The transport of ions across monoolein bilayers mediated by synthetic macrocyclic carriers

The efficiency as carriers for the alkali and the alkaline earth ions across monoolein bilayers of three macrocyclic compounds has been investigated by conductometric measurements. The results show that although the three compounds have the optimum cavity size for fitting potassium and barium cations, their efficiency in ionic transport is quite different. These discrepancies are rationalized on the basis of the overlap of the water-diazacrown and cation-ligand interactions on the carrier mechanism.     

Selective extraction and transport of mercury through a liquid membrane by macrocyclic ligands. Improvement in the transport efficiency and an approach to physiological systems

Extraction and transport of mercury in a H₂OCHCl₃H₂O system containing one of several macrocyclic carriers was studied. Improvement of the transport efficiency was effected, leading in some cases to the almost complete removal of the metal from the source phase and the membrane phase. Comparison of the transport of several cations of biological significance with transport experiments performed in the presence of human albumin and/or a culture medium gives results that provide a promising alternative method for removal of mercury from waste waters or in the treatment of accidental intoxications.     

Factors influencing the transport of tryptophan hydrochloride through supported liquid membranes containing macrocyclic carriers

Commercially available PTFE membranes were used as a support for liquid membranes in amino acid transport. Using tryptophan as a model amino acid, the influence of the type of organic liquid, kind of macrocyclic carrier and counter-ion on transport efficiency was examined. These studies show the strong influence of the kind of the counter-ion co-transported with amino acid cation, and the type of macrocyclic carrier used on the transport efficiency. The transport efficiency depends also on the pH of the source phase and on the nature of the organic liquid used as a membrane solvent. Liquid membranes supported on commercial porous-PTFE-membranes with hydrophobic solvents are stable for more than two months, while those with more hydrophilic solvents, for more than 30 days. The use of dodecylbenzenesulfonic acid as a counter-ion results in the highest flux of tryptophan, but in this case, the stability of membranes appeared to be five times lower.     

Redox-driven transport of copper ions in an emulsion liquid membrane system

A new redox-driven type of emulsion liquid membrane separation is described. Milligram amounts of copper(II) in 0.2 M hydrochloric acid were reduced to copper(I) in the presence of ascorbic acid (1 M≡1 mol l⁻¹). The copper solution was emulsified with a (1+4) mixture of toluene and n-heptane using Span-80 (sorbitan monooleate) as an emusifier. The resulting water-in-oil emulsion was dispersed in 0.2 M hydrochloric acid containing hydrogen peroxide and neocuproine (2,9-dimethyl-1,10-phenanthroline) by stirring for 10 min. The copper in the internal aqueous phase was selectively transported to the external one, leaving other heavy metals (e.g., Mn, Co, Ni, Cd and Pb) in the internal aqueous phase. After collecting the dispersed emulsion globules, they were demulsified by heating and the metals in the segregated aqueous phase were determined by graphite-furnace atomic absorption spectrometry (GFAAS). The selective transport of copper offered the multielement separation of trace heavy metals from a copper matrix, allowing the GFAAS determination of impurities at the 0.01% level in copper metal.     

Selective transport of zinc and copper ions by synthetic ionophores using liquid membrane technology

This work highlights the role of synthetic carrier (ionophore) in the separation of heavy metal ions. A new series of ionophores; 4,4′-nitrophenyl-azo-O,O′-phenyl-3,6,9-trioxaundecane-1,10-dioate (R₁), bis[4,4′nitro-phenylazo-naphthyl-(2,2-dioxydiethylether)] (R₂) 1,8-bis-(2-naphthyloxy)-3,6-dioxaoctane (R₃), 1,11-bis-(2-naphthyloxy)-3,6,9-trioxaunde-cane (R₄), 1,5-bis-(2-naphthyloxy)-3-oxa-pentane (R₅) have been synthesized and used as extractant as well as carrier for the transport of various metal ions (Na⁺, K⁺, Mg²⁺, Ni²⁺, Cu²⁺ and Zn²⁺) through liquid membranes. Effect of various parameters such as metal ion concentration, ionophore concentration, liquid–liquid extraction, back extraction, comparison of transport efficiency of BLM and SLM and different membrane support (hen’s egg shell and PTFE) have been studied. In BLM ionophores (R₂–R₅) transport Zn⁺ at greater extent and the observed trend for the transport of Zn²⁺ is R₂?>?R₄?>?R₃?>?R₅ respectively. Further transport efficiency is increased in SLM. In egg shell membrane ionophores (R₂–R₅) transport Zn⁺ due to their non-cyclic structure and pseudo cavity formation while ionophore R₁ transports Cu²⁺ ions at greater extent due to its cyclic structure and cavity size. Among the membrane support used egg shell membrane is found best for the transport of zinc ions because of its hydrophobic nature and exhibits electrostatic interactions between positively charged zinc ions and –COOH group of egg shell membrane. Thus structure of ionophores, hydrophobicity and porosity of the membrane support plays important role in separation of metal ions.     

