Preconcentration of Superbase Ionic Liquid from Aqueous Solution by Membrane Filtration.

Certain organic superbase ionic liquids (ILs) have shown good cellulose dissolution and fiber regeneration performance, allowing us to obtain high-quality textile fibers. However, there is a lack regarding the IL recovery from the spinning bath and its purification, which is essential for the economic viability of the process. Aiming to understand methods to separate ILs from water for reuse/recycle, the use of pressure-driven membrane processes to recycle ionic liquids from aqueous solution was investigated. The recovery of two superbase ILs, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-enium acetate, [mTBDH][OAc], and 5-methyl-1,5,7-triaza-bicyclo[4.3.0]non-6-enium acetate, [mTBNH][OAc], were studied using different types of membranes (microfiltration, ultrafiltration, nanofiltration, and reverse osmosis, RO). Additionally, pressure, IL concentration, temperature, and multicycle effect were evaluated. Significant retentions (>45%) were obtained for the nanofiltration and RO membranes (NF270-NF and BW30LE-RO). The increase in pressure and temperature resulted in an increase in volumetric flux and a decrease in IL retention. On the other hand, IL concentration decreased the volumetric flow and rejection. For the serial filtration tests, a three-fold ionic liquid concentration was achieved, for a maximum concentration of 14 wt % of the ionic liquid. The membrane filtration methodology proved to be an efficient technique for carrying out the preconcentration of the IL from dilute solutions.

Aliivibrio fischeri L-Asparaginase production by engineered Bacillus subtilis: a potential new biopharmaceutical.

L-Asparaginase (L-ASNase) is an enzyme applied in the treatment of lymphoid malignancies. However, an innovative L-ASNase with high yield and lower side effects than the commercially available preparations are still a market requirement. Here, a new-engineered Bacillus subtilis strain was evaluated for Aliivibrio fischeri L-ASNase II production, being the bioprocess development and the enzyme characterization studied. The pBS0E plasmid replicative in Bacillus sp and containing PxylA promoter inducible by xylose and its repressive molecule sequence (XylR) was used for the genetic modification. Initially, cultivations were carried out in orbital shaker, and then the process was scaled up to stirred tank bioreactor (STB). After the bioprocess, the cells were recovered and submitted to ultrasound sonication for cells disruption and intracellular enzyme recovery. The enzymatic extract was characterized to assess its biochemical, kinetic and thermal properties using L-Asparagine and L-Glutamine as substrates. The results indicated the potential enzyme production in STB achieving L-ASNase activity up to 1.539 U mL-1. The enzymatic extract showed an optimum pH of 7.5, high L-Asparagine affinity (Km = 1.2275 mmol L-1) and low L-Glutaminase activity (0.568-0.738 U mL-1). In addition, thermal inactivation was analyzed by two different Kinect models to elucidate inactivation mechanisms, low kinetic thermal inactivation constants for 25 ºC and 37 ºC (0.128 and 0.148 h-1, respectively) indicate an elevated stability. The findings herein show that the produced recombinant L-ASNase has potential to be applied for pharmaceutical purposes.

A corrosion evaluation of mild carbon steel in reclaimed refinery stripped sour water.

Reclaiming water for cooling systems in oil refineries has been strongly encouraged over the past years for decreasing the large consumption of fresh water, thus contributing to the efficient use of this valuable resource. In a recent study [Journal of Environmental Management 261 (2020) 110229], some of the authors studied the retention of phenols in refinery wastewater through reverse osmosis (RO) and found rejections of up to 98% of phenols and 99% of both chemical oxygen demand (COD) and total organic carbon (TOC). The permeates complied with the quality standards for make-up water in cooling processes. A missing aspect, important for the water to be used in the oil and gas industry, was the level of corrosivity of the new permeates. In this work the corrosion of mild carbon steel in the permeates and in the original cooling tower make-up water was studied by electrochemical techniques. The corrosion rate of steel in the permeates in aerated conditions was lower (between 0.053 ± 0.006 and 0.123 ± 0.011 mm year-1) than in the make-up water (0.167 ± 0.030 mm year-1), confirming their suitability for replacing make-up water in the cooling towers. The low corrosion of carbon steel was attributed to the low conductivity and absence of oxidizing species in the fluids, compared to fresh water.

Use of cork granules as an effective sustainable material to clean-up spills of crude oil and derivatives.

