Iminodiacetic Groups Research Articles

Environmentally Benign and Expeditious Access to 4‐Aryl Methylene‐isoxazole‐5(4H)‐Ones Using Magnetically Separable Nanoparticles

AbstractAn environmentally benign and expeditious protocol was developed for the one‐pot multicomponent synthesis of 4‐aryl‐3‐methylisoxazol‐5(4H)‐ones by the condensation of aldehyde, hydroxyl amine hydrochloride, and ethyl acetoacetate in 50% aq. ethanol at 50 °C. The reaction was catalyzed by magnetically separable carbon microspheres co‐decorated with nanosized iron sulfide and magnetite nanoparticles in 10 wt% amount. The FeS1‐x‐Fe3O4/C nanocatalyst was prepared from iron(III) sulfate loaded iminodiacetate group functionalized styrene‐divinylbenzene based ion exchanger by pyrolysis reaction performed at 600 °C for 4 h. The use of magnetically separable heterogeneous catalyst, aqueous ethanol, short reaction time (30 min), and nonchromatographic purification methods are the striking features of the developed protocol. The isolated yield of the condensation products varied between 81% and 96%. Furthermore, the protocol exhibits high functional group tolerance and includes the use of noncorrosive, nonhazardous reaction conditions affording the product in excellent yields and short reaction time.

Repurposing the Strontium Ranelate Antiosteoporotic Drug as a New Outstanding Biocompatible Blue Dye

Blue dyes are relatively uncommon in nature, and a novel dithiophene dye (RanB) is reported in this paper. This dye is derived from an old anti-osteoporotic drug and is a metal ion complexing agent, displaying a planar molecular structure, with two sets of carboxylate, isonitrile, thiophene, and iminodiacetate groups. The blue color originates from a strong absorption peak at 648 nm, accompanied by an unusual fluorescence at 555 nm, with higher energy compared to the main absorption band. RanB forms complexes with lanthanoid ions through the iminodiacetate groups and serves as an effective sensitizer for Tb3+ ions, heightening their emission and improving their use as luminescent agents. Its photo-physical properties and the interaction with Tb3+ have been investigated using absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy, along with computational methods (ZINDO/S and DFT). The RanB toxicity in human umbilical vein endothelial cells has also been tested, showing a lack of toxicity, holding promising prospects for application as a luminescent and coloring agent in pharmaceuticals and food.

ПЕРСПЕКТИВНЫЕ СОРБЕНТЫ ДЛЯ ИЗВЛЕЧЕНИЯ НИКЕЛЯ И КОБАЛЬТА В ГИДРОМЕТАЛЛУРГИЧЕСКОЙ ПЕРЕРАБОТКЕ НИКЕЛЕВЫХ РУД

The paper provides a critical analysis of the sources, a generalization of the factual and theoretical material on the properties, the use of natural and synthetic sorbents for the extraction of nickel and cobalt from productive solutions after the leaching of nickel ores. Comparison of promising sorbents in terms of efficiency of their use with sorbents used in industry has been carried out. Sorption processes using natural substances or synthetic resins contribute to the selective extraction of nickel and cobalt from aqueous solutions. Zeolites modified with various functional groups are very promising materials for selective recovery. The ability to selectively extract metal cations and the possibility of regeneration makes ion-exchange polymer resins one of the leading sorbents in the modern world. The polymer resin sorption process avoids wastage of reagents, costly filtration, and poor selectivity for nickel and cobalt over other metal ions associated with solvent extraction processes. A comparison of the values of the sorption capacities of natural sorbents shows the promise of using silicate minerals - montmorillonite and palygorskite in industry, as well as the development of technological processes using them. Analysis of the recovery rates of synthetic polymer resins proves the frequent use of Amberlite, Dowex and Ionac in the industry. However, Dowex M4195 has the highest nickel selectivity due to the presence of a bis-picolylamine functional group, unlike other resins with an iminodiacetate group. In addition, the disadvantage of foreign-made chelate resins is their high cost, which cannot be said about the cation exchanger grade KU 2-8 of a Russian manufacturer.

