Ionic Liquids

Effects of an ionic liquid, 1-n-tetradecyl-3-methylimidazolium bromide ([C14MIM] Br), as a foaming additive on the foaming behavior of polypropylene(PP) by supercritical CO2 technique was reported. Mass ratio of PP/[C14MIM] Br up to 100: 10 was incorporated via melt blending. The melting behavior and fractured morphology of PP/[C14MIM] Br samples were investigated by differential scanning calorimetry(DSC) and scanning electron microscopy(SEM), respectively. The CO2 sorption was measured by commonly accepted gravimetric method. The results of DSC and CO2 sorption experiments show that [C14MIM] Br has little effect on the crystallinity, melting point and the mass uptake of CO2 of PP. SEM images reveal that [C14MIM] Br forms a well-dispersed phase, whose size increases with [C14MIM] Br content, in the PP matrix. The foamed PP/[C14MIM] Br samples exhibit close cell structure, increased cell size and decreased unfoamed region and bulk density, compared with pure PP foamed under the same saturation conditions of 155 degrees C/10 MPa, indicating ionic liquid [C14MIM] Br has significant effect on the foaming behavior of PP.
Chemical Journal of Chinese Universities -Chinese Edition- 05/2010; 31(5):861-863.

This paper examined the effect of several pyridinium and imidazolium-based ionic liquids (ILs) on the protease stability in aqueous solutions. In general, the enzyme was found quite active at low concentrations of hydrophilic ILs. In aqueous environment, the enzyme was stabilized by the kosmotropic anions (such as CF3COO− and CH3COO−) and chaotropic cations (such as [BuPy]+ and [EMIM]+), but was destabilized by chaotropic anions (such as tosylate and BF4−) and kosmotropic cations (such as [BMIM]+).Hydrophilic ionic liquids dissociate into individual ions in water. The effect of individual ions on the enzyme activity follows the Hofmeister series: kosmotropic anions and chaotropic cations stabilize the enzyme.

[where trpy = 2,2':6',2''-terpyridine and CN-Me = 3methyl-1-(pyridin-2-yl)-imidazolylidene] has been prepared and thoroughly characterized by spectroscopic and electrochemical techniques. The complex has been tested in epoxidation catalysis both in dichloromethane and dichloromethane:ionic liquid media, displaying excellent performances and selectivities. Reuse of the catalyst in ionic liquid:solvent media has been explored for the first time in ruthenium-mediated epoxidation catalysis and its performance is fully maintained for up to ten runs.

Removal of air pollutants, such as nitrogen and sulphur containing compounds from a model oil (dodecane) was studied. An ionic liquid (1-ethyl-3-methylimidazolium chloride [C 2 mim] [Cl]) was used as an extractant. Liquid-liquid extraction by using 1-ethyl-3-methylimidazolium chloride [C 2 mim] [Cl] was found to be a very promising method for the removal of N-and S-compounds. This was evaluated by using a model oil (dodecane) with indole as a neutral nitrogen compound and pyridine as a basic nitrogen compound. Dibenzothiophene (DBT) was used as a sulphur compound. An extraction capacity of up to 90 wt% was achieved for the model oil containing pyridine, while only 76 wt% of indole in the oil was extracted. The extraction capacity of a model sulphur compound DBT was found to be up to 99 wt%. Regeneration of the spent ionic liquid was carried out with toluene back-extraction. A 1:1 toluene-to-IL wt ratio was performed at room temperature. It was observed that, for the spent ionic liquid containing DBT as a model compound more than 85 wt% (corresponding 3852 mg/kg) could be removed from the oil. After the second regeneration cycle, 86 wt% of the DBT was recovered from the ionic liquid to toluene. In the case of indole as the nitrogen containing species, more than 99 wt%, (corresponding to 2993 mg/kg) of the original indole was transferred from the model oil to the ionic liquid. After the first-regeneration cycle of the spent ionic liquid, 54 wt% of the indole-in-IL was transferred to toluene. Thus, both extractions of nitrogen and sulphur model compounds were successfully carried out from model oil and the back-extraction of these compounds from the ionic liquids to toluene demonstrated the proved the concept of the regeneration point of view.

In this paper, it is shown that high vacuum conditions are not sufficient to completely remove water and oxygen from the ionic liquid 1-ethyl-3-methylimidazolium chloride. Complete removal of water demands heating above 150 1C under reduced pressure, as proven by Nuclear Reaction Analysis (NRA). Dissolved oxygen gas can only be removed by the use of an oxygen scavenger such as hydroquinone, despite the fact that calculations show that oxygen should be removed completely by the applied vacuum conditions. After applying a strict drying procedure and scavenging of molecular oxygen, it was possible to deposit copper directly on tantalum without the presence of an intervening oxide layer.

Densities, viscosities and refractive indices have been determined for mixtures of acetophenone with N,N-dimethylethanolamine or with N,N-diethylethanolamine over the entire composition range at temperatures of (303.15, 313.15 and 323.15) K. The viscosity values were fitted to the Krishnan-Laddha and McAllister models. The thermophysical properties under study were also fitted to the Jouyban-Acree model. The excess values were correlated using the Redlich-Kister polynomial equation. It was found that, in all cases, the obtained data were correlated very well by the corresponding models. The molecular interactions existing between the components are also discussed.

