Enrichment Of Ions Research Articles

Ion-Engineered Clay Nanozyme via Tumor Microenvironment Remodeling for Enhanced Tumor Therapy.

Metal ions show tremendous promise for tumor therapy due to their critical roles in many important catalytic circulations and immune processes. However, the valence state variability and systemic side-effects of metal ions cause ineffective ion enrichment in tumor cells, which limit their further application. Here, a Mn3+ ion delivery system (Mn-HNT) is constructed based on halloysite nanotubes (HNT) via an ion-engineered strategy. Due to the stabilizing effect of HNT on Mn3+ ions, Mn-HNT not only maintained the valence state of Mn3+ ions, but also presented strong catalase (CAT)- and glutathione oxidase (GSHOx)-like catalytic activity to catalyze O2 generation and GSH consumption to relieve the inhibition of tumor microenvironment on photodynamic therapy (PDT). After further coordination with the photosensitizer porphyrin (TCPP), obtained TCPP-Mn-HNT not only inherited the catalytic properties of Mn-HNT to produce oxygen and consume GSH, but acted as photosensitizer for ROS accumulation to effectively destroy tumor cells. Moreover, TCPP-Mn-HNT can promote the maturation of dendritic cells (≈2.8 times), and present the tumor antigen triggered by PDT to T cells to strengthen high-efficient tumor therapy. The study provides new opportunities for designing metal ion delivery system with versatile biofunctions and offers a paradigm of synergistic metal-ion-mediated tumor therapy.

Metal-Phosphonate-Organic Network as Ion Enrichment Layer for Sustainable Zinc Metal Electrode with High Rate Capability.

Zinc (Zn) metal batteries could be the technology of choice for sustainable battery chemistries owing to its better safety and cost advantage. However, their cycle life and Coulombic efficiency (CE) are strongly limited by the dendritic growth and side reactions of Zn anodes. Herein, we proposed an in situ construction of a metal-phosphonate-organic network (MPON) with three-dimensional interconnected networks on Zn metal, which can act as an ion enrichment layer for Zn anodes in Zn-metal batteries. This MPON with abundant porous structure and phosphate sites possesses ion enriching properties and high Zn2+ transference number (0.83), which is beneficial for enhancing Zn2+ migration and self-concentrating kinetics. Meanwhile, MPON offers hydrophobicity to effectively inhibit the water-induced Zn anode corrosion. As a result, the Zn electrode exhibits superior Zn/Zn2+ reversibility of over 4 months at 3 mA cm-2 and a high CE of 99.6%. Moreover, the Zn/NaV3O8 ·1.5H2O and Zn/MnO2 full cells using ultrathin Zn anodes (10 μm) exhibit high-capacity retention of 81% and 78% after 1400 and 1000 cycles, respectively. This work provides a unique promise to design high-performance anode for practical Zn-metal-based batteries.

Metal‐Phosphonate‐Organic Network as Ion Enrichment Layer for Sustainable Zinc Metal Electrode with High Rate Capability

Zinc (Zn) metal batteries could be the technology of choice for sustainable battery chemistries owing to its better safety and cost advantage. However, their cycle life and Coulombic efficiency (CE) are strongly limited by the dendritic growth and side reactions of Zn anodes. Herein, we proposed an in situ construction of a metal−phosphonate−organic network (MPON) with three−dimensional interconnected networks on Zn metal, which can act as an ion enrichment layer for Zn anodes in Zn‐metal batteries. This MPON with abundant porous structure and phosphate sites possesses ion enriching properties and high Zn2+ transference number (0.83), which is beneficial for enhancing Zn2+ migration and self−concentrating kinetics. Meanwhile, MPON offers hydrophobicity to effectively inhibit the water−induced Zn anode corrosion. As a result, the Zn electrode exhibits superior Zn/Zn2+ reversibility of over 4 months at 3 mA cm−2 and a high CE of 99.6%. Moreover, the Zn/NaV3O8 ·1.5H2O and Zn/MnO2 full cells using ultrathin Zn anodes (10 μm) exhibit high−capacity retention of 81% and 78% after 1400 and 1000 cycles, respectively. This work provides a unique promise to design high−performance anode for practical Zn−metal−based batteries.

