthesis and a metal ion exchange-mediated growth strategy. Photocatalysts with flower-like microspheres can be obtained using hydrothermally synthesized In2S3 microspheres as a template, followed by Ostwald ripening growth during the metal cation exchange of Cu+ and In3+. The optimal heterostructured Vs-In2S3/CuInS2 microflowers exhibited CO and CH4 evolution rates of 80.3 and 11.8 μmol g−1 h−1, respectively, under visible-light irradiation; these values are approximately 4 and 6.8 times higher than those reported for pristine In2S3, respectively. The enhanced photocatalytic performance of the Vs-In2S3/CuInS2 catalysts could be attributed to the synergistic effects of the following factors: (i) the constructed heterojunctions accelerate charge-carrier separation; (ii) the flower-like microspheres exhibit highly uniform morphologies and compositions, which enhance electron transport and light harvesting; and (iii) the vs. may trap excited electrons and, thus, inhibit charge-carrier recombination. This study not only confirms the feasibility of the design of heterostructures on demand, but also presents a simple and efficient strategy to engineer metal sulfide photocatalysts with enhanced photocatalytic performance.

Lepidocrocite-type layered sodium titanate (NaxH2−xTi2O5) is widely used in environmental remediation because of its large specific surface area, formed by anisotropic crystal growth, and its ability to store and exchange cations between layers. Additionally, peroxo-titanate nanotubes (PTNTs), which are tubular titanates with peroxy groups, exhibit visible-light absorption capabilities, rendering them suitable for photocatalytic applications under visible light irradiation. However, because of cation exchange reactions, the Na+ concentration and pH of the solution can fluctuate under aqueous conditions, affecting the photocatalytic performance of the PTNTs. Herein, we evaluated the impact of cation exchange reactions on the photocatalytic degradation of Rhodamine B (Rh B) by PTNTs at controlled Na+ ratios. The observed pH of Rh B solutions increases due to the cation exchange reaction with Na+ and H3O+, leading to the formation of zwitter-ionic Rh B molecules, eventually weakening their adsorption and photodegradation performance. Moreover, the results indicate that inhibiting the pH increase of the Rh B solution can prevent the weakening of both the adsorption and photodegradation performance of PTNTs. This study highlights the significance of regulating the sodium ion content in layered titanate materials, emphasizing their importance in optimizing these materials’ photocatalytic efficacy for environmental purification applications.

Therapeutic antibodies play an important role in the public healthcare system to treat patients with a variety of diseases. Protein characterization using an array of analytical tools provides in-depth information for drug quality, safety, efficacy, and the further understanding of the molecule. A therapeutic antibody candidate MAB1 exhibits unique binding properties to both cation and anion exchange columns at neutral pH. This uniqueness disrupts standard purification processes and necessitates adjustments in manufacturing. This study identifies that the charge heterogeneity of MAB1 is primarily due to the N-terminal cyclization of glutamine to pyroglutamine and, to a lesser extent, succinimide intermediate, deamidation, and C-terminal lysine. Using three approaches, i.e., deferential chemical labeling, H/D exchange, and molecular modeling, the binding to anion exchange resins is attributed to negatively charged patches on the antibody’s surface, involving specific carboxylic acid residues. The methodologies shown here can be extended to study protein binding orientation in column chromatography.

Salt stress seriously hinders the normal growth of plant seedling roots. Magnesium, as one of the essential medium elements for plant growth, can effectively alleviate the damage of salt stress to plant roots, but the key genes involved and their mechanism are still unclear. The purpose of this study was to explore the related molecular mechanism of exogenous magnesium regulating cation homeostasis in peanut seedlings under salt stress. Firstly, according to plant physiology experiments, it was found that exogenous magnesium treatment significantly improved the tolerance of peanut seedlings to salt stress. After that, the transcriptome data were integrated, and further gene expression analysis showed that the expression of genes such as CNGC1, NCLs, and NHX7 was regulated under exogenous magnesium treatment, which effectively reduced the accumulation of sodium ions in cells. At the same time, exogenous magnesium also regulates the expression of genes such as ACAs and POTs and maintains the homeostasis of calcium and potassium ions in cells. These results reveal the molecular mechanism of exogenous magnesium regulating the cation homeostasis of peanut seedlings under salt stress, which provides an important reference for further revealing the key genes of salt tolerance in plants.

