Uphill permeation model of gold(III) and its separation from base metals using thiourea derivatives as ionophores across a liquid membrane

This work deals with carrier-facilitated membrane transport of Au(III) from chloride media across a polymer-immobilised liquid membrane (PILM) using as organic reagents N-(thiocarbamoyl)benzamide derivatives and N-benzoylthiourea derivatives, denoted as 2a–c and 3a–f, respectively. Both the composition of the organic membrane solvent and the type of carrier have a marked effect on gold permeation. Recovery and permeability of gold using 2a–c and 3a–f across a PILM proceed in the following order: 3e≈3d≈3c?3f>3b≈3a≈2a≈2b≈2c. In view of the performance of these carriers, 3c was selected as a metal receptor for detailed studies of Au(III) in permeation. A model is presented for the permeation of Au(III) (61 μM) in 0.5 M Cl⁻ at pH 2.5 using 3c as a membrane carrier. The mathematical equations describing the rate of permeation are derived to correlate the membrane permeability coefficient with diffusional and equilibrium parameters. The mass transfer coefficient was calculated from the described model as 1.1×10⁻⁵ m s⁻¹, and the thickness of the aqueous boundary was later calculated to be 65 μm. Several polymeric supports were tested for impregnation of the organic extractant, and Durapore (Millipore) afforded the maximum flux for Au(III), yielding a value of 1.1×10⁻¹⁴ mol m⁻² s. The relationship between flux and support characteristics is derived and a mathematical equation is presented. Of the several diluents used, cumene had the most satisfactory performance in terms of PILM stability and metal transport. Of the different reagents used, 0.5 M sodium thiocyanate in 0.5 M NaCl at pH 2.5 served most efficiently as the stripping agent. More than 80% of the Au(III) could be readily separated using 3c in the presence of various metals such as Cu(II), Fe(III) and Zn(II).     

Ionophores in polymeric membranes for selective ion recognition; impedance studies

Synthetic calix[4]arene-crown ionophores for selective Na⁺ (ionophore L1) and Cs⁺-ions (ionophore L2) recognition find application in ion-selective membrane electrodes (ISE) for analytical purpose. Selectivity coefficients for the electrodes with compounds L1 and L2 are  = −2.6 and  = −2.4, respectively. Electrodes of two different construction: all-solid-state (ASS) (with conducting polymer layer on glassy carbon or platinum as ion-to-electron transducer) and conventional ion-selective electrode (ISE) (with liquid electrolyte and Ag/AgCl) are presented and their properties and lifetime are being compared. Resistance of PVC membrane with ionophores L1 and L2 were within the range 0.15-1.4 MΩ depending on the type of the outer electrolyte and its concentration. Conductivity of the membranes was in the range 0.7 × 10⁻⁸ to 6 × 10⁻⁸ Ω⁻¹ cm⁻¹. Warburg coefficients σ were within 0.16 × 10⁴ to 12.7 × 10⁴ Ω s^−1/2, dielectric constant values ? were in a range 28-60 depending mainly on the type of plasticizer.     

Synthesis and characterization of calix[4]arene-based copolyethers and polyurethanes. Ionophoric properties and extraction abilities towards metal cations of polymeric calix[4]arene urethanes

Copolyethers and polyurethanes containing lower and upper rim calix[4]arene units in the fixed cone conformation were prepared in good yield by polycondensation reactions of distal calix[4]arene diols with bisphenol-A/dibromomethane and 2,4-tolylendiisocyanate (TDI), respectively. In a similar way were prepared calix[4]arene-crown-5 and -crown-6 polyurethanes in the fixed 1,3-alternate conformation by condensation of TDI with lower rim calixcrown-5 and calixcrown-6 diols. However, the poor solubility in common organic solvents of the copolyether derivatives (M_w=11,100-11,600 g/mol) hampered further studies on their ionophoric properties. Aiming to obtain model compounds for the investigation of both extraction abilities and ionophoric properties of the polyurethane materials, several bis-urethanes were also synthesized by reaction of the calix[4]arene diols with p-tolylisocyanate (TI). The extraction ability measurements of monomeric and polymeric calix[4]arene urethanes (M_w=12,300-83,500 g/mol) towards alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺) and Ag⁺showed a remarkable efficiency and selectivity of calixcrown-6 polyurethane toward Rb⁺, Cs⁺and Ag⁺.     

Determination of ionophores in raw bovine milk using LC–MS/MS: Application to residue surveillance

Residues of four ionophores (lasalocid, monensin, narasin, and salinomycin) in raw milk samples were extracted with acetonitrile and subsequently determined using liquid chromatography–tandem mass spectrometry. Ionophores could be determined down to 0.1 ng g⁻¹ level, without additional cleanup or concentration of the resulting extract. The analysis of a series of raw milk samples fortified at analyte concentrations ranging from 1 to 20 ng g⁻¹ yielded average accuracies ranging from 60.7% to 118.3% with percent relative standard deviations below 13%. During six months of a surveillance program, 1072 raw milk samples were collected from the transport chain of dairy producers in Alberta and analysed. Monensin was detected in 736 of 1072 samples tested at concentrations ranging from 0.10 to 0.53 ng g⁻¹ which is well below the current Canadian maximum residue limit of 10 ng g⁻¹.     

Calixarenes, new selective molecular receptors

Calixarenes are easily amenable to chemical modifications, e.g. derivatization of the phenolic hydrogen atoms or substitution at the para-positions, which can be operated separately or combined. They thus assume the role of platforms supporting arrays of functional groups able to act as ligating sites and resulting in a great variety of receptors displaying specific complexing abilities. A selection of examples are presented with the aim of illustrating the different factors of their ionic recognition properties and their already existing applications in the field of chemical sensors.