Insights into the crystal structure and optical property for complexes of iminodiacetic‐terpyridine

AbstractIATPY, a multidentate ligand with strong coordination ability was prepared by connecting iminodiacetic acid with phenylterpyridine, and its Ir(III), Zn(II) and Tb(III) complexes were synthesized in solution or by solvothermal method. The iminodiacetic group on IATPY will be substituted by solvent molecules under weakly basic condition. Coordination reactions will take place between Zn(II) and Tb(III) with IATPY under weakly acidic condition solvothermally. With the contribution from water molecules, a variety of intermolecular hydrogen bonds are formed that make IATPY parallelly arranged in crystals, resulted in intense π‐π stacking and induced its absorption and emission spectra obtained in solution dramatically different from that in solid state. With the participation of terpyridine moiety and carboxyl groups simultaneously, coordination polymers [Zn(IATPY)]n and [Tb2(IATPY)3]n were obtained when Zn(NO3)2 and Tb(CH3COO)3 reacted with IATPY. Intense π‐π stacking effects can be observed in the crystal structures of [Zn(IATPY)]n and [Tb2(IATPY)3]n, which influence their optical properties in solid state.

Designing polymeric membranes with coordination chemistry for high-precision ion separations.

State-of-the-art polymeric membranes are unable to perform the high-precision ion separations needed for technologies essential to a circular economy and clean energy future. Coordinative interactions are a mechanism to increase sorption of a target species into a membrane, but the effects of these interactions on membrane permeability and selectivity are poorly understood. We use a multilayered polymer membrane to assess how ion-membrane binding energies affect membrane permeability of similarly sized cations: Cu2+, Ni2+, Zn2+, Co2+, and Mg2+. We report that metals with higher binding energy to iminodiacetate groups of the polymer more selectively permeate through the membrane in multisalt solutions than single-salt solutions. In contrast, weaker binding species are precluded from diffusing into the polymer membrane, which leads to passage proportional to binding energy and independent of membrane thickness. Our findings demonstrate that selectivity of polymeric membranes can markedly increase by tailoring ion-membrane binding energy and minimizing membrane thickness.

Removal of fluoride from coke wastewater by aluminum doped chelating ion-exchange resins: a tertiary treatment

Coke wastewater is one of the most problematic industrial wastewaters, due to its large volume and complex pollutant load. In this study, ion exchange technology was investigated with the objective of reducing the fluoride content of the effluent from a coke wastewater treatment plant (26.7 mg F-/L). Two Al-doped exchange resins with chelating aminomethyl-phosphonic acid and iminodiacetic groups were assessed: Al-doped TP260 and TP207 resins, respectively. The effect of resin dosage, varying from 5 to 25 g/L, was evaluated. F- removal was within the range 57.8–89.3% and 72.0–92.1% for Al-doped TP260 and TP207, respectively. A kinetic study based on a generalized integrated Langmuir kinetic equation fitted the experimental data (R2 > 0.98). The parameters of the said kinetics met the optimal conditions for the ion exchange process, which seemed to be more favorable with Al-doped TP260 resin than with Al-doped TP207 resin, using the same resin dosage. Furthermore, the experimental data were well described (R2 > 0.98) by Langmuir and Freundlich isotherm models, in agreement with the findings of the kinetic study: the maximum sorption capacity was obtained for the Al-doped TP260 resin.

