Evaluation of some new 14- and 15-crown-formazans as carriers in cesium ion selective electrodes

A number of new crown-formazans with 14 and 15 membered rings have been investigated as selective neutral carriers in cesium ion selective electrodes. Two plasticizers (NPOE and NPBnE) were studied. The new 14-crown-formazan 4a containing the 4-pyridyl N-oxide at the formazyl carbon exhibited the highest selectivity in cesium ion selective electrodes, especially towards the two low selectivity monovalent ions K(+) and NH4(+). Also, membranes containing the plasticizer NPBnE showed better cesium selectivity relative to most ions than those containing NPOE. Membranes containing 4a and variable compositions of plasticizers, potassium tetrakis-(p-chlorophenyl)borate (KTpClPB), and trioctylphosphine oxide (TOPO) were studied in order to prepare an electrode with the optimum cesium selectivity. The highest selectivity for cesium was achieved with the two electrodes designated d and e with membranes containing the ionophore 4a, NPBnE and KTpClPB with and without TOPO. Selectivities are reported relative to sodium, potassium, barium, calcium, ammonium, lithium, cobalt, and magnesium.     

Evaluation of some new 14- and 15-crown-formazans as carriers in cesium ion selective electrodes

A number of new crown-formazans with 14 and 15 membered rings have been investigated as selective neutral carriers in cesium ion selective electrodes. Two plasticizers (NPOE and NPBnE) were studied. The new 14-crown-formazan 4a containing the 4-pyridyl N-oxide at the formazyl carbon exhibited the highest selectivity in cesium ion selective electrodes, especially towards the two low selectivity monovalent ions K⁺ and NH4⁺. Also, membranes containing the plasticizer NPBnE showed better cesium selectivity relative to most ions than those containing NPOE. Membranes containing 4a and variable compositions of plasticizers, potassium tetrakis-(p-chlorophenyl)borate (KTpClPB), and trioctylphosphine oxide (TOPO) were studied in order to prepare an electrode with the optimum cesium selectivity. The highest selectivity for cesium was achieved with the two electrodes designated d and e with membranes containing the ionophore 4a, NPBnE and KTpClPB with and without TOPO. Selectivities are reported relative to sodium, potassium, barium, calcium, ammonium, lithium, cobalt, and magnesium.     

A study of the sorption properties of natural calcium clinoptilolite by using radioactive indicators

The sorption of monovalent ions (cesium, silver, thallium, mercury), bivalent ions (strontium, barium, lead, copper, cobalt, zinc) and polyvalent ions (cerium) on calcium clinoptilolite under dynamic conditions has been studied. Both the dynamic exchange capacities in the different break-through of the ions and the degree of the exchanging ions in sorption of different metal cations have been determined. The good selectivity of calcium clinoptilolite in relation to cesium and strontium is displayed in the presence of sodium. The influence of various factors on the sorption the thermal and radiation treatment of the sorbent, the pH and concentration of solutions, equilibration time, presence of alkali and alkali earth ions deactivating agents—EDTA, citric acid tartaric acid, and boric acid in solution has been studied. The optimum conditions of sorption have been determined. Experiments for the desorption of cesium and strontium have been carried out. The possibility to use calcium clinoptilolite for the purpose of deactivation of radioactive wastes is shown. The better sorption properties of that sorbent, compared to calcium clinoptilolite, can be explained by the higher aluminium content, as well as by a prevalence of calcium and magnesium in its ion exchange complex.     

Cesium-selective optode membrane based on the lipophilic calix[4]biscrown in the 1,3-alternate conformation

One type of lipophilic calix[4]biscrowns in the 1,3-alternate conformation which are highly selective complexant for cesium has been used to construct cesium poly(vinyl chloride) (PVC) membrane optode. The reversible sensing system has been formed by incorporating the lipophilic neutral H⁺—selective chromoionophore ETH5294 in the plasticized PVC membrane with 1,3-calix[4]bisnaphtyl-crown-6. The measuring range of cesium ions can be conditioned by buffering different pH in the cesium solutions. At pH 7.0, the measuring range of the optode membrane for cesium ions is from 1×10⁻⁶ to 1×10⁻² M. The response behavior of optode membrane including response time, selectivity, reproducibility and lifetime, has been described in detail.     