Ningnanmycin is a widely used antibiotic in agricultural production that effectively controls fungal and viral diseases in tea trees and chrysanthemums. The polarity characteristic of ningnanmycin has posed limitations on the development of robust detection methods, thereby hindering effective monitoring and control measures. By combining cation exchange solid phase extraction (SPE) with hydrophilic interaction chromatography tandem mass spectrometry (HILIC-MS/MS), we have effectively tackled the issue pertaining to the separation and retention of ningnanmycin. The average recoveries of ningnanmycin in green tea, black tea, and chrysanthemum were 77.3–82.0%, 80.1–81.5%, and 74.0–80.0%, respectively. The intraday and interday relative standard deviations (RSDs) were below and equal to 7.7%. Good linearity was observed in the concentration range of 1–1000 μg/L (R2 > 0.998). The limits of detection (LODs) ranged from 1.1 μg/kg to 7.1 μg/kg, and the limits of quantification (LOQs) ranged from 3.6 μg/kg to 23.7 μg/kg for ningnanmycin. These results indicate the good accuracy, repeatability, reproducibility, and sensitivity of the method. It is suitable for detecting ningnanmycin in tea and chrysanthemum.

Bicarbonate ions (HCO3−) are abundant in karst water with poor lead (Pb) utilization and biodegradation. This study aimed to investigate the mechanism of HCO3− on the Pb removal efficiency and uptake ability of Pontederia crassipes (a widespread hydrophyte in the karst area) from karst water. The Pb concentration, Pontederia crassipes morphology, and functional group were detected. As the HCO3− molarity in karst water increased (3, 4, and 5 mmol/L), the removal of Pb increased (85.31%, 93.28%, and 95.16%), whereas the bioconcentration amount of Pb decreased (573, 501, and 301 mg/kg), mainly due to the insoluble PbCO3 and Pb (OH)2. The Pb bioconcentration factor was the highest (15,564) at 4 mmol/L HCO3− due to the maximum strength of cation exchange and cell wall protein C=O. High HCO3− molarities changed the variety of positive ions of cation exchange (HCO3− ≤ 4 mmol/L: Na, K, and Mg; HCO3− > 4 mmol/L: Mg and K), and relieved the breaking of roots, stomatal closure, and vascular system shrinking. Moreover, high HCO3− molarities diminished the C≡C oxidation, enlarged the displacement of SO42− and C-O, and stimulated the methyl transfer reaction and the bonding between -CH3 and Pb.

To reduce the efflorescence extent of metakaolin (MK)-based geopolymer, this study introduced thermally activated modified calcium montmorillonite (MT) and 5 A zeolite (ZT) into MK-based geopolymer, and the optimal mixing ratio was acquired by response surface methodology. The effect of the two modified clay minerals on the microstructural and mechanical properties of the MT-ZT-MK geopolymer was explored by compressive strength testing, phase analysis (XRD and FTIR), pore structure analysis (MIP), and morphology analysis (SEM-EDS). To investigate the performance and mechanism of efflorescence inhibition of the ternary geopolymer, the cation concentration in the leaching solution was detected by inductively coupled plasma atomic emission spectrometry (ICP-OES), and the efflorescence area of the geopolymer was calculated using Image Pro Plus (IPP) software. The results of the experiment showed that the optimal mixing ratio, as determined by RSM, was 1.5 wt% of modified MT and 2.9 wt% of modified ZT, with the highest compressive strength at 65.1 MPa and the lowest degree of efflorescence after 28 days of curing. It can be concluded that the two clays gradually exhibit the effect of cation exchange and internal curing. The pore structure is optimized and (N, C)-A-S-H gels are formed with the extension of curing time. On the other hand, the lesser extent of efflorescence possibly is attributed to the restricted channels for Na+ in the matrix to undergo carbonation with CO 2 in the air. • Using thermally activated modified clay minerals to prepare ternary geopolymer. • The optimal mixing ratio of the ternary geopolymer is established by using RSM. • A proper content of modified clays is beneficial for the strength enhancement of geopolymers. • The mechanism of clay minerals to reduce efflorescence of geopolymers involves cation exchange and internal curing. [ABSTRACT FROM AUTHOR]