Titration of chelating fibrous sorbent in the presence of complex-forming divalent cations

Titration curves of H-forms of the fibrous chelating sorbent with iminodiacetic groups based on industrial polyacrylonitrile fiber Nitron with potassium hydroxide in 1M KCl solution in the presence of Ni2+, Co2+, Cu2+ and Ca2+ chlorides were obtained. The method used made it possible to simultaneously measure the pH of the solution and the concentration of the divalent cation at each point of the titration curve. From these data, the dependences of their sorption values on the pH of the equilibrium solution were calculated. The curves of direct and back titration practically coincided in all cases. As the pH changed during titration, precipitation was observed at pH values of precipitation of the corresponding hydroxides. In this case, the increase in pH was suspended or greatly slowed down by adding alkali to the titration cell. The formation of a precipitate occurred mainly in a solution for Co2+ and Ni2+ (pH 8), when the ion exchanger was saturated with a metal ion. In the case of Cu2+ (precipitate formation pH 4), Cu2+ sorption occurs at both lower and higher pH due to ionization of carboxyl groups and partial dissolution of the precipitate. In all cases, the maximum sorption of Ni2+, Co2+, Cu2+, Ca2+ corresponded to the formation of sorption complexes of the R–N(CH2COO-)2Me2+ type.

Novel phenolic antimicrobials enhanced activity of iminodiacetate prodrugs against biofilm and planktonic bacteria.

Prodrugs are pharmacologically attenuated derivatives of drugs that undergo bioconversion into the active compound once reaching the targeted site, thereby maximizing their efficiency. This strategy has been implemented in pharmaceuticals to overcome obstacles related to absorption, distribution, and metabolism, as well as with intracellular dyes to ensure concentration within cells. In this study, we provide the first examples of a prodrug strategy that can be applied to simple phenolic antimicrobials to increase their potency against mature biofilms. The addition of (acetoxy)methyl iminodiacetate groups increases the otherwise modest potency of simple phenols. Biofilm‐forming bacteria exhibit a heightened tolerance toward antimicrobial agents, thereby accentuating the need for new antibiotics as well as those, which incorporate novel delivery strategies to enhance activity toward biofilms.

Design and synthesis of water-soluble chelating polymeric materials for heavy metal ion sequestration from aqueous waste

Sequestration and removal of dissolved heavy metal ions from aqueous waste streams is a challenging task. Ethylenediaminetetraacetic acid (EDTA) is a hexadentate chelating ligand capable of forming 1:1 complex with various heavy metal ions while iminodiacetic acid (IDA) is analogous to half a unit of EDTA. A new styrene based monomer M1 bearing dimethyl iminodiacetate group was designed and synthesized in good yield to meet this objective. Free radical polymerization of M1 generated the homopolymer, which upon base hydrolysis generated the water-soluble chelating homopolymer P10, bearing sodium salt of IDA as the chelating group. The overall yield of P10 was 76.80% and the solubility was 5 mg/mL at room temperature. The water soluble polymer P10 was investigated for its ability to bind various heavy metal ions by UV–vis spectroscopy and was found to efficiently sequester Cu2+, Cd2+, Zn2+, Pb2+, Ni2+, Co2+, Cr3+, Fe2+ and Fe3+. The effect of pH on Cu2+ binding with P10 showed that every two IDA bearing monomeric repeat units binds with one Cu2+ ion at pH 7 suggesting that it forms complexes analogous to EDTA. Thermogravimetric analysis showed that the synthesized polymer possesses high thermal stability up to 400 °C. The potential for recovery and reuse of the polymer has been demonstrated with Cu2+ ion. The reported results suggest that this water-soluble chelating homopolymer is an excellent material with very high potential for application in wastewater treatment.

Highly selective removal of Ni(II) from plating rinsing wastewaters containing [Ni-xNH3-yP2O7]n complexes using N-chelating resins