Preparation and evaluation of composite ion-exchanger for the removal of cesium and strontium radioisotopes

Preparation conditions of composite ion-exchanger based on stannic molybdophosphate (SMP) and poly-acrylamide (PAA) have been described. Batch distribution coefficients for some ions were investigated at 25 °C. Sodium ion exchange capacity and breakthrough curves of cesium and strontium ions have also been determined. The results obtained from the experiments showed that the selectivity of SMP-PAA for cesium and strontium was greater than for other ions. Adsorption amounts of both ions were higher than 99% in demineralized water and their uptake rate were relatively rapid.     

Selectivity of ion exchangers in extracting cesium and rubidium from alkaline solutions

We compare the ion exchange selectivity of phenol-type sorbents based on phenol formaldehyde resins, products of condensation of diatomic phenols with formaldehyde, and crosslinked polymer based on C-phenyl[4]resorcinarene resin, for cesium and rubidium ions. It is shown that phenol formaldehyde sorbents are the ones most selective. The interaction of alkali metal cations with the anion of calix[4]arene is investigated via quantum-chemical modeling. It is shown that the selectivity toward cesium and rubidium ions in ion exchangers of the phenolic type is not due to specific interactions of ions with phenolic groups.     

Comparative characteristics of the ion-exchange properties of natural clinoptilolites from Bulgaria and the USSR for the purpose of purification of liquid wastes from nuclear power plants. Part I: Study of the equilibrium sorption of cesium and strontium ions from solutions of different composition

The ion-exchange equilibrium of cesium and strontium ions on clinoptilolites from different deposits — Dzegvi and Tedzami /Georgian SSR/, Beli Plast and Beli Bair /Bulgaria/ in different cationic forms of the sorbents /natural, sodium, calcium and ammonium/ is studied. The static ion-exchange capacities are determined. The sorption isotherms are plotted and the corresponding distribution coefficients are calculated. Mechanical characteristics which are important for the assessment of the technological use of the sorbents in dynamic conditions are determined. The clinoptilolite from Beli Plast deposit has the highest capacity in comparison with the other studied zeolites. The selectivity of the clinoptilolites from Bulgarian deposits is independent of the cationic form of the sorbent while the selectivity of the Georgian clinoptilolites strongly depends on the cationic form; the selectivity of the ammonium form of Tedzami sorbent is the highest.     

Selectivity coefficient changes for liquid-membrane electrodes

The effects of the activity levels of the measured ion and interfering ions, and of the detection limit of the electrode on the values of selectivity coefficients for liquid-membrane ion-selective electrodes are discussed. The coefficients were determined by the mixed-ion solution method. Depending on the activity of the interfering ion, the activity of the main ion for which the selectivity coefficient is determined may differ. The best conditions of measurement are those which involve the largest contribution from the term containing the selectivity coefficient in the Nikolsky equation; the measurements are then most precise, and the values of the selectivity coefficients describe the electrode behaviour most consistently. When the limit of detection of the electrode is comparable with the other terms, it must be taken into account in calculations. Under the optimal conditions, selectivity coefficients were calculated for the Orion calcium and divalent cation electrodes, with calcium as the main ion and alkali metal ions as interfering ions.     

Adsorption of alkali and alkaline earth radionuclides on zeolite from water solutions

The adsorption of cesium and strontium ions from water solutions on zeolite has been investigated in presence of sodium, potassium, magnesium and calcium ions. Distribution ratios of cesium and strontium on the zeolite were determined in solutions of various compositions and solution volume to sorbent weight ratios (batch factor). Breakthrough curves for zeolite layers are reported.     

Cs(2)CO(3)-promoted efficient carbonate and carbamate synthesis on solid phase

[reaction: see text] Mild and efficient preparation of alkyl carbonates and carbamates on solid supports is described herein. Alcohols or amines were coupled with Merrifield's resin through a CO(2) linker in the presence of cesium carbonate and tetrabutylammonium iodide (TBAI).     

Reversible colorimetric probes for mercury sensing

The selectivity and sensitivity of two colorimetric sensors based on the ruthenium complexes N719 [bis(2,2'-bipyridyl-4,4'-dicarboxylate)ruthenium(II) bis(tetrabutylammonium) bis(thiocyanate)] and N749 [(2,2':6',2' '-terpyridine-4,4',4' '-tricarboxylate)ruthenium(II) tris(tetrabutylammonium) tris(isothiocyanate)] are described. It was found that mercury ions coordinate reversibly to the sulfur atom of the dyes' NCS groups. This interaction induces a color change in the dyes at submicromolar concentrations of mercury. Furthermore, the color change of these dyes is selective for mercury(II) when compared with other ions such as lead(II), cadmium(II), zinc(II), or iron(II). The detection limit for mercury(II) ions--using UV-vis spectroscopy--in homogeneous aqueous solutions is estimated to be approximately 20 ppb for N719 and approximately 150 ppb for N749. Moreover, the sensor molecules can be adsorbed onto high-surface-area mesoporous metal oxide films, allowing reversible heterogeneous sensing of mercury ions in aqueous solution. The results shown herein have important implications in the development of new reversible colorimetric sensors for the fast, easy, and selective detection and monitoring of mercuric ions in aqueous solutions.     

