Interaction Of Ions Research Articles

Numerical analysis of fast ions transport induced by magnetic islands in HL-2A

The transport of beam ions in the presence of single/multiple tearing modes (TMs) under HL-2A geometry has been investigated by test particle method. Simulation results show that there exists a threshold behavior in the number of lost beam ions in the plasma under perturbation of a (2,1) TM with amplitude α0 : when the amplitude α0 is over a critical value, the number of lost beam ions increases linearly with α0 at a much faster pace. Further analysis finds that the lost beam ions have relatively higher percentage of high energy at α0 around the critical value. It also finds that the distribution of lost beam ions which is initially concentrated on the high field side expands gradually toward the low field side as the perturbation amplitude α0 increases. From the phase space analysis, it shows that the enhanced outward transport of fast ions in the presence of magnetic islands results from orbit stochasticity, which is due to the overlap of the drift islands in the interaction of fast ions with TMs. When two TMs are simultaneously present, the stochastic threshold of fast ion orbit is found to be lower than that in their individual TM case. The phase space analysis shows that in the presence of two modes with the same toroidal mode number, the modes increase the loss of fast ions when they are out of phase; however, such the effect of strengthening transport of fast ions turns to weaken when they are in phase. In contrast, when two modes each with a different toroidal mode number, their phase difference phase hardly has any effect on the transport of fast ions.

Thermodynamic description of U(IV) solubility and hydrolysis in chloride systems: Pitzer activity model for the system U4+–Na+–Mg2+–Ca2+–H+–Cl––OH––H2O(l)

This study presents updated chemical, thermodynamic, and activity models for the system U4+–Na+–Mg2+–Ca2+–H+–Cl––OH––H2O(l) derived using the Pitzer formalism and a strict ion interaction approach. The models build on comprehensive solubility datasets in dilute to concentrated NaCl, MgCl2, and CaCl2 solutions. The Nuclear Energy Agency-Thermochemical Database (NEA-TDB) selection of solubility and hydrolysis constants in the reference state were taken as anchoring point, and were extended further with the solid nanocrystalline phase UO2∙H2O(ncr) and the ternary complex Ca4[U(OH)8]4+. The former was identified in long-term solubility experiments at ambient conditions, whereas the latter has been selected in analogy to Th(IV), Np(IV), and Pu(IV) considering experimental evidences available for these An(IV) in alkaline, concentrated CaCl2 solutions. These models represent an improved tool for the calculation of U(IV) solubility and aqueous speciation in a variety of geochemical conditions including concentrated brine systems relevant in salt-based repositories for nuclear waste disposal.

Structural influence on the properties and toxicity of 2-hydroxyethylammonium-based protic ionic liquids

The present study aims to expedite the synthesis of protic ionic liquids (PILs) using solvents to investigate the correlation between hydrogen bond donor interactions and the carbon length's impact on thermal stability and viscosity. PILs consist of anions derived from organic acids paired with the 2-hydroxyethylammonium cation. Structural characterization involved NMR spectroscopy, FTIR, mass spectrometry, elemental analysis, water content assessment, and electrochemical stability. Results confirmed the structures and purity levels of PILs, thermal stability was found to be influenced by ion interactions, with cation vaporization determining the PILs decomposition temperature. Notably, 2-hydroxyethylammonium ascorbate (PIL2), oleate 2-hydroxyethylammonium citrate (PIL3), and 2-hydroxyethylammonium citrate (PIL4) exhibited the highest viscosity values in the samples. Toxicity assessments performed on Artemia salina nauplii revealed moderate toxicity for PILs, except PIL1 with low toxicity (LC50 of 16.14 mmol l-1), with toxicity generally increasing with higher PIL viscosity.

Cell Membrane Engineered Polypeptide Nanonets Mimicking Macrophage Aggregates for Enhanced Antibacterial Treatment.

