Aromatic Ionic Liquids Research Articles

Relationship between structure and properties of bio-based aromatic ionic liquids for tribological applications

This study examined six phosphonium-based room-temperature ionic liquids (PRTILs) having trihexyltetradecyl- or tributyltetradecyl-phosphonium cations with saccharinate, salicylate, or benzoate anions, and obtained a feature parameter to correlate their cationic chain length, anionic ring size, and contact angle with tribological properties. PRTILs with trihexyltetradecyl-phosphonium cations had lower coefficient of friction (COF) and wear than PRTILs with tributyltetradecyl- phosphonium cations, a trend attributed to the additional methylene groups providing lower contact angle. For either cation, PRTILs with the saccharinate anion exhibited much lower COF and wear than single-ring anions, due to the formation of a low-shear-strength-tribofilm facilitated by the double-ring structure and sulfur of saccharinate. Overall, this study revealed PRTIL interfacial mechanisms that can be used to identify anion-cation combinations with optimal tribological performance.

Aromatic vs alicyclic: Hydrophobicity of the ionic liquid on protein stability and fibril formation

Ionic liquids (ILs) are environment-friendly solvents with potential applications in biochemical reactions and as pharmaceutical ingredients. They are used to stabilize proteins and act as anti-aggregation agents in which the hydrophobic effect of ILs is suggested to have a primary role. To understand the differences in the effect of aromatic and alicyclic cations of ILs on thermal stability and fibrillation propensity of proteins, the effect of two alicyclic (butyl-1-methylpyrrolidinium and butyl-1-methylpiperidinium) and two aromatic (butyl-4-methylpyridinium and butyl-3-methylimidazolium) ILs on lysozyme was investigated by spectroscopy, densitometry, and molecular dynamics simulation. The results suggest that all the ILs switch the fibrillation pathway from nucleation-independent to nucleation-dependent mechanism at ≥200 mM. The fibrillation is slowed down by 28–35-fold in 500 mM of ILs, exceptionally pyrrolidinium-IL delays the fibrillation by ∼70-fold. All the ILs destabilize the protein during thermal denaturation. Though in all cases the unfolding is enthalpy-driven, pyridinium-IL at higher concentrations exhibits an entropy-driven unfolding effect. The volumetric analysis shows a higher thermal expansion coefficient for Lyz in pyridinium-IL which might be due to the increased internal cavity volume of the protein upon binding of the IL. These results corroborate with the computational studies that the preferential interaction coefficient of aromatic-ILs is more, particularly at a higher concentration (200 mM). Four preferable binding sites for ILs on the protein could be identified that includes the amyloidogenic regions, β-hairpin and the hydrophobic cluster 5. Also, the ILs are found to preferably interact with the protein through their alicyclic/aromatic ring and alkyl sidechain. These results suggest that the binding of ILs to the amyloidogenic region inhibits the fibril formation which has a similar effect for both alicyclic and aromatic ILs whereas aromatic-ILs show a larger destabilization effect than alicyclic-ILs at higher concentrations.

Investigation on the Effect of Ionic Liquids and Quaternary Ammonium Salts on the Kinetics of Methane Hydrate