Synchronously coupled magnetic field weakening the dynamic deformation response of salt-containing droplet to an electric field

Combining a magnetic field with an electric field offers a promising approach for enhancing oil–water separation, yet its underlying mechanisms are not fully understood. We systematically investigated the dynamic deformation of salt-containing water droplet suspended in oil under an electric–magnetic coupling field. Integrating high-speed camera experiments with molecular dynamics simulations, we found that the dynamic response amplitude of droplet is reduced compared to a single electric field. Our analysis suggests that ions deflect under electric–magnetic coupling, affecting ion enrichment and water molecule polarization, thereby weakening droplet tip charge and induced electric forces, which suppresses droplet deformation. Increasing the electric capillary number and ion concentration enhances suppression, whereas improving the electric field frequency to 500 Hz almost eliminates this suppression effect. Notably, the degree of droplet deformation inhibition remains consistent across different viscosity ratios. These research findings offer insights for designing dehydrators to intensify oil–water separation.

Evaporation-induced ion enrichment for high-performance glucose detection in a microfluidic thread/paper-based analytical system

Evaporation-induced ion enrichment for high-performance glucose detection in a microfluidic thread/paper-based analytical system

A Green and Energy‐Supply‒Free Artificial Plant for Efficient and Non‐Selective Enrichment of Heavy Metal Ions Out of Soil

AbstractRemoving heavy metal (loid) s (HMs) from contaminated soil in a nonselective, highly efficient, and energy‐free manner is a major global challenge. Herein, this work synthesizes and assembles a biomimetic materials system (BMS) consisting of an artificial plant, a hemispherical glass cover, and a reflective plate, capable of non‐selective and highly efficient remediation of soil contaminated by various HM ions under sunlight. Specifically, a water cycle is driven to establish between the soil, artificial plant, and atmosphere by solar energy in the BMS, which induced water‐soluble HM ions to enrich and precipitate at the top edge of the artificial plant. The formed HM precipitate is easily removed, contributing to the extremely strong recyclability of BMS. This system has significant advantages in terms of soil properties, contamination characteristics, energy consumption, processing time, and removal amount over other representative remediation methods, demonstrating its great potential for practical application in the remediation of various HM‐contaminated soils.

Ion current rectification coupled with asymmetric temperature and surface charge in ultrashort conical nanopores

Ion current rectification (ICR) is one of the electrodynamic properties in asymmetric nanochannels, which has been utilized to develop biosensors, heavy metal ion detection, and ion diodes. Previous studies on ICR mainly focused on long nanopores (length >500 nm), and relatively few studies on ion rectification performance in short nanopores. Here, we use a finite element numerical solution to simulate the effect of coupling asymmetric temperature and surface charge distribution on the ion rectification performance of ultrashort conical nanopores (length = 100 nm). The results show that the ion rectification performance is significantly improved when the inner and outer surfaces of the nanopore are charged non-uniformly, which is more than three times that when the inner surface of the nanopore is charged non-uniformly or the outer surface is charged non-uniformly. In addition, the positive temperature difference enhances the ion enrichment and dissipation and improves the ion rectification performance of nanopores. On the contrary, negative temperature difference inhibits ion enrichment and dissipation in pores, which is not conducive to improving ion rectification performance. Abnormal behavior is observed for nanopores non-uniform charged only on the outer wall surface, where the negative temperature gradient enhances the accumulation and dissipation of ions within the pores, thereby increasing the rectification ratio. In addition, in order to more clearly understand the ion transport behavior in the ultrashort nanopore under asymmetric temperature conditions, we further investigated the influence of the tip radius of the nanopore, the solution volume concentration, and the charge type of each surface charge distribution on the ion current rectification performance. The results reveal the ion transport mechanism of ultrashort conical nanopores and provide practical guidance for designing and optimizing nanofluidic devices.