Inorganic complexants, such as ammonia (AA) and pyrophosphate (PP), are often present alongside heavy metal ions in alkaline plating rinsing wastewater. We investigated the removal capacity of Ni(II) from waters containing [Ni-xNH3-yP2O7]n complexes by chelating and ion-exchange resins in sole and dual-ligand systems. D463 (containing iminodiacetic groups) and PAMD (possessing polyamine groups) exerted superior performance under all conditions. Ni(II) adsorption on D463 decreased with AA and PP by 10.3% and 64.4%, respectively. Conversely, the adsorption on PAMD increased by 57.3% and 75.8%, respectively. PAMD exhibited high selectivity toward anionic [Ni-PP] species over free PP. More Ni(II) was captured by PAMD in the dual-ligand systems than sole systems, while the case for D463 was opposite. As confirmed by species tracking and DFT/XPS analyses, complexes breaking-Ni2+ capture was the dominant mechanism for D463, while the dual-site (non-charged and protonated amines) interactions with NiP2O72– on PAMD promoted its adsorption. The tandem combination D463-PAMD was the optimal mode to remove the most Ni(II). The actual wastewater test demonstrated that >210 BV effluent met the limit of 0.1 mg Ni(II)/L and the eluent contained 15 g Ni(II)/L. This study guides the application of chelating adsorption processes in the advanced treatment of plating rinsing wastewaters.

Chelating Performance Evaluation of Ion Exchange Resin Chelex-100

This study aims to answer the question about the chelating capacity of Chelex-100 resin according to the size of grains obtained after different grindings of a 200–400 mesh powder. Optical microscopy was used for size characterization of different new sub-types of resin obtained after grinding. The copper chelating capacity was evaluated using inductively coupled plasma−mass spectrometry. Grinding enables copper to be chelated by all iminodiacetate groups of the resin. Thus, the copper chelating capacity increases by 17% compared to unground resin and is more repeatable from one aliquot to another (1% RSD with optimal grinding versus 3% without grinding).

Chromium and cadmium adsorption on radiation-grafted polypropylene copolymers: regeneration, kinetics, and continuous fixed bed column studies

Metal ion adsorbents bearing amino and iminodiacetic groups were synthesized via radiation-induced graft polymerization of emulsified glycidyl methacrylate monomer from polypropylene non-woven fabric followed by subsequent reaction of the epoxide functional groups with ethylenediamine or iminodiacetic acid. The resulting amino- and iminodiacetic-type adsorbents exhibited excellent Cr(VI) and Cd(II) adsorption performance, respectively, based on the results of batch and column adsorption experiments. The Cr(VI) ions bound on the amino-type adsorbent were desorbed with 2M NaOH solution, while the bound Cd(II) ions were effectively stripped off from the iminodiacetic-type adsorbent by using organic acids, such as citric, acetic and oxalic acid. Both adsorbents showed more than 94% adsorption efficiency after five consecutive adsorption–desorption cycles. The adsorption dynamics of the metal ions to the synthesized grafted adsorbents obeys pseudo-second order kinetics. The radiation-grafted adsorbents exhibited comparable, if not better performance than commercially available ion-exchange resins. Continuous fixed bed column adsorption was performed, and the breakthrough curves were plotted at varying feed solution flow rate. The column-packed amino-type adsorbent can treat more than 4000 BV (> 1500 mL) of 3 ppm Cr(VI) solution at 155 BV hr−1 flow rate before the breakthrough. Lastly, the amino-type adsorbent was successfully applied in the treatment of actual tannery wastewater, with the resulting effluents meeting the national standards.

Ion exchange of lanthanides with conventional and ion-imprinted resins containing sulfonic or iminodiacetic acid groups

ABSTRACT Ion exchange equilibria of samarium, dysprosium, and erbium were measured in conventional and ion-imprinted resins containing sulfonic acid groups or iminodiacetic acid (ida) groups in H,H-form and partially neutralized H,Na-form. The ion-imprinted resins were prepared by copolymerization of complexes prepared from Er3+. Conventional resins have low selectivity because electrostatic interactions are dominant even for the ida resin. In ion imprinting, the complex structure formed a priori in bulk solution was retained in the resin and coordinative interactions became more prominent. As a result, the selectivity coefficient K Er Sm increased from 1.0 of the conventional resin to 3.5 of the imprinted resin.