This study investigates the kinetics of gas hydrate (methane gas) in the presence of Ionic Liquids (ILs) and organic Quaternary Ammonium Salts (QASs). Aqueous solutions of eight ILs (five aromatic ILs and three aliphatic ILs) and three QASs have been studied for the kinetics of methane hydrate formation. In this study, five aromatic-based ILs with cations, viz., 1-hexyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, and 1-octyl-3-methylimidazolium, and anions such as [Br]−, [Cl]−, and [HSO4]− were selected. Three aliphatic ILs with cations, viz., diethylammonium, tripropylammonium, and tributylammonium, attached with the [HSO4]− anion were also selected. In the case of QASs, varying carbon chain lengths such as tetra-n-methyl-, tetra-n-ethyl-, and tetra-n-butylammonium bromide (TMAB, TEAB, TBAB) have been considered for the study. The kinetics of methane hydrate formation were investigated at a pressure of 7.5 MPa and a temperature of 276.15 K in the presence of aqueous solutions of QASs at 0.05 mf (mass fraction) and 0.1 mf concentrations and ILs at 0.01 mf. The results show that 0.05 mf of TBAB assists the methane hydrate to nucleate very rapidly and enhances the rate of growth. Hence, TBAB at 0.05 mf is observed to be most promising for gas storage and gas separation/processing among all investigated QASs. TMAB and TEAB have shown slow kinetics; therefore, their presence in a gas hydrate system may not aid in hydrate gas storage/gas separation applications; nevertheless, they could be used as an inhibitor for the prevention of hydrates in systems where other inhibitors may become unsuitable. The aqueous solution of aromatic-based ILs generally shows hydrate promotion, except for shorter chain lengths. The shorter chain length of ionic liquid with suitable anion (Cl–) behaved as a hydrate as the inhibitor and with Br– as the promoter. In general, a bigger cation acts as a good nucleating agent. The anion [HSO4]− is common in both the categories of ILs (aromatic and aliphatic), and it looks like the hydrate inhibition (no hydrate formation) may have occurred due to its presence. ILs offer more scope to understand the tunability of cations and anions to derive a better solution for gas hydrate inhibition and promotion, which have more applications in the ares of methane storage and transportation.

Long-term stable solid concentrated graphene dispersion assisted by a highly aromatic ionic liquid

HypothesisThe sonochemical exfoliation of graphite in solution has been demonstrated as a promising and easy technique for producing graphene dispersions. This is usually done in organic solvents and leads to unstable dispersions with very low graphene concentration. Ionic liquids (ILs) represent a versatile and safe alternative to traditional organic solvents. A few recent studies reported the use of commercial ILs with bulky anions, such as bis(trifluoromethylsulfonyl)imide, and aromatic cations, such as imidazolium, which favour the exfoliation of graphite through π-π and cation-π interactions. Although recently investigated, the role of aromatic groups on imidazolium cations is still controversial and systematic studies are still necessary. Besides, these studies were limited to liquid dispersions at room temperature. ExperimentsHerein, we prepared four highly aromatic imidazolium-based ILs, including the newly reported 1-(naphthylmethyl)-3-benzylimidazolium bis(trifluoromethanesulfonyl)imide, [(Np)(Bn)im][NTf2]. These ILs were used for the sonochemical exfoliation of graphite and compared with a commercial benchmark, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [Bmim][NTf2]. FindingsInterestingly, [(Np)(Bn)im][NTf2] allowed reaching solid dispersions at room temperature containing thin few layer graphene sheets with long-term stability (up to 2 years) and high concentration (3.6 mg/mL). Such graphene dispersion combines long-term stability in the solid-state and high processability in the liquid state, by a simple heating above 60 °C.

Photodegradation of an ammonium ionic liquid: spiking in urban wastewater and comparison with aromatic ionic liquids

The photodegradation of an emerging pollutant, ammonium ionic liquid, is thoroughly investigated by using an advanced oxidation technique.

Effect of aromatic/aliphatic based ionic liquids on the phase behavior of methane hydrates: Experiments and modeling