MoS2 decorated heteroatoms doped carbon microspheres for efficient separation of uranium from wastewater

Uranium serves as a fundamental element for sustainable nuclear reactor energy. Hence, the extraction and enrichment of uranium from radioactive wastewater is of considerable significance for both nuclear power utilization and environmental protection. In this study, carbon microspheres (TAC) doped with nitrogen, phosphorus and sulfur were derived from ternary polyphosphazene. Subsequently, molybdenum disulfide (MoS2) was integrated using hydrothermal method to fabricate the TAC/MoS2 composite, which is designed for the efficient enrichment and separation of uranyl ions. Owing to the unique two-dimensional structure of MoS2 and its strong affinity towards uranyl ions, the adsorption capacity of the composite was significantly enhanced to 399.6 mg/g within 80 min at pH 5 and 298.15 K. Additionally, the composite exhibited commendable thermal stability and hydrophilicity, declaring that it is an outstanding candidate for the efficient enrichment and separation of uranyl ions. Further mechanism studies through XPS analysis and DFT calculations suggested that the vacancies introduced by MoS2 can generate electrostatic interactions and coordination effects with uranyl ions, thereby improving the adsorption performance of the composite. Due to its straightforward preparation process and exceptional adsorption performance, TAC/MoS2 possesses broad application prospects in the extraction of uranium from wastewater.

High-efficiency phosphorus recovery from hypophosphite and phosphite-containing wastewater via a new electrodialysis enrichment and hydrothermal oxidation coupling process

Hypophosphite is an ideal reducing agent used in industries such as electroplating. However, the presence of high concentrations of hypophosphite and phosphite in industrial wastewater necessitates the consumption of large amounts of strong oxidants to oxidize hypophosphite to phosphate for subsequent removal by precipitation. This study introduces an innovative application of green hydrothermal process for the oxidation treatment of inorganic materials, combined with the ion enrichment advantages of electrodialysis. This novel coupling process achieves efficient enrichment and rapid oxidation of high-concentration hypophosphite and phosphite with minimal chemical consumption and more economical operating costs, yielding high-quality phosphate resources. Under electrodialysis conditions with a particle electrode dosage of 3 %, a voltage of 20 V, and a residence time of 10 h, the total phosphorus in the middle chamber was reduced from 2801.17 mg/L to 119.05 mg/L, achieving an anodic enrichment rate of 95.75 %. Under hydrothermal conditions of 400 °C for 15 min, with an H2O2 doping ratio of 7 % and a Ca(OH)2 doping ratio of 35 g/L, the peak oxidation rates of H2PO2− and HPO32− reached 99.38 %, and 99.39 % of phosphorus was transferred from the liquid phase to the solid phase in recyclable forms such as Ca5(PO4)3OH, Ca3(PO4)2, and FePO4. H2O2 enhances the hydrothermal oxidation process by increasing the concentration of free radicals. Ca(OH)2 acted as a catalyst to enhance •OH generation during the hydrothermal reaction, provided Ca2+ required for phosphorus recycling, and increased the pH to obtain crystalline products with a high Ca/P molar ratio. Compared to conventional advanced oxidation processes, the electrodialysis and hydrothermal coupling process offers a clean alternative for treating high-concentration hypophosphite and phosphite in plating wastewaters, achieving a cost saving of 22.99 %.

A strategy for selective extraction of lanthanides based on self-assembly with MPyEDChDGA from nitric acid solution☆

The development of new and efficient extractants plays a key role in the separation and recovery of rare earth elements. In this paper, the extractant (N,N-methylpyridineethyl-N',N'-dicyclohexyl-3-oxadiglycolamide, MPyEDChDGA) with a new structure was synthesized, and the pyridine group was successfully grafted onto the 3-oxadiglycolamide structure. Using MPyEDChDGA for efficient enrichment of rare earth ions, the self-assembled solids were recovered by simple filtration without further back-extraction and final precipitation, achieving a one-step strategy for the recovery of rare earth ions. Several important parameters affecting the self-assembly extraction, including pH, diluent, temperature, and extractant concentration, were systematically evaluated using La(NO3)3, Tb(NO3)3, and Lu(NO3)3 as representatives. The self-assembled solids were investigated in detail by X-ray diffraction (XRD), scanning electron microscopy (SEM), 1H nuclear magnetic resonance (1H NMR), Fourier transform infrared spectroscopy (FT-IR), Raman, and X-ray photoelectron spectroscopy (XPS) analyses. The stoichiometry of the extraction species was characterized using the Job’s method and electrospray ionization mass spectrometry (ESI-MS). In addition, MPyEDChDGA was applied to the recovery of Sm in SmCoCu simulated liquid, and the results show that MPyEDChDGA has good selectivity of Sm from transition metals (Co, Cu). The separation factor of Sm/Co can reach 6281±117, which provides a new approach to recovering Sm from SmCoCu scrap magnets. This study presents an efficient and convenient new strategy for the recovery and separation of rare earth elements.

