Supported liquid membranes efficiency

The ability of calixarenes to bind large metal ions with high kinetic stability is important in the search for complexants for radionuclides such as Cs (ti/2 = 30.2 yr) and Sr (ti/2 = 65 d) from the reprocessing of exhausted nuclear fuel. There has been considerable interest in caesium-complexed calix[4]-bis-crowns as selective Cs-carriers. Transport isotherms of trace level Cs through supported liquid membranes containing calix[4]-bis-crowns have been determined as a function of the ionic concentration of the aqueous feeder solutions, and l,3-calix[4]-bis-o-benzo-crown-6 appears to be much more efficient in decontamination than mixtures of crown ethers and acidic exchangers, especially in highly acidic media. " ... 

Deblay, P., Delepine, S., Minier, M., Renon, H. (1991). Selection of organic phases for optimal stability and efficiency of flat-sheet supported liquid membranes. Sep. Sci. Technol., 26, 97-116. 

It has been demonstrated that with the appropriate choice of membrane (hydro-phobic or hydrophilic polymers) the per-evaporation procedure can be efficiently applied for the quantitative and selective recovery of organic solutes, such as naphthalene, water, ethyl hexanoate and chlorobutane, from [C4CjIm]PF, IL [110]. It was also reported that the same ILs can be used as supported liquid membranes for the selective transport of secondary amines over tertiary amines with similar boiling points, and this was attributed to the higher hydrogen bond affinity of the secondary derivative with the imidazoHum cation [111,112]. 

In the present paper, we examine the influence of structural variation within series of crown ether carboxylic acid and crown ether phosphonic acid monoalkyl ester carriers upon the selectivity and efficiency of alkali metal transport across three types of liquid organic membranes. Structural variations within the carriers include the polyether ring size, the lipophilic group attachment site and the basicity of ethereal oxygens. The three membrane types are bulk liquid membranes, liquid surfactant (emulsion) membranes and polymer-supported liquid membranes. 

Raut, D.R., Mohapatra, P.K., Manchanda, V.K., A highly efficient supported liquid membrane system for selective strontium separation leading to radioactive waste remediation, J. Membr. Sci. 390-391, 76, 2012. 

Supported liquid membranes (SLMs) consisting of 5% tri-n-octylphosphine oxide (TOPO) dissolved in di-w-hexylether/n-undecane (1 1) have been used in the simultaneous extraction of a mixture of three stUbene compounds (dienestrol, diethylstilbestrol, and hexestrol) in cow s milk, urine, bovine kidney, and liver tissue matrices [183]. The efficiencies obtained after the enrichment of 1 ng/1 stilbenes in a variety of biological matrices of milk, urine, liver, kidney, and water were 60-70, 71-86, 69-80, 63-74, and 72-93%, respectively. A new method to contribute to the discrimination of polyphenols including resveratrol with synthetic pores was proposed [184]. The work [185] evaluated two types of commonly available chiral detectors for their possible use in chiral method development and screening polarimeters and CD detectors. Linearity, precision, and the limit of detection (LOD) of six compounds (trans-stilbene oxide, ethyl chrysanthemate, propranolol, 1-methyl-2-tetralone, naproxen, and methyl methionine) on four common detectors (three polarimeters and one CD detector) were experimentally determined and the limit of quantitation calculated from the experimental LOD. trans-Stilbene oxide worked well across all the detectors, showing good linearity, precision, and low detection limits. However, the other five compounds proved to be more discriminating and showed that the CD detector performed better as a detector for chiral screens than the polarimeters. 

Supported liquid membrane extraction (SLME) is emerging as a fast and efficient sample preparation technique. Aromatic aminophosphonate isolation from water samples based on SLME allowed the identification and study of the operational parameters (pEI and ionic strength of the aqueous phase, composition of the membrane phase, and concentration of analytes) as well as the structure-extraction efficiency relationship. 

Extensive studies including both inner-sphere and outer-sphere complexation of cations were performed with lasa-locid A, which is a small natural ionophore containing a salicylic acid fragment (Figure 1). The ability of lasalocid to form neutral outer-sphere complexes with species like Co(NH3)(5 +, Cr(bpy)3 ", Pt(bpy)(NH3)2 " " allows one to use it as an ionophore for the membrane transport (including chiroselective transport) of such species. The lasalocid ionophore also was shown to be an efficient carrier for toxic water-soluble metal cations such as Pb + and Cd + across artificial flat-sheet-supported liquid membranes, which represent a potential system for separation of these cations. 

Figure 4. Correlation Between Anion Free Energy of Hydration and Transport Efficiency, a) Variation of transport across a chloroform-supported liquid membrane with different anions. Anion source phase concentration is adjusted to 2.0 mM. b) Variation of K transport across a chloroform-supported liquid membrane with increasing anion hydration free energy. Literature values are used for thermodynamic data. (Reproduced with permission from ref. 52. Copyright 1980 American Chemical Society.)...

Calix[4]-W5-crowns 1-7 are used as selective cesium-carriers in supported liquid membranes (SLMs). Application of the D esi diffusional model allows the transport isotherms of trace level Cs through SLMs (containing calix[4]-6/5-crowns) to be determined as a function of the ionic concentration of the aqueous feed solutions. Compound 5 appears to be much more efficient than mixtures of crown ethers and acidic exchangers, especially in very acidic media. Decontamination factors greater than 20 are obtained in the treatment of synthetic acidic radioactive wastes. Permeability coefficient measurements are conducted for repetitive transport experiments in order to determine the SMLs stability with time. Very good results (over 50 days of stability) and high decontamination yields are observed with l,3-calfac[4]-Aw-crowns 5 and 6. 

The use of 13a in the extraction process or in the transport through supported liquid membranes (SLMs) allows to recover more than 98% of the cesium cation present in solution, making this derivative extremely attractive for declassification of nuclear wastes. Ligand 13a was dso used for the selective detection of cesium in ISEs and ISFETs with very high selectivity and low detection limit. Very recently, we anchored calix[4]arene-crown-5 and -crown-6 derivatives on silica-gel via hydrosilanization and we were able to separate by chromatography potassium or cesium fi"om other alkali metal ions with high efficiency. ... 

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