Synthesis and transport studies of new enantiopure lipophilic crown ethers containing a diarylphosphinic acid unit

The synthesis of new enantiopure lipophilic crown ethers (S,S)-6, (R,R)-6 and (S,S)-7 containing a diarylphosphinic acid unit has been carried out. The transport ability of these ligands has been studied in an aqueous source phase/lipophilic organic bulk liquid membrane/aqueous receiving phase system controlled by the pH of the media. The transport of metal ions and amines has also been studied. These studies showed high selectivity for protonated amines.     

Transport of alkali metal cations across liquid membranes by crown ether carboxylic acids

Competitive alkali metal transport from an alkaline aqueous source phase through a chloroform phase to an acidic aqueous receiving phase facilitated by nine crown ethers with pendant carboxylic acid groups has been investigated. Transport selectivity is controlled by the size of the polyether cavity of the carrier. Increasing the lipophilicity of the carrier, while maintaining a constant polyether cavity size, enhances the total transport rate but does not affect the selectivity. There is poor agreement between the results of competitive transport and the behavior anticipated on the basis of single cation transport studies.     

Selective membrane transport of amino acids by functionalised calix[4]arenes

The selective active transport through liquid membrane assisted by the pH gradient of amino acid methylesters by using a series of calix[4]arenes substituted by acid and amido functions, glycolic chains, and hydroxyl groups as carriers has been performed. All these receptors have been found to act as carriers for transport of aromatic amino acid methylesters from the aqueous source phase to the aqueous receiving phase aiming at their separation. The receptors bearing diacid and tetraamido functions have the better ability to transport of amino acids than the other receptors studied. The influence of calixarene and amino acid structures upon transport through liquid membrane is discussed. The obtained results are correlated with those acquired by solvent extraction.     

Synthesis of calix[4]arene-based dipodal receptors: Competitive solvent extraction and liquid bulk membrane transport for selective recovery of Cu2+

A series of new p-tert-butylcalix[4]arene-based dipodal receptors are synthesised in high yields. The calix[4]arene units of all the receptors have been found to be present in cone conformation. To optimise the good extraction ability and high transport rate, we synthesised the receptors that differ from each other in their end groups. These receptors extract Cu²⁺  ion selectively from the buffered aqueous medium containing a mixture of metal ions. The receptor bearing four sp³ nitrogens has by far the greater ability to extract Cu²⁺  than the other receptors. All these receptors were effectively used for Cu²⁺  ion transport from the aqueous buffered source phase to the aqueous receiving phase.

     

Microfluidics with aqueous two-phase systems

An overview is given about research activities in which aqueous two phase systems (ATPSs) are utilized in microfluidic setups. ATPSs consist of two immiscible aqueous phases and have traditionally been used for the separation and purification of biological material such as proteins or cells. Microfluidic implementations of such schemes are usually based on a number of co-flowing streams of immiscible phases in a microchannel, thereby replacing the standard batch by flow-through processes. Some aspects of the stability of such flow patterns and the recovery of the phases at the channel exit are reviewed. Furthermore, the diffusive mass transfer and sample partitioning between the phases are discussed, and corresponding applications are highlighted. When diffusion is superposed by an applied electric field normal to the liquid/liquid interface, the transport processes are accelerated, and under specific conditions the interface acts as a size-selective filter for molecules. Finally, the activities involving droplet microflows of ATPSs are reviewed. By either forming ATPS droplets in an organic phase or a droplet of one aqueous phase inside the other, a range of applications has been demonstrated, extending from separation/purification schemes to the patterning of surfaces covered with cells.     

A hydrodynamic approach to the measurement of the permeability of small molecules across artificial membranes

An in situ analytical approach to the measurement of supported liquid membrane permeability is reported. The method consists of a spectrophotometric method to measure transport through a membrane-supported lipid solution, using a rotating-diffusion cell configuration to overcome limits arising from transport through the aqueous solution boundary layer in stationary systems. Rotation frequencies are almost two orders of magnitude higher than those employed previously for rotating-diffusion studies of membrane transport. The method is illustrated with the transport of warfarin [1-(4'-hydroxy-3'-coumarinyl)-1-phenyl-3-butanone]. The use of the rotating-diffusion approach permits accurate calculation of the aqueous phase boundary layer thickness, which has hitherto been treated as an adjustable parameter in studies of membrane permeability. Further, it is shown that the analyte diffusion coefficient can be determined readily using liquid-liquid electrochemistry.     

Extraction of strontium ions with emulsion liquid membrane technique

The aims of this study are to form a liquid membrane suitable for the extraction of strontium ions from aqueous solutions and to determine the factors influencing the stability of the membrane, the extraction efficiency and the rate of transport. The suggested membrane is composed of kerosene, Span 80 and D2EHPA. It has been observed that the extraction efficiency and the rate of transport increase with increasing ratio of emulsion to outer phase volume, stirring rate and D2EHPA concentration and decreasing pH of the inner phase. As the strontium ion concentration in the outer phase increases, the transport rate increases but the separation efficiency decreases. The maximum separation efficiency achieved in the experiments was 92%.     