Emulsion stability and potassium leakage in emulsion liquid membrane systems

Potassium leakage was studied in liquid membrane systems containing various emulsifiers and compared with emulsion, stability in the storage test. The effects of various parameters upon emulsion stability and the leakage of standard traces are discussed. The transfer of cations can be caused by emulsion breaking, by transport with the specific carrier and/or with surfactants used as emulsifiers. The latter case becomes especially important when hydrophilic surfactants, e.g. ones containing polyoxyethylene chains, are present in liquid membranes. In systems containing hydrophobic emulsifiers the transfer of potassium is relatively low. In each case considered the effect of emulsifiers upon the transfer of the standard tracer should be checked prior to using the leakage test to characterize emulsion stability.     

The synthesis and membrane transport characteristics of macrocyclic polyether ligands composed of 1,10-phenanthroline as carriers for primary amine species

Four macrocyclic polyether derivatives of o-phenanthroline were synthesized and used as neutral carriers for preparing poly(vinyl chloride) (PVC) membrane electrodes to sense primary amine species. The potentiometric response characteristics of the electrodes prepared were investigated. The electrode sensitive to benzyl amine as model analyte showed a linear response range of 8.0 x 10(-6)-0.1 mol/l with a detection limit of 8.9 x 10(-7) mol/l and a slope of 56.5 mV/decade. The linear potentiometric response of the mexiletine-sensitive electrode was 4.7 x 10(-6)-0.1 mol/l, and the detection limit was 5.0 x 10(-7)1 mol/l with a slope of 59.0 mV/decade. The transfer behavior of amines and ammonium ions through an organic phase was investigated by means of the bulk liquid membrane transport experiment. The effects of pH, counter anions and other factors on the transfer of the amine and ammonium species were studied. The mass transfer rates of the test species facilitated by macrocyclic polyether derivatives of o-phenanthroline were determined and the following sequence was found: benzyl amine > ethyl amine > tetramethyl ammonium > triethyl amine > diethyl amine > K(+) > ammonium > Na(+) > Ca(2+) > Mg(2+). This was exactly the potentiometric selectivity sequence of the membrane electrodes prepared by using these carriers. The mechanism of transfer of benzyl amine through a membrane phase induced by the carriers has been elucidated on the basis of experimental observations.     

Transport of carbonate ions through supported liquid membrane by using Alamine 336 and trioctylphosphine oxide as carriers

Abstract

Transport studies were carried out for carbonate ions through supported liquid membrane (SLMs) by using Alamine 336 and trioctylphosphine oxide (TOPO) as carriers. Experimental variables were investigated, such as concentration of carbonate ion (10^?5 to 4×10^?2 M), carriers (10^?5 to 10^?1 M), and alkali (0.01–0.5); and stirring speed (50–150 rpm) of bulk solutions. The use of combined carriers Alamine 336 and TOPO shows a synergic transport of carbonate ions. The stability of the SLM system in relation to the transport of carbonate ions has been studied. The enrichment of carbonate ions (10^?6 to 4×10^?2 M) from the dilute solution was explored. The different combinations of amines with TOPO show synergic permeability of the carbonate ions through SLM system.     

Transport of silver ion through bulk liquid membrane using macrocyclic and acyclic ligands as carriers in organic solvents

The bulk liquid membrane transport of silver (I) ion was studied by dibenzopyridino-18-crown-6(DBPY18C6), 4-nitrobenzo-15-crown-5(NB15C5), 2-aminothiaphenol and a new synthesized ligand, 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione as carriers in nitrobenzene (NB). The effects of pH on the source phase and receiving phase, the nature and concentration of stripping agents in the receiving phase and the picrate concentration as counter ion in source phase were investigated. The results show that the efficiency of transport of the Ag⁺ ion through membranes, changes with the nature of the ligand. The efficiency transport increases for the ligands with donating nitrogen and sulfur atoms with respect to oxygen donor atoms. Maximum transport efficiency was observed for silver (I) ion in the presence of thiosulfate ion ( ) as a suitable stripping agent. The results show that the sequence of transport efficiency for Ag⁺ ion using DBPY18C6, NB15C5, 2-aminothiaphenol and 1,4-dioxa-7,10-dithiacyclododecane-2,3-dione as carriers in organic solvents is: nitrobenzene > dichloromethane > 1,2- dichloroethane > chloroform.     

