Separation of natural compounds using eutectic solvent-based biphasic systems and centrifugal partition chromatography.

A study on the formation of ternary biphasic systems composed of heptane, 1-butanol or ethyl acetate and type III or type V deep eutectic solvents based on levulinic acid and choline chloride or thymol was carried. Binodal curves and densities and phase compositions of phases in equilibrium for seven systems are reported. The partition coefficients of six natural compounds, namely quercetin, apigenin, coumarin, ß-ionone, retinol, and α-tocopherol, in these systems were measured. Results show that the influence of choline chloride on the partition coefficients is more significant in systems with 1-butanol or ethyl acetate than previously reported for ethanol, and that the separation of natural compounds is worst when using DES containing thymol instead of choline chloride. Based on these partition coefficients, one system composed of heptane, 1-butanol and the DES choline chloride:levulinic acid at molar ratio 1:3 was selected to be applied in centrifugal partition chromatography, and the results obtained confirmed that it allows a good separation of apigenin, coumarin, ß-ionone and α-tocopherol.

Commiphora wildii Merxm. Essential Oil: Natural Heptane Source and Co-Product Valorization.

As an alternative to fossil volatile hydrocarbon solvents used nowadays in perfumery, investigation on essential oil of Commiphora wildii Merxm. oleo gum resin as a source of heptane is reported here. Heptane, representing up to 30 wt-% of this oleo gum resin, was successfully isolated from the C. wildii essential oil, using an innovative double distillation process. Isolated heptane was then used as a solvent in order to extract some noble plants of perfumery. It was found that extracts obtained with this solvent were more promising in terms of sensory analysis than those obtained from fossil-based heptane. In addition, in order to valorize the essential oil depleted from heptane, chemical composition of this oil was found to obtain, and potential biological activity properties were studied. A total of 172 different compounds were identified by GC-MS in the remaining oil. In vitro tests-including hyaluronidase, tyrosinase, antioxidant, elastase and lipoxygenase, as well as inhibitory tests against two yeasts and 21 bacterial strains commonly found on the skin-were carried out. Overall, bioassays results suggest this heptane-depleted essential oil is a promising active ingredient for cosmetic applications.

Treatment of Pulp Black Liquor with an Ionic Liquid: Modeling and Optimization by Using Response Surface Methodology and Central Composite Design.

In this study, selective extraction towards ionic liquid trihexyltetradecylphosphonium chloride ([P66614 ]Cl) of lignin residues, polysaccharides and organic acids present in black liquor (BL), the main principal wastewater of pulping industry was studied. With the objective of finding optimized conditions allowing to extract lignin residues while polysaccharides and organic acids remain in aqueous solution, a design of experiments approach based on a response surface methodology was used. Three continuous factors, namely initial pH varying from 9 to 13.5, dilution of BL varying from 5 to 20 and volumetric ratio of black liquor vs. ionic liquid RV ., varying from 1 to 19, were investigated. Concentration of lignin residues, polysaccharides and organic acids were measured using Folin-Ciocalteu method, the anthrone method and HPLC, respectively. Results showed that a multi-response optimization led to the extraction of 84.8 % of lignin residues, 66.0 % of polysaccharides, and no extraction of OA under optimised conditions.

Sustainable extraction of antioxidants from out-of-caliber kiwifruits.

Valorisation of discarded kiwifruits is proposed by extracting bioactive compounds using sustainable solvents namely deep eutectic solvents (DES). A screening of fifteen DES and several hydrogen bonding donor solvents was carried out. Extraction efficiency was measured in terms of antioxidant activity using DPPH and FRAP tests. The influence of solvents characteristics in particular DES structure, presence of ethanol or water, and pH of DES/water mixture on the antioxidant properties of the extracts was studied. Results show that kiwi peels extracts obtained with DES based on carboxylic acids exhibit enhanced antioxidant activity compared to conventional solvents and alcohol-based DES with a maximum DPPH scavenging activity of 42.0 mg TE/g DW. Glycerol or ethylene glycol are also efficient at extracting antioxidant compounds with DPPH scavenging activity of 33.1 and 36.7 mg TE/g DW. Finally, a chemical analysis of extracts using HPTLC revealed that most active compounds extracted are polyphenolic compounds, presumably tannins.

Characterization of Flavor Compounds in Distilled Spirits: Developing a Versatile Analytical Method Suitable for Micro-Distilleries.