Highly selective transport of silver ion through a supported liquid membrane using calix[4]pyrroles as suitable ion carriers

Facilitated transport of silver ion across a supported liquid membrane (SLM) by calix[4]pyrroles, as selective ion carriers, dissolved in kerosene has been investigated. The influences of fundamental parameters affecting the transport of silver ion including ion carrier concentration in the membrane phase, thiosulfate concentration in strip phase, picric acid concentration in the feed phase, stirring speed of aqueous phases, type of membrane solvent and time of transport have been studied. In the presence of thiosulfate as a suitable metal ion acceptor in the strip phase and picrate ion as ion pairing agent in the source phase, transport of silver occurs almost quantitatively after 75 min. The selectivity and efficiency of silver transport from aqueous solution containing Cu²⁺, Mg²⁺, Ni²⁺, Ca²⁺, Zn²⁺, Pb²⁺, Co²⁺, Al³⁺, Hg²⁺, Cd²⁺, Fe³⁺, Fe²⁺ and Cr³⁺ were investigated.     

Protein diffusion across the interface in aqueous two-phase systems

We present a detailed study of the diffusive transport of proteins across a fluid phase boundary within aqueous two-phase systems. The aim of the work is to investigate whether local effects at the phase boundary cause a retardation of the diffusive transport between the phases. Possible modifications of interfacial mass transfer could be due to protein adsorption at the phase boundary or local electric fields from electric double layers. Experiments with a microfluidic system have been performed in which protein diffusion (bovine serum albumin and ovalbumin) within a bilaminated configuration of two phases containing polyethylene glycol and dextran is analyzed. A one-dimensional model incorporating phase-specific diffusion constants and the difference in chemical potential between the phases has been formulated. A comparison of experimental and simulation data shows a good overall agreement and suggests that a potential local influence of the phase boundary on protein transport is insignificant for the systems under investigation.     

Cyanex 272-Span 80-甲苯乳状液膜迁移分离锌、镉及其它元素的研究

用Cyanex 272-Span 80-甲苯乳状液膜研究了Zn²⁺的迁移行为,在适宜条件下,5min内锌的迁移率达95%以上。而在此条件下,与锌性质相近的镉、铜、钴、镍、汞等金属离子不迁移或迁移率很低。因此,用此乳状液膜体系可将锌与镉及其它常见离子分离。     

Competitive bulk liquid membrane transport of Co(Ⅱ),Ni(Ⅱ),Zn(Ⅱ),Cd(Ⅱ),Ag(Ⅰ),Cu(Ⅱ)and Mn(Ⅱ),cations using 2,2'-dithio(bis)benzothiazole as carrier

A series of competitive metal-ion transport experiments has been performed.Each involved transport from an aqueous source phase across an organic membrane phase into an aqueous receiving phase.The source phase contained equimolar concentration of Co（Ⅱ）,Ni（Ⅱ）,Zn（Ⅱ）,Cd（Ⅱ）,Ag（Ⅰ）,Cu（Ⅱ） and Mn（Ⅱ） metal cations.The transport experiments of metal cations were carried out by 2,2’-dithio（bis）benzothiazole（DTB） in chloroform（CHCl₃）.The source phase being buffered at range pH of 4-6.5 and receiving phase being buffered at pH 3.The obtained results show that the selectivity and the efficiency of Ag（I） transport from aqueous solutions are observed in this investigation.The effect of concentration of palmitic acid in the transport efficiency of Ag（Ⅰ） ion was also conformed.     

Mass transfer model of triethylamine across the n-decane/water interface derived from dynamic interfacial tension experiments

This publication presents a detailed experimental and theoretical study of mass transfer of triethylamine (TEA) across the n-decane/water interface. In preliminary investigations, the partition of TEA between n-decane and water is determined. Based on the experimental finding that the dissociation of TEA takes place in the aqueous and in the organic phase, we assume that the interfacial mass transfer is mainly affected by adsorption and desorption of ionized TEA molecules at the liquid/liquid interface. Due to the amphiphilic structure of the dissociated TEA molecules, a dynamic interfacial tension measurement technique can be used to experimentally determine the interfacial mass transport. A model-based approach, which accounts for diffusive mass transport in the finite liquid bulk phases and for adsorption and desorption of ionized TEA molecules at the interface, is employed to analyze the experimental data. In the equilibrium state, the interfacial tension of dissociated TEA at the n-decane/water interface can be adequately described by the Langmuir isotherm. The comparison between the theoretical and the experimental dynamic interfacial tension data reveals that an additional activation energy barrier for adsorption and desorption at the interface has to be regarded to accurately describe the mass transport of TEA from the n-decane phase into the aqueous phase. Corresponding adsorption rate constants can be obtained by fitting the theoretical predictions to the experimental data. Interfacial tension measurements of mass transfer from the aqueous into the organic phase are characterized by interfacial instabilities caused by Marangoni convection, which result in an enhancement of the transfer rate across the interface.     

