Search Results (313)

Recent research on the design and synthesis of new and upgraded materials for secondary batteries is growing to fulfill future energy demands around the globe. Herein, by using DFT calculations, the thermodynamic and electrochemical properties of Na/Na⁺@C₁₂ complexes and then halogens (X⁻ = Br⁻, Cl⁻, and F⁻) as counter anions are studied for the enhancement of Na-ion battery cell voltage and overall performance. Isolated C₁₂ nanorings showed a lower cell voltage (−1.32 V), which was significantly increased after adsorption with halide anions as counter anions. Adsorption of halides increased the Gibbs free energy, which in turn resulted in higher cell voltage. Cell voltage increased with the increasing electronegativity of the halide anion. The Gibbs free energy of Br⁻@C₁₂ was −52.36 kcal·mol⁻¹, corresponding to a desirable cell voltage of 2.27 V, making it suitable for use as an anode in sodium-ion batteries. The estimated cell voltage of these considered complexes ensures the effective use of these complexes in sodium-ion secondary batteries. Full article

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

In polymer-based lithium batteries, polymer electrolytes (PEs) exhibit limited ionic conductivity at room temperature (25 °C). To address this issue, this paper describes a hexagonal-structure-based single-ion conducting gel polymer electrolyte (h-SICGPE) framework with a robust and efficient cross-linked polymer network, applicable to polymer-based batteries even at 25 °C. The proposed cross-linked polymer network backbone of the h-SICGPE, as a semisolid-state thin film type, has the homogeneous honeycomb structure incorporating anion receptor(s) inside each of its hexagonal closed cells and is obtained by cross-linking between trimethylolpropane tris(3-mercaptopropionate) and poly(ethylene glycol) diacrylate in a newly synthesized anion–receptor solution. The excellent structural capability of the h-SICGPE incorporating Li⁺/TFSI⁻ can enhance ionic conductivity and electrochemical stability by suppressing crystallinity and expanding free volume. Further, the anion receptor in its free volume helps to effectively increase the lithium-ion transference number by immobilizing counter-anions. Experimental results demonstrate dramatically superior performance at 25 °C, such as ionic conductivity (2.46 mS cm⁻¹), oxidative stability (4.9 V vs. Li/Li⁺), coulombic efficiency (97.65%), and capacity retention (88.3%). These results confirm the developed h-SICGPE as a promising polymer electrolyte for high-performance polymer-based lithium batteries operable at 25 °C. Full article

Polyamide membranes, such as nanofiltration (NF) membranes, are widely used for water purification. However, the mechanisms of solute transport and solute rejection due to solute charge interactions with the membrane remain unclear at the molecular level. Here, we use molecular dynamics simulations to examine the transport of single-solute feeds through charged nanofiltration membranes with different membrane charge concentrations of ${\mathrm{COO}}^{-}$ and NH${}_2^{+}$ resulting from the deprotonation or protonation of polymeric end groups according to the pH level that the membrane experiences. The results show that ${\mathrm{Na}}^{+}$ and ${\mathrm{Cl}}^{-}$ solute ions are better rejected when the membrane has a higher concentration of negatively charged groups, corresponding to a higher pH, whereas ${\mathrm{CaCl}}_2$ is well rejected at all pH levels studied. These results are consistent with those of experiments performed at the same pH conditions as the simulation setup. Moreover, solute transport behavior depends on the membrane functional group distribution. When ${\mathrm{COO}}^{-}$ functional groups are concentrated at membrane feed surface, ion permeation into the membrane is reduced. Counter-ions tend to associate with charged functional groups while co-ions seem to pass by the charged groups more easily. In addition, steric effects play a role when ions of opposite charge cluster in pores of the membrane. This study reveals solute transport and rejection mechanisms related to membrane charge and provides insights into how membranes might be designed to achieve specific desired solute rejection. Full article

