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An efficient method for prediction in the capture of SO2 from flue gas by imidazolium ionic liquids was reported, where the concentration of SO2 is 2000 ppm. On the basis of quantitative calculations through a combination of Langmuir simulation, theoretical calculation and quantum chemical method, SO2 absorption and desorption performance from flue gas by twelve kinds of imidazolium ionic liquids with different anions were designed and predicted. Then, among them, five kinds of imidazolium ionic liquids were chosen and prepared to investigate their behavior of SO2 absorption capacity, desorption residue, and available absorption capacity. The results indicated that the experimental values were in good agreement with the predicted values. Thus, an ideal ionic liquid [Emim][Tetz] was obtained through the predictive method for the capture of SO2 of 2000 ppm, which showed high available absorption capacity of 0.24 g SO2 per g ionic liquid and excellent reversibility.

Following the initial cation formation, the synthesis of ionic liquids (ILs) often involves an anion-exchange or metathesis reaction. For hydrophobic ILs, this is generally performed through several cross-current contacts of the IL with a fresh salt solution of the desired anion. However, if a large number of contacts is required to attain an adequate conversion, this procedure is not economical because of the large excess of the reagent that is consumed. In this study, the metathesis of an IL, Aliquat 336 or [A336][Cl], to ILs with other anions ([A336][X] with X = HSO4–, Br–, NO3–, I–, and SCN–) was studied in a continuous counter-current mixer-settler setup. McCabe–Thiele diagrams were constructed to estimate the required number of stages for quantitative conversion. Significantly higher IL conversions were achieved, combined with reduced reagent consumption and waste production. This improvement in efficiency was most pronounced for anions placed low in the Hofmeister series, for example, HSO4–, Br–, and NO3–, which are difficult to exchange. The performance of the counter-current experiments was compared with the conventional multistep cross-current batch process by calculating the reaction mass efficiency (RME) and the environmental factor (E-factor). The RMEs of the cross-current experiments were notably smaller, that is, 38–78% of the values observed for the counter-current experiments. The E-factors of the counter-current experiments were a factor of 2.0–6.8 smaller than those of the cross-current experiments. These sustainability metrics indicate a highly efficient reagent use and a considerable, simultaneous decrease in waste production for the counter-current IL metathesis reactions., A counter-current flow diagram facilitates the efficient metathesis of ionic liquids and allows for a high conversion with minimal reagent consumption.

Phosphonium ionic liquids with orthoborate anions have been studied in terms of their interfacial film formation, both physisorbed and sacrificial from chemical breakdown, in sheared contacts of varying harshness. The halogen-free anion architecture was varied through (i) the heteronuclear ring size, (ii) the hybridisation of the constituent atoms, and (iii) the addition of aryl functionalities. Time of Flight-Secondary Ion Mass Spectrometry analysis revealed the extent of sacrificial tribofilm formation allowing the relative stability of the ionic liquids under tribological conditions to be determined and their breakdown mechanisms to be compared to simple thermal decomposition. Overall, ionic liquids outperformed reference oils as lubricants; in some cases, sacrificial films were formed (with anion breakdown a necessary precursor to phosphonium cation decomposition) while in other cases, a protective, self-assembly lubricant layer or hybrid film was formed. The salicylate-based anion was the most chemically stable and decomposed only slightly even under the harshest conditions. It was further found that surface topography influenced the degree of breakdown through enhanced material transport and replenishment. This work thus unveils the relationship between ionic liquid composition and structure, and the ensuing inter- and intra-molecular interactions and chemical stability, and demonstrates the intrinsic tuneability of an ionic liquid lubrication technology.

Cryopreservation has facilitated considerable advances in both medical technology and scientific research. However, further developments have been limited by the relatively low number of effective cryoprotective agents. Even after fifty years of research, most protocols rely on the same two toxic agents, i.e. dimethylsulfoxide or glycerol. Ionic liquids are a class of promising solvents which are known glass formers and may offer a less-toxic alternative. The research presented here investigates ten protic ionic liquids as potential cryoprotective agents. The liquids are screened for key properties including cellular toxicity, permeability and thermal behaviour. The most promising, ethylammonium acetate, was then tested as a cryoprotective agent on a model cell line and was found to be as effective as the common cryoprotectant, dimethylsulfoxide. This work reports the first use of a protic ionic liquid as an effective cryoprotective agent for a mammalian cell line. This will inform the development of a suite of potential new ionic liquid-based cryoprotectants that could potentially allow the cryopreservation of new cell types.

The advance of space technology is deeply affected by the breakthrough of high-performance fuels. Hypergolic ionic liquids (HILs) are one of the most potential fuels for bipropellant systems. However, high viscosity value and low specific impulse of traditional N-based HILs limit their application. Recently, boron-based HILs with low viscosity become the new candidates, and their derivatives are also found to promote the hypergolicity as additives in HILs. Here, the synthesis, physical chemical properties and thermal performance of boron-based HILs and HIL-additive system are reviewed.

International audience; For the first time, the possibility of obtaining porous germanium from both single-crystal and polycrystalline starting materials using environmentally friendly (in contrast to the commonly used HF and HCl) imidazolium ionic liquids (IL) was shown. It was demonstrated that pore formation depended significantly on the viscosity of the IL, on the etching current density and etching time, and on defects and imperfections of the substrate surface. By varying these parameters, the rates of two competing processes - formation and growth of pores and electropolishing - could be adjusted, consequently allowing germanium with a various structured surface, including a porous surface. In particular, using a more viscous IL (for example, [BMIM][PF6] versus [BMIM][BF4]) made it possible to reduce the rate of dissolution of the germanium dioxide surface layer; as a result, the formation and growth of pores became a dominant process. At the same time, the dissolution rate of the already formed porous layer (electropolishing) increased with the etching current density and the number of defects and imperfections of the germanium surface.

We developed a new hybrid material resulting from an innovative supramolecular tripartite association between an ionic liquid covalently immobilized on primary β-cyclodextrins rim and an anionic water-soluble polymer. Two hydrophilic ternary complexes based on native and permethylated β-cyclodextrins substituted with an ionic liquid and immobilized on poly(styrene sulfonate) (CD-IL+PSS− and CD(OMe)IL+PSS−) were obtained by simple dialysis with a cyclodextrin maximal grafting rate of 25% and 20% on the polymer, respectively. These polyelectrolytes are based on electrostatic interactions between the opposite charges of the imidazolium cation of the ionic liquid and the poly(styrene sulfonate) anion. The inclusion properties of the free cavities of the cyclodextrins and the synergic effect of the polymeric matrix were studied with three reference guests such as phenolphthalein, p-nitrophenol, and 2-anilinonaphthalene-6-sulfonic acid using UV-visible, fluorescent, and NMR spectroscopies. The support has been applied successfully in dialysis device to extract and concentrated aromatic model molecule. This simple and flexible synthetic strategy opens the way to new hybrid materials useful for fast and low-cost ecofriendly extraction techniques relevant for green analytical chemistry.

