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[Display omitted] • Surface-active ionic liquid with some biomolecules were studied. • Results were interpreted in the light of computational simulations. • HOMO–LUMO for the ionic liquid amino acids complex have been predicted. • Binding energy and structural changes were predicted using molecular docking. Understanding the influence of ionic liquids (ILs) on the solubility of biomolecules in aqueous solutions is crucial for designing and optimizing novel biotechnological processes. However, the molecular-level mechanisms underlying this influence remain inconclusive and not fully elucidated. To contribute toward the understanding of molecular interactions between amino acids and ionic liquid in aqueous media, measurements of the densities and speeds of sound for L-serine and glycyl-L-serine in (0.00, 0.005, 0.01, 0.03, and 0.05) mol·kg−1 aqueous solutions of 1-octyl-3-methylimidazolium bromide were conducted at T = (288.15, 298.15, 308.15, and 318.15) K. From experimental data various thermodynamics paramours such as apparent molar volume (V ϕ), the partial molar volume (V ϕ 0), standard partial molar volumes of transfer (Δ V ϕ 0) partial molar isentropic compression (K ϕ,s) and partial molar isentropic compression of transfer (Δ K ϕ , S 0) have been examined. Along with experiment results, computational tools were also utilized for a deeper understanding of the molecular changes. From density functional theory (DFT), the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) were calculated and utilized to obtain molecular descriptors such as ionization energy (I), electron affinity (A), hardness (η), softness (S), chemical potential (μ), and electronegativity (χ). Thermochemical properties, including change in enthalpy ( Δ H), and change in Gibbs free energy ( Δ G), were predicted. Molecular docking studies were used to analysis the molecular interaction of ionic liquid with I-Motif structure and structural changes. [ABSTRACT FROM AUTHOR]

• Isomerism of alcohols and the process of solvation in IL. • Systems can be divided into groups: (1) IL-propanol/isopropanol, (2) IL- butanol/isobutanol, pentanol/isopentanol alcohols. • The motion of alcohols' isomers of the first group system is determined by the structure of the solute. • Compaction of local structure near isomers of alcohols of the second group leads to an increase in their mobility. We present the results of a systematic study of the influence of isomerism of selected primary and secondary alcohols on their processes of solvation in dimethylimidazolium (dmim+) chloride ionic liquids. The properties of this system are investigated near the melting temperature by means of the molecular dynamics method. The study of single particle tracking (SPT) trajectories plays a significant role in the present analysis of the features of the microscopic movement of molecules of the dissolved substance in the solution. We demonstrate that the isomerism of alcohol molecules in case of isobutanol and isopentanol leads to the increase of their self-diffusion coefficients due to the growth of the IL's local structure near the solute as we move from the alcohol to its isomer. The motion of butanol/isobutanol and pentanol/isopentanol alcohols molecules in this process is determined both by the mass, and the hydrophobic properties of the solute. Conversely, we demonstrate that the motion of systems with propanol/isopropanol are determined by the structure of the solute. [ABSTRACT FROM AUTHOR]

• [EMIM][TFA], [BMIM][TFA], and [HMIM][TFA] were screened as extractants. • The LLE data of n-hexane - TBA - IL were measured at 303.15 K and atmospheric pressure. • The LLE data were successfully correlated by the NRTL model. • Quantum chemical calculations were used to explore separation mechanism. n-Hexane and tert -Butanol (TBA) are frequently utilized to refine the conditions for Grignard, Wittig, and Friedel-Crafts alkylation reactions. During the synthesis of loratadine, the formation of azeotropic mixtures n-hexane and TBA, which are challenging to separate through conventional distillation, is inevitable. This study utilizes the COSMO-RS model to identify suitable ionic liquids (ILs) for the separation of the n-hexane - TBA azeotropic system. Based on solvent capacity and selectivity, 1-ethyl-3-methylimidazolium trifluoroacetate ([EMIM][TFA]), 1-butyl-3-methylimidazolium trifluoroacetate ([BMIM][TFA]), and 1-hexyl-3-methylimidazolium trifluoroacetate ([HMIM][TFA]) were selected as extractants. The liquid–liquid equilibrium (LLE) data for the n-hexane - TBA - ILs ternary system were measured at 303.15 K and atmospheric pressure. Distribution coefficients and selectivity were calculated to evaluate the performance of the extractants, with the NRTL model used to correlate the experimental LLE data. The consistency of the NRTL model parameters was corroborated through topological analysis associated with the Gibbs tangent principle. Quantum chemical calculations, including interaction energy, ESP analysis, IGMH analysis, and QTAIM topological analysis, were performed to explore the separation mechanism at the molecular level. The results indicated that the interaction energies between the ILs and TBA were higher than those between the ILs and n-hexane, indicating a stronger attraction of ILs to TBA. Consequently, the ILs effectively separated TBA from the n-hexane - TBA azeotropic system, with extraction capacities ranked as [EMIM][TFA] > [BMIM][TFA] > [HMIM][TFA]. The quantum chemical calculations successfully explained the experimental results, aligning with COSMO-RS model predictions and confirming their reliability. IGMH and QTAIM topological analyses systematically explored the types and strengths of interactions, revealing that hydrogen bonds are predominant between the ILs and TBA, with additional contributions from van der Waals forces. Furthermore, the hydrogen bond strengths between TBA and the anions and cations of the ILs are classified as strong and moderate, respectively. This work provides valuable insights into the separation of azeotropic systems using ILs, elucidating the underlying mechanisms behind this process. [ABSTRACT FROM AUTHOR]

Cage molecule combined with tension ring to design new ionic liquid molecules. The resulting ionic liquid has higher energy density due to the high angular and torsional tensions of the tension ring. This provides a new way to improve the energy density of rocket bipropellants. [Display omitted] • We propose to combine cage structures with tension rings to design new ionic liquid molecules. • The obtained ionic liquids possess higher energy density up to 1.87 kJ·ml−1. • Ignition delay time of hypergolic ionic liquid containing tension ring has 52.5 % shorter than that of straight-chain alkane. Hypergolic ionic liquids are a new type of liquid propellants, and the energy density is critical to propulsion performance. We propose to combine cage structures with tensile rings to design and synthesize new ionic liquid molecules. Cycloalkane-substituted 1-aza-bicyclo[2.2.2]octane and 1,4-diazabicyclo[2.2.2]octane-like ionic liquids were synthesized using dicyanamide root as an anion, and their structure and properties were determined. The obtained ionic liquids possess higher energy density up to 1.87 kJ·mL−1. The three-membered ring substituent can increase the energy density of ionic liquids by 79.8 % and reduce the ignition delay time by 52.5 % than that of straight-chain alkanes. This work provides an important basis for the design and synthesis of the new type of hypergolic ionic liquids. [ABSTRACT FROM AUTHOR]

[Display omitted] • Catalytic performance of PHSe/AC and PH2P/AC is studied for the first time. • Biochar, PHSe/AC and PH2P/AC samples are mixed microporous-mesoporous materials. • More dispersed PH2P species on AC due to stronger surface interaction are noted. • Higher thermal stability of PH2P/AC in comparison with PHSe/AC is established. • Superior catalytic behavior for PH2P/AC in butyl acetate production is observed. Catalytic performance of pyridinium hydrogen selenate (PHSe) and pyridinium dihydrogen phosphate (PH2P) ionic liquids immobilized on algae-based biochar (AC) was studied for the first time. For that purpose, acetic acid esterification with butanol was used as a test reaction. To investigate the surface effects, textural properties and thermal behavior for PHSe/AC and PH2P/AC, physicochemical methods such as X-ray powder diffraction (XRD), nitrogen adsorption–desorption isotherms (S BET) scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) were applied. In addition, influence of the catalyst content (5–12 wt%) and reaction temperature (60–80 °C) on the butyl acetate yield and rate constant of esterification were evaluated. S BET and SEM measurements revealed that all of the samples (AC, PHSe/AC and PH2P/AC) obtained are mixed microporous-mesoporous materials. XRD and XPS data showed more highly dispersed PH2P particles than PHSe on the carrier surface due to stronger surface ionic liquid-support interaction for PH2P/AC in comparison with PHSe/AC. The latter was responsible for higher thermal stability of PH2P/AC with respect to PHSe/AC. In addition, more obvious PH2P sites (than PHSe) on the biochar surface favored the ester production in the presence of PH2P/AC (77.4 % and 53.26 × 10−4 l/mol × min) more evidently than PHSe/AC (58.1 % and 28.82 × 10−4 l/mol × min). [ABSTRACT FROM AUTHOR]

[Display omitted] • Polymer ionic liquid [PEP-MIM]Cl-modified graphene shows improved dispersibility in various solvents. • The composite [PEP-MIM]Cl-GO forms liquid crystals in solvents, offering potential in optics and material science. • Ion-exchange properties of [PEP-MIM]Cl-rGO enable phase transfer and tunable composites for broader applications. In this study, a new method for the preparation of graphene using poly(ionic liquid) [PEP-MIM]Cl was found and the complex [PEP-MIM]Cl-GO, which combines with graphene oxide (GO) via electrostatic and π-π interactions, was investigated to be dissolved in the organic or aqueous phase, depending on the concentration of the poly(ionic liquid), and to be stably dispersed and liquid crystalline. After reduction to graphene (rGO) by L(+)-ascorbic acid, this stable dispersion can still exist without any agglomerates, and thus the poly(ionic liquid)- functionalised graphene [PEP-MIM]Cl-rGO with good dispersibility in water was prepared, and some explorations of phase transfer and anion exchange of [PEP-MIM]Cl-rGO based on the ion exchangeability of the poly(ionic liquid) were made. exchange, and the success of the preparation of poly(ionic liquid)-functionalized graphene was confirmed by TEM, AFM, FTIR, Raman and other characterizations. [ABSTRACT FROM AUTHOR]