[Display omitted] • The ionic liquid [HOEmim][NTf 2 ] can strengthen the extraction performance of TBP for Co2+. • The extraction efficiency of TBP/kerosene/[HOEmim][NTf 2 ] system for Co2+ is up to 99.6 %. • DFT calculations and FT-IR analysis indicate that Co2+ mainly binds to P=O in TBP. • A theoretical basis for removing Co2+ from waste water based on ionic liquids was laid. • ABSTRACT In order to achieve effective removal of radioactive Co(II) from the primary circuit wastewater of nuclear power plants and promote the safe use of nuclear energy, an efficient and eco-friendly method using ionic liquid as a co-extractant was proposed. The effects of ionic liquids 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C 2 mim][NTf 2 ]) or 1-(2-hydroxyethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([HOEmim][NTf 2 ]) as co-extractants on the extraction of Co(II) using tributyl phosphate (TBP) as an extractant were investigated in this work. The results reveal that the optimal extraction conditions for Co(II) are as follows: V TBP : V kerosene : V [HOEmim][NTf2] = 18:1:1, R(O/A) = 1, pH=4. Under these conditions, the extraction efficiency of Co(II) (E Co) reaches 99.6 %, with a distribution ratio (D Co) of 257. Notably, a single TBP or ionic liquid exhibits minimal ability to extract Co2+, while adding only 5 % (v/v) ionic liquid based on TBP/kerosene system can increase D Co by 104 times. The slope method and FT-IR analysis demonstrate that the TBP/kerosene/[HOEmim][NTf 2 ]/ system extracted Co2+ by a cation exchange mechanism. In addition, density functional theory (DFT) calculations were employed to explain the influence of different ionic liquid systems on the E Co , and further elucidate the extraction mechanism of Co2+. The striping results indicate that 92.2 % of Co2+ is stripped with 1.0 mol L−1 HNO 3. The extraction efficiency of Co(II) from the TBP/kerosene/[HOEmim][NTf 2 ] system remained at 98 % after 6 cycles. Therefore, the extraction system exhibits great practical potential in removing Co(II) from contaminated water. This work not only proposes an extraction system with excellent reusability and stability, but also lays a theoretical foundation for the ionic liquid-based cobalt extraction process. [ABSTRACT FROM AUTHOR]

The study presents a novel integrated three-compartment electrochemical continuous electrodeionization reactor that was constructed in a laboratory environment. In order to extract large amounts of carbon dioxide from naturally occurring oceanwater in the form of bicarbonate and carbonate, it develops a innovative electrolytic cation exchange process. At the same time, it produces hydrogen gas for possible hydrocarbon synthesis. The study employs the Box-Behnken experimental design approach implemented through the Design Expert software to investigate and optimize the performance of electrochemical hydrogen extraction from Ocean water from an integrated reactor. The integrated electrochemical continuous-type electrodeionization reactor comprises two cation-permeable membranes that operate as boundaries between three compartments: a central compartment and electrode compartments that house the cathode and anode, each of which may reverse polarity. These membranes are made of gel polystyrene cross-linked with divinylbenzene, which has acidic properties that allow cation transport while inhibiting anions. The integrated reactor's electrode chambers are enclosed in plexiglass end plates and contain distinct Plexiglass electrode compartments. These compartments have mesh and solid steel anode and cathode electrodes, with an electrode active area of 176.71 cm2. The influence of various factors, such as voltage and electrolyte amount, on the production of hydrogen synthesis is examined. The study results demonstrate a maximum hydrogen production rate of 2.2 mg/min and a hydrogen production efficiency of 7.82%. The lab testing was carried out using experimental equipment to determine viability. The tests included 35-min runs that measured hydrogen generation under various parameters, such as applied voltage, electrolyte concentration, and pH levels. The ocean salt solutions of 0.5M, 1M, and 2M were initially prepared and evaluated for hydrogen generation. Each concentration is assessed at a voltage range of 4–15V, with matching solution pH values ranging from 2 to 7. Optimization studies were conducted to enhance the hydrogen production rate. The results indicate that hydrogen production rises proportionally with applied voltage and electrolyte concentration but falls with pH growth. Within the Design Expert software, the statistical methods for response surface analysis and optimization are utilized accordingly. • The paper develops an integrated three-compartment system for hydrogen production. • The paper investigates the system overall efficiencies for assessment. • It discusses how varying voltage and concentration affects hydrogen production. [ABSTRACT FROM AUTHOR]