Lithium metal batteries are gaining increasing attention due to their potential for significantly higher theoretical energy density than conventional lithium ion batteries. Here, we present a novel mechanochemical modification method for lithium metal anodes, involving roll-pressing the lithium metal foil in contact with ionic liquid-based solutions, enabling the formation of an artificial solid electrolyte interphase with favorable properties such as an improved lithium ion transport and, most importantly, the suppression of dendrite growth, allowing homogeneous electrodeposition/-dissolution using conventional and highly conductive room temperature alkyl carbonate-based electrolytes. As a result, stable cycling in symmetrical Li∥Li cells is achieved even at a high current density of 10 mA cm–2. Furthermore, the rate capability and the capacity retention in NMC∥Li cells are significantly improved.

The ionoSolv process is one of the most promising technologies for biomass pretreatment in a biorefinery context. In order to evaluate the transition of the ionoSolv pretreatment of biomass from bench-scale experiments to commercial scale, there is a need to get better insight in process intensification. In this work, the effects of biomass loading, particle size, pulp washing protocols and 100-fold scale up for the pretreatment of the grassy biomass Miscanthus giganteus with the IL triethylammonium hydrogen sulfate, [TEA][HSO4], are presented as a necessary step in that direction. At the bench scale, increasing biomass loading from 10 to 50 wt% reduced glucose yields from 68 to 23% due to re-precipitation of lignin onto the pulp surface. Omitting the pulp air-drying step maintained saccharification yields at 66% at 50 wt% loading due to reduced fiber hornification. 100-fold scale-up (from 10 mL to 1 L) improved the efficacy of ionoSolv pretreatment and increasing loadings from 10 to 20 wt% reduced lignin reprecipitation and led to higher glucose yields due to the improved heat and mass transfer caused by efficient slurry mixing in the reactor. Pretreatment of particle sizes of 1–3 mm was more effective than fine powders (0.18–0.85 mm) giving higher glucose yields due to reduced surface area available for lignin re-precipitation while reducing grinding energy needs. Stirred ionoSolv pretreatment showed great potential for industrialization and further process intensification after optimization of the pretreatment conditions (temperature, residence time, stirring speed), particle size and biomass loading. Pulp washing protocols need further improvement to reduce the incidence of lignin precipitation and the water requirements of lignin washing.

trans,trans-Muconic acid has been widely used as a biomarker in biological monitoring of benzene-exposed workers during routine occupational health services. In the present study, a novel microextraction technique, in-syringe ionic liquid-dispersive liquid-liquid microextraction, was implemented for preconcentration of trans,trans-muconic acid followed by analytical determination by high-performance liquid chromatography with ultraviolet detection. Moreover, the important variables affecting the performance of applied microextraction technique including needle diameter, volume of the spiked sample, volume of the ionic liquid, salt addition, rotation speed of centrifugation, centrifuge time, and ultrasonic time were optimized by experimental design. A good linear relationship was observed at the range of 0.032-10 μg/mL between the peak area and the concentration levels (R2 = 0.9997). The limit of detection and extraction recovery for trans,trans-muconic acid were 0.011 μg/mL and >96.2%, respectively. This method provided easy and rapid analysis of low amounts of trans,trans-muconic acid in human urine with simple equipment.

An effective process to remove nitrogen-based compounds from fossil fuels without harming the process of sulfur removal is an actual gap in refineries. A success combination of desulfurization and denitrogenation processes capable of completely removing the most environmental contaminates in diesel under sustainable conditions was achieved in this work, applying polyoxometalates as catalysts, hydrogen peroxide as oxidant, and an immiscible ionic liquid as an extraction solvent. The developed process based in simultaneous oxidative desulfurization (ODS) and oxidative denitrogenation (ODN) involved initial extraction of sulfur and nitrogen compounds followed by catalytic oxidation. Keggin-type polyoxomolybdates revealed much higher reusing capacity than the related polyoxotungstate. Effectively, the first catalysts practically allowed complete sulfur and nitrogen removal only in 1 h of reaction and for ten consecutive cycles, maintaining the original catalyst and ionic liquid samples.

The most important developments in solvent-based fluid separations, separations involving at least one fluid phase, are reviewed. After a brief introduction and discussion on general solvent trends observed in all fields of application, several specific fields are discussed. Important solvent trends include replacement of traditional molecular solvents by ionic liquids and deep eutectic solvents and, more recently, increasing discussion around bio-based solvents in some application fields. Furthermore, stimuli-responsive systems are discussed; the most significant developments in this field are seen for CO2-switchable and redox-responsive solvents. Discussed fields of application include hydrocarbons separations, carbon capture, biorefineries, and metals separations. For all but the hydrocarbons separations, newly reported electrochemically mediated separations seem to offer exciting new windows of opportunities.

As green solvents, ionic liquids (ILs) are quite suitable for the absorption of volatile organic compounds (VOCs) such as benzene and its homologues. However, solvent selection is the key to the VOC absorption process. In the present study, a rapid solvent screening tool, Conductor-like Screening Model for Real Solvents (COSMO-RS), was used to predict the solubility of toluene in 816 ILs. The effects of four structure characters, namely, the type and alkyl chain length of the cations and anions on the solubility of toluene were discussed. The following conclusions were drawn from the results: (1) ILs with pyrrolidinium-based cations showed better solubility than pyridinium- and imidazolium-based ones. (2) The solubility of toluene in PF6-based ILs increased with the increasing alkyl chain length, while its solubility in Ac-based ILs exhibited the opposite trend. (3) Toluene showed greater solubility in Cl-based ILs than those based on other anions. (4) The solubility of toluene increased with the anion alkyl chain length. Ac-based ILs were chosen as the most promising potential solvents, and further studied to determine the relationship between various interaction energy parameters and toluene solubility. The results showed that the misfit energy played a dominant role during the absorption process. Furthermore, several ILs were selected for experimental verification of the predicted solubility behavior using liquid and gaseous toluene. The results demonstrated that COSMO-RS could be used to semi-quantitatively and qualitatively predict the solubility of toluene, and this model had promising prospects in screening ILs for VOCs absorption. In summary, this study provided a fundamental basis and practical data for the control and treatment of VOCs.

Proteins generally tend to aggregate with less desirable properties in numerous solvents, which is one of the major challenges in the development of solvents for functional proteins. This work aims to utilize fluorescence spectroscopy and small angle X-ray scattering (SAXS) to understand the effects of ionic liquids (ILs) on the fluorescence and aggregation behavior of superfolder green fluorescent protein (sfGFP). The studied ILs consisted of four different anions coupled with primary, tertiary and quaternary ammonium cations. The results show that the chromophore fluorescence was generally maintained in 1 mol% IL-water mixtures, then decreased with increasing IL concentration. We primarily employed the pseudo-radius of gyration (pseudo-Rg) to evaluate sfGFP aggregation. The sfGFP was less aggregated with nitrate-based ILs compared to in buffer, and more aggregated in the mesylate-based ILs. Further, we show that the polyol additives of glycerol and glucose in IL-water mixtures slightly decreased the sfGFP propensity to aggregate. Size-exclusion chromatography (SEC)-SAXS was used to characterize the monomeric sfGFP in ethylammonium nitrate (EAN) and triethylammonium mesylate (TEAMs)-water mixtures. The presence of 1 mol% TEAMs maintained the sfGFP fluorescence, promoted the compact structure, but slightly increased the amount of large aggregates, which contrasted with that of EAN.

