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The diffusion of cations in organic solvent solutions is important for the performance of metal-ion batteries. In this article, pulsed field gradient nuclear magnetic resonance experiments and fully atomistic molecular dynamic simulations were employed to study the temperature-dependent diffusive behavior of various liquid electrolytes representing 1M propylene carbonate solutions of metal salts with bis(trifluoromethylsulfonyl)imide (TFSI−) or hexafluorophosphate (PF6−) anions commonly used in lithium-ion batteries and beyond. The experimental studies revealed the temperature dependence of the diffusion coefficients for the propylene carbonate (PC) solvent and for the anions following an Arrhenius type of behavior. It was observed that the PC molecules are the faster species. For the monovalent cations (Li+, Na+, K+), the PC solvent diffusion was enhanced as the cation size increased, while for the divalent cations (Mg2+, Ca2+, Sr2+, Ba2+), the opposite trend was observed, i.e., the diffusion coefficients decreased as the cation size increased. The anion diffusion in LiTFSI and NaTFSI solutions was found to be similar, while in electrolytes with divalent cations, a decrease in anion diffusion with increasing cation size was observed. It was shown that non-polarizable charge-scaled force fields could correspond perfectly to the experimental values of the anion and PC solvent diffusion coefficients in salt solutions of both monovalent (Li+, Na+, K+) and divalent (Mg2+, Ca2+, Sr2+, Ba2+) cations at a range of operational temperatures. Finally, after calculating the radial distribution functions between cations, anions, and solvent molecules, the increase in the PC diffusion coefficient established with the increase in cation size for monovalent cations was clearly explained by the large hydration shell of small Li+ cations, due to their strong interaction with the PC solvent. In solutions with larger monovalent cations, such as Na+, and with a smaller solvation shell of PC, the PC diffusion is faster due to more liberated solvent molecules. In the salt solutions with divalent cations, both the anion and the PC diffusion coefficients decreased as the cation size increased due to an enhanced cation–anion coordination, which was accompanied by an increase in the amount of PC in the cation solvation shell due to the presence of anions. [ABSTRACT FROM AUTHOR]

Experimentally, in the presence of the crowding agent polyethylene glycol (PEG), sodium ions compact double-stranded DNA more readily than potassium ions. Here, we have used molecular dynamics simulations and the "ion binding shells model" of DNA condensation to provide an explanation for the observed variations in condensation of short DNA duplexes in solutions containing different monovalent cations and PEG; several predictions are made. According to the model we use, externally bound ions contribute the most to the ion-induced aggregation of DNA duplexes. The simulations reveal that for two adjacent DNA duplexes, the number of externally bound Na+ ions is larger than the number of K+ ions over a wide range of chloride concentrations in the presence of PEG, providing a qualitative explanation for the higher propensity of sodium ions to compact DNA under crowded conditions. The qualitative picture is confirmed by an estimate of the corresponding free energy of DNA aggregation that is at least 0.2kBT per base pair more favorable in solution with NaCl than with KCl at the same ion concentration. The estimated attraction free energy of DNA duplexes in the presence of Na+ depends noticeably on the DNA sequence; we predict that AT-rich DNA duplexes are more readily condensed than GC-rich ones in the presence of Na+. Counter-intuitively, the addition of a small amount of a crowding agent with high affinity for the specific condensing ion may lead to the weakening of the ion-mediated DNA–DNA attraction, shifting the equilibrium away from the DNA condensed phase. [ABSTRACT FROM AUTHOR]

This study focuses on the systematic exploration of the emodepside conformations bound to monovalent K+ ion using quantum mechanical density functional theory (DFT) calculations at the M06‐2X/6‐31+G(d,p) level of theory. Nine conformers of emodepside and their complexes with K+ ion were characterized as stationary points on the potential energy surface. The conformational isomers were examined for their 3D structures, bonding, energetics, and interactions with the cation. A cavitand‐like structure (CC) is identified to be the energetically most stable arrangement. To arrive at a better understanding of the K+ ion binding, calculations were initially performed on complexes formed by the K+ and Na+ ions with model ligands (methyl ester and N,N‐dimethyl acetamide). Both the natural bond orbital (NBO) method and the block‐localized wavefunction (BLW) energy decomposition approach was employed to assess the bonding and energetic contributions stabilizing the ion‐bound model complexes. Finally, the solvent effect was evaluated through complete geometry optimizations and energy minimizations for the model ion‐ligand complexes and the emodepside‐K+ bound complexes using an implicit solvent model mimicking water and DMSO. [ABSTRACT FROM AUTHOR]

Synthetic membrane technology plays an increasingly dominant role in modern industry, boasting remarkable efficiency and low carbon attributes. The ever-growing demand for molecular-level separation necessitates precise structures at the angstrom range with a concomitant low transport resistance, but it still remains a great challenge. Here, we demonstrate an enhanced separation performance towards monovalent cations of two-dimensional (2D) conjugated polymeric carbon nitride (PCN) membranes with angstrom pores, achieved through the strategic incorporation of multivalent ions. Based on the additional ions, the energy barrier of transmembrane transport for individual alkali metal ions could be effectively manipulated. Remarkably, the presence of LaCl3 substantially improves monovalent cation selectivity ratios, improving from 7 to 22 for K+/Li+ in mixtures. More importantly, under an initial concentration gradient, the transport rate of K+ was further enhanced over 1 kmol m−2 h−1, primarily attributed to the low ion transfer barrier. [ABSTRACT FROM AUTHOR]

Artificial membranes with ion‐selective nanochannels for high‐efficiency mono/divalent ion separation are of great significance in water desalination and lithium‐ion extraction, but they remain a great challenge due to the slight physicochemical property differences of various ions. Here, the successful synthesis of two‐dimensional TpEBr‐based covalent organic framework (COF) nanosheets, and the stacking of them as consecutive membranes for efficient mono/divalent ion separation is reported. The obtained COF nanosheet membranes with intrinsic one‐dimensional pores and abundant cationic sites display high permeation rates for monovalent cations (K+, Na+, Li+) of ≈0.1–0.3 mol m−2 h−1, while the value of divalent cations (Ca2+, Mg2+) is two orders of magnitude lower, resulting in an ultrahigh mono/divalent cation separation selectivity up to 130.4, superior to the state‐of‐the‐art ion sieving membranes. Molecular dynamics simulations further confirm that electrostatic interaction controls the confined transport of cations through the cationic COF nanopores, where multivalent cations face i) strong electrostatic repulsion and ii) steric transport hindrance since the large hydrated divalent cations are retarded due to a layer of strongly adsorbed chloride ions at the pore wall, while smaller monovalent cations can swiftly permeate through the nanopores. [ABSTRACT FROM AUTHOR]

Achieving precise selective separation of monovalent and divalent cations, as well as anions, is vital yet challenging in practical applications involving complex component treatments. Current membranes are typically effective for separating either cation pairs or anion pairs. To address this issue, a straightforward strategy for fabricating a nanofiltration (NF) membrane is developed that selectively permeates monovalent ions. This study focused on neutralizing the surface charge and tuning the pore size distribution of the polyamide membranes through a secondary interfacial polymerization using a zwitterionic copolymer consisting of 2‐methacryloyloxyethyl phosphorylcholine and 2‐aminoethyl methacrylate hydrochloride. The optimized NF membrane prepared in this study, with a near‐neutrally charged membrane surface and appropriate pore size distribution, demonstrates favorable performance in precisely separating monovalent and divalent ions, irrespective of the ion charge sign. The optimum NF membrane features high selectivity for both Cl−/SO42− (93) and Li+/Mg2+ (67) ion pairs, along with high water permeance of 8.5 L m−2 h−1 bar−1, making it competitive with many reported membranes. This study offers new insights into the ion‐selective mechanisms of polyamide membranes for monovalent/divalent ions and may guide the development of advanced membranes with single‐solute selectivity. [ABSTRACT FROM AUTHOR]