• Theoretical evaluation of protein separations by simultaneous independent pH & NaCl gradients. • Experimental demonstration of two dimensional LC pH & NaCl gradients. • Isocratic [NaCl] in pH gradients and vice versa vary MAb isoform retention times in WCX LC. • Separation of proteins by uncoupled pH and [NaCl] gradients enhances & improves resolution. • No one single set of uncoupled salt and pH gradients optimizes the resolution of all MAb isoforms. In previous publications we have described the pISep dual simultaneous, independent gradients (DSIGs) liquid chromatography (LC) for uncoupling gradients of non-buffering solute (NaCl, urea or acetonitrile) from externally generated pH gradients. In DSIGs the shape and slope of the [salute] gradient does not depend on the shape and slope of the pH gradient. The technique allows in a single run true simultaneous two dimensional LC separation of complex protein mixtures on various stationary phases including anion, cation exchangers (AEX, CEX), reversed phase (RP), mixed mode and mixed bed. Using a humanized IgG 1 (HIgG 1) monoclonal antibody (MAb) and a variety of pH & [NaCl] DSIGs, we show that most of MAb isoforms can be successfully separated from each other. These experimental observations are supported by an initial theoretical argument presented here predicting an overall improvement of all MAb isoforms separation by DSIGs of pH & [NaCl]. Theoretical calculations predict that, in general, there exists an optimal non-zero isocratic salt concentration in a pH gradient separation that will resolve isoforms close in binding energy, but a wide range of salt concentrations will be required for acceptable resolution of all isoforms. Theory also predicts better separation of weaker rather than stronger binding isoforms. Experimentally, we have found that no one set of DSIGs LC conditions could optimally baseline resolve all identifiable MAb isoforms in a single run of reasonable duration. The versatility and simplicity of the pH & [NaCl] pISep DSIGs LC allows fast, automated scouting of protein separations over any range of pH from 2.4 to 10.8 and [NaCl] from 0 to 1 M without changing the chemistry of the buffering system. Due to the universal applicability of the pISep buffering system in IEX LC, the researcher is given a powerful tool to easily develop pH & [NaCl] DSIGs protocols that vary mobile phase compositions to achieve high resolution separations of targeted proteins. [ABSTRACT FROM AUTHOR]

Currently, the deep geological repository approach for spent nuclear fuel is regarded as the most dependable and secure method for permanently disposing of this kind of waste. Among its key safety components is an engineered barrier made from compacted bentonite, which isolates the encapsulated waste from the surrounding host rock. As a result, understanding how bentonites react to varying compositions of groundwater is crucial. This is where numerical modelling becomes essential. It is generally approved by the scientific community to idealise bentonite as a material structured under a double porosity system composed of the macro and microstructure. In this context, this paper illustrates the capabilities of a double-porosity reactive transport model for bentonites fully implemented in the multiphysics COMSOL platform. For this purpose, different experimental tests were simulated based on the evaluation of diffusive ion transport, mineral dissolution and cation exchange processes in MX-80 bentonite, obtaining very satisfactory results. • A new reactive transport model for bentonites was implemented in COMSOL Multiphysics. • The model includes a geochemical system composed of 14 chemical species and gypsum. • The model considers diffusive-dispersive-advective transport in double-porosity media. • The model validation was run by 3 tests set in the Task Force on Engineered Barrier. [ABSTRACT FROM AUTHOR]

The sorption of Eu(III) by Na + -substituted bentonite (Na-bentonite) was investigated as a function of pH and NaNO 3 concentration ([NaNO 3 ] 0 ). At pH < ∼7.5, Eu(III) sorption decreased with the increasing [NaNO 3 ] 0 , whereas at pH > ∼7.5, it remained nearly complete, independent of [NaNO 3 ] 0 . Our thermodynamic model indicated that the sorption at pH < ∼7.5 occurred via a combination of cation exchange and surface complexation, with the former diminishing as [NaNO 3 ] 0 increased. Meanwhile, the sorption at pH > ∼7.5 was primarily due to surface complexation. By X-ray diffraction, the incorporation of hydrated Eu(III) in the interlayers of montmorillonite increased its lattice spacing and crystallinity along the c-axis, where cation exchange was predominant. Also, Eu L III -edge X-ray absorption spectroscopy revealed that the sample dominated by cation exchange had an absorption edge energy and coordination structure similar to aqueous Eu(III), indicating outersphere complex formation. In other cases, Eu(III) sorption was characterized by innersphere complexation, as indicated by increased covalency and the presence of more pronounced second coordination shells. Importantly, the analysis of dissolved Si and Al suggested that the increased stability of Na-bentonite was likely due to the surface complexation of Eu(III) with aluminol groups at the edges, especially at higher surface coverages. Given its high sorption capacity for Eu(III) and stabilization effect mediated by sorption, Na-bentonite could be serve as an effective backfill material and migration barrier for containing actinides in nuclear waste repositories., Competing Interests: Declaration of Competing Interest ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:, (Copyright © 2024. Published by Elsevier Ltd.)

