João A. P. Coutinho

Evaluation of Anion Influence on the Formation and Extraction Capacity of Ionic-Liquid-Based Aqueous Biphasic Systems

Extractive fermentation using aqueous biphasic systems (ABS) is a promising separation process since it provides a nondenaturing environment for biomolecules and improves the stability of cells. Due to environmental concerns and toxicity issues related with common volatile organic solvents, ionic liquids (ILs), a new class of nonvolatile alternative solvents, are being currently investigated for extraction purposes. In this work, a wide range of imidazolium-based ILs was studied aiming at obtaining new insights regarding their ability toward the formation of ABS and their capacity to the extraction of biomolecules. On the basis of the IL cations 1-ethyl-3-methylimidazolium and 1-butyl-3-methylimidazolium, the IL anion influence on ABS formation was assessed through their combination with chloride, bromide, acetate, hydrogensulfate, methanesulfonate, methylsulfate, ethylsulfate, trifluomethanesulfonate, trifluoroacetate, and dicyanamide. Ternary phase diagrams (and respective tie-lines) formed by these hydrophilic ILs, water, and the inorganic salt K(3)PO(4), were measured and are reported. The results indicate that the ability of an IL to induce ABS closely follows the decrease in the hydrogen bond accepting strength or the increase in the hydrogen bond acidity of the IL anion. In addition, the extraction capacity of the studied ABS was evaluated through their application to the extraction of an essential amino acid, L-tryptophan. It is shown that the partition coefficients obtained between the IL and the K(3)PO(4)-aqueous rich phases were substantially larger than those typically obtained with polymers-inorganic salts or polymers-polysaccharides aqueous systems.

Evaluation of Cation−Anion Interaction Strength in Ionic Liquids

Electrospray ionization mass spectrometry with variable collision induced dissociation of the isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) ions of imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ionic liquids (ILs) combined with a large set of anions, such as chloride, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and bis[(trifluoromethyl)sulfonyl]imide, was used to carry out a systematic and comprehensive study on the ionic liquids relative interaction energies. The results are interpreted in terms of main influences derived from the structural characteristics of both anion and cation. On the basis of quantum chemical calculations, the effect of the anion upon the dissociation energies of the ionic liquid pair, and isolated [(cation)(2)anion](+) and/or [(anion)(2)cation](-) aggregates, were estimated and are in good agreement with the experimental data. Both experimental and computational results indicate an energetic differentiation between the cation and the anion to the ionic pair. Moreover, it was found that the quantum chemical calculations can describe the trend obtained for the electrostatic cation-anion attraction potential. The impact of the cation-anion interaction strengths in the surface tension of ionic liquids is further discussed. The surface tensions dependence on the cation alkyl chain length, and on the anion nature, follows an analogous pattern to that of the relative cation-anion interaction energies determined by mass spectrometry.

Ion Specific Effects on the Mutual Solubilities of Water and Hydrophobic Ionic Liquids

Ion specific effects on the mutual solubilities between hydrophobic ionic liquids (ILs) and water are complex and not fully understood. The aim of this work is to obtain further evidence about the molecular mechanism behind this phenomenon by evaluating the effect of a large series of inorganic and organic salts on the mutual solubilities of water and the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(4)mim][Tf(2)N]. The magnitudes of the salting-in and salting-out effects were assessed by changing either the cation or the anion, in a series of salts, as well as the salt concentration. It was observed that the influence of the ions on the solubility followed the Hofmeister series. Both salting-in and salting-out effects were observed and they showed to be dependent on both the nature of the salt and its concentration, while the pH had only a marginal effect on the studied solubilities. On the basis of the solubility changes of the ionic liquid in water in the presence of salts and on NMR spectroscopic data, it will be shown that salting-out inducing ions (high charge density) and salting-in inducing ions (low charge density) act through different mechanisms. While the former act mainly through an entropic effect resulting from the formation of water-ion hydration complexes which cause the dehydration of the solute and the increase of the surface tension of the cavity, the salting-in results from a direct ion binding of the low charge density ions to the hydrophobic moieties of the solute.

Measurements and Correlation of High-Pressure Densities of Imidazolium-Based Ionic Liquids

In the present work, experimental density measurements are reported along with the derived thermodynamic properties, such as the isothermal compressibility (κT), the isobaric expansivity (Rp), and the thermal pressure coefficient (γV) for imidazolium-based ionic liquids (ILs), namely, 1-ethyl-3-methylimidazolium methylsulfate [C2mim][MeSO4], 1-ethyl-3-methylimidazolium ethylsulfate [C2mim][EtSO4], 1,3-diethylimidazolium bis(trifluoromethylsulfonyl)imide [C2eim][Tf2N], and 1-decyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C10mim][Tf2N] in the pressure (0.10 < P/MPa < 35.00) and temperature (293.15 < T/K < 393.15) domains. It is shown that experimental densities are in good agreement with the predicted densities obtained by the Gardas and Coutinho method and the correlation using the Tait equation and Sanchez-Lacombe equation of state.

Towards an Understanding of the Mutual Solubilities of Water and Hydrophobic Ionic Liquids in the Presence of Salts: The Anion Effect

The understanding of the specific interactions between salt ions and ionic liquids (ILs) in aqueous solutions is relevant in multiple applications. The influence of a series of anions on the solubility of 1-butyl-3-methylimidazolium tricyanomethane in aqueous environment was here studied. This study aims at gathering further information to evaluate the recently proposed mechanisms of salting-in- and salting-out-inducing ions in aqueous solutions of ILs and to provide insights at the molecular-level on the phenomena occurring in these systems. The observed effect of the inorganic species on the aqueous solubility of the ionic liquid qualitatively follows the Hofmeister series, and it is dependent on the nature and concentration of the anions. The liquid-liquid equilibrium data and 1H NMR results here reported support a model according to which salting-in- and salting-out-inducing ions operate by essentially different mechanisms. While salting-out is an entropically driven effect resulting from the formation of hydration complexes and the increase of the surface tension of cavity formation, the salting-in phenomena is a consequence of the direct binding of the ions to the hydrophobic moieties of the IL. Further evidence here obtained suggests that the interactions of the inorganic ions are not only established with the cation of the IL, but also with the anion, with the observed solubility effect the result of a balance between those two types of interactions.

