Application of Nafion／Cobalt Hexacyanoferrate Chemically Modified Electrodes for the Determination of Electroinactive Cations by Ion Chromatography

Ｉｎｔｒｏｄｕｃｔｉｏｎ　　Ｉｏｎｃｈｒｏｍａｔｏｇｒａｐｈｙ (ＩＣ)ｈａｓｂｅｅｎｒｅｃｏｇｎｉｚｅｄａｓａｕｓｅｆｕｌｍｅｔｈｏｄｆｏｒｔｈｅｓｅｐａｒａｔｉｏｎｏｆｉｎｏｒｇａｎｉｃａｎｉｏｎｓａｎｄｃａｔｉｏｎｓｓｉｎｃｅｉｔｓｉｎｔｒｏｄｕｃｔｉｏｎｂｙＳｍａｌｌｅｔａｌ .ｉｎ 1975 .1ＡｓｉｇｎｉｆｉｃａｎｔｔｒｅｎｄｉｎｔｈｅｄｅｖｅｌｏｐｍｅｎｔｏｆＩＣｍｅｔｈｏｄｉｓｓｅａｒｃｈｆｏｒｓｅｎｓｉｔｉｖｅａｎｄｕｎｉｖｅｒｓａｌｄｅｔｅｃｔｉｏｎｍｅｔｈｏｄｓ .Ｔｈｅｍａｉｎｄｅｔ…     

Affinity capillary electrophoresis and density functional theory study of noncovalent interactions of cyclic peptide [Gly6]‐antamanide with small cations

ACE and density functional theory were employed to study the noncovalent interactions of cyclic decapeptide glycine‐6‐antamanide ([Gly⁶]AA), synthetic derivative of native antamanide (AA) peptide from the deadly poisonous fungus Amanita phalloides , with small cations (Li⁺, Rb⁺, Cs⁺, NH₄⁺, and Ca²⁺) in methanol. The strength of these interactions was quantified by the apparent stability constants of the appropriate complexes determined by ACE. The stability constants were calculated using the nonlinear regression analysis of the dependence of the effective electrophoretic mobility of [Gly⁶]AA on the concentration of the above ions in the BGE (methanolic solution of 20 mM chloroacetic acid, 10 mM Tris, pH_MeOH 7.8, containing 0–70 mM concentrations of the above ions added in the form of chlorides). Prior to stability constant calculation, the effective mobilities measured at actual temperature inside the capillary and at variable ionic strength of the BGEs were corrected to the values corresponding to the reference temperature of 25°C and to the constant ionic strength of 10 mM. From the above ions, Rb⁺ and Cs⁺ cations interacted weakly with [Gly⁶]AA but no interactions of [Gly⁶]AA with univalent Li⁺ and NH₄⁺ ions and divalent Ca²⁺ ion were observed. The apparent stability constants of [Gly⁶]AA‐Rb⁺ and [Gly⁶]AA‐Cs⁺ complexes were found to be equal to 13 ± 4 and 22 ± 3 L/mol, respectively. The structural characteristics of these complexes, such as position of the Rb⁺ and Cs⁺ ions in the cavity of the [Gly⁶]AA molecule and the interatomic distances within these complexes, were obtained by the density functional theory calculations.     

Selective complexation of alkali metal ions and nanotubular cyclopeptides: a DFT study

A density functional theory based on interaction of alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) with cyclic peptides constructed from 3 or 4 alanine molecule (CyAla3 and CyAla4), has been investigated using mixed basis set (C, H, O, Li⁺, Na⁺ and K⁺ using 6-31+G(d), and the heavier cations: Rb⁺ and Cs⁺ using LANL2DZ). The minimum energy structures, binding energies, and various thermodynamic parameters of free ligands and their metal cations complexes have been determined with B3LYP and CAM-B3LYP functionals. The order of interaction energies were found to be Li⁺ > K⁺ > Na⁺ > Rb⁺ > Cs⁺ and Li⁺ > Na⁺ > K⁺ ? Rb⁺ > Cs⁺, calculated at CAM-B3LYP level for the M/CyAla3 and M/CyAla4 complexes, respectively. Their selectivity trend shows that the highest cation selectivity for Li⁺ over other alkali metal ions has been achieved on the basis of thermodynamic analysis. The main types of driving force host–guest interactions are investigated, the electron-donating O offers lone pair electrons to the contacting LP* of alkali metal cations.     