Cesium-formamidinium lead triiodide perovskite quantum dot (CsxFA1-xPbI3 PQD) is very promising for photovoltaic applications due to its good phase stability and outstanding optoelectronic properties. However, achieving the CsxFA1-xPbI3 PQDs with tunable compositions and robust surface matrix remains a challenge. Here, the surface matrix-mediated cation exchange of PQDs is proposed, in which a bi-functional molecule, tetrafluoroborate methylammonium (FABF4), is applied for the cation exchange and stabilizing surface matrix of PQDs. The results reveal that the FA+ of FABF4 molecules could exchange the Cs+ of CsPbI3 PQDs forming alloy CsxFA1-xPbI3 PQDs, allowing to tune the spectroscopies of PQDs. Meanwhile, the BF4- of FABF4 molecules can effectively stabilize the surface lattice and substantially diminish the surface vacancies of PQDs, improving the phase stability and optoelectronic properties of PQDs. Consequently, CsxFA1-xPbI3 PQD solar cells deliver an efficiency of up to 17.49%, which is the highest value of CsxFA1-xPbI3 PQD solar cells. This work provided important design principles for the composition and surface matrix regulation of PQDs for high-performance solar cells or other optoelectronic devices., (© 2024 Wiley‐VCH GmbH.)

In this study, sugarcane bagasse (SB), which was preliminarily treated with H 3 PO 4 , was utilized to produce biochar (SB-BC). The SB-BC was subsequently modified with KOH to enrich oxygen-containing functional groups (OCFGs) for the enhanced adsorption of NH 4 + from wastewater. Batch tests revealed that KOH-modified SB-BC (SB-MBC) increased the maximum Langmuir adsorption capacity of NH 4 + by approximately twofold, from 27.1 mg/g for SB-BC to 53.1 mg/g for SB-MBC. The optimal operational conditions for NH 4 + adsorption onto SB-MBC were pH of 7.0 and a biochar dose of 3.0 g/L for the removal of 50 mg/L NH 4 + confirmed that cation exchange, electrostatic attraction and surface complexation were the main mechanisms controlling the adsorption process. The desorption and reusability tests of NH 4 + onto SB-MBC was due to the important contribution of the OCFGs enriched on the surface of biochar, which was increased by about fourfold, after being modified by KOH. The NH 4 + adsorption dynamics were better fitted by the Elovich and the NH 4 + adsorption isotherms were better described by Langmuir and Sips models, showing that the adsorption process was dominated by monolayer chemisorption. The properties of the adsorption materials before and after adsorption of NH 4 + confirmed that cation exchange, electrostatic attraction and surface complexation were the main mechanisms controlling the adsorption process. The desorption and reusability tests of NH 4 + -saturated SB-MBC revealed that NH 4 + adsorption slightly decreased after three successive sorption‒desorption cycles. The findings suggested that SB-MBC is a promising and feasible adsorbent for the effective treatment of NH 4 + -contaminated water sources. Future work should conduct tests for treatment of NH 4 + -rich real wastewater and utilize NH 4 + -saturated SB-MBC as slow releasing fertilizer for plants growth., (© 2024. The Author(s), under exclusive licence to Springer Nature B.V.)

Achieving efficient doping in n-type conjugated polymers is crucial for their application in electronic devices. In this study, an n-type doping method is developed based on cation exchange that maintains a high doping level while ensuring a high degree of structural order, leading to significantly improved electrical conductivity. By investigating various dopants and ionic liquids, it is discovered that the choice of dopant influences doping efficiency, while the selection of ionic liquid affects cation exchange efficiency. Through careful selection of suitable dopants and ionic liquids, High doping levels are achieved remarkably in a short period, resulting in the highest conductivity (nearly 1 × 10 - 2 ¹) compared to other doping methods for poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (N2200). The findings highlight the robustness and efficiency of cation exchange doping as an effective approach for achieving high-quality n-type doping in conjugated polymers, thereby opening new avenues for the development of advanced polymer-based electronic devices.- ¹) compared to other doping methods for poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (N2200). The findings highlight the robustness and efficiency of cation exchange doping as an effective approach for achieving high-quality n-type doping in conjugated polymers, thereby opening new avenues for the development of advanced polymer-based electronic devices., (© 2024 Wiley‐VCH GmbH.)