Selective detection of cesium by a water-soluble fluorescent molecular sensor based on a calix[4]arene-bis(crown-6-ether)

A tetrasulfonated calixarene with two appended crowns, each including a dioxycoumarin fluorophore, is highly soluble in water and shows excellent selectivity for cesium ions.     

A mild and highly convenient chemoselective alkylation of thiols using Cs2CO3-TBAI

A mild and improved method for the synthesis of thioethers has been developed. In the presence of cesium carbonate, tetrabutylammonium iodide, and DMF, various alkyl and aryl thiols underwent S-alkylation to afford structurally diverse sulfides in high yield. Unprotected mercaptoalcohols and thioamines reacted chemoselectively at the sulfur moiety exclusively. An example of a one-pot, solid-phase synthesis of a thioether is also described.     

Anion partitioning and ion-pairing behavior of anions in the extraction of cesium salts by 4,5' '-Bis(tert-octylbenzo)dibenzo-24-crown-8 in 1,2-dichloroethane

A systematic study of anion partitioning and ion pairing was performed for an extraction of individual cesium salts into 1,2-dichloroethane (1,2-DCE) using 4,5' '-bis(tert-octylbenzo)dibenzo-24-crown-8 as the cesium receptor. Equilibrium constants corresponding to the extraction of ion pairs and dissociated ions, formation of the 1:1 cesium/crown complex (confirmed by electrospray mass spectrometry), and dissociation of the ion pairs in water-saturated 1,2-DCE at 25 degrees C were obtained from equilibrium modeling using the SXLSQI program. The standard Gibbs energy of partitioning between water and water-saturated 1,2-DCE was determined for picrate, permanganate, trifluoromethanesulfonate, methanesulfonate, trifluoroacetate, and acetate anions. The dissociation of the organic-phase complex ion pair [Cs(4,4' '-bis(tert-octylbenzo)dibenzo-24-crown-8]+NO3- observed in the extraction experiments was shown to be consistent with the dissociation constant determined independently by conductance measurements. As attributed to the large effective radius of the complex cation, the evident anion discrimination due to ion pairing in the 1,2-DCE phase was relatively small, by comparison only a tenth of the discrimination exhibited by the anion partitioning. Only chloride and picrate exhibit evidence for significantly greater-than-expected ion-pairing tendency. These results provide insight into the inclusion properties of the clefts formed by opposing arene rings of the crown ether upon encapsulation of the Cs+ ion, whose weak anion recognition likely reflects the preferential inclusion of 1,2-DCE molecules in the clefts. Observed anion extraction selectivity in this system, which may be ascribed predominantly to solvent-induced Hofmeister bias selectivity toward large charge-diffuse anions, was nearly the same whether cesium salts were extracted as dissociated ions or ion pairs.     

Poly(vinyl chloride) membrane cesium ion-selective electrodes based on lipophilic calix[6]arene tetraester derivatives

New lipophilic tetraesters of calix[6]arene and calix[6]diquinone are investigated as cesium ion-selective ionophores in poly(vinyl chloride) membrane electrodes. For an ion-selective electrode based on calix[6]arene tetraester I, the linear response is 1x10(-6)-1x10(-1) M of Cs(+) concentrations. The selectivity coefficients for cesium ion over alkali, alkaline earth and ammonium ions are determined. The detection limit (log a (Cs (+))=-6.31) and the selectivity coefficient (log k (Cs (+),Rb (+))(pot )=-1.88) are obtained for polymeric membrane electrode containing calix[6]arene tetraester I.     