Ion exchange in complexing media – Nickel removal from ammoniacal ammonium sulfate solutions

In real hydrometallurgical systems, ion exchange of metal cations is often accompanied by competing processes, such as complex formation. In this paper, we have analyzed influence of complex formation on nickel uptake in a chelating ion exchanger that contains iminodiacetate groups. Both outer-sphere complexation with sulfate and inner-sphere complexation with ammonia were studied at 22 and 80 °C. In ammoniacal ammonium sulfate matrix, both these complexes are formed and prediction of nickel uptake becomes challenging. According to the results, nickel uptake can be substantially enhanced by complex formation. Under acidic conditions and at 80 °C, proton is complexed by sulfate more effectively than nickel and as a result, the exchange equilibrium favors nickel uptake. High sulfate background concentration further enhances the positive effect. In ammonium sulfate solutions, however, complexation with ammonia is needed to prevent nickel precipitation. The solution is stable near pH 7 and high nickel uptake can be obtained, because competition by H+ is practically absent and Ni2+/NH4+ selectivity is high. Complexation with NH3 thus makes the conditions favorable for Ni uptake rather than affects directly on Ni exchange. All these findings were successfully correlated with a dynamic model including pertinent complexation and dissociation equilibria.

Functionalized polystyrene beads as carriers in release studies of two herbicides: 2,4-dichlorophenoxyacetic acid and 2-methyl-4-chlorophenoxyacetic acid

The extensive usage of pesticides in agriculture has adverse effect on the quality of water and soil; therefore, the proper dosage is of great concern. The aim of this study was to use the functionalized polystyrene beads (QuadraPure™) as a reservoir for the storage and controlled release of two herbicides: 2,4-dichlorophenoxyacetic acid and 2-methyl-4-chlorophenoxyacetic acid. It was proved that desorption of herbicides was strongly affected by the surface properties of polystyrene beads characterized by different pore size distributions and modified with various functional groups. We suggest that the optimal hybrid systems are the mixtures that are able to release the high amount of herbicides for a long time. For 2,4-dichlorophenoxyacetic acid, these conditions were fulfilled by polystyrene beads with the attached imino diacetate or thiourea functional groups. For 2-methyl-4-chlorophenoxyacetic acid, the appropriate results were obtained when polystyrene beads with the thiourea functional groups were applied. Additionally, QuadraPure™ scavengers could form stable complexes with copper and nickel ions, and therefore, the pesticide release was limited. The application of a hybrid system permitted to control the distribution of the herbicide by the formation of complexes between metal ions and organic groups of QuadraPure™ materials. The results proved that by using the polystyrene beads the release of herbicide could be controlled.Graphical abstract

Effects of Functional Group Density in Stylene-Divinylbenzene Copolymer Phase and of Supporting Electrolyte Concentration in Aqueous Phase on Performance of Iminodiacetate-type Chelating Resin in Terms of Contribution of Ion-Exchange Mechanism.

The effects of the functional group density in the stylene-divinylbenzene copoymer phase and of the supporting electrolyte concentration in the aqueous phase on the perfomance of the iminodiacetate (IDA)-type chelating resin were studied in terms of contribution of an ion-exchange mechanism. High hydrophobicity of the resin having a low functional group density interfered with penetration of aqueous solutions into the resin phase to slow the acid-base reaction and the adsorption reaction. Uptake of the cation in the supporting electrolyte into the resin phase was clearly indicated in each of two acid dissociation reactions. The high concentration of the supporting electrolyte enhanced acid dissociation of the IDA group, and a singly deprotonated species interacting with the supporting electrolyte cation strongly interfered with adsorption by the ion-exchange mechanism, while only slightly interfering with adsorption by the complexation. Both the complexed and ion-exchanged species respectively involving two or more IDA groups were destabilized to reduce the adsorption capacity of the resin having the low functional group density.