Enhancing the Performance of Tyndall-Powell Gate Ion Mobility Spectrometry by Combining Ion Enrichment, Discrimination Reduction, and Temporal Compression into a Single Gating Process.

The broad applications of ion mobility spectrometry (IMS) demand good sensitivity and resolving power for ion species with different reduced mobilities (K0). In this work, a new Tyndall-Powell gate (TPG) gating method for combining ion enrichment, mobility discrimination reduction, and temporal compression into a single gating process is proposed to improve IMS analysis performance. The two-parallel-grid structure and well-confined gate region of the TPG make it convenient to spatiotemporally vary the electric fields within and around the gate region. Under the new gating method, a potential wave is applied on TPG grid 1 to enrich ions within the ionization region adjacent to the TPG during the gate-closed state; meanwhile, a potential wave is applied on TPG grid 2 to enhance mobility discrimination reduction and temporal compression simultaneously during the gate-open state. For triethyl phosphate (TEP) and dimethyl methylphosphonate mixtures, product ion peaks within K0 of 1.9 to 1.1 cm2/V·s exhibit a 19-fold increase in ion current compared to the traditional TPG gating method, while maintaining a resolving power of 85. The estimated limit of detection for the TEP dimer is lowered from 8 ppb to 135 ppt. The new gating method can be applied to other TPG-based IMS systems to enhance their performance in analyzing complex samples.

Enrichment of Terbium(III) under synergistic effect of biosorption and biomineralization by Bacillus sp. DW015 and Sporosarcina pasteurii.

A weak microbially induced calcium carbonate precipitation (MICP) promotes the enrichment of Tb(III) by bacteria, while a strong MICP leads to the release of Tb(III). However, existing explanations cannot elucidate these mechanisms. In this study, the morphology of the bioprecipitation and the degree of Tb(III) enrichment were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectroscopy (EDS). The data revealed that MICP could drive stable attachment of Tb(III) onto the cell surface, forming a Tb-CaCO3 mixed solid phase. Excessive rapid rate of calcite generation could disrupt the Tb(III) adsorption equilibrium, leading to the release of Tb(III). Therefore, in order for Tb(III) to be stably embedded in calcite, it is necessary to have a sufficient number of adsorption sites on the bacteria and to regulate the rate of MICP. This study provides theoretical support for the process design of MICP for the enrichment of rare earth ions.

Improved efficiency of ion trapping time-of-flight mass spectrometry for the analysis of pesticide residues and mycotoxins at trace levels in baby food

The analysis of pesticide residues and mycotoxins in baby food demands exceptionally low limits of quantitation, necessitating the use of highly sensitive instruments capable of conducting trace analyses. High-resolution instruments typically fail to detect such low levels. However, the latest advancements in liquid time-of-flight technology, when coupled with ion trapping, enable ion enrichment, thereby improving detection levels. This allows for the analysis of these substances at low concentration levels, benefiting from enhanced mass accuracy. Additionally, the use of mass accuracy data helped eliminate matrix interferences, thereby enabling high-confidence identification. We developed a multi-residue method to analyse 219 pesticide residues and 9 mycotoxin residues in baby food matrices. Utilizing a QuEChERS-based extraction method, the samples were then analysed using an LC-ZenoTOF 7600 system with mass window screening acquisition. For pesticides, the limit of quantitation was 0.001–0.003 mg/kg for 81 % of the evaluated compounds, 0.005 mg/kg for 13 %, 0.010 mg/kg for 4 % and 0.020–0.030 for 2 %; good linearities were obtained at these levels. Apparent recoveries were evaluated at 0.003, 0.005, and 0.010 mg/kg. At the lowest recovery level, 93 % of compounds showed recoveries between 70 and 120 %. The rest of the compounds were in the range of 63–129 %, with relative standard deviation values below 20 %. For mycotoxins, the limits of quantitation ranged from 0.0001 to 0.100 mg/kg, with matrix-matched concentrations assessed within this range. Recoveries were evaluated at low concentration range (0.001–0.003 mg/kg) and high range (0.020–0.050) with apparent recoveries values between 92 and 140 %. Finally, a total of 31 commercial baby food samples were analysed using this method. The results indicated that 16 samples contained pesticide residues, while two samples were found to have mycotoxins.

