COMPARISON OF ION EXCHANGE AND DONNAN EQUILIBRIUM MODELS FOR THE PH-DEPENDENT ADSORPTION OF SODIUM AND CALCIUM IONS ONTO KRAFT WOOD PULP FIBERS

ABSTRACT

Management of nonprocess element (NPE) accumulation in pulp washing operations requires equilibrium models that predict the distribution of metals between the wash liquor and the pulp fibers. The overall goal of this study was to assess models for predicting the multi-component adsorption of hydrogen ions (H⁺), sodium ions (Na⁺), and calcium ions (Ca⁺²) onto bleached and unbleached kraft pulp fibers over a pH range of 2.7–11. As part of this study, binary equilibrium constants for hydrogen and metal ion exchange on carboxylate sites in bleached pulp (0.041 meq/g dry pulp) were measured at 25°C, with log K ^Na/Ca = ?1.604 ± 0.119, log K ^H/Ca = 0.633 ± 0.087, and intrinsic dissociation constant pK _io of 3.64 ± 0.46. Ion exchange and Donnan equilibrium models adequately predicted the multi-component equilibrium data for competitive adsorption of H⁺, Na⁺, and Ca⁺² onto bleached kraft wood pulp fibers. The ion exchange model was fully predictive, whereas the Donnan model required that the solution pH be known. At pH 2.7–6, the Donnan model predicted the adsorption of Na⁺ and Ca⁺² onto both bleached and unbleached wood pulp fibers better than the ion exchange model. The ion exchange model assumed that residual carboxylate in the pulp served as the only site for the competitive binding of hydrogen and metal ions. In contrast, the Donnan model assumed a non site-specific distribution of metal ions between charged fiber and external solution phases and a carboxylate site specific adsorption of hydrogen ions. Above pH 6, both models failed to predict that the calcium adsorption on unbleached brownstock pulp increased beyond the carboxylate site capacity, suggesting that other functional groups within the brownstock pulp with intrinsic dissociation constant values higher than carboxylate were providing additional binding sites for calcium.     

Synthesis and properties of a cellulose exchanger with the crown ether diaminodibenzo-17-crown-5 as anchor group

A new cellulose exchanger was synthesized from “o-aminophenolcellulose” by diazotation and coupling with diaminodibenzo-17-crown-5. The distribution coefficients for Ca²⁺, Sr²⁺, Ba²⁺, Na⁺ and K⁺ were determined in water/methanol mixtures as a function of the water content. Separation of Ca²⁺, Na⁺ and K⁺ and fractionation of the calcium isotopes ⁴⁸Ca and ⁴⁰Ca were investigated. The enrichment factor ε = 4.9 · 10^?3 for ⁴⁸Ca²⁺ is appreciably higher than that found for cation exchange resins with ? SO₃H groups, but lower than that reported for certain cryptands.     

Influence of K+ and Na+ ions on the degradation of wet‐spun alginate fibers for tissue engineering

A synthetic type of wet‐spun alginate fibers were immersed in simulated body fluid(SBF) composed of K⁺, Na⁺, and Ca²⁺ cations with various concentrations. Experimental measurements revealed that Na⁺ had a greater impact on degradability than that of K⁺ ion. The finding was further confirmed by the characterization of mass loss, ICP, XRD, and theoretical analyses. The degradation process and mechanism were demonstrated through the research on swelling behavior and mass loss. Besides, the wet‐spun alginate fibers were characterized by FT‐IR, XRD, and SEM. The results showed that the degradation mechanism could be attributed to the ion‐exchange between Ca²⁺ of the synthetic alginate fibers and Na⁺, K⁺ of the solutions under the osmotic pressure. The synthetic fibers were swelled and then degraded faster with the presence of Na⁺ ion presented greater influence on degradability compared with K⁺ ion. The degradation results of a mechanical rupture of fibers due to excessive water uptake without the occurrence of any chemical changes in the spun alginates structure. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44396.     