The use of cork granules for cleaning up crude oil or oil derivative spills and further oil recovery appears as a promising option due to their unique properties, which allow a high oil sorption capacity, low water pickup and excellent reuse. The present work reports the effect of oil viscosity on cork sorption capacity by using five types of oils (lubricating oil, 5.7 goil gcork-1; heavy oil, 4.2 goil gcork-1; light oil, 3.0 goil gcork-1; biodiesel, 2.6 goil gcork-1; and diesel, 2.0 goil gcork-1). The cork sorption capacity for light petroleum was also evaluated as a function of temperature and sorbent particle size. Additionally, improvements on oil recovery from cork sorbents by a mechanical compression process have been achieved as a result of a design of experiments (DOE) using the response surface methodology. Such statistical technique provided remarkable results in terms of cork sorbent reusability, as the oil sorption capacity was preserved after 30 cycles of sorption-squeezing steps. The sorbed oils could be removed from the sorbent surface, collected simply by squeezing the cork granules and further reused. The best operational region yielded near 80% oil recovery, using a cork mass of 8.85 g (particle size of 2.0-4.0 mm) loaded with 43.5 mL of lubricating oil, at 5.4 bar, utilising two compressions with a duration of 2 min each. Graphical abstract.

Correction to: Use of cork granules as an effective sustainable material to clean-up spills of crude oil and derivatives.

The original publication of this paper contains a mistake.

Binary Mixtures of Ionic Liquids in Aqueous Solution: Towards an Understanding of their Salting-In/Salting-Out Phenomena.

The order of the salting-in or salting-out inducing ability of ions on the aqueous solubility of macromolecules in aqueous solutions is known as the Hofmeister series. Taking into account that ionic liquids (ILs) are constituted by ions, they can exert similar effects on the solubility of other ILs in aqueous media. In order to expand the knowledge on the salting-in/-out ability of ILs, experimental studies on the solubility of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonylimide) in water in presence of other IL/salts were conducted at 298.15 K at atmospheric pressure. Both the impact of the anion and cation of the IL were evaluated with the following ILs/salts: 1-butyl-3-methylimidazolium chloride, 1-butyl-3-methylimidazolium hydrogensulfate, cholinium bis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide and lithium bis(trifluoromethylsulfonyl)imide, in a wide composition range. As happens with common salts, both salting-in and salting-out effects exerted by ILs were observed, with a higher impact exerted by the IL anion on the salting-out phenomenon. These data allow to better understand the ILs impact when designing liquid-liquid separation processes.

Surface crystallization of ionic liquid crystals.

The evidence for surface crystallization in ionic liquids is scarce. The existing reports seem to be contradictory as for its driving forces, since in the two compounds investigated in the literature, the contribution of coloumbic and van der Waals forces is very different. In this work 1-dodecyl-3-methylimidazolium tetrafluoroborate was studied and its surface crystallization characterized by surface tension, ellipsometry and optical microscopy. The results obtained seem to reconcile previous observations, and it was further shown, using the same techniques, that this phenomenon is prevalent in other ionic liquids. MD simulation results illustrate the different possibilities of organization, providing reasonable models to rationalize the experimental observations.

A methodology to parameterize SAFT-type equations of state for solid precursors of deep eutectic solvents: the example of cholinium chloride.

Given the recent boom of applications for deep eutectic solvents (DES), there is a need for robust and accurate thermodynamic models that are able to describe them. Recent works have used molecular-based equations of state, derived from the Statistical Associating Fluid Theory (SAFT), to model DES due to their ability to explicitly account for hydrogen bonding, which is thought to govern the formation of a DES. However, the application of these association models to DES is a non-trivial task, because pure fluid data for several DES precursors are not available to be used in the model parameterization. The alternative parameterization procedures currently employed have evident flaws including the use of oversimplified association schemes, lack of transferability, inability to provide fundamental solid-liquid equilibrium data, and an overall poor accuracy. This work highlights the disadvantages of the current approaches while providing a novel methodology for the development of coarse-grained models applicable to DES. By proposing a more realistic association scheme and regressing the model parameters from experimental data that can be easily measured for a representative DES, a new coarse-grained model for [Ch]Cl, the most used DES precursor, was developed for soft-SAFT. The good performance and versatility of the new model were then successfully demonstrated through the modelling of a wide variety of [Ch]Cl-based DES, providing accurate descriptions of densities, vapor-liquid equilibria and solid-liquid equilibria data, for both binary and ternary systems. Furthermore, the novel approach can easily be applied to other SAFT-type models and extended to other solid DES precursors such as urea.

Odd-even effect on the formation of aqueous biphasic systems formed by 1-alkyl-3-methylimidazolium chloride ionic liquids and salts.

