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A series of task-specific ionic liquids (TSILs) based on glycerylimidazolium cations have been prepared by reaction of 1-chloropropanediol, a compound obtainable from glycerol (a widely available and in-expensive waste product), with the appropriate base (1-H-imidazole, 1,2-dimethylimidazole and 1-methyl-1-H-imidazole). The reaction of 3-(1H-imidazol-1-yl)propane-1,2-diol with chloroalkanes, bromoalkanes and alkyl mesylates gave the corresponding salts which were characterized. The possibility to use these ILs in palladium catalyzed reactions was evaluated, evidencing good catalyst stability and a high recyclability. [ABSTRACT FROM AUTHOR]

In this paper we derive a straightforward computational approach to predict the optimal ionic liquid (IL) solvent for a given compound, based on COSMO-RS calculations. These calculations were performed on 18 different active pharmaceutical ingredients (APIs) using a matrix of 210 hypothetical ILs. These results indicated that the 18 APIs could be classified into three distinct categories based on their relative hydrogen bond donating or accepting ability, with similar optimal IL solvent predictions within each class. Informed by these results, a family of strongly hydrogen bond donating ILs based on the N-alkylguanidinium cation were prepared and characterized. The solubility of the APIs in each of these classes was found to be qualitatively consistent with the predictions of the COSMO-RS model. The suitability of these novel guanidinium salts as crystallization solvents was demonstrated by the use of N-butylguanidinium bis(trifluoromethanesulfonyl)imide for the purification of crude fenofibrate using dimethylsulfoxide as an antisolvent, which resulted in good yields and excellent purities. Finally, a simple descriptor based model is proposed to suggest the best IL solvent for arbitrary APIs., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This paper describes the ability of several ionic liquids cations for electroosmotic flow modulation in capillary electrophoresis. Organic salts based on phosphonium, sulfonium, cysteinium, ammonium, and guanidinium cations were selected to study this property. In addition, the synergistic effect of these compounds in cyclodextrin chiral separation was also evaluated. In comparison with most studied imidazolium-based ionic liquids, several of the cations studied, are stronger modifiers in terms of electroosmotic flow (EOF) modulation. Phosphonium-based compounds and tri-octyl methylammonium chloride ([Aliquat]Cl) had the strongest ability to reverse EOF both in acidic and in basic conditions and had the lowest EOF reversal concentrations in the presence of hydroxypropyl-β-cyclodextrin. EOF modulation ability of phosphonium cations also contributed to the improvement of chiral separation of DL-propranolol by hydroxypropyl-β-cyclodextrin at lower concentrations in comparison with most commonly used EOF modulators such as tetrabutylammonium phosphate., (© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

• The mechanism of organic electrode weakening self-discharge effect of dual-ion battery was explored. • The performance of metal-free dual-ion batteries in different ionic liquid electrolytes was investigated. • The method of reducing the dissolution of organic electrode in ionic liquid electrolyte was discussed. The strong self-discharge reaction is one of the key factors limiting the practical use of dual-ion batteries, which leads to low coulombic efficiency and discharge capacity loss. It is of great significance to effectively reduce the self-discharge effect through redox reactions between organic electrodes and electrolytes. Herein, a dual-ion battery study that uses 1,4,5,8-naphthalenetetracarboxylic dianhydride as the anode and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide as the electrolyte is conducted. Due to the introduction of organic materials, the storage mechanism of cations on the anode is changed, which weakens the self-discharge effect. The battery shows a low self-discharge rate of 6.12% h−1 and a high discharge capacity of 114 mAh g−1. The voltage declines by only 0.14 V after resting for 15 h due to the strong redox reaction between Pyr 14 + cations and the C O groups of NTCDA. Meanwhile, a double-layer filter paper system with small porosity is used to improve the cycle performance of the battery. [ABSTRACT FROM AUTHOR]

Over several decades, a wealth of literature has been devoted to correlations between the chemistries of phyllosilicates and their crystallographic unit-cell parameter values. The c parameter is currently used because of its relation to the layer-to-layer distance, characteristic of the various families of phyllosilicates. The b parameter is also of interest because it allows measurement of the layer lateral dimensions and inherent structural adjustments. This unit-cell distance can be extracted from X-ray diffraction traces from the (06ℓ;33ℓ) diffraction region and by attributing the main diffraction peak observed to a 060 reflection, leading to the relationship b = 6.d(060). The aim of this paper is to revisit the relationships between the b value (or equivalent) of the phyllosilicate (i.e. TO, TOT and TOTO) or hydroxide (i.e. hydroxide, oxyhydroxide and layered double hydroxide) families and the layer chemistry based on a mean ionic radius R of octahedral cations, calculated as R = ∑i=1n (ri.xi), where ri is the ionic radius of the octahedral cation i and xi is its molar fraction over n types of octahedral cations (∑i=1n (xi) = 1). The data were collected from the literature and involved both natural and synthetic samples with both dioctahedral and trioctahedral structures of the octahedral sheet. The results showed that b values can be linked strongly to R, leading to suitable linear regressions for all of the studied structures. All correlations were found to be applicable irrespective of the di- or trioctahedral nature of the octahedral sheet, and these are discussed in light of (1) the lateral dimension of the octahedral sheet and (2) the dimensional misfit between the tetrahedral and octahedral sheets. For hydroxide families, all data can be gathered on a single b vs R correlation line, and the dimensional properties of the octahedral sheet can be interpreted simply based on an oxygen–cation–oxygen mean distance. For TO structures, two general b vs R correlation trends were reported, and these were assigned to two adjustment mechanisms corresponding to distinct types of tetrahedral and octahedral distortions. For the mica TOT family, two main trends were also reported, whereas the use of the synthetic mica series allowed us to demonstrate that the obtained scattering of data was mainly driven by the presence of multiple limited solid solutions. Such chemical complexity was also noted for smectites, especially regarding the tetrahedral composition and associated variability in layer charge. This variability made it difficult to propose a general regression correlating b to R values for smectites, although the regression obtained for neutral TOT layers can apply as a first-order relation. Finally, a single general b vs R correlation was obtained for chlorites, and the observed slope of the regression was interpreted according to the role played by the isolated hydroxide sheet on the evolution of the lateral dimension of the structures. [ABSTRACT FROM AUTHOR]

Systemic acquired resistance (SAR) is one of the most promising ways to support plants in the fight against viruses. Using this approach biological or chemical factors interact with plants and stimulate their immune system against infections before infection occurs. This paper presents synthesis, physical properties, phytotoxicity and SAR induction efficacy of 15 ionic liquids, derivatives of SAR inducers paired with the cholinium cation, an essential nutrient for organisms. SAR induction efficacy tests were performed on tobacco Nicotiana tabacum var. Xanthi infected by tobacco mosaic virus (TMV). [ABSTRACT FROM AUTHOR]