Die Selektivität Kristalliner Cer(IV)-Phosphatsulfathydrate gegenüber Li+, Na+, K+, Rb+, Cs+ und NH in absolutem Methanol und absolutem Dimethylsulfoxid

Selectivity of Crystalline Ce^IV Phosphate Sulphate Hydrates for Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, and NH in Absolute Methanol and Absolute Dimethylsulphoxide The sequence of exchange capacities of Cerium(IV) phosphate sulphate hydrate (CePO₄)₂(HPO₄)_0.74(SO₄)_0.26 · 4,74 H₂O for alkalimetal ions and ammoniumions in absolute methanol at 25°C for the case of a small excess of the exchanger (in relation to the equivalent amount) is given by K⁺ > Rb⁺ ≥ NH₄⁺ > Cs⁺ > Na⁺ > Li⁺. Between the exchange capacity A of these cations and their ionic radii r (given by Ladd) exists the simple relation A = const./r. For Na⁺ the radius of the inner hydration shell must be considered. In absolute dimethyl-sulphoxide under the same conditions the sequence is K⁺ ≥ NH₄ > Rb⁺ > Na⁺ > Cs⁺ > Li⁺. For K⁺, NH₄, Rb⁺ and Cs⁺ the exchange capacity is given by A = const./r + const. · r⁴. The sequences of the alkali ions in both solvents are among the group of 13 sequences which are physicaly significant according to EISENMANNS 's theory. The results are compared with the observations made with water as solvent.     

Ionophores in Rubidium Ion‐Selective Membrane Electrodes

Binaphthyl‐based crown ethers incorporating anthraquinone, benzoquinone, and 1,4‐dimethoxybezene have been synthesized and tested for Rb⁺ selective ionophores in the poly(vinyl chloride) (PVC) membrane. The membrane containing NPOE gave a better Rb⁺ selectivity than those containing either DOA or BPPA as a plasticizer. The response was linear within the concentration range of 1.0×10^?5–1.0×10^?1 M and the slope was 54.7±0.5 mV/dec. The detection limit was determined to be 9.0×10^?6 M and the optimum pH range of the membrane was 6.0–9.0. The ISE membrane exhibits good selectivity for Rb⁺ over ammonium, alkali metal, and alkaline earth metal ions. Selectivity coefficients for the other metal ions, log K^Pot were ?2.5 for Li⁺, ?2.4 for Na⁺, ?2.0 for H⁺, ?1.0 for K⁺, ?1.2 for Cs⁺, ?1.6 for NH₄⁺, ?4.5 for Mg²⁺, ?5.0 for Ca²⁺,?4.9 for Ba²⁺. The lifetime of the membrane was about one month.     

WQD-1沸石离子交换性能的研究

测定了W_QD-1沸石在一价碱金属离子混合溶液中的分配系数、饱和交换量和在25℃时，NH⁺₄/K⁺、NH⁺₄/Na⁺交换等温线。得出该沸石一价离子选择性序列为：Cs⁺>Rb⁺>K⁺>Na⁺>Li⁺, Na⁺/K⁺交换自由焓变ΔG(T,P)=-6.745 KJ/mol。     

Selectivity ratios of cation-sensitive glass electrodes in ethanol-water mixtures

Summary The response of cation-sensitive glass electrodes to univalent cations in ethanol-water mixtures shows increasing e.m.f. values with increasing fractions of ethanol for Na⁺, K⁺, Cs⁺, Rb⁺, Li⁺, and NH₄ ⁺, but anomalous behavior for H⁺. The calculated selectivity of the glass electrode for metal ions over the hydrogen ion thus increases sharply over the range of 10–70 weight % ethanol. It is suggested that sodium rather than hydrogen ion may be adopted as the reference ion for the definition of selectivity ratios in mixed solvents.