• Computational analysis of phosphonium ILs for CO 2 electro-reduction (CO2RR) evaluating gas solubility and transport properties. • Computational determination of enthalpy and entropy confirmed negative enthalpy of solvation; [P 1444 ][TFSI] had a lower penalty for solvation (less negative entropy). • Analysis showed ion competition for gas interaction, with Oxygen and Fluorine in anion cage interacting more with C CO2 atom than Nitrogen. • Viscosity and density calculations indicated slight changes with increased CO 2 content. • Experimental determination of CO 2 solubility, density, and viscosity in [P 1444 ][TFSI] confirmed computational trends. Since phosphonium-based ionic liquids (ILs) are suitable electrolytes for electrochemical reduction, a computationally informed analysis of these ILs was conducted to assess their ability to absorb CO 2. In this work, theoretical and experimental approaches were mixed with a focus on gas solubility, transport properties, and structural characterization. The calculations included free energy of solvation (ΔG), the Henry constant (K h), and short-range energies (Coulomb plus Lennard–Jones). Two ILs, [P 1444 ][TFSI] and [P 1444 ][FSI], were selected for further evaluation because of their lower K h values. The enthalpy and entropy of the solvation process for these selected ILs were computationally determined; both ILs were found to have a favourable enthalpy of solvation for gas dissolution, and [P 1444 ][TFSI] had a lower penalty for solvation (less negative entropy). Moreover, the analysis revealed competition among the ions interacting with the gas. The structural characterization of the [P 1444 ][TFSI] and [P 1444 ][FSI] with the CO 2 systems involved radial and spatial distribution functions. The gas was likely enveloped by an anion cage, and oxygen and fluorine exhibited greater interactions with the carbon atom of CO 2 than nitrogen. The viscosity and density were also calculated for the two systems, and the addition of CO 2 only caused a slight change on these values. Experiments on viscosity and density confirmed the computational results; here, compared with those of neat ionic liquids, an approximate 4 % decrease in the viscosity of CO 2 -saturated systems was observed. Finally, the actual CO 2 solubility in [P 1444 ][TFSI] was experimentally determined to be 120 mM; this value was nearly four times greater than those of typical aqueous bicarbonate solutions. [ABSTRACT FROM AUTHOR]

• Investigation of binary DMSO-IL solvation behaviour. • Calculations of volumetric and acoustic properties. • DFT calculations, NCI and QTAIM analysis to examine DMSO-IL interactions. The aim of this study is to examine the cation and anion influence on intermolecular interactions of mixtures comprising ionic liquids (ILs): 1-butyl-3-methylimidazolium chloride [Bmim][Cl], 1-butyl-3-methylimdazolium thiocyanate [Bmim][SCN] and 1-butyl-1-methylpyrrolidium chloride [Bmpym][Cl] with dimethyl sulfoxide (DMSO) at various temperatures. To understand the influence of cation and anion as well as temperature on interactions between the mixtures, thermodynamics parameters: apparent molar properties were calculated from the measured density (ρ) and sound velocity (u) data and fitted to the Redlich-Mayer type equation in order to obtained limiting apparent molar properties of the studied mixtures. A detailed non-covalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analysis was done using density functional theory calculations. These calculations provided information on the electrostatic interactions between the anion, cation, and solvent. The experimental and computational results show that there is hydrogen bonding and strong ionic interactions in the studied systems. [ABSTRACT FROM AUTHOR]

[Display omitted] A cost-effective and environmentally friendly one-pot method for synthesizing 2,3′-bi-indole derivatives has been developed, utilizing a Brønsted acidic ionic liquid as an organocatalyst via tandem cyclization reaction. This process involves imine formation, nucleophilic addition, and cyclization, with water as the only by-product. The advantages of this protocol include metal-free, mild reaction conditions, easy workup, simple purification technique, broad substrate scope, high product yields, and lower E-factors. Furthermore, the synthesized products exhibit promising biological activities, and the antibacterial activities have been studied for some randomly taken synthesized compounds. [ABSTRACT FROM AUTHOR]

[Display omitted] • Ionic liquids as carriers are used for the extraction of diclofenac and tetracycline. • Pseudo-emulsion hollow fiber strip dispersion system is used. • Membrane phase and pseudo-emulsion are characterized by FTIR, micrograph images and turbiscan. • Effect of multiple runs and recyclability of pseudo-emulsion is studied under optimum conditions. Diclofenac (DCF) and Tetracycline (TC) are used as non-steroidal anti-inflammatory drugs (NSAID) and antibiotics, respectively. Both these drugs, when released into the environment through various routes, cause adverse effects on aquatic life and humans. The traditional approaches employed for the removal of these drugs have various drawbacks and adverse effects on the environment. The present work gives a deeper insight into the potential application of ionic liquids as carriers in the pseudo-emulsion hollow fiber strip dispersion (PEHFSD) technique for removing these compounds from the simulated aqueous solution. The extraction of DCF and TC was performed using different organic carriers, Di-(2-ethylhexyl)phosphoric acid (D2EHPA), Tributyl phosphate (TBP), Trioctyl amine (TOA), and also using ionic liquids, 1-Ethyl-3-methylimidazolium Bis(trifluoromethanesulfonyl)imide ([EMIM][[TFSI]), 1-Butyl-1-methylpyrrolidinium Bis(trifluoromethanesulfonyl)imide ([BMPy][[TFSI]) and 1-Octyl-3-methylimidazolium Hexafluorophosphate ([OMIM][PF 6 ]). Comparing the performance of all carriers, it was found that [OMIM][PF 6 ] showed 100 % extraction of DCF, while for TC, the maximum extraction obtained was 91.85 %. Effective extraction of DCF and TC up to the 4th cycle indicated the stability of the membrane phase inside the micropore. Membrane phase and pseudo-emulsion are also characterized by FTIR, micrograph images and Turbiscan. A recyclability study of pseudo-emulsion showed that with the increase in the number of cycles for extraction, the stripping phase was gradually saturated by extracting feed (DCF/TC), which led to a drop in extraction efficiency. [ABSTRACT FROM AUTHOR]

[Display omitted] • Electrostatic interactions have the most important role in the adsorption of ILs on the surfaces. • The interaction strength in the pure ILs decreases upon adsorption on the surfaces. • The adsorption of ILs on the surfaces is accompanied by charge transfer from the surfaces to the ILs. • The IL adsorption leads to the decrease of E g and η values and an increase of ω values of the surfaces. • Electron excitation in the IL@surface complexes is generally intra-fragment electron transfer. The adsorption of nine common ionic liquids (ILs) on two well-known structures of graphitic carbon nitride (g-C 3 N 4) nanosheets, including Triazine-g-C 3 N 4 and Heptazine-g-C 3 N 4 has been investigated using density functional theory (DFT) method in gas phase and water solvent. The interactions between the ILs and the nanosheets are characterized by several techniques, such as quantum theory of atoms in molecules (QTAIM) analysis, noncovalent interaction (NCI) plots, and energy decomposition analysis (EDA) method. Interestingly, the obtained results showed that electrostatic interactions have the highest contributions to the interaction energies between the ILs and the surfaces, followed by dispersion interactions and orbital interactions (ΔE elec > ΔE disp > ΔE orb) The most important Van der Waals (vdW) interactions between the ILs and the surfaces include π–π, C H...N, C H...π (C N), and C N...X (X = F, N, O) interactions. On the other hand, the adsorption of ILs is accompanied by charge transfer from the surfaces to the ILs. The calculated adsorption energy (E ads) showed that the [Bmim][PF 6 ] IL has the highest adsorption affinity on the Triazine-g-C 3 N 4 (−28.28 kcal/mol) and Heptazine-g-C 3 N 4 (−26.68 kcal/mol) surfaces. Thermochemistry calculations showed that the E ads , ΔH ads , and ΔG ads values of IL@surface complexes decrease on moving from gas phase to water media. However, our results showed that the adsorption of ILs on the surfaces is still exothermic and proceeds spontaneously. Upon adsorption of ILs, a decrease in the HOMO–LUMO energy gap (E g) is observed and is accompanied by an increase in the reactivity and electrophilic character of the surfaces. TD-DFT calculations showed that the weak adsorption of ILs leads to small red or blue shifts in the absorption bands of the Triazine-g-C 3 N 4 and Heptazine-g-C 3 N 4 surfaces. However, no significant changes are observed in the shape of the absorption spectra of the surfaces. Furthermore, the transition density matrix (TDM) heat maps of the IL@surface complexes showed that the electrons and holes are generally concentrated on the Triazine-g-C 3 N 4 and Heptazine-g-C 3 N 4 surfaces in the IL@surface complexes, signifying that the electronic transitions occur mainly on the surfaces. [ABSTRACT FROM AUTHOR]

[Display omitted] • Binder-free electrocatalyst for oxygen evolution reaction. • A greener electrocatalyst with high Eco-score and less E-factor values. • 100% atom economic synthesis of green electrocatalyst. • Tafel slope is as small as 53.17 mV dec−1. A binary mixture of ionic liquids (BmIL 1) has been designed from [C 12 mim][Br] and [MPIM][HCOO] and used as a green and metal free electrocatalyst for oxygen evolution reaction (OER). BmIL 1 was found to possess notable electrochemical stability in an alkaline medium to be used as an electrocatalyst in water splitting. Under alkaline conditions, the overpotential to achieve a current density of 10 mA/cm2 is 0.63 V and the Tafel slope is as small as 53.17 mV dec−1. The electrocatalyst can be stabilized over a glassy carbon electrode without adding any binder. To the best of our knowledge, this is the first report on designing an electrocatalyst for water splitting using ionic liquids without adding any binder. Moreover, the minimal E-factor, 100% atom economy and greater Eco Scale associated with the BmIL 1 justifies the sustainable synthesis of the green electrocatalyst. [ABSTRACT FROM AUTHOR]

[Display omitted] • Six ionic liquids capable of degrading human hair identified from the literature. • Modeling of ker6, a potential keratinase for human hair hydrolysis, using AlphaFold2. • Assessing the stability of ker6 in water and the different ionic liquids through molecular dynamic simulations. • TMAOH is the best solvent for extracting human hair keratin using ker6, based on RMSD, RMSF, Rg, hydrogen bonds, and SASA. In this study, the stability of ker6, a keratinase produced by Bacillus cereus , was investigated in water and six distinct ionic liquids through molecular dynamic simulations. The analysis of ker6 stability involved comparisons of root mean square deviation (RMSD), radius of gyration (Rg), solvent accessible surface area (SASA), root mean square fluctuation (RMSF), and intra-protein hydrogen bonds. Notably, the simulations revealed reduced fluctuations in RMSD and RMSF, an increased number of intra-protein hydrogen bonds and lower values of Rg and SASA in Tetramethylammonium hydroxide (TMAOH) simulation system all pointing towards the stability of ker6. Our computational analysis identified TMAOH as the most stable environment for ker6. ker6 is a keratinase recognized from literature as a potential candidate for the degradation of human hair keratin. We have modeled its structure using AlphaFold2. The six ionic liquids taken here for simulation are selected based on their documented efficiency in human hair degradation. This study aligns with the growing interest in identifying ionic liquids that enhance protein stability, particularly in the context of extracting valuable biomaterials like human hair keratin in an environmental sustainable way. The findings suggest that TMAOH could serve as a promising solvent for keratin extraction from human hair when utilizing ker6, thereby making the extraction process more environmentally friendly. [ABSTRACT FROM AUTHOR]