Background/Objectives: In diabetic ketoacidosis (DKA), absolute insulin deficiency and elevation of counter-regulatory hormones may cause osmotic diuresis and water and electrolyte loss, which may lead to dehydration and renal failure. Fluids with high Na content are preferred in the DKA fluid therapy algorithm due to the association of Na with β-Hydroxybutyrate (β-HB) and the renal excretion of Na-β-HB. However, these fluids may cause hyperchloremic metabolic acidosis due to their high chloride concentration. In the literature, base-excess chloride (BE_Cl) has been suggested as a better approach for assessing the effect of chloride on acid–base status. Our aim in this study was to investigate the effect of fluids with BE_Cl values less than zero versus those with values equal to or greater than zero on the metabolic acid–base status in the first 6 h of DKA. Methods: This retrospective study included DKA cases managed in the tertiary intensive care units of five hospitals in the last 10 years. Patients were divided into two groups according to the Na-Cl difference of the administered fluids during the first 6 h of treatment: Group I [GI, fluids with Na-Cl difference = 0, chloride-rich group] and Group II [GII, fluids with Na-Cl difference > 32 mmol, chloride non-rich group]. Demographic data, blood gas analysis results, types and amounts of administered fluids, urea–creatinine values, and urine ketone levels were recorded. Results: Thirty-five patients with DKA in the ICU were included in the study (GI; 22 patients, GII; 13 patients). There was no difference between the patients in the two groups in terms of age, gender, and LOS-ICU. According to the distribution of the administered fluids, the main fluid administered in GI was 0.9% NaCl, whereas in the GII, it was bicarbonate, Isolyte-S, and 0.9% NaCl. In GI, the chloride load administered was higher; the BE_Cl level of the fluids was lower than in GII. At the end of the first 6 h, although sodium and strong ion gap values were similar, patients in GI were more acidotic due to iatrogenic hyperchloremia and, as a result, were more hypocapnic than GII. Conclusions: In conclusion, administering chloride-rich fluids in DKA may help reduce unmeasured anion acidosis. Still, risks cause iatrogenic hyperchloremic acidosis, which can hinder the expected resolution of acidosis and increase respiratory workload. Therefore, it is suggested that DKA guidelines be revised to recommend an individualized approach that avoids chloride-rich fluids and includes monitoring of metabolic parameters like Cl and BE_Cl. Full article

Background: This study aimed to explore the therapeutic potential of a dietary regimen of banaba leaf extract (BNB), policosanol (PCO, Raydel^®), and their combination (BNB+PCO), to mitigate high cholesterol (HC) and high galactose (HG) diet-induced dyslipidemia, hyperglycemia, oxidative stress, senescence, and organ damage in zebrafish (Danio rerio). Methodology: Zebrafish (n = 28/group) were fed with HC (4% w/w)+HG (30% w/w) or HC+HG supplemented either with BNB (0.1% w/w) or PCO (0.1% w/w) or BNB+PCO (0.1% w/w each). Following 6 weeks of dietary intervention, biochemical and histopathological examinations across the groups were performed. Results: Post 6 weeks of consumption, the BNB+PCO group exhibited a significant 40% decrease in body weight (BW) relative to the BW of the HC+HG group, while the BNB or PCO groups displayed nonsignificant changes in BW. Both BNB and PCO reduced HC+HG-induced dyslipidemia and hyperglycemia; however, co-administration (BNB+PCO) demonstrated a significantly greater therapeutic effect in countering these conditions compared to either BNB or PCO alone. A similar effect of the BNB+PCO combination was observed on the elevation of plasma sulfhydryl content, paraoxonase (PON), and ferric ion reduction activity (FRA), with notably ~1.2-times (p < 0.01) higher levels compared to their corresponding values observed in the BNB or PCO groups. Significantly diminished plasma AST, ALT, hepatic interleukin 6 (IL-6) levels, and fatty liver changes were observed in response to BNB+PCO, compared to either BNB or PCO alone. Also, BNB+PCO displayed a higher curative effect against HC+HG-induced impairment of tissue regeneration than BNB or PCO alone. A notable effect of BNB+PCO was perceived in protecting kidneys, testis, and ovary damage. Consistently, BNB+PCO showed a profound impact on mitigating HC+HG elevated reactive oxygen species (ROS) generation, apoptosis, cellular senescence, and accumulation of brain-binding lipid proteins (BLBPs) and 4-hydroxynoneal (4-HNE) in the brain. Conclusions: The findings highlight the synergistic effects of the BNB and PCO combination to mitigate the adversity posed by the consumption of the HC+HG diet. Full article