Pertraction of cadmium and zinc ions using a supported liquid membrane impregnated with different carriers

An experimental study on the removal of Cd²⁺ and Zn²⁺ through a supported liquid membrane using a mixture of mono-(2-etylhexyl) ester of phosphoric acid (M2EHPA) and bis-(2-etylhexyl) ester of phosphoric acid (D2EHPA) as carriers is presented. Parameters affecting the Cd²⁺ and Zn²⁺ pertraction such as feed concentration, carrier concentration, pH of the stripping phase, and TBP (tributyl phosphate) concentration were analyzed using the Taguchi method. Optimal experimental conditions for Cd²⁺ and Zn²⁺ pertraction were obtained using the analysis of variance (ANOVA) after a 6 h separation with the initial feed concentration of 8.9 × 10^?4 mol L^?1, carrier concentration of 20 vol. %, TBP concentration of 4 vol. %, and pH of 0.5. Then, under optimum conditions, a comparison of M2EHPA, D2EHPA, and bis-(2,4,4-trimethylpentyl)monothiophosphinic acid (Cyanex 302) was performed. Effective pertraction of Cd²⁺ and Zn²⁺ using these carriers was observed in the following order: mixture of M2EHPA and D2EHPA, D2EHPA, Cyanex 302. It was also found that the presence of one metal ion in the feed solution reduces the pertraction rate of the other one.     

Selective transport of copper(II) ions across a liquid membrane mediated by Piroxicam

Piroxicam was found to be a highly selective carrier for uphill transport of Cu²⁺ ions through a chloroform liquid membrane. The transport occurs via a counterflow of protons from the receiving phase to the source phase. The effects of several parameters on the transport of Cu²⁺ ions, such as the carrier concentration, pH of the source phase, composition of the receiving phase, and duration are described. A high transport efficiency (98±2%) was provided by the carrier for Cu²⁺ ions in a receiving phase of 0.01 mol l⁻¹ sulfuric acid after 4 h. Different metal ion transport experiments showed that Cu²⁺ ions were selectively transported over other ions, such as Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Zn²⁺, UO₂²⁺ and ZrO₂²⁺. In the presence of fluoride ions (used as a suitable masking agent in the source phase), the interfering effects of UO₂²⁺ and ZrO₂²⁺ ions were eliminated. The applicability of the method was tested on a real sample, and the results obtained show that it is potentially useful for solvent extraction of copper.     

K+ ion - dependent,active transport of amino acid anions by macrocyclic carriers

Active and selective transport of amino acid anions was successfully mediated by macrocyclic carriers, coupled with K⁺ ion transport.     

Generation and transport of charge carriers in the charge-transfer complex anthracene-pyromellitic-dianhydride

In single crystals of the zone-refined charge-transfer complex anthracene-pyromellitic-dianhydride the temperature dependences of the photocurrent quantum yield and of the electron and hole mobilities ⊥ [001] and ⊥ (010) have been studied. A hot transition in the action spectrum and microscopic electron mobilities are observed.     

Highly selective transport of lead cation through bulk liquid membrane by macrocyclic ligand of decyl-18-crown-6 as carrier

The liquid membrane transport of Pb²⁺ cation using decyl-18-crown-6 as selective ion carrier was studied. The transport of lead ion across the liquid membrane in the presence of S₂O ₃ ^2? , P₂O ₇ ^4? , CN^?, SCN^?, and DDC^? as stripping agents in the receiving phase shows that the nature and the concentration of the stripping agents affect on Pb²⁺ cation transport and the maximum transport occurs when the sodium thiosulfate (Na₂S₂O₃) was used. The effects of various parameters influencing the transport efficiency such as the pH of the source and receiving phases, the concentration of picrate ion as counter ion in the source phase were also studied. Five replicated experiments show that a value 82.12 ± 2.09% of the initial concentration of the Pb²⁺ cation in the source phase is extracted into the receiving phase after 4 hours. Also the selectivity and efficiency of lead ion transport from the source phase containing equimolar mixtures of Na⁺, K⁺, Ca²⁺, Ni²⁺, Cu²⁺, Cd²⁺ and Ag⁺ metal cations were investigated.     