[Display omitted] • The number of amine groups and alkyl chain length affect the CO 2 absorption process. • Aminate-anion ILs with multiple amine groups have higher CO 2 absorption. • Aminate-anion ILs perform better than amino-cation and non-functionalized ILs. • Kinetics and mechanism of CO 2 absorption are confirmed at the molecular level. Amino acid ionic liquids (AAILs) have good absorption performance for carbon dioxide (CO 2). However, there is no unified understanding of the absorption mechanism. In this study, synthesis and characterization of four ionic liquids (ILs) based on amino acid (aminate) anions, namely 1-butyl-3-methylimidazolium L-alaninate ([BMIm]Ala), 1-butyl-3-methylimidazolium arginate ([BMIm]Arg), 1-butyl-3-methylimidazolium glycinate ([BMIm]Gly) and 1-butyl-3-methylimidazolium lysinate ([BMIm]Lys), were accomplished, where the cation adopted was [BMIm]+. Further, their CO 2 absorption capacities were examined. The CO 2 molar uptake rankings for the investigated aminate-ILs are [BMIm]Arg > [BMIm]Lys > [BMIm]Gly > [BMIm]Ala, with [BMIm]Arg displaying stronger CO 2 absorption (0.85 mol CO 2 /mol IL under 10.0 bar). In contrast to non-functionalized ILs and amine functionalized cation ILs, the CO 2 solubility of as-synthesized aminate-ILs is higher. More importantly, the Quantum Theory of Atoms-in-Molecules (QTAIM) at the M06-2X/6-311++G(d, p) level was exploited to theoretically explore the CO 2 absorption mechanism and kinetics of the aminate-ILs. It was found that the alkyl chain length along with the quantity of amine (–NH 2) groups in aminate anions affected their absorption of CO 2. Facilitated absorption of CO 2 was noted when the amine group quantity of ILs structures rose. The chemisorption nature was determined according to the enthalpy changes in the process of CO 2 capture. As suggested by the kinetic findings, [BMIm]Gly exhibited higher absorption rate of CO 2 compared to [BMIm]Ala, since the steric hindrance in the latter is higher because of an extra methyl group in the aminate chain. Additionally, topological exploration revealed that the C–N bond critical point had a covalent nature, indicating that CO 2 capture was a chemisorption event. In conclusion, based on the kinetic energy findings combined with the interaction and topological analyses, [BMIm]Arg was identified as the optimal candidate for CO 2 absorption from the thermodynamic and kinetic perspectives, which was consistent with the CO 2 absorption experiment. Finally, four other aminate-ILs were synthesized using 1-ethyl-3-methylimidazolium ([EMIm]+) as a cation, namely 1-ethyl-3-methylimidazolium asparagine ([EMIm]Asn), 1-ethyl-3-methylimidazolium glutamine ([EMIm]Gln), 1-ethyl-3-methylimidazolium threonine ([EMIm]Thr) and 1-ethyl-3-methylimidazolium glutamic ([EMIm]Glu). The universality of the above conclusions was verified through theoretical calculations and CO 2 absorption experiments. [ABSTRACT FROM AUTHOR]

[Display omitted] • Evaporation and thermolysis of the studied methanesulfonates proceed independently. • Vapor pressures and enthalpies of vaporization of ionic liquids are determined. • Thermolysis proceeds with formation of gaseous products with IL activity equal to 1. • The kinetics of [EtMIm][CH 3 SO 3 ](l) thermolysis reactions is described in two ways. • Thermolysis rate is determined by product flux and expressed by IL concentration. Knudsen cell mass spectrometry was used to study the evaporation of two ionic liquids, 1-ethyl-3-methylimidazolium methanesulfonate ([EtMIm][MS], MS = CH 3 SO 3) and 1-butyl-3-methylimidazolium methanesulfonate ([BuMIm][MS]), accompanied by thermal decomposition (thermolysis). The independent occurrence of evaporation and thermolysis reactions made it possible to determine their thermodynamic and kinetic characteristics under identical experimental conditions. The saturated vapor pressures were measured and the standard enthalpies of vaporization of [EtMIm][MS](l) and [BuMIm][MS](l) were obtained. The standard thermodynamic functions of formation in the liquid and gaseous states at 298.15 K were estimated from the available experimental data and the results of quantum chemical calculations. The gaseous decomposition products of ionic liquids were identified and the pressures of the thermolysis products of [EtMIm][MS](l) were determined. According to the experimental data and quantum chemical calculations, the thermolysis of [EtMIm][MS](l) occurs through heterogeneous reactions far from the equilibrium state. The kinetics of the reactions is described in two ways. When the degree of sample conversion is used as a variable, the constant reaction rates at the initial stage of thermolysis correspond to a pseudo -zero order reaction with a monotonic increase in the degree of conversion. In the proposed alternative approach, the reaction rates are estimated from the fluxes of thermolysis products and are expressed in terms of ionic liquid concentration. [ABSTRACT FROM AUTHOR]

The prevailing strategies for synthesizing Brønsted acidic ionic liquids have primarily relied on ▪ functionalization and the use of acidic anions (e.g. ▪ and ▪), which limit the range of viable new compounds that can be developed. In this work, we propose enhancing the intrinsic acidity of imidazolium through functionalization with electron-withdrawing groups, a strategy that resulted in room-temperature Brønsted acidic protic ionic liquids. Specifically, nitro- and cyano-functionalized room temperature protic ionic liquids were successfully synthesised and characterised. Compared to a prototypical protic ionic liquid such as ▪, the addition of a nitro- or cyano-group led to increased acidity, as demonstrated by converging experimental results obtained by spectroscopic methods and molecular modelling. This functionalization significantly impacted thermal and transport properties, with the nitro- and cyano-functionalized protic ionic liquids displaying reduced thermal stability, higher viscosity and lower ionic conductivity. In addition, this functionalization affects the temperature dependence of the ionic conductivity with a supposed influence also on fragility, a parameter that, in the case of ionic liquids, requires more dedicated studies for a more comprehensive understanding. • Two new Brönsted acidic protic ionic liquids have been synthesized and characterized. • Cyano- and nitro-functional groups on the imidazolium cation are the origin of increased acidity of the N-H bond. • Transport properties and fragility are directly affected by this type of functionalization. [ABSTRACT FROM AUTHOR]

[Display omitted] • Solvent extraction chemistry with 4-acylpyrazolones. • Selectivity between various s-, p-, d- and f-ions. • Stoichiometry of MoO 4 2− and Zr4+ complexes. • Effect of diluents on selectivity. • EPR and NMR, DTA-TG-MS, IR investigations of d- and f-containing extracts. Solvent extraction chemistry of metals needs the use of suitable organic ligands like 4-acylpyrazolones to coordinate the studied cation, to make it soluble in an organic phase and then allow its phase transfer from the aqueous phase. The competitive solvent extraction test of almost 25 metal ions by one powerful ligand, i.e. 3-methyl-1-phenyl-4-(4-trifluoromethylbenzoyl)-pyrazol-5-one diluted in one ionic liquid ([C 1 C n im+][Tf 2 N−]) has been conducted to get a snapshot of its efficacy. Effect of diluents on the liquid–liquid extraction of 4f-ions with a series of chelating ligands of 4-acylpyrazolones family (∼5) is presented comparing ionic liquids and typical organic diluents: 14 in number. In addition, the solvent extraction of 12 refractory metals with a series of chelating extractants is investigated in five diluents: four 4-acylpyrazolones with different radicals. The solvent extraction stoichiometry of MoO 4 2− and Zr4+ is studied in detail using molecular and ionic diluent for comparative purposes through slope analysis method. Ethylene glycol is used to develop a non-aqueous process for Gd3+ switchable extraction, i.e. boost of two immiscible organic phases. Furthermore, EPR, NMR, IR and DTA-TG-MS spectroscopies have been used to study the extracted d- and f-species in the obtained organic extracts in ionic liquid solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] • A delicate balance among anion-cation-cellulose interactions is essential. • Cation facilitates cellulose dissolution in AA ILs, differing from imidazole-based ionic liquids. • Typically provide the interaction mechanism of cellulose with the next-gen ILs featuring amino acid-derived cations. This work systematically explores the interaction between cellulose and various ionic liquids (ILs) formed by the pairing of glycine cations with diverse anions. Results show that the interaction of anions with cellulose decreases in the order of [CH 3 COO]− > [Im]− > [SCN]− > Cl− > [PF 6 ]−, differing from imidazole-based ionic liquids. The synergistic effect of anions and cations is crucial for cellulose dissolution. Moreover, the electronegativity of anions can enhance their interaction with cellulose. Short alkyl chains (n = 1, 3, 5) reduce hydrogen bonding due to steric hindrance, while longer chains (n = 9) promote diffusion and hydrogen bond formation. The introduction of electron-withdrawing groups to anions weakens their interaction with cellulose, while marginally strengthening the association between cations and cellulose. Overall, a delicate balance among anion-cation-cellulose interactions is essential for effective cellulose dissolution. The obtained results are anticipated to be of significant importance in the rational design of innovative amino acid-based ionic liquids, aiming to achieve efficient cellulose dissolution. [ABSTRACT FROM AUTHOR]

