Chelation Reaction Research Articles

Interfacial Metal-Solvent Chelation for Direct Regeneration of LiFePO4 Cathode Black Mass.

Direct regeneration of spent lithium-ion batteries presents a promising approach to effectively reuse valuable resources and benefit the environment. Unlike controlled laboratory conditions that commonly facilitate impurity purification and minimize structural damage, the LiFePO4 cathode black mass faces significant interfacial challenges, including structure deterioration, cathode-electrolyte interphase residues, and damage from storage procedures, which hinder lithium replenishment and structure regeneration. Here, a metal-solvent chelation reaction using a lithium acetylacetonate solution is introduced to address these challenges under ambient conditions. This method regulates the near-surface structure through strong chelation between Acac‒ anions and Fe (III) elements, thus effectively eliminating the degraded amorphous phase and residual fluorine compounds. By direct lithium connection and reducing diffusion barriers, the reconstructed surface facilitates the re-lithiation process. The regenerated LiFePO4 cathodes demonstrate a capacity retention of 88.5% after 400 cycles at 1 C, while also outperforming traditional recycling methods in terms of environmental and economic benefits. This approach provides a promising solution for regenerating degraded LiFePO4 cathodes from actual dismantled black mass, thereby accelerating the practical application of battery recycling.

Zinc Oxide Nanoparticles Incorporated in Poly-Hydroxyethyl Methacrylate/Acrylamide Membrane Trigger the Key Events of Full-Thickness Wound Healing in a Rabbit Model.

Zinc oxide nanoparticles are known to possess anti-inflammatory, antibacterial, and antiseptic properties and find wide application in the preparation of topical ointments. Wound dressings in the form of hydrogels can replenish the wound microenvironment to aid the healing process in a multidimensional way. We have fabricated a composite hydrogel using 1-3 wt. % ZnO nano-particles, synthesized by chelation reaction, and poly-2-hydroxyethyl methacrylate (pHEMA)/acrylamide, synthesized, and co-polymerized in 8 kGy gamma irradiation. Developed powders and composite membranes have been thoroughly analyzed for XRD, FTIR, SEM-EDX mapping, DTA/TGA, particle size, shape, morphology, porosity, water uptake, and contact angle. Thermally stable phase-pure ZnO spherical nanoparticles with an average crystallite size of 40 ± 2 nm have been used for fabricating well-dispersed composite with contact angle varying 78o-88o. These membranes, when used invivo, rendered a suitable environment conducive to tissue regeneration and ECM component deposition sequentially. Endowed with antibacterial properties, these hydrogels also demonstrated excelling swelling capacity which proved beneficial in maintaining a moist wound environment aiding in the healing process. An earlier wound closure was achieved with 2%-3% ZnO-pHEMA/acrylamide hydrogels which demonstrate the potential of ZnO nanoparticles in signaling and instructing the wound bed milieu towards the efficient repair.

An intelligent chitosan/polyvinyl alcohol film with two types of anthocyanins for improved color recognition accuracy and monitoring fresh-cut pineapple freshness

In this study, chitosan (CS), polyvinyl alcohol (PVA), and sodium tripolyphosphate (STPP) were used as bases to introduce a blend of black wolfberry (BW) and red cabbage (RC) anthocyanins. The chelation reaction of CS, PVA, and STPP resulted in the composite anthocyanins being fixed within the matrix with an appropriate ratio of composite anthocyanins stably distributed in the film. The FTIR and X-ray analyses revealed that the addition of both types of anthocyanins strengthened hydrogen bond interactions. Moreover, the CP/BR-4 film exhibited excellent antioxidant, mechanical, and antibacterial properties, as well as a sensitive and rapid response to acidic substances. The freshness of pineapples stored under refrigeration for 6 d was also evaluated, showing more significant color changes with the CP/BR-4 film than the other treatment groups. Therefore, the composite anthocyanin film can potentially serve as an intelligent film for the detection of postharvest freshness in practical applications.