Ionic liquids (ILs) have shown excellent performance in the separation of binary azeotropes through extractive distillation [1]. But the role of the ionic liquid in azeotropic system is not well understood. In this paper, COSMO-RS model was applied to screen an appropriate IL to separate the binary azeotrope of ethyl acetate (EA) and ethanol and 1-octyl-3-methylimidazolium tetrafluoroborate ([OMIM][BF4]) was selected. The Quantum Mechanics (QM) calculations and molecular dynamics (MD) simulation are performed to study the interactions between the solvent molecules and [OMIM][BF4], in order to investigate the separation mechanism at the molecular level. The nature of the interactions is studied through the reduced density gradient (RDG) function and quantum theory of Atom in Molecule (QTAIM). Hydrogen bonds and van der Waals interactions are the key interactions in the complexes. The results of MD simulations indicate that the introduction of ILs has a prominent effect on the interaction between the solvent molecules, especially on reducing the number of hydrogen bonds among the solvent molecules. The radial distribution function (RDF) reveals that the interaction between the cation and solvent molecules will increase while the concentration of ILs increases. This paper provides important information for understanding the role of ILs in the separation of the azeotropic system, which is valuable to the development of new entrainers. National Key R&D Program of China (2018YFB0604900); National Natural Science Foundation of China (No. 21878219); Natural Sciences and Engineering Research Council (NSERC) of Canada (RGPIN-4903-2014); China Scholarship Council (No. 201500090106)

1,5-Pentanediamine (PDA) produced by biological fermentation becomes popular, but the separation of PDA from the broth is a typical difficult problem. In this work, the performance of 200 ionic liquids (ILs), formed by combining 25 cations and 8 anions, in the extraction of PDA from aqueous solution were evaluated using COSMO-RS model. The extraction mechanism was investigated with the help of σ-profile and interaction energy analyses. Both the cation and anion have impacts on the extraction efficiency, where cation mainly influences the interaction of IL with PDA and anion affects the hydrophobicity of IL. The IL composed of long alkyl-chain in cation and the anion of [PF6]- or [TF2N]-, which has the σ-profile more likely distributed in the nonpolar region but less distributed in the polar region, is favorable for extraction. The experimental liquid–liquid equilibrium demonstrated the effects of cation and anion on extraction performance, which validated the reliability of COSMO-RS model in IL screening for PDA extraction. The IL [IM-1,8][PF6] could serve as a promising extractant for the downstream separation process of the biological production of PDA.

In the process of liquid–liquid extraction, it is necessary to look for green solvents as extractants. Ionic liquids have been studied as extractants due to their green recyclability in recent years. The infinite dilution activity coefficients of 100 ionic liquids with a combination of 10 cations and 10 anions were calculated by COSMO-SAC model, and the σ-profiles were plotted. The distribution coefficient and separation coefficient of n-heptane + tert-butanol + ILs were determined. [OMIM] [OTF], [HMIM] [OTF] and [BMIM] [OTF] were selected as solvents for this study. The interaction energy, bond length and charge density of ionic liquids with tert-butanol were calculated by quantum chemistry calculation method. According to these results, the rationality of selected ionic liquids as extractants could be analyzed from the molecular level. At 298.15 K and 101.325 kPa, the liquid–liquid equilibrium data of the ternary system {n-heptane + tert-butanol + [OMIM] [OTF], n-heptane + tert-butanol + [BMIM] [OTF], n-heptane + tert-butanol + [HMIM] [OTF]}) were measured. The distribution coefficient and separation coefficient for judging the extraction effect were obtained. The NRTL model was used to correlate liquid–liquid equilibrium experimental data, and correlation result proved that the correlated and experimental data had a good correlation. The research on ionic liquids is of great significance to the development of green and sustainable chemical industry.

High-temperature molten salt research is undergoing somewhat of a renaissance these days due to the apparent advantage of these systems in areas related to clean and sustainable energy harvesting and transfer. In many ways, this is a mature field with decades if not already a century of outstanding work devoted to it. Yet, much of this work was done with pioneering experimental and computational setups that lack the current day capabilities of synchrotrons and high-performance-computing systems resulting in deeply entrenched results in the literature that when carefully inspected may require revision. Yet, in other cases, access to isotopically substituted ions make those pioneering studies very unique and prohibitively expensive to carry out nowadays. There are many review articles on molten salts, some of them cited in this perspective, that are simply outstanding and we dare not try to outdo those. Instead, having worked for almost a couple of decades already on their low-temperature relatives, the ionic liquids, this is the perspective article that some of the authors would have wanted to read when embarking on their research journey on high-temperature molten salts. We hope that this will serve as a simple guide to those expanding from research on ionic liquids to molten salts and vice versa, particularly, when looking into their bulk structural features. The article does not aim at being comprehensive but instead focuses on selected topics such as short- and intermediate-range order, the constraints on force field requirements, and other details that make the high- and low-temperature ionic melts in some ways similar but in others diametrically opposite.

Ionic liquids are composed of an organic cation and a highly delocalized perfluorinated anion, which remain tight to each other and neutral across the extended liquid framework. Here we show that n-alkanes in millimolar amounts enable a sufficient ion charge separation to release the innate acidity of the ionic liquid and catalyze the industrially relevant alkylation of phenol, after generating homogeneous, self-stabilized, and surfactant-free microdroplets (1–5 μm). This extremely mild and simple protocol circumvents any external additive or potential ionic liquid degradation and can be extended to water, which spontaneously generates microdroplets (ca. 3 μm) and catalyzes Brönsted rather than Lewis acid reactions. These results open new avenues not only in the use of ionic liquids as acid catalysts/solvents but also in the preparation of surfactant-free, well-defined ionic liquid microemulsions., R.G. thanks the ITQ and Severo Ochoa program for the concession of a fellowship. M.A.R.-C. thanks MINECO for the concession of an FPU fellowship. We thank Prof. Hans–Peter Steinrück, Dr. Florian Maier, and Bettina Heller for fruitful discussions and José M. Coll–Marqués for performing the microfluorescence measurements.

N‐alkyl‐N‐alkyl pyrrolidinium‐based ionic liquids (ILs) are promising candidates as non‐flammable plasticizers for lowering the operation temperature of poly(ethylene oxide) (PEO)‐based solid polymer electrolytes (SPEs), but they present limitations in terms of lithium‐ion transport, such as a much lower lithium transference number. Thus, a pyrrolidinium cation was prepared with an oligo(ethylene oxide) substituent with seven repeating units. We show, by a combination of experimental characterizations and simulations, that the cation's solvating properties allow faster lithium‐ion transport than alkyl‐substituted analogues when incorporated in SPEs. This proceeds not only by accelerating the conduction modes of PEO, but also by enabling new conduction modes linked to the solvation of lithium by a single IL cation. This, combined with favorable interfacial properties versus lithium metal, leads to significantly improved performance on lithium‐metal polymer batteries., Ionic liquids (ILs) allow improvement of the ionic conductivity of ternary PEO‐based solid polymer electrolytes. However, the lack of Li‐ion coordination of these plasticizers and the addition of extra ions results in a low Li‐ion conductivity. An oligo(ethylene oxide)‐based IL was synthesized to overcome these limitations and enable additional transport modes, resulting in a high Li‐ion conductivity.

