Anion Exchange Research Articles

Process-induced protein aggregates influenced pea globulins’ structure formation upon heating

Pea protein ingredients play key role in formulations of plant-based foods. However, functional properties of pea ingredients are inconsistent depending on extraction process. Protein aggregation occurs simultaneously during protein extraction, thus examining the protein aggregated states as induced by processing is essential for better process design. This study investigated the influence of process-induced protein aggregated states on structure formation upon heating of pea protein ingredients. Combining rheological, spectroscopic, and microscopic techniques, the mechanisms underlining heat-induced structure formation have been unveiled from microscopic to macroscopic scales. The salt-extracted isolate (PPI*) where protein aggregation was minimized, developed mesh-like structure through intermolecular protein-protein interaction upon gelling similar to commercial protein concentrate (PPC). In turn, commercial isolate (PPI) as appeared as microscopic particles, formed gel through accumulation of protein particles with no structure development. The aggregated states of PPI* and PPI seemed to dictate vicilin and legumin purification by means of anion exchange chromatography. Purification process promoted intermolecular protein aggregate structures. However, these purified fractions regardless of parent isolates showed similar structure development as PPC and PPI* during gelling. Monitoring protein aggregation during extraction process can be a key to limit functional property variation in pea protein ingredients.

EXTRACTION AND CONCENTRATION OF RHENIUM FROM NITRATE-CONTAINING RHENIUM DESORBATE

Extraction technology plays a key role in the industrial production of rhenium, accounting for more than 70% of the world's production of this element. In aqueous and alkaline solutions, rhenium is present in the form of the anion ReO4 - , which necessitates the use of anion exchange extractants based on tertiary amines. Despite the widespread application and many years of research on rhenium extraction with amines, the obtained data remain contradictory. The extraction of rhenium from aqueous solutions by an amine extractant occurs through an anion exchange mechanism with the formation of the complex TAAHReO4. To increase the solubility of amine salts in the organic phase, high-molecular-weight aliphatic alcohols, such as decyl alcohol, are added, which act as modifiers of the organic phase without extracting rhenium themselves. The aim of this work is to investigate the extraction of rhenium with trialkylamine from a model solution that simulates the composition of nitrate desorbate obtained from the processing of uranium ores. Specifically, various factors affecting the extraction and reextraction of rhenium are studied to determine the optimal parameters of these processes. The study uses trialkylamine as the extractant and decyl alcohol as the modifying additive. The results of the study show that the optimal parameters for rhenium extraction are: an extractant concentration of TAA:DA:kerosene=40:5:55 (% by volume), an organic to aqueous phase ratio of V_org/aq = 1:5, an extraction time of 5 minutes, and a rhenium extraction rate of up to 75%. Similar results were obtained with an extractant concentration of TAA:DA:kerosene = 30:10:60 and an extraction time of 5 minutes, where the rhenium extraction rate was about 74%. The re-extraction of rhenium is most efficiently carried out using an ammonia solution with a concentration of 114 g/L NH3⋅H2O and a phase contact time of 10 minutes, with a re-extraction rate of 85.5%. Similar results were obtained with the addition of 174 g/L (NH4)2SO4, where the rhenium re-extraction rate was 82%.

The emerging application of LC-based metallomics techniques to unravel the bioinorganic chemistry of toxic metal(loid)s

The on-going anthropogenic emission of toxic metal(loid) species into the environment contaminates the food supply and drinking water resources in various parts of the world. Given that inorganic pollutants cannot be degraded, their increased influx into the bloodstream of babies, children and pregnant women is inevitable. Since the ramifications of the ensuing environmental exposure on human health remain poorly defined, fundamentally new insight into their bioinorganic chemistry in organisms is urgently needed. Based on the flow of dietary constituents through organisms, the interaction of toxic metal(loid) species with biomolecules in the bloodstream deserve particular attention as they play an integral role in the mechanisms of their chronic toxicity. Gaining insight into these bioinorganic processes is hampered by the biological complexity of plasma/red blood cells and the low concentrations of the metal(loid) species of interest, but can be overcome by employing LC techniques hyphenated to atomic spectroscopic detectors (i.e. metallomics techniques). This perspective aims to highlight the potential of unconventional hyphenated separation modes to advance our understanding of the bioinorganic chemistry of toxic metal(loid) species in the bloodstream-organ system. Four examples are illustrated. The application of anion-exchange (AEX) and size-exclusion chromatography (SEC) provided new insight into the blood-based bioinorganic mechanisms that direct Cd2+ and MeHg+ to target organs. AEX chromatography also allowed to observe the formation of complexes between Hg2+ and MeHg+ with L-cysteine at pH 7.4, that are implicated in their organ uptake. Lastly, the application of reversed phase (RP) chromatography revealed a possible cytosolic mechanism by which N-acetyl-L-cysteine binds to MeHg+ in the presence of cytosolic glutathione (GSH). New insight into other bioinorganic processes may advance the regulatory framework to better protect public health.