Over the last few years, the development of micro-distilleries producing diverse spirits with various flavors has been observed. Versatile analytical techniques for the characterization of aroma compounds in such alcoholic beverages are therefore required. A model mixture embodying a theoretical distilled spirit was made according to the data found in literature to compare usual extraction techniques. When it was applied to the model liquor, the headspace solid phase microextraction (HS-SPME) extraction method was preferred to the liquid-liquid extraction (LLE), solid phase extraction (SPE) and stir bar/headspace sorptive extraction (SBSE/HSSE) methods according to efficiency, cost, and environmental criteria. An optimization study using the model mixture showed that the extraction was optimal with a divinylbenzene/carboxen/poly(dimethylsiloxane) DVB/CAR/PDMS fiber, during 60 min, at 35 °C and with the addition of 10% NaCl. This method was successfully applied to three different commercial liquors and led to the identification of 188 flavor compounds, including alcohols, esters, lactones, carbonyls, acetals, fatty acids, phenols, furans, aromatics, terpenoids, alkenes, and alkanes.

Rh(III) Aqueous Speciation with Chloride as a Driver for Its Extraction by Phosphonium Based Ionic Liquids.

In this work, the aqueous speciation of Rh(III) in chloride medium was investigated by UV-vis spectroscopy for ligand to metal ratios R = (Cl-)/(Rh) ranging from 300 to 5000, at fixed Rh concentration (2.4 × 10-3 M). Under the chemical conditions of this work, no time evolution was observed, which allows for the fitting of the UV-vis data by Principal Component Analysis (PCA) and Multi-Curve Resolution (MCR). From this, and by comparison with literature data, the three independent species [RhCl4]-, [RhCl5]2- and [RhCl6]3- were identified, their individual absorption spectra derived and their respective contribution to the collected experimental UV-vis spectra calculated. Then, extraction of Rh(III) towards the ionic liquid trihexyltetradecylphosphonium chloride was performed. Comparison with the speciation data gives insight into the extraction mechanism and the extracted species.

Mechanisms of phase separation in temperature-responsive acidic aqueous biphasic systems.

The temperature responsive solubility of ionic liquids with 'bulky' polar regions, such as tributyltetradecyl phosphonium chloride ([P44414]Cl), in acidic aqueous solutions is elucidated through a combined experimental and computational approach. The temperature effect in the acidic aqueous biphasic system HCl/[P44414]Cl/H2O was characterised in the range 273 K to 373 K and was found to significantly deviate from the corresponding aqueous biphasic system with NaCl. A new transferable coarse grained MARTINI model for [P44414]Cl was developed, validated and applied to provide a molecular understanding of the experimental results. It is shown that the presence of large aliphatic moieties around the central phosphorus atoms of [P44414]Cl results in a decrease in the electrostatic repulsion between the cationic moieties, leading the [P44414]+ cation to present a behaviour conventionally associated with non-ionic surfactants. This difference in behaviour between HCl and NaCl was shown to result from the greater interaction of the hydronium cation with the micelle surface, thereby enhancing the [P44414]Cl aggregation.

Understanding the fundamentals of acid-induced ionic liquid-based aqueous biphasic system.

Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated exceptional performance in bioseparation processes. However, IL-based ABS are of limited interest for metal extraction as most metals are not stable in their neutral or alkaline pH conditions. In the quest for better extraction systems for metals, the development of IL-based ABS with highly acidic solutions (AcABS), induced by the mixture of a hydrophilic IL ([P44414]Cl), a mineral acid (HCl, HNO3 or H2SO4) and water, opens new possibilities. A comprehensive investigation of fundamental aspects of IL-based AcABS was performed, including the temperature dependence of the phase diagrams, tie-lines and ion exchange behavior, evidencing the unique characteristics of these new systems. In particular, the favorable biphasic formation with an increase in temperature showcases the lower critical solution temperature (LCST) behavior of the phosphonium-based IL and opens many possibilities for AcABS application by creating stimuli responsive systems. The anion exchange identified highlights the IL-based AcABS complexity that renders the analytical characterization of the phases mandatory, instead of the traditional method coupling an empirical fit of the binodal with the lever-arm rule. Through judicious selection of the inorganic acid, different extraction systems can be obtained by tuning the degree of anion-exchange, underlining the versatility of the proposed AcABS system.

Mechanism of ionic-liquid-based acidic aqueous biphasic system formation.