Abstract In this study, eight ionic liquids (ILs) from the two varieties of ILs, namely, aromatic and aliphatic ILs, have been considered to carry out experimental studies for their effect on the phase behavior of methane hydrate. We have employed five aromatic based ILs with several cations, such as 1-butyl-3-methyl imidazolium, 1-hexyl-3-methyl imidazolium, 1-octyl-3-methyl imidazolium and various anions, such as [Cl]−, [Br]−, [HSO4]−, and three aliphatic based ILs with various cations, such as di-ethyl-ammonium, tri-propyl-ammonium, tri-butyl-ammonium and [HSO4]− anion. All the experiments were performed in the hydrate equilibrium pressure and temperature ranges of 3.86–7.66 MPa and 276.68–283.18 K, respectively. It has been observed that all the investigated ILs have shown inhibition effect on methane hydrate system. Aromatic ionic liquids have shown their dominance over aliphatic ionic liquids in terms of methane hydrate inhibition. ILs with similar class of cation with varying carbon chain length have not shown significant improvement in hydrate inhibition. However, the replacement of anion by [HSO4]− in imidazolium-based ILs improves methane hydrate inhibition. 1-butyl-3-methyl imidazolium sulphate ([BMIM]+[HSO4]−) found to be the best methane hydrate inhibitor among all investigated ILs. In addition, a phase behavior model incorporating a single tuning parameter has been proposed to predict the phase behavior of methane hydrate in the presence of various ionic liquids and salt solutions. The absolute average deviation in pressure (AARD-P, %) for proposed model with an experimental data generated in this work and for various data sets from the literature has been found to be within ±2.90% of the experimental values. Both cation and anion of the ionic liquids have shown to exhibit inhibition effect on the methane hydrate phase stability. The study indicates that the selection of ionic liquids with tunable cation and anion may provide an opportunity to design the best inhibitor for methane hydrate.

Chromatographic and spectroscopic studies on β-cyclodextrin functionalized ionic liquid as chiral stationary phase: Enantioseparation of NSAIDs

Recently, we reported a new chiral stationary phase prepared using β-cyclodextrin functionalized with aromatic ionic liquid which is aimed to enhance the performance of enantioseparation of flavonoids and β-blockers. In this paper, the characteristics and performance of previously prepared chiral stationary phase denoted as β-CD-BIMOTs were compared with the newly synthesized chiral stationary phase denoted as β-CD-DIMOTs. β-CD-DIMOTs were prepared by functionalization of β-cyclodextrin with aliphatic ionic liquid. The obtained β-CD-BIMOTs and β-CD-DIMOTs stationary phases were compared with native β-CD stationary phase for the enantioseparation of non-steroidal anti-inflammatory drugs (NSAIDs) (ibuprofen, indoprofen, ketoprofen and fenoprofen). The β-CD-BIMOTs stationary phase showed greater chiral resolution capabilities rather than β-CD-DIMOTs and native β-CD stationary phases. Further, in order to understand the interaction of enantioseparation, the inclusion complex formation between NSAIDs and β-CD-BIMOTs was studied using 1H NMR, NOESY and UV/Vis. The enantioseparated NSAIDs were found to form multiple interactions with β-CD-BIMOTs-CSP.

Fused coarse-grained model of aromatic ionic liquids and their behaviour at electrodes.

A fused coarse-grained model of aromatic ionic liquids 1-alkyl-3-methylimidazoliums tetrafluoroborate ([CnMIM(+)][BF4(-)]) has been constructed. Structural and dynamical properties calculated from our model are compared with experimental data as well as with corresponding results from simulations of other suggested models. Specifically, we adopt a fused-sphere coarse-grained model for cations and anions. This model is utilized to study structure and differential capacitance in models of flat and porous carbon electrodes. We find that the capacitance varies with pore size, in a manner that is related to the packing of ions inside the pore. For very narrow pores, diffusion is slow and the establishment of thermodynamic equilibrium may exceed the practical limits for our molecular dynamics simulations.

Rheology of Imidazolium-Based Ionic Liquids with Aromatic Functionality.

A series of imidazolium-based ionic liquids with cyclic and aromatic groups and a bis[(trifluoromethane)sulfonyl]amide anion were characterized using dynamic and steady shear rheology in a wide temperature range. The cations investigated include 1-(cyclohexylmethyl)-3-methylimidazolium ([CyhmC1im](+)), 1-benzyl-3-methylimidazolium ([BnzC1im](+)), 1,3-dibenzylimidazolium ([(Bnz)2im](+)), and 1-(2-naphthylmethyl)-3-methylimidazolium ([NapmC1im](+)). Rheological properties are reported from terminal flow to the glassy state. All ionic liquids show very similar flow behavior with a glassy modulus approaching 1 GPa. The temperature dependences of the shift factors used for time-temperature superposition and the viscosity both follow the same VFT or WLF relationship, and the dynamic fragility at Tg ranges from 117 to 130 for the aromatic ionic liquids investigated, considerably more fragile, in the Angell sense, than the aliphatic analogs. Additionally, an anomalous aging effect in the dynamic viscosity response (i.e., a maximum observed at intermediate frequencies) was found using a strain-controlled rheometer but not using a stress-controlled rheometer.