The valorization of abundant agrowastes into chemicals and advanced materials is of key importance in the context of the circular bioeconomy and biorefinery. Herein, we report the ionothermal carbonization (ITC) of sugarcane bagasse, a fibrous residue made of lignocellulose, to engineer advanced carbonaceous materials, namely ionochars. We prepared a series of imidazolium tetrachloroferrate ionic liquids (IL) bearing modular substituents, e.g., alkyl chains with different lengths or benzyl groups. The effect of the cation on both textural and morphological properties is highlighted. Ionochars with high specific surface area (up to 800 m2 g−1), tuneable pore volume (up to 0.8 cm3 g−1), singular nanostructures and adjustable CO2 uptake/retention were obtained. [ABSTRACT FROM AUTHOR]

In this paper, the influence of three alkylimidazolium-based ionic liquids with the same cation (1-ethyl-3-methylimidazolium) and different anions (chloride, tetrafluoroborate and hexafluorophosphate) on the structure and properties of cellulose, have been studied by using Fourier transform infrared spectroscopy measurements, fluorescence microscopy imaging, viscometric and methylene blue sorption tests. Cellulose treated with ionic liquids showed better stability to UV light, as demonstrated by the lower variations of the polymerization degree, carboxyl groups content, moisture index, crystallinity index, lateral order index and allomorph index, with the increase of the UV exposure period, by comparing to non-treated cellulose. The results show that the tested ionic liquids could be effective as 'green' plasticizers and UV stabilizers for cellulose-based materials. [ABSTRACT FROM AUTHOR]

Room temperature ionic liquids (ILs) are stable liquids composed of anions and cations. 1-ethyl-3-methyl-imidazolium (EMIm, EMI) is a popular and important cation that produces thermally stable ILs with various anions. In this study two amide-type anions, bis(trifluoro-methanesulfonyl)amide [N(SO2CF3)2, TFSA, TFSI, NTf2, or Tf2N] and bis(fluorosulfonyl)amide [(N(SO2F)2, FSA, or FSI] were investigated by multinuclear NMR spectroscopy. In addition to EMIm-TFSA and EMIm-FSA, lithium-salt-doped binary systems were prepared (EMIm-TFSA-Li and EMIm-FSA-Li). The spin-lattice relaxation times (T1) were measured by 1H, 19F, and 7Li NMR spectroscopy and the correlation times of 1H NMR, τc(EMIm) (8 × 10-10 to 3 × 10-11 s) for the librational molecular motion of EMIm and those of 7Li NMR, τc(Li) (5 × 10-9 to 2 × 10-10 s) for a lithium jump were evaluated in the temperature range between 253 and 353 K. We found that the bulk viscosity (η) versus τc(EMIm) and cation diffusion coefficient DEMIm versus the rate 1/τc(EMIm) have good relationships. Similarly, linear relations were obtained for the η versus τc(Li) and the lithium diffusion coefficient DLi versus the rate 1/τc(Li). The mean one-jump distances of Li were calculated from τc(Li) and DLi. The experimental values for the diffusion coefficients, ionic conductivity, viscosity, and density in our previous paper were analyzed by the Stokes-Einstein, Nernst-Einstein, and Stokes-Einstein-Debye equations for the neat and binary ILs to clarify the physicochemical properties and mobility of individual ions. The deviations from the classical equations are discussed. [ABSTRACT FROM AUTHOR]

Room temperature ionic liquids differ from molten salts in many ways, our work concentrates on two distinguishing features. These are large cation-anion size disparities and at least one ionic species where the center of mass and the center of charge do not coincide. In earlier work, we examined the influences of these features in isolation on simple spherical models. This paper extends this work to ionic liquid models where both features are present, and where the characteristic distance σ+-′ determining the strength of the Coulombic attractions is unconstrained. We consider the interplay among these molecular features and elucidate their relative importance to the behavior of ionic liquids. Particular attention is focused on the transport properties. We find that size disparity, charge location, and σ+-′ can all have large (often competing) effects. In our models, size disparity and small charge displacements lead to weakly bound, directional ion pairs, and the resulting asymmetric ion-counterion distribution gives rise to increased diffusion coefficients, consequently lower viscosity, and increased conductivity. These observations are analogous to effects reported in the literature, and we see similarities between the directional ion pairs in our models and directional cation-anion pairing through weak hydrogen bonding in room temperature ionic liquids. In our models, large charge displacements lead to strongly bound, long-lived, directional ion pairs, and in this regime the trends noted above are reversed, increased viscosities, and decreased conductivities are observed. Recently, creating more strongly hydrogen bonded, directional ion pairs has been put forward as possible means of achieving larger viscosity reductions. The trend reversal that we observe suggests that this might not work in practice. [ABSTRACT FROM AUTHOR]

A systematic molecular dynamics study is performed to determine the dynamics and transport properties of 12 room-temperature ionic liquids family with 1-alkyl-3-methylimidazolium cation, [amim]+ (alkyl=methyl, ethyl, propyl, and butyl), with counterions, PF6-, NO3-, and Cl-. The goal of the work is to provide molecular level understanding of the transport coefficients of these liquids as guidance to experimentalists on choosing anion and cation pairs to match required properties of ionic liquid solvents. In the earlier paper (Part I), we characterized the dynamics of ionic liquids and provided a detailed comparison of the diffusion coefficients for each ion using the Einstein and Green–Kubo formulas. In this second part, other transport properties of imidazolium salts are calculated, in particular, the electrical conductivity is calculated from the Nernst–Einstein and Green–Kubo formulas. The viscosity is also determined from the Stokes–Einstein relation. The results of the calculated transport coefficients are consistent with the previous computational and experimental studies of imidazolium salts. Generally, the simulations give electrical conductivity lower than experiment while the viscosity estimate is higher than experiment. Within the same cation family, the ionic liquids with the NO3- counterion have the highest electrical conductivities: σ[NO3]->σ[PF6]->σ[Cl]-. The [dmim][X] series, due to their symmetric cationic structure and good packing and the [bmim][X] series due to higher inductive van der Waals interactions of [bmim]+, have the highest viscosities in these ionic liquid series. Our simulations show that the major factors determining the magnitude of the self-diffusion, electrical conductivity, and viscosity are the geometric shape, ion size, and the delocalization of the ionic charge in the anion. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) including novel superbase-derived ILs and imidazolium-based ILs with the potential to be used as green solvents for biomass utilization should be deeply evaluated with respect to their corrosion ability towards metallic equipment in industrialization. Herein, the corrosion susceptibility of 304SS in [DBUH][CH3CH2OCH2COO] was investigated for the first time and compared with that in common [EMIM][Ac] and [AMIM][Cl] by electrochemical, surface, and theoretical analyses. [DBUH][CH3CH2OCH2COO] exhibited an unprecedentedly excellent corrosion inhibition for 304SS compared to imidazolium-based ILs. This may be due to the presence of electron-donating carboxylate anions and macrocyclic superbase cations, which reacted with metals to form a compact layer and protected metals from damage. [EMIM][Ac] showed a slightly unfavorable corrosion inhibition compared to [DBUH][CH3CH2OCH2COO]. However, the corrosion rate of 304SS was dramatically increased in [AMIM][Cl] by increasing the temperature and water contents, which was reflected by pitting corrosion with plenty of pits (5–10 μm in diameter) on the 304SS surface after a polarization test. By studying the corrosion behaviour of five common steels in [DBUH][CH3CH2OCH2COO] and taking economy into consideration, 304SS with high Rct (26.69 × 105 Ω cm2) and Rp values (1230.8 Ω cm2) was the top priority for industrial equipment materials. According to the possible corrosion mechanism of metals in ILs from the viewpoint of DFT calculations and complex physico-chemical interactions, carboxylate ILs displaying outstandingly low contributions to corrosion particularly involving superbase cations or imidazolium cations and carboxylate anions with electron-donating groups such as –OCH2CH3, –OCH3, and –HC＝CH2 should be designed to mitigate corrosion damage in industrialized operations. [ABSTRACT FROM AUTHOR]