Altres ajuts: acords transformatius de la UAB The application of molecular switches for the fabrication of multistimuli-responsive chromic materials and devices still remains a challenge because of the restrictions imposed by the supporting solid matrices where these compounds must be incorporated: they often critically affect the chromic response as well as limit the type and nature of external stimuli that can be applied. In this work, we propose the use of ionogels to overcome these constraints, as they provide a soft, fluidic, transparent, thermally stable, and ionic-conductive environment where molecular switches preserve their solution-like properties and can be exposed to a number of different stimuli. By exploiting this strategy, we herein pioneer the preparation of nitrospiropyran-based materials using a single solid platform that exhibit optimal photo-, halo-, thermo-, and electrochromic switching behaviors.

To determine the trace amount of four benzoic acid esters in cosmetics, ionic dispersive liquid–liquid microextraction (DLLME) and magnetic solid-phase extraction were combined and optimized. After solvent optimization, 1-octyl-3-methylimidazolium hexafluorophosphate was selected as the extraction solvent to form hydrophobic droplets in the process of ionic DLLME, followed by removal of ions from the sample solution containing Fe3O4@GO nano-materials. The magnetic nano-materials were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and vibrating sample magnetometer. Some parameters affecting the efficiency of extraction were optimized using Box-Behnken design. Under optimized conditions, the limit of detection for all the preservatives was less than 0.135 mg/L and the accuracy ranged from 88.5% to 101%. This technology could determine the trace amount of preservatives in cosmetics with comparatively higher accuracy and sensitivity.

Cationic glycopolymers with structures similar to those of typical poly(ionic liquid)s (PILs) were synthesized via the quaternization reaction of poly(4-vinyl pyridine) with halogen-functionalized d-mannose and tetraphenylethylene units. Such postpolymerization modification provided PILs with aggregation-induced emission effect as well as specific carbohydrate-protein recognition with lectins such as concanavalin A. The interactions between cationic glycopolymers and different microorganisms, including Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli, were used for the killing, imaging, and detection of bacteria. Besides, these sugar-containing PILs showed a relatively low hemolysis rate due to the presence of saccharide units, which may have potential application in the field of biomaterials.

Chemotherapeutic cytotoxic agents such as paclitaxel (PTX) are considered essential for the treatment of various cancers. However, PTX injection is associated with severe systemic side effects and high rates of patient noncompliance. Micelle formulations (MFs) are nano-drug delivery systems that offer a solution to these problems. Herein, we report an advantageous carrier for the transdermal delivery of PTX comprising a new MF that consists of two biocompatible surfactants: cholinium oleate ([Cho][Ole]), which is a surface-active ionic liquid (SAIL), and sorbitan monolaurate (Span-20). A solubility assessment confirmed that PTX was readily solubilized in the SAIL-based micelles via multipoint hydrogen bonding and cation-π and π-π interactions between PTX and SAIL[Cho][Ole]. Dynamic light scattering (DLS) and transmission electron microscopy revealed that in the presence of PTX, the MF formed spherical PTX-loaded micelles that were well-distributed in the range 8.7-25.3 nm. According to DLS, the sizes and size distributions of the micelle droplets did not change significantly over the entire storage period, attesting to their physical stability. In vitro transdermal assessments using a Franz diffusion cell revealed that the MF absorbed PTX 4 times more effectively than a Tween 80-based formulation and 6 times more effectively than an ethanol-based formulation. In vitro and in vivo skin irritation tests revealed that the new carrier had a negligible toxicity profile compared with a conventional ionic liquid-based carrier. Based on these findings, we believe that the SAIL[Cho][Ole]-based MF has potential as a biocompatible nanocarrier for the effective transdermal delivery of poorly soluble chemotherapeutics such as PTX.

In this work, we show how the structure and intermolecular interactions affect the dynamic heterogeneity of aprotic ionic liquids. Using calorimetric data for 30 ionic samples, we examine the influence of the strength of van der Waals and Coulombic interactions on dynamic heterogeneity. We show that the dynamic length scale of spatially heterogeneous dynamics decreases significantly with decreasing intermolecular distances. Additionally, we assume that the magnitude of the number of dynamically correlated molecules at the liquid-glass transition temperature can be treated as an indicator for a dynamical crossover.

Green solvents such as ionic liquids (ILs) unlock possibilities for developing innovative biomedical and pharmaceutical solutions. ILs are the most investigated solvents for compound extractions, as reaction media and/or catalysts, and a desired eco-friendly solvent to process biomacromolecules for biomaterial production. Investigations demonstrate that the tunable nature and physicochemical features of ILs are also beneficial for building up delivery systems through their combination with bioactive compounds. Bioactive compounds from synthetic origins, like ibuprofen, ketoprofen, and natural sources such as curcumin, flavonoids, and polyphenols are essential starting points as preventive and therapeutic agents for treating diseases. Therefore, the association of those compounds with ILs opens up windows of opportunities in this research field. This Review assesses some of the main and important recent information and the current challenges concerning delivery platforms based on ILs combined with bioactive compounds of both natural and synthetic origins. Moreover, the chemistry, bioavailability, and biological functions of the main bioactive compounds used in the ILs-based delivery platforms are described. These data are presented and are discussed, together with the main delivery routes of the systems., The authors especially acknowledge Portuguese FCT’s financial support (PD/BD/135247/2017 and CEECIND/ 01306/2018). This work was also financially supported by a PhD programme in Advanced Therapies for Health (PATH) (PD/00169/2013); FCT R&D&I projects with references PTDC/BII-BIO/31570/2017, R&D&I Structured Projects with reference NORTE-01−0145-FDER-000021; BREAST-IT FCT-Portugal project to SCK (PTDC/BTM-ORG/28168/ 2017), and European Union Framework Programme for Research and Innovation Horizon 2020, under Grant Agreement No. 668983. FoReCaST to SCK and RLR.

Solvents are an inevitable part of industries. They are widely used in manufacturing and processing industries. Despite the numerous controlling measures taken, solvents contaminate our environment to a vast extent. Green and sustainable solvents have been a matter of growing interest within the research community over the past few years due to the increasing environmental concerns. Solvents are categorized as “green” based on their nonvolatility, nonflammability, availability, biodegradability and so on. The use of ionic liquids, super critical carbon dioxide and aqueous solvents for the fabrication of polymer composites is discussed in this review. The progress of utilizing solvent-free approaches for polymer composite preparation and efforts to produce new biobased solvents are also summarized.