The Fischer‐Lactonization‐Driven Mechanism for Ultra‐Efficient Recycling of Spent Lithium‐Ion Batteries

AbstractHydrometallurgy remains a major challenge to simplify its complex separation and precipitation processes for spent lithium‐ion batteries (LIBs). Herein, we propose a Fischer‐lactonization‐driven mechanism for the cascade reaction of leaching and chelation of spent LIBs. Citric acid undergoes a two‐step dissociation of the carboxylic acid (−COOH) and complexes with the leached metal ion, while the residual −COOH is attacked by H protons to form a protonated carboxyl ion (−COO −). Subsequently, the lone pair of electrons in the hydroxyl of the same molecule attack the carbon atom in −COO − to facilitate ester bonding, leading to the formation of a lactonized gel. The leaching rates of Li, Ni, Co and Mn are 99.3, 99.1, 99.5 and 99.2 %, respectively. The regenerated monocrystalline LiNi0.5Co0.2Mn0.3O2 (NCM523) has a uniform particle size distribution and complete lamellar structure, with a capacity retention rate of 70.6 % after 250 cycles at 0.5 C. The mechanism achieves a one‐step chelation reaction, and the energy consumption and carbon emissions are only 26 % and 44 %, respectively, of that of the conventional hydrometallurgical. The strategy achieves a double breakthrough in simplifying the process and improving environmental friendliness, offering a sustainable approach to the re‐utilization of spent LIBs.

The Fischer-Lactonization-Driven Mechanism for Ultra-Efficient Recycling of Spent Lithium-Ion Batteries.

Hydrometallurgy remains a major challenge to simplify its complex separation and precipitation processes for spent lithium-ion batteries (LIBs). Herein, we propose a Fischer-lactonization-driven mechanism for the cascade reaction of leaching and chelation of spent LIBs. Citric acid undergoes a two-step dissociation of the carboxylic acid (-COOH) and complexes with the leached metal ion, while the residual -COOH is attacked by H protons to form a protonated carboxyl ion (-COO -). Subsequently, the lone pair of electrons in the hydroxyl of the same molecule attack the carbon atom in -COO - to facilitate ester bonding, leading to the formation of a lactonized gel. The leaching rates of Li, Ni, Co and Mn are 99.3, 99.1, 99.5 and 99.2 %, respectively. The regenerated monocrystalline LiNi0.5Co0.2Mn0.3O2 (NCM523) has a uniform particle size distribution and complete lamellar structure, with a capacity retention rate of 70.6 % after 250 cycles at 0.5 C. The mechanism achieves a one-step chelation reaction, and the energy consumption and carbon emissions are only 26 % and 44 %, respectively, of that of the conventional hydrometallurgical. The strategy achieves a double breakthrough in simplifying the process and improving environmental friendliness, offering a sustainable approach to the re-utilization of spent LIBs.

Synthesis and Electrochemical Performance of High‐Entropy Spinel‐Type Oxides Derived from Multimetallic Polymeric Precursors

High‐entropy spinel‐type oxides are synthesized by a modified Pechini process, wet chemistry approach, and solid‐state synthesis method and characterized as anode materials for Li‐ion batteries. The Pechini process that involves chelation and polyesterification reactions facilitates the formation of high‐entropy spinel‐type oxides without compositional segregation at ≈600 °C as confirmed by in situ and ex situ XRD. XAFS analysis and the Rietveld refinement of room‐temperature neutron diffraction data suggest the composition (Mn0.05Fe0.48Co0.47, tetrahedral)(Cr0.61Mn0.52Fe0.11Co0.09Ni0.68, octahedral)O4 for phase‐pure specimens. Compared to high‐entropy spinel‐type oxides synthesized by the solid‐state method, the precursor‐derived materials demonstrate higher specific capacity as anodes, in which the materials without citric acid addition exhibit low capacity fading at high current densities and maintained a capacity of ≈200 mAh g−1 after 1000 cycles. The generation of a rock‐salt‐type phase during cycling is confirmed for the first time by in situ charging–discharging XRD. The charging–discharging of this anode material is achieved mainly through the embedding–disembedding of lithium ions in the lattice of the generated rock‐salt‐type phase.