The management of water resources in hyper-arid coastal regions is a challenging task because proper information regarding groundwater recharge and water budget is needed for maintaining the hydraulic balance in optimal conditions, avoiding salinization and seawater intrusion. Thus, this article deals with the estimation of the hydraulic recharge and the study of the effects of salinization on the dynamics of major and trace elements in an alluvial aquifer located in the world's driest zone, the northern Atacama Desert. The result of stable water isotopes (δD and δ 18 O) and tritium ( 3 H) indicated that groundwater in the area is not recent, whereas 14 C results estimated a groundwater residence time ranging between 11,628 and 16,067 yBP. The estimation of the artificial recharge coming from the urban water-supply-system leaks and wastewater/river-water/groundwater infiltration during irrigation was about 19.84 hm 3 /year, which represents an annual negative water balance of 177 hm 3 /year for the aquifer. The groundwater salinization triggered by seawater intrusion (up to 32.6 %) has caused the enrichment of Li, Rb, Ca, Ba, and Sr in groundwater by cationic exchange, where the excess of aqueous Na is exchanged by these elements in the aquifer sediments. Other elements such as B, Se, Si, and Sb are enriched in groundwater by ionic strength and/or anionic exchange during salinization. The heightened B concentrations derived from the B-rich alluvial sediments were higher than the limit suggested by international guidelines, representing a risk to consumers. Vanadium seems to be unaffected by salinization, whereas Pb, Mo, As, U, and Zr did not show a clear behavior during saline intrusion. Finally, this article highlights the consequences of conducting improper water management in coastal hyper-arid regions with exacerbated agriculture., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

High concentrations of Na + and NH 4 + in landfill leachate lead to deterioration of bentonite barrier and pose a threat to the environment. This study focused on the pollution interception and permeability characteristics of the bentonite barrier exposed to NaCl and NH 4 Cl solutions. Based on previous findings, salt solution concentrations were established at 74.80, 37.40, 18.70, and 9.4 mmol/L. The bentonite contents in the mixture were set at 0, 5, 10, and 15%. The results indicate that the samples exhibit better interception of NH 4 . This difference arises from the cation exchange sequence, the size of the hydration radius, and the hydrogen bonding of the two cations. Additionally, the difference in hydration enthalpy between the two cations leads to variations in the swelling of bentonite, resulting in a higher hydraulic conductivity coefficient in NH + compared to Na + . This difference arises from the cation exchange sequence, the size of the hydration radius, and the hydrogen bonding of the two cations. Additionally, the difference in hydration enthalpy between the two cations leads to variations in the swelling of bentonite, resulting in a higher hydraulic conductivity coefficient in NH 4 Cl solution. This study shows that although bentonite barriers have better interception for NH 4 + , they exhibit greater hydraulic conductivity in NH 4 Cl solution, increasing the risk of leachate carrying other contaminants., Competing Interests: The authors declare there is no conflict., (© 2024 The Authors This is an Open Access article distributed under the terms of the Creative Commons Attribution Licence (CC BY-NC-ND 4.0), which permits copying and redistribution for non-commercial purposes with no derivatives, provided the original work is properly cited (http://creativecommons.org/licenses/by-nc-nd/4.0/).)

Efficient and stable photocathodes are crucial for the development of photoelectrochemical (PEC) water-splitting devices. Silicon heterojunction (SHJ) solar cell is one of the most advanced photovoltaic cells. However, due to the instability of its outermost indium tin oxide (ITO) layers in the electrolyte, a protective layer needs to be introduced on its surface. Previously reported high-quality protective layers almost all involved the use of expensive thin film manufacturing techniques such as atomic layer deposition (ALD). In this work, for the first time, a new strategy is proposed of modifying SHJ-based photocathode with yttrium hydroxide (Y(OH) 3 ) through two-step solution methods to simultaneously improve the stability and activity. The optimized SHJ photocathode exhibits a high applied bias photon-to-current efficiency (ABPE) of 8.4% under simulated 100 mW cm -2 (1 Sun) with an AM 1.5G filter in 0.5 m KOH. Furthermore, the obtained SHJ photocathode demonstrates excellent stability of at least 110 h at 0.3 V versus RHE. In this work, combining facile direct current magnetron sputtering with a solution treatment technique provides a novel design strategy, which lowers the threshold for preparing high-quality protective layer, and paves the way for developing economic, efficient, and stable SHJ-based PEC devices., (© 2024 Wiley‐VCH GmbH.)

