Combination of size selective binding ability of 18-crown-6 dissolved in aqueous phase and extractive properties of an amic acid; toward enhancement of rare earths separation

The separation of La(III), Eu(III) and Er(III) ions by an amic acid, N,N-dioctyldiglycolamic acid (HL), dissolved in carbon tetrachloride has been improved in the presence of 18-crown-6 (18C6) in aqueous phase as a selective masking agent. The interaction between the studied metal ions and 18C6 resulted a shift in the extraction curve of the studied metal ions versus pH toward higher pH region. The displacement of the extraction curves was more pronounced for lanthanum ions and was varied as La(III) > Eu(III) > Er(III). This order of complexing ability of 18C6 toward the studied ions was attributed to the size adaptation of the ions and that of the crown ether cavity. The stability constants of the lanthanide–crown ether complexes in aqueous phase were evaluated. The influence of temperature on the extraction of studied metal ions from aqueous phase in the absence and the presence of 18C6 was tested in the range 298–308 K. This investigation allowed evaluating the thermodynamic parameters associated with the extraction process and those of the complexation of cations by 18C6 in the aqueous phase.     

Extraction of technetium by DB18C6 and 18C6 into nitrobenzene and acetylacetone from an aqueous phase containing NaBH4

The extraction of technetium by DB18C6 and 18C6 into nitrobenzene and different solvents from aqueous phase containing NaBH₄ was investigated. The experimental data indicate that the main extracted species have the formulas TcO/OH/₂.CE or 2TcO/OH/₂.3CE, where CE refers to the crown ethers. The effects of crown ether concentration, pH and organic solvent on the distribution ratio are discussed. The extent of extraction from different solvents decreases in the order nitrobenzene >acetylacetone>1-butanol>toluene> benzene.     

Synergism of crown ethers in the thenoyl trifluoroacetone extraction of americium(III) in benzene medium

The synergism of the crown ethers (CE) dicyclohexano-18-crown-6 (DC18C6), dibenzo-18-crown-6 (DB18C6) and 18-crown-6 (18C6) has been investigated in the thenoyl trifluoroacetone (HTTA) extraction of americium(III) in benzene medium from an aqueous phase of ionic strength 0.5 and pH 3.50 at room temperature (23°C). The extracted synergistic species have the general formula Am(TTA)₃ · CE except for DC18C6 in which case the species Am(TTA)₃·2CE was also observed at high CE concentrations. The order of synergism was found to be DC18C6>DB18C6>18C6, which is the order of the basicity of CE as indicated by their ability to extract hydrogen ions from nitric acid solutions.     

Kinetics study of selective removal of lead(II) in an aqueous solution containing lead(II), copper(II) and cadmium(II) across bulk liquid membrane

Transport of Pb(II) ion from equimolar aqueous solutions of Pb(II), Cu(II) and Cd(II) as well as from aqueous solutions containing only Pb(II) source phase (C_metal = 1.0 × 10^?4 mol L^?1) through bulk liquid membranes containing crown ether and oleic acid as carrier has been investigated. The initial fluxes of transported metal ions depend on the hydrophile–lipophile balance (HLB) and molar volumes (Vx) of crown ethers. The initial fluxes of Pb(II), Cu(II), and Cd(II) decrease with increase of HLB value for azacrown ether, i.e., tetraaza-14-crown-4 (A₄14C4), L1 > benzo-15-crown-5 (B15C5), L2 > 4′-Aminobenzo-15C5, L3 > nitrobenzo-15-crown-5 (NB15C5), L4. The selectivity of the metal ions showed the following separation factors (SF): SF_Pb–Cu = 2.15, SF_Cu–Cd = 2.10, SF_Pb–Cd = 4.52. The highest transport recovery for Pb(II) was observed for L1 (99.3 %).     