• Three cholinium-based magnetic ionic liquids (MILs) were synthesized and characterized. • MILs were used to construct magnetically responsive aqueous two-phase systems. • The effects of MILs structure, temperature and salt types on the phase behavior were investigated. • The phase separation mechanism of the MIL-ATPs was well established. In this work, three cholinium-based MILs were synthesized, characterized and successfully applied to construct the magnetically responsive aqueous two-phase system (ATPs). This ATPs combined the advantages of ILs and magnetic responsiveness, and showed great potential in the field of extraction and separation. Phase behavior for the magnetic ionic liquid aqueous two-phase systems (MIL-ATPSs) containing [N 1 1n 2OH ] [TEMPO-OSO 3 ] + salts + water was investigated experimentally at different temperatures. Merchuk equation was adopted to fit the experimental binodal data with satisfactory correlation performances. The effects of the structure of MILs, temperature and types of salts on the phase behavior were evaluated. Investigation on the phase separation mechanism showed that the phase formation was affected by the structure and viscosity of MILs. The salting-out effect is recognized as the major force for phase separation, which is closely related to the Gibbs free energy of hydration (Δ hyd G) and entropy of hydration (Δ hyd S) of salts. In addition, a larger biphasic area was obtained by increasing the temperature, indicating the phase separation process was endothermic and entropically driven. The binodal curve at different temperature confirms that this MIL-ATPs has low critical solution temperature (LCST) phase transition behavior. All these experimentally measured data and the theoretical correlations can provide meaningful and valuable information that may promote further research and application. [ABSTRACT FROM AUTHOR]

The swelling and dissolution molecular mechanism of cellulose in ILs-H 2 O was proposed based on in-situ PLM and MD simulation, which benefit the selection of suitable ILs and the recovery of ILs from coagulation bath in the spinning process. [Display omitted] • An in-situ method to observe the behaviors of cellulose in ILs-H 2 O was established. • Suitable swelling and dissolving parameters provide a new idea for the spinning process. • Interaction between cellulose, IL and H 2 O were calculated by MD simulations. • Underlying swelling and dissolution molecular mechanism of cellulose was proposed. Swelling and dissolution of cellulose in ionic liquids (ILs) as the pretreatment processes are key steps for the high-value conversion and utilization of cellulose. However, the molar ratio of H 2 O to ILs has a significant effect on the swelling and dissolution of cellulose, and its molecular-scale mechanism is still unclear, which limits screening out the suitable ILs and recovery of ILs from coagulation bath in the spinning process. Herein, three phosphate-based ILs were chosen to couple with water as solvents for swelling and dissolution of cellulose by combining in-situ observation and molecular dynamics (MD) simulation. The results show that the redissolution time of swollen cellulose is greatly reduced, especially [Emim]DEP-H 2 O has the best swelling and dissolution performance for cellulose due to its high β value and low viscosity. Meanwhile, when the molar ratio of IL to H 2 O was more than 1: -1, the IL-H 2 O system still has the ability to dissolve cellulose. While with the molar ratio further decreased, cellulose was no longer dissolved and began to swell, and the fiber diameter obtained the maximum swelling rate with 40.1% at a molar ratio of 1:3. Moreover, MD simulation was used to calculate the interaction between IL/water/cellulose, which further illustrated that the combination of IL with water molecular has a significant influence on the behavior of cellulose in IL-H 2 O systems at the molecular scale. Thus, the potential swelling and dissolution mechanism of cellulose in ILs-H 2 O binary systems was proposed based on experimental and simulation results. Furthermore, the characterization results of swollen cellulose indicate that the crystal structure and degree of polymerization (DP) were almost unchanged, but the specific surface area and pore size increased significantly, and the thermal stability and heat absorption were decreased, all the results prove that the swelling process increased the accessibility of cellulose and benefited to the subsequent dissolution. Consequently, preferable swelling and dissolving parameters of experiments and simulations will provide a new idea for the selection of suitable ILs and the recovery of ILs from a coagulation bath in the dry-wet spinning process. [ABSTRACT FROM AUTHOR]

[Display omitted] • Highest oil yield (28.67 %) achieved with ethyl acetate as sole solvent, 1:6 seed to solvent ratio, and 50 °C extraction. • 1-Butyl-3-methylimidazolium acetate improved oil yield by 3–6 % regardless of ionic liquid mass. • Presence of ionic liquid co-solvent lowered extraction temperature while maintaining oil yield. • Extraction followed second-order kinetic model with rate constant of 0.0133 min−1. The extraction of oil from Balanites seed (desert date) using ultrasound-assisted extraction was investigated using organic solvent (ethyl acetate) and ionic liquid as co-solvent. The study found that an optimum oil yield of 28.67 % was obtained using a seed to solvent ratio of 1:6, an extraction temperature of 50 °C and an extraction time of 30 min when ethyl acetate was used as the sole solvent in the extraction system. Different types of ionic liquids as co-solvents were screened in this study and an improvement of oil yield (3–6 %) was observed using 1-butyl-3-methylimidazolium acetate. Additionally, the presence of ionic liquid as a co-solvent during the extraction process could achieve a similar oil yield at a lower extraction temperature. This indicates the potential breakdown of the lignocellulosic cell wall of the seed using 1-butyl-3-methylimidazolium acetate. The presence of 1-butyl-3-methylimidazolium acetate as co-solvent can enhance the penetration of the organic solvent into the Balanites seed matrix for oil extraction and can reduce the energy required for the extraction process. [ABSTRACT FROM AUTHOR]

[Display omitted] • Hydration influences the structure of the electric double layer, affecting ion density on electrode surfaces. • Hydration optimizes gravimetric energy density. • Positive ions are more concentrated on graphene electrodes compared to graphyne. This study systematically analyzes the structural properties of the ionic liquids 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim][BF 4 ]) and choline-glycine ([cho][gly]) to evaluate hydration effects on their electrical properties in supercapacitors with graphene or graphyne electrodes. The research examines how hydration impacts the electric window, total capacitance and gravimetric energy density of the devices. The goal is to enhance energy storage performance through innovative materials, focusing on sustainable, eco-friendly technologies. Results show that hydration influences the structure of the Electric Double Layer (EDL), with water molecules affecting ion mass density on the surface of the electrodes. Positive ion concentration is higher in graphene electrodes compared to graphyne. The study projects gravimetric energy density and energy efficiency based on potential difference and hydration level, highlighting the critical role of hydration in optimizing supercapacitor electrical properties and industrial application opportunities. [ABSTRACT FROM AUTHOR]

• The aromatic compounds are generally removed by catalytic hydro-dearomatization (HDA) procedure. • The HDA has high energy consumption and limited effectiveness in removing certain aromatic species. • This review focused on the selective liquid–liquid extraction method using Ionic and deep eutectic solvents. • The factors affecting the absorption capacity of these solvents are analyzed. • The optimization of the ionic liquids and deep eutectic solvents is reviewed. The catalytic hydro-dearomatization (HDA) procedure is generally used in industry to remove aromatic compounds from fossil fuels. However, high energy consumption and limited effectiveness in removing certain aromatic species are two crucial limitations of the method. To dissolve these problems and improve the procedure's effectiveness, in this study, we focused on the selective liquid–liquid extraction method using Ionic and deep eutectic solvents (DESs) solvents. As DESs originate from natural sources and can be tailored to specific characteristics, they are widely considered in green chemistry and economically and ecologically sustainable reagents for various chemical and environmental applications. This review focuses on recent studies on the simultaneous extraction of sulfur and nitrogen compounds by Ionic and DES solvents, aiming to provide a comprehensive understanding of DES extraction processes and to identify new research directions in this field. [ABSTRACT FROM AUTHOR]

[Display omitted] • Research of ILs with high cellulose solubility and low degradation for spinning. • Reveal the difference of microscopic process of cellulose bunch dissolving in four ILs via molecular dynamics simulation. • Use DFT calculations to analyze hydrogen bond strength to reflect the degree of cellulose degradation by different ILs. Ionic liquids (ILs) as green solvents have been utilized in dissolving cellulose and fabricating regenerated cellulose fibers. Imidazolium-based ILs with acetate or phosphate anions present advantage, due to the low viscosity and melting point, as well as its excellent ability to form hydrogen bonds (H-bonds) with the hydroxyl groups of cellulose chains. In this work, the microscopic dissolution processes of a cellulose bunch in four ILs were reproduced via molecular dynamics (MD) simulations. The cellulose bunch dissolution capabilities of these four ILs are [Emim][OAc] > [Emim][DMP] > [Emim][DEP] > [Bmim][DMP], as verified through in-situ polarized optical microscope. It is important to note that cellulose may degrade in some ILs during dissolution, affecting the performance of regenerated cellulose, while the underlying mechanism is unclear, and the strength of H-bonds formed between ILs and cellulose chains can reflect their degradation strength Combined with density functional theory (DFT) calculations, the H-bonds formed between different anions and cellulose hydroxyl groups were analyzed in depth and the order of H-bond strength is [OAc]− > [DEP]− > [DMP]−, which is different from the dissolution order of cellulose bunch in [Emim][DEP] and [Emim][DMP]. Further analysis revealed that the difference in diffusion coefficients leads to faster dissolution of cellulose in [Emim][DMP]. This study elucidates the dissolution and degradation processes of cellulose in ILs at the molecular level, offering theoretical insights crucial for the development of novel ILs that are efficient in the process of cellulose spinning. [ABSTRACT FROM AUTHOR]

• A novel method for synthesis of benzimidazolone using ionic liquid as a catalyst without solvent. • Employed carbon dioxide as an environmentally friendly carbonyl source, reducing reliance on hazardous chemicals. • Identified an ionic liquid that significantly enhances reaction yield and selectivity. • Provided detailed mechanistic studies elucidating the role of the ionic liquid in the reaction. • Demonstrated a sustainable and reusable catalytic system up to six run that aligns with green chemistry principles. In this study, we report synthesis of benzimidazolones from o-phenylene diamine by utilizing carbon dioxide as a carbonyl source under mild reaction conditions in the presence of ionic liquid as a catalyst. Six bifunctional protonic ionic liquids (PILs) were synthesised by reacting superbases 1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) and 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU) with proton donors such as Trifluoroethanol (TFE), Cyclopropane carboxylic acid (CPCA) and 2,2,2-Trifluoroacetic acid (TFA). Among them, [TBDH+][TFE−] was the most effective, achieving high conversion rates of o-phenylene diamine to 2-benzimidazolone at 1 bar CO 2 pressure and 60° C. This PIL could be reused for up to six cycles. Our method offers a green and efficient approach for producing 2-benzimidazolone derivatives, with potential applications in pharmaceuticals and materials science. [ABSTRACT FROM AUTHOR]