Influence of ion pairing in ionic liquids on electrical double layer structures and surface force using classical density functional approach

We explore the influence of ion pairing in room temperature ionic liquids confined by planar electrode surfaces. Using a coarse-grained model for the aromatic ionic liquid [C4MIM(+)][BF4 (-)], we account for an ion pairing component as an equilibrium associating species within a classical density functional theory. We investigated the resulting structure of the electrical double layer as well as the ensuing surface forces and differential capacitance, as a function of the degree of ion association. We found that the short-range structure adjacent to surfaces was remarkably unaffected by the degree of ion pairing, up to several molecular diameters. This was even the case for 100% of ions being paired. The physical implications of ion pairing only become apparent in equilibrium properties that depend upon the long-range screening of charges, such as the asymptotic behaviour of surface forces and the differential capacitance, especially at low surface potential. The effect of ion pairing on capacitance is consistent with their invocation as a source of the anomalous temperature dependence of the latter. This work shows that ion pairing effects on equilibrium properties are subtle and may be difficult to extract directly from simulations.

Use of Aromatic Ionic Liquids in the Reduction of Surface Phenomena of Crude Oil–Water System and their Synergism with Brine

Enhanced oil recovery is governed primarily by the role of interfacial tension between crude oil and water. Interfacial tension (IFT) of the crude oil–water system is one of the vital factors in the analysis of the capillary forces affecting trapped oil within the reservoir rocks. High salinity and temperature of the reservoirs tend to make researchers search for new surfactants to lower the interfacial tension in crude oil–water systems. The current study hopes to create a move toward solving the above problem through the use of aromatic ionic liquids (ILs) based on imidazolium as the cation and various anions such as [Cl]−, [Br]−, [BF4]−, [H2PO4]−, [HSO4]−, and [PF6]− in different concentrations. This work involves the study of the effect of concentration, temperature, time, and brine on the fate of surface tension (SFT) of water and interfacial tension of crude oil–water systems. The present study also addresses the trend in the electrical conductivity of ILs in water along with the effect of temperatu...

Classical Density Functional Study on Interfacial Structure and Differential Capacitance of Ionic Liquids near Charged Surfaces

We have implemented a generic coarse-grained model for the aromatic ionic liquid [CnMIM+][Tf2N-]. Various lengths for the alkyl chain on the cation define a homologous series, whose electric properties are expected to vary in a systematic way. Within the framework of a classical density functional theory, the interfacial structures of members of this series are compared over a range of surface charge densities, alkyl chain lengths, and surface geometries. The differential capacitance of the electric double layer, formed by ionic liquids against a charged electrode, is calculated as a function of the surface electric potential. A comparison of planar, cylindrical, and spherical surfaces confirms that the differential capacitance increases and varies less with surface potential as the surface curvature increases. Our results are in qualitative agreement with recent atomistic simulations. (Less)

Aggregation behavior of dodecyltriphenylphosphonium bromide in aqueous solution: Effect of aromatic ionic liquids

The effects of ionic liquids (ILs), 1-butyl-3-methylimidazolium acetate ([Bmim][OAc]) and 1-butyl-3-methylimidazolium benzoate ([Bmim][PhCOO]) on the aggregation behavior of dodecyltriphenylphosphonium bromide (C12TPB) in aqueous solution were investigated by surface tension measurements, dynamic light scattering (DLS) measurements and 1H NMR spectroscopy. The introduction of benzene rings in the anions of [Bmim][PhCOO] can promote the micellization of C12TPB more efficiently with a smaller CMC value and a bigger micellar size. The 1H NMR spectra revealed that [Bmim][PhCOO] can participate in the micelle formation. The combined effect of intermolecular interactions, such as electrostatic attraction, hydrophobic effect and π–π stacking interaction is proposed to be responsible for the enhancement in the micellization of C12TPB.