Earlier, we developed (Russ. J. Electrochem., 2018, vol. 54, p. 879) a new nonlocal electrostatic method for calculating an electric field distributions in systems containing spatially constrained regions filled with polar media with nonlocal dielectric properties. This method is used for nonlocal electrostatic analysis of the stabilization of a monovalent cation in a spherical cavity filled with water and surrounded by a local dielectric. For one- and three-mode models of the dielectric function, nonlocal electrostatic formulas are obtained for the field distribution inside such a cavity, if the ion is located at its center. The nonlocal electrostatic relations are derived for the change in the cation solvation energy ΔW during its transfer from solution to the center of such a cavity. It is shown that when the correlation length of water in the cavity decreased as compared with the solution (at the same values of the dielectric constant of water in the cavity and in the solution bulk), the amount of work required for the ion transfer from the solution into the cavity (−ΔW) decreased significantly as compared to that calculated by using the local theory used in the work of Roux, B. and MacKinnon, R. (Science, 1999, vol. 285, p. 100). [ABSTRACT FROM AUTHOR]

Advancing membranes with enhanced solute-solute selectivity is essential for expanding membrane technology applications, yet it presents a notable challenge. Drawing inspiration from the unparalleled selectivity of biological systems, which benefit from the sophisticated spatial organization of functionalities, we posit that manipulating the arrangement of the membrane's building blocks, an aspect previously given limited attention, can address this challenge. We demonstrate that optimizing the face-to-face orientation of building blocks during the assembly of covalent-organic-framework (COF) membranes improves ion-p interactions with multivalent ions. This optimization leads to extraordinary selectivity in differentiating between monovalent cations and anions from their multivalent counterparts, achieving selectivity factors of 214 for K+/Al3+ and 451 for NO3-/PO4 3-. Leveraging this attribute, the COF membrane facilitates the direct extraction of NaCl from seawater with a purity of 99.57%. These findings offer an alternative approach for designing highly selective membrane materials, offering promising prospects for advancing membrane-based technologies. [ABSTRACT FROM AUTHOR]

Membranes with precise Li+/Na+ and Li+/K+ separations are imperative for lithium extraction from brine to address the lithium supply shortage. However, achieving this goal remains a daunting challenge due to the similar valence, chemical properties, and subtle atomic‐scale distinctions among these monovalent cations. Herein, inspired by the strict size‐sieving effect of biological ion channels, a membrane is presented based on nonporous crystalline materials featuring structurally rigid, dimensionally confined, and long‐range ordered ion channels that exclusively permeate naked Li+ but block Na+ and K+. This naked‐Li+‐sieving behavior not only enables unprecedented Li+/Na+ and Li+/K+ selectivities up to 2707.4 and 5109.8, respectively, even surpassing the state‐of‐the‐art membranes by at least two orders of magnitude, but also demonstrates impressive Li+/Mg2+ and Li+/Ca2+ separation capabilities. Moreover, this bioinspired membrane has to be utilized for creating a one‐step lithium extraction strategy from natural brines rich in Na+, K+, and Mg2+ without utilizing chemicals or creating solid waste, and it simultaneously produces hydrogen. This research has proposed a new type of ion‐sieving membrane and also provides an envisioning of the design paradigm and development of advanced membranes, ion separation, and lithium extraction. [ABSTRACT FROM AUTHOR]

TRPM4 is a non-selective cation channel activated by intracellular Ca2+ but only permeable to monovalent cations, its activation regulates membrane potential and intracellular calcium. This channel participates in the migration and adhesion of non-excitable cells and forms an integral part of the focal adhesion complex. In neurons, TRPM4 expression starts before birth and its function at this stage is not clear, but it may function in processes such as neurite development. Here we investigate the role of TRPM4 in neuritogenesis. We found that neurons at DIV 0 express TRPM4, the inhibition of TRPM4 using 9-Ph reduces neurite number and slows the progression of neurite development, keeping neurons in stage 1. The genetic suppression of TRPM4 using an shRNA at later stages (DIV2) reduces neurite length. Conversely, at DIV 0, TRPM4 inhibition augments the Cch-induced Ca2 +i increase, altering the calcium homeostasis. Together, these results show that TRPM4 participates in progression of neurite development and suggest a critical role of the calcium modulation during this stage of neuronal development. [ABSTRACT FROM AUTHOR]

Sub‐nanoporous membranes with ion selective transport functions are important for energy utilization, environmental remediation, and fundamental bioinspired engineering. Although mono/multivalent ions can be separated by monovalent ion selective membranes (MISMs), the current theory fails to inspire rapid advances in MISMs. Here, we apply transition state theory (TST) by regulating the enthalpy barrier (ΔH) and entropy barrier (ΔS) for designing next‐generation monovalent cation exchange membranes (MCEMs) with great improvement in ion selective separation. Using a molecule‐absorbed porous material as an interlayer to construct a denser selective layer can achieve a greater absolute value of ΔS for Li+ and Mg2+ transport, greater ΔH for Mg2+ transport and lower ΔH for Li+ transport. This recorded performance with a Li+/Mg2+ perm‐selectivity of 25.50 and a Li+ flux of 1.86 mol ⋅ m−2 ⋅ h−1 surpasses the contemporary "upper bound" plot for Li+/Mg2+ separations. Most importantly, our synthesized MCEM also demonstrates excellent operational stability during the selective electrodialysis (S‐ED) processes for realizing scalability in practical applications. [ABSTRACT FROM AUTHOR]

Conventional alginate microcapsules are widely used for encapsulating therapeutic cells to reduce the host immune response. However, the exchange of monovalent cations with divalent cations for crosslinking can lead to a sol-gel phase transition, resulting in gradual degradation and swelling of the microcapsules in the body. To address this limitation, we present a biocompatible and nondegradable epigallocatechin-3-gallate (EGCG)-based microencapsulation with ethylamine-bridged EGCG dimers (EGCG(d)), denoted as 'Epi-Capsules'. These Epi-Capsules showed increased physical properties and Ca2+ chelating resistance compared to conventional alginate microcapsules. Horseradish peroxidase (HRP) treatment is very effective in increasing the stability of Epi-Capsule((+)HRP) due to the crosslinking between EGCG(d) molecules. Interestingly, the Epi-Capsules(oxi) using a pre-oxidized EGCG(d) can support long-term survival (>90 days) of xenotransplanted insulin-secreting islets in diabetic mice in vivo, which is attributed to its structural stability and reactive oxygen species (ROS) scavenging for lower fibrotic activity. Collectively, this EGCG-based microencapsulation can create Ca2+ chelating-resistance and anti-oxidant activity, which could be a promising strategy for cell therapies for diabetes and other diseases. Herein, a non-degradable microcapsule with pre-oxidized EGCG(d) is developed for the cell's functionality. This Epi-Capsule(oxi) shows Ca2+ chelating resistance, increased structural stability, and H 2 O 2 scavenging ability compared to alginate microcapsules. [Display omitted] • EGCG-based microencapsulation for successful cell transplantation • Ca2+ chelating-resistant Epi-Capsule(oxi) for improving degradation • H 2 O 2 scavenging effect of Epi-Capsule(oxi) • Enhanced structural stability of Epi-Capsule(oxi) • Long-term effect of Epi-Capsule(oxi) with lower degradation after implantation [ABSTRACT FROM AUTHOR]

Polymer cation exchange membranes (CEMs) are widely used in water treatment processes. The fundamental factors that control the separation and selectivity of cations with different valences in CEMs are not fully understood. In this study, we use atomistic molecular dynamics simulations to investigate the underlying molecular mechanisms that control the mobility of cations with different valences in Nafion membranes. Our results indicate structural differences in binding of monovalent and divalent cations, which gives rise to differences in ion diffusion in Nafion. Monovalent cations are shown to be "territorially" bound, i.e., bound while partially hydrated, to the fixed charge groups whereas divalent cations are shown to be "site" bound, i.e., bound while fully dehydrated, to the charge groups on the polymer. This difference in binding structure gives rise to differences in transport characteristics of cations in Nafion. [ABSTRACT FROM AUTHOR]