Conductometric studies of thermodynamics of complexation of Li+, Na+ and K+ ions with 4′,4″(5″)-di-tert-butyldibenzo-18-crown-6 in binary acetonitrile–nitromethane mixtures

The complexation reactions between 4′,4″(5″)-di-tert-butyldibenzo-18-crown-6 (DTBDB18C6) and Li⁺, Na⁺ and K⁺ ions were studied conductometrically in different acetonitrile–nitromethane mixtures at various temperatures. The formation constants of the resulting 1:1 complexes were calculated from the computer fitting of the molar conductance-mole ratio data at different temperatures. At 20 °C and in nitromethane solvent, the stability of the resulting complexes varied in the order K⁺ > Na⁺ > Li⁺. The enthalpy and entropy changes of the complexation reactions were evaluated from the temperature dependence of formation constants. It was found that the stability of the resulting complexes increased with increasing nitromethane in the solvent mixture. The TΔS° versus ΔH° plot of thermodynamic data obtained shows a fairly good linear correlation indicating the existence of enthalpy–entropy compensation in the complexation reactions. The ab initio studies calculated at B3LYP/6-31G level of theory, indicate the binding energy of complexes decreases with increasing cation size in the gas phase. In the solution phase, DTBDB18C6 preferentially forms complexes with the larger ions rather than the smaller ions because the solvation energies of the smaller ions are large enough to overcome and reverse the trends in gas phase complexation. The findings of this study suggest that the current understanding of the factors influencing the selectivity of metal ion complexation by crown ethers may be in need of revision.     

Synergistic behaviour of crown ethers in the thenoyltrifluoroacetone extraction of technetium

The synergism of the crown ethers /CE/ dibenzene-18-crown-6 /DB18C6/ and 18-crown-6 /18C6/ has been investigated in the thenoyltrifluoroacetone /HTTA/ extraction of technetium from aqueous phase containing NaBH₄ into benzene at room temperature. The extracted synergistic species have the general formula TcO/OH/.TTA.CE. The order of synergism was found to be 18C6>DB18C6.     

Structural and Chemical Features of Extraction with Crown Ethers

Unlike linear extracting agents, in the extraction of metal salts from aqueous solutions of inorganic acids with crown ethers, the inclusion compounds, whose composition depends on several external and internal factors, go to the organic phase. The study of the molecular structure of the formed complexes by X-ray diffraction analysis showed that adducts of crown ethers with inorganic acids are host–guest complexes in which the hydroxonium ion is in the polyether macrocycle cavity. When the aqueous phase contains metal ions capable of displacing the hydroxonium ions from the macrocycle (K⁺, Pb²⁺, Hg²⁺, Sr²⁺, NH₄ ⁺), complexes containing metal cations as the guest in the macrocycle cavity, according to X-ray diffraction data, go to the organic phase. In addition, metals forming ionic associates (AuCl₄ ^-, FeCl₄ ^-, GaCl₄ ^-) in an aqueous solution are extracted with crown ethers in accordance with the anion-exchange mechanism. A system in which traces of metals in the 2 M HNO₃ +5 M HCl mixture serve as the aqueous phase was proposed for estimation of the general extraction ability of crown ethers. Such a system can be used for metal extraction via any possible mechanism. The stereochemical peculiarities of the extraction ability of crown ethers (compared to linear molecules) can be used for selective extraction and separation of metals.     

Selective complexation of alkali metal ions using crown ethers derived from calix[4]arenes: a computational investigation of the structural and energetic factors

A systematic analysis of the structural, energetic, and thermodynamic factors involved in alkali metal (i.e., Na⁺, K⁺, Rb⁺, and Cs⁺) complexation by four calix[4]arene crown-6 ethers in the 1,3-alternate conformation is presented here. The ligands (or hosts) in this work are identical to, or closely related to, the four molecules whose selectivity towards complexing Na⁺, K⁺, Rb⁺, and Cs⁺ from aqueous solutions was studied experimentally by Casnati et al. (Tetrahedron 60(36):7869–7876, 2004). By dividing the complexation process into three different contributions, namely, the binding energy of the ion to the crown, the elastic energy of the crown, and the solvation effect, it becomes clear that the primary factor that determines ion selectivity in crown-6-ethers is not the size of the crown, as currently believed. All four crown ethers preferentially complex with the smallest ion (Na⁺) in the gas phase. In the condensed phase, these crown-6 ethers preferentially complex with the larger ions only because the aqueous solvation energies of the alkali metal ions make it thermodynamically less favorable to extract the smaller ions from aqueous solutions. This suggests that the current understanding of the factors influencing the selectivity of metal ion complexation by crown ethers may be in need of revision.     