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Zusammenfassung Die Ansprechbarkeit von kation-empfindlichen Glaselektroden auf einwertige Kationen (Na⁺, K⁺, Cs⁺, Rb⁺, Li⁺, NH₄ ⁺) in Äthanol-Wassergemischen weist mit steigendem Äthanolgehalt steigende E.M.K.-Werte auf; H⁺ zeigt ein abweichendes Verhalten. Die berechnete SelektivitÄt der Glaselektrode für Metallionen nimmt daher im Bereich von 10–70% Äthanol stark zu. Es wird empfohlen, für die Definition von SelektivitÄtsverhÄltnissen in Lösungsmittelgemischen Na⁺ an Stelle von H⁺ als Bezugsion zu verwenden.

     

Quantum simulation on donor and acceptor II calix[4]arene substrate and alkali metal ions: the driven inclusion

The energetic and structural optimized of a calix[4]arene with and without alkali-metal cations are presented with performance of various quantum chemical methods such as Hartree--Fock, second order Møller-Plesset perturbation theory, and density functional theory. The geometry optimizations have been carried out with the 3-21G (Li⁺--Cs⁺) and 3-21G(d,p) (Li⁺--K⁺) and the 3-21G basis sets for Cs⁺ and Rb⁺. Additional single-point energy ab initio calculations for Li⁺–K⁺ were carried out at HF/6--31G, HF/6-31G (d,p), HF/6--311G(d,p) for complexes of Li⁺ and Na⁺. The calculations were carried out to analyze the complexation of calix[4]arene with alkali metal cationic species (Li⁺, Na⁺, K⁺, Rb⁺, and Cs⁺). Assumption to isolate the effects of the aromatic core and cation-π interactions. Particular emphasis has been on conformational binding selectivity and the structural characterization of the complexes, the smaller cation as Li⁺ and Na⁺ has been placed in the lower rim's of the calix[4]arene's cavity. The large cations like K⁺, Rb⁺, and Cs⁺ take placed in upper rim and the endo (inclusive) complexation is driven by cation-π interactions, that reflect a superior interaction with two phenol rings. The endo complexation of Cs⁺ with calix[4]arene is in agreement with X-ray diffraction data. The binding modes of calixarene-cation systems are studied to involve cooperative effects between cation-π and electrostatic forces.     

Synergistic extraction of some univalent cations into nitrobenzene by using cesium dicarbollylcobaltate and dibenzo-30-crown-10

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq) + 1·Cs⁺(nb) ? 1·M⁺(nb) + Cs⁺(aq) taking place in the two-phase water–nitrobenzene system (M⁺ = Li⁺, Na⁺, H⁺, NH₄ ⁺, Ag⁺, K⁺, Rb⁺, Tl⁺; 1 = dibenzo-30-crown-10; aq = aqueous phase, nb = nitrobenzene phase) were determined. Furthermore, the stability constants of the 1·M⁺ complexes in water-saturated nitrobenzene were calculated; they were found to increase in the series of Cs⁺ < H⁺, Ag⁺ < NH₄ ⁺ < Na⁺ < Rb⁺ < Li⁺ < K⁺, Tl⁺.     

Polydiphenylamine-dodecyl sulfate films for the simultaneous amperometric determination of electroinactive anions and cations in ion-exclusion cation-exchange chromatography

An amperometric detector with two working electrodes both modified with polydiphenylamine-dodecyl sulfate (PDPA-DS) was successfully used for the simultaneous determination of electroinactive anions (SO₄ ^2–, Cl^–, NO₃ ^–) and cations (Na⁺, NH₄ ⁺ and K⁺) in single-column ion-exclusion cation-exchange chromatography (IEC-CEC). The PDPA-DS chemical modified electrode (CME) was based on the incorporation of dodecyl sulfate (DS) into PDPA by electropolymerization of diphenylamine in the presence of sodium dodecyl sulfate. The electrochemical responses against the anions and cations at the PDPA-DS CME in differential pulse voltammetry were studied. A set of well-defined peaks of electroinactive anions and cations were obtained. The anions and cations were detected conveniently and reproducibly in a linear concentration range 0.01–5.0 mmol/L and their detection limits were in the range 5–9 μmol/L at a signal-to-noise ratio of 3 (S/N = 3). The proposed method was quick, sensitive and simple and was successfully applied to the analysis of lake water samples. The working electrode was stable over one week period of operation with no evidence of chemical and mechanical deterioration.     