Indirect ultraviolet detection method is a simple and effective method for the determination of ionic liquid cations without ultraviolet absorption group. This paper focused on the influence of different background ultraviolet absorption reagents on the determination of piperidinium ionic liquid cations by ion pair chromatography with indirect ultraviolet detection. Ultraviolet absorption reagents are divided into cationic (4-aminophenol hydrochloride, 1-ethyl-3-methylimidazolium tetrafluoroborate, and N-ethylpyridinium tetrafluoroborate), anionic (potassium biphthalate and 5-sulfosalicylic acid), and amphiprotic (p-aminobenzoic acid). The results showed that piperidinium cations can be separated and detected by cationic and anionic ultraviolet absorption reagents. In general, the cationic ultraviolet absorption reagents have the best effect for separation and detection of the piperidinium cations by ion pair chromatography with indirect ultraviolet detection. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) have been labeled as a promising green alternative to traditional materials; however, many ILs have been discovered to be toxic, especially hydrophobic ILs (HILs). HILs are limited in their structural diversity as most are composed of heteroaromatic cations with long alkyl chains and paired with [BF4], [PF6], or [NTf2] anions. This study aims to diversify HILs by synthesizing two sets of HILs with unique cations and anions. The first set of HILs contain cholinium- and dicholinium-based cations paired with the [NTf2] anion. The [DC-ether] cation is identified as a promising cation and is paired with an array of asymmetric bis(sulfonyl)amide anions to form the second set of HILs. In total, twenty HILs are synthesized. Each HIL is characterized using traditional physicochemical techniques and is evaluted for toxicity using in vitro and in vivo methods. [ABSTRACT FROM AUTHOR]

Two types of layered sulfido stannates or a molecular cluster compound are obtained upon ionothermal treatment of the simple sulfido stannate salt K4[SnS4] · 4H2O that is based on binary tetrahedral [SnS4]4− anions. The formation of the respective products, novel compounds (C4C1C1Im)2[Sn3S7] (1 a), (C4C1C2Im)2[Sn3S7] (1 b), and (C4C1C2Im)2[Sn4S9] (2) with layered anionic substructures, or the recently reported compound (C4C1C1Im)4+x[Sn10O4S16(SMe)4][An]x (A) comprising a molecular cluster anion, is controlled by both the choice of the ionic liquid cation and the reaction temperature. We report the scale‐up of the syntheses by a factor of 100 with regard to other reported ionothermal syntheses of related compounds, and a procedure of how to isolate them in phase‐pure form – both being rare observations in chalcogenido stannate chemistry in ionic liquids. Moreover, the synthesis of compound 1 a can be achieved by rapid cation exchange starting out from 1 b, which has not been reported for organic cations in any chalcogenido stannate salt to date. [ABSTRACT FROM AUTHOR]

In this paper, a series of ionic liquids (ILs) contains cholinium as cations were prepared. These ILs were used as extractants to separate some model drug molecules. The partition coefficients of these drug molecules between ILs and aqueous solutions were determined. Furthermore, the influence of different extraction parameters was investigated: volume ratio, equilibrium time, pH values, temperature, and ILs structure. It is shown that these ILs are highly effective materials for the extraction of drug molecules. The results imply that these ILs may have potential in drug extraction or separation as a new type of media. [ABSTRACT FROM AUTHOR]

In the third issue of the then new journal Green Chemistry (2001, 3, 156-164), we published our first paper describing the physical properties of a few hydrophilic and hydrophobic ionic liquids (ILs) representing one of the first such studies to be published. To help celebrate the 15th anniversary of the Journal, we revisit the 'design' aspect of ILs by reviewing the growing area of what most are calling 'ionic liquid mixtures'. In 2001, designing IL properties meant essentially independent variation or synthesis of the cations and anions and determining what physical or chemical properties these liquid salts possessed. Recently, however, the mixing of ILs has been proposed and investigated as a way to add increased scope to the accessible properties of IL media. In this review, we question whether the same thinking and approach used for organic solvent mixtures should be applied to ILs simply because of the way they were made. Unlike organic solvent mixtures, IL compositions of varied ions, do not retain their individual nature, need not be made by simple mixing of two-ion salts, and preferential interactions of a given cation for a given anion are possible in these 3-ion, 4-ion, or higher order liquids. When two ILs are mixed together, one can't identify which ion is from which IL, and the chemistry is simply not based on the identity of the individual ILs, but on the ions comprising them and the interactions of each individual ion, independently of the counterion. Thus, we ask if it would not be better to consider these as unique ion combinations whose solvent properties are derived from the specific choice and abundance of each ion in the system. Through this review of the available literature, we support the concept of Double Salt Ionic Liquids (DSILs) and discuss the interactions involved in these systems, by examining their physicochemical properties and the novel applications they offer. [ABSTRACT FROM AUTHOR]