Synthetic ionophores for the separation of Li, Na, K, Ca, Mg metal ions using liquid membrane technology

Carrier-assisted transport through liquid membranes is one of the important applications of supramolecular chemistry. This work investigates the use of synthetic carrier (ionophore) for the separation of metal ions. We have tested the effect of structure of ionophore on the separation of metal ions. For this purpose, we have used a new series of non-cyclic ionophores having different end groups and chain length (R₁–R₅). 1,5 bis (2-naphthyloxy)-3-oxapentane (R₁), 1,8 bis (2-naphthyloxy)-3,6-di-oxaoctane (R₂), 1,11 bis (2-naphthyloxy)-3,6,9-tri-oxaundecane (R₃) 1,11-(dianthraquinonyloxy) 3,6,9-trioxaundecane (R₄), 1,8 (dianthraquinonyloxy) 3, 6-dioxaoctane (R₅) have been used in extraction, bulk liquid membrane (BLM) and supported liquid membrane (SLM) transport of alkali (Li⁺, Na⁺, K⁺) and alkaline earth metal cations (Ca²⁺, Mg²⁺). The supported liquid membrane consisted of a porous cellulose nitrate and and an onion membrane support impregnated with ionophore using chloroform as a solvent. The results reveal that ionophores R₁, R₂ and R₃ are better extractants for K⁺ while R₄ and R₅ are better extractants for Ca²⁺. Among these ionophores R₃ and R₄ are best extractants for K⁺ and Ca²⁺ ions. The results of BLM reveal that ionophores R₁, R₂ and R₃ transport Na⁺ at a greater extent, while R₄ and R₅ transport Ca²⁺ and K⁺ at a greater extent. In SLM experiments using a cellulose nitrate membrane support, it was observed that naphthyl end group bearing ionophores (R₁–R₃) transports Na⁺ > K⁺, and anthraquinone bearing ionophores (R₄ and R₅) transport K⁺ > Na⁺ > Ca²⁺ respectively. In the onion membrane support R₄ transports Ca²⁺ and Na⁺ equally and R₅ transports K⁺ selectively. On comparing the membrane support, the cellulose nitrate membrane is found better support for the transport of metal ions. The results suggest that due to the presence of different end groups and chain lengths the selectivity of non-cyclic ionophores towards metal ions is enhanced. Thus selectivity of ionophores may have fruitful application in ion selective electrodes and separation of metal ions.     

Rapid Separation of Tl+ and Pb2+ from Various Binary Cation Mixtures Using Dicyclohexano-18-crown-6 Incorporated into Emulsion Membranes

Abstract

Relative transport rates of metal cation nitrates (Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, Tl⁺, Ca²⁺, Sr²⁺, Ba²⁺, and Pb²⁺) in a water-toluene-water emulsion membrane system were measured. The toluene component contained the surfactant Span 80 and the crown ether dicyclohexano-18-crown-6. The aqueous receiving phase contained Li₄P2O₇. When each metal cation was individually present in the aqueous source phase, metal extraction was complete within 10 min with the order of extraction being Tl⁺ > Cs⁺ > Ag⁺ > Rb⁺ > K⁺ ≥m Na⁺ and Pb⁺ > Ca²⁺ > Sr²⁺ > Ba²⁺ for uni-and bivalent cations, respectively. Significant extraction was found for all cations except Na⁺, K⁺, and Ba²⁺. Some metal ions were concentrated nearly 10-fold in a 10-min period. Relative transport rates were determined when binary cation mixtures of either Tl⁺ or Pb²⁺ were present at equal concentrations with each of the remaining metal ions in the source phase. Tl⁺, when present with either Na⁺, Cs⁺, or Rb⁺, was selectively extracted from the source phase. Complete and nearly exclusive extraction of Pb²⁺ was observed in the presence of all cations including Tl⁺. The enrichment ratios of Pb²⁺ in the binary mixtures were approximately 10 while those of the second cation were less than 0.5 except for Sr²⁺ which was 0.86. Corresponding separation factors for Pb²⁺ ranged from 1000 to > 6000.     