Drug-resistant bacterial infections and their lipopolysaccharide-related inflammatory complications continue to pose significant challenges in traditional treatments. Inspired by the rapid initiation of resident macrophages to form aggregates for efficient antibacterial action, this study proposes a multifunctional and enhanced antibacterial strategy through the construction of novel biomimetic cell membrane polypeptide nanonets (R-DPB-TA-Ce). The design involves the fusion of end-terminal lipidated polypeptides containing side-chain cationic boronic acid groups (DNPLBA) with cell membrane intercalation engineering (R-DPB), followed by coordination with the tannic acid-cerium complex (TA-Ce) to assemble into a biomimetic nanonet through boronic acid-polyphenol-metal ion interactions. In addition to the ability of RAW 264.7 macrophages cell membrane components' (R) ability to neutralize lipopolysaccharide (LPS), R-DPB-TA-Ce demonstrated enhanced capture of bacteria and its LPS, leveraging nanoconfinement-enhanced multiple interactions based on the boronic acid-polyphenol nanonets skeleton combined with polysaccharide. Utilizing these advantages, indocyanine green (ICG)is further employed as a model drug for delivery, showcasing the exceptional treatment effect of R-DPB-TA-Ce as a new biomimetic assembled drug delivery system in antibacterial, anti-inflammatory, and wound healing promotion. Thus, this strategy of mimicking macrophage aggregates is anticipated to be further applicable to various types of cell membrane engineering for enhanced antibacterial treatment.

Analytical Solutions of Symmetric Isotropic Spin Clusters Using Spin and Point Group Projectors

Spin models like the Heisenberg Hamiltonian effectively describe the interactions of open-shell transition-metal ions on a lattice and can account for various properties of magnetic solids and molecules. Numerical methods are usually required to find exact or approximate eigenstates, but for small clusters with spatial symmetry, analytical solutions exist, and a few Heisenberg systems have been solved in closed form. This paper presents a simple, generally applicable approach to analytically solve isotropic spin clusters, based on adapting the basis to both total spin and point group symmetry to factor the Hamiltonian matrix into sufficiently small blocks. We demonstrate applications to small rings and polyhedra, some of which are straightforward to solve by successive spin-coupling for Heisenberg terms only; additional interactions, such as biquadratic exchange or multi-center terms necessitate symmetry adaptation.

Vacuum‐ultraviolet‐photoionization chamber for the investigation of ion‐based surface treatment and thin film deposition at atmospheric pressure

AbstractThe vacuum‐ultraviolet‐photoionization chamber was constructed to allow controlled ion generation and well‐defined surface treatment with these ions at atmospheric pressure. It utilizes atmospheric helium plasma as a photon source and separates the ion generation from the plasma by an aerodynamic window. The ions are guided to the grounded substrate by a weak electric field, while the diffusive transport of neutrals is reduced by a helium gas flow along the substrate. Ionic species and the absolute ion flux were determined in the substrate region. Ion‐based thin film deposition using a precursor was investigated as a model process. The proposed system enables future investigation of e.g. the isolated interaction of ions with biological substrates.

Modifying Specific Ion Effects: Studies of Monovalent Ion Interactions with Amines.

Specific ion effects in the interactions of monovalent anions with amine groups─one of the hydrophilic moieties found in proteins─were investigated using octadecylamine monolayers floating at air-aqueous solution interfaces. We find that at solution pH 5.7, larger monovalent anions induce a nonzero pressure starting at higher areas/molecules, i.e., a wider "liquid expanded" region in the monolayer isotherms. Using X-ray fluorescence at near total reflection (XFNTR), an element- and surface-specific technique, ion adsorption to the amines at pH 5.7 is confirmed to be ion-specific and to follow the conventional Hofmeister series. However, at pH 4, this ion specificity is no longer observed. We propose that at the higher pH, the amine headgroups are only partially protonated, and large polarizable ions such as iodine are better able to boost amine protonation. At the lower pH, on the other hand, the monolayer is fully protonated, and electrostatic interactions dominate over ion specificity. These results demonstrate that ion specificity can be modified by changing the experimental conditions.

Chiral Supramolecular Self-Assembly Catalysts with Enhanced Metal Ion Interaction for Higher Enantioselectivity.