Dynamic Response of Ionic Current in Conical Nanopores.

Ionic current rectification (ICR) of charged conical nanopores has various applications in fields including nanofluidics, biosensing, and energy conversion, whose function is closely related to the dynamic response of nanopores. The occurrence of ICR originates from the ion enrichment and depletion in conical pores, whose formation is found to be affected by the scanning rate of voltages. Here, through time-dependent simulations, we investigate the variation of ion current under electric fields and the dynamic formation of ion enrichment and depletion, which can reflect the response time of conical nanopores. The response time of nanopores when ion enrichment forms, i.e., at the "on" state is significantly longer than that with the formation of ion depletion, i.e., at the "off" state. Our simulation results reveal the regulation of response time by different nanopore parameters including the surface charge density, pore length, tip, and base radius, as well as the applied conditions such as the voltage and bulk concentration. The response time of nanopores is closely related to the surface charge density, pore length, voltage, and bulk concentration. Our uncovered dynamic response mechanism of the ionic current can guide the design of nanofluidic devices with conical nanopores, including memristors, ionic switches, and rectifiers.

A coarse-grained Poisson–Nernst–Planck model for polyelectrolyte-modified nanofluidic diodes

Abstract Polyelectrolyte (PE)-modified synthetic nanopores have gained substantial research attention because molecular modification promotes ion gating and rectification. However, theoretical research on PE-modified nanopores is relatively scarce because it is difficult to establish an elaborate model for PEs, and it accordingly causes a trade-off between the computational resources needed and the accuracy. Therefore, an appropriate simulation method for the PE-modified nanopore is in high demand and still an enormous challenge. Herein, we report the simulation result of ion transport through PE-modified nanopores through a coarse-grained Poisson–Nernst–Planck method. By modeling the stuffed PE molecules as PE particles in a well-established continuum model, adequate computational accuracy can be achieved with acceptable computational cost. Based on this model, we study the ion transport in PE-modified nanofluidic diodes and reveal the PE around ion selectivity, which can explain the previous experimental works. Intriguingly, we found that the ion enrichment state in the nanofluidic diode is sensitive to steric hindrance and charge distribution near the heterojunction region. This property is critical for the ion transport behavior in the PE-modified nanofluidic diodes. Based on this property, we predict a heterogeneous structure that can realize the single molecule response to charged analytes. These findings provide insights for understanding the ion transport in PE-modified nanofluidic systems and bring inspiration to the design and optimization of high-performance chemical sensors.

Effect of Argon in Nitrogen Gliding Arc Plasma for Ammonium Ions Enrichment in Water

Effect of Argon in Nitrogen Gliding Arc Plasma for Ammonium Ions Enrichment in Water

Bioinspired Bone Seed 3D‐Printed Scaffold via Trapping Black Phosphorus Nanosheet for Bone Regeneration

Significance of endogenous mineralization in bone reconstruction is paramount, as it facilitates the accumulation of calcium ions for bone tissue deposition. However, conventional 3D‐printed scaffolds lack the capacity for calcium ion enrichment and mineralization, coupled with their low bone inductive activity. Inspired from the development of natural plant seeds, a biomimetic 3D printing scaffold is developed by implanting photosensitive black phosphorus “bone seeds” (BS), guiding a sequential process mirroring rooting (osteoblast recruitment), sprouting (fibrous callus mineralization), flowering (osseous callus formation), and fruiting (callus plasticity). BS were trapped onto porous 3D polycaprolactone (PCL) scaffolds with aminated surfaces via electrostatic interactions between phosphates and amino groups, creating the PCL‐BS scaffold that can actively capture calcium ions for accelerating the endogenous regeneration of critical bone defects. In vitro and in vivo experiments show that the PCL‐BS scaffold has good biocompatibility and strong osteogenic ability for rapid new bone regeneration under near‐infrared (NIR) stimulation. In addition, whole transcriptome sequencing analysis is performed to reveal the transcriptomic mechanism of BS involved in signal transduction and network regulation during bone regeneration. This NIR light‐regulated biomimetic BS inspired by seed planting, introduces a pioneering concept in the design of 3D printing bone repair scaffolds.