Critical Assessment of the Formation of Ionic-Liquid-Based Aqueous Two-Phase Systems in Acidic Media

In this work, the ability of Na(2)SO(4) and ionic liquids to induce the formation of acidic aqueous two-phase systems (ATPS) is investigated. Ternary phase diagrams, tie lines, and tie-line lengths for several systems were determined and reported at 298 K and atmospheric pressure. It is here shown that among the ionic liquids studied only those containing long alkyl side chains at the ions and/or anions with low hydrogen bond basicity are capable of undergoing liquid-liquid demixing in the presence of Na(2)SO(4) aqueous solutions. The results obtained indicate that, besides the salting-out ability of the inorganic salt, the pH of the aqueous solution plays a crucial role toward the formation of ionic-liquid-based ATPS. In acidic media the range of ionic liquids that are able to undergo ATPS formation is substantially reduced when compared to alkaline aqueous salt solutions. The use of inorganic salts and ionic liquids to promote acidic ATPS is envisaged as particularly valuable in the extraction of compounds that exhibit low acid dissociation constants.

Mutual Solubility of Water and Structural/Positional Isomers of N-Alkylpyridinium-Based Ionic Liquids

Despite many previous important contributions to the characterization of the liquid-liquid phase behavior of ionic liquids (ILs) plus water systems, a gap still exists as far as the effect of isomers (of ILs) is concerned. Therefore, in this work, a comprehensive study of the liquid-liquid equilibria between water and isomeric pyridinium-based ionic liquids has been performed. Atmospheric pressure mutual solubilities between water and pyridinium-based ionic liquids combined with the common anion bis[(trifluoromethyl)sulfonyl]imide were experimentally determined between (288.15 and 318.15) K. The main goal of this work is to study the isomeric effects on the pyridinium-based cation, namely, the structural and positional isomerism, as well as the alkyl side chain length. To the best of our knowledge, the influence of both structural and positional isomerism on the liquid-liquid behavior in ionic-liquid-water-containing systems is an unexplored field and is here assessed for the first time. Moreover, from the experimental solubility data, several infinite dilution molar thermodynamic functions of solution, namely, the Gibbs energy, the enthalpy, and the entropy, were estimated and discussed. In addition, aiming at gathering a broader picture of the underlying thermodynamic solvation phenomenon, molecular dynamics simulations were also carried out for the same experimental systems.

On the Interactions between Amino Acids and Ionic Liquids in Aqueous Media

The understanding of the molecular-level interactions between biomolecules and ionic liquids (ILs) in aqueous media is crucial for the optimization of a number of relevant biotechnological processes. In this work, the influence of a series of amino acids on the liquid-liquid equilibria between 1-butyl-3-methylimidazolium tricyanomethane and water was studied to evaluate the preferential interactions between these three compounds. The solubility effects observed are dependent on the polarity, size, and charge distribution of the amino acid side chains and are explained in terms of a refined version of the model proposed earlier (Freire et al. J. Phys. Chem. B 2009, 113, 202; Tome et al. J. Phys. Chem. B 2009, 113, 2815) for ion specific effects on aqueous solutions of imidazolium-based ILs. Although acting through different mechanisms, salting-in and salting-out phenomena possess a common basis which is the competition between water-amino acid side chain, IL-amino acid side chain, and water-IL interactions. The delicate balance between these interactions is dependent on the relative affinities of the biomolecules to water molecules or to IL cation and anion and determines the trend and magnitude of the solubility effect observed.

The pressure effect on the wax formation in diesel fuel

The prevention of wax formation under high pressure on new diesel engine requires a good understanding of the behaviour of the paraffin molecules crystallization. In this work a diesel from a Petrogal refinery was investigated under pressure. In particular the melting curve was measured from atmospheric pressure to 100 MPa by an optical technique. The behaviour of the solid phase with the pressure was also investigated up to 50 MPa by filtration. The results obtained show an increase in the diesel cloud point of about 25 8C at the operating pressure of a common rail engine. It is clear from our results that the increase of the diesel cloud point must be taken into account in the development of new diesel engines where the diesel is injected under high pressure. All the results obtained were successfully predicted with a thermodynamic model able to describe multiphase equilibrium. q 2002 Elsevier Science Ltd. All rights reserved.

Toward an understanding of the aqueous solubility of amino acids in the presence of salts: a molecular dynamics simulation study.

Ion-specific effects on the aqueous solubilities of biomolecules are relevant in many areas of biochemistry and life sciences. However, a general and well-supported molecular picture of the phenomena has not yet been established. In order to contribute to the understanding of the molecular-level interactions governing the behavior of biocompounds in aqueous saline environments, classical molecular dynamics simulations were performed for aqueous solutions of four amino acids (alanine, valine, isoleucine, and 2-aminodecanoic acid), taken as model systems, in the presence of a series of inorganic salts. The MD results reported here provide support for a molecular picture of the salting-in/salting-out mechanism based on the presence/absence of interactions between the anions and the nonpolar moieties of the amino acids. These results are in good qualitative agreement with experimental solubilities and allow for a theoretical interpretation of the available data.