Understanding the interaction between metal ions as catalytic centers and supramolecular scaffolds as chiral substrates plays an important role in developing chiral supramolecular catalysts with high enantioselectivity. Herein, we found that compared with l-norleucine chiral amphiphile (l-NorC16), l-methionine chiral amphiphile (l-MetC16) with the only heteroatom of S site difference in the hydrophilic group can form a similar supramolecular chiral nanoribbon (NR) with the bilayer structure through the self-assembly approach; yet, the interaction between the Cu(II) ion catalytic centers and supramolecular scaffolds is reinforced, favoring the chirality transfer and therefore enhancing their catalytic enantioselectivity of Diels-Alder reaction from 23% [l-NorC16-NR-Cu(II)] to 78% [l-MetC16-NR-Cu(II)]. Our work demonstrates a new strategy from the perspective of strengthening the metal ion-supramolecular scaffold interaction for the preparation of chiral supramolecular catalysts with good catalytic enantioselectivity.

Inosine pranobex-derived coordination complexes for self-adjuvant, self-carrier, and self-assembled vaccines in cancer immunotherapy

Inosine pranobex (InP), an immunomodulatory drug approved for clinical use worldwide, is a potential adjuvant for cancer vaccines with a low clinical translation barrier. However, the administration of soluble InP agents in free format is associated with drawbacks of a short half-life period and limited efficacy. In this study, a rapid self-assembly approach was proposed for the synthesis of cancer vaccines due to the coordination interaction of ferric ion and acedoben (Ace) in InP. The self-assembled cancer vaccines can be readily adjusted from the microscale to the nanoscale, with shapes including rods, fibers, and spheres. Herein, Fe-Ace coordination complexes not only serve as carriers for tumor antigens, but also enhance antigen-specific antitumor immunity due to their intrinsic adjuvant properties. Nanofibrous self-assembled cancer vaccines based on Fe-Ace coordination complexes more effectively induced an antitumor immune response, exerted a remarkable therapeutic effect, and inhibited the tumor growth at distant site in vivo, compared to free InP and other self-assembled cancer vaccines. The presented work provides a promising strategy for the rapid manufacture of InP-derived self-adjuvant, self-carrier, and self-assembled vaccines for cancer immunotherapy.

Thermodynamic properties and revised Helgeson-Kirkham-Flowers equations of state parameters of the hydrated and dehydrated monomeric silica species at t = 0.01–600oC, P = 1–3000 bars, ρH2O = 0.35–1.1 g cm−3, and Im= 0 m

The thermodynamic properties and revised Helgeson-Kirkham-Flowers equations of state (r-H-K-F EoS) parameters of the hydrated (Si(OH)4(aq), SiO(OH)3– and SiO2(OH)22−) and corresponding dehydrated (SiO2(aq), HSiO3− and SiO32−) monomeric silica species are important to describe the pH, composition, temperature, and pressure dependence of formation/breakdown reactions of all silicon-bearing compounds globally. Experimental log10 equilbrium constant, K values describing the formation reactions of these hydrated and dehydrated monomeric silica species were therefore compiled from the literature, extrapolated to zero ionic strength by specific ion interaction theory as required and used to derive their thermodynamic properties and r-H-K-F EoS parameters.Consideration of all formation reactions in the same study provides a collective, internally consistent update to the thermodynamic properties and r-H-K-F EoS parameters of the monomeric silica species that are able to provide satisfactory matches to the available experimental log10 K values at t = 0.01–600oC, P = 1–3000 bars, ρH2O = 0.35–1.1 g cm−3, and zero ionic strength. These temperature and pressure limits comfortably bracket t = 0.01–100oC and P = 1–270 bars relevant to the geological disposal of radioactive wastes at depths of up to 1 km.Updates to the thermodynamic properties of silicon-bearing compounds in all of the available geochemical thermodynamic databases are necessary, especially if reaction properties are used or given. Internal consistency between the hydrated and dehydrated species means that the hydrated species alone can be used as entries in geochemical thermodynamic databases.