This work provides a comprehensive evaluation of the effect of the cation alkyl side chain length of the 1-alkyl-3-methylimidazolium chloride series ([C n C1im]Cl, n = 2-14) of ionic liquids (ILs) on their capability to form aqueous biphasic systems (ABSs) with salts and self-aggregation derived properties. The liquid-liquid phase behavior of ternary systems composed of [C n C1im]Cl, water, and K3PO4 or K2CO3 and the respective Setschenow salting-out coefficients (ks ), a quantitative measure of the two-phase formation ability, were determined. An odd-even effect in the ks values along the number of methylene groups of the longest IL cation alkyl side chain was identified for the ABS formed by K2CO3, a weaker salting-out agent where the phenomenon is clearly identified. In general, cations with even alkyl side chains, being likely to display higher molar volumes, are more easily salted-out and thus more prone to undergo phase separation. The odd-even effect in the ks values is, however, more significant in ILs up to n = 6, where the nanostructuration/nanosegregation of ILs plays a less relevant role. Still, with the [C n C1im]Cl (n = 7-14) series of ILs, an odd-even effect was also identified in the ILs' ionization degree, molar conductivity, and conductivity at infinite dilution. In summary, it is shown here that the ILs' odd-even effect occurs in IL aqueous solutions and not just in neat ILs, an already well-established phenomenon occurring in a series of ILs' properties described as a result of the orientation of the terminal methyl groups to the imidazolium ring cation and consequent effect in the ILs' cohesive energy.

Vapor Liquid Equilibria of Binary Mixtures of 1-Butyl-3-methylimidazolium Triflate (C4mimTfO) and Molecular Solvents: n-Alkyl Alcohols and Water.

Isobaric vapor liquid equilibria (VLE) of binary mixtures of the ionic liquid (IL) 1-butyl-3-methylimidazolium trifluoromethanesulfonate (C4mimTfO) with either water or short chained n-alkyl alcohols (methanol, ethanol, propan-1-ol, and butan-1-ol) are described in this study. Two different microebulliometers and a classical VLE apparatus were compared and the VLEs were determined in the composition range 0.4 ≤ x(solvent) ≤ 1 at three different pressure levels ( p = 500 mbar, 700 mbar, and 1000 mbar). The experimental data were modeled using the soft-SAFT equation of state, which was able to accurately describe the nonideal behavior of these mixtures. The combined experimental-modeling results obtained contribute to establish the structure-property relationship between the C4mimTfO and n-alkyl alcohol molecules and to infer about its influence on the phase behavior of these solvents.

Densities, Viscosities and Derived Thermophysical Properties of Water-Saturated Imidazolium-Based Ionic Liquids.

In order to evaluate the impact of the alkyl side chain length and symmetry of the cation on the thermophysical properties of water-saturated ionic liquids (ILs), densities and viscosities as a function of temperature were measured at atmospheric pressure and in the (298.15 to 363.15) K temperature range, for systems containing two series of bis(trifluoromethylsulfonyl)imide-based compounds: the symmetric [C n C n im][NTf2] (with n = 1-8 and 10) and asymmetric [C n C1im][NTf2] (with n = 2-5, 7, 9 and 11) ILs. For water-saturated ILs, the density decreases with the increase of the alkyl side chain length while the viscosity increases with the size of the aliphatic tails. The saturation water solubility in each IL was further estimated with a reasonable agreement based on the densities of water-saturated ILs, further confirming that for the ILs investigated the volumetric mixing properties of ILs and water follow a near ideal behaviour. The water-saturated symmetric ILs generally present lower densities and viscosities than their asymmetric counterparts. From the experimental data, the isobaric thermal expansion coefficient and energy barrier were also estimated. A close correlation between the difference in the energy barrier values between the water-saturated and pure ILs and the water content in each IL was found, supporting that the decrease in the viscosity of ILs in presence of water is directly related with the decrease of the energy barrier.

Surface Tensions of Ionic Liquids: Non-Regular Trend Along the Number of Cyano Groups.