Using ab initio electronic structure methods with flexible atomic orbital basis sets, we investigated the electronic structure and stability of reduction products of selected representative cations (C+) constituting ionic liquids. We found that an electron attachment to such cations leads to the neutral radicals, whereas a subsequent attachment of another (i.e., excess) electron leads to adiabatically stable anions only in two cases {[P(CH3)4]− and [MeMePyr]−}. The possibility of the formation of various dimers (such as CC+, CC, and CC−) was also considered, and the resulting systems were characterized by predicting their lowest energy structures, ionization potentials, electron affinities, and susceptibilities to the fragmentation process. Among the cations studied, only the [MeMePyr]+ was found to form a typical Rydberg radical (MeMePyr) and double-Rydberg anion ([MeMePyr]−), whereas the remaining cations were predicted to form neutral radicals of a primarily valence (MeMeIm and MePy) or mixed Rydberg-valence [P(CH3)4] character. Our calculations confirmed the stability of all CC+ and CC dimers against fragmentation yielding the corresponding monomers (the binding energies of 12.2–20.5 kcal/mol and 11.3–72.3 kcal/mol were estimated for CC+ and CC dimers, respectively). [(MeMePyr)2]− was identified as the only adiabatically stable CC− dimeric anion having its vertical electron detachment energy of 0.417 eV. We also found that in the [(MeMePyr)2]− anionic state, three outermost electrons are described by Rydberg orbitals, which results in the (σ)2(σ*)1 configuration. [ABSTRACT FROM AUTHOR]

Here we report for the first time that unreacted N-methylimidazole (MIM) which is often a common impurity, can corrupt the results of a photophysical investigation of a probe molecule in imidazolium cation based RTILs. In addition, we propose a new type of sensor (functionalised 2-benzyledinemalononitrile derivative) for easy colorimetric detection and quantitative estimation of unreacted colourless MIM in RTILs. [ABSTRACT FROM AUTHOR]

Current research indicates that replacing organic solvents with room-temperature ionic liquids may lead to remarkable improvements in well-known processes. Ionic liquids have already been utilized as alternative solvents in organic synthesis and catalysis, and also in electrochemistry and in separation sciences. Their wide applicability will soon result in their production on an industrial scale. Therefore, analytical methods applicable to various matrices for product control and environmental monitoring will be very much in demand. In this study, the usefulness of π...π interactions between alkylimidazolium and pyridinium cations and the aromatic π...π active moiety of the stationary phase was investigated for the selective separation and analysis of some ionic liquids. With phenyl-bonded phases, very good separations of the cations were achieved. Special attention was paid to the short-chain hydrophilic entities, known to be poorly separated on conventional reversed-phase columns. Further, the nature of the interactions occurring in the system under study was investigated by varying the content of methanol/acetonitrile used as organic modifiers in the mobile phases. The analytical method developed here is simple and reproducible, and its quantitative analytical performance was excellent. The paper also discusses the applicability of the method for monitoring degraded cations of 1-butyl-3-methylimidazolium salts obtained in the Fenton process. [ABSTRACT FROM AUTHOR]

Owing to their favorable properties, ionic liquids have recently gained recognition as possibly environmentally benign solvents. Now among the most promising industrial chemicals, they have already been labeled “green”, but this appellation seems due entirely to their very low vapor pressure. This growing interest in the various applications of ionic liquids will soon result in their presence in the environment. Therefore, reliable analytical tools for the environmental analysis of ionic liquids need to be developed urgently. This paper presents a newly developed analytical procedure for the enrichment of 1-alkyl- and 1-aryl-3-methylimidazolium ionic liquids from water samples. The method is based on cation exchange solid-phase extraction followed by selective elution. Pre-concentrated samples are subjected to high-performance liquid chromatography (HPLC) with an advanced methodology for qualitative and quantitative analysis. The overall procedure was verified by using standard spiked samples of tap water, seawater, and freshwater. [ABSTRACT FROM AUTHOR]

This paper explores the thermodynamic behavior of aqueous solutions of four ionic liquids (ILs), namely 1-butyl-1-methylpyrrolidinium dicyanamide [BMPYR][DCA], 1-butyl-3-methylimidazolium dicyanamide [BMIM][DCA], 1-butyl-1-methylpyrrolidinium 1,1,2,2-tetrafluoroethanesulfonate [BMPYR][TFES], and 1-butyl-3-methylimidazolium 1,1,2,2-tetrafluoroethanesulfonate [BMIM][TFES]. The ionic liquids with [TFES] – anion (tetraflates) have been scarcely researched so far and therefore were characterized here with 1 H NMR spectroscopy and DSC calorimetry. In all four systems studied, water activity was systematically measured, the determinations being carried out in the whole composition range and at seven temperatures in the range from 288.15 K to 318.15 K. In addition, the mixing enthalpies in the IL dilute region for (water + DCA IL) systems and the solid-liquid equilibria for (water + TFES IL) systems were experimentally determined. The dependences of activity coefficients on temperature and composition were correlated ( i ) separately with appropriate flexible equations and ( ii ) simultaneously with an extended NRTL model. Both correlation approaches provide adequate description of mixture energetics and, as documented by comparisons with other relevant data, allow extrapolations of activity coefficients to both higher and lower temperatures as well as good predictions of excess enthalpy. Furthermore, the volumetric and viscosity behavior of highly dilute solutions of the ILs was explored. The concentration dependences of the apparent volume and viscosity were fitted well by the respective classical Redlich-Meyer and Jones-Dole equations. The values of partial molar volumes at infinite dilution were found to perfectly obey the ion additivity and correlate well with the intrinsic volume of IL molecule. Thermodynamic behavior of studied systems was compared to each other and discussed with respect to molecular interactions and nanostructure as well as to how involved ions affect it. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) are being considered as greener alternatives to conventional organic solvents. Recent applications of ILs in the dissolution and stability of biomolecules have led to increasing demand for biocompatible ILs. In the present work, we report the synthesis and toxicity study of tetramethylguanidinium [TMG] cation based ILs with benzoate, salicylate, lactate, dihydrogen phosphate, nitrate, formate, acetate, propanoate, butanoate and valerate anions. The results obtained from toxicological evaluation with normal HEK293 and cancerous DLD-1 cell cultures show that all studied ILs are non-toxic. Subsequent biodegradability tests with bacterial cultures Pseudomonas putida and Bacillus subtilis and a closed bottle test show that these ILs are also biodegradable. Our study suggests that the side-chain of the IL anions and anion–cation combination can influence the biocompatibility of the ILs immensely. [ABSTRACT FROM AUTHOR]

The present paper discusses the electrodeposition of nano-Aluminum using aromatic cation based ionic liquids. Three imidazolium chloride salts were employed, in ultrapure quality: l-ethyl-3-methyl-imidazolium chloride [EMIm]Cl, l-benzyl-3-methyl-imidazolium chloride [BzMIm]Cl and l,3-dibenzyl-imidazolium chloride [DBzIm]Cl, respectively. Anhydrous Aluminum chloride (AlCl 3 ) salt was used as a source of Aluminum ions in the ionic liquids. This research aims to achieve this goal by investigating the Aluminum coatings on gold substrate and study the effect of changing the organic cation on the properties of the resulting Al-coatings. SEM-EDAX analyses were used to determine the film composition. It was found that the particle size of the Al-deposites was dramatically reduced from the micrometer regime down to the nanometer regime with a change in the substituents of the imidazolium cations from EMIm to DBzIm, respectively. This means that the more the aromatic rings in the cation, the finer the particle size. Thickness and adhesion of the Al-deposits were decreased in the presence of the aromatic rings. [ABSTRACT FROM AUTHOR]