Epigallocatechin gallate (EGCG), the main polyphenolic substance in tea, exhibits well-known biological benefits. In order to improve fat solubility and bioavailability, a novel path for the lipase enzymatic transesterification synthesis of acylated EGCG derivatives in an ionic liquid solvent was established. The optimal reaction parameters were determined and a maximum conversion of the transesterification reaction was achieved at 98.65%. [Bmim][BF4] was the best reaction medium and the immobilized lipase Novozym 435 was the best catalyst. The enzyme was added to a final concentration of 2% (w/w, EGCG), and the reaction was performed at an optimum temperature of 70°C stirring for 10 h at 250 rpm. The most suitable acyl donor, vinyl acetate, and EGCG were mixed at a molar ratio of 90:1 for the reaction. The structure of the purified acetylated EGCG was determined to be 5″-O-acetyl-EGCG and 3″, 5″-2-O-acetyl-EGCG by mass spectrometry, NMR, and infrared analyses.

The absorption of CO2 is of importance in carbon capture, utilization, and storage technology for greenhouse gas control. In the present work, we clarified the mechanism of how metal-based ionic liquids (MBILs), Bmim[XCln]m (X is the metal atom), enhance the CO2 absorption capacity of ILs via performing molecular dynamics simulations. The sparse hydrogen bond interaction network constructed by CO2 and MBILs was identified through the radial distribution function and interaction energy of CO2-ion pairs, which increase the absorption capacity of CO2 in MBILs. Then, the dynamical properties including residence time and self-diffusion coefficient confirmed that MBILs could also promote the diffusion process of CO2 in ILs. That's to say, the MBILs can enhance the CO2 absorption capacity and the diffusive ability simultaneously. Based on the analysis of structural, energetic and dynamical properties, the CO2 absorption capacity of MBILs increases in the order Cl− → [ZnCl4]2−→ [CuCl4]2−→ [CrCl4]− → [FeCl4]−, revealing the fact that the short metal–Cl bond length and small anion volume could facilitate the performance of CO2 absorbing process. These findings show that the metal–Cl bond length and effective volume of the anion can be the effective factors to regulate the CO2 absorption process, which can also shed light on the rational molecular design of MBILs for CO2 capture and other key chemical engineering processes, such as IL-based gas sensors, nano-electrical devices and so on.

Ionic liquids (ILs) are molten salts composed of a large organic cation and an organic/inorganic anion. Due to their ionic character, most ILs present advantageous properties over conventional solvents, such as negligible volatility at atmospheric conditions and high thermal and chemical stabilities. The wide variety of IL anion–cation combinations allows these solvents to be designed to display a strong solvation ability for a myriad of active pharmaceutical ingredients (APIs) and (bio)polymers. Given these properties, ILs have been used as solvents and as formulation components in different areas of drug delivery, as well as novel liquid forms of APIs (API-ILs) applied in different stages of development of novel drug delivery systems. Furthermore, their combination with polymers and biopolymers has enabled the design of drug delivery systems for new therapeutic routes of administration.

Utilization of carbon dioxide (CO2) is of great significance in the development of CO2 absorption and the solution of greenhouse gas effect. Highly efficient conversion of CO2 into cyclic carbonate with green catalysts is essential for the more sustainable expansion of CO2 fixation. Traditional batch reactor is limited by low efficiency, high cost and low security. Meanwhile, continuous flow system showcased a myriad of virtues, including shortening the residence time from hours to seconds, and decreasing reaction temperature, and possessing the nature of easy industrial scale-up. In this paper, a continuous-flow microreaction system was developed to synthesis propylene carbonate (PC) from propylene oxide (PO) and CO2 using 1-butyl-3-methylimidazolium bromide ([BMIM]Br) as catalyst. By observing the flow patterns inside microreaction system, the effects of reaction temperature, molar fraction of catalyst, operating pressure, residence time, molar ratio of CO2/PO as well as recycling performance of catalyst on the overall performances were comprehensively evaluated into details. Under different reaction conditions, the flow patterns were set to vary between slug flow and annular flow. The results showed that the yield of propylene carbonate (PC) can reach 99.7% at 140 °C and 3.0 MPa with the residence time of 166 s, while the recycling performance of the designed system greatly conforms the future trend of green chemistry.

Ionic liquids are regarded as one of the most prodigious materials for sustainable technological developments with superior performance and versatility. Hence, in this study, we have reported the design and synthesis of electroactive disubstituted ferrocenyl ionic liquids (Fc-ILs) with two different counter anions and demonstrated the significance of their anion tuneable physicochemical characteristics towards multifunctional electrochemical applications. The Fc-IL synthesized with chloride counter anion (Fc-Cl-IL) displays water-solubility and can be used as a redox additive in the fabrication of supercapacitor. Supercapacitor device with Fc-Cl-IL based redox electrolyte exhibits outstanding energy and power densities of 91 Wh kg−1 and 20.3 kW kg−1, respectively. Meanwhile, ferrocenyl IL synthesized with perchlorate anion (Fc-ClO4-IL) exhibits water-insolubility and can serve as a redox mediator towards construction of a glucose biosensor. The biosensor comprising Fc-ClO4-IL is able to detect glucose at an exceptionally lower potential of 0.2 V, with remarkable sensitivity and selectivity. This study implies that the introduction of electroactive ILs could afford supercapacitor devices with high energy and power densities and biosensors with less detection potential.

Trace detection based on surface-enhanced Raman scattering (SERS) has attracted considerable attention, and exploiting efficient strategies to stretch the limit of detection and understanding the mechanisms on molecular level are of utmost importance. In this work, we use ionic liquids (ILs) as trace additives in a protein-TiO2 system, allowing us to obtain an exceptionally low limit of detection down to 10-9 M. The enhancement factors (EFs) were determined to 2.30 × 104, 6.17 × 104, and 1.19 × 105, for the three systems: one without ILs, one with ILs in solutions, and one with ILs immobilized on the TiO2 substrate, respectively, corresponding to the molecular forces of 1.65, 1.32, and 1.16 nN quantified by the atomic force microscopy. The dissociation and following hydration of ILs, occurring in the SERS system, weakened the molecular forces but instead improved the electron transfer ability of ILs, which is the major contribution for the observed excellent detection. The weaker diffusion of the hydrated IL ions immobilized on the TiO2 substrate did provide a considerably greater EF value, compared to the ILs in the solution. This work clearly demonstrates the importance of the hydration of ions, causing an improved electron transfer ability of ILs and leading to an exceptional SERS performance in the field of trace detection. Our results should stimulate further development to use ILs in SERS and related applications in bioanalysis, medical diagnosis, and environmental science.

Accomplishing slow translocation speed with high sensitivity has been the most critical mission for solid-state nanopore (SSN) device to electrically detect nucleobases in ssDNA. In this study, a method to detect nucleobases of ssDNA using a 2D SSN is introduced by considerably reducing the translocation speed and effectively increasing its sensitivity. The ultra-thin titanium dioxide coated hexagonal boron nitride nanopore was fabricated, along with an ionic-liquid 1-butyl-3-methylimidazolium hexafluorophosphate/2.0 M KCl aqueous (cis/trans) interface, for increasing both the spatial and the temporal resolutions. As the ssDNA molecules entered the nanopore, a brief surge of electrical conductivity occurred, which was followed by multiple resistive pulses from nucleobases during the translocation of ssDNA and another brief current surge flagging the exit of the molecule. The continuous detection of nucleobases using a 2D SSN device is a novel achievement: the water molecules bound to ssDNA increased the molecular conductivity and amplified electrical signals during the translocation. Along with the experiment, computational simulations using COMSOL Multiphysics are presented to explain the pivotal role of water molecules bound to ssDNA to detect nucleobases using a 2D SSN.

