The effect of the cation alkyl chain branching on mutual solubilities with water and toxicities
authors Kurnia, KA; Sintra, TE; Neves, CMSS; Shimizu, K; Lopes, JNC; Goncalves, F; Ventura, SPM; Freire, MG; Santos, LMNBF; Coutinho, JAP
nationality International
journal PHYSICAL CHEMISTRY CHEMICAL PHYSICS
keywords HYDROPHOBIC IONIC LIQUIDS; MOLECULAR-FORCE FIELD; COSMO-RS; UNIFAC MODEL; CELL-LINE; CYTOTOXICITY; IMIDAZOLIUM; EXTRACTION; BIS(TRIFLUOROMETHYLSULFONYL)IMIDE; SEPARATION
abstract The design of ionic liquids has been focused on the cation-anion combinations but other more subtle approaches can be used. In this work the effect of the branching of the cation alkyl chain on the design of ionic liquids (ILs) is evaluated. The mutual solubilities with water and toxicities of a series of bis(trifluoromethylsulfonyl)-based ILs, combined with imidazolium, pyridinium, pyrrolidinium, and piperidinium cations with linear or branched alkyl chains, are reported. The mutual solubility measurements were carried out in the temperature range from (288.15 to 323.15) K. From the obtained experimental data, the thermodynamic properties of the solution (in the water-rich phase) were determined and discussed. The COnductor like Screening MOdel for Real Solvents (COSMO-RS) was used to predict the liquid-liquid equilibrium. Furthermore, molecular dynamic simulations were also carried out aiming to get a deeper understanding of these fluids at the molecular level. The results show that the increase in the number of atoms at the cation ring (from five to six) leads to a decrease in the mutual solubilities with water while increasing their toxicity, and as expected from the well-established relationship between toxicities and hydrophobicities of ILs. The branching of the alkyl chain was observed to decrease the water solubility in ILs, while increasing the ILs solubility in water. The inability of COSMO-RS to correctly predict the effect of branching alkyl chains toward water solubility on them was confirmed using molecular dynamic simulations to be due to the formation of nano-segregated structures of the ILs that are not taken into account by the COSMO-RS model. In addition, the impact of branched alkyl chains on the toxicity is shown to be not trivial and to depend on the aromatic nature of the ILs.
publisher ROYAL SOC CHEMISTRY
issn 1463-9076
year published 2014
volume 16
issue 37
beginning page 19952
ending page 19963
digital object identifier (doi) 10.1039/c4cp02309a
web of science category Chemistry, Physical; Physics, Atomic, Molecular & Chemical
subject category Chemistry; Physics
unique article identifier WOS:000341359700021
link 25119425
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journal impact factor 3.906
5 year journal impact factor 4.224
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