Structural changes and in vitro bioaccessibility of CPP-febisgly complexes: Dependence on iron load

The effect of casein phosphopeptides (CPP) and ferrous bisglycinate (FebisGly) at different ratios (1:20, 1:10, and 1:5 w/w) on iron supplementation was investigated. The in vitro bioaccessibility, structural changes, antioxidant activity, and the effect of absorption inhibitors were also explored. The results demonstrated that CPP enhanced the bioaccessibility of FebisGly by 68.72 % ± 0.18 % and increased the β-sheet content from 21.60 % ± 0.23 % to 67.92 % ± 0.12 %, forming a stable secondary structure. The particle size distribution (PSD) and rheological analyses indicated that CPP significantly contributed to the formation of chelated irons, resulting in a uniform PSD and enhanced viscoelasticity. Moreover, it prolonged the gastric emptying time, reducing gastric irritation further. The carboxyl and amino groups in the CPP molecules participated in chelation reaction, improved the antioxidant activity, and competed with phytic acid, tannic acid, and cellulose for iron. Overall, these results laid a foundation for developing novel iron supplementation strategies.

Synthesis, structural characterization and in vitro digestion stability of a soluble soybean polysaccharide‑zinc chelate

The chelation reaction of soluble soybean polysaccharide (SSPS) with zinc was investigated. Using response surface methodology, the optimum parameters for SSPS-Zn synthesis were obtained: pH 5.3, SSPS-ZnCl2 mass ratio of 9.44:1, reaction temperature 50.44 °C, and reaction time 1.5 h, with the highest zinc content of 24.73 %. Compared with SSPS, SSPS-Zn increased in rhamnogalacturonan content and decreased in that of neutral monosaccharides (Fuc, Ara, Gal, Glu and Xyl). UV–vis spectra indicated that SSPS-Zn was lower than SSPS in protein content. FTIR spectra indicated that CO group of SSPS was bonded to Zn2+. X-ray diffraction spectra demonstrated that SSPS-Zn had higher crystallinity. Congo red reactions showed that SSPS possessed a triple-helix conformation while SSPS-Zn formed an irregular free-coiled conformation. EDX confirmed SSPS-Zn synthesis successfully. TGA curves exhibited that SSPS-Zn required higher temperature to undergo degradation. AFM revealed that SSPS-Zn was clustered while SSPS was filamentous. SEM micrographs showed the cracked fragments on the surface of SSPS-Zn. By in vitro simulation of gastrointestinal digestion, Zn2+ release reached 68.87 % after 2 h digestion. Consequently, the chelation of SSPS with zinc could change structure and provide a basis for research and application of novel zinc supplements.

Deer Skin Collagen Peptides Bound to Calcium: In Vitro Gastrointestinal Simulation of Digestion, Cellular Uptake and Analysis of Antioxidant Activity.

The by-product of deer skin, which has mostly been used as a decorative material, is rich in collagen and amino acids that could bind to Ca2+. Therefore, the preparation process, stability, antioxidant activity and calcium transport capacity of deer skin collagen peptide calcium chelate (Ca-DSCP) were investigated. In addition, the structure of the new chelate was characterized. The preparation process of Ca-DSCP was optimized using one-way experiments and response surface methodology. The ideal conditions were pH 9, 48 °C, and a peptide-to-calcium mass ratio of 5:1. The chelation rate was (60.73 ± 1.54)%. Zeta potential, XRD, UV-vis and FTIR analyses yielded that deer skin collagen peptides (DSCP) underwent a chelating reaction with calcium ions to form new structures. The stability of Ca-DSCP and the fraction of bioavailability of calcium ions were determined using in vitro gastrointestinal digestion and a Caco-2 cell monolayer model. The results showed that fraction of bioavailability and stability of DSCP were improved by influencing the structural characterization. The antioxidant activities of DSCP and Ca-DSCP were evaluated by measuring relevant oxidative stress indicators, DPPH radical scavenging capacity and hydroxyl radical scavenging capacity. Finally, bioinformatics and molecular docking techniques were utilized to screen and study the antioxidant mechanism of DSCP.