Robustness evaluation of weak anion exchange chromatography method for the purity analysis of therapeutic oligonucleotides

Therapeutic oligonucleotides are becoming an important class of therapeutics. Their manufacturing processes can result in the formation of impurities, particularly truncated species. To ensure the quality and safety of the product, it is crucial to evaluate the presence of these species. Liquid chromatography analysis enables such purity determination. In this context, a recently described weak anion exchange chromatography method was optimized to allow the effective separation of different impurities. The optimization addressed the complexity and instability of the mobile phases, which contained salts and organic compounds. Adjustments were made to the mobile phase composition and gradient to meet the requirements of QC laboratories. Additionally, to ensure the method's reliability, a robustness study was conducted based on a risk assessment. Five factors were considered potential risks and were assessed experimentally on different chromatographic outputs. This led to the definition of a robust space, ensuring the method's reliability for the purity determination of oligonucleotides.

Anion exchange effect on structural, antibacterial activity and molecular docking of 1-methyl-3-(4-vinylbenzyl) imidazol-3-ium chloride/bis(trifluoromethylsulfonyl)imide/hexaflurophosphate: Experimental and DFT approach

The impact of NTF2− and PF6− anions on the physical, chemical and antibacterial characteristics of ionic liquids (ILs) based 1-methyl-3-(4-vinylbenzyl) imidazol-3-ium VBMIM+ cations is the subject of this work. The molecular structures were compared to the DFT-optimized ones after being investigated experimentally using FTIR and NMR spectroscopy. As a result, the different vibrational modes were identified and assigned. However, DSC and TGA have been used to examine the thermal properties of the ILs. The compounds depicted good thermal stability. Furthermore, different parameters were computed to get insights on the stability and reactivity of the chemical. The ILs were tested for their antibacterial and fungicidal activities against nine reference strains of gram-negative and gram-positive bacteria. Finally, the discovered biological results were supported by the molecular docking analysis.

Strong electronic metal-support interaction of Ni4Mo/N-SrMoO4 promotes alkaline hydrogen electrocatalysis

Ni4Mo electrocatalyst stands out as the promising candidate for hydrogen evolution/oxidation reaction (HER/HOR), yet the intensive hydrogen adsorption leads to sluggish kinetics, decreasing hydrogen catalysis efficiency. Herein, the structure of Ni4Mo nanoparticles anchored on wafer-biscuit-like N-SrMoO4 nanorods (Ni4Mo/N-SrMoO4) is developed to accelerate reaction kinetics by modulating electronic structure. The designed N-SrMoO4 support enables strong electronic metal-support interaction with Ni4Mo, resulting in a downward shift of d-band center and achieving thermally neutral hydrogen adsorption. Ni4Mo/N-SrMoO4 exhibits HER performance with an ultralow overpotential of 15 mV at 10 mA cm−2, superior to Pt/C (η10=18 mV). The outstanding exchange current density of 10.2 mA cm−2 for HOR is three times higher than that of Pt/C (3.5 mA cm−2). Ni4Mo/N-SrMoO4 is further assembled in anion exchange membrane water electrolyzer (AEMWE), resulting in a current density of 100 mA cm−2 at voltage of 1.71 V and the excellent stability of 300 hours. Theoretical calculations and in-situ spectroscopy indicate that the introduction of Sr in N-SrMoO4 effectively enhances electronic metal-support interaction, facilitates the enrichment of adsorbed hydroxyl (OHads) on active sites and weakens hydrogen adsorption on Ni4Mo, thereby accelerating reaction kinetics of hydrogen electrocatalysis.

