Ionic liquids (ILs) have been proposed as promising media for the extraction and separation of bioactive compounds from the most diverse origins. This critical review offers a compilation on the main ...results achieved by the use of ionic-liquid-based processes in the extraction and separation/purification of a large range of bioactive compounds (including small organic extractable compounds from biomass, lipids, and other hydrophobic compounds, proteins, amino acids, nucleic acids, and pharmaceuticals). ILs have been studied as solvents, cosolvents, cosurfactants, electrolytes, and adjuvants, as well as used in the creation of IL-supported materials for separation purposes. The IL-based processes hitherto reported, such as IL-based solid–liquid extractions, IL-based liquid–liquid extractions, IL-modified materials, and IL-based crystallization approaches, are here reviewed and compared in terms of extraction and separation performance. The key accomplishments and future challenges to the field are discussed, with particular emphasis on the major lacunas found within the IL community dedicated to separation processes and by suggesting some steps to overcome the current limitations.
A stricter definition of a deep eutectic solvent (DES) is urgent, so that it may become a sound basis for further developments in this field. This communication aims at contributing to deepening the ...understanding of eutectic and deep eutectic mixtures concerning their definition, thermodynamic nature and modelling. The glut of literature on DES applications should be followed by a similar effort to address the fundamental questions on their nature. This hopefully would contribute to correct some widespread misconceptions, and help to establish a stringent definition of what a DES is. DES are eutectic mixtures for which the eutectic point temperature should be lower to that of an ideal liquid mixture. To identify and characterize them, their phase diagrams should be known, in order to compare the real temperature depression to that predicted if ideality is assumed, and to define composition ranges for which they are in the liquid state at operating temperatures. It is also shown that hydrogen bonding between the DES components should not be used to define or characterize a DES, since this would describe many ideal mixtures. The future of deep eutectic solvents is quite promising, and we expect that this work will contribute to the efficient design and selection of the best DES for a given application, and to model properties and phase equilibria without which the process design is impractical.
Many separation processes in petrochemical and refining industries are applied to close boiling point compounds and/or azeotropic mixtures which make difficult the application of simple distillation, ...requiring alternative separation processes. Ionic liquids, with their unique and tunable properties, may constitute an advantageous alternative as extractive solvents in separation processes that involve hydrocarbon systems. In this work, a review on the experimental data available for ternary systems composed of ionic liquids and hydrocarbons is reported. The gathered information was shown to be essential in the understanding of the molecular interactions and of the effect of the various structural features of both the ionic liquids and the hydrocarbons on their phase behavior, allowing the development of guidelines for the choice of the most suitable ionic liquid for hydrocarbon separation. To be able to carry out the design and selection of new and improved ionic liquids, the development of predictive models and their validation is required, since the experimental screening of the huge number of potential ionic liquids is not feasible. In this context, the ability of COSMO-RS (COnductor-like Screening MOdel for Real Solvents) as a predictive tool to describe the liquid–liquid equilibria of ternary systems composed of ionic liquids and hydrocarbons, is evaluated. The results obtained with COSMO-RS testify its ability for the qualitative, and in some cases the quantitative, description of the phase behavior of the systems studied.
In the past few years, ionic liquids (ILs) with cyano-functionalized anions have shown to be improved candidates for electrochemical and separation applications. Nevertheless, only scattered data ...exist hitherto and a broad analysis of their structure–property relationship has yet to be attempted. Therefore, in this work, a systematic study of the densities, viscosities and refractive indices of imidazolium-based ILs with cyano-functionalized anions was carried out at 0.1 MPa within a broad temperature range (from 278 to 363 K). The ILs under study are based on 1-alkyl-3-methylimidazolium cations (alkyl = ethyl, butyl and hexyl) combined with the SCN−, N(CN)2−, C(CN)3− and B(CN)4− anions. The selected matrix of cation/anion combinations allows us to provide a detailed and comprehensive investigation of the influence of the −CN group through an analysis of the thermophysical properties of the related ILs. The results show that, regardless of the cation, the densities decrease with an increase in the number of cyano groups or anion molecular weight. Moreover, for a fixed cation and temperature, the refractive index of the ILs decreases according to the rank: SCN− > N(CN)2− ≈ C(CN)3− > B(CN)4−. On the other hand, no clear trend was observed for the viscosity of ILs and the respective number of −CN groups. The viscosity dependence on the cyano-functionalized anions decreases in the order: SCN− > B(CN)4− > N(CN)2− > C(CN)3−. The isobaric thermal expansion coefficient, the derived molar refraction, the free volume, and the viscosity energy barrier of all compounds were estimated from the experimental data and are presented and discussed. Finally, group contribution models were applied, and new group contribution parameters are presented, extending these methods to the prediction of the ILs properties.