Eco-efficient and green method for the enhanced dissolution of aromatic crude oil sludge using ionic liquids

Proposed mechanism for the enhancement in the dissolution of aromatic TBS in solvents in the presence of aromatic ionic liquids.

Classical density functional theory & simulations on a coarse-grained model of aromatic ionic liquids

A new classical density functional approach is developed to accurately treat a coarse-grained model of room temperature aromatic ionic liquids. Our major innovation is the introduction of charge-charge correlations, which are treated in a simple phenomenological way. We test this theory on a generic coarse-grained model for aromatic RTILs with oligomeric forms for both cations and anions, approximating 1-alkyl-3-methyl imidazoliums and BF₄⁻, respectively. We find that predictions by the new density functional theory for fluid structures at charged surfaces are very accurate, as compared with molecular dynamics simulations, across a range of surface charge densities and lengths of the alkyl chain. Predictions of interactions between charged surfaces are also presented.

Self-Assembly Behavior of N-Methly-N-Hexadecyl-Pyrrolidinium Bromide in Water

N-methyl-N-hexadecylpyrrolidinium bromide (IL) was synthesized for the design of ionic liquid crystals which is a fascinating class of molecular materials, offering the combination of order and mobility. In binary mixtures with water, lyotropic liquid crystalline phase appears in the range of IL content from 35% to 70% and the temperature range from -1.1 to 24 °C in the heating run. The SAXS curves explored the self-assembly processes and hexagonal phase of the IL apparent sol. The saturated aliphatic ionic liquid in water assemble less tightly compared with aromatic ionic liquid based on imidazolium in water, which is due to the absence of aromatic package effect.

Electronic and Steric Effects: How Do They Work in Ionic Liquids? The Case of Benzoic Acid Dissociation

The need to have a measure of the strength of some substituted benzoic acids in ionic liquid solution led us to use the protonation equilibrium of sodium p-nitrophenolate as a probe reaction, which was studied by means of spectrophotometric titration at 298 K. In order to evaluate the importance of electronic effect of the substituents present on the aromatic ring, both electron-withdrawing and -donor substituents were taken into account. Furthermore, to have a measure of the importance of the steric effect of the substituents both para- and ortho-substituted benzoic acids were analyzed. The probe reaction was studied in two ionic liquids differing for the ability of the cation to give hydrogen bond and pi-pi interactions, namely [bm(2)im][NTf(2)] and [bmpyrr][NTf(2)]. Data collected show that benzoic acids are less dissociated in ionic liquid than in water solution. Furthermore, the equilibrium constant values seem to be significantly affected by both the nature of ionic liquid cation and the structure of the acid. In particular, the ortho-steric effect seems to operate differently in water and in the aromatic ionic liquid, determining in this solvent medium a particular behavior for ortho-substituted benzoic acids.

Comparison of interionic/intermolecular vibrational dynamics between ionic liquids and concentrated electrolyte solutions

In this study, we have compared the interionic/intermolecular vibrational dynamics of ionic liquids (ILs) and concentrated electrolyte solutions measured by femtosecond optically heterodyne-detected Raman-induced Kerr effect spectroscopy. A typical anion in ILs, bis(trifluoromethanesulfonyl)amide ([NTf(2)](-)), has been chosen as the anion for the sample ILs and concentrated electrolyte solutions. ILs used in this study are 1-butyl-3-methylimidazolium, 1-butylpyridinium, N-butyl-N,N,N-triethylammonium, and 1-butyl-1-methylpyrrolidinium with [NTf(2)](-). Li[NTf(2)] solutions (approximately 3.3 M) of water, methanol, propylene carbonate, and poly(ethylene glycol) have been selected as control samples. Kerr transients of the ILs and electrolyte solutions show intra- and interionic/intermolecular vibrational dynamics followed by slow picosecond overdamped relaxation. Fourier transform Kerr spectra have shown a difference in the relative intensities of intraionic vibrational bands of [NTf(2)](-) (280-350 cm(-1)) between the ILs and electrolyte solutions. The origin of the difference is attributed to the change in the conformational equilibrium between cisoid and transoid forms of [NTf(2)](-), which is caused by a favorable stabilization of dipolar cisoid form due to Li(+) and dipolar solvent molecules in the electrolyte solutions. Low-frequency Kerr spectra (0-200 cm(-1)) exhibit unique features with the variation of cation and solvent species. The aromatic ILs have a prominent high-frequency librational motion at about 100 cm(-1) in contrast to the case for the nonaromatic ones. The common structure of the spectra observed at about 20 cm(-1) likely comes from an interionic motion of [NTf(2)](-). The nonaromatic ILs allow a fair comparison with the electrolyte solutions of propylene carbonate and poly(ethylene glycol) because of the structural similarities. The comparison based on the first moment of the interionic/intermolecular vibrational spectrum suggests the stronger interionic/intermolecular interaction in the concentrated electrolyte solutions than the ILs.