The performance of an electric double-layer capacitor is strongly influenced by the choice of electrolyte, and the use of ionic liquid (IL) mixtures as an electrolyte has shown great promise. In this study, a model IL made of a mixture of anions and size-polydisperse cations in equal numbers and confined between two electrodes is investigated by means of molecular dynamics simulations. In particular, using the extent of size-polydispersity (characterized by polydispersity index, δ) as a control parameter, we systematically explore its effect on the local structure, charge profile, ion size distribution in the vicinity of electrode surfaces, and differential capacitance. It is observed that the charge density profiles near cathode, i.e., region comprising both Stern and diffused layers, are significantly affected under the variation of δ in addition to the electrode charge density. Ion population, ordering of different-size cations, and its effective size in the vicinity of electrodes under neutral and applied potential conditions are also quantified. An interesting observation is that the effective cation size in the Stern layer decreases with increasing value of δ in the case of moderate to strong electrode surface charge density. This behaviour can be qualitatively understood from the interplay of enthalpic and entropic forces in the system. Finally, a non-monotomic dependence of capacitance on δ is observed with maximum value of capacitance at a rather small value of δ (≈ 3 %) for the model system. • Effect of ion size-polydispersity in a model ionic liquid. • Polydispersity affects the morphology of Stern layer. • Entropy-enthalpy competition drives ion size selection. • Non-monotonic dependence of capacitance on polydispersity. [ABSTRACT FROM AUTHOR]

[Display omitted] • The phosphorus and sulfur free protic ionic liquid have been successfully synthesized. • The synthesized protic ionic liquids as water-based lubricants were observed to significantly reduce the coefficient of friction and the wear volume. • The protic ionic liquid also possess excellent anti-corrosion properties. • The system is suitable for different load ranges, sliding speed ranges and types of alcohol. Three kinds of P and S-free 1,8-Diazabicyclo[5.4.0] undec-7-ene water-soluble protic ionic liquids (PILs) were successfully synthesized and applied as additives in water-1,2-Propylene glycol (PG). The physicochemical properties of PILs and the anti-friction, anti-wear and anti-corrosion properties were investigated. Research results demonstrated that the addition PILs lubricant additive could greatly improve the tribological properties of water-1,2-PG. The addition of 5 wt% PILs with long alkyl chain will result in the reduction of friction coefficient and wear volume by about 45 % and 95 %, respectively. Meanwhile, the PILs with long-chain show more effect lubrication behavior than the short one. In addition, the obtained PILs also possess excellent anti-corrosion properties as water-based lubrication additives. The elemental analysis of the contact area showed that the PILs would generate a chemical reaction film during the friction process, and the carboxylate anion could form a chemical and physical adsorption film on the surface of contact area, which would provide better anti-friction and anti-wear properties. [ABSTRACT FROM AUTHOR]

[Display omitted] • Lab scale and industrial scale plastic oils were tested under pin on disk setup. • Aromatic structures in plastic oil reduced the friction and wear significantly. • [P6,6,614][Sacc] ionic liquid (IL) was used as a novel additive to Plastic oils. • IL increased viscosity, film thickness and tribofilm formation ability of blends. • 2 % ionic liquid additive, reduced the friction upto 50 % and wear upto 75 %. Improper disposal of waste plastic contributes significantly to environmental pollution. A promising solution to address this issue involves converting such plastics into valuable lubricating oils. This study investigated the tribological performance of both an aromatic-lean industrial plastic oil (PO) and aromatic-rich lab-scale plastic oils (LPO) using a ball-on-disk setup. The results revealed that PO exhibited considerably higher coefficients of friction (COF) and specific wear rates compared to LPO. To enhance the lubrication performance, a bio-based ionic liquid (IL: trihexyltetradecyl phosphonium saccharinate) with an unsaturated anion was incorporated. The COF and wear rates were further reduced with an IL blend in both PO and LPO. The IL additive promoted increased film thickness, beneficial micelle formation, facilitated adsorption film formation, and provided a phosphorus-rich tribofilm. These mechanisms collectively contributed to the notable improvement in tribological performance. Overall, this research demonstrates the potential of IL additives to enhance the tribological performance of both PO and LPO, thereby mitigating waste plastic pollution, and fostering a sustainable future. [ABSTRACT FROM AUTHOR]

In the field of non-linear Optics, the additivity rule, which both experimental and theoretical researchers utilize, provides a simple and reliable method for calculating polarizability. However, this model neglects crucial factors, such as the solvent, the interaction distance, and external optical fields, leading to inaccurate results. In this study, the role of these parameters on the non-linear optical behavior of the ionic liquid BMIM+⋯BF 4 − , a system extensively studied for its intriguing non-linear optical properties, is investigated. To do that, first-principles calculations based on the density functional theory are developed; the Lennard-Jones potential is used as the reference model. The results of this study reveal the significant influence of the solvent on the second- and third-order non-linear optical responses, which are strongly affected by ion interactions, underscoring the limitations of the additivity rule in terms of molecular polarizability. The EFISHG values for each solvent are inversely proportional to the dielectric constant; for all considered solvents, it observed a clear dependence of polarizability values on the external field, ranging from 1.675 to 1.638× 10−23 esu. It was also found high sensitivity of the static polarizability to changes in the interaction distance and the solvent choice, ranging from 1.57 to 2.05× 10−30 esu, while considering the additivity rule, this parameter changed to 1.59× 10−30 esu. This information can serve as a reference for both theoretical and experimental researchers. • Theoretical study based on density functional theory. • Evaluation of the additive rule of the polarizability and the NLO properties. • Analysis of the effects of solvents and external fields on the first, second, and third hyperpolarizability. [ABSTRACT FROM AUTHOR]

[Display omitted] • ILs improve safety, biodegradability, efficiency, and sustainability of extraction of Ag and Au. • Most published reports and best extraction efficiency of Ag and Au were achieved using imidazolium-based ILs. • Weakest extraction efficiency result from utilizing phosphonium-based ILs. • The mechanism of Au and Ag extraction by ILs are ion exchange and ion pairing. • The combination of microwave extraction, green sorbents, and greening the metal recovery step are recommended prospects. The traditional methods for extraction of the two precious metals, gold and silver, from different sources, including ore, environmental water, and metallic water, entail the use of dangerous chemicals and the production of plenty of harmful wastes. Thus, the emerging use of ionic liquids for gold and silver extraction offers many merits, such as high recovery efficiency, safety, limited waste production, time efficiency, and environmental friendliness. Also, the recyclability of ionic liquids overcomes their cost and makes them a cost-effective choice. This review presents the uses of ionic liquids for the extraction and purification of gold and silver from ores, leachates, and different secondary sources. An overview of gold and silver, their sources, and their uses in modern technologies are addressed. A discussion of ionic liquids, their properties, safety, and greenness profile is also presented. An inclusive summary of the published research focusing on the utilization of ionic liquids for the retrieval of gold and silver is presented, as well as the advantages of using ionic liquids. Approximately 60 and 65 % of the ionic liquids applied for Au(III) and Ag(I) extraction, respectively, are imidazolium-based ionic liquids. Imidazolium-based ionic liquids showed the best performance as extractants, while phosphonium-based ionic liquids have the weakest extraction efficiency. [ABSTRACT FROM AUTHOR]

• A novel guanidine salt ionic liquid ([DIETMG][NTf 2 ]) was synthesized, and its gold extraction capacity was 295.7 mg·g-1. • The system avoids using organic diluents. • The extraction mechanism is anion exchange mechanism. • The extraction process is spontaneous, accompanied by heat release and entropy reduction. • The system exhibited satisfactory selectivity and reusability. As gold is a non-renewable resource, it holds both economic and environmental importance to enhance the recycling of precious metal waste from secondary resources. Herein, a guanidine salt ionic liquid ([DIETMG][NTf 2 ]) with low water solubility and viscosity was synthesized by molecular design of guanidine salt ionic liquid with good biocompatibility and biodegradability, and a solvent-free system of [DIETMG][NTf 2 ]-water was constructed to extract Au(Ⅲ). The findings reveal that the extraction efficiency of Au(Ⅲ) can reach 97.57 % under optimal extraction conditions. Further thermodynamic and kinetic studies revealed that the reaction process is spontaneous and exothermic, with the extraction rate being primarily controlled by interfacial chemical reactions. The system demonstrates remarkable selectivity for Au(Ⅲ) in solutions containing a mix of various metal ions. Finally, ascorbic acid (Vc) was employed as a stripping agent to obtain gold at room temperature. After 8 cycles, [DIETMG][NTf 2 ] still achieved a 90% extraction efficiency. This study provides a new idea and method for recovery of gold from secondary resources. [ABSTRACT FROM AUTHOR]

[Display omitted] • This review focused on natural analogs consisting of 1,3-benzodioxole motif. • The anticancer potential and mechanism of action of 1,3-benzodioxole motif discussed. • 1,3-benzodioxole motif and ionic liquids based on 1,3-benzodioxole motif discussed. • Anticancer activity of 1,3-benzodioxole motif-based ionic liquids discussed. Cancer treatment remains challenging despite advancements in the field of medical science. Traditional therapies such as chemotherapy, surgery, and radiation have limitations in terms of high costs and adverse side effects. To address this issue, researchers are exploring innovative approaches that can provide effective cancer treatment with minimal side effects. In literature, various natural and synthetic compounds containing 1,3-benzodioxole scaffolds have shown effective anticancer activities. Due to the unique and tunable properties of ionic liquids, they have attracted researchers for the treatment of several cancers while minimizing harm to healthy tissues. The incorporation of the 1,3-benzodioxole scaffold with other organic compounds in the form of ionic liquid enhanced their therapeutic potential. This review aims to provide a comprehensive overview of the recent progress in the development of 1,3-benzodioxole-based ionic liquids. The review encompasses a detailed synthesis protocol, computational studies, and different spectroscopic approaches including UV–visible, fluorescence, and Circular Dichroism spectroscopy. Furthermore, it encompasses in-vitro studies, collectively representing a potentially transformative strategy to address the limitations associated with conventional drugs. Additionally, it underscores an emerging research domain with significant implications for the future of oncology. [ABSTRACT FROM AUTHOR]