Fractionation, characterization, and assessment of nutritional and immunostimulatory protein-rich polysaccharide-protein complexes isolated from Lentinula edodes mushroom

This study aimed to fractionate and characterize the protein-rich polysaccharide-protein (PSP) complexes from a well-known edible mushroom, Lentinula edodes, and assess their nutritional and immunostimulatory properties. Crude PSP isolated from the mushroom water extract was purified by anion exchange chromatography, yielding fractions PSP-F1 and PSP-F2 containing 66.1 % and 74.0 % protein, respectively. Both fractions exhibited primarily β-sheet and random-coil protein structures, though the crude PSP fraction exhibited an additional α-helix structure. On SDS-PAGE, PSP-F1 showed two molecular weight bands, one below 10 kDa and another at 34 kDa, and PSP-F2 showed several bands, one below 10 kDa and others between 34 and 95 kDa. The nutritional value of essential and non-essential amino acid profiles was in the order of PSP-F2 > PSP-F1 > crude PSP; the amino acid ratio coefficient values of the crude PSP, PSP-F1, and PSP-F2 were 63 %, 67 %, and 72 %, respectively. The combination of PS and PSP fractions exhibited stronger immunoactivity than PSP-F1 or PSP-F2 alone. PSP-F2 showed a higher immunostimulatory activity than PSP-F1 in RAW264.7 cell culture. PSP-F2 was also more abundant of easily absorbed high-quality proteins. The results provide useful references for dietary and medicinal uses of PSP fractions in L. edodes and other edible mushrooms.

Impact of functionalized titanium oxide on anion exchange membranes derived from chemically modified PET bottles

The accessibility of newly affordable materials has drawn significant attention to the anion exchange membrane (AEM) technology. However, developing a high-performance AEM with excellent hydroxide conductivity and long-term durability is still challenging. The present work aims to improve the overall properties of AEMs synthesized by chemical modification of Polyethylene terephthalate (PET) bottles as the starting material. The modified PET structure was confirmed using IR, NMR, and HPLC-ESIMS analyses. AEMs were developed by incorporating quaternary ammonium (QA) functional groups into the modified PET structure, necessary for transporting anionic species (OH−). In addition, TiO2 nanoparticles grafted with silane coupling agents containing amine functional groups were synthesized via the sol-gel method and embedded in the polymer matrix. Then, the prepared nanocomposite membranes were thoroughly characterized, and the results displayed an overall improvement in the membrane's physicochemical properties. The composite membrane with 3wt% content of nanoparticle (NC3 %/M-PETm) showed remarkable conductivity, reaching 126 mS/cm at 80 °C, doubling the value of pristine membranes (64 mS/cm) while also displaying alkaline stability, retaining up to 92.2 % of conductivity after 20 days in harsh 2 M KOH at 80 °C. These results proved the suitability of these membranes for electrochemical energy applications. This innovative approach offers potential cost savings in preparing the new membranes while aligning with sustainable and circular economy principles.

Simultaneous efficient production of hydrogen peroxide, urea and H2 by bifunctional Cu-doped TiO2 electrocatalyst from CO2, N2 and water

The production of three separated, high-value chemicals (H2O2, urea and H2) from CO2, N2, and H2O represents a significant challenge. It is a prospective and innovative way to simultaneously produce these chemicals in an anion exchange membrane (AEM) electrolyzer, which couples anodic 2e- water oxidation (2e-WOR) and cathodic CO2, N2 and water reduction reaction (CNWRR), but has not yet been realized. Here, we found that bifunctional CuxTi1-xO2-y catalysts can be employed in the electrochemical production of H2O2, urea and H2 from CO2, N2 and water, and the optimized Cu0.12Ti0.88O2-y catalyst exhibits an excellent productivity of 11.8 μmol cm−2 min−1, 0.3 mg cm-2h−1 and 0.82 mmol cm-2h−1 for H2O2, urea and H2 at 4.0 V (50 mA cm−2) in AEM electrolyzer, respectively. Theoretical calculations reveal that the superior performance of the 2e-WOR and CNWRR is attributed to the Cu doping effect, which not only promotes the coupling of *OH but also optimizes the adsorption energy barriers of COOH* and NNH*. It is worth noting that the AEM electrolyzer assembled by bifunctional Cu0.12Ti0.88O2-y reaches a current density of 50 mA cm−2 with a cell voltage of 4.0 V and exhibits excellent stability of 50-hour continuous operation.

