Metal Ion Concentration Research Articles

Transient Metallo-Lipidoid Assemblies Amplify Covalent Catalysis of Aqueous and Non-Aqueous Reactions.

Dissipative supramolecular assemblies are hallmarks of living systems, contributing to their complex, dynamic structures and emerging functions. Living cells can spatiotemporally control diverse biochemical reactions in membrane compartments and condensates, regulating metabolite levels, signal transduction or remodeling of the cytoskeleton. Herein, we constructed membranous compartments using self-assembly of lipid-like amphiphiles (lipidoid) in aqueous medium. The new double-tailed lipidoid features Cu(II) coordinated with a tetravalent chelator that dictates the binding of two amphiphilic ligands in cis-orientation. Hydrophobic interactions between the lipidoids coupled with intermolecular hydrogen bonding led to a well-defined bilayer vesicle structure. Oil-soluble SNAr reaction is efficiently upregulated in the hydrophobic cavity, acting as a catalytic crucible. The modular system allows easy incorporation of exposed primary amine groups, which augments the catalysis of retro aldol and C-N bond formation reactions. Moreover, a higher-affinity chelator enables consumption of the Cu(II) template leveraging the differential thermodynamic stability, which allows a controllable lifetime of the vesicular assemblies. Concomitant temporal upregulation of the catalytic reactions could be tuned by the metal ion concentration. This work offers new possibilities for metal ion-mediated dynamic supramolecular systems, opening up a massive repertoire of functionally active dynamic "life-like" materials.

Transient Metallo‐Lipidoid Assemblies Amplify Covalent Catalysis of Aqueous and Non‐Aqueous Reactions

AbstractDissipative supramolecular assemblies are hallmarks of living systems, contributing to their complex, dynamic structures and emerging functions. Living cells can spatiotemporally control diverse biochemical reactions in membrane compartments and condensates, regulating metabolite levels, signal transduction or remodeling of the cytoskeleton. Herein, we constructed membranous compartments using self‐assembly of lipid‐like amphiphiles (lipidoid) in aqueous medium. The new double‐tailed lipidoid features Cu(II) coordinated with a tetravalent chelator that dictates the binding of two amphiphilic ligands in cis‐orientation. Hydrophobic interactions between the lipidoids coupled with intermolecular hydrogen bonding led to a well‐defined bilayer vesicle structure. Oil‐soluble SNAr reaction is efficiently upregulated in the hydrophobic cavity, acting as a catalytic crucible. The modular system allows easy incorporation of exposed primary amine groups, which augments the catalysis of retro aldol and C−N bond formation reactions. Moreover, a higher‐affinity chelator enables consumption of the Cu(II) template leveraging the differential thermodynamic stability, which allows a controllable lifetime of the vesicular assemblies. Concomitant temporal upregulation of the catalytic reactions could be tuned by the metal ion concentration. This work offers new possibilities for metal ion‐mediated dynamic supramolecular systems, opening up a massive repertoire of functionally active dynamic “life‐like” materials.

Development of MXene for removal of lead (Pb+) ions from wastewater

Abstract A new family of 2D materials with enhanced properties than graphene plays a crucial role in environmental remediation and sustainability. The concentration of heavy metal ions in wastewater is an emerging issue in the global scenario. Heavy metals such as lead, chromium, cadmium, etc. are natural carcinogens and adversely affect environmental species, which tend to have potential activities on the surface of the new families. Lead poisoning is a very raising issue in some parts of India and is a major effluent disposed of to the waterbodies from various industrial streams. The removal of the lead components is studied in this research using adsorption experimentation using MXene as the surface-active adsorbent. The possible mechanism for lead removal from wastewater is also discussed, as well as the effective regeneration and reusability of the adsorbent over long adsorption cycles. MXenes were applied after the confirmation using X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy and zeta-potential. The induced coupled plasma–optical emission spectroscopy confirms the lead remediation by over 96% in the first adsorption cycle, which was then reduced to over 92% in the second adsorption cycle. The lead contamination was under the permissible limits as per the water standards.

Characterization of the Zinc Uptake Repressor (Zur) from Acinetobacter baumannii.