A handy way for forming N-doped TiO2/carbon from pectin and d,l-serine hydrazide hydrochloride

N-doped TiO2/carbon composites (N-TiPC) have shown excellent photodegradation performances to the organic contaminants but are limited by the multistage preparation (i.e., preparation of porous carbon, preparation of N-doped TiO2, and loading of N-doped TiO2 on porous carbon). Here, we develop a handy way by combining the Pickering emulsion-gel template route and chelation reaction of polysaccharides. The N-TiPC is obtained by calcinating pectin/Dl-serine hydrazide hydrochloride (SHH)-Ti4+ chelate and is further described by modern characterization techniques. The results show that the N atom is successfully doped into the TiO2 lattice, and the bandgap value of N-TiPC is reduced to 2.3 eV. Moreover, the particle size of N-TiPC remains about 10 nm. The configurations of the composites are simulated using DFT calculation. The photocatalytic experiments show that N-TiPC has a high removal efficiency for methylene blue (MB) and oxytetracycline hydrochloride (OTC-HCL). The removal ratios of MB (20 mg/L, 50 mL) and OTC-HCL (30 mg/L, 50 mL) are 99.41 % and 78.29 %, respectively. The cyclic experiments show that the photocatalyst has good stability. Overall, this study provides a handy way to form N-TiPC with enhanced photodegradation performances. It can also be promoted to other macromolecules such as cellulose and its derivatives, sodium alginate, chitosan, lignin, etc.

Isolation, identification, and chelation mechanism of ferrous-chelating peptide from peanut protein hydrolysate.

Peanut peptides can chelate iron but their chelation mechanism remains unclear. The purpose of this study is to separate peanut ferrous-chelating peptides and explore the chelation mechanism of peanut peptides with iron. Peanut peptide component F-122, which had a higher chelation rate, was separated using ultrafiltration, gel filtration chromatography, and ion exchange chromatography, achieving a ferrous chelation rate of 90.7%. Six peptide segments were screened and their amino acid sequences were identified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Spectral analysis confirmed that the chelation between peanut peptides and ferrous ions occurred and a new substance was formed. Molecular docking simulation indicated that the amino acids in peanut peptides involved in the chelating reaction were glutamic acid, arginine, glycine, threonine, phenylalanine, and lysine. The binding sites included the main chain oxygen atom, side chain oxygen atom, and carboxyl oxygen atom of amino acid. The isolated peanut peptide had a higher ferrous-chelation rate. The chelating mechanism of peanut peptide with ferrous ion was elucidated. This study provides a theoretical basis for the development of new peptide-ferrous preparations. © 2024 Society of Chemical Industry.

Engineering Bis-Pyridine N-Functionalized Cellulose Aerogel for Efficient Extraction of Cu2+ from High-Acidity Wastewaters: Coupling Molecular Scale Interpretation with Experiment.

In order to address the issue of protonation of functional groups and structural instability on the surface of aerogel due to strong acidic wastewater, a three-dimensional bis-pyridine N cellulose aerogel [PEIPD/carboxymethyl cellulose (CMC)] with protonation resistance was prepared in this paper by grafting pyridine onto polyethylenimine. The adsorption capacity for Cu2+ of the as-prepared aerogel is as high as 1.64 mmol/g (pH 5) and is maintained well in high-acidity solutions (1.15 mmol/g at pH = 2). It reveals high selectivity, splendid anti-interference ability, and also reliable on the recycle performance. Through the zeta potential tests, this adsorbent reveals a rather low zero charge point (pHpzc = 2.2). The adsorption of Cu2+ on the adsorbent is consistent with the pseudo-second-order kinetic model and the Langmuir model, suggesting that the adsorption process is dominated by chemisorption in a monolayer. The characterizations by Fourier transform infrared spectrometry and X-ray photoelectron spectroscopy proved pyridine N as responsible binding sites, based on which two possible mechanisms are proposed, including chelation and cation-π interaction. Density functional theory calculations are further used to precisely investigate the pathway. By comparing the binding energies, molecular electrostatic potentials, electron densities, and differential charge densities, the bis-pyridine N functional group is finally determined to be of much higher affinity to Cu2+ following chelation reaction as designated. By integrating bis-pyridine N with the CMC and understanding their crucial roles, this will provide significant insights into the rational design of aerogel adsorbents to enhance the recovery of Cu from strongly acidic wastewaters.