Multi-ion migration of Ca2+, Mg2+, Na+ and K+ in the CREDI process

In this paper, the migration of Ca²⁺, Mg²⁺, Na⁺ and K⁺ in cation-bed electrodeionisation was studied. The results showed that it was longer for divalent cations to be balanced compared with monovalent cations. At relatively low current densities, the membrane fluxes of monovalent cations were higher than that of divalent cations, whereas the results were reversed at relatively high current densities. In the resin phase, it was observed that the ionic transport was in relation to various hydration ionic radii. The reaction orders for Ca²⁺, Mg²⁺, Na⁺ and K⁺ were 2, 2, 1 and 1.5, respectively.     

Adsorption of metal cations from aqueous solutions onto the pH responsive poly(vinylidene fluoride grafted poly(acrylic acid) (PVDF-PAA) membrane

This study investigated the influence of pH of adsorption medium and co-adsorptive metal cations for the adsorption of potassium (K⁺) and magnesium (Mg²⁺) ions onto poly (vinylidene fluoride) grafted poly(acrylic acid) (PAA-PVDF) membrane. At pH 4.8, the adsorption of potassium and magnesium was minimal, because of nearly non-dissociated carboxylic acid groups of PAA-chains, but adsorption increased with increasing ion concentration. The interaction of the studied cations between PVDF-PAA membranes increased considerably at pH 7.0 the dissociation of carboxylic acid groups of PAA. The addition of ionic substances (calcium (Ca²⁺) and sodium (Na⁺) to the adsorption medium reduced the adsorption of potassium and magnesium onto the membrane, because of co-adsorption. Divalent calcium reduced more effectively than univalent sodium the adsorption of potassium and magnesium onto the membrane. In conclusion, co-adsorbing ions reduced the adsorbed amount of potassium and magnesium ions due to binding competition. The percentual adsorbed values suggest that adsorption affinity of studied ions onto the PVDF-PAA membrane followed the order Na⁺ < K⁺ < Mg²⁺ < Ca²⁺. The effect of metal cations on drug adsorption from biological fluids needs research in the future, because e.g. PVDF-PAA membrane has been used in drug separation processes.     

Complexation of poly(methyl methacrylate-g-propylene oxide) and alkali-metal ions

Summary Copolymers of poly(methyl methacrylate-g-propylene oxide) with grafted branches having different molecular weights were complexed with K⁺, Na⁺ and Ca²⁺. The efficiency of the graft copolymers in binding cations was evaluated from salt distribution equilibria in water-methylene chloride. Among the used cations, K⁺ was more easily complexed than Na⁺ and Ca²⁺.     

An RNA‐Cleaving Catalytic DNA Accelerated by Freezing

The EtNa DNAzyme was isolated during the isopropanol precipitation step of an in vitro selection effort. Although inactive with the intended cofactor, its RNA cleavage activity was observed under a few conditions. With Na⁺, EtNa was highly active in ～50 % ethanol, whereas in water, it was highly active with Ca²⁺. In this work, we showed that the EtNa DNAzyme was accelerated by freezing in water in the presence of Na⁺. The apparent K_d value reached 6.2 mm Na⁺ under the frozen condition, over 20 times tighter than that in water at room temperature. With 10 mm Na⁺, EtNa had a cleavage rate of 0.12 h^?1 after freezing at ?20 °C. This effect was unique to EtNa, as all other tested DNAzymes were inhibited by freezing except for the Na⁺‐specific NaA43. Freezing also inhibited EtNa if Ca²⁺ was used. We attributed this to the concentrations of EtNa and Na⁺ in the micropockets between ice crystals, but divalent metals might misfold DNA. Overall, we have systematically studied the effect of freezing on the RNA‐cleavage activity of DNAzymes. The DNAzyme sequence and the metal ion species are both crucial to determine the effect of freezing.     