Atomistic Insight on Effect of Silica Fume on Intermolecular Interactions between Poly(carboxylate) Superplasticizer and Calcium Ions in Concrete.

Understanding how poly(carboxylate)s of chemical admixtures interact with calcium ions in cement pore solutions in the presence of silica fume is fundamental to developing better chemical admixtures for concrete production. In this work, the intermolecular interactions of calcium ions with a poly(carboxylate) superplasticizer type of chemical admixture was investigated via classical all-atom molecular dynamics (MD) simulations and Density Functional Theory (DFT) calculation methods in the presence of silica fume. The classical all-atom MD simulation and DFT calculation results indicate that calcium ions are interacting with oxygen atoms of the carboxylate group of PCE. The better interaction energy could mean an improved adsorption of the PCE segment with calcium ions. In this regard, it can be noted that the ester-based PCE segment could have a better adsorption onto calcium ions in comparison with the ether-based PCE segment. Moreover, the presence of silicon dioxide could improve the adsorption of the PCE segment onto calcium ions.

Strategies for the development of metalloimmunotherapies.

Metal ions play crucial roles in the regulation of immune pathways. In fact, metallodrugs have a long record of accomplishment as effective treatments for a wide range of diseases. Here we argue that the modulation of interactions of metal ions with molecules and cells involved in the immune system forms the basis of a new class of immunotherapies. By examining how metal ions modulate the innate and adaptive immune systems, as well as host-microbiota interactions, we discuss strategies for the development of such metalloimmunotherapies for the treatment of cancer and other immune-related diseases.

Valorization of castor seed shell waste as lead adsorbent by treatment with hot phosphoric acid: Optimization and evaluation of adsorption properties

Lead is used in many industries such as refining, mining, battery manufacturing, smelting. Releases of lead from these industries is one of the major public health concerns due to widespread persistence in the environment and its resulting poisoning character. In this work, the castor seed shell (CSS) waste was exploited for preparing a beneficial bio-adsorbent for removal of Pb(II) ions from water. The raw CSS was modified with H3PO4 at different acid concentrations, impregnation ratios, activation times, and temperatures. An optimum adsorption capacity was observed for CSS modified with 2 M acid, 5 mL g−1 solid to liquid ratio, treated at 95 °C for 160 min. Exploiting acid modification, the SEM, XRD, and FTIR analyses show some alterations in functional groups and the surface morphology of the biomass. The impacts of physiochemical variables (initial lead ions concentration, pH, adsorbent dose and adsorption time) on the lead removal percentage were investigated, using response surface methodology (RSM). Maximum removal of 72.26% for raw CSS and 97.62% for modified CSS were obtained at an initial lead concentration (50 mg L−1), pH (5.7), adsorption time (123 min) and adsorbent dosage (1.1 g/100 mL). Isothermal and kinetics models were fitted to adsorption equilibrium data and kinetics data for the modified CSS and the adsorption system was evaluated thermodynamically and from the energy point of view. Isothermal scrutinization indicated the mono-layer nature of adsorption, and the kinetics experimental outcomes best fitted with the pseudo-second-order, implying that the interaction of lead ions and hot acid-treated CSS was the rate-controlling phenomenon of process. Overall, results illustrated that the hot acid-treated biomass-based adsorbent can be considered as an alternative bio-adsorbent for removing lead from water media.

Assessing the Impact of Hexavalent Chromium (Cr VI) at Varied Concentrations on Spirulina platensis for Growth, Metal Sorption, and Photosynthetic Responses.