Selected layered clay minerals of smectite group with different chemical composition (e.g. synthetic hectorite, synthetic smectite and natural smectite) were modified by rare earth cations such as Er3+ and a stochiometric mixture of Er3+/Yb3+. Raw and modified smectites were systematically heated up to temperatures ensuring their dehydration (400 °C), dehydroxylation (800 °C) and formation of new high temperature phases (1200 °C). The products of heating were investigated by terahertz-time domain spectroscopy to follow changes of their dielectric properties in the far-infrared region. The frequency-dependent refractive index of raw and modified clays was determined in the range of 0.2–3.8 THz (6.6–126.5 cm−1). The heating at 800 °C and above resulted in increase frequency dependent index of refraction and decrease absorption coefficient in comparison to the raw clays. The ion-exchanged smectites by rare earth cations further decreased the absorption coefficient of the samples heated at 1200 °C. Raw natural smectite sample revealed a low frequency band at 0.86 THz, already reported in the literature, which shifted to 0.67 THz after sample modification by rare earth cations. Heating of modified JP to 1200 °C resolved a new absorption band at ∼3.40 THz in the ceramic phase produced from raw natural smectite. • Cation exchange reaction was used for modification of clays by selected rare earth elements. • Effect of sample heating up to 400, 800 and 1200 °C was studied. • Terahertz time domain spectroscopy was used to study the refractive index dispersion. • The frequency dependence of absorption in THz region resolved new typical absorption bands. • The high temperature treatment can be used for synthesis of new ceramic phosphor materials. [ABSTRACT FROM AUTHOR]

Fibrous erionite is the only zeolite classified as Group 1 carcinogen by the International Agency for Research on Cancer (IARC). Carcinogenesis induced by erionite is thought to involve several factors as biopersistence, the iron role and cation exchange processes. To better understand these mechanisms, a detailed investigation at the micro scale was performed, collecting elemental information on iron and cation release and their distribution in biological systems by synchrotron micro-X-ray fluorescence mapping (SR-micro-XRF) and synchrotron micro-X-ray absorption spectroscopy (SR-micro-XANES) at the TwinMic beamline (Elettra synchrotron) and at the ID21 beamline of the European Synchrotron Radiation Facility (ESRF). By microscopy and chemical mapping, highly detailed maps of the chemical and morphological interaction of biological systems with fibres could be produced. In detail, THP-1 cell line derived macrophages, used as in vitro model, were analysed during erionite-Na phagocytosis at different time intervals, after single dose exposure. For comparison, cellular fluorescent probes were also used to evaluate the intracellular free sodium and calcium concentrations. Synchrotron analyses visualised the spatial distribution of both fibre and mineral particle associated metals during the phagocytosis, describing the mechanism of internalisation of erionite-Na and its accessory mineral phases. The intracellular distribution of metals and other cations was mapped to evaluate metal release, speciation changes and/or cation exchange during phagocytosis. The fluorescent probes complemented microchemical data clarifying, and confirming, the cation distribution observed in the SR-micro-XRF maps. The significant cytoplasmic calcium decrease, and the concomitant sodium increase, after the fibre phagocytosis seemed due to activation of plasma membrane cations exchangers triggered by the internalisation while, surprisingly, the ion-exchange capacity of erionite-Na could play a minor role in the disruption of the two cations intracellular homeostasis. These results help to elucidate the role of cations in the toxicity of erionite-treated THP-1 macrophages and add knowledge to its carcinogenicity process. [Display omitted] • Synchrotron XRF microscopy used to study fibrous erionite-Na phagocytosis for 96 h. • No metal release from the fibres was observable inside the macrophage cells. • No extraframework cation exchange was observable on the fibres inside the cells. • Intracellular imbalance of Na+ and Ca2+ concentrations was observed inside the cells. • The cation imbalance is the result of an influx/efflux from the extracellular space. [ABSTRACT FROM AUTHOR]