This paper studies the wetting properties of seven phosphonium cation-based ionic liquids: trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate [P66614][(iC8)2PO2], trihexyltetradecylphosphonium bis(2-ethylhexyl)phosphate [P66614][BEHP], trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl) imide [P66614][NTf2], tributyltetradecylphosphonium dodecylbenzenesulfonate [P44414][DBS], tributylethylphosphonium diethylphosphate [P4442][DEP], trihexyltetradecylphosphonium dicyanamide [P66614][DCA], and trihexyltetradecylphosphonium chloride [P66614][Cl]. The surface tension was analyzed using the Gibbs free energy in a temperature range of 293-353 K, obtaining the expected linear decrease with temperature rise. The contact angle was measured on four different surfaces (AISI 52100 steel, CrN, TiN, and ZrN) and all liquids with high surface tensions interacting with hydrophobic systems displayed high contact angles as expected. The polarity fraction (PF) and the spreading parameter (SP) were estimated to complete and improve the wetting characterization of these ionic liquids, finding TiN-[P66614][BEHP] and TiN-[P66614][(iC8)2PO2] as the most favorable surface-ionic liquid combinations from a wetting point of view. [ABSTRACT FROM AUTHOR]

In this work, by combining maleic anhydride-grafted polypropylene (PPgMA) and three different ionic liquids (ILs), i.e., tributyl (ethyl) phosphonium diethyl phosphate (denoted P+DEP), 1-ethyl-3-methylimidazolium diethyl phosphate (denoted EMIM DEP), and 1-ethyl-3-methylimidazolium acetate (denoted EMIM Ac), new ionic PP/IL polymer materials are generated and denoted as LIonomers. The structuration of ILs in LIonomers occurs from a nano/microphase separation process proved by TEM. NMR analyses reveal the existence of ionic–ionic and ionic–dipolar interactions between PPgMA and ILs within LIonomers. The rheological behavior of such IL/polymer combinations interpret the existence of interactions between maleic anhydride group and cation or anion composing the ionic liquid. These interactions can be tuned by the nature of cation (P+DEP vs. EMIM DEP) and anion (EMIM DEP vs. EMIM Ac) but also depend on the IL content. Thermal analyses demonstrate that IL could affect the crystallization process according to different pathways. Thanks to the maleic anhydride/IL interactions, an excellent compromise between stiffness and stretchability is obtained paving the way for processing new polyolefin-based materials. [ABSTRACT FROM AUTHOR]

Developing new synthetic strategies has long been a focus of chalcogenidometalate chemistry. This study demonstrated that the synergetic structure ‐ directing effect of ionic liquids (IL) and metal–amine complexes (MACs) in ionothermal syntheses could result in selenidostannate compounds with unprecedented crystal structures. The variation of selenidostannate skeletons is closely related to the synergy of two different structure ‐ directing agents (SDAs), the IL 1 ‐ butyl ‐ 2,3 ‐ dimethyl ‐ imidazolium chloride and the MACs with different polyamine ligands. More information can be found in the Full Paper by Xiao ‐ Ying Huang et   al. on page   1555 in Issue 10, 2016 (DOI: 10.1002/asia.201600073). [ABSTRACT FROM AUTHOR]

Solvatochromic probes are often used to understand solvation environments at the molecular scale. In the case of ionic liquids constituted by an anion and a cation, which are designed and paired in order to obtain a low melting point and other desirable physicochemical properties, these two indivisible components can interact in a very different way with the probe. This is the case with one of the most common probes: Reichardt's Dye. In the cases where the positive charge of the cation is delocalized on an aromatic ring such as imidazolium, the antibonding orbitals of the positively charged aromatic system are very similar in nature and energy to the LUMO of Reichardt's Dye. This leads to an interesting, specific cation-probe interaction that can be used to elucidate the nature of the ionic liquids' cations. Parallel computational and experimental investigations have been conducted to elucidate the nature of this interaction with respect to the molecular structure of the cation. [ABSTRACT FROM AUTHOR]

Description of the local microscopic structure in ionic liquids (ILs) is a prerequisite to obtain a comprehensive understanding of the influence of the nature of ions on the properties of ILs. The local structure is mainly determined by the spatial arrangement of the nearest neighboring ions. Therefore, the main interaction patterns in ILs, such as cation-anion H-bond-like motifs, cation-cation alkyl tail aggregation, and ring stacking, were considered within the framework of the nearest-neighbor approach with respect to each particular interaction site. We employed classical molecular dynamics (MD) simulations to study in detail the spatial, radial, and orientational relative distribution of ions in a set of imidazolium-based ILs, in which the 1-butyl-3-methylimidazolium (C4mim+) cation is coupled with the acetate (OAc-), chloride (Cl-), tetrafluoroborate (BF4 -), hexafluorophosphate (PF6 -), trifluoromethanesulfonate (TfO-), or bis(trifluoromethanesulfonyl)amide (TFSA-) anion. It was established that several structural properties are strongly anion-specific, while some can be treated as universally applicable to ILs, regardless of the nature of the anion. Namely, strongly basic anions, such as OAc- and Cl-, prefer to be located in the imidazolium ring plane next to the C-H2/4-5 sites. By contrast, the other four bulky and weakly coordinating anions tend to occupy positions above/below the plane. Similarly, the H-bond-like interactions involving the H² site are found to be particularly enhanced in comparison with the ones at H4-5 in the case of asymmetric and/or more basic anions (C4mimOAc, C4mimCl, C4mimTfO, and C4mimTFSA), in accordance with recent spectroscopic and theoretical findings. Other IL-specific details related to the multiple H-bond-like binding and cation stacking issues are also discussed in this paper. The secondary H-bonding of anions with the alkyl hydrogen atoms of cations as well as the cation-cation alkyl chain aggregation turned out to be poorly sensitive to the nature of the anion. [ABSTRACT FROM AUTHOR]

This paper studies physicochemical properties (density, viscosity, corrosion, thermogravimetry, and conductivity) and tribological behavior of five phosphonium cation-based ionic liquids ([P 66614 ][BEHP], [P 66614 ][C 8 C 8 PO 2 ], [P 66614 ][NTf 2 ], [P 44414 ][DBS], and [P 4442 ][DEP]) as neat lubricants within steel–steel contact. A reciprocating ball-on-disc configuration was used to perform tribological tests. Worn surfaces were analyzed by confocal microscopy, SEM, EDS and XPS. Main results showed that: [P 66614 ][NTf 2 ], [P 44414 ][DBS], and [P 4442 ][DEP] showed corrosion activity; the ionic liquids with more reactive phosphate type anion ([P 66614 ][BEHP] and [P 4442 ][DEP]) had the best tribological behavior; the best tribological results were related to the tribofilm formation of two phosphate species. [ABSTRACT FROM AUTHOR]