Uranyi ion transport through tri-n-octylamine-xylene based supported liquid membranes

Tri-n-octylamine (TOA) dissolved in xylene has been used as carrier, constituting liquid membrane supported in Celgard 2400 polypropylene microporous film for the transport of uranyl ions against their concentration gradient from aqueous acid solutions to an alkaline aqueous phase. Effect of sttrring rate, nitric acid concentration and TOA concentration in the organic membrane phase, on the flux of uranyl ions through the membrane has been studied. Viscosity and density data have been obtained to estimate diffusion coefficients and hence the permeability coefficients to compare the same with experimental values, using distribution coefficient data, measured from solvent extraction experiments and available in the literature. Analysis of the flux data has been performed to study the stoichiometry of the chemical reaction involved in complex formation reaction. The results have been compared with simple liquid-liquid extraction data.     

Proton-ionizable crown compounds. 12. Proton-Coupled selective membrane transport of Li+ using a proton-ionizable pyridono macrocycle

The macrocycle-mediated fluxes of several alkali metal cations have been determined in a H₂O-CH₂Cl₂-H₂O liquid membrane system. Water-insoluble proton-ionizable macrocycles of the pyridono type were used. The proton-ionizable feature allows the coupling of cation transport to reverse H⁺ transport. This feature offers promise for the effective separation and/or concentration of alkali metal ions with the metal transport being driven by a pH gradient. A counter anion in the source phase is not co-transported. The desired separation of a particular metal ion involves its selective complexation with the macrocycle, subsequent extraction from the aqueous phase to the organic phase, and exchange for H⁺ at the organic phase-receiving phase interface. Factors affecting transport which were studied include ring size, source phase pH, and receiving phase pH. Lithium was transported at a rate higher than that of the other alkali metals in both single and competitive systems using a 15-crown-5 pyridono carrier.     

Transport and separation of carboxylic acids through bulk liquid membranes containing tributylamine

In this study, transport and separation of carboxylic acids (formic, acetic, propionic, and butyric acids) from their aqueous solutions through bulk liquid membrane (BLM) containing tributylamine (TBA) and the parameters affecting the transport were investigated. The influence of the parameters on the separation process such as the stirring of membrane phase, the stripping phase type and concentration, the feed phase type, and the feed:membrane:stripping phase ratio (F/M/S phase ratio) were examined. In the experiments, 10% (w/w) acid solutions (formic, acetic, propionic, and butyric acids) were used as the feed phase, different concentrations of NaOH solutions within the range of 0–2?N were used as the stripping phase, and 0.5?mol/lt TBA, dissolved in oleyl alcohol, was used as the membrane phase. It was determined that the stirring of the membrane phase increases the transport of acids. In the case of 2 N NaOH solution in the stripping phase and F/M/S phase ratio 1:2:1 gave the best recovery (96.75%) for butyric acid. It was observed that BLM was an effective technique for the separation of carboxylic acids from aqueous solutions.     

Facilitated Transport of Cr(VI) through Polymer Inclusion Membrane System Containing Calix[4]arene Derivative as Carrier Agent

Chromium(VI) is one of the major toxic elements present in environmental samples. The polymer inclusion membrane (PIM), has been developed to provide metal ion transport with high selectivity. This study was conducted to discover efficient methods for removing Cr(VI) from wastewater. A functionalized calix[4]arene carrier 1 in a PIM system was used to transport Cr(VI) from an acidic aqueous donor phase solution to an acceptor phase that contained an acetic acid/ammonium acetate solution at pH 6. The prepared PIM was characterized with Fourier Transform Infrared (FT-IR) spectroscopy and the Atomic Force Microscopy (AFM) techniques as well as with contact angle measurements. The efficiency of Cr(VI) transport through the PIM was investigated by studying the effects of carrier concentration on the membrane phase as well as by measuring the amount of plasticizer in the membrane, the pH in the acceptor phase and the membrane's stability and thickness. The kinetic parameters were calculated as rate constant (k), permeability coefficient (P), flux (J) and diffusion coefficient (D_o). The transport efficiency of Cr(VI) was observed to be 98.61% after 10 h under optimized conditions. The experimental results show that Cr(VI) can transport from the donor phase to the acceptor phase with high efficiency through the PIM. The results also suggest that the transport efficiency of the PIM was reproducible and that a PIM is effective for long-term separation processes.     

