Ionic liquid-salt based aqueous biphasic system for separation of 109Cd from silver target

Aqueous biphasic system (ABS) is greener alternative to the conventional liquid liquid extraction as ABS does not involve any organic or volatile reagents. Generally ABS systems are composed of polymer and salt rich phases. In this paper a new ABS system is proposed replacing polymer rich phase by water soluble room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium Chloride ([bmim]Cl) and kosmotropic salt K₂HPO₄. The system has been applied to separate the no-carrier-added (NCA) ¹⁰⁹Cd (T _1/2 = 462.6 days) from the α-particle irradiated bulk Ag target. The optimum separation condition was achieved with the addition of 6 M HNO₃ to the ABS, where ~87 % of the bulk Ag was extracted in the IL phase, leaving ~96 % NCA ¹⁰⁹Cd in the salt rich phase. The salt rich phase was re-extracted twice with the RTIL to free from bulk Ag. This process achieved an overall separation of 91 % NCA ¹⁰⁹Cd free from bulk Ag. The developed method demonstrates minimum requirement of RTIL to carry out the separation. The method is environmentally benign and cost effective.     

Advances in aqueous biphasic systems for biotechnology applications

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Separation of thorium from aqueous solution using silk fibroin

In this study we investigate the basic features of thorium adsorption from aqueous systems by silk fibroin. Our previous study showed that this biopolymer has high efficiency for U(VI) adsorption. It is well-known that thorium, which is a tetravalent metal, is a more reactive element than uranium. Thorium(IV) adsorption proves to be very rapid and dependent on pH, temperature, retention time, concentration of ion, amount of fibroin, volume of solution and volume-to-mass ratio.     

Separation of ionic liquids from dilute aqueous solutions using the method based on CO2 hydrates

Ionic liquids (ILs) have been regarded as the potential novel solvents for improved analytical-and process-scale separation methods. The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydr...     

Separation of carrier-free 95Tc from alpha-irradiated natural niobium

⁹⁵Tc has been produced through -particle activation of a natural niobium target. The carrier-free ⁹⁵Tc radionuclide has been separated from the bulk target using tri-n-octylamine (TOA) diluted by cyclohexane as extracting agent and HCl, HNO₃ as aqueous phase. Solid-liquid extraction has also been carried out with TOA impregnated Kieselguhr mineral acid system. Technetium-95 was recovered from the organic phase by stripping with 0.1M EDTA above pH 9.     

Separation of zinc from aqueous samples using a molecular imprinting technique

In this article, the separation of zinc from aqueous samples by solid-phase extraction based on a molecular imprinting technique is described. Zn-imprinted polymer was prepared by free radical solution polymerisation in a glass tube containing ZnSO₄, morin, 4-vinylpyridine as a functional monomer, ethyleneglycoldimethacrylate as a cross-linking monomer, and 2,2′-azobisisobutyronitrile as an initiator. The obtained polymer block was ground and sieved (55–75 µm) and the Zn–morin complex was separated from polymer particles by leaching with 2M HCl. The synthesised polymer particles have been characterised by IR and differential scanning calorimetric studies either before or after leaching. The effects of different parameters, such as pH, adsorption and desorption time, type and minimum amount of the eluent for elution of the complex from polymer were evaluated. Extraction efficiency more than 99% was obtained by elution of the polymers with 10 mL of CH₂Cl₂–dimethyl sulfoxide (1 : 1, v/v). The detection limit of the proposed method was 2.9 µg L^?1. A dynamic linear range in the range of 25–200 µg L^?1 was obtained. The relative standard deviation was found to be below 9.2%. In addition, the influence of various cationic and anionic interferences on the complex recovery was studied. The method was applied to the recovery and determination of Zn in a few different real samples.     