Efficient and selective transport of ω-amino acids across a bulk chloroform membrane by a macrocyclic dicopper(II) complex

The Cu(II) complex of a ditopic macrocyclic ligand efficiently transports ω-amino acids of different length across a bulk chloroform membrane with promising selectivity.     

Transport of Na+, K+ ions in a bubbling pseudo-emulsion liquid membrane system with p-tert-butylcalixarenes as carriers

The liquid membrane transport of Na⁺ ions by p-tert-butylcalix[6]arene and that of K⁺ ions by p-tert-butylcalix[8]arene were investigated by means of a bubbling pseudo-emulsion liquid membrane system. This system represents a proton-coupled transport with a flow of protons in the opposite direction. The driving force for the transport is the pH gradient between the source and receiving phases. When the pH difference between the two phases is sufficient, the carriers calix[6]arene(or calix[8]arene) can successfully transport Na⁺ (or K⁺) ions from the source phase with a lower Na⁺ (or K⁺) concentration into the receiving phase with a higher Na⁺ (or K⁺) concentration, like a Na⁺ (or K⁺) ion pump.     

Synergetic transport of europium through a contained supported liquid membrane using trioctylamine and tributyl phosphate as carriers

Contained supported liquid membrane (CSLM) system has been explored for synergic liquid membranes. Different experimental variables such as concentration of acid, carrier, metal ion and complexing agents, stirring speed, etc. have been investigated. Trioctylamine (TOA) + tributyl phosphate (TBP) system has been explored for europium.     

The intrinsic stability of the noble gas-coordinated transition-metal complex ions.

Density-functional-theory and high-level ab initio calculations have been performed on the [AuXe4]2+ ion and some other hypothetical xenon-, krypton-, and argon-coordinated transition-metal complex cations in the gas phase. Geometry optimization at the QCISD(T) level using a (6s7p4d2f1g) basis set for Au and a (4s4p2d1f) set for Xe predicted Au-Xe bond lengths in good agreement with the AuXe4(2+)(Sb2F11-)2 crystal structure. The ligand-binding energies of the [AuXe4]2+, [AuXe4]3+, and [PtXe4]2+ ions were predicted to be 229, 565, and 233 kcal/mol, respectively, at the CCSD(T) level. It is found that higher-level correlation effects are important to obtain accurate geometry parameters. The calculated results also indicated that various trivalent, tetravalent, and hexavalent transition-metal complexes of xenon or krypton might also be intrinsically stable.     

The effect of charged centers on the transport of charge carriers in molecularly doped polymers

The effect of charged centers on the mobility of charge carriers in molecularly doped polycarbonate is experimentally studied by the method of accelerated electrons for the generation of charge carriers in the surface layer and in the polymer bulk. The hypersensitivity of mobility toward the presence of charged sites that is predicted by the theory of correlated disorder (dipolar glass) is not found. With accumulation of charged centers, transformation of the time-of-flight curves with a well-pronounced plateau region, which is indicative of quasiequilibrium transport according to theory, proceeds in full agreement with the classical concepts on the role of a space charge or bimolecular recombination during high-signal irradiation. Transport of charge carriers in the molecularly doped polymer is not quasiequilibrium but dispersive.     

Extraction and carrier mediated transport of urea using noncyclic receptors through liquid membrane systems

Extraction and carrier mediated transport through bulk liquid membrane and supported liquid membrane systems have wide applications in separation technology. This paper highlights the use of six noncyclic receptors (podands) having variations in chain length and end group for the removal of urea using liquid membrane system. These receptors R_1, R_2, R_3, R_4, R_5, R₆ are diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, diethylene glycol dibenzoate, diethylene glycol, triethylene glycol and tetraethylene glycol respectively. The sequence of extraction and transport of urea by BLM system using various receptors is R₂ > R₃ > R₁ > R₄ > R₅ > R₆ and R₆ ≈ R₃ > R₅ > R₄ > R₁ > R₂ respectively. Receptor R₂ containing butyl end group is best extractant while receptor R₆ with flexible backbone is best carrier and this carrier efficiency is used to remove urea using BLM system from the feed phase by recyclization process up to 88.16%. The experimental results influenced by concentration of receptors and urea. Effect of time was also studied.