Biomolecular aggregates ensure the optimum concentration and proximity required for biochemical processes to take place. Synthetic aggregating systems are becoming increasingly essential to study/mimic dynamic condensates in nature. Herein the ratiometric DNA aggregation of self‐assembled DNA constructs using lanthanide salts is reported. In addition, the aggregation is shown to be reversed by the addition of specific lanthanide‐binding ligands. The aggregate formation is confirmed by dynamic light scattering experiment, electrophoretic mobility shift assay, and field emission scanning electron microscope. This programmed DNA aggregation and its reversion are applied to evaluating the lanthanide‐DNA and lanthanide‐ligand binding constants, respectively. To achieve this, Forster resonance energy transfer (FRET) pair dyes at the 3′ or 5′ end of the DNA strands are strategically placed that generate unique fluorescence patterns upon interaction with the DNA constructs and different triggers such as lanthanides/ligands/monovalent cations, thus enabling the tracking of various states of binding. It also demonstrates a “fast method” to form and stabilize G‐quadruplex (GQ) using lanthanides which complements the existing slow formation of GQs with Na+/K+ ions. The formation of GQ by lanthanides is corroborated by FRET, circular dichroism (CD), and enzyme linked immunosorbent assay (ELISA) experiments. These DNA constructs, formed by lanthanides, have shown resistance to cleavage by DNase I, and distinctive binding to Protoporphyrin dyes and Thioflavin T. [ABSTRACT FROM AUTHOR]

Membranes facilitate scalable and continuous lithium concentration from hypersaline salt lakes and battery leachates. Conventional nanofiltration (NF) membranes, however, exhibit poor monovalent selectivity in high‐salinity environments due to weakened exclusion mechanisms. This study examines polyamide NF membranes coated with polyelectrolytes enriched with ammonium groups to maintain high monovalent cation selectivity in hypersaline conditions. Over 8000 ion rejection measurements are recorded using salt lake brines and battery leachates. The experiments exemplify the coated membrane's ability to reduce magnesium concentrations to 0.14% from salt lakes and elevate lithium purity to 98% from battery leachates, in a single filtration stage. The membrane's selectivity is retained after 12 weeks in acidic conditions. Molecular dynamics analyses reveal that the ammonium groups create an electrostatic barrier at low pH, selectively hindering multivalent cation transport. This is corroborated by the Coulombic attraction between cations and carboxylate groups, along with a repulsive barrier from ammonium groups. Despite a 14.7% increase in specific energy, a two‐stage NF system using the coated membranes for lithium recovery significantly reduces permeate magnesium composition to 0.031% from Chilean salt lake brines. For NMC leachates, the coated membranes achieve permeate lithium purity exceeding 99.5%, yielding enhanced permeate quality with minor increases in energy demands. [ABSTRACT FROM AUTHOR]

The isotopic and elemental composition of the fossil shells of foraminifera are often used for reconstructing past environments and climates. These so-called proxy relations are based on the effect of environmental conditions (e.g. seawater temperature, pH) on the isotopic ratio (e.g. δ11 B or δ18 O) or partitioning of elements (commonly expressed as El/Ca or DEl ) during calcification. Whereas many studies focused on proxy-calibrations of divalent cations, incorporation of monovalent cations are less well constrained. Here we calibrate shell potassium content (K/Cacc) as a function of 1) seawater K+ concentration, 2) the ratio of potassium and calcium in seawater (K/Casw) and 3) temperature. Moreover, we analyze Na+ incorporation into the calcite as a function of seawater K+ and Ca2+ concentrations. First, we cultured specimens of the larger benthic foraminifer at four different seawater [Ca2+] and constant [K+], resulting in a range of K/Casw. Secondly, we cultured specimens of the same species at four different [Ca2+]sw and [K+]sw while keeping the ratio between these two ions constant. Finally, we tested the effect of temperature (from 18 to 28°C) on K-incorporation in this species. Measured K/Cacc values are not notably affected by [Ca2+]sw, while seawater [K+] positively influences potassium incorporation, resulting in a positive correlation between seawater K/Ca values and K/Cacc. Although the [Na+] in the culture media was constant throughout both experiments, incorporated Na responded positively to decreasing [Ca2+]sw, resulting in a positive correlation between sea water Na/Ca and Na/Cacc. The difference in the controls on K- and Na-incorporation suggests that the (biological) control on these ions differs. Part of the observed variability in element partitioning may be explained by differences in chemical speciation and crystallographic coordination in the calcite lattice. [ABSTRACT FROM AUTHOR]

Ionomeric polymer‐metal composites (IPMC) are advanced materials designed to mimic biological systems. Their performance depends on various factors, including electrical stimulus intensity, membrane hydration, ionic migration, and Young's modulus. However, there is a lack of studies in the literature investigating how the water absorption capacity and elastic modulus change over time in IPMCs. Understanding the hydration level variation as a function of time is essential because as this parameter deviates, the ionic migration capacity and Young's modulus also change, altering the device's electromechanical efficiency over time. To address this research gap, Nafion/Pt‐based IPMC devices exchanged with four monovalent cations (H+, Li+, Na+, and K+) and one ionic liquid (1‐butyl‐3‐methylimidazolium—BMIM+) were prepared, and a comprehensive investigation on how the water absorption capacity and Young's modulus vary as a function of time, relative humidity (RH), and counterion size was performed. The results revealed that the water uptake capacity is significantly higher and occurs more rapidly at higher RH levels and when the counterion's ionic radius decreases. Consequently, the time required for the device to reach osmotic equilibrium can range from 40 to 270 min, depending on the RH and counterion used. Furthermore, it was observed that the first natural frequency and Young's modulus also exhibit time‐dependent behavior. Under constant RH conditions, the mechanical properties of the IPMC can vary by up to 50% in less than 60 min. Notably, the combined results from water uptake capacity, Young's modulus, electrochemical impedance spectroscopy, and electromechanical response analyses (including blocking force, displacement, displacement rate, current, coulombic efficiency, and voltage) suggest that a morphological transformation within the polymer is likely to occur once RH exceeds 60%. This finding strengthens the hypothesis that ion migration is mainly influenced by their movement through Nafion's ionomeric channels rather than the filling of ionic agglomerates. [ABSTRACT FROM AUTHOR]

Aquaporin (AQP) channels found in all domains of life are transmembrane proteins which mediate passive transport of water, glycerol, signaling molecules, metabolites, and charged solutes. Discovery of new classes of ion-conducting AQP channels has been slow, likely reflecting time- and labor-intensive methods required for traditional electrophysiology. Work here defines a sensitive mass-throughput system for detecting AQP ion channels, identified by rescue of cell growth in the K+-transport-defective yeast strain CY162 following genetic complementation with heterologously expressed cation-permeable channels, using the well characterized human AQP1 channel for proof of concept. Results showed AQP1 conferred transmembrane permeability to cations which rescued survival in CY162 yeast. Comprehensive testing showed that growth response properties fully recapitulated AQP1 pharmacological agonist and antagonist profiles for activation, inhibition, dose-dependence, and structure--function relationships, demonstrating validity of the yeast screening tool for AQP channel identification and drug discovery efforts. This method also provided new information on divalent cation blockers of AQP1, pH sensitivity of antagonists, and ion permeability of human AQP6. Site-directed mutagenesis of AQP1 channel regulatory domains confirmed that yeast growth rescue was mediated by the introduced channels. Optical monitoring with a lithium-sensitive photoswitchable probe in living cells independently demonstrated monovalent cation permeability of AQP1 channels in yeast plasma membrane. Ion channel properties of AQP1 expressed in yeast were consistent with those of AQP1 expressed in Xenopus laevis oocyte and K+-transport defective Escherichia coli. Outcomes here establish a powerful new approach for efficient screening of phylogenetically diverse AQPs for yet untested functions as cation channels. [ABSTRACT FROM AUTHOR]

Polycystin-2 (PC2) is mutated in ~15% of patients with autosomal dominant polycystic kidney disease (ADPKD). PC2 belongs to the family of transient receptor potential (TRP) channels and can function as a homotetramer. We investigated whether three disease-associated mutations (F629S, C632R, or R638C) localized in the channel’s pore loop alter ion channel properties of human PC2 expressed in Xenopus laevis oocytes. Expression of wild-type (WT) PC2 typically resulted in small but measurable Na+ inward currents in the absence of extracellular divalent cations. These currents were no longer observed when individual pore mutations were introduced in WT PC2. Similarly, Na+ inward currents mediated by the F604P gain-of-function (GOF) PC2 construct (PC2 F604P) were abolished by each of the three pore mutations. In contrast, when the mutations were introduced in another GOF construct, PC2 L677A N681A, only C632R had a complete lossof-function effect, whereas significant residual Na+ inward currents were observed with F629S (~15%) and R638C (~30%). Importantly, the R638C mutation also abolished the Ca2+ permeability of PC2 L677A N681A and altered its monovalent cation selectivity. To elucidate the molecular mechanisms by which the R638C mutation affects channel function, molecular dynamics (MD) simulations were used in combination with functional experiments and site-directed mutagenesis. Our findings suggest that R638C stabilizes ionic interactions between Na+ ions and the selectivity filter residue D643. This probably explains the reduced monovalent cation conductance of the mutant channel. In summary, our data support the concept that altered ion channel properties of PC2 contribute to the pathogenesis of ADPKD. [ABSTRACT FROM AUTHOR]