Ionic liquids (ILs) are a novel class of solvents with interesting physicochemical properties. Many different applications have been reported for ILs as alternatives to organic solvents in chemical ...and bioprocesses. Despite the argued advantage of having low vapor pressure, even the most hydrophobic ILs show some degree of solubility in water, allowing their dispersion into aquatic systems and raising concerns on its pollutant potential. Moreover, nowadays most widespread notion concerning the ILs toxicity is that there is a direct relationship with their hydrophobicity/lipophilicity. This work aims at enlarging the currently limited knowledge on ILs toxicity by addressing negative impacts in aquatic ecosystems and investigating the possibility of designing hydrophobic ILs of low ecotoxicity, by the manipulation of their chemical structures. The impact of aromaticity on the toxicity of different cations (pyridinium, piperidinium, pyrrolidinium and imidazolium) and hydrophobic anions (bis(trifluoromethylsulfonyl)imide NTf
2
and hexafluorophosphate PF
6
) was analysed. Concomitantly, several imidazolium-based ILs of the type C
n
C
m
C
j
imNTf
2
were also studied to evaluate the effects of the position of the alkyl chain on the ILs’ toxicity. For that purpose, standard assays were performed using organisms of different trophic levels,
Vibrio fischeri
,
Pseudokirchneriella subcapitata
and
Daphnia magna
, allowing to evaluate the consistency of the structure–activity relationships across different biological targets. The results here reported suggest the possibility of designing ILs with an enhanced hydrophobic character and lower toxicity, by elimination of their aromatic nature.
•Bacillus subtilis isolates from Brazilian crude oils produce biosurfactants under reservoir conditions.•Sucrose was found to be the best carbon source for biosurfactant production.•Similar mixtures ...containing C13-, C14- and C15-surfactin were found for the biosurfactants produced.•Biosurfactants have better interfacial activity and lower critical micellar concentrations than chemical surfactants.•The produced biosurfactants are promising for Microbial Enhanced Oil Recovery applications.
Biosurfactant production by three Bacillus subtilis strains (#309, #311 and #573) isolated from Brazilian crude oils was optimized based on different carbon and nitrogen sources. The lowest surface tension values were obtained using sucrose containing media for the three isolates. Biosurfactants produced by each strain were characterized by Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (1H NMR), and matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF). The chemical characterization showed that the three isolates produced very similar mixtures, containing C13-, C14- and C15-surfactin, although in different proportions. The structure of surfactins produced by the three strains was shown to be in good agreement with their surface-activities. The interfacial-activities of the biosurfactants were characterized and compared with chemical surfactants. Furthermore, the application of biosurfactants and chemical surfactants in oil recovery was evaluated. The results obtained showed that biosurfactants have better interfacial-activity and oil recovery efficiency than common chemical surfactants, thus being more attractive to be applied in Microbial Enhanced Oil Recovery.
For an adequate choice or design of ionic liquids, the knowledge of their interaction with other solutes and solvents is an essential feature for predicting the reactivity and selectivity of systems ...involving these compounds. In this work, the activity coefficient of water in several imidazolium-based ionic liquids with the common cation 1-butyl-3-methylimidazolium was measured at 298.2 K. To contribute to a deeper insight into the interaction between ionic liquids and water, COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies. The results showed good agreement between experimental and predicted activity coefficient of water in ionic liquids and that the interaction of water and ionic liquids was strongly influenced by the hydrogen bonding of the anion with water. Accordingly, the intensity of interaction of the anions with water can be ranked as the following: CF3SO3− < SCN− < TFA− < Br– < TOS− < Cl– < CH3SO3− DMP− < Ac−. In addition, fluorination and aromatization of anions are shown to reduce their interaction with water. The effect of temperature on the activity coefficient of water at infinite dilution was measured by inverse gas chromatography and predicted by COSMO-RS. Further analysis based on COSMO-RS provided information on the nature of hydrogen bonding between water and anion as well as the possibility of anion–water complex formation.
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