[Display omitted] • The increase in the alkyl chain of PILs can alter their physicochemical properties. • The PILs with shorter alkyl chains would lead to better lubrication performance. • From Q-MS, the degradation species mainly came from cations during friction. • The shorter-chain PILs exhibit stronger intermolecular forces. • Extending the chain of PILs can lower the pour points, making it widely applicable. Since the lubrication performances of ionic liquids are closely linked to their unique structures, four protic ionic liquids (PILs), [N 44 HH][DEHP], [N 444 H][DEHP], [N 448 H][DEHP] and [N 4412 H][DEHP], are designed to investigate the effect of cationic structures on the lubrication behaviors and lubrication mechanisms. Vacuum tribological tests were carried out to minimize the impact of the atmospheric environment. The structure–activity relationships and lubrication mechanisms of PILs were emphatically examined by in-situ quadrupole mass spectrometer (Q-MS) and XPS analyses. Results demonstrated that all four PILs exhibited outstanding lubrication performance under a vacuum condition. Unusually, extended alkyl chain cationic structures resulted in a changed lubrication mechanism, leading to a slight decrease in performance. In-situ Q-MS analyses and XPS further revealed that the length of the alkyl chain in cations influenced the strength of intermolecular forces in PILs, leading to changes in their lubrication performance and mechanisms. [ABSTRACT FROM AUTHOR]

• The density, viscosity, and excess volume of three alkanolammonium-based PILs were measured and modeled. • VFT and Redlich-Kister models accurately described viscosity and excess volume. • The synthesized PILs showed greater thermal stability in relation to similar PILs with smaller anion carbon chain length. Alkanolammonium ionic liquids such as (2-hydroxyethyl)ammonium hexanoate ([2HEA][Hex]), bis(2-hydroxyethyl)ammonium hexanoate ([BHEA][Hex]), and tris(2-hydroxyethyl)ammonium hexanoate ([THEA][Hex]) were synthesized and characterized by 1H NMR and FTIR, respectively. The thermophysical properties such as density, viscosity, and thermal stability of all alkanolammonium ionic liquids were measured at several temperatures and 0.1 MPa. The excess molar volumes for binary mixtures of alkanolammonium ionic liquids + water at temperatures between 298.15 K and 343.15 K were also determined over the entire composition range. The excess molar volumes were correlated with the Redlich-Kister equation with average absolute deviations smaller than 0.0164. The viscosities of pure alkanolammonium ionic liquids were regressed using two models: the Ostwald-de Waele relationship and the Vogel-Fulcher-Tammann equation. The influence of the degradation mechanism on thermal stability was examined by thermogravimetry. The results showed a degradation stage above 100 °C for all alkanolammonium ionic liquids. The impact of cation and anion carbon numbers on the thermophysical properties of alkanolammonium ionic liquids is discussed. [ABSTRACT FROM AUTHOR]

• Six alkali alkanoate ionic liquids were synthetized and fully structurally and thermal–physically characterized. • Five of the prepared ionic liquids exhibited solid-liquid transition enthalpies ranging from 119.0 J/g to 197.2 J/g at mid-to-high temperatures. • [Na][MeOC 2 ], [K][MeOC 2 ], [Na][MeOC 4 ] and, [K][MeOC 4 ] ionic liquids have showed excellent thermal stability above 380 °C. • [Na][MeOC2], [K][MeOC2], [Na][MeOC4] passed the cyclability test for category F (RAL-GZ 896) with no notable ΔH loses, <3%. • Prepared ILs could be competitive with sugar alcohols and inorganic salts used as PCMs in the mid-to-high temperature range. Thermal energy storage is gaining much attention and experiencing a renascence in last years. In this sense, storing thermal energy in form of latent heat is of special interest due higher energy density, lower energy losses and higher energy efficiency. To store thermal energy as latent heat the presence of a phase change material (PCM) is needed and its performance the key for its implementation in a thermal energy storage (TES) system and the temperature at which the phase change takes place, low (<150 °C) or high (>150 °C) temperature, will condition the application of a given PCM. In this context, the development of PCM materials to store latent heat at mid-to-high temperature in between 150 °C and 350 °C is of special interest e.g., in the field of concentrated solar power or heat recovery. There are already some solid–liquid phase change materials working in this range of temperature e.g., sugar alcohols, aromatic organic compound, inorganic salts, or blend of inorganic salts but all of them present different drawbacks, such as vapor pressure, degradation, low thermal conductivity, corrosion, etc. In consequence, there is a need to explore new PCM materials in this range of temperature applications. In this context, ionic liquids could play a key role in the development of novel PCMs due to their intrinsic properties. Indeed, ILs are gaining increased attention in the field of thermal energy storage in the last years but mainly in the low temperature range (<150 °C) remaining their application in the mid-to-high temperature range in between 150 °C and 350 °C underestimated. In this work, we prepared six different alkali alkanoate ionic liquids, namely [Na][MeOC 2 ], [K][MeOC 2 ], [Na][MeOC 3 ], [K][MeOC 3 ], [Na][MeOC 4 ] and, [K][MeOC 4 ] by direct reaction between the desired methyl methoxycarboxylate ester with NaOH or KOH. The prepared ionic liquids were structurally characterized, and their thermal–physical properties evaluated. Five of them but [K][MeOC 3 ] showed good enthalpy values ranging from 119 J/g to 197 J/g and four of them [Na][MeOC 2 ], [K][MeOC 2 ], [Na][MeOC 4 ] and, [K][MeOC 4 ] have showed excellent thermal stability above 380 °C. In addition, these four ionic liquids have successfully passed the cyclability test showing no significant enthalpy losses (between 0 % minimum and 7 % maximum) after 50 heating/cooling cycles compiling with the cycling category F of the RAL-GZ 896 (Quality Association PCM). All in all, these prepared ionic liquids surpass sugar alcohols in terms of cyclability and thermal stability and are comparable with the inorganic salts e.g. NaNO 3 employed in the studied range of mid-to-high temperature (150–350 °C). [ABSTRACT FROM AUTHOR]

[Display omitted] • Zwitterionic and vinyl imidazolium ILs with anions of 7 acids are studied. • Their thermal properties and conductivity are reported and analysed. • The effect of the cation on the properties of ILs are discussed. In this paper, we present employing our own and literature data the results of investigation of the thermal behavior and ion transport properties of vinyl and alkyl imidazolium zwitterions containing an alkane sulfonic acid group and salts on their basis. For comparison, we present the results of investigation the respective vinyl and alkyl imidazolium ILs without these functional groups. The phase behavior of zwitterionic and vinyl imidazolium ionic liquids is studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). [ABSTRACT FROM AUTHOR]

• An overview of the history of non-stoichiometric PILs (NSPILs) is given in this first review of NSPILs. • NSPILs, as a variation of PILs, are formed by the combination of neat PILs with an excess of the (precursor) acids or bases. • The unique properties of NSPILs lie in the interaction between neat salts and excess acids or bases and the ion structures. • The applications of NSPILs in various fields are discussed systematically. • An outlook of the development of NSPILs is given. Protic ionic liquids (PILs) have a set of properties that make them interesting candidates for many applications including energy storage and conversion, gas absorption, biological applications and organic synthesis. Compared to stoichiometric (neat) PILs, non-stoichiometric PILs are formed by the combination of neat PILs with an excess of the (precursor) acids or bases, which is generally ignored by many researchers and there are only limited studies. Non-stoichiometric PILs have a variety of specific physicochemical properties, which are likely caused by the unique interaction between neat salts and excess acids or bases and in some cases by particular anion structures. In this first review of non-stoichiometric PILs, we briefly discuss the history of PIL development and how non-stoichiometric PILs differ in properties. An analysis of the physicochemical properties of non-stoichiometric PILs is presented and their application in various fields is discussed. Finally, we give a prospect on the development of non-stoichiometric PILs including conceivable future challenges. [ABSTRACT FROM AUTHOR]

[Display omitted] • A DAB18C6-ILs mixed system was synthesized for a high-efficient extraction of Cs+. • The system displayed a high %E Cs (99.94 %), β Cs/K (1216.7) and β Cs/Rb (139.03). • A high stability of the mixed system is ascribed to the hydrogen bond interaction. • The complex of DAB18C6 with Cs+ showed a low hydration binding energy and high selectivity. • DAB18C6-Cs+-[NTF 2 ]− as the most stable structure formed is based on cation exchange. Efficient extraction of Cs+ from aqueous solution was investigated by liquid–liquid extraction based on ionic liquids (ILs). In this study, Di(aminobenzo)-18-crown-6 (DAB18C6) was used as the extractant and three ILs (1-butyl-3-methylimidazolium hexafluorophosphate ([C 4 mim][PF 6 ]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([C 6 mim][PF 6 ]), and 1-butyl-3-methylimidazolium bis-trifluoromethyl sulfonamide ([C 4 mim][NTf 2 ])) were employed as co-extractants in the construction of a liquid–liquid extraction system for efficient and selective extraction of Cs+ from aqueous solutions. It was demonstrated that the DAB18C6-[C 4 mim][NTf 2 ] mixed solvent system at 0.12 mol/L DAB18C6, a mass ratio of ILs/CHCl 3 of 1:4 and a volumetric ratio of O/A of 1:1 exhibited a high % extraction of Cs+ up to 99.94 %, with a higher selectivity for Cs+ relative to coexisting ions such as K+ (β Cs/K = 1216.7) and Rb+ (β Cs/Rb = 139.03). The high selectivity of the extraction system for Cs+ was attributed to the lower hydration binding energy of Cs+ (−366.51 kJ/mol) and the stronger interaction between DAB18C6 and Cs+, g(r) = 12.7. Further, the hydrogen bonding interaction between the amino crown ether and ionic liquid increases the viscosity and surface tension of the extraction system, thus enhancing the stability of the system. Noteworthy, the most stable structure formed by DAB18C6-Cs+-[NTF 2 ]− is attributed to cation exchange. In summary, this study demonstrates the great potential for efficient separation and extraction of cesium from aqueous solutions. [ABSTRACT FROM AUTHOR]