Ionic-liquid-based acidic aqueous biphasic systems (IL-based AcABS) represent a promising alternative to the solvent extraction process for the recovery of critical metals, in which the substitution of the inorganic salt by an acid allows for a 'one-pot' approach to the leaching and separation of metals. However, a more fundamental understanding of AcABS formation remains wanting. In this work, the formation mechanisms of AcABS are elucidated through a comparison with traditional aqueous biphasic systems (ABS). A large screening of AcABS formation with a wide range of IL identifies the charge shielding of the cation as the primary structural driver for the applicability of an IL in AcABS. Through a systematic study of tributyltetradecylphosphonium chloride ([P44414]Cl) with various chloride salts and acids, we observed the first significant deviation to the cationic Hofmeister series reported for IL-based ABS. Furthermore, the weaker than expected salting-out ability of H3O+ compared to Na+ is attributed to the greater interaction of H3O+ with the [P44414]+ micelle surface. Finally, the remarkable thermomorphic properties of [P44414]Cl based systems are investigated with a significant increase in the biphasic region induced by the increase in the temperature from 298 K to 323 K. These finding allows for the extension of ABS to new acidic systems and highlights their versatility and tunability.

Ionic-Liquid-Based Acidic Aqueous Biphasic Systems for Simultaneous Leaching and Extraction of Metallic Ions.

The first instance of an acidic aqueous biphasic system (AcABS) based on tributyltetradecyl phosphonium chloride ([P44414 ][Cl]) and an acid is here reported. This AcABS exhibits pronounced thermomorphic behavior and is shown to be applicable to the extraction of metal ions from concentrated acidic solutions. Metal ions such as cobalt(II), iron(III), platinum(IV) and nickel(II) are found to partition preferentially to one of the phases of the acidic aqueous biphasic system and it is here shown that it successfully allows the difficult separation of CoII from NiII , here studied at 24 and 50 °C.

Quantitative extraction of Rh(iii) using ionic liquids and its simple separation from Pd(ii).

The extraction of Pd(ii) and Rh(iii) from acidic solutions containing between 1 and 8 M HCl towards three ionic liquids, namely [P66614][Cl], [P66614][Br] and [P66614][DCA], based on the trihexyltetradecylphosphonium cation ([P66614]) and chloride, bromide or dicyanamide (DCA) anions, respectively, is reported. Extraction of Pd(ii) is quantitative up to 6 M HCl (D > 3000). A value of 258 for the distribution coefficient of Rh(iii) extracted from 1 M HCl towards [P66614][Br] is also reported. [P66614][Cl] and [P66614][Br] were found to be very efficient at separating these two metals from aqueous solutions containing at least 6 mol L-1 HCl.

Dramatic Changes in the Solubilities of Ions Induced by Ligand Addition in Biphasic System D2O/DNO3//[C1C4im][Tf2N]: A Phenomenological Study.

The solubilities of C1C4im(+) and Tf2N(-) in nitric aqueous phases have been measured for several ligand types and concentrations (0.04 M tributylphosphine oxide, 0.05 M N,N'-dimethyl-N,N'-dibutylmalonamide, 0.10 M 1-methyl-3-[4-(dibutylphosphinoyl)butyl]-3H-imidazol-1-ium bis(trifluoromethylsulphonyl)imidate, and 1.1 M N,N-dihexyloctanamide). The data evidence a significant difference between the solubilities of the cations and anions of the ionic liquid as a consequence of several ion-exchange and/or ion-pairing mechanisms involving all ions present in the system as well as the protonation/nitric-extraction ability of the ligand.

Possibilities and limitations in separating Pt(IV) from Pd(II) combining imidazolium and phosphonium ionic liquids.

An investigation on a process designed for separating Pt(IV) and Pd(II) dissolved in acidic aqueous solution containing HCl using two ionic liquids, 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([OMIM][NTf2]) and trihexyltetradecylphosphonium bromide (Cyphos 102), is presented. To this end, the single extraction of platinum in [OMIM][NTf2] has been investigated as a function of the initial concentration of Pt(IV) ions dissolved in 1 M HCl. The distribution coefficient for Pt(IV), present in water as a PtCl6(2-) anion, decreases with the concentration of Pt(IV). The extraction of Pd(II) towards [OMIM][NTf2] or Cyphos 102 as a function of the concentration of HCl in the aqueous phase is also reported. Pd(II), present as PdCl4(2-) in water, is not extracted using [OMIM][NTf2]. On the other hand, the distribution coefficients of Pd(II) using Cyphos 102 are above 2000. In this ionic liquid, Pd(II) is extracted as a PdBr4(2-) anion. Separation of Pt(IV) from Pd(II) was then carried out starting from aqueous phases containing 1 M HCl and various initial concentrations of Pt(IV). The influence of the number of extraction steps using [OMIM][NTf2] on the extraction of Pt(IV) was also studied. Unlike the results obtained from single extraction experiments of Pt(IV), consecutive extraction of Pt(IV) in water using [OMIM][NTf2] does not improve significantly the extraction of this metal ion. The second step of the extraction process carried out using Cyphos 102 leads to the quantitative extraction of Pd(II) and Pt(IV) remaining in the aqueous phase.