To date, the nitrogen metabolism pathways and salt-tolerance mechanisms of halophilic denitrifying bacteria have not been fully studied, and full-scale engineering trials with saline fly ash-washing wastewater have not been reported. In this study, we isolated and screened a halophilic denitrifying bacterium (Marinobacter sp.), GH-1, analyzed its nitrogen metabolism pathways and salt-tolerance mechanisms using whole-genome data, and explored its nitrogen removal characteristics under both aerobic and anaerobic conditions at different salinity levels. GH-1 was then applied in a full-scale engineering project to treat saline fly ash-washing leachate. The main results were as follows: (1) Based on the integration of whole-genome data, it is preliminarily hypothesized that the strain possesses complete nitrogen metabolism pathways, including denitrification, a dissimilatory nitrate reduction to ammonium (DNRA), and ammonium assimilation, as well as the following three synergistic strategies through which to counter hyperosmotic stress: inorganic ion homeostasis, organic osmolyte accumulation, and structural adaptations. (2) The strain demonstrated effective nitrogen removal under aerobic, anaerobic, and saline conditions (3–9%). (3) When applied in a full-scale engineering system treating saline fly ash-washing wastewater, it improved nitrate nitrogen (NO₃⁻-N), total nitrogen (TN), and chemical oxygen demand (COD) removal efficiencies by 31.92%, 25.19%, and 31.8%, respectively. The proportion of Marinobacter sp. increased from 0.73% to 3.41% (aerobic stage) and 2.86% (anoxic stage). Overall, halophilic denitrifying bacterium GH-1 can significantly enhance the nitrogen removal efficiency of saline wastewater systems, providing crucial guidance for biological nitrogen removal treatment. Full article

Mechanogated (MG) ion channels play a crucial role in mechano-transduction and immune cell regulation, yet their impact on blood cancers, particularly acute lymphoblastic leukemia (ALL), remains poorly understood. This study investigates the pharmacological effects of GsMTx4, an MG channel inhibitor, in human ALL cells both in vitro and in vivo. Unexpectedly, we found that GsMTx4 remarkably increased basal calcium (Ca²⁺) levels in ALL cells through constitutive Ca²⁺ entry and enhanced store-operated Ca²⁺ influx upon thapsigargin stimulation. This increase in basal Ca²⁺ signaling promoted ALL cell viability and proliferation in vitro. Notably, chelating intracellular Ca²⁺ with BAPTA-AM reduces GsMTx4-mediated leukemia cell viability and proliferation. However, in vivo, GsMTx4 decreases cytosolic Ca²⁺ levels in Nalm-6 GFP⁺ cells isolated from mouse blood, effectively countering leukemia progression and significantly extending survival in NSG mice transplanted with leukemia cells (median survival: GsMTx4 vs. control, 37.5 days vs. 29 days, p = 0.0414). Our results highlight the different properties of GsMTx4 activity in in vitro and in vivo models. They also emphasize that Ca²⁺ signaling is a key vulnerability in leukemia, where its precise modulation dictates disease progression. Thus, targeting Ca²⁺ channels could offer a novel therapeutic strategy for leukemia by exploiting Ca²⁺ homeostasis. Full article