Separation of lignosulfonate from its aqueous solution using supported liquid membrane

This paper presents an experimental and theoretical study on facilitated transport of lignosulfonate (LS) through a flat sheet supported liquid membrane using trioctylamine (TOA) as carrier and dichloroethane as diluent. The studies were carried out with various support materials and operating conditions (viz. carrier concentration, strip phase concentration, salt concentration, etc.) and their effects on the transport of LS. The results were analyzed to identify a suitable combination of support and operating condition that would yield best performance of the supported liquid membrane (SLM) in terms of fast and efficient transport of LS. The stability of the SLM was assessed in terms of loss of liquid from the pores of membrane support. The SLM is found to be stable till 10 h. Co-transport mechanism has been adopted in this work by using NaOH as the strip phase. It was observed that extraction of LS is increased with increase in concentration of NaOH up to a limiting value of 0.5 M NaOH. Difference of salt concentration between feed and strip phase considerably affect the separation process. The diffusional resistances of organic membrane (Δorg) and aqueous solution (Δaq) calculated from the permeation model, which is again a combination of three unique mechanisms viz., diffusion through a feed aqueous layer, a fast interfacial chemical reaction, and diffusion of carrier–complex through the organic membrane, are found to be 609.9 and 176.6 s cm⁻¹, respectively. The values of the diffusion coefficient in the membrane (D_org) and in the bulk organic phase (D_complex) are 1.67×10⁻⁹ and 6.68 × 10⁻⁸ m²s⁻¹, respectively. The extraction of LS is about 90%. Nearly 43% of LS can be recovered at optimum condition.     

Separation of endo-polygalacturonase using aqueous two-phase partitioning

The partitioning of endo-polygalacturonase (endo-PG) in polyethylene glycol (PEG)-polyvinyl alcohol (PVA10000) and PEG-hydroxypropyl starch (Reppal PES100) aqueous two-phase systems was studied, and revealed the possibility of using aqueous two-phase extraction to purify and concentrate endo-PG from its clarified fermentation broth. For the PEG8000-PVA10000 system, endo-PG presented in the fermentation broth (at concentration that is more than 40% of total protein) mainly dominates in the top phase with a partitioning coefficient of 6, while total protein concentrates in the bottom phase. A separation scheme consisting of two consecutive aqueous two-phase extraction steps was proposed: a first extraction in polyethylene glycol (PEG8000)-polyvinyl alcohol system, followed by a second extraction in PEG8000-(NH4)2SO4 system. This allowed the separation of endo-PG from polymer and the recycling of PEG polymer, since endo-PG was very strongly partitioned into the bottom phase of the PEG8000-(NH4)2SO4 system. Laboratory-scale experiments were performed to test the efficiency of this scheme. It was found that enzyme recovery was up to 91% with a total purification factor of about 1.9 and a concentration factor of more than 5. About 90% of the total PEG added into the systems can be recovered, and no reduction was obtained in the purification factor using recycled PEG.     

Hypoglycaemic activity of saponin fraction extracted from Momordica charantia in PEG/salt aqueous two-phase systems

Momordica charantia (family, Cucurbitaceae), commonly known as karela or bitter melon (Japanese name 'Tsurureishi'), is used as a folk medicine in China, the Indian subcontinent and South America. In Chinese traditional medicine, the plant is usually used as a hypoglycaemic and anti-diabetic agent. The hypoglycaemic activity of saponin fraction (SF) extracted from M. charantia in PEG/salt aqueous two-phase systems was studied in this article. Alloxan-induced hyperglycaemic mice were used in the study. The blood glucose, insulin secretion, glycogen synthesis and the body weight of the mice were analysed. At the same time, the sugar tolerance of the normal mice was also determined. After the mice were administered (i.g.) with SF (500 mg kg(-1)), the blood glucose of alloxan-induced hyperglycaemic mice decreased (p < 0.05), the level of insulin secretion and glycogen synthesis of alloxan-induced hyperglycaemic mice elevated (p < 0.05, p < 0.01) and the sugar tolerance of the normal mice was improved. Also, the body weight of the alloxan-induced hyperglycaemic mice was increased gradually. The saponin constituents extracted from M. charantia in an aqueous two-phase extraction system induced significant hypoglycaemic activity in hyperglycaemic and normal mice.     