[Display omitted] • Cl−-water halogen bonds enable the Zn2+ structural diffusion. • Halogen bonds reduce the Zn2+ de-solvation energy barrier. • Accelerated ions diffusion enhance the Zn anode reversibility. Despite their low cost and intrinsic safety, aqueous rechargeable zinc-ion batteries suffer from rapid performance deterioration originating from parasitic reactions and inhomogeneous deposition on the Zn anode. Halogen bonds share similarities with hydrogen bonds, yet their unique directionality, strength tunability, and hydrophobicity provide a promising approach for enhancing the reversibility of Zn anodes. Herein, a systematic comparison of ionic liquids with different anions, acetate (Ac−) and chloride (Cl−), is performed to explore the non-covalent interactions in regulating ion solvation and dynamic behaviors of electrolytes. Different from the Ac− possessing a strong capacity to form hydrogen bonds with water, the Cl−-water halogen bonds not only enable the structural diffusion of Zn2+ with better diffusion efficiency but also reduce the Zn2+ de-solvation energy barrier to promote uniform Zn nucleation. Consequently, the accelerated ions diffusion and homogeneous Zn deposition work in synergy to ensure high reversibility of Zn anode. These fundamental insights highlight the importance of hydrogen and halogen bonds in determining the dynamics and electrochemical behavior of electrolytes, providing theoretical guidance for the rational design of high-performance electrolytes. [ABSTRACT FROM AUTHOR]

• Ionic liquids exert a distinct effect on coal dust wettability from conventional surfactants. • Chain length and adsorption mode of ionic liquids dominate the coal dust wettability. • The long-chain can penetrate pores of coal dust, serving as a bridge to electrostatically attract water molecules. • Ionic liquids reduce coal dust surface energy to quickly balance polar and non-polar interactions, improving wettability. The wettability of bituminous coal is critical for the coal dust suppression and can be apparently modulated by ionic liquids. However, the modulation mechanism still remains elusive. Here, a combination of macroscopic experiments, mesoscopic characterization, and microscopic simulations (quantum mechanics and molecular dynamics) are leveraged to parse the effect on the wettability of coal dust surfaces of three novel ionic liquids ([C 12 MIm]Br, [BMIm]Br, [BMIm]Cl) featuring the varying chain lengths and anions in the coal-water system. The results show that the selected ionic liquids exert a distinct bridging function from traditional surfactants which invoke the hydrogen bonding interaction. This ionic liquids-mediated bridging mechanism heavily depends on their chain length structure, which can firstly penetrate deeply the internal pores of coal dusts and then adsorb on the coal surfaces to rapidly strike a dynamic equilibrium. Ionic liquids interacting with coal dust can primarily reduce the energy difference between polar and nonpolar interactions within coal dust, thereby enhancing the electrostatic interactions between coal dust and water molecules and effectively improving coal dust wetting properties. These findings provide a theoretical basis for the rational design of high-performance ionic liquids for coal mine dust control. [ABSTRACT FROM AUTHOR]

• The article summarises the corrosion inhibition ability of different imidazole-based ionic liquids on mild steel and carbon steel. • Different studies employed for corrosion inhibition were given: Electrochemical techniques, Surface morphology, spectroscopic methods, etc. • Theoretical studies like DFT and MD/MC simulations were also explained to confirm the inhibitor's adsorption. • The article also explains how imidazole-based ionic liquids are better than other non-aromatic ionic liquids. Corrosion refers to the degradation of materials caused by exposure of materials to the corrosive environment. The toxicity of some of the synthesised chemical compounds used as inhibitors has initiated the search for eco-friendly inhibitors. Primary goal of this review is to endorse the development of greener corrosion inhibitors and the study of ionic liquids as a viable alternative to chemical inhibitors. Ionic liquids are biodegradable, less volatile, non-inflammable, and less toxic and can be used as inhibitors to protect various metals and alloys from corrosion. Ionic liquids adsorb at the interface of metal and electrolyte. Adsorption of ionic liquids on metals and alloys creates a barrier that prevents corrosion. Ionic liquids are used in a variety of environments to prevent corrosion. This review of imidazolium-based ionic liquids as corrosion inhibitors provides a systematic evaluation of their inhibiting properties against mild steel/carbon steel corrosion. The electrochemical study of different ionic liquids, along with their inhibition efficiencies, are reported in this review. The adsorption of the ionic liquid onto the metal surface was characterised by various techniques such as spectroscopic, surface morphology and theoretical studies. From various reported literature, it is clear that as the increase in the number of hetero atoms, mainly halogens, increases inhibition efficiency of the ionic liquid, inhibition efficiency was also found to increase with the increase in the hydrocarbon chain length. The significant adsorption of the ionic liquid on the metal surface was studied by Monte Carlo simulation and the Molecular dynamics simulation. This review also discusses the scope of research in using imidazolium based ionic liquids as an effective corrosion inhibition of steels. [ABSTRACT FROM AUTHOR]

[Display omitted] • Measurements of the LLE data of aqueous two-phase systems: ionic liquid + sodium citrate + water, at 298.1 K. • First time in which the [BMIM][OH] ionic liquid was used and studied in an aqueous two-phase system. • Sigma profiles and interaction energies of ionic liquids predicted by COSMO-RS. • Thermodynamic modeling and phase stability using the NRTL model. • Data consistency by quality tests using mass balance and mixture Gibbs energy curves. Liquid-liquid extraction has long been the preferred option for process engineers to develop separation processes and it is used to separate and purify various biological products, metallic ions, colorants, pharmaceutical molecules, and small organic species. Ionic liquids (ILs) are special ecological solvents that can be used as possible substitutes for traditional organic solvents used for extraction and separation processes, becoming them more sustainable and safer. In combination with salts or inorganic polymers, they can form a liquid system of two phases, advantageous due to its wide polarity and viscosity. In this scenario, liquid–liquid equilibrium (LLE) data and phase diagrams for new aqueous two-phase systems containing ionic liquid ([BMIM][OH], [BMIM][Cl], [BMIM][Br]) (1) + sodium citrate (2) + water (3) were determined experimentally at 298.15 K. The ionic liquids were synthesized and characterized in the first part of the study. COSMO-RS was used as a tool to calculate polarity graphs of study molecules. In the second part, liquid–liquid equilibrium was studied using experimental measurements of the binodal curve and tie-lines, testing the quality of experimental data by mass balance, thermodynamic modeling using the NRTL model to correlate liquid–liquid equilibrium data and to do their phase stability. The accuracy of the model data results was verified by Gibbs energy topological mixing surface analysis and σ profiles. The experimental results indicated that the studied systems had type I liquid–liquid phase behavior. It was demonstrated that the ionic liquid [BMIM][OH] demonstrated better behavior to form Aqueous Two-Phase Systems mixed with sodium citrate and water. The results obtained by the thermodynamic modeling and stability with NRTL model weren't satisfactory, because, besides the low deviations for the liquid phases compositions, the majority of calculated tie-lines was not tangent with the Gibbs surface, showing the limitations of the model for systems with electrolytes. [ABSTRACT FROM AUTHOR]

• The interaction between IL and PET plays a decisive role in the glycolysis of PET. • The relative interface adhesion between IL and PET was measured by AFM and LFM. • A novel method for screening efficient IL catalysts is proposed. Ionic liquids (ILs) have been recognized as environmentally friendly and effective catalysts for poly (ethylene terephthalate) (PET) glycolysis. However, further investigation is required to gain a deeper understanding of the depolymerization mechanism. In this study, a series of experiments are conducted to investigate the impact of metallic and non-metallic ILs, containing diverse anions, on the interaction with PET surfaces. The findings indicate that the catalytic efficiency of IL is strongly correlated to the intensity of the interaction with PET. When the interface adhesion strength is more than twice that of PET/PET, the IL exhibits efficient catalytic properties in PET glycolysis. Therefore, an innovative approach involving the use of AFM for efficiently assessing highly effective IL catalysts is proposed. In addition, attenuated total reflectance Fourier transform-infrared (ATR-FTIR) spectroscopy and density functional theory (DFT) calculations further demonstrate the predominant interaction mechanism between ILs and PET. This research provides guiding significance for understanding the mechanism of PET glycolysis. [ABSTRACT FROM AUTHOR]

[Display omitted] • Synthesized and characterized SAILs based on mono- and dicationic imidazolium ions. • Ether moieties in SAILs enhanced micellization compared to commercial surfactants. • SAILs with the longest alkyl chain spacer showed the highest biological activity. • These SAILs act as effective antimicrobial and surface-active agents. A series of 16 imidazolium-based surface-active ionic liquids (SAILs) were synthesized. The designed SAILs, consisted of either one amphiphilic center, 3-alkoxymethyl-1-benzylimidazolium or 3-alkoxymethyl-1-benzyl-2-methylimidazolium, and two amphiphilic centers, 3,3′-[α,ω-(dioxaalkane)]bis(1-benzylimidazolium) or 3,3′-[α,ω-(dioxaalkane)]bis(1-benzyl-2-methylimidazolium). These compounds were investigated in terms of thermal analysis, ability to self-organize to micelles, and antimicrobial activity. The insertion of an ether moiety in the alkyl side or spacer chain favored adsorption at the air–water interface and micellization in the bulk solution when compared to commercial chloride surfactants. The results showed that attachment of a methyl group to the imidazolium ring led to lower the critical micelle concentration (CMC) than lengthening the alkyl chain or spacer in the imidazolium cation. Additionally, biological activity increased with increasing hydrophobicity of the compounds. The methylation of the imidazole ring at positions 2 and 2′ yielded in a notable increase in bacteriostatic activity, especially against Gram-positive bacteria, notably the Staphylococcus aureus strains. It has been demonstrated that minor structural modifications, specifically substituting the imidazole ring instead of elongating the alkyl chain or spacer, can modify the micellization and aggregation behavior, leading to differences in both the efficacy and variety of antimicrobial activity of amphiphilic SAILs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Imidazolium based monotopic compounds derived from amino acids were synthetized. • Easily to tune their physicochemical and macromolecular properties, improving pharmacological properties. • Good cancer cell growth inhibition against different cancer cell lines have been observed. • High degree of selectivity against healthy cells under acidic pH conditions. • Accumulation of the ionic liquid on the cellular membrane and on lysosomes or autophagosomes. A set of fourteen imidazolium ionic liquids, each derived from L -amino acids and featuring distinct hydrophobic and hydrophilic components, were synthesized and physicochemically characterized. Thermal analysis showed transition temperatures remaining below 100 °C, being the rigid solid to elastic solid transition temperatures between −27 °C to + 57 °C. The aggregation studies investigated by fluorescence in water and buffered media showed two critical micellar concentrations (CMC) in aqueous media for compounds 7 , 8 and 9 , with the formation of well-defined aggregates in the second step. The synthesized ILs were assessed for their effects on two cancer cell lines, namely human lung adenocarcinoma A-549 and colon adenocarcinoma HT-29, under both physiological and acidic pH conditions. Furthermore, the influence of the ILs on embryonic kidney cells (HEK-293) was investigated to assess their effect on non-cancerous cells. This study demonstrates that the manipulation of various design vectors allowed for the precise tuning of the structure of ILs, resulting in IC 50 values within the micromolar range. ILs featuring a NC12 alkyl side chain in the amide consistently exhibited low IC 50 values and a high degree of selectivity against non-tumoral cells under acidic pH conditions. Subsequent investigations were carried out to gain insights into the cellular-level mechanisms of action. These findings provide strong evidence that by meticulously adjusting the molecular structure of these functionalized ILs, it is possible to design potent and selective chemotherapeutic agents. [ABSTRACT FROM AUTHOR]