New Iminodiacetate Chelating Resin-Functionalized Fe3O4 Nanoparticles: Synthesis, Characterization, and Application for the Removal of Some Noxious Metal Ions from Wastewater

A new type of magnetic chelating resin (MIDA) beads bearing iminodiacetate groups derived from acrylamide–N,N′-methylenebis(acrylamide) copolymer was synthesized in the presence of Fe3O4 nanoparticles and tested for the removal of Cu(II), Pb(II), Zn(II), and Cd(II) from aqueous solution. The prepared Fe3O4 nanoparticles were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM)-energy dispersive X-ray, transmission elelctron microscopy, and X-ray diffraction (XRD). The obtained MIDA was characterized by FTIR, SEM, Brunauer–Emmett–Teller analysis, XRD, thermal analysis, and water regain (W%). Different factors affecting the adsorption process such as pH of solution, initial concentration of the metal ions, shaking time, and temperature of solution, were investigated by batch technique. The maximum adsorption capacities were 4.1, 3.6, 2.4, and 2.2 mmol·g–1 for Cu(II), Pb(II), Zn(II), and Cd(II), respectively. Langmuir isotherm and pseudo-second-order equation co...

The Equilibrium, Kinetics and Thermodynamics of Cu<sup>2+</sup>, Zn<sup>2+</sup>, Cd<sup>2+</sup> and Pb<sup>2+</sup> Sorption in Sorbents with Different Functional Groups

The equilibrium condition and kinetics of the sorption of Cu2+, Zn2+, Cd2+ and Pb2+ ions with Amberlite IRC 748 (with iminodiacetic group, Na+), Duolite C 467 (with amino-fosfon group, Na+), Dowex MAC-3 (with carboxyl group, H+) and Amberlite IR 120 (with sulpho-group, H+) cationites have been studied and thermodynamic parameters of the processes have been calculated on the basis of data gained from the equilibrium and kinetic studies. Sorption isotherms have been organized and relevant equations have been suggested. It has been defined that the kinetics of the processes in the selected concentrations under the control of the internal diffusion. Kinetic parameters have been calculated and it has been noted that heat release and entropy reduction are managed with enthalpy factor.

Editors' Choice—The Effectiveness of Multifunctional Li-Ion Battery Separators past Their Saturation with Transition Metal Ions

Li-ion batteries (LIBs) for electric vehicles necessitate a 10-year useful life. The dissolution of manganese and other transition metal ions from positive electrodes, and the loss of Li+ ions are two main causes for reduced LIB durability. Multifunctional separators (MFSs) designed to mitigate these degradation modes enable improvements in the electrochemical performance of LIBs at both room and above-ambient temperatures. We report herein on the benefits for the cycle life and rate performance of LixMn2O4||graphite cells by composite MFSs that incorporate a crosslinked styrene-divinylbenzene copolymer functionalized with disodium iminodiacetate groups. Our study shows that: (1) forming effective passivating electrode surface films early in LIB life is essential for good performance and long life; (2) saturation of MFSs with manganese ions does not subsequently lead to an increased capacity loss rate during high-temperature (55°C) cycling; (3) MFSs also improve rate performance. These benefits originate from a diminished crossover of dissolved Mn ions to the negative electrode, reduced losses of electroactive Li+ ions, and smaller interfacial resistances at both positive and negative electrodes.

Removal of Cu(II) ions from aqueous solutions by an ion‐exchange process: Modeling and optimization

In this paper, an optimal artificial neural network determined by a self‐adaptive differential evolution approach is applied to model and optimize the removal of copper from wastewater by an ion‐exchange process. The Purolite S930+ resin with iminodiacetic group was used in batch mode for Cu(II) removal from synthetic aqueous solutions in different working conditions (initial solution pH, stirring rate, initial concentration of copper, temperature, contact time and resin amount). The obtained results indicated that the used methodology was able to provide good models for the studied process, the mean squared error in the testing phase obtained by the best network being 0.0034. In addition, the optimal combination of parameters leading to the maximization of removal efficiency determined with the proposed approach was experimentally validated, the prediction being in correlation with the observed data. © 2017 American Institute of Chemical Engineers Environ Prog, 37: 605–612, 2018