Bacterial cells tightly regulate the intracellular concentrations of essential transition metal ions by deploying a panel of metal-regulated transcriptional repressors and activators that bind to operator-promoter regions upstream of regulated genes. Like other zinc uptake regulator (Zur) proteins, Acinetobacter baumannii Zur represses transcription of its regulon when ZnII is replete and binds more weakly to DNA when ZnII is limiting. Previous studies established that Zur proteins are homodimeric and harbor at least two metal sites per protomer or four per dimer. CdII X-ray absorption spectroscopy (XAS) of the Cd2Zn2 AbZur metalloderivative with CdII bound to the allosteric sites reveals a S(N/O)3 first coordination shell. Site-directed mutagenesis suggests that H89 and C100 from the N-terminal DNA binding domain and H107 and E122 from the C-terminal dimerization domain comprise the regulatory metal site. KZn for this allosteric site is 6.0 (±2.2) × 1012 M-1 with a functional "division of labor" among the four metal ligands. N-terminal domain ligands H89 and C100 contribute far more to KZn than H107 and E122, while C100S AbZur uniquely fails to bind to DNA tightly as measured by an in vitro transcription assay. The heterotropic allosteric coupling free energy, ΔGc, is negative, consistent with a higher KZn for the AbZur-DNA complex and defining a bioavailable ZnII set-point of ≈6 × 10-14 M. Small-angle X-ray scattering (SAXS) experiments reveal that only the wild-type Zn homodimer undergoes allosteric switching, while the C100S AbZur fails to switch. These data collectively suggest that switching to a high affinity DNA-binding conformation involves a rotation/translation of one protomer relative to the other in a way that is dependent on the integrity of C100. We place these findings in the context of other Zur proteins and Fur family repressors more broadly.

Application of Red Mineral Soil As Adsorbent for Removing Cd (II) Metal Ion from Synthetic Waste Water

This study investigates the adsorption of Cadmium (II) ions onto red mineral soil. The red mineral soil has been applied as an adsorbent for the treatment of Cadmium contaminated synthetic waste water. The adsorption study was conducted based on the parameters of pH, initial metal ion concentration, dosage amount, contact time, and temperature.

Metalloproteome plasticity - a factor in bacterial pathogen adaptive responses?

Through homeostatic processes, bacterial cells maintain intracytoplasmic metal ions at concentrations which enable the 'correct' metal to be inserted into an enzyme, thereby ensuring function. However, fluctuations in intracytoplasmic metal ion concentrations mean that under different conditions certain enzymes may contain different metals at their active site. This perspective describes examples of such cases and suggests that metalloproteome plasticity may contribute to the dynamic adaptation of pathogens to stresses in the host environment.

Efficient removal of heavy metals in water utilizing facile cross-link conjugated linoleic acid micelles.

Micellar-enhanced ultrafiltration (MEUF) technology is an effective method to treat low-concentration heavy metal wastewater. However, the leakage of surfactants in the ultrafiltration (UF) process will inevitably cause secondary pollution. In this study, a biosurfactant of conjugated linoleic acid (CLA) with conjugated double bonds was selected to bind its micelles by simple thermal crosslinking to obtain morphologically stable stearic acid (SA) nanoparticles. The pure SA nanoparticles were obtained by repeated dialysis. The stability of the SA nanoparticles was verified by comparing the particle size distribution and solubility of the materials before and after crosslinking at different pH levels. The effectiveness of SA nanoparticle-enhanced UF in removing heavy metals was verified by exploring the adsorption performance of SA nanoparticles. The dialysis device was used to simplify the UF device, wherein SA nanoparticles were assessed as adsorbents for the elimination of Cu2+, Pb2+, and Cd2+ ions from aqueous solutions under diverse process parameters, including pH, contact time, metal ion concentration, and coexisting ions. The findings indicate that the SA nanoparticles have no evidence of secondary contamination in UF and exhibit compatibility with a broad pH range and coexisting ions. The maximum adsorption capacities for Cu2+, Pb2+, and Cd2+ were determined to be 152.77, 403.56, and 271.46 mg/g, respectively.

Gold Nanoparticle-Modified Carbon-Fiber Microelectrodes for the Electrochemical Detection of Cd2+ via Fast-Scan Cyclic Voltammetry.