Ionic liquids (ILs) with cyano-functionalized anions are a set of fluids that are still poorly characterized despite their remarkably low viscosities and potential applications. Aiming at providing a comprehensive study on the influence of the number of -CN groups through the surface tension and surface organization of ILs, the surface tensions of imidazolium-based ILs with cyano-functionalized anions were determined at atmospheric pressure and in the (298.15 to 343.15) K temperature range. The ILs investigated 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. Although the well-known trend regarding the surface tension decrease with the increase of the size of the aliphatic moiety at the cation was observed, the order obtained for the anions is more intricate. For a common cation and at a given temperature, the surface tension decreases according to: [N(CN)2]- > [SCN]- > [C(CN)3]- > [B(CN)4]-. Therefore, the surface tension of this homologous series does not decrease with the increase of the number of -CN groups at the anion as has been previously shown by studies performed with a more limited matrix of ILs. A maximum in the surface tension and critical temperature was observed for [N(CN)2]-based ILs. Furthermore, a minimum in the surface entropy, indicative of a highly structured surface, was found for the same class of ILs. All these evidences seem to be a result of stronger hydrogen-bonding interactions occurring in [N(CN)2]-based ILs, when compared with the remaining CN-based counterparts, and as sustained by cation-anion interaction energies derived from the Conductor Like Screening Model for Real Solvents (COSMO-RS).

Influence of Nanosegregation on the Surface Tension of Fluorinated Ionic Liquids.

We have investigated, both theoretically and experimentally, the balance between the presence of alkyl and perfluoroalkyl side chains on the surface organization and surface tension of fluorinated ionic liquids (FILs). A series of ionic liquids (ILs) composed of 1-alkyl-3-methylimidazolium cations ([CnC1im] with n = 2, 4, 6, 8, 10, or 12) combined with the perfluorobutanesulfonate anion was used. The surface tensions of the investigated liquid salts are considerably lower than those reported for non-fluorinated ionic liquids. The most surprising and striking feature is the identification, for the first time, of a minimum at n = 8 in the surface tension versus the length of the IL cation alkyl side chain. Supported by molecular dynamics (MD) simulations, it was found that this trend is a result of the competition between the two nonpolar domains (perfluorinated and aliphatic) pointing toward the gas-liquid interface, a phenomenon which occurs in ILs with perfluorinated anions. Furthermore, these ILs present the lowest surface entropy reported to date.

Robust regression with CUDA and its application to plasma reflectometry.

In many applications, especially those involving scientific instrumentation data with a large experimental error, it is often necessary to carry out linear regression in the presence of severe outliers which may adversely affect the results. Robust regression methods do exist, but they are much more computationally intensive, making it difficult to apply them in real-time scenarios. In this work, we resort to graphics processing unit (GPU)-based computing to carry out robust regression in a time-sensitive application. We illustrate the results and the performance gains obtained by parallelizing one of the most common robust regression methods, namely, least median of squares. Although the method has a complexity of O(n(3)logn), with GPU computing, it is possible to accelerate it to the point that it becomes usable within the required time frame. In our experiments, the input data come from a plasma diagnostic system installed at Joint European Torus, the largest fusion experiment in Europe, but the approach can be easily transferred to other applications.

Thermophysical properties of two ammonium-based protic ionic liquids.

Experimental data for density, viscosity, refractive index and surface tension are reported, for the first time, in the temperature range between 288.15 K and 353.15 K and at atmospheric pressure for two protic ionic liquids, namely 2-(dimethylamino)-N,N-dimethylethan-1-ammonium acetate, [N11{2(N11)}H][CH3CO2], and N-ethyl-N,N-dimethylammonium phenylacetate, [N112H][C7H7CO2]. The effect of the anion aromaticity and the cation's aliphatic tails on the studied properties is discussed. From the measured properties temperature dependency the derived properties, such as the isobaric thermal expansion coefficient, the surface entropy and enthalpy, and the critical temperature, were estimated.

Thermophysical properties of phosphonium-based ionic liquids.

Experimental data for density, viscosity, refractive index and surface tension of four phosphonium-based ionic liquids were measured in the temperature range between (288.15 and 353.15) K and at atmospheric pressure. The ionic liquids considered include tri(isobutyl) methylphosphonium tosylate, [P i(444)1][Tos], tri(butyl)methylphosphonium methylsulfate, [P4441][CH3SO4], tri(butyl)ethylphosphonium diethylphosphate, [P4442][(C2H5O)2PO2], and tetraoctylphosphonium bromide, [P8888][Br]. Additionally, derivative properties, such as the isobaric thermal expansion coefficient, the surface thermodynamic properties and the critical temperatures for the investigated ionic liquids were also estimated and are presented and discussed. Group contribution methods were evaluated and fitted to the density, viscosity and refractive index experimental data.

Vapor-Liquid Equilibria of Imidazolium Ionic Liquids with Cyano Containing Anions with Water and Ethanol.