Dynamic Cross-Linking, Self-Healing, Antibacterial Hydrogel for Regenerating Irregular Cranial Bone Defects.

Given the widespread clinical demand, addressing irregular cranial bone defects poses a significant challenge following surgical procedures and traumatic events. In situ-formed injectable hydrogels are attractive for irregular bone defects due to their ease of administration and the ability to incorporate ceramics, ions, and proteins into the hydrogel. In this study, a multifunctional hydrogel composed of oxidized sodium alginate (OSA)-grafted dopamine (DO), carboxymethyl chitosan (CMCS), calcium ions (Ca2+), nanohydroxyapatite (nHA), and magnesium oxide (MgO) (DOCMCHM) was prepared to address irregular cranial bone defects via dynamic Schiff base and chelation reactions. DOCMCHM hydrogel exhibits strong adhesion to wet tissues, self-healing properties, and antibacterial characteristics. Biological evaluations indicate that DOCMCHM hydrogel has good biocompatibility, in vivo degradability, and the ability to promote cell proliferation. Importantly, DOCMCHM hydrogel, containing MgO, promotes the expression of osteogenic protein markers COL-1, OCN, and RUNX2, and stimulates the formation of new blood vessels by upregulating CD31. This study could provide meaningful insights into ion therapy for the repair of cranial bone defects.

Pb2+ Transfer‐Enabled Recoverable Hydrogel‐Based H2S Colorimetric Sensing with Assistance of Multimodal Deep Learning for Multifunctional Applications

AbstractRecoverable and humidity‐tolerant colorimetric sensors are extremely difficult to overcome. In this work, a composite hydrogel sensor based on chelation reaction is proposed for the first time to achieve ultra‐fast recovery and ultra‐low detection limit (LOD) of H2S colorimetric sensing. The composite hydrogel sensor is constructed by polyvinyl alcohol/boric acid/Pb2+ (PVA/Bn/Pb) hydrogel sensing layer and polyacrylamide/sodium alginate (PAM/SA) hydrogel adsorption layer. The change from white to brown is achieved in H2S and can be restored when placed in the air. The response/recovery mechanism is explained by the transfer of Pb2+ between hydrogels and the formation of an “Alginate‐Pb2+” with egg‐box structure during the process. The multimodal fusion deep neural network (MF‐DNN) can overcome the error caused by hydrogel aging. Due to the excellent loading and diffusion function provided by the 3D structure of hydrogel, the sensor has a broad detection range of 0.2–100 ppm, a response/recovery time of 10s/32s, and a theoretical LOD of 0.026 ppm. A smartphone‐based H2S sensing system is developed to enable non‐invasive halitosis diagnosis, egg freshness detection, and remote H2S monitoring and alarming. The system is recoverable, humidity‐tolerant, capable of ultrafast detection and widely applicable. This work provides inspiration for humidity‐tolerant and recoverable H2S gas sensing.