Neurotoxic heavy metals, such as Cd2+, pose a significant global health concern due to their increased environmental contamination and subsequent detrimental health hazards they pose to human beings. These metal ions can breach the blood-brain barrierblood-brain barrier, leading to severe and often irreversible damage to the central nervous system and other vital organs. Therefore, developing a highly sensitive, robust, and rapid in vivo detection method for these hazardous heavy metal ions is of the utmost importance for early detection, thus initiating timely therapeutics. Detecting ultra-low levels of toxic metal ions in vivo and obtaining accurate speciation information remains a challenge with conventional analytical techniques. In this study, we fabricated a novel carbon carbon-fiber microelectrode (CFM)-based sensor that can detect Cd2+ ions using fast-scan cyclic voltammetry by electrodepositing gold nanoparticles (AuNP). We optimized electrochemical parameters that generate a unique cyclic voltammogram (CV) of Cd2+ at a temporal resolution of 100 ms with our novel sensor. All our experiments were performed in tris buffer that mimics the artificial cerebellum fluid. We established a calibration curve resulting in a limit of detection (LOD) of 0.01 µM with a corresponding sensitivity of 418.02 nA/ µM. The sensor's selectivity was evaluated in the presence of other metal ions, and it was noteworthy to observe that the sensor retained its ability to produce the distinctive Cd2+ CV, even when the concentration of other metal ions was 200 times higher than that of Cd2+. We also found that our sensor could detect free Cd2+ ions in the presence of complexing agents. Furthermore, we analyzed the solution chemistry of each of those Cd2+-ligand solutions using a geochemical model, PHREEQC. The concentrations of free Cd2+ ions determined through our electrochemical data align well with geochemical modeling data, thus validating the response of our novel sensor. Furthermore, we reassessed our sensor's LOD in tris buffer based on the concentration of free Cd2+ ions determined through PHREEQC analysis, revealing an LOD of 0.00132 µM. We also demonstrated the capability of our sensor to detect Cd2+ ions in artificial urine samples, showcasing its potential for application in actual biological samples. To the best of our knowledge, this is the first AuNP-modified, CFM-based Cd2+ sensor capable of detecting ultra-low concentrations of free Cd2+ ions in different complex matrices, including artificial urine at a temporal resolution of 100 ms, making it an excellent analytical tool for future real-time, in vivo detection, particularly in the brain.

Recyclable magnetic nickel ferrite–carboxymethyl cellulose–sodium alginate bio-composite for efficient removal of nickel ion from water

In waste water treatment, magnetic bio-composites are frequently investigated as an adsorbent recently due to their great capacity for adsorption and affordability. In this current work, an attempt has been made to develop spinel nickel ferrite–carboxymethyl cellulose (NiFCMC) composite and modified its surface by alginate polymer to form NiFCMC–Alg composite. Several techniques were utilized to characterize these adsorbents including Fourier transform infrared spectroscopy, x-ray diffraction, field emission scanning electron microscopy, energy-dispersive spectra, thermogravimetric analysis, vibration sample magnetometry and pH of point zero charge. These adsorbents were explored to check their potentiality to remove Ni (II) ions in aqueous medium on various parameters such as contact time, initial metal ion concentration, pH, adsorbent dose and temperature. The optimum time for establishment of equilibrium was 180 minutes at pH 8 with adsorbent dose of 0.1 g. Results of kinetic studies revealed that the best fit for the metal ion adsorption data was the Lagergren pseudo-second-order mode indicating the chemisorption nature. Likewise, the Langmuir isotherm model also showed good agreement with adsorption equilibrium data with maximum adsorption capacities 47.84 ± 2.39 and 60.24 ± 3.01 mg/g for NiFCMC and NiFCMC–Alg respectively. The calculated adsorption thermodynamic parameters confirmed the spontaneous nature of adsorption process. The regeneration efficiency of both adsorbents was studied for five cycles and showed significant results. This study has shown that NiFCMC and NiFCMC–Alg can be a good substitute for removing Ni (II) ions in aqueous medium.