Monovalent-cation homeostasis, crucial for all living cells, is ensured by the activity of various types of ion transport systems located either in the plasma membrane or in the membranes of organelles. A key prerequisite for the functioning of iontransporting proteins is their proper trafficking to the target membrane. The cornichon family of COPII cargo receptors is highly conserved in eukaryotic cells. By simultaneously binding their cargoes and a COPII-coat subunit, cornichons promote the incorporation of cargo proteins into the COPII vesicles and, consequently, the efficient trafficking of cargoes via the secretory pathway. In this review, we summarize current knowledge about cornichon proteins (CNIH/Erv14), with an emphasis on yeast and mammalian cornichons and their role in monovalent-cation homeostasis. Saccharomyces cerevisiae cornichon Erv14 serves as a cargo receptor of a large portion of plasma-membrane proteins, including several monovalent-cation transporters. By promoting the proper targeting of at least three housekeeping ion transport systems, Na+, K+/H+ antiporter Nha1, K+ importer Trk1 and K+ channel Tok1, Erv14 appears to play a complex role in the maintenance of alkali-metal-cation homeostasis. Despite their connection to serious human diseases, the repertoire of identified cargoes of mammalian cornichons is much more limited. The majority of current information is about the structure and functioning of CNIH2 and CNIH3 as auxiliary subunits of AMPAR multi-protein complexes. Based on their unique properties and easy genetic manipulation, we propose yeast cells to be a useful tool for uncovering a broader spectrum of human cornichons´ cargoes. [ABSTRACT FROM AUTHOR]

Lately, children's daily consumption of some products, such as cereals and candies, has been rising, which provides a compelling rationale for determining any metallic substances that may be present. Monitoring the concentration of certain metals, like nickel, in these products is necessary due to medical issues in humans when consumed regularly. So, in this work, a novel and highly selective carbon paste as a Ni(II) ion-selective sensor was prepared and investigated using ceramic magnesium aluminum spinel nanoparticles as the ionophore and tritolyl phosphate (TOCP) as a plasticizer. A modified co-precipitation method was used to synthesize the spinel nanoparticles. X-ray diffraction, scanning electron microscope with EDAX, transmission electron microscope, and BET surface area were used to determine the phase composition, microstructure, pores size, particle size, and surface area of the synthesized nanoparticles. The spinel nanoparticle was found to have a nano crystallite size with a cubic crystal system, a particle size ranging from 17.2 to 51.52 nm, mesoporous nature (average pore size = 8.72 nm), and a large surface area (61.75 m2/g). The composition ratio of graphite carbon as a base: TOCP as binder: spinal as ionophore was 67.3:30.0:2.7 (wt%) based on potentiometric detections over concentrations from 5.0 × 10−8 to 1.0 × 10−2 mol L−1 with LOD of 5.0 × 10−8 mol L−1. A measurement of 29.22 ± 0.12 mV decade−1 over pH 2.0–7.0 was made for the Nernstian slope. This sensor demonstrated good repeatability over nine weeks and a rapid response of 8 s. A good selectivity was shown for Ni(II) ions across many interferents, tri-, di-, and monovalent cations. The Ni(II) content in spiked real samples, including cocaine, sweets, coca, chocolate, carbonated drinks, cereals, and packages, were measured. The results obtained indicated no significant difference between the proposed potentiometric method and the officially reported ICP method according to the F- and t-test data. In addition to utilizing ANOVA statistical analysis, validation procedures have been implemented, and the results exceed the ICP-MS methodology. [ABSTRACT FROM AUTHOR]

Electrochemical decarboxylation of carboxylic acids is considered a sustainable method to improve the quality of pyrolysis oil. In this study, we assess the effect of monovalent alkali cations (of the acetates) on the performance of Pt electrodes in acid decarboxylation and the competing OER, using various electrochemical methods. We reveal a strong cation dependence generally following the trend Li+

The conformation of proteins is closely related to their biological functions, and it is affected by many factors, including the type of cations in solution. However, it is difficult to detect the conformational changes of a protein in situ. As a single-molecule sensing technology, nanopores can convert molecular structural information into analyzable current signals within a reasonable time range. Herein, we detect and analyze the effects of two different types of monovalent cations (Na+ and Li+) on a model protein bovine serum albumin (BSA) conformation using SiNx nanopores with different diameters. The quantitative analysis results show that the excluded volume of BSA in LiCl salt solutions is larger than the value in NaCl solution, indicating that Li+ is more prone to unfolding the proteins and making them unstable. This study demonstrated that nanopores enable the in situ detection of the structure of proteins at the single-molecule level and provide a new approach for the quantitative analysis of proteins. [ABSTRACT FROM AUTHOR]

The Xingluokeng deposit is the largest granite-related tungsten deposit within the Wuyi metallogenic belt in South China. The Xingluokeng intrusion primarily consists of porphyritic biotite granite, biotite granite, and fine-grained granite. The deposit is represented by veinlet-disseminated mineralization with K-feldspathization and biotitization, alongside quartz-vein mineralization with greisenization and sericitization. This study investigates in-situ analyses of quartz compositions from both the intrusion and hydrothermal veinlets and veins. Trace element correlations indicate that trivalent Al3+ and Fe3+ replace Si4+ within the quartz lattice, with monovalent cations (such as Li+, Na+, and K+) primarily serving as charge compensators. Low Ge/Al ratios (< 0.013) of quartz from granites suggest a magmatic origin. The low Al/Ti and Ge/Ti ratios, accompanied by high Ti contents in quartz, suggest that the porphyritic biotite granite and biotite granite are characterized by relatively low levels of differentiation and high crystallization temperatures. In contrast, the fine-grained granite exhibits a higher degree of fractionation, lower crystallization temperatures, and a closer association with tungsten mineralization. Ti contents in quartz from quartz veins indicate Qz-I formed at temperatures above 400 °C, while Qz-II to Qz-V formed at temperatures below 350 °C. Variations in different generations of quartz, as indicated by Al content and (Al + Fe)/(Li + Na + K) ratio, suggest that Qz-I precipitated from a less acidic fluid with a stable pH, whereas Qz-II to Qz-V originated from a more acidic fluid with notable pH variations. Consequently, alkaline alteration and acidic alteration supplied the essential Ca and Fe for the precipitation of scheelite and wolframite, respectively, highlighting a critical mechanism in tungsten mineralization at the Xingluokeng deposit. [ABSTRACT FROM AUTHOR]

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Negative temperature coefficient (NTC) materials are usually based on ceramic semiconductors, and electrons are involved in their transport mechanism. A new type of NTC material, adequate for alternating current (AC) applications, is represented by zeolites. Indeed, zeolites are single charge carrier ionic conductors with a temperature-dependent electrical conductivity. In particular, electrical transport in zeolites is due to the monovalent charge-balancing cations, like K+, capable of hopping between negatively charged sites in the aluminosilicate framework. Owing to the highly non-linear electrical behavior of the traditional electronic NTC materials, the possibility to have alternative types of materials, showing linearity in their electrical behavior, is very desirable. Among different zeolites, natural clinoptilolite has been selected for investigating NTC behavior since it is characterized by high zeolite content, a convenient Si/Al atomic ratio, good mechanical strength due to its compact microstructure, and low toxicity. Clinoptilolite has shown a rapid and quite reversible impedance change under heating, characterized by a linear dependence on temperature. X-ray diffraction (XRD) has been used to identify the natural zeolite, to establish all types of crystalline phases present in the mineral, and to investigate the thermal stability of these phases up to 150 °C. X-ray photoelectron spectroscopy (XPS) analysis was used for the chemical characterization of this natural clinoptilolite sample, providing important information on the cationic content and framework composition. In addition, since electrical transport takes place in the zeolite free-volume, a Brunauer–Emmett–Teller (BET) analysis of the mineral has also been performed. [ABSTRACT FROM AUTHOR]