Selective and Efficient Liquid Membrane Transport of Thallium (III) Ion by Potassium‐dicyclohexyl‐18‐crown‐6 as Specific Carrier

Abstract

Potassium‐dicyclohexyl‐18‐crown‐6 was used as a selective and efficient carrier for the uphill transport of thallium (III) ion as [TlCl₄]^? complex ion through a chloroform bulk liquid membrane. By using oxalate anion as a metal ion acceptor in the receiving phase, the amount of thallium (III) transported across the liquid membrane after 120 min was 96±2%. The selectivity and efficiencies of thallium transport from aqueous solutions containing Cu²⁺, Zn²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Co³⁺, Mn²⁺ _, Cr³⁺, Mg²⁺, Ca²⁺, K⁺, Na⁺, and Fe³⁺ ions were investigated. In the presence of Na₃PO₄ (0.01 M) at pH=3 as a suitable precipitation agent in the source phase, the interfering effect of Pb²⁺ ion were diminished drastically.     

Effects of Additives on the Activity and Enantioselectivity of Candida rugosa Lipase in a Biphasic Medium

The effects of Li⁺, Na⁺, K⁺, Mg²⁺ and Zn²⁺ ions on the activity and enantioselectivity of Candida rugosa lipase (CRL) were investigated in a biphasic medium composed of phosphate buffer solution (containing a metal ion within a 50–500 mM concentration range) and isooctane. The hydrolytic activities of CRL towards p‐nitrophenyl acetate were measured after incubation of the enzyme in the presence of metal ions for 24 h, and they were compared to that obtained after incubation in the absence of any metal ion. The CRL activity was stimulated by the chloride salts of Li⁺, K⁺ and Mg²⁺ for all concentrations considered and the highest enhancement was achieved by Li⁺ with a 1.24–1.75 fold increase observed. The effects of metal ions on the enantioselectivity of CRL were investigated by performing the hydrolysis of racemic Naproxen methyl ester in the same biphasic medium containing Li⁺, Na⁺, K⁺, Mg²⁺ and Zn²⁺ ions. The addition of metal ions increased the hydrolysis rate by ca. 1.31–1.45 fold relative to the control, whereas the enantiomeric excess of product increased slightly in the presence of the metal ions. The effect of Triton X‐100 on the activity and enantioselectivity of the CRL was also investigated by employing 0.05, 0.1, 0.2, 0.3, 0.4, and 0.5 mM concentrations of it in phosphate buffer solution of the biphasic medium. High concentrations of Triton X‐100 stimulated the enzyme activity up to 1.66 fold after 24 h incubation. Triton X‐100 increased the hydrolysis rate almost independently of the concentration.     

Ion-Exchange Properties of lon-Sieve-Type Manganese Oxides Prepared by Using Different Kinds of Introducing Ions

Abstract

Three ion-sieve-type manganese oxides, HMnO(Li), HMnO(Na), and HMnO(K), were prepared by acid treatments of Li⁺-, Na⁺-, and K⁺-introduced manganese oxides, respectively. Three oxides were obtained from γ-MnO² and the corresponding alkali metal hydroxides by heating at 600°C. The ion-exchange properties of the adsorbents were investigated by pH titration, K_d measurements, and the adsorption of metal ions from seawater. The selectivity sequences of alkali metal ions were Na⁺ < Cs⁺ < Rb⁺ < K⁺ < Li⁺ for HMnO(Li) and Li⁺ Na⁺ < Cs⁺ < K⁺ < Rb⁺ for HMnO(Na) and HMnO(K). The high selectivity of Li⁺ on HMnO(Li) can be ascribed to an ion-sieve effect of spinel-type manganese oxide which was produced from LiMn₂O₄ Since HMnO(Na) and HMnO(K) had [2 × 2] tunnels of edge-shared [MnO₆] octahedra, the high selectivities of K⁺ and Rb⁺ on these samples were used to explain that the sizes of the [2 × 2] tunnels were suitable for filling ions of about 1.4 Å in radius in a stable configuration. The order of metal-ion uptake from seawater was Sr²⁺ < K⁺ < Mg²⁺ < Ca²⁺ < Na⁺ < Li⁺ for HMnO(Li), Li⁺ < Sr²⁺ < Mg²⁺ < Ca²⁺ < Na⁺ < K⁺ for HMnO(Na), and Li⁺ < Sr²⁺ < Ca²⁺ < Mg²⁺ < K⁺ < Na⁺ for HMnO(K).     