In this work, neoteric and biodegradable ionic liquids (ILs) based on various hydroxyl ammonium cations and formic acid anions have been used as media for biocatalytic oxidoreductions catalyzed by different metalloproteins. The effect of these ILs on the biocatalytic behavior and structure of solubilized enzymes was investigated using cytochrome c (cyt c) as a model protein. The use of IL-based media enhances the tolerance of cyt c against the denaturing effect of H2O2 and increases (up to 20 fold) its catalytic efficiency compared to that observed in buffer. This beneficial effect strongly correlates with the concentration of ILs used, as well as the chaotropicity of their cations. UV–vis, circular dichroism and Fourier transform infrared (FT-IR) spectroscopic studies indicated that, the effect of ILs on the catalytic behavior of cyt c could be correlated with slight structural changes on the protein molecule and/or perturbations of the heme microenvironment. The use of hydroxyl ammonium-based ILs as reaction media increased (up to 4-fold) the decolorization activity of cyt c. All ILs used were recycled and successfully reused three times indicating the potential application of these novel ILs as environmentally friendly media for biocatalytic processes of industrial interest. [ABSTRACT FROM AUTHOR]

Hydrotropes are compounds able to enhance the solubility of hydrophobic substances in aqueous media and therefore are widely used in the formulation of drugs, cleaning and personal care products. In this work, it is shown that ionic liquids are a new class of powerful catanionic hydrotropes where both the cation and the anion synergistically contribute to increase the solubility of biomolecules in water. The effects of the ionic liquid chemical structures, their concentration and the temperature on the solubility of two model biomolecules, vanillin and gallic acid were evaluated and compared with the performance of conventional hydrotropes. The solubility of these two biomolecules was studied in the entire composition range, from pure water to pure ionic liquids, and an increase in the solubility of up to 40-fold was observed, confirming the potential of ionic liquids to act as hydrotropes. Using dynamic light scattering, NMR and molecular dynamics simulations, it was possible to infer that the enhanced solubility of the biomolecule in the IL aqueous solutions is related to the formation of ionic-liquid–biomolecules aggregates. Finally, it was demonstrated that hydrotropy induced by ionic liquids can be used to recover solutes from aqueous media by precipitation, simply by using water as an anti-solvent. The results reported here have a significant impact on the understanding of the role of ionic liquid aqueous solutions in the extraction of value-added compounds from biomass as well as in the design of novel processes for their recovery from aqueous media. [ABSTRACT FROM AUTHOR]

The crystal structures of dicationic ILs [DBMIM][2BF4] (1) and [DBMIM][2Br]·[2H2O] (2) were investigated in order to explore the intermolecular interactions in these compounds. An energetic and topological approach for characterization of supramolecular clusters in organic crystals was used. The study of the crystals was done by considering the stabilization energy and topological properties such as contact surfaces and energy content between cations and neighboring anions (supramolecular clusters). The study showed that: 1 is auto-organized into layers (one-dimensional structure) by an anion–cation interaction (weak electrostatic and ionic), and the three-dimensional supramolecular structure of 2 is constructed through simultaneous interactions between cations, anions, and water molecules. This network results in interaction chains in two different directions. Additionally, the supramolecular cluster approach allowed evaluation of the participation of the topological component during the formation of the crystals of 1 and 2. Among the different types of interactions proposed, the most predominant was the one classified as type III, which has small and medium energy values, and a medium-sized contact surface. The thermal and morphological properties were also studied to further characterize these materials and to better understand the resulting structure–property relationships. [ABSTRACT FROM AUTHOR]

To investigate the influence of ionic liquids on the structures and properties of the complexes, ionothermal synthesis of 1,4-benzenedicarboxylate acid (H2BDC) reacting with Co(NO3)2 with four different 1-alkyl-3- methylimidazolium bromides produced three layered metal-organic frameworks with the chemical formula [RMI]2[Co3(BDC)3Br2], (R = ethyl for 1; n-propyl for 2, and n-butyl for 3; MI = imidazolium) and a 3D architecture [AMI]2[Co3(BDC)4] (4) (A = amyl). Compounds 1-3 have the same (3,6) skeleton with [RMI]+ cations located in the interlayer space. Compound 4 grows into a 3D architecture based on BDC2- ligands linking similar 2D grids as those in 1-3. The [RMI]+ templates exert their influence on the diagonal sizes of the quadrilateral grids, the interlamellar spacing, and the solvent-accessible cavities through steric hindrance. By comparison of 1-3, the [RMI]+ templates also have an effect on the properties. As the alkyl chains in [RMI]+ increase, the decomposing temperatures increase, emission peaks around 400 nm blue shift, and the cavities of 1-3 decrease. 1-3 exhibit ferromagnetism with similar magnetic parameters, while 4 reveals antiferromagnetism. [ABSTRACT FROM AUTHOR]

Ionic liquids (ILs) are considered to be excellent alternatives to organic solvents, and are commonly used nowadays. However, introducing new classes of compounds always comes with the possibility of environmental threat and health issues they may induce. This work was aimed at examining which structural features of ILs are responsible for their toxicity. There are examples of structure-activity relationship models for ILs in the literature. However, in our approach, we have analysed this issue globally for a wide range of ionic liquids and their toxicity was measured by multiple toxicological tests (multiple endpoints). We have collected the experimentally measured available literature data on the toxicity of ILs for various organisms. Then, by employing Principle Component Analysis (PCA), we examined the structural similarity of 375 different ionic liquids having six different types of cations (namely imidazolium, ammonium, phosphinium, pyridinium, pyrolidinium and sulfonium). For expressing the structural features of studied ILs we used Weighted Holistic Invariant Molecular (WHIM) descriptors, calculated for cations and anions separately. The geometry of each structure was optimized at the level of the semi-empirical PM7 method. The toxicological response was thereafter analyzed in the space of the first and second principle components. We pointed out that for most of the tested cases there is a strong relationship between the variance in the observed toxicity and the cations' descriptors. We also proved the anions' influence on the IL toxicity to be less meaningful. After repeating PCA using only the cations' descriptors, we proved that the toxicity of ILs against selected targets depends mostly on the size and branching of the cation. On this basis, we have proposed a Toxicity Ranking Index based on the structural similarity of Cations (TRIC) for the initial toxicity screening studies of ILs. It should be mentioned however that the use of TRIC is limited to the prediction of toxicity endpoints used in its development. The use of TRIC as a preliminary toxicity indicator would provide a general view on ILs' toxicological potential and its predictions may provide valuable conclusions, which, taken under consideration, may help in simplifying the procedure of designing new greener and safer ionic liquids in future. [ABSTRACT FROM AUTHOR]