Native potato starch is an excellent carrier of minerals due to its inherent ion exchange capacity. Mineral enrichment not only changes the nutritional value but also influences starch pasting and swelling properties. Hydrothermal treatments like annealing constitute a straightforward and green way to tune functional properties. Here, novel combinations of mineral enrichment and annealing were studied. Ion exchange was readily achieved by suspending starch in a salt solution at room temperature over 3 h and confirmed by ICP-OES. Annealing at 50 °C for 24 h using demineralized water or salt solutions strongly affected pasting, thermal, and swelling properties. The obtained XRD and DSC results support a more ordered structure with relative crystallinity increasing from initially 41.7% to 44.4% and gelatinization onset temperature increasing from 60.39 to 65.94 J/g. Solid-state NMR spectroscopy revealed no detectable changes after annealing. Total digestible starch content decreased after annealing from 8.89 to 7.86 g/100 g. During both ion exchange at room temperature and annealing, monovalent cations promoted swelling and peak viscosity, and divalent cations suppressed peak viscosity through ionic crosslinking. The presented combination allows fine-tuning of pasting behavior, potentially enabling requirements of respective food applications to be met while offering an alternative to chemically modified starches. [ABSTRACT FROM AUTHOR]

Lipopolysaccharides (LPSs) are negatively charged molecules covering the surface of Gram-negative bacteria (GNB). Adding divalent cations (DCs) is important to stabilize the LPS bilayer. Thus, DCs are always only considered as membrane stabilizing ions. Here, on the basis of a coarse-grained (CG) Martini force field, we conduct molecular dynamic (MD) simulations to study the divalent cation mediated LPS interaction and the stability of the LPS membrane in a wide range of DC concentrations. By measuring the LPS binding free energy and the LPS–LPS aggregate from the association course between two LPS molecules, we find that the initial addition of DCs may significantly facilitate the aggregation of LPSs into a compact structure, while sequentially adding more DCs only unpacks the LPS aggregate and drives the dissolution of LPSs. With an increasing concentration of DCs, we find a gradual replacement of DCs to monovalent cations as condensed counterions on the LPS, which follows a sign change from negative to positive in terms of the LPS effective charge and a switch of LPSs in solution from undergoing precipitation to resolubilization on adding DCs. This interaction change in the level of two LPSs accounts for the structure variation of the LPS assembly on a larger scale, where the LPS packing rigidity in the assembly bilayer is found with a similar nonmonotonic dependence with the DC concentration. Thus, our results demonstrate for the first time the presence of a re-entrant condensation behavior for LPS molecules, which can be exploited for developing novel membrane-perturbing agents based on multivalent ions as efficient GNB antibiotics. [ABSTRACT FROM AUTHOR]

We here extend the cluster‐plus‐glue‐atom model, originally developed for metallic glasses, to the interpretation of silicate glass compositions. By referring to β‐SiO2 crystal structure and to the widely recognized random network model, our model identifies a 16‐basic‐unit (or 32‐cation) composition formula {M1+2O}n–{M3+2O3}16−(m+n)–{M4+2O4}m, where monovalent unit {M1+2O} and quadrivalent unit {M4+2O4} cannot coexist and the trivalent units {M3+2O3} are constructed from pure trivalent cations such as {(Al,B)2O3} and from combinations of monovalent and divalent cations with the base quadrivalent Si such as {(Na,K)2/3Si4/3O3} and {(Mg,Ca)SiO3}. After analyzing some glasses of historical importance, it is pointed out that most of soda–lime–silica and aluminosilicate glasses satisfy closely {M3+2O3}16, as exemplified by ancient glasses as well as by modern ones, such as Container glass, 1980, Jena Standard Glass, and Corning Gorilla glasses of the first generation. On the other hand, borosilicate glasses feature extra {Si2O4} units ranging from 4 to 9.5 in their 16‐unit formulas, as exemplified by Corning E‐glass and Schott thermometer glass with {Si2O4}4 and Corning Pyrex with {Si2O4}9.5 containing the highest silica proportion. The number of monovalent cations in 32‐cation formulas follows linear dependences on the average cation valence e/c and on the 16‐unit parameters 2 m − 4n, showing that, except alkali‐free glasses, the compositions of soda–silicate glasses converge to 2N2 + N3 ≈ 8, where N2 and N3 are, respectively, the numbers of divalent and trivalent cations in the 32‐cation formula. The revelation of the composition rule shows the capacity of the cluster‐plus‐glue‐atom model in understanding the compositions of complex glassy systems. [ABSTRACT FROM AUTHOR]

Gerty T. and Carl F. Cori discovered, during research on the metabolism of sugars in organisms, the important role of the phosphate ester of a simple sugar. Glucose molecules are released from glycogen—the glucose stored in the liver—in the presence of phosphates and enter the blood as α-D-glucose-1-phosphate (Glc-1PH2). Currently, the crystal structure of three phosphates, Glc-1PNa2·3.5·H2O, Glc-1PK2·2H2O, and Glc-1PHK, is known. Research has shown that reactions of Glc-1PH2 with carbonates produce new complexes with ammonium ions [Glc-1P(NH4)2·3H2O] and mixed complexes: potassium–sodium and ammonium–sodium [Glc-1P(X)1.5Na0.5·4H2O; X = K or NH4]. The crystallization of dicationic complexes has been carried out in aqueous systems containing equimolar amounts of cations (1:1; X–Na). It was found that the first fractions of crystalline complexes always had cations in the ratio 3/2:1/2. The second batch of crystals obtained from the remaining mother liquid consisted either of the previously studied Na+, K+ or NH4+ complexes, or it was a new sodium hydrate—Glc-1PNa2·5·H2O. The isolated ammonium–potassium complex shows an isomorphic cation substitution and a completely unique composition: Glc-1PH(NH4)xK1−x (x = 0.67). The Glc-1P2− ligand has chelating fragments and/or bridging atoms, and complexes containing one type of cation show different modes of coordinating oxygen atoms with cations. However, in the case of the potassium–sodium and ammonium–sodium structures, high structural similarities are observed. The 1D and 2D NMR spectra showed that the conformation of Glc-1P2− is rigid in solution as in the solid state, where only rotations of the phosphate group around the C-O-P bonds are observed. [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]

Slc4a genes encode various types of transporters, including Na+-HCO3− cotransporters, Cl−/HCO3− exchangers, or Na+-driven Cl−/HCO3− exchangers. Previous research has revealed that Slc4a9 (Ae4) functions as a Cl−/HCO3− exchanger, which can be driven by either Na+ or K+, prompting investigation into whether other Slc4a members facilitate cation-dependent anion transport. In the present study, we show that either Na+ or K+ drive Cl−/HCO3− exchanger activity in cells overexpressing Slc4a8 or Slc4a10. Further characterization of cation-driven Cl−/HCO3− exchange demonstrated that Slc4a8 and Slc4a10 also mediate Cl− and HCO3−-dependent K+ transport. Full-atom molecular dynamics simulation on the recently solved structure of Slc4a8 supports the coordination of K+ at the Na+ binding site in S1. Sequence analysis shows that the critical residues coordinating monovalent cations are conserved among mouse Slc4a8 and Slc4a10 proteins. Together, our results suggest that Slc4a8 and Slc4a10 might transport K+ in the same direction as HCO3− ions in a similar fashion to that described for Na+ transport in the rat Slc4a8 structure. [ABSTRACT FROM AUTHOR]

In hyperglycemia, the serum sodium concentration ([Na]S) receives influences from (a) the fluid exit from the intracellular compartment and thirst, which cause [Na]S decreases; (b) osmotic diuresis with sums of the urinary sodium plus potassium concentration lower than the baseline euglycemic [Na]S, which results in a [Na]S increase; and (c), in some cases, gains or losses of fluid, sodium, and potassium through the gastrointestinal tract, the respiratory tract, and the skin. Hyperglycemic patients with hypernatremia have large deficits of body water and usually hypovolemia and develop severe clinical manifestations and significant mortality. To assist with the correction of both the severe dehydration and the hypovolemia, we developed formulas computing the fractional losses of the body water and monovalent cations in hyperglycemia. The formulas estimate varying losses between patients with the same serum glucose concentration ([Glu]S) and [Na]S but with different sums of monovalent cation concentrations in the lost fluids. Among subjects with the same [Glu]S and [Na]S, those with higher monovalent cation concentrations in the fluids lost have higher fractional losses of body water. The sum of the monovalent cation concentrations in the lost fluids should be considered when computing the volume and composition of the fluid replacement for hyperglycemic syndromes. [ABSTRACT FROM AUTHOR]