Enhanced Crystallinity of MIL-53 (Fe) and Improved Pb2+ Ion Removal by MIL-53(Fe) in the Presence of TiO2

Water pollution due to improper disposal of various contaminants is one of the most serious threats faced by living beings all around the world. Lead (Pb) is a heavy metal which is commonly added to the environment by the industries such as battery manufacturing, paints etc. According to the world health organization, the maximum bearable Pb concentration of the human body is 70 μg dL- 1. However, in a contaminated water sample, this value could range from 200 to 500 mg L-1. Thus, the efficient removal of heavy metals from contaminated water is vital. Among various removal techniques available, adsorption plays a major role due to its high efficiency, low cost and ease of designing. MOFs are a class of crystalline porous adsorbent material that consists of a metal ion/cluster and an organic linker. Owing to their tailoring ability, high porosity, and high surface area they have been widely used in the removal of contaminants from wastewater. The main objectives of this study are to synthesize MIL-53 (Fe) MOF and MIL-53/TiO2 composite and determine the Pb (II) removal efficiency under light and dark conditions. MIL-53 (Fe) MOF was synthesized using iron (III) and 1, 4-dicarboxylic acid under solvothermal conditions. The composite was synthesized similarly in the presence of TiO2 nanoparticles. The successful synthesis of MIL-53 (Fe) MOF and MOF/TiO composite was confirmed by powder X-ray diffraction and Fourier-transform infrared spectroscopy. By the Debye−Scherrer equation, 79.06 nm and 65.46 nm of crystallite size were obtained by the MOF and the MOF/TiO22 composite. Atomic absorption spectroscopy was used to determine the metal ion concentration before and after adsorption. The optimum conditions for the Pb(II) removal are as; 50 mg L-1, 25 mg L-1 initial Pb ion concentration, 10 mg, 12.5 mg of adsorbent dose (for 25 ml of 50 mg L-1 Pb (II)) and 90 min, 90 min contact time for both adsorbents at light and dark conditions respectively. The pH of the solution was kept at a neutral level to ensure the reusability of wastewater after the removal of pollutants. The adsorption isotherms of both adsorbents were well fitted with the Langmuir model indicating the monolayer adsorption. Thus, at pH 7, 396.35 mg g-1 and 786.16 mg g-1 of maximum Pb (II) adsorption capacity were obtained by the MOF and the MOF/TiO2 composite respectively. Thus, a significant improvement in the Pb (II) ion removal was observed with the composite compared to the MOF. 
 Keywords: Adsorption, Heavy metal, Isotherm, MIL-53 (Fe)

Noble Metal Nanoparticles with Nanogel Coatings: Coinage Metal Thiolate-Stabilized Glutathione Hydrogel Shells.

Developing biocompatible nanocoatings is crucial for biomedical applications. Noble metal colloidal nanoparticles with biomolecular shells are thought to combine diverse chemical and optothermal functionalities with biocompatibility. Herein, we present nanoparticles with peptide hydrogel shells that feature an unusual combination of properties: the metal core possesses localized plasmon resonance, whereas a few-nanometer-thick shells open opportunities to employ their soft framework for loading and scaffolding. We demonstrate this concept with gold and silver nanoparticles capped by glutathione peptides stacked into parallel β-sheets as they aggregate on the surface. A key role in the formation of the ordered structure is played by coinage metal(I) thiolates, i.e., Ag(I), Cu(I), and Au(I). The shell thickness can be controlled via the concentration of either metal ions or peptides. Theoretical modeling of the shell's molecular structure suggests that the thiolates have a similar conformation for all the metals and that the parallel β-sheet-like structure is a kinetic product of the peptide aggregation. Using third-order nonlinear two-dimensional infrared spectroscopy, we revealed that the ordered secondary structure is similar to the bulk hydrogels of the coinage metal thiolates of glutathione, which also consist of aggregated stacked parallel β-sheets. We expect that nanoparticles with hydrogel shells will be useful additions to the nanomaterial toolbox. The present method of nanogel coating can be applied to arbitrary surfaces where the initial deposition of the seed glutathione monolayer is possible.