Heats of adsorption of water on vermiculite having large singly-charged cations in the exchange complex

The isotherms and differential heats of adsorption of water vapor on K-, NH₄-, Rb-, and Cs-vermiculites have been studied by means of a Calvet microcalorimeter having a microweighing adsorption attachment. The results are interpreted taking into account that the large cations K₊, NH₄ ⁺, Rb⁺, and especially Cs⁺, may not replace the initial exchange complexes (Na⁺ or Mg²⁺) of the mineral completely, so that besides hydration of the principal exchange cations the reaction of water molecules being adsorbed with the residual Na⁺ or Mg⁺ cations also takes place. The presence of a certain number of the initial cations (Na⁺ or Mg²⁺) in the Cs form of vermiculite is confirmed by the results of studying the ion exchange equilibria on the Na and natural (Mg) forms of the mineral involving the participation of the Cs₊ ions. The nature of the variation in the dependence of the differential heats of adsorption with an increase in the amount of adsorbed substance indicates the segregation (isolation) of the principal (K⁺, NH₄ ⁺, Rb⁺, Cs⁺) and the residual (Na⁺, Mg²⁺) exchange cation in the structure of the mineral.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 1, pp. 91–96, January–February, 1986.     

Solvent extraction of calcium and strontium into nitrobenzene by using hydrogen dicarbollylcobaltate in the presence of polypropylene glycol PPG 425

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq) + Cs⁺(org) ⟺ M⁺(org) + Cs⁺(aq) taking place in the two-phase water–phenyltrifluoromethyl sulfone (abbrev. FS 13) system (M⁺ = Li⁺, H₃O⁺, Na⁺, NH₄⁺ \hbox{NH}_{4}{}^{+} , Ag⁺, Tl⁺, K⁺, Rb⁺; aq = aqueous phase, org = FS 13 phase) were evaluated. Furthermore, the individual extraction constants of the M⁺ cations in the mentioned two-phase system were calculated; they were found to increase in the series of Li⁺ < H₃O⁺ < Na⁺< NH₄ ⁺ \hbox{NH}_{4}{}^{ + } < Ag⁺ < Tl⁺ < K⁺ < Rb⁺ < Cs⁺.     

Synthesis of macrocyclic tetraamides derived from α-amino acids and their investigations using ESI-MS technique

Chiral α,ω-diesters react under high-pressure conditions (10 kbar) with α,ω-diamines to give chiral cyclic tetraamides of C₂-symmetry. The complexation properties of tetraamides towards alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) were estimated on the basis of ESI-MS spectra.     

Cations Insertion in Molybdenum Cluster Compounds: Electronic Structure and Electrochemical Study Using Cavity Microelectrode

Owing to the high lability of cations in the three-dimensional framework of K_1+x Mo₁₂S₁₄ (0 ≤ x ≤ 1.6), first-principles calculations and electrochemical methods have been carried out to study the insertion of cations in the empty channels of this compound. The cavity microelectrode that is a suitable electrode for powder material analysis has been used in voltammetric experiments. Results obtained for Li⁺, Na⁺, Rb⁺, K⁺, Cs⁺ and NH₄ ⁺ cations are presented and discussed.     

Probing the microstructure of Nafion-117 using positron annihilation spectroscopy

We report a new result on positron annihilation studies in acid- and cation-neutralized (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺, UO₂²⁺, Ni²⁺) Nafion membranes using positron lifetime and Doppler-broadened annihilation radiation (DBAR) measurements. The free-volume structure is characterized using a simple quantum mechanical model of positronium (Ps) in a spherical well. Our studies indicate that formation and expansion of clusters is always associated with a change in free-volume structure resulting in smaller free-volume holes. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 771–776, 1997     

Preparation of a hybrid monolithic stationary phase with allylsulfonate for the rapid and simultaneous separation of cations in capillary ion chromatography