C,N‐Pyridylpyrazole‐Based Ligands: Synthesis and Preliminary Use in Metal Ion Extraction

Abstract

The synthesis of new N‐donor pyridylpyrazole ligands with a functionalized arm is described. The complexation capabilities of these compounds towards bivalent metal ions (Hg²⁺, Cd²⁺, Pb²⁺, Cu²⁺, and Zn²⁺) and alkali metal ions (K⁺, Na⁺, and Li⁺) were investigated using the liquid‐liquid extraction process. The percentage limits of extraction were determined by atomic absorption measurements.     

Poly[poly(oxypropylene) phosphate] macroionophores for transport and separation of cations in a hybrid: Cation‐exchange polymer and liquid membrane system

Poly[poly(oxypropylene) phosphate]s (PPOPP, M_n = 5800, 8100, 10,400), with different POP units (400, 1200, 2000), were synthesized and applied as cation‐selective macroionophores in a multimembrane hybrid system (MHS). The solution of PPOPP in dichloroethane formed the flowing liquid membrane (FLM) circulating between two polymer cation‐exchange membranes, and subsequently, between two polymer‐made pervaporation (PV) membranes. It was found that the PPOPP macroionophores activate the preferential transport of Zn²⁺ cations from aqueous solutions containing competing Cu²⁺, Ca²⁺, Mg²⁺, K⁺, and Na⁺ cations. The following separation orders were observed for PPOPPs with POP‐400 and POP‐1200: Zn²⁺ > Cu²⁺ ? Ca²⁺, Mg²⁺, K⁺, Na⁺, and for PPOPP with POP‐2000: Zn²⁺ > Cu²⁺,Ca²⁺ ? Mg²⁺, K⁺, Na⁺. Always, the particular cations are separated as: Zn²⁺ > Cu²⁺, Ca²⁺ > Mg²⁺, and K⁺ > Na⁺. The properties of PPOPPs were compared to respective transport and separation characteristics corresponding to those of respective poly(propylene glycol)s and poly(oxypropylene) bisphosphates. The results of investigation indicate that the bifunctional character of PPOPPs is caused by the presence of ionizable groups and probably pseudocyclic POP structures. By comparing the separation of cations in the simple MHS[FLM] system and the system supported by pervaporation unit [MHS[FLM‐PV] it was found that continuous dehydration of an organic FLM improves the system overall performance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1436–1445, 2004     

SPOTLIGHT ON MANUFACTURING TRENDS IN JAPAN

Three reactive and functional polymers were synthesized by reacting formaldehyde with the phenolic Schiff bases derived from 4,4′-diaminodiphenylsulfone and o-, m-, and p-hydroxybenzaldehydes, respectively. The metal ion uptake behavior of these resins towards Cu²⁺, Ni²⁺, Co²⁺, and UO₂ ²⁺ ions in dilute aqueous media was studied. The optimum conditions for the absorption of metal ions were determined by varying the various parameters like contact time, size of the sorbents, concentration of the metal ion solutions, and the pH of the reaction medium. Suitable conditions were ascertained for preferential adsorption of the above metal ions from the salt solutions containing other interfering ions such as Na⁺, K⁺, and Mg²⁺. Presence of these alkali and alkaline earth metal ions in the salt solutions did not affect the adsorption behavior of the resins. It was observed that the structural features of the resins have a profound effect on the uptake characteristics. The position of the OH group present in the meta position with respect to the imine nitrogen atom in the resin, demonstrated a significant influence on the extent of metal ion adsorption by the resin. Out of the three resins reported here, the resin derived from the Schiff base of m-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone showed higher efficiency in uptake of metal ions from the solutions than the corresponding resins derived from the Schiff bases of o- and p-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone.     