Current Status and Future Prospects of Kesterite Cu2ZnSn(S,Se)4(CZTSSe) Thin Film Solar Cells Prepared via Electrochemical Deposition

AbstractThe fabrication of kesterite Cu2ZnSn(S,Se)4(CZTSSe) thin‐film solar cells using the electrochemical deposition (ED), which is valued for its industrial feasibility, offers a cost‐effective and environmentally friendly approach to the carbon‐free and clean energy production. However, the reported power conversion efficiency of approximately 10 % for electrodeposited CZTSSe thin‐film solar cells is lower compared to the alternative methods like sputtering and spin‐coating, which is mainly attributed to the phase inhomogeneity and the rough morphology generated during the ED process. Ensuring the microscopic and macroscopic uniformity of the electrodeposited films is crucial for the improvement of the film quality and the device performances. In this review, strategies to address these challenges including the intrinsic film control such as the deposition mode, pH, concentration of metal ions, and complexing agents, as well as the extrinsic approaches such as doping, substitution of metal elements, and the introduction of interfacial layers. In addition, the prospects for the electrochemically deposited CZTSSe solar cells were presented, focusing on the promising applications in tandem, flexible, and solar water‐splitting devices. Finally, this review will provide technical insights into the ED process for preparing CZTSSe solar cells, outlining a perspective for the future development of highly efficient CZTSSe thin film solar cells.

Investigating the Metallic Nanoparticles Decoration on Reduced Graphene Oxide-Based Sensors Used to Detect Sulfur Dioxide

This paper presents the impact of the decoration of reduced graphene oxide (rGO) with metallic nanoparticles to detect sulfur dioxide (SO2). Copper and platinum were employed to produce metal nanoparticles (NPs) for the chemical and physical decoration of rGO to form the nanocomposites (rGO/NPs). We optimized NP loading by varying the concentrations of metal ions and deposition times for chemical and physical decoration, respectively. The chemical decoration presents a random nanoparticle distribution on the rGO surface with a broad particle size distribution (1 to 100 nm with a majority less than 40 nm). In comparison, the physical decoration presents uniformly distributed nanoparticles with particles of a size between 1 and 20 nm, with a majority less than 10 nm. The chemically decorated structures present the best gas responses and show that lower NP loading provides better responses. The nanocomposites present responses owing to a better synergy between NPs and the rGO surface, combined with the catalytic action of the NPs on the rGO. The physical decoration allows higher NP surface coverage than the chemical one but implies a lower remaining rGO naked surface for gaseous molecule interaction. These results illustrate that the NPs’ surface and the uncovered rGO contribute to the gas response.

Concentrations of Cobalt, Chromium and Titanium and Immunological Changes after Primary Total Knee Arthroplasty-A Cohort Study with an 18-Year Follow-Up.

Background: Total knee arthroplasty (TKA) generates elevated metal ion concentrations, but long-term changes in the concentrations of cobalt (Co), chromium (Cr) and titanium (Ti) after primary TKA and potential subsequent immune system activation-not limited to the joint but systemically-are not known. Patients and Methods: We conducted a cohort study on 26 patients with TKA (19 women; 16 with metal-backed and 10 with all-polyethylene tibial components) 18.3 years (min. 16.7, max. 20.5) after index TKA. A total of 69% of patients additionally underwent subsequent arthroplasty of the contralateral knee or either hip after the index surgery. Blood samples were analysed by inductively coupled plasma-mass spectrometry, and leukocytes were characterised by flow cytometry. Patients were clinically assessed using the Knee Society score and by plain radiography of the knee. Results: The median metal ion concentrations were 0.7 (0.1-13.0) µg/L for Co, 0.9 (0.4-5.0) µg/L for Cr, and 1.0 (0.2-13.0) µg/L for Ti. There was no relevant difference in systemic metal ion concentrations between patients exposed to single and multiple arthroplasties. The absolute count and proportion of CD3+CD4+CD8+ T cells was inversely correlated with both Co (rho -0.55, p = 0.003) and Cr concentrations (rho -0.59, p = 0.001). Conclusions: Between the first and second decades after primary TKA, in most patients, the concentrations of Co, Cr and Ti in blood samples were below the thresholds that are considered alarming. The negative correlation of Co and Cr concentrations with a subset of lymphocytes that commonly increases during immune activation is reassuring. This represents a worst-case scenario, underscoring that the investigated metal ions remain within reasonable ranges, even after additional hardware exposure.