Humic acid enhances adsorption effect: Application foundation of high-temperature composting products for remediation of heavy metals pollution

High-temperature composting products are rich in humic acid, which contains abundant oxygenated functional groups capable of binding to heavy metals, and thus can be considered for remediation of heavy metals pollution. However, the specific adsorption properties of high-temperature composting humic acid (HHA) remain unclear. In this study, humic acid was extracted from composting products using the acid-base extraction method, and the adsorption effect and mechanism were investigated. The experimental results showed that the maximum adsorption capacity of HHA for Cu(II), Zn(II), and Pb(II) was 69.43 mg/g, 58.55 mg/g, and 65.84 mg/g, respectively, representing an average enhancement of 21.80 % compared to conventional composting humic acid. Spectra analysis revealed that the enhanced adsorption mechanism of HHA was mainly due to a 51.63 % increase in hydroxyl and carboxyl groups, which were bound to heavy metals through chelation reactions. Furthermore, kinetics and thermodynamics studies indicated that the adsorption process was an endothermic reaction and predominantly driven by ion exchange. Additionally, the application of high-temperature composting products is economical and feasible due to their production from cheap organic waste. This study aims to demonstrate the superiority of HHA in the adsorption of heavy metals and enhance the comprehension of the adsorption mechanism, which provides an application foundation of composting products for the remediation of heavy metals pollution.

Application of Cations, Acids, and Antioxidants on Mitigating Acrylamide Formation in Food with a Special Focus on Potato and Cereal Based Foods - A Review

Acrylamide is a toxic substance that formsin food during high-temperature processing methods such as deep-frying, baking, and roasting, through the Maillard reaction or the acrolein pathway. Since acrylamide has been identified for its carcinogenicity, genotoxicity, and neurotoxicity, global food authorities have established benchmark levels for different food categories. Consequently, researchers have proposed various mitigation strategies, focusing on agronomical, chemical, physical, and microbial approaches. However, most of these approaches are associated with high cost, technology, extended time, and poor sensory and nutritional quality. In this context, application of various additives such as metal cations, organic and inorganic acids, and antioxidants in optimum amounts have been effective in reducing acrylamide formation. Additives contribute to reducing acrylamide either by interacting with its precursors and/or intermediate products or by breaking down acrylamide into other non-toxic substances. Since cations can form thermostable asparagine/matrix intermediates through chelation reaction between asparagine and metal cations, asparagine will be unavailable to react with carbonyl compounds to form the Schiff base. Lower pH conditions inhibit the acrylamide formation by blocking the protonation of the α-amino group of asparagine and reducing any possibility for nucleophilic addition reactions with carbonyl groups. Toxicity associated with Maillard products can be reduced by using antioxidants in the frying oil or the food. Polyphenols are capable of reducing the acrylamide formation by directly trapping acrylamide at elevated temperature. It is essential to identify the most appropriate additive, its concentration and the optimum process conditions when applying additives to get an optimal acrylamide inhibition. This review article highlights the effect of various additive applications, their effectiveness and possible future advances in food to control acrylamide formation within the accepted level.Keywords: Acrylamide, Antioxidant, Carcinogenicity, Deep-frying, Maillard reaction

In Situ Growth and Dynamic Transformation of Nickel Chelate Nanoarrays into Reactive Surface Reconstituted Heterostructure for Overall Water Splitting

AbstractIn this work, self‐derivation and surface reconstruction strategies are innovatively introduced into the synthetic route of the metal complex‐derived catalysts. The in situ grown nanorod arrays of Ni‐based complex are prepared by a simple self‐derivation and rapid ligand chelation reaction. Furthermore, highly active heterogeneous electrocatalysts are developed by mild‐temperature calcination. Attributed to the maintained morphology and highly dispersed Ni/Ni(OH)2 heterojunction active sites, the as‐prepared electrode exhibits superior hydrogen evolution activity (38.4 mV–10 mA cm−2). In particular, the dynamic reconstruction during oxygen evolution through in situ Fourier transform infrared and in situ Raman spectroscopies are observed. The reconstructed Ni(OH)2/NiOOH by activation gives the electrode higher oxygen evolution performance (369 mV–200 mA cm−2). Further density functional theory mechanism studies disclose that Ni/Ni(OH)2 contributes to the adsorption of H* in hydrogen evolution and the activated Ni(OH)2/NiOOH optimizes the formation of intermediates in oxygen evolution.