Triton X surfactants to form aqueous biphasic systems: Experiment and correlation

During the last years, the extraction of biomolecules and chemicals by means of Aqueous Biphasic Systems (ABS) has triggered a renewed interest, making it necessary to characterize fully the solubility data of this kind of system. In this study, two surfactants belonging to Triton X series (Triton X-100 and Triton X-102) are proposed as candidates to form ABS, by adding different potassium-based salts (K₃PO₄, K₂HPO₄, K₂CO₃, K₂S₂O₃ and K₂SO₃) at T = 298.15 K. Several equations were used to fit the solubility data which were previously obtained by means of the cloud point method. The different phase forming capacities were analyzed in the light of the Hofmeister series, the Effective Excluded Volume (EEV) theory and the molar Gibbs free energy of hydration (Δ_hydG). The Othmer–Tobias equation was proposed to correlate the tie-line data.     

Separation of niobium and tantalum from zirconium with salicylhydroxamic acid

Salicylhydroxamic acid can be used for the separation of zirconium from niobium above pH 2 5 in presence of hydrogen peroxide. Niobium can be precipitated from the filtrate with N-benzoyl-N-phenylhydroxylamine.     

Adsorption of 103Ru from aqueous solutions by clinoptilolite

The aim of this research is adsorption of ruthenium by natural zeolite, clinoptilolite. The experimental conditions were optimized in order to obtain higher adsorption capacity and the study was done under optimum conditions. Maximal adsorption capacity was obtained using ¹⁰³Ru as a tracer at 25 °C, pH 2.0 and contact time of 10 h and found to be 0.074 meq g^?1. Ruthenium measurments were done using inductively coupled plasma-optical emission spectrometry (ICP-OES) and gamma spectrometer methods. Break points were calculated from breakthrough curve at the 1%, 5% and 50%. The obtained results are respectively 2.8, 4.5 and 19.5 mL, which are equal to 2.5 × 10^?3, 1.35 × 10^?2 and 5.85 × 10^?2 meq g^?1. Desorption behavior of column packed zeolite using some eluents was also investigated. The highest recovery of 97.4 ± 0.2% was obtained using 2 mol L^?1 HCl solution as an eluent. The results of this study can be used for separation and preconcentration of ruthenium.     

Recent progress in biphasic catalytic systems using ionic liquids

Catalytic reactions in two liquid phases containing ionic liquids (ILs), in which organic reactions proceed in the ILs phase and products are extracted to the other liquid phase, are efficient and environmentally benign. This short review briefly reports the development of catalytic application in biphasic systems containing ILs in the last two years. Recent progress for the functionalization of ILs themselves and combinations of homogeneous and heterogeneous catalysts with ILs are described. Prospects and future challenges are also addressed.     

The half-lives of 90mY and 97Ru

In an attempt to improve the accuracy of neutron activation analysis, gamma-ray spectrometry and least-squares methods developed for other nuclides have been applied to redetermine the decay constants of ^90mY and ⁹⁷Ru. Several irradiated samples of each pure element were counted continually through several half-lives, acquiring up to 100 spectra with good statistics. Photopeaks from each nuclide were evaluated with a region of interest integration routine, and each data point corrected for rate-related losses before fitting to an exponential function by a nonlinear least-squares procedure. The half-lives found are 3.204 ± 0.008 h for ^90mY and 2.836 ± 0.014 days for ⁹⁷Ru, where the uncertainty is an estimate of the 95 % confidence level. Although (by Chi squared criteria) the fits to the decay curves were very good and the uncertainty of the resulting half-lives an order of magnitude smaller than the previously published uncertainty, care is necessary before assigning a best value with a totally defensible uncertainty to the overall data set.     