The first and committed step in proline synthesis from glutamate is catalyzed by δ1‐pyrroline‐5‐carboxylate synthetase (P5CS). Two P5CS genes have been found in most angiosperms, one constitutively expressed to satisfy proline demand for protein synthesis, the other stress‐induced. Despite the number of papers to investigate regulation at the transcriptional level, to date, the properties of the enzymes have been subjected to limited study. The isolation of Arabidopsis thaliana P5CS isoenzymes was achieved through heterologous expression and affinity purification. The two proteins were characterized with respect to kinetic and biochemical properties. AtP5CS2 showed KM values in the micro‐ to millimolar range, and its activity was inhibited by NADP+, ADP and proline, and by glutamine and arginine at high levels. Mg2+ ions were required for activity, which was further stimulated by K+ and other cations. AtP5CS1 displayed positive cooperativity with glutamate and was almost insensitive to inhibition by proline. In the presence of physiological, nonsaturating concentrations of glutamate, proline was slightly stimulatory, and glutamine strongly increased the catalytic rate. Data suggest that the activity of AtP5CS isoenzymes is differentially regulated by a complex array of factors including the concentrations of proline, glutamate, glutamine, monovalent cations and pyridine dinucleotides. Summary statement: In Arabidopsis thaliana, the two forms of the enzyme leading to proline synthesis, P5C synthetase, show different functional features and posttranslational regulation, suggesting activity modulation in vivo by an array of factors including related amino acids, cations and pyridine dinucleotides. [ABSTRACT FROM AUTHOR]

We investigated the structural changes in clay minerals after Cs adsorption and understood their low desorption efficiency using an ion-exchanger. We focused on the role of interlayers in Cs adsorption and desorption in 2:1 clay minerals, namely illite, hydrobiotite, and montmorillonite, using batch experiments and XRD and EXAFS analyses. The adsorption characteristics of the clay minerals were analyzed using cation exchange capacity (CEC), maximum adsorption isotherms (Qmax), and radiocesium interception potential (RIP) experiments. Although illite showed a low CEC value, it exhibited high selectivity for Cs with a relatively high RIP/CEC ratio. The Cs desorption efficiency after treatment with a NaCl ion exchanger was the highest for illite (74.3%), followed by hydrobiotite (45.5%) and montmorillonite (30.3%); thus, Cs adsorbed onto planar sites, rather than on interlayers or frayed edge sites (FESs), is easily desorbed. After NaCl treatment, XRD analysis showed that the low desorption efficiency was due to the collapse of the interlayer-fixed Cs, which tightly narrowed the interlayers' hydrobiotite due to the ion exchange of divalent cations (Mg2+ or Ca2+) into the monovalent cation (Na+). Moreover, EXAFS analysis showed that hydrobiotite formed inner-sphere structures after NaCl desorption, indicating that it was difficult to remove Cs from NaCl desorption due to the collapsed hydrobiotite and montmorillonite interlayers as well as the strong bonding in FESs of illite. In contrast, chelation desorption using oxalic acid effectively dissolved the narrowed interlayers of hydrobiotite (98%) and montmorillonite (85.26%), enhancing the desorption efficiency. Therefore, low desorption efficiency for Cs clays using an ion exchanger was caused by the collapsed interlayer due to the exchange between monovalent cation and divalent cation. [ABSTRACT FROM AUTHOR]

Considering growing efforts to understand and improve the solute-specific selectivity of nanofiltration (NF) membranes, we explored the ion-specific effects that govern the charge and performance of a loose polyamide NF membrane that is commonly used for solute-solute separations. Specifically, we systematically evaluated the zeta potential of the membrane under different conditions of pH, salinity, and ionic composition, and correlated the obtained data with membrane performance tested under similar conditions. Our results identify the pKa of both carboxylic and amine groups bonded to the membrane surface and suggest that the highly polarizable chloride anions in the solution adsorb to the polyamide, increasing its negative charge. We also show that monovalent cations of different "stickiness" can neutralize the negative membrane charge to different extents due to their varying tendency to sorb to the polymer matrix or screen the fixed carboxyl groups on the membrane surface. Notably, our correlation between zeta potential measurements and permeability experiments indicates the substantial contribution of solution ions to Donnan exclusion in NF membranes. [ABSTRACT FROM AUTHOR]

The electrochromic (EC) polymer poly (3,4‐(2,2‐dimethylpropylenedioxy)thiophene) (PProDOT‐Me2) is expected to be used in flexible e‐paper displays because of its great optical modulation ability and inherent flexibility. While the EC effect is primarily determined by the anions and cations in the electrolyte, yet suffers from inorganic salt based on monovalent Li+ cations and corresponding anions, such as lithium perchlorate(LiClO4), lithium bis(trifluoromethane sulfonyl) imide (LiTFSI), and lithium trifluoromethane sulfonate (LiTRIF), which may impact the overall EC performance of the EC device caused by insufficient ion doping/de‐doping processes. Herein, the divalent viologen cation‐based ionogel (VGE) is developed to tackle the challenge. Owing to its more anions design, the doping/de‐doping process in the PProDOT‐Me2 is more sufficient, thereby enhancing the optical modulation range (ΔR = 39.4%) of PProDOT‐Me2, compared to monovalent Li+ cation‐based ionogel (ΔR = 13.3%). Meanwhile, the VGE has good interface contact with PProDOT‐Me2 and the flexible electrode, which makes the VGE‐based EC device (V‐ECD) exhibit commendable mechanical stability. To demonstrate the potential application in flexible e‐paper displays, the simple eight‐digit EC display device is assembled from seven V‐ECDs, each of which hasa high switching speed, robust cycling stability, and low operating energy consumption. [ABSTRACT FROM AUTHOR]

Two coding variants of apolipoprotein L1 (APOL1), called G1 and G2, explain much of the excess risk of kidney disease in African Americans. While various cytotoxic phenotypes have been reported in experimental models, the proximal mechanism by which G1 and G2 cause kidney disease is poorly understood. Here, we leveraged 3 experimental models and a recently reported small molecule blocker of APOL1 protein, VX-147, to identify the upstream mechanism of G1-induced cytotoxicity. In HEK293 cells, we demonstrated that G1-mediated Na+ import/K+ efflux triggered activation of GPCR/IP3--mediated calcium release from the ER, impaired mitochondrial ATP production, and impaired translation, which were all reversed by VX-147. In human urine-derived podocyte-like epithelial cells (HUPECs), we demonstrated that G1 caused cytotoxicity that was again reversible by VX-147. Finally, in podocytes isolated from APOL1 G1 transgenic mice, we showed that IFN-γ--mediated induction of G1 caused K+ efflux, activation of GPCR/IP3 signaling, and inhibition of translation, podocyte injury, and proteinuria, all reversed by VX-147. Together, these results establish APOL1-mediated Na+/K+ transport as the proximal driver of APOL1- mediated kidney disease. [ABSTRACT FROM AUTHOR]