Density Functional Theory Study of Selectivity of Crown Ethers to Li+ in Spent Lithium-Ion Batteries Leaching Solutions

It is a challenge to recover lithium from the leaching solution of spent lithium-ion batteries, and crown ethers are potential extractants due to their selectivity to alkali metal ions. The theoretical calculations for the selectivity of crown ethers with different structures to Li ions in aqueous solutions were carried out based on the density functional theory. The calculated results of geometries, binding energies, and thermodynamic parameters show that 15C5 has the strongest selectivity to Li ions in the three crown ethers of 12C4, 15C5, and 18C6. B15C5 has a smaller binding energy but more negative free energy than 15C5 when combined with Li⁺, leading to that the lithium ions in aqueous solutions will combine with B15C5 rather than 15C5. The exchange reactions between B15C5 and hydrated Li⁺, Co²⁺, and Ni²⁺ were analyzed and the results show that B15C5 is more likely to capture Li⁺ from the hydrated ions in an aqueous solution containing Li⁺, Co²⁺, and Ni²⁺. This study indicates that it is feasible to extract Li ions selectively using B15C5 as an extractant from the leaching solution of spent lithium-ion batteries.     

Synergistic extraction of Am(III), Th(IV) and U(VI) by PMBP and crown ethers

The extraction of UO ₂ ²⁺ , Am³⁺, and Th⁴⁺ by 1-phenyl-3-methyl-4-benzylpyrazolone with crown ethers was studies using 0.1M (NaClO₄) aqueous phase and toluene. The crown ethers were 12C4, 15C5, 18C6, DB18C6 and DCH18C6. The synergic equilibrium constant did not show correlation between the cationic radii and the ether cavity size nor did the values follow a simple order of ether basicity. The ether basicity, steric effects, and the number of ether oxygens bound to the cation are the combined factors which seemingly determine the pattern of M(PMBP)_n—CE interaction.     

Green and efficient extraction strategy to lithium isotope separation with double ionic liquids as the medium and ionic associated agent

The paper reported a green and efficient extraction strategy to lithium isotope separation. A 4-methyl-10-hydroxybenzoquinoline (ROH), hydrophobic ionic liquid—1,3-di(isooctyl)imidazolium hexafluorophosphate ([D(i-C₈)IM][PF₆]), and hydrophilic ionic liquid—1-butyl-3-methylimidazolium chloride (ILCl) were used as the chelating agent, extraction medium and ionic associated agent. Lithium ion (Li⁺) first reacted with ROH in strong alkali solution to produce a lithium complex anion. It then associated with IL⁺ to form the Li(RO)₂IL complex, which was rapidly extracted into the organic phase. Factors for effect on the lithium isotope separation were examined. To obtain high extraction efficiency, a saturated ROH in the [D(i-C₈)IM][PF₆] (0.3 mol l^?1), mixed aqueous solution containing 0.3 mol l^?1 lithium chloride, 1.6 mol l^?1 sodium hydroxide and 0.8 mol l^?1 ILCl and 3:1 were selected as the organic phase, aqueous phase and phase ratio (o/a). Under optimized conditions, the single-stage extraction efficiency was found to be 52 %. The saturated lithium concentration in the organic phase was up to 0.15 mol l^?1. The free energy change (ΔG), enthalpy change (ΔH) and entropy change (ΔS) of the extraction process were ?0.097 J mol^?1, ?14.70 J mol K^?1 and ?48.17 J mol^?1 K^?1, indicating a exothermic process. The partition coefficients of lithium will enhance with decrease of the temperature. Thus, a 25 °C of operating temperature was employed for total lithium isotope separation process. Lithium in Li(RO)₂IL was stripped by the sodium chloride of 5 mol l^?1 with a phase ratio (o/a) of 4. The lithium isotope exchange reaction in the interface between organic phase and aqueous phase reached the equilibrium within 1 min. The single-stage isotope separation factor of ⁷Li–⁶Li was up to 1.023 ± 0.002, indicating that ⁷Li was concentrated in organic phase and ⁶Li was concentrated in aqueous phase. All chemical reagents used can be well recycled. The extraction strategy offers green nature, low product cost, high efficiency and good application prospect to lithium isotope separation.     

Extraction of some lanthanides by 12-crown-4 and 15-crown-5 from perchlorate media as ion pairs

The extraction of the trivalent lanthanides Eu, Tm and Yb(Ln) by crown ethers (CE) 12-crown-4 (12C4) and 15-crown-5 (15C5) in chloroform from perchlorate aqueous media of constant ionic strength is investigated. The effect of [H⁺], [CE] and [ClO ₄ ^– ] on the respective distribution ratio (D) is elucidated. Slope analysis of these results indicated that the extracted species are of the type Ln(OH) ₂ ⁺ ·ClO ₄ ^– (CE)₂. The extraction constants obtained are in the sequence 15C5>12C4 for the CE's and EuTm<Yb for the elements investigated. Based on the separation factors elucidated, Tm(III) and Yb(III) are separated from Eu(III) with high radiochemical purity; >99.5% by three (or four) successive extraction and strippings.     