Retention study of some cation-type compounds using bile acid sodium salts as ion pairing agents in liquid chromatography

The possibility of forming ion-pairs between bile acids (sodium taurocholate, sodium taurodeoxycholate and sodium taurochenodeoxycholate) and different compounds (pralidoxime, obidoxime and pyridostigmine) having a cationic character has been studied in reversed-phase liquid chromatography (RP-LC). This study can be useful in understanding the role of bile acids in the transport of ionic species through hydrophobic membrane. The present study focused on the influence of mobile phase composition on the retention parameters of chosen compounds (percentage of acetonitrile, pH of aqueous component or ionic strength). For constant concentration of bile acids in aqueous component of mobile phase the functional dependencies between the logarithm of the retention factor (k) and the methanol content in the mobile phase followed a binomial pattern (U-shaped), with a minimum positioned within the interval 70-85% methanol.     

Silver(I) complexation of linked 2,2'-dipyridylamine derivatives. Synthetic, solvent extraction, membrane transport and X-ray structural studies

Synthesis of the 2,2'-dipyridylamine derivatives di-2-pyridylaminomethylbenzene 1, 1,2-bis(di-2-pyridylaminomethyl)benzene 2, 1,3-bis(di-2-pyridylaminomethyl)benzene 3, 2,6-bis(di-2-pyridylaminomethyl)pyridine 4, 1,4-bis(di-2-pyridylaminomethyl)benzene 5, and 1,3,5-tris(di-2-pyridylaminomethyl)benzene 6 are reported together with the single-crystal X-ray structures of 2, 3, and 5. Reaction of individual salts of the type AgX (where X = NO(3)(-), PF(6)(-), ClO(4)(-), or BF(4)(-)) with the above ligands has led to the isolation of thirteen Ag(I) complexes, nine of which have also been characterised by X-ray diffraction. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a range of coordination arrangements. A series of liquid-liquid (H(2)O/CHCl(3)) extraction experiments of Ag(I) with varying concentrations of 1-6 in the organic phase have been undertaken, with the counter ion in the aqueous phase being respectively picrate, perchlorate and nitrate. In general, extraction efficiencies for a given ionophore followed the Hofmeister order of picrate > perchlorate > nitrate; in each case the tris-dpa derivative 6 acting as the most efficient extractant of the six systems investigated. Competitive seven-metal bulk membrane transport experiments (H(2)O/CHCl(3)/H(2)O) employing the above ligands as the ionophore in the organic phase and equimolar concentrations of Co(II), Ni(II), Zn(II), Cu(II), Cd(II), Pb(II) and Ag(I) in the aqueous source phase were also undertaken, with transport occurring against a pH gradient. Under the conditions employed 1 and 5 yielded negligible transport of any of the metals present in the source phase while sole transport selectivity for Ag(I) was observed for 2-4 and 6.     

Chiral calix[4]arenes bearing α-hydroxy amide units as membrane carriers for amino acid methyl esters

Novel chiral calix[4]arene derivatives functionalized at the lower rim have been prepared from the reaction of p-tert-butylcalix[4]arene diamine or acylhydrazine derivative with mandelic acid or hydroxyisovaleric acid. The structures of these receptors were characterized by FTIR, ¹H, ¹³C and 2D COSY NMR spectroscopy and elemental analysis. The transport of amino acid derivatives (phenylalanine, phenylglycine and tryptophan methyl ester hydrochlorides) was studied through bulk liquid membrane in the presence of chiral calix[4]arene derivatives. The receptors have been found to act as carriers for transport of aromatic amino acid methylesters from the aqueous source phase to the aqueous receiving phase. The transport rate and L/D selectivity of amino acid esters studied depend strongly upon the structure of the chiral receptors and guests. The best enantioselectivity was obtained in the case of phenylglycine methyl ester for all chiral carriers.     

Studies on transport mechanism of Cr(VI) extraction from an acidic solution using liquid surfactant membranes

A mathematical model for analysing the extraction of Cr(VI) from aqueous acidic solution by emulsion liquid membrane using Aliquat 336 as extractant and NaOH as stripping agent has been presented. The existing models developed so far do not account for the existence of different forms of Cr(VI) ions in the aqueous phase depending on pH conditions. Accordingly, in the present model, reaction equilibrium has been considered instead of distribution coefficient to represent realistically the transport mechanism for this type of system through liquid surfactant membrane. Unlike other models, liquid–liquid equilibrium of sodium hydroxide-chloride of Aliquat 336 has also been considered. The carrier thus exists in the membrane phase in hydroxide and chloride forms and extraction of hexavalent chromium from the external phase proceeds by the two carriers. The validity of the model has been checked from comparison of the simulated curves and experimental data using chemical reaction equilibrium constant and D_eff/R² as fitting parameters.