Research progress and prospect of anionic exchange membrane electrolyzer and OER electrocatalysts

Research progress and prospect of anionic exchange membrane electrolyzer and OER electrocatalysts

Plasma Induced Atomic-Scale Soldering Enhanced Efficiency and Stability of Electrocatalysts for Ampere-Level Current Density Water Splitting.

Industrial water electrolysis typically operates at high current densities, the efficiency and stability of catalysts are greatly influenced by mass transport processes and adhesion with substrates. The core scientific issues revolve around reducing transport overpotential losses and enhancing catalyst-substrate binding to ensure long-term performance. Herein, vertical Ni-Co-P is synthesized and employed plasma treatment for dual modification of its surface and interface with the substrate. The (N)Ni-Co-P/Ni3N cathode exhibits an ultra-low overpotential of 421 mV at 4000 mA cm-2, and the non-noble metal system only requires a voltage of 1.85 V to reach 1000 mA cm-2. When integrated into an anion exchange membrane (AEM) electrolyzer, it can operate stably for >300 h at 500 mA cm-2. Under natural light, the solar-driven AEM electrolyzer operates at a current density up to 1585 mA cm-2 with a solar-to-hydrogen efficiency (SHT) of 9.08%. Density functional theory (DFT) calculations reveal that plasma modification leads to an "atomic-scale soldering" effect, where the Ni3N strong coupling with the Co increases free charge density, simultaneously enhancing stability and conductivity. This research offers a promising avenue for optimizing ampere-level current density water splitting, paving the way for efficient and sustainable industrial hydrogen production.

Itching for Answers: A Comprehensive Review of Cholestatic Pruritus Treatments

Cholestasis is a clinical and laboratory syndrome indicating impaired bile production or excretion. One of the hallmark symptoms of cholestasis is pruritus. Itch can be severe and debilitating for patients, impacting their quality of life similarly to pain, and, in some cases, it can be refractory. Current therapies like anion exchange resins and rifampicin, offer partial relief but with side effects. Effective, well-tolerated treatments are urgently needed. This literature review examines existing options (bile acid sequestrants, antihistamines, opioid antagonists, sertraline, and rifampicin) and explores novel therapies (monoclonal antibodies, PPAR agonists, and bile-acid-based therapies). We analyze mechanisms, limitations, and adverse effects to aid clinicians and researchers. Novel approaches include monoclonal antibodies to inhibit bile recirculation and PPAR agonists targeting pruritus signaling. Despite the limited current options, ongoing research promises better treatments for cholestatic pruritus, addressing its distressing impact. In summary, cholestasis-associated pruritus poses a significant challenge with limited treatments. Advancements in understanding its pathophysiology offer hope for more effective therapies in the future.

Impact of side chain length on the properties and alkaline fuel cell performance of OEG-grafted poly(terphenyl piperidinium) anion exchange membranes

In designing comb-shaped anion exchange membranes (AEMs), replacing alkyl side chains with ethylene glycol (EG)-based ones significantly enhances membrane properties and boosts AEM fuel cell performance. Although much research has focused on optimizing the placement of EG segments within the polymer matrix, the effect of EG chain length remains less explored. In this work, a series of poly(terphenyl piperidinium) AEMs with N-oligo(ethylene glycol) (OEG) terminal pendants having two to five EG repeating units were prepared by simple post-polymerization quaternization. The membrane properties showed a strong correlation with the length of the OEG side chains, influenced by both chemical composition and phase behavior. Among the OEG-grafted AEMs, PTP-OEG3 with moderate three EG repeating units, exhibited the best properties due to a careful balance between EG and cationic groups, leading to a favorable microphased separation. It achieved high hydroxide conductivity (114 mS cm−1 at 80 °C in water), robust mechanical strength (tensile strength >52 MPa), and good ex situ alkaline stability. As a result, the AEM fuel cells with the property-balanced PTP-OEG3 membrane achieved the highest peak power density of 976 mW cm−2. The in situ stability of these AEMs was also investigated. Evidently, understanding the optimal EG side chain length is an important criterion for designing AEM materials for alkaline fuel cells.

