Project description:Ionic Liquids are a broad group of salts with low melting points that can be specifically tuned for a broad range of applications. Despite being initially considered “green” solvents, their better environmental friendliness compared to traditional solvents has been increasingly challenged. In this study, we aimed to investigate the molecular effects of ILs exposure by using RNA-sequencing to study differential gene expression patterns. Thus, we exposed Daphnia magna to 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl), 1-dodecyl chloride-3-methylimidazolium ([C12mim]Cl) and cholinium chloride ([Chol]Cl). Results suggest that the three ILs share several mechanisms of toxicity, including cellular membrane and cytoskeleton damage, oxidative stress, inhibition of antioxidant enzymes, mitochondrial affectation, changes in protein biosynthesis and energy production, DNA damage, and ultimately, programmed cell death and disease initiation. Overall, the dataset revealed that [C2mim]Cl and [C12mim]Cl were, respectively, the least and the most toxic ILs at the transcriptional level. Also, it is reinforced that [Chol]Cl is not devoid of environmental hazardous potential. Unique gene expression signatures could also be identified for each IL.
Project description:We performed terahertz time-domain spectroscopy and infrared spectroscopy of imidazolium-based, pyridinium-based, and tetraalkylammonium-based tetrafluoroborate ionic liquids to study their characteristic intermolecular and intramolecular vibrational modes to clarify interactions between various cations and the tetrafluoroborate anion. It was found that the central frequency of the intermolecular vibrational band for these ionic liquids has a relatively high frequency, ranging from 90 to 100 cm-1. In the 900-1150 cm-1 range, the intramolecular vibrational absorption band of the 3-fold degenerate mode of tetrafluoroborate anions in the ionic liquids was observed. Although the tetrafluoroborate anion is attributable to one of the weakly coordinated anions, the spectroscopic splitting behavior of the 3-fold degenerate mode differs depending on the cation species. It was revealed that the degenerate mode is very sensitive to local interactions between the tetrafluoroborate anion and each cation.
Project description:Biological properties of ionic liquids (ILs) have been usually tested with the help of standard biodegradation or ecotoxicity tests. So far, several articles on the identification of intermediate metabolites of microbiological decay of ILs have been published. Simultaneously, the number of novel ILs with unrecognized characteristics regarding biodegradability and effect on organisms and environment is still increasing. In this work, seven imidazolium ionic liquids of different chemical structure were studied. Three of them are 1-alkyl-3-methyl-imidazolium bromides, while the other four are tetra- or completely substituted imidazolium iodides. This study focused on the identification of intermediate metabolites of the aforementioned ionic liquids subjected to biodegradation in a laboratory activated sludge system. Both fully substituted ionic liquids and 1-ethyl-3-methyl-imidazolium bromide were barely biodegradable. In the case of two of them, no biotransformation products were detected. The elongation of the alkyl side chain made the IL more susceptible for microbiological decomposition. 1-Decyl-3-methyl-imidazolium bromide was biotransformed most easily. Its primary biodegradation up to 100 % could be achieved. Nevertheless, the cleavage of the imidazolium ring has not been observed.
Project description:Ionic liquids (ILs) are organic molten salts with low-temperature melting points that hold promise as next-generation environmentally friendly boundary lubricants. This work examines the relationship between tribological and rheological behavior of thin films of five imidazolium ILs using a surface force apparatus to elucidate lubrication mechanisms. When confined to films of a few nanometers, the rheological properties change drastically as a function of the number of confined ion layers; not only the viscosity increases by several orders of magnitude but ILs can also undergo a transition from Newtonian to viscoelastic fluid and to an elastic solid. This behavior can be justified by the confinement-induced formation of supramolecular clusters with long relaxation times. The quantized friction coefficient is explained from the perspective of the strain relaxation via diffusion of these supramolecular clusters, where higher friction correlates with longer relaxation times. A deviation from this behavior is observed only for 1-ethyl-3-methylimidazolium ethylsulfate ([C2C1Im][EtSO4]), characterized by strong hydrogen bonding; this is hypothesized to restrict the reorganization of the confined IL into clusters and hinder (visco)elastic behavior, which is consistent with the smallest friction coefficient measured for this IL. We also investigate the contrasting influence of traces of water on the thin-film rheology and tribology of a hydrophobic IL, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [C2C1Im][FAP], and a hydrophilic IL, [C2C1Im][EtSO4]. [C2C1Im][EtSO4] remains Newtonian under both dry and humid conditions and provides the best lubrication, while [C2C1Im][FAP], characterized by a prominent solid-like behavior under both conditions, is a poor lubricant. The results of this study may inspire molecular designs to enable efficient IL lubrication.