Spirulina platensis, a photosynthetic cyanobacterium, has garnered attention for its potential role in environmental remediation due to its ability to absorb and metabolize toxic heavy metals. Understanding its response toward toxicity of one of the most common contaminants, Cr(VI) is crucial for assessing its efficacy in bioremediation efforts. This study aims to investigate the physiological and biochemical responses of Spirulina platensis to varying concentrations of Cr(VI) from 0.5 to 5ppm, shedding light on its potential as a bioindicator for environmental contamination and its suitability for bioremediation purposes. The impact of Cr(VI) on cell density, biosorption, pigment levels, nutrient content, fluorescence response, and photosynthetic efficiency was examined. The study revealed a gradual reduction in cell density, biomass production, and biosorption efficiency with increasing Cr(VI) concentrations. Pigment levels, carbohydrate, protein, and lipid content showed significant decreases, indicating physiological stress. Fluorescence response and photosynthetic efficiency were also adversely affected, suggesting alterations in electron transfer dynamics. A threshold for chromium toxicity was observed at 0.5ppm, beyond which significant physiological disturbances occurred. This investigation highlights the sensitivity of Spirulina platensis to Cr(VI) toxicity and its potential as a bioindicator for heavy metal contamination. Metal sorption was highest in 0.5ppm Cr(VI) with 56.56% removal. Notably, at lower concentrations, Cr(VI) acted as an intermediate electron acceptor, enhancing the electron transport chain and potentially increasing biomass under controlled conditions. The findings underscore the importance of understanding the mechanisms underlying heavy metal stress in microalgae for effective environmental remediation strategies. The research highlights the dual role of chromium(VI) in influencing S. platensis, depending on the concentration, and underscores the importance of understanding metal ion interactions with photosynthetic organisms for potential applications in bioremediation.

Bimetallic Photo-Activated and Steerable Janus Micromotors as Active Microcleaners for Wastewater.

Photoactive colloidal motors whose motion can be controlled and even programed via external magnetic fields have significant potential in practical applications extending from biomedical fields to environmental remediation. Herein, we report a "three in one" strategy in a Co/Zn-TPM (3-trimethoxysilyl propyl methacrylate) bimetallic Janus colloidal micromotor (BMT-micromotor) which can be controlled by an optical field, chemical fuel, and magnetic field. The speed of the micromotors can be tuned by light intensity and with the concentration of the chemical fuel of H2O2, while it could be steered and programed through magnetic field due to the presence of Co in the bimetallic part. Finally, the BMT-micromotors were employed to effectively remove rubidium metal ions and organic dyes (methylene blue and rhodamine b). Benefited of excellent mobility, multiple active sites, and hierarchical morphology, the micromotors exhibit excellent adsorption capacity of 103 mg·g-1 to Rb metal ions and high photodegradation efficiency toward organic dyes in the presence of a lower concentration of H2O2. The experimental characterizations and DFT calculations confirmed the strong interaction of Rb metal ions on the surface of BMT-micromotors and the excellent decomposition of H2O2 which enhanced the photodegradation process. We expect the combination of light and fuel sensitivity with magnetic controllability to unlock an excess of opportunities for the application of BMT-micromotors in water treatments.

Investigation of ion association kinetics in Na2SO4-H2O by excess Raman spectroscopy and 2D correlation Raman spectroscopy

The ion association of salts aqueous solutions have long captivated the attention of researchers within the field of physical chemistry. In this paper, we have performed a comprehensive analysis of ion interactions in sodium sulfate (Na2SO4) aqueous solutions using a combination of high-resolution techniques, including excess (ERS) and two-dimensional correlation (2DCRS) Raman spectroscopy in conjunction with molecular dynamics (MD) calculations. The Raman spectrum shows that two inflection points in the Raman shift of the O–H vibration are observed with the increase in Na2SO4 concentration. Simultaneously, a new peak of the SO42- vibration appears at first inflection point, representing the formation of ion association. Further analysis based on ERS and 2CRS reveals that these two inflection points correspond respectively to the formation of ion pairs (CIPs) and small ion clusters. Importantly, MD simulations confirm the above experimental results. Our study provides evidence for ion association and clustering in aqueous in salt ion aqueous solutions.

Nobody's Perfect: Choice of the Buffer and the Rate of Cu2+ Ion-Peptide Interaction.