1H-NMR, HPSEC-RID, and HPAEC-PAD Characterization of Polysaccharides Extracted by Hydrodynamic Cavitation from Apple and Pomegranate By-Products for Their Valorization: A Focus on Pectin

Several chemical analytical methods were applied to characterize the chemical structure of polysaccharides extracted from discarded apples and pomegranate peels using hydrodynamic cavitation methods in a circular economy perspective. In particular, the purity of the polysaccharides and the degrees of acetylation and methylation were evaluated by proton Nuclear Magnetic Resonance (1H-NMR) analysis; simple sugars and galacturonic acid were analyzed simultaneously by High-Performance Anion Exchange Chromatography—Pulsed Amperometric Detector (HPAEC-PAD); the molecular weight of the extracted polysaccharides was determined by High-Performance Size Exclusion Chromatography-Refractive Index Detector (HPSEC-RID). The results showed a negligible presence of co-precipitated proteins/tannins, easily removed by dialysis, as well as other co-precipitated molecules such as monosaccharides and organic acids. Polysaccharides from apples consisted mainly of pectic material with a prevalence of homogalacturonans. Polysaccharides from pomegranate peels showed greater compositional variability with significant amounts of arabinose and galactose, a lower content of pectin, and the presence of rhamnogalacturonans I. Both polysaccharides were highly methylated and differed in the degree of acetylation, which could lead to different properties. Polysaccharides from apples presented two main molecular weights (>805 kDa and 348–805 kDa, respectively), while those from pomegranate peel showed a major fraction at 348 kDa and minor fractions < 23 kDa. In conclusion, the research tools proposed by this study have allowed defining the macrostructure of polysaccharides in a quick and efficient way to valorize these food by-products.

Deciphering Anion Exchange Membrane Water Electrolysis: A Distribution of Relaxation Times Approach

Anion exchange membrane water electrolysis (AEM-WE) is a promising method for hydrogen production, offering advantages over proton exchange membrane water electrolysis (PEM-WE), such as the use of nonprecious metal catalysts and perfluorosulfonic acid free membranes. Despite achieving impressive current densities, challenges in efficiency and stability remain. This study employs electrochemical impedance spectroscopy (EIS), the equivalent circuit model (ECM) and distribution of relaxation times (DRT) analysis to investigate AEM-WE cells. DRT analysis identifies and quantifies five loss mechanisms within the AEM-WE system, including hydrogen and oxygen evolution reactions and ionic transport losses. Long-term experiments reveal catalyst degradation and its impact on performance, providing insights for targeted optimisation. The findings enhance understanding of the electrochemical processes in AEM-WE, offering pathways to improve stability and efficiency.

Weakening O-Intermediates Adsorption Strength Over the Pd Metallene via Lewis-Acidic Site Modulation for Enhanced Oxygen Reduction.

The reasonable design and modulation of the electronic properties of Pd metallene are acknowledged as a promising avenue for enhancing the oxygen reduction reaction (ORR) in anion exchange membrane fuel cells (AEMFCs), yet they remain a formidable challenge. Herein, a thin-sheet structure of Zr-doped Pd metallene (PdZr metallene) with abundant defects is proposed using a facile wet-chemical approach for efficient and highly durable ORR electrocatalysis. Multiple microstructural analyses uncover that orchestrated electronic and oxophilic regulation of PdZr metallene via Lewis-acidic Zr site modulation could concurrently optimize the electronic configuration of Pd, downshift the d-band center of Pd, and, thus, promote the intrinsic activity. Benefiting from the unique two-dimensional morphology and electronic structure optimization facilitated by the Zr coupling effect, the resultant PdZr metallene demonstrates significantly enhanced ORR electrocatalytic performance in basic solutions, with a high half-wave potential (E1/2) of 0.87 V and commendable stability for 30 000 s, surpassing those of Pd metallene and various advanced Pd-based catalysts reported in the literature. Encouragingly, the PdZr metallene-based AEMFC achieves an increased maximum power density (90.4 mW cm-2) and impressive robustness over 12 h in an alkaline environment, manifesting the practical application of PdZr metallene in AEMFCs. This study showcases the applicability of PdZr metallene via Lewis acid site regulation for fabricating highly active electrocatalysts for high-performance AEMFCs.

