In comparison with the well-described ionic eutectic mixtures, hydrophobic eutectic solvents (HESs) composed of two non-ionic compounds represent a relatively new class of eutectics. In this work, a ...number of non-ionic HESs liquid at room temperature were identified from a large initial screening of potential mixtures. Three new HESs based on thymol + TOPO (trioctylphosphine oxide), TOPO + capric acid and hydrocinnamic acid + capric acid were investigated as extracting media for the recovery and separation of platinum group and transition metals in HCl media. Full phase diagrams and physical properties including viscosities, densities, chemical stability and the influence of water were characterised, with these HESs presenting low viscosities and high hydrophobicity suitable for application as solvents for liquid-liquid extraction. By simple variation of the eutectic component the selectivity of the system for a given metal could be tuned, with the TOPO-based system displaying good to excellent selectivity towards Pt
4+
, Pd
2+
and Fe
3+
under a range of conditions. The extraction mechanism was found to vary due to a complex interplay between the HES composition, acid concentration and the predominant metal complex present. The observed extraction behaviour in HESs composed of two metal complexing ligands such as TOPO + capric acid, in which each respective component is responsible for metal extraction under given conditions, opens the possibility to design hydrophobic eutectic mixtures presenting synergistic effects. Finally, the HES phase following palladium extraction was used as the template for the formation of palladium nanoparticles. The results presented highlight the great potential of HESs as environmentally benign and tuneable media for the solvent extraction of metal ions.
The potential of HESs as environmentally benign and tunable media for the solvent extraction of metal ions is presented.
In the past few years, the number of studies regarding the application of ionic liquids (ILs) as alternative solvents to extract value-added compounds from biomass has been growing. Based on an ...extended compilation and analysis of the data hitherto reported, the main objective of this review is to provide an overview on the use of ILs and their mixtures with molecular solvents for the extraction of value-added compounds present in natural sources. The ILs (or IL solutions) investigated as solvents for the extraction of natural compounds, such as alkaloids, flavonoids, terpenoids, lipids, among others, are outlined. The extraction techniques employed, namely solid-liquid extraction, and microwave-assisted and ultrasound-assisted extractions, are emphasized and discussed in terms of extraction yields and purification factors. Furthermore, the evaluation of the IL chemical structure and the optimization of the process conditions (IL concentration, temperature, biomass-solvent ratio,
etc.
) are critically addressed. Major conclusions on the role of the ILs towards the extraction mechanisms and improved extraction yields are additionally provided. The isolation and recovery procedures of the value-added compounds are ascertained as well as some scattered strategies already reported for the IL solvent recovery and reusability. Finally, a critical analysis on the economic impact
versus
the extraction performance of IL-based methodologies was also carried out and is here presented and discussed.
A literature review and critical analysis of the use of ionic liquids for the extraction of value-added compounds from biomass.
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.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
Mixtures of non-ionic compounds have been reported as DES but most are just ideal mixtures. In the thymol-menthol system, an abnormal strong interaction was identified stemming from the acidity ...difference of the phenolic and aliphatic hydroxyl groups. This type of interaction is found to be the key to prepare non-ionic DES, that may be classified as type V.
An abnormal strong interaction was identified, which was found to be the key to prepare non-ionic DES, that may be classified as type V.
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.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
6.
Laccase Activation in Deep Eutectic Solvents Toledo, Mariah L; Pereira, Matheus M; Freire, Mara G ...
ACS sustainable chemistry & engineering,
07/2019, Volume:
7, Issue:
13
Journal Article
Peer reviewed
Open access
The research on alternative solvents and cosolvents is relevant when envisioning the improvement of biocatalytic reactions. Among these solvents and cosolvents, deep eutectic solvents (DES) may be ...considered as customizable new reaction media for biocatalysis. Accordingly, in this work, 16 DES aqueous solutions, as well as the individual DES components at the same conditions, have been investigated in laccase-catalyzed reactions. Cholinium- and betaine-based DES formed with polyols at different molar ratios and concentrations were evaluated. The results reported show that in the presence of most DES the laccase activity is preserved and, with a particular DES, enhanced up to 200%. Molecular docking studies demonstrated that while most DES components establish hydrogen bonds with the enzyme amino acids, those that establish stronger interactions with the enzyme (expressed by absolute values of docking affinity energies) lead to an enhanced laccase activity. Finally, the laccase stability was evaluated in additional tests under extreme storage temperatures (60 °C and −80 °C). Although no significant protection to high temperatures was afforded by DES, an enhanced laccase activity when stored at low temperatures was found, at least up to 20 days. Combining experimental results and molecular docking, this work shows that DES can be designed as cosolvents to improve biocatalytic reactions.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
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.
Full text
Available for:
EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
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.
Full text
Available for:
IJS, KILJ, NUK, PNG, UL, UM
In the past decade, ionic liquids (ILs) have been the focus of intensive research regarding their use as potential and alternative solvents in many chemical applications. Targeting their ...effectiveness, recent investigations have attempted to establish polarity scales capable of ranking ILs according to their chemical behaviours. However, some major drawbacks have been found since polarity scales only report relative ranks because they depend on the set of probe dyes used, and they are sensitive to measurement conditions, such as purity levels of the ILs and procedures employed. Due to all these difficulties it is of crucial importance to find alternative and/or predictive methods and to evaluate them as a priori approaches capable of providing the chemical properties of ILs. Furthermore, the large number of ILs available makes their experimental characterization, usually achieved by a trial and error methodology, burdensome. In this context, we firstly evaluated COSMO-RS, COnductor-like Screening MOdel for Real Solvents, as an alternative tool to estimate the hydrogen-bond basicity of ILs. After demonstrating a straight-line correlation between the experimental hydrogen-bond basicity values and the COSMO-RS hydrogen-bonding energies in equimolar cation-anion pairs, an extended scale for the hydrogen-bond accepting ability of IL anions is proposed here. This new ranking of the ILs' chemical properties opens the possibility to pre-screen appropriate ILs (even those not yet synthesized) for a given task or application.
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.
Full text
Available for:
EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OBVAL, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
PDF