Extraction of tetrachloroaurate or tetrabromoaurate anions has been carried out using several ionic liquids bearing trialkyl(2-ethoxy-2-oxoethyl)ammonium (alkyl group = C2H5 [EtGBOEt+], n-C3H7 [PrGBOEt+] or n-C4H9 [BuGBOEt+]) cations and halide (Cl− or Br−), bis(trifluoromethanesulfonyl)imide (Tf2N−) and dicyanamide (Dca−) anions. The removal of gold anionic moieties from water was first studied by mixing aqueous solutions containing gold complexes and water soluble bromide ionic liquids. This led to the formation of a solid precipitate corresponding to a hydrophobic ionic liquid based on a tetrahalogenoaurate anion. Liquid–liquid extraction of anionic gold complexes using hydrophobic ionic liquids was also investigated. [ABSTRACT FROM AUTHOR]

Ionothermal reactions of uranyl salts in several ionic liquids containing cyclic cations produced single crystals of five new uranyl compounds. (C4H7N2)[(UO2)(AsO4)] (1), (C8H15N2)2[(UO2)4(SeO3)5](2), (C6H11N2)2[(UO2)3(C2H5PO4)4](3), and (C5H5N)2[(UO2)2(SeO4)3](4) are each comprised of two-dimensional structural units. (C4H7N2)[(UO2)5(PO4)3(HPO4)(H2O)2]⋅3H2O(5) is composed of a three-dimensional network. While the uranyl structural units in all five compounds are directly related to ones found in either uranyl minerals or compounds produced in aqueous media, each contain cyclic ionic liquid constituents as charge-balancing agents. These results suggest that the cation selectivity of these structural units is low, even under various solvation conditions and templating effects from cyclic cations donated from ionic liquid media. [ABSTRACT FROM AUTHOR]

A range of ionic liquids containing dialkylimidazolium cations and halobismuthate anions ([BiBrxClyIz]- and [Bi2BrxClyIz]-) were synthesised by combining dialkylimidazolium halide ionic liquids with bismuth(III) halide salts. The majority were room temperature liquids, all with very high densities. The neat ionic liquids and their mixtures with 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide were characterised using Densitometry, Viscometry, NMR Spectroscopy, Electrospray Ionisation Mass Spectrometry (ESI), Liquid Secondary Ion Mass Spectrometry (LSIMS), Matrix-assisted Laser Desorption/Ionization Mass Spectrometry (MALDI), X-Ray Photoelectron Spectroscopy (XPS) and Thermogravimetric Analysis (TGA), to establish their speciation and suitability for high-temperature applications. [ABSTRACT FROM AUTHOR]

Thermal conductivity is an importantthermophysical propertyof ionic liquids (ILs). In this paper, a database for the thermalconductivity of ILs was established by collecting experimental datafrom literature covering the period from 2007 to 2013, including 359data points, 45 ILs. The influences of temperature and the alkyl chainlength of the cation on thermal conductivity were also discussed.A topological index method was proposed to estimate the thermal conductivityof ILs based on collected data which were divided into training (299data points, 38 ILs) and testing (60 data points, 7 ILs) sets. Thetotal average absolute deviation between the calculated and literaturedata was found to be 2.3%, with 2.1% for the training set and 2.9%for the testing set. The topological index method guarantees satisfactoryprecision with a simple form and can be easily expanded to new kindsof ILs. [ABSTRACT FROM AUTHOR]

The chemical and thermal stability of ionic liquids (ILs) makes them interesting for a large variety of applications in nearly all areas of the chemical industry. However, this stability is often reflected in their recalcitrance towards biodegradation, which comes with the risk of persistence when they are released into the environment. In this study we carried out a systematic investigation of the biodegradability of pyrrolidinium, morpholinium, piperidinium, imidazolium and pyridinium-based IL cations substituted with different alkyl or functionalised side chains and using halide counterions. We examined their primary degradability by specific analysis and/or their ultimate biodegradability using biochemical oxygen demand tests according to OECD guideline 301F. Biological transformation products were investigated using mass spectrometry. A comparison of the biodegradation potential of these ILs shows that for all five head groups, representatives can be found that are readily or inherently biodegradable, thus permitting the structural design of ILs with a reduced environmental hazard. [ABSTRACT FROM AUTHOR]

As a kind of promising solvents, ionic liquids (ILs) have been used to dissolve cellulose and great progress has been made in recent years. However, the dissolution mechanism, especially the role of cations of ILs in the dissolution of cellulose, is still in debate. In this work, 13 kinds of ILs with a fixed anion [CH3COO]- but varied cationic backbones and alkyl chains have been prepared and characterized. The solubilities of cellulose in these ILs were measured at different temperatures. This allowed us to systematically study the effect of cationic structures on the cellulose dissolution at a given temperature. In order to investigate the dissolution mechanism, Kamlet-Taft parameters of these ILs in the temperature range from 25 to 65°C and 13C NMR spectra of 1-benzyl-3-methylimidazolium acetate ([phC1mim][CH3COO]) + cellulose systems at 90°C were also determined. It was found that acidic protons on the heterocyclic rings of the cations are essential for the dissolution of cellulose in the ILs, but the van der Waals interaction of cation with cellulose is not important. These protons may form C-H···O hydrogen bonds with hydroxyl and ether oxygen of cellulose to increase cellulose solubility. Cations of the ILs may also decrease cellulose solubility by strong interaction with anions or steric hindrance effect of large size group in their alkyl chains. These interactions together with strong O-H···O hydrogen bonds between the anion and hydroxyl protons of cellulose resulted in the disruption of the inter- and intra-molecular hydrogen bonds and thus effective dissolution of cellulose. [ABSTRACT FROM AUTHOR]