Mitochondrial Metal Ion Transport in Cell Metabolism and Disease

Mitochondria are vital to life and provide biological energy for other organelles and cell physiological processes. On the mitochondrial double layer membrane, there are a variety of channels and transporters to transport different metal ions, such as Ca²⁺, K⁺, Na⁺, Mg²⁺, Zn²⁺ and Fe²⁺/Fe³⁺. Emerging evidence in recent years has shown that the metal ion transport is essential for mitochondrial function and cellular metabolism, including oxidative phosphorylation (OXPHOS), ATP production, mitochondrial integrity, mitochondrial volume, enzyme activity, signal transduction, proliferation and apoptosis. The homeostasis of mitochondrial metal ions plays an important role in maintaining mitochondria and cell functions and regulating multiple diseases. In particular, channels and transporters for transporting mitochondrial metal ions are very critical, which can be used as potential targets to treat neurodegeneration, cardiovascular diseases, cancer, diabetes and other metabolic diseases. This review summarizes the current research on several types of mitochondrial metal ion channels/transporters and their functions in cell metabolism and diseases, providing strong evidence and therapeutic strategies for further insights into related diseases.     

Ion—solvent interaction: viscosity of ternary electrolytes in dioxane-water mixtures at 35°

The viscosities of the chlorides, bromides and nitrates and perchlorates of Mg²⁺ and Ba²⁺, of the chlorides and nitrates of Ca²⁺ and Sr²⁺, and of the sulphates of Na⁺ and K⁺ at mass fraction of dioxane, 10, 20 and 30% have been measured at 35°. The values of the constant A and B of the viscosity equation indicate ion—ion and ion—solvent interaction respectively. The ion-solvent interaction is found to be of the order NO^?₃ > ClO^?₄ > Br^? > Cl^? and K⁺ > Na⁺.     

13C and 23Na n.m.r. studies of the interactions between cations and kryptofix (2,2) bound to soluble or gel polyacrylamide

Interactions between univalent cations (Li⁺, Na⁺, K⁺, Ag⁺) and bivalent cations (Ba²⁺, Ca²⁺) with kryptofix (2,2) substituted polyacrylamide have been investigated using ¹³C n.m.r. The tendency to form complexes involves the dimensions of both the hydrated ion and the cavity size macrocycle and for Ag⁺ the nature of the interaction site. The sensitivity of the ²³Na n.m.r. method for detecting complex formation in solution from macromolecular species has been applied to the determination of the conditional formation constants of Na⁺ and Ba²⁺ complexes.     

THERMODYNAMICS OF ALKALI AND ALKALINE EARTH METAL ION - EXCHANGE ON CERIUM(IV) HYDROGEN PHOSPHATE

ABSTRACT

Thermodynamics of alkali and alkaline earth metal ions/hydrogen ions exchange on a fibrous cerium(IV) hydrogen phosphate have been investigated. Selectivities for alkali and alkaline earth metal ions increase in the order; Na⁺<<K⁺<Rb⁺<Cs⁺ and Mg²⁺<Ca²⁺<Sr²⁺<Ba²⁺, respectively. The enthalpy changes for alkali metal and Ba2+ ions/H⁺ exchange are negative, those for the other alkaline earth metal ions/H⁺ exchange are positive, indicating that the enthalpy changes for monovalent ions are more favorable than those for divalent ions. In comparison with ions of the same valency, the enthalpy change decreases with the atomic number of the metal ion corresponding to a decrease in the entropy change of dehydration in response to enthalpy-entropy compensation.     

Development of thin‐film composite membranes for carbon dioxide and methane separation using sulfonated poly(phenylene oxide)

Novel membranes based on sulfonated poly (phenylene oxide) (SPPO) was developed. SPPO membranes in the hydrogen form were converted to metal ion forms. The effect of exchange with metal ions including monovalent (Li⁺, Na⁺, K⁺), divalent (Mg²⁺, Ba²⁺, Ca²⁺) and trivalent (Al³⁺) ions was investigated in terms of permeation rate and permeation rate ratios for CO₂ and CH₄ gases. Both dense homogeneous membranes and thin‐film composite (TFC) membranes were studied for their gas separation characteristics. The effect of membrane preparation conditions and operating parameters on the membrane performance were also investigated. The selectivity of the TFC membrane increased as the cationic charge density increased as a result of electrostatic cross‐linking. TFC membrane of very high selectivity was achieved by coating a thin layer of SPPO‐Mg on a PES substrate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 735–742, 2000