Mechanism of Jinteng Qingbi granules in the treatment of rheumatoid arthritis using metabolomics analysis.

This study investigated the differential metabolites after rheumatoid arthritis (RA) rats were treated with Jinteng Qingbi granules. Collagen-induced arthritis rats were divided into three groups, namely normal group, model group, and Jinteng Qingbi granules group. Serum compounds were identified, annotated, and classified using metabolomics to explain the physicochemical properties and biological functions. The metabolites were screened using univariate and multivariate statistical analyses. There were differences in serum metabolites between RA and normal rats; Jinteng Qingbi granules improved RA and recovered the metabolite levels to normal. Compared to the normal group, 51 differential ions were screened, and 108 ions were changed in the Jinteng Qingbi granules group compared to the RA model. Eight metabolites were upregulated in the RA model group compared to the normal group, whereas 10 metabolites were downregulated. Treatment with Jinteng Qingbi granules increased the levels of 12 metabolites such as cinnamate and decreased the levels of 16 metabolites such as allamandin in the RA model. Differential ion enrichment was mainly related to the histidine metabolic pathway in amino acid metabolism. Jinteng Qingbi granules resulted in improvements in the RA model, which were mainly associated with lipids and lipid-like molecules, organic acids, and derivatives, providing a new possibility and basis for screening biomarkers for the diagnosis and treatment of RA.

Efficient rare earth enrichment through highly reversible physisorption on a negatively charged few-layer nanobelt platform

Effective extraction of rare earth elements (REE) from the surrounding aqueous environment would relieve the thirsty demand of mining as well as the environmental pollution, thus advancing sustainability progress. Nevertheless, limited extraction capability and harsh enrichment conditions are still the notorious critical problems hindering this environmentally favorable path. Herein, we showcase a physisorption driving platform (InVO4) for effective REE enrichment. This delicately designed platform exhibits a unique few-layer structure and thus robust negatively charged surface in the aqueous environment, which implies its powerful attraction towards positively charged species. The adsorption trials towards REE ions have proved this anticipation with a superior adsorption capability of 317.3 mg/g towards Yb3+ and the adsorption reached quasi-equilibrium in only about 10 min. Moreover, this platform could be regenerated quickly and completely in a mild NaCl environment based on the quasi-cationic exchange strategy benefiting from the physisorption nature. Impressively, a ppb-level enrichment of REE ions from the aqueous was realized 78-fold increase from an initial concentration of 100 ppb. This environmentally benign and highly efficient adsorbent will be inspiring for a more sustainable utilization route for the recovery of REE resources.

Fluorescent porous hybrid silsesquioxane-based semiconductor polymer for sunlight-driven gold recovery with high efficiency and selectivity

As an important precious metal, the recovery of gold can not only relieve the shortage of resources, but also has a high economic value. In this work, a novel silsesquioxane-based fluorescent porous hybrid polymer (PTSC) was prepared successfully by Heck coupling reaction of octavinylsilsesquioxane with a dibromated distyry-bithiophenes containing cyano groups. The structure of PTSC was fully investigated, which featured a high surface area of 455 m2 g−1, wide light adsorption band, narrow optical band gap (1.73 eV) and excellent semiconductor performance. As Au(III) adsorbent, the adsorption capacity of PTSC reached 3080 mg g−1 under light irradiation for 4 h at pH = 5, and the purity of the recovered gold in e-waste could reach 23.92 K. The adsorption mechanism showed that photoelectrons produced by PTSC could reduce all Au(III) adsorbed to Au(I) and Au(0). Moreover, a hybrid aerogel device based on PTSC and chitosan was fabricated to realize the enrichment and recovery of gold ions in wastewater. Besides, PTSC could also act as a probe to detect Au(III) with high selectivity and specificity. This study provided a new strategy for efficient recovery and detection of Au(III).