[Display omitted] • Evaporation of [BuMIm+][Cl-](l) is accompanied by thermolysis and C2-methylation to form in situ new ion pairs. • At a low rate of thermolysis the pressures and the enthalpy of evaporation of [BuMIm+][Cl-] ion pairs are determined. • The suppression of [BuMIm+][Cl-] evaporation is a consequence of an increase involvement of ion pairs in side reactions. • The priority and possible directions of reactions involving ion pairs were revealed using quantum chemical calculations. The evaporation and thermal decomposition (thermolysis) of 1-butyl-3-methylimidazolium chloride ionic liquid, [BuMIm][Cl](l), were studied in the temperature range of 373–463 K by thermogravimetry–mass spectrometry (TG–MS) and Knudsen cell mass spectrometry (KCMS) methods. The saturated vapor pressures and the enthalpy of vaporization of [BuMIm][Cl](l) were determined within 373–398 K, where the thermolysis of this ionic liquid occurs via the S N 2 mechanism at a low rate. With increasing temperature, the thermolysis becomes more extensive, which is accompanied by the C2-methylation of [BuMIm][Cl](l). The resulting ion pairs [BuMMIm+][Cl-] are thermally unstable and decomposed. A decrease in the vapor pressure of the ion pairs [BuMIm+][Cl-] at a constant temperature takes place due to side reactions, resulting in the suppression of the evaporation. Complex ionic compounds were found in the thermolysis/evaporation residues using atmospheric pressure chemical ionization (APCI) and matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) methods. The priority and possible pathways of reactions involving ion pairs and the thermolysis products were established by quantum chemical calculations. [ABSTRACT FROM AUTHOR]

[Display omitted] • Change in the polarity of the medium leads to solubilization in micellar systems. • The aggregation patterns of surface active ionic liquid (SAIL) and surfactant (SDS) differ. • Imidazolium cation of BMImOS reduces repulsion between polar head groups, facilitating SAIL micellization. • Imidazolium cation of BMImOS and BMImBr serves as a quencher, leading to a reduction in emission intensity. • BMImBr with the least surface activity prefers to exist as an AR-BMImBr salt-like ion pair. The investigation was conducted on the interaction of acridine red (AR) with sodium dodecyl sulfate (SDS) and 1-butyl-3-methyl imidazolium octyl sulfate (BMImOS) in both premicellar and post micellar concentrations. The interaction between AR and room temperature ionic liquid (RTIL) 1-butyl-3-methyl imidazolium bromide (BMImBr) was studied to understand the effect of imidazolium cation on micellization. Spectroscopic experiments, such as UV–visible absorption spectroscopy, steady-state fluorescence spectroscopy, time-resolved fluorescence spectroscopy, and dynamic light scattering, have been introduced. Various important parameters like spectral shifts, anisotropy, and aggregation number have been determined spectroscopically. However, a fresh insight into density functional theory calculations has also been provided. The observed results have been explained in terms of the aggregation behavior of the amphiphiles. A prominent redshift accompanied by a change in intensity is observed in the presence of surfactant and SAIL. However, in the case of BMImBr, no such spectral shift has been observed; only a decrease in spectral intensity highlights the quenching ability of the imidazolium cation. Average lifetime also provides some additional information regarding the difference in the formation of aggregates by SDS and BMImOS, which is further established from particle size density obtained from DLS. The salt like role of 1-butyl-3-methyl imidazolium cation also has been logically explained by anisotropy measurement and the determination of aggregation number. Using Gauss View 5.0 and Gaussian 09 package, the energy of optimization of each set of amphiphiles along with dye has been determined to follow the interaction at the molecular level. TDDFT calculations have also been performed to determine the structure of HOMO and LUMO. [ABSTRACT FROM AUTHOR]

[Display omitted] • DNA maintains the B-conformation after interacting with ILs ([bmim]Cl and [omim]Cl). • ILs induce unwinding and softening of DNA. • ILs binding to DNA surface reduce DNA torsional stiffness and twist-stretch coupling. • ILs reduce Na+ and water binding on DNA and take part in the solvation process of DNA. The functions of DNA are related to its mechanical properties, including elasticity and conformational transitions. Ionic liquids, known as green solvents, are used for DNA separation and as a solvent medium for long-term DNA storage. This paper elucidated DNA interaction mechanisms with two imidazolium-based ionic liquids: 1-butyl-3-methylimi-dazolium chloride ([bmim]Cl) and 1-octyl-3-methylimidazolium chloride ([omim]Cl), via magnetic tweezers, bulk techniques and molecular dynamic simulation (MD). By stretching and twisting individual DNA molecules, we measured the elasticity of DNA in the presence of ILs ([bmim]Cl and [omim]Cl). As results, the persistence length, stretch modulus, torsional stiffness and twist-stretch coupling exhibited a significant decrease compared to the DNA without ILs binding. Isothermal titration calorimetry analysis indicated that the ILs in the presence of DNA were thermodynamically favored driven by enthalpy and entropy. DNA underwent size transition and conformational change induced by ILs, and the charges of DNA were neutralized by the added ILs. The binding of ILs induced unwinding and softening of DNA. Circular dichroism spectra and MD results indicated that DNA maintained B-conformation after interacting with ILs. Compared to [bmim]+, [omim]+ showed stronger binding affinity to DNA and tended to aggregate on the DNA surface. ILs binding reduced Na+ and water binding on DNA, which likely prevented the hydrolytic reactions that denatured DNA and helped stabilize DNA for the long term. This research provides a critical theoretical foundation for the utilization of ionic liquids in life sciences. [ABSTRACT FROM AUTHOR]

• The IL safety issues and risks were focused on through digestive tract pathway. • It is the first report for ILs permeation on porcine gastric and intestine membranes. • Transdermal behavior was investigated in both acidic and alkaline environments. • It is feasible for montmorillonite to adsorb residual ionic liquid in gastric juice. • The detoxification with adsorption has guiding significance for clinical research. Considering the controversial safety and risk solutions of ionic liquids (ILs), more essential basic researches are required as their applied fields become broader and applied scale grows larger. Under this background, the permeation behaviors of six common imidazole ILs on porcine gastric and enteric membranes together with the feasibility of their removal by adsorption with montmorillonite were investigated in vitro. Through the single-factor investigation of different cations, anions and ionic liquid concentrations, the current results show that the IL of 1-ethyl-3-methylimidazolium bromide ([Emim]Br) has the strongest permeation capacity on the gastric membrane during the tests. The cumulative permeation amount of Q n can reach 0.72 mg/cm2, and the cumulative permeation percentage alsoreaches 95.77 %; the whole permeation process conforms to the Hixcon-Crowell model. As comparison, the maximum cumulative penetration percentage of [Emim]Br on enteric member was determined as 89.11 %, and related models was also compared. In order to remove the potential IL in digestive tract, montmorillonite was screened out from those popularily used antidotes in clinic and the adsorption of [Emim]Br in gastric fluid by montmorillonite has been proved more consistent with the second-order kinetics and Langmuir model. The results of molecular simulation, infrared spectrum (IR), X-ray diffraction (XRD) and thermogravimetric (TG) characterization exhibit that [Emim]Br has been successfully adsorbed into the interlayer of montmorillonite. As a whole, the study provided a scientific and effective way to diminish the hidden danger of ionic liquid entering the blood through the digestive system. [ABSTRACT FROM AUTHOR]

[Display omitted] • Significance and current state of affairs in ionic liquids (ILs), Deep Eutectic solvent (DESs), and their structure–property relationship. • Recent developments and application of ILs and DESs in drug delivery systems. • Physiological toxicity of ILs and DESs. • The significance of block copolymer nanostructures in drug delivery and the current status of their development. • Role and emergence of block copolymers and their self-assembly within ILs and DESs media and the current state of affairs. In the past decades, deep eutectic solvents (DESs) and ionic liquids (ILs) have garnered significant interest in various disciplines of the chemical, physical and biological sciences as task-oriented (designer) and emerging "green" solvent substitutes to the hazardous and volatile organic solvents. The physicochemical properties of these green designer solvents are precisely customizable by tuning the structures of their constituents for a particular application. These unique substances have shown enormous application potentials in several interdisciplinary research fields, like, catalysis, synthesis, biocatalysis, separation and extraction, biomolecular dissolution and stability, nanoscience, pharmaceutics, and drug delivery. Furthermore, block copolymers (BCPs) self-assembled nanostructures such as vesicles, micelles, microemulsions, polymersomes, etc. formed within different solvent media have attracted various researchers around the world owing to their immense potential for application in several domains of science and technology including drug delivery, photonic material, data storage, etc. This review highlights current advancements in the self-assembly of BCPs forming nanostructures within green designer solvent media like ILs and DESs. Additionally, it also gives an overview of applications of ILs, DESs, and external stimuli-responsive BCP within ILs and DESs, as drug delivery vehicles. This review will further enhance the potential utility of these unique materials (so-called designer solvents) and will help researchers design novel ILs and DESs for suitable applications including polymer science, nanoscience, pharmaceutics, drug delivery, etc. [ABSTRACT FROM AUTHOR]