In recent years, bipolar organic electrode materials have gained recognition as competitive alternatives to inorganic materials due to their unique multielectron redox mechanism for energy storage. In this study, we examined the mechanism of redox reactions in naphthalimide (NI) derivatives when used as electrodes in lithium half-cells with ionic liquid electrolytes. The NI derivatives consist of three building fragments: an aromatic naphthalene core, N-alkylated imide unit, and a peri-dichalcogenide bridge. The integration of electrochemical and microscopic methods with DFT calculations facilitates the delineation of the role of each fragment in the oxidation and reduction reactions of NI derivatives. It is found that the peri-dichalcogenide bridge is mainly involved in the oxidation of NI derivatives above 3.9 V, the charge compensation being achieved by electrolyte TFSI⁻ counter-ions. The reduction of NI derivatives with two Li⁺ ions is mainly due to the participation of the chalcogenide bridge, while after interaction with the next two Li⁺ ions, the imide fragment and the naphthalene moiety contribute equally to the reduction. Based on the leading role of the peri-dichalcogenide bridge, the redox properties of NI derivatives are effectively controlled by the gradual replacement of S with Se and Te atoms in the bridge. To improve the electronic conductivity of NIs, composites with rGO are also synthesized by a simple procedure of mechanical mixing in a centrifugal mixer. The composites rGO/NIs display a good storage performance, the best being the Se-containing analogue. Full article

The high treatment costs associated with wastewater and waste solutions produced by the anodic oxidation polishing section significantly limit industry development. To address this challenge, the present study investigates the characteristics of polishing wastewater and waste solutions, employing extraction and ion exchange combined with diffusion dialysis to recover effective acids. For waste tank solutions, single and dual solvent extraction experiments were conducted to determine the optimal extraction system. Electrostatic potential and interaction region indicator (IRI) analyses were performed to provide theoretical justification. Regarding cleaning wastewater, resin adsorption was applied to selectively remove aluminium ions from waste acid solutions, facilitating effective acid recovery. Static and dynamic adsorption–desorption experiments were initially performed to identify suitable resins. Subsequently, optimised parameters—including adsorption and desorption concentrations, volumes, and flow rates—were systematically established through conditional experiments, and diffusion dialysis was applied to recover acids from the desorbed solutions. The experimental results indicate that tributyl phosphate (TBP) emerged as the optimal single extractant, achieving an effective acid extraction rate of 88.67% under a solvent ratio of 4:1 at a room temperature of 28 °C. A binary solvent system, composed of TBP with 20% sulfonated kerosene, demonstrated superior engineering feasibility due to its reduced viscosity and satisfactory extraction rate of 82.19%. Moreover, adsorption–desorption tests confirmed that the resin-based method effectively recovered acids from cleaning wastewater. Specifically, under optimal operational conditions—downstream adsorption at 0.3–0.5 bed volumes (BV) and 1.0 BV/h, coupled with counter-current desorption at 2 BV and 2.4 BV/h—the acid recovery rate reached ≥95% while removing ≥90% of aluminium ions. Additionally, employing 20% sulfuric acid solution for desorption in diffusion dialysis enabled cyclic desorption. Consequently, this study successfully achieved acid reuse and substantially lowered wastewater treatment costs, representing a promising advancement for anodic oxidation polishing processes. Full article

¹³⁷Cs is a persistent β/γ-emitter (t_1/2 = 30.1 years) generated from ²³⁵U and ²³⁹Pu fission. It is a critical challenge to efficiently capture ¹³⁷Cs⁺ for nuclear waste management due to its high solubility, environmental mobility, and propensity for biological accumulation. Herein, we prepare a two-dimensional (2D) thiotitanate Rb_0.32TiS₂·0.75H₂O (denoted Rb-TiS₂) using a special molten salt synthesis method, “Mg + RbCl”. Rb-TiS₂ can selectively capture Cs⁺ from aqueous solutions. Its structure features a flexible anionic thiotitanate layer with Rb⁺ as counter ions located at the interlayer spaces. As an ion exchanger, it possesses high adsorption capacity (q_m^Cs = 232.70 mg·g⁻¹), rapid kinetics (the removal rate R > 72% within 10 min), and a wide pH tolerance range (pH = 4–12) for Cs⁺ adsorption. Through a single-crystal X-ray structural analysis, we elucidated the mechanism of Cs⁺ capture, revealing the ion exchange pathways between Cs⁺ and Rb⁺ in Rb-TiS₂. This work not only provides an important reference for the synthesis of transition metal sulfides with alkali metal cations but also proves the application prospect of transition metal sulfides in radionuclide remediation. Full article