Oil Palm Biomass Sap-Rotten Rice as a Source to Remove Metal Ions and Generate Electricity as By-Products through Microbial Fuel Cell Technology

Microbial fuel cell (MFC) is a new and interesting technology that can be used to treat wastewater without using electricity. The current research focuses on electron generation, which is one of the technique’s major challenges. According to the latest literature, the study was planned to successfully remove the metals from artificial wastewater at high concentrations and generate electricity. On average, after 18 days of operation, it offered 610 mV with 1000 ῼ constant external resistance. The internal resistance was found to be 520 ῼ. The achieved power density was 3.164 mW/m2 at an external resistance of 1000 ῼ. The achieved removal efficiencies of Pb2+, Cd2+, Cr3+, and Ni2+ were 83.67%, 84.10%, 84.55%, and 95.99%, respectively. The operation lasted for 25 days. The cyclic voltameter studies show that there is a gradual oxidation rate of organic substances, while on day 25, the removal efficiency reached its maximum. The specific capacitance was found to be high between days 15 and 20, i.e., 0.0000540 F/g. It also indicated that biofilm was stable around day 18. Furthermore, the biological characterization also demonstrated that MFC operation was very smooth throughout the process, even at high concentrations (100 mg/L) of metal ions. Finally, there is the MFC method, as well as some new challenges and future recommendations.

Lignin‐Alkali Metal Ion Self‐Catalytic System Initiated Rapid Polymerization of Hydrogel Electrolyte with High Strength and Anti‐Freezing Ability

AbstractHydrogel electrolyte is not resistant to freezing and has weak mechanical properties, and its fabrication is time‐consuming and energy‐consuming, limiting its application. Here, a simple, universal, and fast gelation based on dealkaline lignin (DL) ‐alkali metal ions is developed. The complex formed by catechol and alkali metal ions promotes the equilibrium of redox reactions. The produced SO4−·, OH· and singlet oxygen (1O2) radicals are responsible for the rapid polymerization of vinyl monomers. Alkali metal ions play a dual role in the rapid polymerization and frost resistance of hydrogel electrolytes. By modulating the mass ratio of DL and metal ion concentration, the preferred hydrogel electrolyte can be fabricated in an alkaline aqueous solution for 4 min at room temperature and possesses excellent anti‐freezing performance (0.51 mS cm−1 at −40 °C) and strong mechanical properties (tensile stress: 0.4 MPa, strain: 1125%). The hydrogel electrolyte‐assembled supercapacitor exhibits high stability at low temperatures. The specific capacitance retention is 89.7 % and 88.7 % after 5000 charge/discharge cycles at 25 and −20 °C, respectively. The lignin‐alkali metal ions self‐catalytic system completely different from the reported lignin‐oxidizing metal ion system will open up a new way for the fabrication of anti‐freezing ionic conductors and energy storage devices.

Overexpression of vacuolar transporters OsVIT1 and OsVIT2 reduces cadmium accumulation in rice.

Excessive cadmium in rice grain in agricultural production is an important issue to be addressed in some southern regions of China. In this study, we constructed transgenic rice overexpressing OsVIT1 and OsVIT2 driven by 35S promoter in the cultivar ZH11. Compared with ZH11, OsVIT1 expression in leaves was significantly increased by 3-6.6 times and OsVIT2 expression in leaves was significantly increased by 2-2.5 times. Hydroponic experiments showed that overexpression of OsVIT1 and OsVIT2 increased the tolerance to Fe deficiency, significantly reduced Cd content in shoot and xylem sap, and had no effect on Cd tolerance in rice. Two years of field trials showed that the Fe content in the grain of OsVIT1 and OsVIT2 overexpressed materials was significantly reduced by 20-40% and the straw Fe content was significantly increased by 10-45%, and the grain Fe content distribution ratio was significantly decreased and the straw Fe distribution ratio was significantly increased compared with the wild type. The OsVIT1 and OsVIT2 overexpressed materials significantly reduced the Cd content of grain by 40-80% and the Cd content of straws by 37-77%, and the bioconcentration factor of Cd was significantly reduced in both grains and straw of OsVIT1 and OsVIT2 overexpressed materials. Overexpression of OsVIT1 and OsVIT2 did not affect the concentration of other metal ions in rice straw and grain. qRT-PCR analysis showed that the expression of the low affinity cation transporter OsLCT1 was significantly downregulated in the OsVIT1 and OsVIT2 overexpressed materials. In conclusion, overexpression of OsVIT1 and OsVIT2 reduced Cd accumulation in straw and grains, providing a strategy for Cd reduction in rice.