Separation of lidocaine and its metabolites by capillary electrophoresis using volatile aqueous and nonaqueous electrolyte systems

The separation of the basic drug lidocaine and six of its metabolites has been investigated both by using volatile aqueous electrolyte system, at low pH and by employing non-aqueous electrolyte systems. In aqueous systems, the best separation of the compounds under the investigated conditions was achieved by using the electrolyte 60 mM trifluoroacetic acid (TFA)/triethylamine (TEA) at pH 2.5 containing 15% methanol. With this electrolyte, all seven compounds were well separated with high efficiency and migration time repeatability. The separations with bare fused-silica capillaries and polyacrylamide-coated capillaries were compared with higher separation efficiency with the latter. On the other hand, near baseline separation of all the seven compounds was also obtained by employing the non-aqueous electrolyte, 40 mM ammonium acetate in methanol and TFA (99:1, v/v), with comparable migration time repeatability but lower separation efficiency relative to the aqueous system.     

Phase diagrams of ionic liquids-based aqueous biphasic systems as a platform for extraction processes

In the past few years, ionic liquid-based aqueous biphasic systems have become the subject of considerable interest as a promising technique for the extraction and purification of several macro/biomolecules. Aiming at developing guidelines for more benign and efficient extraction processes, phase diagrams for aqueous biphasic systems composed of ionic liquids and inorganic/organic salts are here reported. Several combinations of ionic liquid families (imidazolium, pyridinium, phosphonium, quaternary ammonium and cholinium) and salts [potassium phosphate buffer (KH₂PO₄/K₂HPO₄ at pH 7), potassium citrate buffer (C₆H₅K₃O₇/C₆H₈O₇ at pH 5, 6, 7 and 8) and potassium carbonate (K₂CO₃ at pH ∼13)] were evaluated to highlight the influence of the ionic liquid structure (cation core, anion and alkyl chain length), the pH and the salt nature on the formation of aqueous biphasic systems. The binodal curves and respective tie-lines reported for these systems were experimentally determined at (298 ± 1) K. In general, the ability to promote the aqueous biphasic systems formation increases with the pH and alkyl chain length. While the influence of the cation core and anion nature of the ionic liquids on their ability to form aqueous biphasic systems closely correlates with ionic liquids capacity to be hydrated by water, the effect of the different salts depends of the ionic liquid nature and salt valency.     

Evaluation of the impact of phosphate salts on the formation of ionic-liquid-based aqueous biphasic systems

The present study aims at evaluating the capability of phosphate-based salts, whose anions can coexist in water depending on the media pH, to promote aqueous biphasic systems (ABS) formation with 1-butyl-3-methylimidazolium-based ionic liquids, as well as to infer on the influence of the ionic liquid anion in the overall process of liquid–liquid demixing. In this context, novel phase diagrams of ABS composed of several imidazolium-based ionic liquids and three phosphate salts and a mixture of salts (K₃PO₄, K₂HPO₄, K₂HPO₄ + KH₂PO₄, and KH₂PO₄) were determined by the cloud point titration method at 298 K and atmospheric pressure. The corresponding tie-line compositions, tie-line lengths, and pH values of the coexisting phases were also determined. The ionic liquids ability to promote ABS is related with the hydrogen-bond basicity of the composing anion – the lower it is the higher the ability of the ionic fluid to undergo liquid–liquid demixing. Moreover, similar patterns on the ionic liquids sequence were observed with the different phosphate salts. The phosphate anion charge plays a determinant role in the formation of ABS. The two-phase formation aptitude (with a similar ionic liquid) decreases in the rank: K₃PO₄ > K₂HPO₄ > K₂HPO₄ + KH₂PO₄ > KH₂PO₄. Yet, besides the charge of the phosphate anion, the pH and ionic strength of the aqueous media also influence the phase separation ability.