A hybrid monolithic column with sulfonate functionality was successfully prepared for the simultaneous separation of common inorganic cations in ion‐exchange chromatographic mode through a simple and easy single‐step preparation method. The strong cation‐exchange moieties were provided directly from allylsulfonate, which worked as an organic monomer in the single‐step reaction. Inorganic cations (Li⁺, Na⁺, K⁺, NH₄⁺, Cs⁺, Rb⁺, Mg²⁺, Ca²⁺, and Sr²⁺) were separated satisfactorily by using CuSO₄ as the eluent with indirect UV detection. The allysulfonate hybrid monolith showed a better performance in terms of speed and pressure drop than the capillary packed column. The number of theoretical plates achieved was 19 017 plates/m (in the case of NH₄⁺ as the analyte). The relative standard deviations (n = 6) of both retention time and peak height were less than 1.96% for all the analyte cations. The allysulfonate hybrid monolithic column was successfully applied for the rapid and simultaneous separation of inorganic cations in groundwater and the effluent of onsite domestic wastewater treatment system.     

Tricaesium tris(oxalato‐κ2O1,O2)chromate(III) dihydrate

The title compound, Cs₃[Cr(C₂O₄)₃]·2H₂O, has been synthesized for the first time and the spatial arrangement of the cations and anions is compared with those of the other members of the alkali metal series. The structure is built up of alternating layers of either the d or l enantiomers of [Cr(oxalate)₃]³⁻. Of note is that the distribution of the [Cr(oxalate)₃]³⁻ enantiomers in the Li⁺, K⁺ and Rb⁺ tris(oxalato)chromates differs from those of the Na⁺ and Cs⁺ tris(oxalato)chromates, and also differs within the corresponding BEDT‐TTF [bis(ethylenedithio)tetrathiafulvalene] conducting salts. The use of tris(oxalato)chromate anions in the crystal engineering of BEDT‐TTF salts is discussed, wherein the salts can be paramagnetic superconductors, semiconductors or metallic proton conductors, depending on whether the counter‐cation is NH₄⁺, H₃O⁺, Li⁺, Na⁺, K⁺, Rb⁺ or Cs⁺. These materials can also be superconducting or semiconducting, depending on the spatial distribution of the d and l enantiomers of [Cr(oxalate)₃]³⁻.     

Assessment of Potassium Zinc Ferrocyanide as an Alkali-Metal Ion-Exchanger in Ion-Selective Electrodes

Abstract

Silicone rubber membranes containing potassium zinc ferrocyanide have been assessed as ion-selective electrode sensors for the determination of alkali metal ions. The slope of the calibration graph for potassium ion is 59 mV per decade change in concentration within the concentration range 5 × 10^?4 to 10^?1 M at 25°C. Selectivity constants (K_K + _/M+)are 9. 5, Cs⁺; 3. 3, Rb⁺; 0. 025, Na⁺; 0. 003, Li⁺; and 1.8, NH₄ ⁺, calculated from potential data obtained at 10^?1 M concentrations of each ion separately. Similar membranes prepared from PVC responded similarly with a slight improvement in selectivity.     

On the complexation of some univalent cations with beauvericin in nitrobenzene saturated with water

From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium M⁺(aq)?+?1·Cs⁺(nb) ? 1·M⁺(nb)?+?Cs⁺(aq) taking place in the two-phase water–nitrobenzene system (M⁺?=?Li⁺, Na⁺, K⁺, Rb⁺, H₃O⁺, NH₄ ⁺, Tl⁺; 1?=?beauvericin; aq?=?aqueous phase, nb?=?nitrobenzene phase) were determined. Moreover, the stability constants of the 1·M⁺ complexes in water-saturated nitrobenzene were calculated; they were found to increase in the series of Rb^+?<?Na⁺, H₃O^+?<?Tl^+?<?NH ₄ ^+? <?K^+?<?Li⁺.     

Mobility of water molecules in Li+, Na+ and Cs+ ionic forms of Nafion membrane studied by NMR

Correlation times and diffusion coefficients of water molecules were measured for the first time by ¹H spin relaxation and pulsed field gradient NMR in Li⁺, Na⁺ and Cs⁺ ionic forms of Nafion 117 membrane. Hydration numbers of Li⁺, Na⁺ and Cs⁺ cations were calculated. It was shown that at high humidity macroscopic transfer is controlled by the local translational motion of water molecules.