Different cell channels and transporters tightly regulate cytoplasmic levels and the intraorganelle distribution of cations. Perturbations in these processes lead to human diseases that are frequently associated with kidney impairment. The family of melastatin-related transient receptor potential (TRPM) channels, which has eight members in mammals (TRPM1–TRPM8), includes ion channels that are highly permeable to divalent cations, such as Ca2+, Mg2+ and Zn2+ (TRPM1, TRPM3, TRPM6 and TRPM7), non-selective cation channels (TRPM2 and TRPM8) and monovalent cation-selective channels (TRPM4 and TRPM5). Three family members contain an enzymatic protein moiety: TRPM6 and TRPM7 are fused to α-kinase domains, whereas TRPM2 is linked to an ADP-ribose-binding NUDT9 homology domain. TRPM channels also function as crucial cellular sensors involved in many physiological processes, including mineral homeostasis, blood pressure, cardiac rhythm and immunity, as well as photoreception, taste reception and thermoreception. TRPM channels are abundantly expressed in the kidney. Mutations in TRPM genes cause several inherited human diseases, and preclinical studies in animal models of human disease have highlighted TRPM channels as promising new therapeutic targets. Here, we provide an overview of this rapidly evolving research area and delineate the emerging role of TRPM channels in kidney pathophysiology. The family of melastatin-like transient receptor potential (TRPM) channels comprises eight multifunctional cation channels. Here, the authors examine the functional role of each TRPM channel, including insights from channelopathies, and discuss the implications for kidney homeostasis and pathology. Key points: Melastatin-like transient receptor potential (TRPM) channels are multifunctional cation channels with diverse biophysical and physiological characteristics. Eight family members have been defined (TRPM1–TRPM8). TRPM1 and TRPM3 are channels permeable to Ca2+ and Zn2+ regulated by neuroactive steroids that have crucial roles in ON-bipolar neurons of the retina, dorsal root ganglia neurons and other cells. TRPM6 and TRPM7 are bifunctional kinase-coupled channels that control cellular and body homeostasis of Zn2+, Mg2+ and Ca2+. TRPM4 and TRPM5 are Ca2+-activated monovalent cation channels that influence the excitability of neurons and cardiomyocytes, and control the chemosensory activity of taste receptor cells and tuft cells. TRPM2 and TRPM8 are non-selective cation channels. TRPM2 mediates ADP-ribose and reactive oxygen species signalling in neurons, immunocytes and kidney epithelial cells, whereas TRPM8 is a cold-sensing channel that regulates organismal thermal responses. Multiple TRPM channel types are expressed in the kidney, especially TRPM6 and TRPM7. Their physiological relevance awaits clarification, but they might have a role in renal cation homeostasis. [ABSTRACT FROM AUTHOR]

The results of previously published studies of the ion mobility, phase transitions, and electrophysical properties of tetrafluoroantimonates(iii) with heteroatomic cation sublattices composed of alkali metal and ammonium cations are analyzed, corrected, supplemented, and summarized. The influence of outer-sphere monovalent cations of different nature on the character of ion mobility, phase transitions, and conductivity in crystalline tetrafluoroantimonates(iii) is considered. It was found that phase transitions of most compounds in question are followed by the formation of superionic β-phases with a high conductivity of the order of 10−4–10−2 S cm−1 in the temperature range of 400–500 K. [ABSTRACT FROM AUTHOR]

Lawsonite is important as a carrier of H2O in subduction zones and as a petrological tracer. The trace-element content of lawsonite in mafic rocks has been used as a record of fluid–rock interactions but has received less attention in metamorphosed oceanic sediments. This study documents the major, and trace-element composition, together with 87Sr/86Sr isotopic ratios, of the different lawsonite types identified in the upper units of the Schistes Lustrés complex of the Western Alps, a paleo-accretionary prism of the Liguro-Piemont slow-spreading ocean subducted up to 40 km. The lawsonite-rich upper units of the Schistes Lustrés complex are principally composed of metamorphosed pelitic sediments and carbonates. Lawsonite content reaches 40 vol.% in the rock matrix and in veins. All lawsonite types originate from prograde metamorphic reactions which occurred up to peak metamorphism. Lawsonite compositions have been measured in situ with electron microscopy, microprobe, and laser-ablation mass spectrometry. Lawsonite separates have been measured for Sr content and 87Sr/86Sr isotopic ratios using TIMS. Bulk rock compositions have been measured with ICP-OES and ICP-MS. Analysis contamination by minute retrograde white mica inclusions in lawsonite crystals precluded using univalent cations for petrological interpretations. For other trace elements, the variability of lawsonite appears extremely high, with crystal compositions varying between samples and between crystals in individual samples. However, clear patterns emerge between lawsonite types, reflecting equilibrium and out-of-equilibrium processes unrelated to pressure–temperature conditions. At crystal scale, textural hourglass zoning predominates in lawsonite from the schist, while growth zoning is found in both schists and veins. The combination of both mechanisms results in spectacular zoning in Ti and in rare-earth element contents spanning four orders of magnitude. Over time, the La/Yb ratio decreases strongly (from ~100 to ~1), as La appears much more sensitive to surface effects leading to textural hourglass zoning. Interface-coupled dissolution–precipitation also contributes to decoupling of less mobile elements in the schist. This is best observed for Ti, but rare-earth element and chromium contents are affected too. These processes are considered to occur near closed-system conditions. Late lawsonite overgrowths with higher Sr contents are interpreted as reflecting system opening in the veins, yet sometimes observed in the schists. Strontium isotopic ratios measured on separated lawsonite crystals and on bulk rocks also show very large spreads. This indicates that the system did not equilibrate during blueschist-facies metamorphism, due to bulk rock heterogeneities during deposition and limited mineral reactivity at the local scale. Strontium isotopic ratios do not correlate with Sr content which rules out limestone devolatilization as the main driver of lawsonite overgrowths. In places, lawsonite is far more radiogenic than the host rocks, indicating either the destabilization of local Rb-rich phases (such as mica, illite, and smectite) or the infiltration of externally derived fluids. The overall compositional evolution of lawsonite records incremental system opening. However, lawsonite offers no evidence of large-scale mass transfer and external fluid influx in the Schistes Lustrés complex, even though the vein network is abundant and extends over time. [ABSTRACT FROM AUTHOR]

The sorption/desorption processes of the cationic herbicide paraquat (PQ) onto various clays, namely, kaolinite (KLN), illite (ILT), and montmorillonite (MNT), were investigated. After the attainment of sorption equilibrium, PQ was extracted from the clays by a double-stage desorption process utilizing an electro–ultrafiltration (EUF) procedure. The Freundlich isotherm model and a pseudo-first kinetic release model were found to adequately fit the sorption and desorption data, respectively. The experimental maximum sorbable amounts of paraquat were 5.56, 31.88, and 91.63 mg g−1 for KLN, ILT, and MNT, respectively, consistently with the order of magnitude of the cation-exchange capacity (CEC) of the clay minerals. The desorption experiments revealed that the amounts of PQ retained by the MNT samples were significantly larger than the respective amounts retained by KLN or ILT. The EUF-PQ desorption patterns of differently cation-saturated MNT samples indicated that the presence of monovalent cations could further hamper PQ release, while the opposite seemed to be true for divalent cations. Our results clearly show that a substantial aliquot of PQ is strongly retained by montmorillonite, probably via interlayering, thus suggesting that smectitic clays could act as a stable soil sink for cationic herbicides such as paraquat, favoring soil long-term contamination. [ABSTRACT FROM AUTHOR]

Dynamic fluctuations in the hydrogen-bond network of water occur from femto- to nanosecond timescales and provide insight into the structural/dynamical aspects of water at ion–water interfaces. Employing terahertz spectroscopy assisted with molecular dynamics simulations, we study aqueous chloride solutions of five monovalent cations, namely, Li, Na, K, Rb, and Cs. We show that ions modify the behavior of the surrounding water molecules and form interfacial layers of water around them with physical properties distinct from those of bulk water. Small cations with high charge densities influence the kinetics of water well beyond the first solvation shell. At terahertz frequencies, we observe an emergence of fast relaxation processes of water with their magnitude following the ionic order Cs > Rb > K > Na > Li, revealing an enhanced population density of weakly coordinated water at the ion–water interface. The results shed light on the structure breaking tendency of monovalent cations and provide insight into the properties of ionic solutions at the molecular level. [ABSTRACT FROM AUTHOR]