This project studies the relationship between the carbonization temperature and ionic liquid (IL) ([Bmim]Cl and [Bmim]OAC) solution and its impact on the structure, properties and gasification reactivity of the hydrochar obtained from eucalyptus via hydrothermal carbonization (HTC). The structure of hydrochar was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy while its gasification reactivity with air was measured by thermogravimetric analysis at 340 °C. Results showed that the reactivity of hydrochar prepared in the presence of IL was much higher than that prepared using water. SEM analysis revealed some vesicles on the hydrochar surface during HTC at 220 °C, while Raman and XRD results showed more disordered crystal structure of the hydrochar in the presence of ILs. XPS and Raman results revealed that C O contents on the hydrochar surface increased after adding IL which implied that IL can promote opening the loop of aromatic nucleus of biomass. This study provides important information for the preparation of highly active biochar based on IL assisted HTC of eucalyptus for practical applications.

The intra- and intermolecular interactions in ether-functionalized ionic liquids (ILs) are studied by means of infrared (IR) spectroscopy measurements of N-ethoxyethyl-N-methylpiperidiniumbis(fluorosulfonyl)imide (P1,2O2-FSI) and N-ethoxyethyl-N-methylmorpholiniumbis(fluorosulfonyl)imide (M1,2O2-FSI). The temperature dependence of the spectra in the medium IR range allows the study of the anion conformer distribution and its variation during phase transitions. In particular, it is found that for both ILs the trans conformer of FSI is more stable than the cis conformer, and the enthalpy differences between them are calculated and are found to decrease upon the addition of a Li salt. The results obtained in the far IR range, combined with ab initio calculation of the ionic couple performed using the B3LYP-D functional and considering both empirical dispersion corrections and the presence of a polar solvent, provide evidence for the occurrence of a hydrogen bonding between the O atom of the anion and its closest H atoms directly linked to a C atom of the cation. The comparison with samples having the same cations but with bis(trifluoromethanesulfonyl)imide (TFSI) as an anion, that is, M1,2O2-TFSI and P1,2O2-TFSI, as well as with samples having cations without the ether-functionalization neither in the ring nor in the side chain, such as N-propyl-N-methylpyrrolidinium-FSI (PYR13-FSI) and 1-butyl-1-methylpyrrolidinium-TFSI (PYR14-TFSI), indicates that the occurrence of such highly directional interaction between anion and cation is better observable in the ether-functionalized samples, in particular in those containing FSI as an anion.

This study investigated the dissolution of silk multifilament fibres in the ionic liquid 1-ethyl-3-methylimidazolium acetate. The dissolution process was found to create a silk composite fibre, comprising undissolved silk multi-filaments surrounded by a coagulated silk matrix. The dissolution procedure was carried out for a range of temperatures and times. The resulting composite fibres were studied using a combination of optical microscopy, wide angle X-ray diffraction (XRD) and tensile testing. An azimuthal (alpha) XRD scan enabled the orientation of the composite silk filaments to be quantified through a 2nd Legendre Polynomial function (P2). The P2 results could be shifted to construct a single master curve using time-temperature superposition (TTS). The shifting factors were found to have an Arrhenius behaviour with an activation energy of 138 ± 13 kJ/mol. Using a simple rule of mixtures the P2 measurements were used to calculate the dissolved silk matrix volume fraction (Vm), which also displayed TTS forming a single master curve with an activation energy 139 ± 15 kJ/ mol. The tensile Young’s Modulus of each silk composite filament was measured and these results similarly formed a master curve with an activation energy of 116 ± 12 kJ/mol.

Precursor solubility is a crucial factor in industrial applications, dominating the outcome of reactions and purification steps. The outcome and success of thermodynamic modelling of this industrially important property with equations of states, such as Perturbed‐Chain Statistical Associating Fluid Theory (PC‐SAFT), vastly depends on the quality of the pure‐component parameters. The pure‐component parameters for low‐volatile compounds such as ionic liquids (ILs) have been commonly estimated using mixture properties, e. g. the osmotic pressure of aqueous solutions. This leads to parameters that depend on the solvent, and transferability to other mixtures often causes poor modeling results. Mixture‐independent experimental properties would be a more suitable basis for the parameter estimation offering a way to universal parameter sets. Model parameters for ILs are available in the literature [10.1016/j.fluid.2012.05.029], but they were estimated using pure‐IL density data. The present work focuses on a step towards a more universal estimation strategy that includes new experimental vapor‐pressure data of the pure IL. ILs exhibit an almost negligible vapor pressure in magnitude of usually 10−5 Pa even at elevated temperatures. In this work, such vapor‐pressure data of a series of 1‐ethyl‐3‐methyl‐imidazolium‐based [C2mim]‐ILs with various IL‐anions (e. g. tetrafluoroborate [BF4]−, hexafluorophosphate [PF6]−, bis(trifluoromethylsulfonyl)imide [NTf2]−) were experimentally determined and subsequently used for PC‐SAFT parameter estimation. The so‐determined parameters were used to predict experimental molecular precursor solubility in ILs and infinitely diluted activity coefficients of various solvents in ILs. The parameters were further compared to modeling results using classical parametrization methods (use of liquid‐density data only for the molecular PC‐SAFT and the ion‐based electrolyte PC‐SAFT). As a result, the modeled precursor solubilities using the new approach are much more precise than using the classical parametrization methods, and required binary parameters were found to be much smaller (if needed). In sum, including the pure‐component vapor‐pressure data of ILs opens the door towards parameter estimation that is not biased by mixture data. This procedure might be suitable also for polymers and for all kind of ionic species but needs extension to ion‐specific parametrization in the long term., The conventional way to fit ionic liquid parameters of equations of state to density is compared using a new method. The experimental vapor pressures as well as the density have been used as input to the model parameter estimation. The work was performed within the framework of the EOS PC‐SAFT (perturbed‐chain statistical associating fluid theory). The new method allows modeling density and vapor pressure accurately, and still allows for an improved modeling of the solubility of precursors in ionic liquids.

Metal sulfides are among the most promising materials for a wide variety of technologically relevant applications ranging from energy to environment and beyond. Incidentally, ionic liquids (ILs) have been among the top research subjects for the same applications and also for inorganic materials synthesis. As a result, the exploitation of the peculiar properties of ILs for metal sulfide synthesis could provide attractive new avenues for the generation of new, highly specific metal sulfides for numerous applications. This article therefore describes current developments in metal sulfide nanoparticle synthesis as exemplified by a number of highlight examples. Moreover, the article demonstrates how ILs have been used in metal sulfide synthesis and discusses the benefits of using ILs over more traditional approaches. Finally, the article demonstrates some technological challenges and how ILs could be used to further advance the production and specific property engineering of metal sulfide nanomaterials, again based on a number of selected examples., Current developments in metal sulfide nanoparticle synthesis using ionic liquids are reviewed. The article focuses on the benefits of using ionic liquids over more traditional approaches. The Minireview also presents the technological challenges associated with the use of ionic liquids to further advance the production and specific property engineering of metal sulfide nanomaterials.