Structural and physical–chemical evaluation of Bradykinin Potentiating Peptide and its high soluble supramolecular complex

The supramolecular interactions between a Bradykinin Potentiating Peptide (BPP10c) and β-cyclodextrin (βCD) have been investigated by using several techniques. These new properties acquired by the inclusion phenomena are important in developing a strategy for pharmaceutical formulation. The BPP10c structural elucidation and its inclusion complex formed have been investigated using Nuclear Magnetic Resonance techniques. The peptide secondary structure was investigated using infrared spectroscopy in solution, Circular Dichroism and NMR. In addition, the thermodynamic parameters of the inclusion process were also evaluated using Isothermal Titration Calorimetry. The results obtained by these physical–chemical techniques suggested a 1:1 complex formed by interaction between the Tryptophan amino acid residue and the βCD cavity. The peptide secondary structure was not substantially modified for the inclusion process. In addition, the inclusion process proved to be spontaneous (ΔGº = ?2.53 kcal mol^?1), with an enthalpy reduction (ΔHº = ?3.72 kcal mol^?1) and a favored entropic variation (TΔSº = ?1.19 kcal mol^?1).     

Synthesis,characterization, and ion‐complexing properties of polymers displaying densely packed arrays of crown‐ethers as lateral substituents

We report the synthesis and ion‐binding properties of four poly(crown‐ethers) displaying either one or two crown‐ethers (15‐crown‐5 or 18‐crown‐6) on every third carbon alongside the backbone. The polymers were synthesized by living anionic ring‐opening polymerization of disubstituted cyclopropane‐1,1‐dicarboxylates monomers. Cation binding of the polychelating polymers and corresponding monomers to Na⁺ and K⁺ was evaluated by picrate extraction and isothermal calorimetry titration. This novel family of poly(crown‐ethers) demonstrated excellent initial binding of the alkali ions to the polymers, with a higher selectivity for potassium. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2337–2345     

Application of magnetic nanoparticles for the extraction of radium-226 from water samples

Bare (unmodified) and crown ether (CE)-modified Fe₃O₄ magnetic nanoparticles (MNPs) were investigated for the rapid extraction of ²²⁶Ra from water samples. It involved synthesizing the MNPs, introducing them into the sample solutions, ultrasonicating and agitating the suspension, magnetically separating the nanoparticles from solution, and measuring the ²²⁶Ra content in the supernatant. Experimental parameters such as salt choice, salt concentration and pH were optimized to achieve maximum extraction of ²²⁶Ra onto the MNPs. ²²⁶Ra content was determined using a Hidex 300SL liquid scintillation counter with α/β separation capability, or a gamma spectrometric detection system. The bare Fe₃O₄ nanoparticles showed significant pH dependence for the extraction of ²²⁶Ra from an aqueous solution over a pH range of 2–10. They gave an extraction of 95 ± 1 and 98 ± 1 % at pH 9 in 0.1 M NaCl and 0.1 M NaClO₄, respectively, whereas an extraction of 8–24 % was obtained, over the pH ranges from 2 to 5. The CE-modified MNPs yielded extraction efficiencies as high as 99 ± 1 % in the presence of 0.01 M picric acid at pH 4. This study demonstrates that the surface functionalization of Fe₃O₄ MNPs with suitable ligand modification can offer a selective mode of extraction for ²²⁶Ra in the presence of its daughter progenies.     

Synergic extraction of trivalent gadolinium,europium and americium radionuclides by 15-crown-5 or 18-crown-6 mixed with thenoyltrifluoroacetone from perchlorate medium

Synergic extraction of trivalent Eu, Gd and Am from aqueous perchlorate medium has been studied using mixtures of thenoyltrifluoroacetone (HTTA) and 15-crown-5 or 18-crown-6 (CE) in chloroform at (25±1) °C. Slope analysis of the extraction results indicated a general formula of M(TTA)₃·(CE)₂ for the extracted species. The stability order took the sequence Eu(TTA)₃·(CE)₂>Am(TTA)₃)·(CE)_2>>Gd(TTA)₃·(CE)₂ with 15C5 and Am(TTA)₃·(CE)₂>Eu(TTA)₃·(CE)₂>Gd(TTA)₃·(CE)₂ with 18C6. The synergic factors, extracton constants and formation constants of the extracted species were determined and discussed in terms of the correspondence between cavity size of the crown ethers and ionic crystal radii.     