Charge Trapping in Imidazolium Ionic Liquids

Room-temperature ionic liquids (ILs) are a promising class of solvents for applications ranging from photovoltaics to solvent extractions. Some of these applications involve the exposure of the ILs to ionizing radiation, which stimulates interest in their radiation and photo- chemistry. In the case of ILs consisting of 1,3-dialkylimidazolium cations and hydrophobic anions, ionization, charge transfer and redox reactions yield charge-trapped species thought to be radicals resulting from neutralization of the constituent ions. Using computational chemistry methods and the recent results on electron spin resonance (ESR) and transient absorption spectroscopy of the ionized ILs, we argue that electron localization in the imidazolium ILs yields a gauche dimer radical cation with the elongated C(2)-C(2) bond. This species is shown to absorb in the near-infrared and the visible regions and accounts for the observed ESR spectra. We suggest that the excess electron in these aromatic ILs is localized as such a dimeric ion, and consider the chemical implications of this attribution. We also suggest that three-electron N-N bonding with the formation of a dimer radical anion occurs for amide anions, such as dicyanamide, when the parent anion traps holes; steric hindrance prevents the analogous reaction for bis(triflyl)amide anion. For another anion of practical importance, bis(oxalato)borate, a pathway involving the elimination of CO(2) is suggested. Together, these results indicate the unanticipated tendency of the ILs to localize primary charges as radical ions as opposed to neutral radicals. Thus, it appears that secondary chemistry in the ionized ILs may be dominated by radical ion reactions, similarly to the previously studied conventional organic liquids, depending on the composition of the IL.

Picosecond Time-Resolved Fluorescence Study on Solute−Solvent Interaction of 2-Aminoquinoline in Room-Temperature Ionic Liquids: Aromaticity of Imidazolium-Based Ionic Liquids

Time-resolved fluorescence spectra and fluorescence anisotropy decay of 2-aminoquinoline (2AQ) have been measured in eight room-temperature ionic liquids, including five imidazolium-based aromatic ionic liquids and three nonaromatic ionic liquids. The same experiments have also been carried out in several ordinary molecular liquids for comparison. The observed time-resolved fluorescence spectra indicate the formation of pi-pi aromatic complexes of 2AQ in some of the aromatic ionic liquids but not in the nonaromatic ionic liquids. The fluorescence anisotropy decay data show unusually slow rotational diffusion of 2AQ in the aromatic ionic liquids, suggesting the formation of solute-solvent complexes. The probe 2AQ molecule is likely to be incorporated in the possible local structure of ionic liquids, and hence the anisotropy decays only through the rotation of the whole local structure, making the apparent rotational diffusion of 2AQ slow. The rotational diffusion time decreases rapidly by adding a small amount of acetonitrile to the solution. This observation is interpreted in terms of the local structure formation in the aromatic ionic liquids and its destruction by acetonitrile. No unusual behavior upon addition of acetonitrile has been found for the nonaromatic ionic liquids. It is argued that the aromaticity of the imidazolium cation plays a key role in the local structure formation in imidazolium-based ionic liquids.