This minireview describes two strategically different and unexplored approaches to use ionic liquids (IL) containing weakly solvated and highly reactive chalcogenide anions [E‐SiMe3]− and [E−H]− of the heavy chalcogens (E=S, Se, Te) in materials synthesis near room temperature. The first strategy involves the synthesis of unprecedented trimethylsilyl chalcogenido metalates Cat+[M(E‐SiMe3)n]− (Cat=organic IL cation) of main group and transition metals (M=Ga, In, Sn, Zn, Cu, Ag, Au). These fully characterized homoleptic metalates serve as thermally metastable precursors in low‐temperature syntheses of binary, ternary and even quaternary chalcogenide materials such as CIGS and CZTS relevant for semiconductor and photovoltaics (PV) applications. Furthermore, thermally and protolytically metastable coinage metalates Cat+[M(ESiMe3)2]− (M=Cu, Ag, Au; E=S, Se) are accessible. Finally, the use of precursors BMPyr[E‐SiMe3] (E=Se,Te; BMPyr=1‐butyl‐1‐methylpyrrolidinium) as sources of activated selenium and tellurium in the synthesis of high‐grade thermoelectric nanoparticles Bi2Se3 and Bi2Te3 is shortly highlighted. The second synthesis strategy involves the metalation of ionic liquids Cat[S−H] and Cat[Se−H] by protolytically highly active metal alkyls or amides RnM. This rather general approach towards unknown chalcogenido metalates Catm[Rn‐1M(E)]m (E=S, Se) will be demonstrated in a research paper following this short review head‐to‐tail., Low temperature materials syntheses: Ionic liquids with highly reactive anions [E‐SiMe3]− and [E−H]− (E=S, Se, Te) are valuable synthons for the synthesis of chalcogenido metalates Cat+[M(E‐SiMe3)n] and Catn[RmM(E)]n serving as thermally metastable precursors in binary and multinary metal chalcogenide materials preparation.

Herein, we developed a novel effervescence-assisted dual microextraction method, abbreviated as EM-LPSH, using lighter-than-water phosphonium-based ionic liquids (LPILs) and switchable hydrophilic/hydrophobic fatty acids (SHFAs). The EM-LPSH method was utilized for quick enrichment/extraction of polycyclic aromatic hydrocarbons (PAHs) in edible oils. Owing to lower density than water, LPILs used as the first extractant were floated on the upper layer of the aqueous phase, leading to a convenient separation/collection compared with traditional heavier-than-water imidazolium-based ionic liquids. Interestingly, SHFAs play triple functions: a dispersive solvent in the microextraction process, an acidic source in effervescent reaction, and the second extractant in dual microextraction, due to switchability from hydrophilicity to hydrophobicity. Consequently, the integration of LPILs with SHFAs greatly enhanced the extraction efficiency for PAHs owing to the quick dual microextraction process. Some important variables were rigorously optimized using a one-factor-at-a-time approach. Under optimized conditions, the EM-LPSH/HPLC-FLD method provided a wide linear range (0.07~0.63–200 μg kg−1), satisfactory recovery (80.12–103.27%), and low limit of detection (0.02–0.19 μg kg−1), as well as high intra-day and inter-day precision (0.03–6.55) for six PAHs in edible oils. By using certified reference material in olive oil samples (GBW10162), the recoveries ranged from 97.40 to 98.39%, demonstrating high accuracy and precision. According to the detected levels of PAHs in six unheated and heated oils, their edible safety was evaluated in detail. In short, the newly developed method is simple, convenient, and highly efficient, thereby showing great prospects for application in conventional monitoring of trace-level PAHs in edible oils.

Self-assembly performed in ionic liquids (ILs) as a unique solvent promises distinct functions and applications in sensors, therapeutics, and optoelectronic devices due to the rich interactions between nanoparticle building blocks and ILs. However, the general consideration that common nanoparticles are readily destabilized by counterions in an IL has largely prevented researchers from investigating controlled nanoparticle assembly in IL-based systems. This study explores the assembling behaviour of double-stranded (ds) DNA-functionalized gold nanoparticles (dsDNA-AuNPs) in hydrated ionic liquids. The DNA base pair stacking assembly of dsDNA-AuNPs occurs at a low IL concentration (5%). However, a moderate ionic liquid concentration (5-40%) can de-hybridize dsDNA and leaves single-stranded (ss) DNA stabilizing the AuNPs. In concentrated ionic liquids (40%), interestingly, the higher ionic strength leads to the assembly of DNA-AuNPs. The triphasic assembly trend is also generally observed regardless of the type of IL. By down-regulation of DNA's melting temperature with the IL, the assembly of DNA-AuNPs affords robust response to a lower temperature range, promising applications in plasmonic devices and range-tunable temperature sensors.

Boosted by the simplicity of their synthesis and low toxicity, cholinium and amino acid-based ionic liquids have attracted the attention of researchers in many different fields ranging from computational chemistry to electrochemistry and medicine. Among the uncountable IL variations, these substances occupy a space on their own due to their exceptional biocompatibility that stems from being entirely made by metabolic molecular components. These substances have undergone a rather intensive research activity because of the possibility of using them as greener replacements for traditional ionic liquids. We present here a short review in the attempt to provide a compendium of the state-of-the-art scientific research about this special class of ionic liquids based on the combination of amino acid anions and cholinium cations.

Operations with nucleic acids are among the main means of studying the mechanisms of gene function and developing novel methods of molecular medicine and gene therapy. These endeavours usually imply the necessity of nucleic acid storage and delivery into eukaryotic cells. In spite of diversity of the existing dedicated techniques, all of them have their limitations. Thus, a recent notion of using ionic liquids in manipulations of nucleic acids has been attracting significant attention lately. Due to their unique physicochemical properties, in particular, their micro-structuring impact and tunability, ionic liquids are currently applied as solvents and stabilizing media in chemical synthesis, electrochemistry, biotechnology, and other areas. Here, we review the current knowledge on interactions between nucleic acids and ionic liquids and discuss potential advantages of applying the latter in delivery of the former into eukaryotic cells.

