Jesus Lemus

A quantum-chemical-based guide to analyze/quantify the cytotoxicity of ionic liquids

A COSMO-RS descriptor (Sσ-profile) has been used in quantitative structure–activity relationship studies (QSARs) based on a neural network for the prediction of the toxicological effect of ionic liquids (ILs) on a leukemia rat cell line (LogEC50 IPC-81) for a wide variety of compounds including imidazolium, pyridinium, ammonium, phosphonium, pyrrolidinium and quinolinium ILs. Sσ-profile is a two-dimensional quantum-chemical parameter capable of characterising the electronic structure and molecular size of cations and anions. By using a COSMO-RS descriptor for a training set of 105 compounds (96 ILs and 9 closely related salts) with known biological activities (experimental LogEC50 IPC-81 values), a reliable neural network was designed for the systematic analysis of the influence of structural IL elements (cation side chain, head group, anion type and the presence of functional groups) on the cytotoxicity of ∼450 IL compounds. The Quantitative Structure–Activity Map (QSAM), a new concept developed here, was proposed as a valuable tool for (i) the molecular understanding of IL toxicity, by relating Log EC50 IPC-81 parameters to the electronic structure of compounds given by quantum-chemical calculations; and (ii) the sustainable design of IL products with low toxicity, by linking the chemical structure of counterions to the predictions of IL cytotoxicity in handy contour plots. As a principal contribution, quantum-chemical-based QSAM guides allow the analysis/quantification of the non-linear mixture effects of the toxicophores constituting the IL structures. Based on these favorable results, the QSAR model was applied to estimate IL cytotoxicities in order to screen commercially available compounds with comparatively low toxicities.

Composition and structural effects on the adsorption of ionic liquids onto activated carbon

The applications and variety of ionic liquids (ILs) have increased during the last few years, and their use at a large scale will require their removal/recovery from wastewater streams. Adsorption on activated carbons (ACs) has been recently proposed for this aim and this work presents a systematic analysis of the influence of the IL chemical structures (cation side chain, head group, anion type and the presence of functional groups) on their adsorption onto commercial AC from water solution. Here, the adsorption of 21 new ILs, which include imidazolium-, pyridinium-, pyrrolidinium-, piperidinium-, phosphonium- and ammonium-based cations and different hydrophobic and hydrophilic anions, has been experimentally measured. This contribution allows an expansion of the range of IL compounds studied in previous works, and permits a better understanding of the influence of the IL structures through the adsorption on AC. In addition, the COSMO-RS method was used to analyze the measured adsorption isotherms, allowing the understanding of the role of the cationic and anionic structures in the adsorption process, in terms of the different interactions between the IL compound and AC surface/water solvent. The results of this work provide new insights for the development of adsorption as an effective operation to remove/recover ILs with very different chemical nature from water solution.

Ionic Liquid Mixtures—An Analysis of Their Mutual Miscibility

The use of ionic liquid mixtures (IL-IL mixtures) is being investigated for fine solvent properties tuning of the IL-based systems. The scarce available studies, however, evidence a wide variety of mixing behaviors (from almost ideal to strongly nonideal), depending on both the structure of the IL components and the property considered. In fact, the adequate selection of the cations and anions involved in IL-IL mixtures may ensure the absence or presence of two immiscible liquid phases. In this work, a systematic computational study of the mixing behavior of IL-IL systems is developed by means of COSMO-RS methodology. Liquid-liquid equilibrium (LLE) and excess enthalpy (H(E)) data of more than 200 binary IL-IL mixtures (including imidazolium-, pyridinium-, pyrrolidinium-, ammonium-, and phosphonium-based ILs) are calculated at different temperatures, comparing to literature data when available. The role of the interactions between unlike cations and anions on the mutual miscibility/immiscibility of IL-IL mixtures was analyzed. On the basis of proposed guidelines, a new class of immiscible IL-IL mixtures was reported, which only is formed by imidazolium-based compounds.

Ammonia capture from the gas phase by encapsulated ionic liquids (ENILs)

Encapsulated ionic liquids (ENILs) based on carbonaceous submicrocapsules were designed, synthesized and applied to the sorption of NH3 from gas streams. The ENILs were prepared using three different task-specific ILs with adequate properties for NH3 capture: 1-(2-hydroxyethyl)-3-methylimidazolium tetrafluoroborate (EtOHmimBF4), choline bis(trifluoromethylsulfonyl)imide (CholineNTf2) and tris(2-hydroxyethyl)methylammonium methylsulfate [(EtOH)3MeNMeSO4]. The ENILs synthesized were analyzed by different techniques to assess their morphology, chemical composition, porous structure and thermal stability. The capture of NH3 was tested in fixed-bed experiments under atmospheric pressure. The influence of the type and load of IL, temperature (30, 45 and 60 °C) and NH3 inlet concentration was analyzed. Desorption of NH3 from the exhausted ENILs was also studied at atmospheric pressure and temperatures in the range of 150 to 200 °C. The ENILs prepared with task-specific ILs were found to be suitable for NH3 capture in the fixed-bed operation. These systems can be a promising alternative to conventional absorption or adsorption due to: (i) high sorption capacity controlled by IL selection, (ii) remarkable mass transfer rate, (iii) low sensitiveness to high temperatures of the gas stream, (iv) fast and complete regeneration of the exhausted ENIL at mild conditions; and (v) recovery of NH3.

Impact of Surface Active Ionic Liquids on the Cloud Points of Nonionic Surfactants and the Formation of Aqueous Micellar Two-Phase Systems

Aqueous micellar two-phase systems (AMTPS) hold a large potential for cloud point extraction of biomolecules but are yet poorly studied and characterized, with few phase diagrams reported for these systems, hence limiting their use in extraction processes. This work reports a systematic investigation of the effect of different surface-active ionic liquids (SAILs)-covering a wide range of molecular properties-upon the clouding behavior of three nonionic Tergitol surfactants. Two different effects of the SAILs on the cloud points and mixed micelle size have been observed: ILs with a more hydrophilic character and lower critical packing parameter (CPP < 1/2) lead to the formation of smaller micelles and concomitantly increase the cloud points; in contrast, ILs with a more hydrophobic character and higher CPP (CPP ≥ 1) induce significant micellar growth and a decrease in the cloud points. The latter effect is particularly interesting and unusual for it was accepted that cloud point reduction is only induced by inorganic salts. The effects of nonionic surfactant concentration, SAIL concentration, pH, and micelle ζ potential are also studied and rationalized.