Selective extraction of gold and platinum in water using ionic liquids. A simple two-step extraction process.

We report an all-ionic liquid process for the separation of tetrachloroaurate and hexachloroplatinate complexes. In a first step, gold is removed from water by liquid-liquid extraction with a hydrophobic ionic liquid, 1,2-dimethyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide. Platinum is subsequently extracted from the solution in the presence of KSCN using 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide.

Correlating the structure and composition of ionic liquids with their toxicity on Vibrio fischeri: A systematic study.

A systematic screening of the toxicity of ionic liquids (IL) towards Vibrio fischeri, a bioluminescent marine bacteria generally used in ecotoxicological bioassays, was carried out. The objectives of this work were to find hydrophilic or hydrophobic low toxicity IL and to investigate structure-toxicity relationship of IL. Toxicity of 54 IL to V. fischeri have been measured, some referring to new IL based on quinuclidinol or tropinol and some to generic IL (i.e., imidazolium, pyridinium, pyrrolidinium or piperidinium). For 47 of them, toxicity values have not been reported elsewhere. Water-soluble IL containing hydrophilic anions halide, thiocyanate, dicyanamide, trifluoromethansulfonate were studied. Some IL were found to exhibit very low toxicity towards V. fisheri. Hydrophobic IL based on bis(trifluoromethanesulfonyl)imide, tetrafluoroborate tetraphenylborate and tetracyanoborate were also studied. Toxicity was measured in a consistent way starting from aqueous solutions saturated with IL. The least toxic hydrophobic IL found in this study was [EMIM][B(CN)(4)]. A multifactorial analysis was found to be convenient for finding relevant structure parameters influencing the toxicity of IL. From this analysis, the planarity of the cation ring appeared to be a relevant parameter. Finally, good linear correlations were found when toxicity of IL was plotted either against the number of aliphatic carbons surrounding a pyridinium cation or the total number of carbons of a cation.

A new ozone denuder for aerosol sampling based on an ionic liquid coating.

A new ionic liquid 1-octyl-3,5-dimethylpyridinium iodide ([O35LUT](+)[I](-)) was synthesized and utilized as coating for an ozone denuder device based on a high-volume aerosol sampler (30 m(3) h(-1)). Particle transmission of the denuder was studied, and over 99% of particles ranging from 10 to 2,500 nm were transmitted. The device, containing 4.66 g of ionic liquid, was used outdoors, under dry and damp atmospheric conditions. In order to expose the device to an average concentration of 120 ppbv (240 microg m(-3)) of ozone in air, an additional production of ozone was directly injected into the denuder. Under these conditions, over 97% of ozone was removed for approximately 120 h (5 days). Therefore, iodide-based ionic liquids can be used as a new alternative to conventional denuder coatings in order to reduce artifacts occurring during sampling of particulate matter. Future applications are not limited to ozone removal for specific aerosol sampling methods.

In vitro cytotoxicities of ionic liquids: effect of cation rings, functional groups, and anions.

In vitro cytotoxicities were measured for ionic liquids (ILs) containing various cations and anions using the MCF7 human breast cancer cell line. We measured the cytotoxicities of ionic liquids containing the cations pyridinium, pyrrolidinium, piperidinium, or imidazolium with various alkyl chain lengths, and the anions bromide, bis(trifluoromethanesulfone)imide (Tf(2)N), trifluoromethylsulfonate (TfO), or nonafluoromethylsulfonate (NfO). Three new hydrophobic, task-specific ionic liquids (TSILs), namely, [MBCNPip](+)[Tf(2)N](-), [MPS(2)Pip](+)[Tf(2)N](-), and [MPS(2)Pyrro](+)[Tf(2)N](-) designed for metal-ion extraction were also evaluated. IC(50) values of the ionic liquids toward the MCF7 cells ranged from 8 microM to 44 mM. The toxicity depended significantly on the nature of the cations and anions, especially when the cations contained a long side chain. TSILs studied in this work were less toxic than the classical ILs.