We generated stable amphiphilic copolymer-based polymeric micelles (PMs) with temperature-responsive properties utilizing Pluronic® L35 and a variety of ionic liquids (ILs) to generate different aqueous two-phase micellar systems (ATPMSs). The partitioning of the hydrophobic model compound curcumin (CCM) into the PM-rich phase and the drug delivery capabilities of the PMs were investigated. ATPMSs formed using more hydrophobic ILs (i.e., [Ch][Hex] [Ch][But] > [Ch][Pro] > [Ch][Ac] [Ch]Cl) were the most effective in partitioning (KCCM) and recovering (RECRich) CCM into the PM-rich phase (15.2 < KCCM < 22.0 and 90% < RECRich < 95%, respectively). Moreover, using 1.2 M [Ch][But] and 0.2 M [Ch][Hex] ILs yielded higher encapsulation efficiency (EE) (94.1 and 96.0%, respectively) and drug loading (DL) capacity (14.8 and 16.2%, respectively), together with an increase in the average hydrodynamic diameter of the PMs (DH) (42.5 and 45.6 nm, respectively). The CCMPM formulations were stable at 4.0, 25.0, and 37.0 °C and the release of CCM was faster with the less hydrophobic ILs (i.e., [Ch]Cl and [Ch][Ac]). Furthermore, due to the lower critical solution temperature properties of Pluronic® L35, the PMs exhibit temperature responsiveness at 37.0 °C. In vitro cytotoxicity assays were also performed to determine the potency of CCMPM formulations, and a 1.8-fold decrease in IC50 values was observed between the CCMPMs/[Ch][Hex] and CCMPMs/[Ch]Cl formulations for PC3 cells. The lower IC50 value for the [Ch][Hex] version corresponded to a greater potency compared to the [Ch]Cl version, since a lower concentration of CCM was required to achieve the same therapeutic effect. The ATPMSs investigated in this study serve as a novel platform for Pluronic® L35/PBS buffer (pH 7.4) + IL-based ATPMS development. The unique properties reported here may be useful in applications such as controlled-release drug delivery systems (DDS), encapsulation, and bioseparations., This study was funded by the Coordination for Higher Level Graduate Improvements (CAPES/Brazil, finance code 001), the National Council for Scientific and Technological Development (CNPq/Brazil) and the State of São Paulo Research Foundation (FAPESP/Brazil, processes #2014/16424-7, #2017/10789-1, #2018/10799-0, #2018/05111-9, #2019/05624-9, #2019/08549-8, and #2020/03727-2)., info:eu-repo/semantics/publishedVersion

Cholinium amino acid-based (Ch-AA) biocompatible ionic liquids (bio-ILs) are synthesized from renewable components and are efficiently used for biomass processing. However, their microscopic structural features that lead to their application as biomass solvents remain undetermined. Herein, we use atomistic simulations to investigate the structures of six different Ch-AA bio-ILs up to the nanometer length scale and demonstrate that, depending on the anion side chain structure, the respective IL exhibits structural ordering at different length scales. All the six Ch-AA bio-ILs investigated here show a generic feature of having a strong hydrogen bonding network between the hydroxyl group of the cholinium cation and the carboxyl group of the amino acid anions. We illustrate that each of these bio-ILs also displays a unique feature. Distinctive intermediate range structural ordering leads to heterogeneity in methioninate- and phenylalaninate-based ILs caused by the anion side chain segregation. Intermediate range ordering is not observed in glutaminate- and glutamate-based ILs because significant anion side chain and backbone interactions hinder the formation of side chain clusters. Interestingly, for the cysteinate-based IL, the side chains do not interact with the backbones and the intermediate range ordering is not observed because of a shorter anionic side chain.

Electrospun poly(vinylidene fluoride) (PVDF) fiber membranes doped with different ionic liquids (ILs) and sharing the same anion were produced and their potential as separator membranes for battery applications was evaluated. Different types of ILs containing the same anion, bis(trifluoromethylsulfonyl)im ide [TFSI] , were used with IL concentrations ranging between 0 and 15 wt% The morphology, microstructure, thermal and electrical properties (ionic conductivity and electrochemical window) of the membranes were evaluated. The presence of ILs in the PVDF polymer matrix influences the fiber diameter and the content of the polar 13 phase within the polymer, as well as the degree of crystallinity. The thermal stability of the membranes decreases with the incorporation of IL. Impedance spectroscopy tests show a maximum ionic conductivity of 2.8 mS.cm(-1) for 15% of 1-ethyl-3-methylimidazolium bis(tri fluoromethylsulfonyl)imide ([Emim][TFSI]) at room temperature. The electrochemical stability of the samples ranges from 0.0 to 6.0 V. When evaluated as battery separator membranes in C-LiFePO4 halfcells, a maximum discharge capacity of 119 mAh.g(-1) at C-rate was obtained for the PVDF membrane with 15% [Emim][TFSI], with a coulombic efficiency close to 100%. The results demonstrate that the produced electrospun membranes are suitable for applications as separators for lithium ion batteries (LIBs)., Work supported by the Portuguese Foundation for Science and Technology (FCT): projects UID/FIS/04650/2019, UID/QUI/0686/2019, UID/CTM/50025/2019, UID/QUI/50006/2019, PTDC/FIS-MAC/28157/2017, and Grants SFRH/BD/140842/2018 (J.C.B.), SFRH/BPD/121526/2016 (D.M.C), CEECIND/00833/2017 (R.G.) and SFRH/BPD/112547/2015 (C.M.C.). Financial support from the Spanish State Research Agency (AEI) and the European Regional Development Fund (ERFD) through the project PID2019-1060 99RB-C43/AEI/10.13039/501100011033 and from the Basque Government Industry and Education Departments under the ELKARTEK and HAZITEK programs is also acknowledged.

Organosulfur compounds have a pivotal role in the functionalities of many natural products, pharmaceuticals and organic materials. For these reasons, the search for new methodologies for the formation of carbon-sulfur bonds has been the object of intensive work for organic chemists. However, the proposed strategies suffer from various drawbacks, such as volatility, toxicity, and instability of the sulfur sources or the use of VOC solvents. In this review, we summarise the recent protocols which have the goal of obtaining sulfones, thioethers, thiazines, thiazepines and sulfonamides in an unconventional and/or sustainable way. The use of starting materials less invasive and toxic with respect to the traditional reagents, alternative solvents such as water, ionic liquids or deep eutectic solvents, the exploitation of ultrasound and electrochemistry, increasing the efficiency of the process, are reported. Moreover, representative reaction mechanisms are also discussed.

In this short review I shall highlight the basic principle and the difficulties that arise in attempting the computational modeling of seemingly simple systems which hide an unexpected complexity. Biocompatible ionic liquids which are based on the coupling of organic or amino acid anions with metabolic cations such as cholinium are the target of this review. These substances have been the subject of intense research activities in the last few years and have attracted the attention of computational chemists. I shall show that the computational description of these substances is far from trivial and requires the use of sophisticated techniques in order to account for a surprisingly rich chemistry that is due to several phenomena such as polarization, charge transfer, proton transfer equilibria and tautomerization reactions.

A detailed understanding of the local dynamics in ionic liquids remains an important aspect in the design of new ionic liquids as advanced functional fluids. Here, we use small-angle X-ray scattering and quasi-elastic neutron spectroscopy to investigate the local structure and dynamics in a model ionic liquid as a function of temperature and pressure, with a particular focus on state points (P,T) where the macroscopic dynamics, i.e., conductivity, is the same. Our results suggest that the initial step of ion transport is a confined diffusion process, on the nanosecond timescale, where the motion is restricted by a cage of nearest neighbors. This process is invariant considering timescale, geometry, and the participation ratio, at state points of constant conductivity, i.e., state points of isoconductivity. The connection to the nearest-neighbor structure is underlined by the invariance of the peak in the structure factor corresponding to nearest-neighbor correlations. At shorter timescales, picoseconds, two localized relaxation processes of the cation can be observed, which are not directly linked to ion transport. However, these processes also show invariance at isoconductivity. This points to that the overall energy landscape in ionic liquids responds in the same way to density changes and is mainly governed by the nearest-neighbor interactions.