The choice of correct pH buffer is crucial in chemical studies modeling biological processes involving Cu2+ ions. Popular buffers for physiological pH are known to form Cu(II) complexes, but their impact on kinetics of Cu(II) complexation has not been considered. We performed a stopped-flow kinetic study of Cu2+ ion interactions with four popular buffers (phosphate, Tris, HEPES, and MOPS) and two buffers considered as nonbinding (MES and PIPPS). Next, we studied their effects on the rate of Cu2+ reaction with Gly-Gly-His (GGH), a tripeptide modeling physiological Cu(II) sites, which we studied previously at conditions presumably excluding the buffer interference [Kotuniak, R.; Angew. Chem., Int. Ed. 2020, 59, 11234-11239]. We observed that (i) all tested pH 7.4 buffers formed Cu(II) complexes within the stopped-flow instrument dead time; (ii) Cu(II)-peptide complexes were formed via ternary complexes with the buffers; (iii) nevertheless, Good buffers affected the observed rate of Cu(II)-GGH complex formation only slightly; (iv) Tris was a competitive inhibitor of Cu(II)-GGH complexation; while (v) phosphate was a reaction catalyst. This is particularly important as phosphate is a biological buffer.

Erratum: Electronic interaction of slow hydrogen, helium, nitrogen, and neon ions with silicon [Phys. Rev. B 107 , 155145 (2023)

Erratum: Electronic interaction of slow hydrogen, helium, nitrogen, and neon ions with silicon [Phys. Rev. B <b>107</b> , 155145 (2023)

Autocatalytic bifunctional supramolecular hydrogels for osteoporotic bone repair.

Conventional bone scaffolds, which are mainly ascribed to highly active osteoclasts and an inflammatory microenvironment with high levels of reactive oxygen species and pro-inflammatory factors, barely satisfy osteoporotic defect repair. Herein, multifunctional self-assembled supramolecular fiber hydrogels (Ce-Aln gel) consisting of alendronate (Aln) and cerium (Ce) ions were constructed for osteoporotic bone defect repair. Based on the reversible interaction and polyvalent cerium ions, the Ce-Aln gel, which was mainly composed of ionic coordination and hydrogen bonds, displayed good injectability and autocatalytic amplification of the antioxidant effect. In vitro studies showed that the Ce-Aln gel effectively maintained the biological function of osteoblasts by regulating redox homeostasis and improved the inflammatory microenvironment to enhance the inhibitory effect on osteoclasts. Ribonucleic acid (RNA) sequencing further revealed significant downregulation of various metabolic pathways, including apoptosis signaling, hypoxia metabolism and tumor necrosis factor-alpha (TNF-α) signaling via the nuclear factor kappa-B pathway after treatment with the Ce-Aln gel. In vivo experiments showed that the clinical drug-based Ce-Aln gel effectively promoted the tissue repair of osteoporotic bone defects by improving inflammation and inhibiting osteoclast formation at the defect. Notably, in vivo systemic osteoporosis was significantly ameliorated, highlighting the strong potential of clinical translation for precise therapy of bone defects.

Carbon dots as a sustainable electrolyte enhancer in aqueous alkaline electrochemical capacitors

In the endeavour to increase the energy density and to widen the potential window of aqueous alkaline electrochemical capacitors (EC), this study explores the role of carbon dots (CDs) as an additive in potassium hydroxide electrolyte. The CDs with an average size of ∼2.2 nm and negative surface potential are synthesized from a dispersion of palm kernel shell powder in water using a low-temperature hydrothermal process. Electrochemical measurements show that the CD–electrolyte ion (K+) interaction has improved counter ion adsorption in porous carbon electrodes via lowering the characteristic resistances and time constants, which significantly improved the fraction of adsorbed charges than diffusively stored. The improved ionic conductivity is attributed to the improved wettability introduced by the hydrophilic functional groups in the CDs. These parametric changes widened the potential window and marked an 80 % increase in the specific energy and over a 10 % increase in specific power in a practical EC with similar mass-loading as commercial devices. The device with CDs demonstrated superior cycling stability and Coulombic efficiency than the control device without them. These findings underscore the potential of CDs as a promising avenue for advancing the performance parameters of aqueous electrolyte EC, aligning with the overarching goal of realising economical, environmentally friendly, and sustainable energy storage solutions.