Transport Mechanism of Hydroxide Ions Focused on the Vehicle Mechanism Near the Cation Sites in Anion Exchange Membranes

We investigated the transport factors of hydroxide ions in anion exchange membrane (AEM). We used partially fluorinated quaternized QPAF-4 polymer with trimethylammonium groups as the AEM material and analyzed it using classical molecular dynamics (MD) simulations. Analysis of the dependence of density on water content (λ) suggested that the voids in the QPAF-4 polymer are fully filled with water molecules under high λ conditions (λ = 15), and as the polymer absorbs additional water molecules, it expands, resulting in a decrease in density. Furthermore, radial distribution function analysis and existence ratio analysis of hydroxide ions in the solvation shells of trimethylammonium groups indicated that increasing λ reduces the overlap of the first solvation shells and causes hydroxide ions to migrate from the first to the second solvation shell. This result indicates that these structural factors contribute to the enhanced diffusivity of hydroxide ions under high λ conditions.

Development of a Superior Anion Exchange Membrane with Hyperbranched Polymer for Anion Exchange Membrane Water Electrolysis

The production of hydrogen using membrane-based electrolyzersposes significant advantages and benefits compared to traditionalelectrolysis methods. Among the electrolyzers, anion exchangemembrane water electrolysis (AEMWE) has emerged as one of thepromising technologies owing to its unique advantages. However,the development of efficient AEMs for water electrolysis presentssignificant challenges, particularly in achieving enhanceddimensional stability and conductivity. In this study, ahyperbranched polyesteramide (HPEA) was synthesized andblended with poly(ether sulfone) (PES) to address the challenges.The resulting QPES-HPEA blend membrane exhibited a lowswelling ratio and high water uptake, which are critical formaintaining dimensional stability and enhancing the hydroxide iontransport efficiency of AEM. The enhanced physical properties andoptimized structure of the membrane make it a promising candidatefor next-generation AEMs in water electrolysis systems.

Deciphering Anion Exchange Membrane Water Electrolysis: A Distribution of Relaxation Times Approach

Anion exchange membrane water electrolysis (AEM-WE) is a promising method for hydrogen production, offering advantages over proton exchange membrane water electrolysis (PEM-WE), such as the use of nonprecious metal catalysts and perfluorosulfonic acid free membranes. Despite achieving impressive current densities, challenges in efficiency and stability remain. This study employs electrochemical impedance spectroscopy (EIS), the equivalent circuit model (ECM) and distribution of relaxation times (DRT) analysis to investigate AEM-WE cells. DRT analysis identifies and quantifies five loss mechanisms within the AEM-WE system, including hydrogen and oxygen evolution reactions and ionic transport losses. Long-term experiments reveal catalyst degradation and its impact on performance, providing insights for targeted optimisation. The findings enhance understanding of the electrochemical processes in AEM-WE, offering pathways to improve stability and efficiency.

Ion exchange in semiconductor magic-size clusters.

As a crucial post-synthesis method, ion exchange allows for precise control over the composition, interface, and morphology of nanocrystals at the atomic scale, achieving material properties that are difficult to obtain with traditional synthesis techniques. In nanomaterial science, semiconductor magic-size clusters (MSCs), with their atomic-level precision and unique quantum confinement effects, serve as a bridge between molecules and nanocrystals. Despite this, research on ion exchange in MSCs is still in its infancy. This review introduces the principles of ion exchange and reactions in colloidal nanocrystals and MSCs, analyzing the importance and challenges of ion exchange in studying MSCs. This paper begins with a focus on the current research progress of cation and anion exchange in II-VI and III-V semiconductor MSCs. Then, the common methods for characterizing MSCs during the ion exchange process are discussed. Finally, the article envisions future research directions based on MSCs' ion exchange. Research on MSCs' ion exchange not only aids in designing MSCs with complex functionalities, but also plays an essential role in elucidating the ion exchange mechanisms in nanocrystals, providing new insights for the innovative design and synthesis of nanomaterials.