Ion-pair extraction of Co(II) by crown ethers from perchlorate medium

The extraction of cobalt(II) by chloroform solutions of the crown ethers (CE) 12C4, I5C5, 18C6, Dbl8C6, Dchl8C6 or Dch24C8 from aqueous perchlorate medium was investigated. Slope analysis of the experimental data suggested that the extraction of Co(II) by these CEs takes place through ion-pair formation, and that the chemical formula of the main extracted species is Co(OH)(+)ClO(-)(4).CE. The magnitudes of the extraction constants are in the sequence 18C6 > Dch18C6 > Dch24C8 > Db18C6 > 15C5 > 12C4, which is discussed in terms of the correspondence between the CE cavity size and the ionic radius of cobalt(II).     

Preconcentration of beryllium via octadecyl silica gel microparticles doped with aluminon, and its determination by flame atomic absorption spectrometry

A simple and sensitive method is presented for solid phase extraction (SPE) and preconcentration of trace quantities of beryllium using octadecyl silica gel modifed with aurin tricarboxylic acid (aluminon). Beryllium is then determined by flame atomic absorption spectroscopy. Parameters affecting SPE such as pH, sample solution and eluent flow rate, type, concentration and volume of eluent, interfering ions and breakthrough volume, were investigated. Under optimal conditions, the beryllium ions were retained on the sorbent at pH 6–6.7, while 3.0 mL of 0.05 mol L^?1 HNO₃ is sufficient to elute the ions. The limit of detection (LOD) based on 3σ was 0.8 µg L^?1 for 250 mL sample solution and 5 mL 0.05 mol L^?1 HNO₃ as eluent. The LOD can reach 0.1 µg L^?1 for 1 L sample solution and 3 mL of 0.05 mol L^?1 HNO₃. The accuracy and precision (RSD %) of the method is >90% and <10%, respectively. The method was applied to the determination of beryllium in aqueous samples.     

Effects of pH, concentration and temperature on radionuclides sorption onto polyhydroxyethyl methacrylate-expanded perlite composite

Poly (hydroxyethylmethacrylate-expanded perlite) [P(HEMA-EP)], was synthesized and its adsorptive features were investigated for natural radionuclides (TI⁺, Ra²⁺, Bi³⁺, Ac³⁺ and Pb²⁺) in aqueous media at differing initial pH, initial radionuclides concentration and adsorption thermodynamics. The amounts of natural radionuclides at equilibrium were determined by gamma spectrometry. The Langmuir adsorption capacities (X_L) were found to be in the order of ²¹²Pb (0.4 MBq kg^?1) > ²²⁸Ac and ²⁰⁸Tl (0.3 MBq kg^?1) > ²²⁶Ra and ²¹²Bi (0.2 MBq kg^?1). These findings indicated that P(HEMA-EP) adsorbed natural radionuclides with high affinity. It was also demonstrated that the adsorption mechanism was spontaneous (ΔG < 0), the process was exothermic (ΔH < 0) thus increasing entropy (ΔS > 0). The composite was reused for four more times after regeneration without any detectable changes either in its structure or adsorptive capability.     

Synthesis of a fluorescent 14-crown-4 derivative bearing a proton-dissociable moiety and its use for selective lithium-ion extraction

The fluorescent 14-crown-4 derivative possesses a p-(1,8-naphthalenedicarboxi-mido) phenol moiety as the proton -dissociable fluorophore; its synthesis is described. Highly selective extraction of lithium is achieved with the crown ether, based on a proton/metal ion-exchange mechanism. Extraction is accompanied by significant changes in the absorption and fluorescence spectra of the organic phase. Extraction equilibrium constants for the lithium and sodium ions are evaluated, the Li⁺/Na⁺ selectivity ratio being 200; other alkali metal ions were not extracted. The Li⁺ extraction quenched the fluorescence intensity of the crown ether, in correlation with the initial cation concentration in the aqueous phase.