Project description:Understanding electron transport with electroactive microbes is key to engineering effective and scalable bio-electrochemical technologies. Much of this electron transfer occurs through small-molecule flavin mediators that perform one-electron transfers in abiotic systems but concerted two-electron transfer in biological systems, rendering abiotic systems less efficient. To boost efficiency, the principles guiding flavin electron transfer must be elucidated, necessitating a tunable system. Ionic liquids (ILs) offer such a platform due to their chemical diversity. In particular, imidazolium-containing ILs that resemble the amino acid histidine are bio-similar electrolytes that enable the study of flavin electron transfer. Using the model IL 1-ethyl-3-methylimidazolium ([Emim][BF4]), we observe concerted two-electron transfer between flavin mononucleotide and an unmodified glassy carbon electrode surface, while a one-electron transfer occurs in standard inorganic electrolytes. This work demonstrates the power of ILs to enable the mechanistic study of biological electron transfer, providing critical guidelines for improving electrochemical technologies based on these biological properties.
Project description:New thiol-functionalized carboxylate ionic liquids (ILs), varying both for the cation and for the anion structures, have been prepared as new potential redox switching systems by reacting either 3-mercapto propionic acid (3-MPA) or N-acetyl-cysteine (NAC) with commercially available methyl carbonate ILs. Different ratios of thiol/disulfide ILs were obtained depending both on the acid employed in the neutralization reaction and on the reaction conditions used. Surprisingly, the imidazolium ILs displayed limited thermal stability which resulted in the formation of an imidazole 2-thione and a new sulfide ionic liquid. Conversely, the formation of the imidazole 2-thione was not observed when phosphonium disulfide ILs were heated, thus confirming the involvement of the imidazolium ring in an unexpected side reaction. An insight into the mechanism of the decomposition has been provided by means of DFT calculations.
Project description:New thiol-functionalized carboxylate ionic liquids (ILs), varying both for the cation and for the anion structures, have been prepared as new potential redox switching systems by reacting either 3-mercapto propionic acid (3-MPA) or N-acetyl-cysteine (NAC) with commercially available methyl carbonate ILs. Different ratios of thiol/disulfide ILs were obtained depending both on the acid employed in the neutralization reaction and on the reaction conditions used. Surprisingly, the imidazolium ILs displayed limited thermal stability which resulted in the formation of an imidazole 2-thione and a new sulfide ionic liquid. Conversely, the formation of the imidazole 2-thione was not observed when phosphonium disulfide ILs were heated, thus confirming the involvement of the imidazolium ring in an unexpected side reaction. An insight into the mechanism of the decomposition has been provided by means of DFT calculations.
Project description:Composite silica xerogels were prepared via acid catalysed sol-gel route using tetraethoxysilan (TEOS) as silica precursor, and 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] or 1-butyl-3-methylimidazolium chloride [BMIM][Cl] ionic liquids, used simultaneously as co-solvents, catalysts and pore templates, at various IL-to-silica ratios. Morphology of the xerogels prepared using the different IL templating agents were investigated using scanning electron microscopy (SEM), nitrogen sorption and small angle neutron scattering (SANS). The thermal behavior of the composites was analyzed by thermal gravimetry, whereas the compositions were checked by infrared spectroscopy and EDX. The differences in the morphology and thermal behavior of the composites due to the different IL additives were revealed.
Project description:In this study, a series of 10 novel 1-methyl-3-octyloxymethylimidazolium derivatives carrying various anionic moieties (4-hydroxybenzenesulfonate, benzenesulfonate, carvacroloxyacetate, chloride, formate, propionate, thymoloxyacetate, vanillinoxyacetate, eugenoloxyacetate and trimethylacetate) were synthesized. Compounds were tested for their antimicrobial activity against six microbe strains (Staph-ylococcus aureus, Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Enterococcus faecalis, and Candida albicans), cytotoxic activity against the mouse melanoma cell line (B16 F10), and surface active properties. All synthesized compounds exhibited antimicrobial activity (expressed as minimum inhibitory concentration; in range of 0.10-27.82 mM/L), especially against Gram-positive bacteria and fungi. In addition, all compounds demonstrated cytotoxicity on B16 F10 cells (IC50 values 0.0101-0.0197 mM/L). Surface properties defined as CMC values, ranged from 0.72 to 32.35 mmol L-1. The obtained results provide an insight into the promising activity of a novel group of quaternary imidazolium derivatives having ionic liquid properties. The most potent compounds, containing a thymoloxyacetate and eugenoloxyacetate moiety, could be candidates for new antimicrobial agents or surfactants.