Prussian blue analogs (PBAs) are an important material class for aqueous electrochemical separations and energy storage owing to their ability to reversibly intercalate monovalent cations. However, incorporating interstitial H 2 O molecules in the ab initio study of PBAs is technically challenging, though essential to understanding the interactions between interstitial water, interstitial cations, and the framework lattice that affect intercalation potential and cation intercalation selectivity. Accordingly, we introduce and use a method that combines the efficiency of machine-learning models with the accuracy of ab initio calculations to elucidate mechanisms of (1) lattice expansion upon intercalation of cations of different sizes, (2) selectivity bias toward intercalating hydrophobic cations of large size, and (3) semiconductor–conductor transitions from anhydrous to hydrated lattices. We analyze the PBA nickel hexacyanoferrate [ NiFe (CN) 6 ] due to its structural stability and electrochemical activity in aqueous electrolytes. Here, grand potential analysis is used to determine the equilibrium degree of hydration for a given intercalated cation (Na + , K + , or Cs +) and NiFe (CN) 6 oxidation state based on pressure-equilibrated structures determined with the aid of machine learning and simulated annealing. The results imply new directions for the rational design of future cation-intercalation electrode materials that optimize performance in various electrochemical applications, and they demonstrate the importance of choosing an appropriate calculation framework to predict the properties of PBA lattices accurately. [ABSTRACT FROM AUTHOR]

Thermodynamically metastable glasses that can contain metastable species are important functional materials. X-ray absorption near-edge structure (XANES) spectroscopy is an effective technique for determining the valence states of cations, especially for the doping element in phosphors. Herein, we first confirm the valence change of silver cations from monovalent to trivalent in aluminophosphate glasses by X-ray irradiation using a combination of Ag L3-edge XANES, electron spin resonance, and simulated XANES spectra based on first-principles calculations. The absorption edge of the experimental and simulated XANES spectra demonstrate the spectral features of Ag(III), confirming that AgO exists as Ag(I)Ag(III)O2. A part of Ag(I) changes to Ag(III) by X-ray irradiation, and the generation of Ag(III) is saturated after high irradiation doses, in good agreement with conventional radiophotoluminescence (RPL) behaviour. The structural modelling based on a combination of quantum beam analysis suggests that the local coordination of Ag cations is similar to that of Ag(III), which is confirmed by density functional theory calculations. This demonstration of Ag(III) in glass overturns the conventional understanding of the RPL mechanism of silver cations, redefining the science of silver-related materials. [ABSTRACT FROM AUTHOR]

In the northern Patagonian region of Argentina, some of the largest bentonite deposits exist. Four bentonite samples (B1, B2, B3, and B4) from two deposits were thoroughly characterised and evaluated as potential adsorbents of anthocyanins extracted from red cabbage. Anthocyanins (ACys) are natural colourants obtained from fruits and plants and have shown excellent antioxidant properties that have promising applications in health. The adsorption of ACys onto bentonites enhances their stability relative to that observed in aqueous solutions. Material characterisation showed that three of the samples are soFdium bentonites (Na-bentonites: B2, B3, and B4), while the fourth exhibits a large quantity of magnesium and calcium in its interlayer, classifying it as a Mg-Ca-Na-bentonite (B1). Na-bentonites demonstrated higher ACy adsorption capacities, occurring through cation exchange, while Mg-Ca-Na-bentonite adsorption occurs by another type of interaction and a cooperative adsorption mechanism, resulting in the lowest ACy adsorption. The highest adsorption capacity was noted for B3, characterised by the highest smectite content, cation exchange capacity, and proportion of monovalent cations in its interlayer. Under the conditions studied, sodium smectites proved to be capable of retaining red cabbage ACys, thereby introducing a novel avenue for potential applications of regional materials with potential implications for health-related uses. [ABSTRACT FROM AUTHOR]

Aqueous batteries with high safety and cost efficiency usually employ metallic cations as charge carriers. Recently, ammonium (NH4+) ion batteries using the nonmetal NH4+ as a charge carrier exhibit distinct electrochemical features from conventional aqueous batteries. Herein, the electrochemical performances of a bimetallic hydroxide material are systematically studied with different charge carriers in the electrolytes, including NH4+, as well as the conventional monovalent metallic cations K+ and Na+, respectively. Electrochemical results indicate that the charge storage process using NH4+ as the working ions exhibits a higher discharge plateau, smaller electrochemical polarization, and larger discharge capacity than that using conventional metallic charge carriers. Experimental characterizations and theoretical calculations suggest that the strong interaction between NH4+ and the electrode material, as well as the low NH4+‐ion diffusion barrier lead to these superior electrochemical features. The assembled NH4+‐ion battery exhibits a good energy density of 123 Wh kg(cathode+anode)−1 at the power density of 480 W kg(cathode+anode)−1. These fundamental findings are important for developing good safety, low‐cost, and high‐energy aqueous batteries with sustainable NH4+ charge carriers. [ABSTRACT FROM AUTHOR]

Data on the structure of G-quadruplexes, noncanonical nucleic acid forms, supporting an idea of their potential participation in regulation of gene expression in response to the change in intracellular Na+i/K+i ratio are considered in the review. Structural variety of G-quadruplexes, role of monovalent cations in formation of this structure, and thermodynamic stability of G-quadruplexes are described. Data on the methods of their identification in the cells and biological functions of these structures are presented. Analysis of information about specific interactions of G-quadruplexes with some proteins was conducted, and their potential participation in the development of some pathological conditions, in particular, cancer and neurodegenerative diseases, is considered. Special attention is given to the plausible role of G-quadruplexes as sensors of intracellular Na+i/K+i ratio, because alteration of this parameter affects folding of G-quadruplexes changing their stability and, thereby, organization of the regulatory elements of nucleic acids. The data presented in the conclusion section demonstrate significant change in the expression of some early response genes under certain physiological conditions of cells and tissues depending on the intracellular Na+i/K+i ratio. [ABSTRACT FROM AUTHOR]

Aminocarboxylic acid (monoamine-based) chelating agents such as GLDA, MGDA, NTA, and EDG are widely used in a variety of products and processes. In the European Union, based on the Green Deal and the Chemicals Strategy for Sustainability (CSS), there is an increasing tendency to speed up chemical hazard evaluation and to regulate chemicals by grouping substances based on molecular structure similarity. Recently, it was proposed to group polycarboxylic acid monoamines, hydroxy derivatives and their salts with monovalent cations, and to consider all group members as potential carcinogens based on the official CLP classification of one group member, viz. NTA, which is classified as suspected carcinogen Cat. 2. In this review, we show that a grouping approach for harmonized classification and labeling based on molecular structure alone, disregarding existing animal test data as well as current scientific and regulatory knowledge, would result in incorrect classification. Using such a simplistic, although considered pragmatic approach, classification of all group members upfront would not improve protection of human health. Instead, it could not only lead to unnecessary additional vertebrate animal testing but also to onerous and disproportionate restrictions being placed on the use of these valuable substances; some of these even being considered as green chemicals. [ABSTRACT FROM AUTHOR]

The cyclic nucleotide cyclic guanosine monophosphate (cGMP) is a powerful cell signaling molecule involved in biotic and abiotic stress perception and signal transduction. In the model plant Arabidopsis thaliana, salt and osmotic stress rapidly induce increase in cGMP which plays role by modulating the activity of monovalent cation transporters, possibly by direct binding to these proteins and by altering the expression of many abiotic stress responsive genes. In a recent study, a membrane permeable analogue of cGMP (8-bromo-cGMP) was found to have a promotive effect on soluble sugar, flavonoids and lignin content, and membrane integrity in Solanum lycopersicum seedlings under salt stress. However, it remains to be elucidated how salt stress affects the endogenous cGMP level in S. lycopersicum and if Br-cGMP-induced improvement in salt tolerance in S. lycopersicum involves altered cation fluxes. The current study was conducted to answer these questions. A rapid increase (within 30 s) in endogenous cGMP level was determined in S. lycopersicum roots after treatment with 100 mM NaCl. Addition of membrane permeable Br-cGMP in growth medium remarkably ameliorated the inhibitory effects of NaCl on seedlings' growth parameters, chlorophyll content and net photosynthesis rate. In salt stressed plants, Br-cGMP significantly decreased Na+ content by reducing its influx and increasing efflux while it improved plants K+ content by reducing its efflux and enhancing influx. Furthermore, supplementation with Br-cGMP improved plant's proline content and total antioxidant capacity, resulting in markedly decreased electrolyte leakage under salt stress. Br-cGMP increased the expression of Na+/H+ antiporter genes in roots and shoots of S. lycopersicum growing under salt stress, potentially enhancing plant's ability to sequester Na+ into the vacuole. The findings of this study provide insights into the mechanism of cGMP-induced salt stress tolerance in S. lycopersicum. [ABSTRACT FROM AUTHOR]