Synthesis of Nano-silica Oxide for Heavy Metal Decontamination from Aqueous Solutions

In the current study, nano-silica oxide (nano-SiO2) was fabricated via the sol-gel technique. Then, the prepared nano-SiO2 was characterized using X-ray diffractometer (XRD), transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and Brunauer-Emmett-Teller (BET) specific surface area analysis. Furthermore, the fabricated nano-SiO2 was applied for the adsorption of lead Pb (II) and chromium Cr (VI) from aqueous solutions. Additionally, the influence of different operating factors such as contact time (0–180 min), initial pH (1–11), nano-SiO2 dose (0.1–8 g L−1), initial metal ion concentration (5–100 mg L−1), and the temperature (30–85 °C) was investigated. The nano-SiO2 doses of 0.5 and 1 g L−1 were selected as the optimal adsorbent dose for the removal of Pb (II) and Cr (VI), respectively. These doses achieved a removal efficiency of 82.3% and 78.5% for Pb (II) and Cr (VI), after 60 and 90 min, at initial pH values of 5 and 2, respectively, using 10 mg L−1 initial metal concentration, and at room temperature. Lastly, kinetic and equilibrium studies were competently fitted using the pseudo-second-order and Freundlich models, respectively. Adsorption thermodynamic studies designate the spontaneous and thermodynamic nature of the adsorption process. These results reveal the efficiency of the fabricated nano-SiO2 as an adsorbent for heavy metal removal from aqueous solutions.Graphical

Heavy metal decontamination by ion exchange polymers for water purification: counterintuitive cation removal by an anion exchange polymer

Ion exchange polymers were used for mercury and lead ions removal in water. The heavy metal ion concentration was analyzed by two independent methods: inductively coupled plasma–optical emission spectroscopy (ICP-OES) and gravimetry. The studied cation exchange polymer (CEP) was sulfonated poly(ether ether ketone) (SPEEK), and the anion exchange polymer (AEP) was poly(sulfone trimethylammonium) chloride (PSU-TMA). The removal capacity was connected with the ion exchange capacity (IEC) equal to 1.6 meq/g for both polymers. The concentration ranges were 0.15–0.006 mM for Hg2+ and 10.8–1.0 mM for Pb2+. SPEEK achieved 100% removal efficiency for mercury and lead if the concentration was below the maximum sorption capacity (Qmax), which was about 210 mg/g for Pb2+ with SPEEK. For PSU-TMA, the surprising removal efficiency of 100% for Hg2+, which seemed incompatible with ion exchange, was related to the formation of very stable complex anions that can be sorbed by an AEP. Langmuir adsorption theory was applied for the thermodynamic description of lead removal by SPEEK. A second-order law was effective to describe the kinetics of the process.

Achieving Less Than 100 ppb Total Metal Ion Concentration in ESCAP Resins Synthesized by Atom Transfer Radical Polymerization

AbstractIn the photolithography process of integrated circuits （IC） manufacturing, it is desired that the photoresist resins have both smaller polydispersity index (PDI) and lower trace metal ion concentrations. The commercial environmentally stable chemical amplified photoresist (ESCAP) resins for 248 nm lithography are synthesized by free radical polymerization with PDI >1.5. Although using atom transfer radical polymerization (ATRP) can result in lower PDI, the potential of high metal ion contamination is a major concern, as the reaction initiators usually are copper‐containing compounds. In this study, copolymer of p‐acetoxy styrene and tert‐butyl acrylate [poly(AOST‐co‐TBA)] is synthesized via ATRP achieving PDI as low as 1.25. It is then purified by ion exchange with two different resins, IRC747 and A15, which are effective at removing Cu and other metal ions. This reduces the total metal ion concentration in the copolymer powder to <30 ppb with individual metal ion <6 ppb. This is the first reported ATRP synthesized ESCAP resin having both low PDI and metal ion concentrations suitable for 248 nm photoresist application.