Recent advances and trends in innovative biosensor-based devices for heavy metal ion detection in food.

Low-cost, reliable, and efficient biosensors are crucial in detecting residual heavy metal ions (HMIs) in food products. At present, based on distance-induced localized surface plasmon resonance of noble metal nanoparticles, enzyme-mimetic reaction of nanozymes, and chelation reaction of metal chelators, the constructed optical sensors have attracted wide attention in HMIs detection. Besides, based on the enrichment and signal amplification strategy of nanomaterials on HMIs and the construction of electrochemical aptamer sensing platforms, the developed electrochemical biosensors have overcome the plague of low sensitivity, poor selectivity, and the inability of multiplexed detection in the optical strategy. Moreover, along with an in-depth discussion of these different types of biosensors, a detailed overview of the design and application of innovative devices based on these sensing principles was provided, including microfluidic systems, hydrogel-based platforms, and test strip technologies. Finally, the challenges that hinder commercial application have also been mentioned. Overall, this review aims to establish a theoretical foundation for developing accurate and reliable sensing technologies and devices for HMIs, thereby promoting the widespread application of biosensors in the detection of HMIs in food.

Fe3+-modified polyamide membrane with a porous network structure: Rapid permeation and efficient interception of trace organic compounds

Forward osmosis (FO) is a promising technology in the treatment of trace organic substances. However, the development of this technology is limited by membrane material selection and the long-term chemical stability and durability of the membrane. Whereas ibuprofen, a representative trace organic substances that is hydrophobic and negatively charged, poses potential environmental hazards due to its bioactivity. In this work, polyethersulfone (PES) membranes were modified with iron metal complexes via chelation reactions to achieve high rejection rates for ibuprofen. The Fe3+-modified composite FO membrane increased the ibuprofen rejection rate to 98.3 % compared to less than 80.0 % for the original PES membrane. Additionally, the modified membrane enhanced water flux by at least 25.0 % and reduced reverse solute flux to a maximum of 73.0 % of that of the polyamide composite membrane, while significantly improving anti-fouling capabilities. Membrane characterization results revealed that the significant enhancement in the ibuprofen retention rate was due to the addition of a negative charge by forming complexes with Fe3+, which increased intermolecular interactions. Additionally, the dense network structure developed by the Fe3+-EDTA-2Na modification also contributed to the enhanced membrane performance.

Kinetics and molecular structure of the binding process between coal-based fulvic acid and zinc ions

The fulvic acid (FA) extracted by lignite oxygenolysis contains a variety of reactive functional groups that leading to trace element zinc (Zn) can be chelated at these sites, and has great potential in life science and environmental remediation. The interaction mechanism of FA with Zn ions (Zn(II)) was studied by reaction kinetics. Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) were applied in products characterization. The three-dimensional molecular structures of the zinc fulvate (FA-Zn) were explored by using quantum chemical calculations. The results show that the chelation reaction of FA with Zn(II) had pseudo-second-order reaction kinetics; the carboxyl, hydroxyl, carbonyl, amino and mercapto groups in FA act as monodentate or multidentate ligands to form chelates with Zn(II). The molecular structure formation of FA-Zn was related to its specific functional group binding sites and binding energy. when FA bound Zn(II) intramolecularly, the model was most stable when the ortho-dicarboxylic acid site was bound, the minimum energy of this model was −4095.9342 a.u. and the bond lengths were 1.87 Å and1.86 Å; when FA bound Zn(II) intermolecularly, among the models without water, the model with carbonyl and phenolic hydroxyl sites binding was the most stable, the minimum energy of this model was −6108.2298 a.u. and the bond lengths were 1.97 Å and1.89 Å; when Zn(II) was combined with two water molecules, the model with binding at the amino site was the most stable, the minimum energy of this model was −6261.0946 a.u. and the bond lengths were 1.93 Å and 2.04 Å.