Isobaric vapor-liquid equilibria of 1-butyl-3-methylimidazolium thiocyanate ([C4C1im][SCN]), 1-butyl-3-methylimidazolium dicyanamide ([C4C1im][N(CN)2]), 1-butyl-3-methylimidazolium tricyanomethanide ([C4C1im][C(CN)3]), and 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1im][B(CN)4]), with water and ethanol were measured over the whole concentration range at 0.1, 0.07, and 0.05 MPa. Activity coefficients were estimated from the boiling temperatures of the binary systems, and the data were used to evaluate the ability of COSMO-RS for describing these molecular systems. Aiming at further understanding the molecular interactions on these systems, molecular dynamics (MD) simulations were performed. On the basis of the interpretation of the radial and spatial distribution functions along with coordination numbers obtained through MD simulations, the effect of the increase of CN-groups in the IL anion in its capability to establish hydrogen bonds with water and ethanol was evaluated. The results obtained suggest that, for both water and ethanol systems, the anion [N(CN)2](-) presents the higher ability to establish favorable interactions due to its charge, and that the ability of the anions to interact with the solvent, decreases with further increasing of the number of cyano groups in the anion. The ordering of the partial charges in the nitrogen atoms from the CN-groups in the anions agrees with the ordering obtained for VLE and activity coefficient data.

Thermophysical properties of sulfonium- and ammonium-based ionic liquids.

Experimental data for the density, viscosity, refractive index and surface tension of four sulfonium- and ammonium-based Ionic Liquids (ILs) with the common bis(trifluoromethylsulfonyl)imide anion were measured in the temperature range between 288.15 and 353.15 K and at atmospheric pressure. The ILs considered include butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N4111][NTf2], tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N4441][NTf2], diethylmethylsulfonium bis(trifluoromethylsulfonyl)imide, [S221][NTf2], and triethylsulfonium bis(trifluoromethylsulfonyl)imide, [S222][NTf2]. Based on the gathered results and on data taken from literature, the impact of the cation isomerism and of the size of the aliphatic tails, as well as the effect resulting from the substitution of a nitrogen by a sulfur atom as the cation central atom, on the thermophysical properties of sulfonium- and ammonium-based ILs is here discussed. Remarkably, more symmetric cations present a lower viscosity for the same, and sometimes even for higher, alkyl chain lengths at the cation. Additional derivative properties, such as the isobaric thermal expansion coefficient, the surface thermodynamic properties and the critical temperature for the investigated ILs were also estimated and are presented and discussed.

Understanding the impact of the central atom on the ionic liquid behavior: phosphonium vs ammonium cations.

The influence of the cation's central atom in the behavior of pairs of ammonium- and phosphonium-based ionic liquids was investigated through the measurement of densities, viscosities, melting temperatures, activity coefficients at infinite dilution, refractive indices, and toxicity against Vibrio fischeri. All the properties investigated are affected by the cation's central atom nature, with ammonium-based ionic liquids presenting higher densities, viscosities, melting temperatures, and enthalpies. Activity coefficients at infinite dilution show the ammonium-based ionic liquids to present slightly higher infinite dilution activity coefficients for non-polar solvents, becoming slightly lower for polar solvents, suggesting that the ammonium-based ionic liquids present somewhat higher polarities. In good agreement these compounds present lower toxicities than the phosphonium congeners. To explain this behavior quantum chemical gas phase DFT calculations were performed on isolated ion pairs at the BP-TZVP level of theory. Electronic density results were used to derive electrostatic potentials of the identified minimum conformers. Electrostatic potential-derived CHelpG and Natural Population Analysis charges show the P atom of the tetraalkylphosphonium-based ionic liquids cation to be more positively charged than the N atom in the tetraalkylammonium-based analogous IL cation, and a noticeable charge delocalization occurring in the tetraalkylammonium cation, when compared with the respective phosphonium congener. It is argued that this charge delocalization is responsible for the enhanced polarity observed on the ammonium based ionic liquids explaining the changes in the thermophysical properties observed.

Chameleonic behavior of ionic liquids and its impact on the estimation of solubility parameters.

The possibility of developing a scale for solubility parameters, with the purpose of predicting the performance and aiding the selection of ILs, was evaluated. For the estimation of solubility parameters, infinite-dilution activity coefficient data were used. The results allowed the identification of a curious behavior for ILs that seem to present more than one solubility parameter, acting as polar molecules in some situations and as nonpolar molecules in others, depending on the medium. This behavior was confirmed by solubility measurements of [C(4)MIM][PF(6)] in solvent mixtures. In this work, the solubility parameters were also estimated from other properties, namely, viscosities and enthalpies of vaporization, and the relation between the various sets of solubility parameters is discussed. The results obtained suggest that, given the complexity of IL molecules and their liquid phases, a one-dimensional scale for solubility parameters that is able to characterize these fluids is not feasible.