Measuring quaternary ammonium cleaning agents with ion selective electrodes

Data for coated-wire, ion selective electrodes (ISEs) are presented for cationic surfactant ions found in common cleaners including benzyldimethyltetradecylammonium, benzyldimethyldodecylammonium, and benzyldimethylhexadecylammonium. The ion exchangers dinonylnaphthalene sulfonic acid, tetraphenyborate, and tetrakis(4-chlorophenyl)borate are examined, showing dinonylnaphthalene sulfonic acid to be the favored species. The ISEs exhibit approximately Nernstian behavior down to the 10⁻⁶ M limit of detection with lifetimes in excess of 50 days when used continuously, and a shelf life of over 100 days. Reaching the upper detection limit at the critical micelle concentration requires use of polymeric-membrane reference electrodes including a new membrane cocktail, which allow response measurements of an order of magnitude higher than the traditional fritted-glass reference electrode. The surfactant ISEs show excellent selectivity over the common metal ions Na⁺, K⁺, Mg²⁺, Ca²⁺, and Cu²⁺ with selectivity coefficients less than 10^−5.3. The ISEs are also selective over the lower molecular weight quaternary ammonium ions tetradecyltrimethylammonium, dodecyltrimethylammonium, benzyldimethyl(2-hydroxyethyl)ammonium, and tetrabutylammonium with selectivity coefficients ranging from 10^−1.7 to 10^−5.5. Use of a single electrode to determine accurately the total cationic surfactant concentration in common cleaning solutions is accomplished with information about concentration dependent interferences and a modified Nikolsky–Eisenman model. Finally, quaternary ammonium surfactants have a deleterious effect on the measurements of pH and common ions like K⁺, Mg²⁺ and Ca²⁺ with polymeric ISEs. This makes it critical to include surfactant electrodes in a detector array when cleaning agents are present.     

Selectivity of Transport of Sodium, Magnesium, and Calcium Ions through a Sulfo-Cationite Membrane in Mixtures of Solutions of Their Chlorides

The transport numbers and the selectivity of transport of sodium, magnesium, and calcium ions through a heterogeneous sulfo-cationite membrane in solutions of sodium, magnesium, and calcium chlorides and their mixtures are studied at various current densities. Equations for calculating the selectivity of transport of the ions through the membrane are suggested for two extreme cases. One case corresponds to low currents, when one can assume that the membrane is at equilibrium with the outside solution. The selectivity of transport of the ions is defined in this case by their migration through the membrane. The other case occurs at currents that are close to a limiting value. Under these conditions the transport of the ions through the membrane is defined by their transport through a diffusion layer that forms near the membrane surface. Calculations with the aid of these equations satisfactorily conform to experiment. The deviation from calculation in the case of the magnesium cation is connected probably with its hydration being substantially greater as compared with sodium and calcium. It is established that the selectivity of transport of the ions through the membrane may be controlled to a certain extent by varying the current density.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 997–1000.Original Russian Text Copyright © 2005 by Greben’, Rodzik.     

Sulfonium and phosphonium, new ion-pairing agents with unique selectivity towards polarizable anions

Ion-pair chromatography (IPC) almost universally relies upon ammonium-based ion-pairing agents (IPAs) for anion separations. This work compares tetrabutylammonium (TBA) with tetrabutylphosphonium (TBP) and tributylsulfonium (TBS). To best understand the retention behavior analytes used for characterization of the IPAs spanned the Hofmeister series; from kosmotropic monoanions (iodate, chloride, nitrite) and intermediate anions (nitrate, bromide) to chaotropic ions (perchlorate, thiocyanate, iodide). The studies demonstrate that tetrabutylphosphonium is the most chaotropic IPA, followed by tetrabutylammonium and finally tributylsulfonium is the least chaotropic. In the case of the chaotropic anions, the retention of perchlorate was least with tributylsulfonium, and greatest for tetrabutylphosphonium, with tetrabutylammonium being intermediate. The multivalent kosmotropic anions (sulfate, chromate, thiosulfate) demonstrated unique selectivity changes depending on the kosmotropic/chaotropic nature of the IPA. Demonstrating increases in retention with increasing IPA concentration only with tributylsulfonium, whereas the more chaotropic IPAs universally decreased the retention of the multivalent anions.     

Selective mono protection of diols, diamines, and amino alcohols using cesium bases

Efficient synthetic methods were developed for the synthesis of mono xanthates, as well as mono dithiocarbamates of diamines and amino alcohols. This protocol utilizes the three component coupling of diols, diamines, and amino alcohols using alkyl bromides and carbon disulfide in the presence of a cesium base and tetrabutylammonium iodide (TBAI).     

Synthesis of novel calix[4]crown telomers and selective extraction of cesium ions

p-tert-Butylcalix[4]diazacrown-4 telomer, which contains hard and soft ion binding sites, was synthesized. It exhibited high selectivity toward cesium ions. The binding sites may complex alkali metal ions selectively.