This study aims to investigate the effects of different fluoride salts added in the PEO bath on the corrosion resistance and morphology of AZ31 magnesium alloy coatings. The PEO process was performed using a bipolar cycle with varying durations (4 and 30 min) in baths containing different fluoride salts (NaF, LiF, Na₂SiF₆) and a reference bath without fluoride. The coatings were characterised using SEM-EDS, XRD, and electrochemical impedance spectroscopy (EIS) to assess their morphology, chemical composition, and corrosion resistance. The results indicate that the presence of fluorides significantly influences the coating properties. NaF and Na₂SiF₆ coatings exhibited better corrosion resistance and more compact microstructures compared to LiF and the fluoride-free reference. The study highlights the importance of the fluoride counter ion in the PEO bath, demonstrating that NaF and Na₂SiF₆ provide superior protection against corrosion, making them suitable for biomedical applications where both porosity and corrosion resistance are critical. Full article

In this study, an in situ electrochemical modulation method based on an ultramicro interdigitated array electrode (UIAE) sensor chip was developed for the detection of ammonia nitrogen (NH₃-N) in neutral aqueous solutions. One comb of the UIAE was used as the working electrode for both the modulating and sensing functions, while the other comb was used as the counter electrode. Utilizing its enhanced mass transfer and proximity effects, the feasibility of in situ modulation of the solution environment near the UIAE chip to generate an electrochemical response for NH₃-N was investigated using electrochemical methods. The proposed method enhances the concentration of hydroxide ions and active chloride in the local solution near the sensor chip. These reactive species play a key role in improving the sensor’s electrocatalytic oxidation capability toward ammonia nitrogen, facilitating the sensitive detection of ammonia nitrogen in neutral environments. A linear relationship was displayed, ranging from 0.15–2.0 mg/L (as nitrogen) with a sensitivity of 3.7936 µA·L·mg⁻¹ (0.0664 µA µM⁻¹ mm⁻²), which was 2.45 times that in strong alkaline conditions without modulation. Additionally, the relative standard deviation of the measurement remained below 2.9% over five days of repeated experiments, indicating excellent stability. Full article

Electron–ion radiative recombination in the presence of a bicircular laser pulse is analyzed beyond the dipole approximation. A bicircular pulse consists of two counter-rotating circularly polarized laser pulses with commensurate carrier frequencies. It is demonstrated that the broad bandwidth radiation can be generated in the process and that its spectrum can be significantly enhanced by tailoring the laser field. A special emphasis is put on analyzing temporal properties of generated radiation. Full article

Mechanically improved polymeric membranes with high ionic conductivity (IC) and good permeability are highly desired for next-generation anion exchange membranes (AEMs) in order to reduce Ohmic losses and enhance water management in alkaline membrane fuel cells. To move towards the fabrication of such high-performance membranes, the creation of hydrophilic ion-conducting double gyroid (DG) nanochannels within block copolymer (BCP) AEMs is a promising approach. However, this attractive solution remains difficult to implement due to the complexity of constructing a well-developed ion-conducting DG morphology across the entire membrane thickness. To deal with this issue, water permeable polystyrene-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) membranes with ion-conducting DG nanochannels were produced by combining a solvent vapor annealing (SVA) treatment with a methylation process. Here, the SVA treatment enabled the manufacture of DG-forming BCP AEMs while the methylation process allowed for the conversion of pyridine sites to N-methylpyridinium (NMP⁺) cations via a Menshutkin reaction. Following this SVA-methylation method, the IC value of water-permeable (~384 L h⁻¹ m⁻² bar⁻¹) DG-structured BCP AEMs in their OH⁻counter anion form was measured to be of ~2.8 mS.cm⁻¹ at 20 °C while a lower IC value was probed, under the same experimental conditions, from as-cast NMP⁺-containing analogs with a non-permeable disordered phase (~1.2 mS.cm⁻¹). Full article