Future applications of ionic liquids (ILs) in a variety of areas, especially those having high radiation fields such as the nuclear fuel cycle and in space technology, are under serious consideration nowadays. For such applications to be possible, however, radiation stability of the ILs is an important issue that needs to be addressed. We envisaged that the ultra-hydrophobic, bulky and hydrolytically stable FAP (tris(perfluoroalkyl) trifluorophosphate) anion might shield the radiolytically vulnerable imidazolium cations from degradation and our result shows that these anions indeed enhance their radiolytic stability. However, introduction of a hydroxyl group into the alkyl side chain of the imidazolium moiety resulted in significant changes in the physical properties of the IL with respect to onset temperatures, conductivity and the electrochemical window. Furthermore, a nonlinear trend in absorbance with an increase in radiation dose accompanied by NMR (nuclear magnetic resonance) and mass spectrometry studies clearly demonstrated that the presence of the hydroxyl group promotes various degradation channels. Interestingly, a perturbation of the hydrogen bond between the hydroxyl group (present in the side chain of the cation) and the fluorine atom of the anion (OH＝F) was evident in the case of irradiated hydroxyl functionalized FAP ILs. Besides, the hydrogen gas yields of the ILs were determined and found to be comparable to those of a radiolytically stable aromatic compound, benzene. Finally, through transient spectroscopic studies we could delineate the mechanism of the radiation induced changes in the physicochemical properties of the non-hydroxyl and hydroxyl containing FAP ILs. We have clearly demonstrated that a simple functionalization of the molecular structure of the FAP based imidazolium ILs might cause marked differences in the reactivity, reaction center and the nature of the radiolytic products, which eventually lead to significant changes in their physicochemical properties. [ABSTRACT FROM AUTHOR]

Polyvinylpyrrolidone-stabilized heteropolyacids (PVP-HPAs) are synthesized by self-assembling in alcohol. The structure of PVP-HPAs is determined by various characteristic techniques. HPAs can protonate PVP to form polymeric cations. In turn, the protonated PVP interacts strongly with the heteropolyanion by forming an ionic liquid (IL)-like structure. The self-assembling separation and recyclability characteristics are related to the PVP's IL-like structure. The catalyzing performance of PVP-HPAs varies with the species of HPA and the content of PVP. The optimized PVP-H4SiW12O40·5H2O (HSiW) (1/5 : 3/4) gives more than 60% conversion of cellulose and complete conversion of highly selective cellobiose into butylglucosides. The optimized PVP-HSiW is separated directly by centrifugation and retains the activity without any post-treatment during recycling. The deactivation of PVP-HPAs is related to the loss of the catalyst during recycling. The functional mechanism of the IL-like structure is explored in this control experiment. [ABSTRACT FROM AUTHOR]

Supportedionic liquid membranes (SILMs) are promising tools for the separationof carbon dioxide from other gases. In this paper, new imidazolium,pyrrolidinium, piperidinium, and morpholinium ionic liquids with atriethylene glycol side chain and tosylate anions, as well as theirsymmetrical dicationic analogues, have been synthesized and incorporatedinto SILMs. The selectivities for CO2/N2andCO2/CH4separations have been measured. Theselectivities exhibited by the dicationic ionic liquids are up totwo times higher than the values of the corresponding monocationicionic liquids. Quantum chemical calculations have been used to investigatethe difference in the interaction of carbon dioxide with monocationicand dicationic ionic liquids. The reason for the increased gas separationselectivity of the dicationic ionic liquids is two-fold: (1) a decreasein permeance of nitrogen and methane through the ionic liquid layer,presumably due to their less favorable interactions with the gases,while the permeance of carbon dioxide is reduced much less; (2) anincrease in the number of interaction sites for the interactions withthe quadrupolar carbon dioxide molecules in the dicationic ionic liquids,compared to the monocationic analogues. [ABSTRACT FROM AUTHOR]

Nafion® is the polymer electrolyte membrane most used in fuel cells (PEMFC), however Nafion® presents some limitations due to the water loss with increasing temperature. In this work is presented the study of the molecular dynamics in modified Nafion®/ionic liquids (IL) cations membranes with increasing temperature, by proton NMR relaxometry (1H NMRD). Three Nafion® membranes modified with Phenyltrimethylammonium (TMPA+), 1- n-butyl-3-methylimidazolium (BMIM+) and n-dodecyltrimethylammonium (DTA+) IL cations were considered. This study allowed the evaluation of the effect of the IL cations incorporation in Nafion® membranes and to assess the degree of confinement of the IL cations in the membranes matrix in relation with the water content. Thermogravimetry analysis was also performed to study the water loss with increasing temperature of the Nafion®/IL cations membranes. It was possible to establish a correlation between the water content and the IL cations self-diffusion coefficients. The sequential order of the hydration level obtained for the studied systems was Nafion®/DTA+>Nafion®/BMIM+ ≳ Nafion®/H+>Nafion®/TMPA+, while the water loss follows the sequence Nafion®/H+>Nafion®/BMIM+∼Nafion®/DTA+>Nafion®/TMPA+. The Nafion®/BMIM+ presented the largest temperature variation of both the self-diffusion coefficient and the hydration conditions. In terms of PEMFCs efficiency, the Nafion®/DTA+ modified membrane seems to offer the largest and stable hydration conditions with temperature. [ABSTRACT FROM AUTHOR]

A series of novel halogen-free ionic liquids (ILs) based on N, N'-dialkylimidazolium, tetra-alkylphosphonium, and di-alkylpyrrolidinium cations paired with two aprotic heterocyclic anions (AHAs) were synthesized and tested as potential electrolytes. In addition, the corresponding lithium salts were prepared to investigate the impacts of the Li salts on the physical properties of the IL-Li mixtures. Physicochemical and electrochemical properties (density (ρ), viscosity (η), electrical conductivity (σ) and electrochemical window (EW) of the neat ILs and their mixtures with the lithium salts at various concentrations were measured at temperatures between 283.15 K and 343.15 K and at atmospheric pressure. The results indicate that ILs with both planar anions and cations exhibit lower viscosities, and better conductivities than those with more spherical geometries, while maintaining competitive EWs. The Walden plot behavior of the ILs provides qualitative insight into the suitability of these ILs as electrolytes. Based on systematic studies shown in this paper, it can be concluded that these new ILs are promising halogen-free electrolytes that deserve further investigation [ABSTRACT FROM AUTHOR]

Room temperature ionic liquids (ILs) are effective matrices in secondary ion mass spectrometry (SIMS) and matrix assisted laser desorption ionization (MALDI). In this paper, we examine the role of proton transfer in the mechanism of secondary ion enhancement using IL matrices in SIMS. We employ hydrogenated and deuterated 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) as analytes to investigate the origin of proton transfer. The data indicate that protons from the IL anion transfer to the analyte in solution leading to an increase in the secondary ion intensity of the protonated molecular ion. The chemical identity of the matrix cation also affects analyte signal intensities. Using deuterated DPPC we observe that protons (deuterium) from the DPPC tail group react with the cation of the IL liquid leading to an increase in (cation + D) ion intensities. Further, the data suggest that the transfer kinetics of deuterium (hydrogen) is correlated with the secondary ion enhancements observed. The highest secondary ion enhancements are observed for the least sterically hindered cation. Neither the proton affinity nor the pK of the IL cation have a large effect on the analyte ion intensities, suggesting that steric factors are important in determining the efficacy of IL matrices for a given analyte. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]