The differential capacitance of the electrical double layer at glassy carbon, platinum and gold electrodes immersed in various ionic liquids was measured using impedance spectroscopy. We discuss the influence of temperature, the composition of the ionic liquids and the electrode material on the differential capacitance/potential curves. For different systems these curves have various overall shapes, but all include several extremes and a common minimum near the open circuit potential. We attribute this minimum to the potential of zero charge (PZC). Significantly, the differential capacitance generally decreases if the applied potential is large and moving away from the PZC. This is attributed to lattice saturation [A. A. Kornyshev, J. Phys. Chem. B, 2007, 111, 5545] effects which result in a thicker double layer. The differential capacitance of the double layer grows and specific adsorption diminishes with increasing temperature. Specific adsorption of both cations and anions influences the shapes of curves close to the PZC. The general shape of differential capacitance/potential does not depend strongly on the identity of the electrode material.

Recently, ionic liquids (ILs) are used for biomass valorization into valuable chemicals because of their remarkable properties such as thermal stability, lower vapor pressure, non-flammability, higher heat capacity, and tunable solubility and acidity. Here, we demonstrate a method for the synthesis of C5 sugars (xylose and arabinose) from the pentosan present in jute biomass in a one-pot process by utilizing a catalytic amount of Brønsted acidic 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate IL. The acidic IL is synthesized in the lab and characterized using NMR spectroscopic techniques for understanding its purity. The various properties of BAIL are measured such as acid strength, thermal and hydrothermal stability, which showed that the catalyst is stable at a higher temperature (250 °C) and possesses very high acid strength (Ho 1.57). The acidic IL converts over 90% of pentosan into sugars and furfural. Hence, the presenting method in this study can also be employed for ...

In this study, a different class of high nitrogen content ionic liquids were designed. The physicochemical properties of [DMT][4-XPhSO3], (X = NH2, OH, H, F, Br, CHO, CF3, CN and NO2) IPs based on the triazolium cation and substituted benzene sulfonate anions were fully investigated using M06–2X functional in conjunction with the aug-ccpvdz basis set. For all of the designed ILs the structural parameters, interaction energy between constructing parts, enthalpy of formation, natural charges and topological properties were calculated and discussed. The effect of the substituent change at anion part on the interaction energy and physicochemical properties is taking into account for the first time. As revealed from the results, the strength of the interaction between constructing ionic parts had a linear correlation with the electron content of the anionic part in a way that the more stable ion pairs with higher interaction energies constructed as the electron content of the anionic part increased. Melting point, critical-point temperature, electrochemical stability and conductivity which are some of the important IL,s characteristic physical properties were estimated, compared with each other and discussed with the help of the quantum chemical computationally obtained thermochemical data for nine designed various X substituted [DMT][4-XPhSO3] ILs. Finally, the enthalpy and Gibbs free energy of the formation for nine various substituted anions were calculated.

The selection of separation process of organic compounds is a critical issue in the chemical industry. Different conventional methods, such as coagulation, precipitation, ion exchange, electrodialysis, adsorption, ultrafiltration and liquid-liquid extraction have been used for the separation processes since last so many years, but supported liquid membrane (SLM)-based separation processes have been predicted as a promising option. Ionic liquids (ILs) are considered a new miraculous chemical due their unique properties and large variety of applications in all areas of the chemical sciences. The use of ionic liquids as a liquid membrane phase results in the stabilization of the SLMs due to their negligible vapor pressure, possibility of minimizing their solubility in the surrounding phases and greater capillary force associated with their high viscosity, which can reduce the displacement of liquids from micron pores under pressure. This review article summarizes the role of ionic liquids in supported liquid membrane technology for extraction processes, stability of the membranes and show promise in the liquid/liquid extraction of organics from water, gases, amino acids, toxic metal ions from their aqueous solution and separating isomeric organic compounds. © 2011 Elsevier B.V.

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Nanostructured polyanilines (PANIs) with a variety of morphologies were synthesized in acidic aqueous solutions with an added ionic liquid, 1-butyl-3-methylimidazolium chloride. The influence of various reaction conditions, i.e., the molar ratio of aniline to ionic liquid and initial aniline concentration, on the morphology and properties of the synthesized PANIs were investigated. The morphologies of the PANIs, as studied by scanning electron microscopy (SEM), range from nanowires to complex three-dimensional structures and were influenced particularly by the molar ratio of aniline to ionic liquid. The chemical structure and molecular-weight characteristics, as determined by Fourier-transform infrared spectroscopy (FTIR), UV-Vis spectroscopy and size-exclusion chromatography (SEC), were not affected by the reaction conditions, indicating that the aniline polymerization mechanism did not change in the presence of the ionic liquid, which acted as a soft template. The conductivities of the prepared PANI samples, as measured by impedance spectroscopy, were of the order of 10 −2 S/cm.

The magnetic, optical, and catalytic properties of soluble metal nanoparticles (MNPs) depend primarily on their size, shape, and type, and on the nature of the stabilizer. The generation of MNPs of controlled size and shape has been achieved by using a variety of methods that are mainly based on the use of ligands. Indeed, the vast majority of stable and soluble MNPs formed from transition metals have a ligand and/or oxide environment that has a substantial effect on the metal-surface properties of the nanoparticles. The synthesis of stable, soluble, naked, and ligand-free MNPs of controlled size and shape still remains a challenge. Although these MNPs can be produced in organic solvents (e.g., alcohols or tetrahydrofuran) by the simple decomposition of organometallic precursors, the properties of these nanoparticles cannot be investigated in solution because of their poor stability and the volatility of the solvents. Since imidazolium ionic liquids (ILs) possess preorganized structures that can adapt or are adaptable to many species-as they provide hydrophobic or hydrophilic regions with high directionality-they are emerging as alternative liquid templates for the generation of a plethora of size-and shapecontrolled nanostructures. In particular, the size of "soluble" MNPs is apparently directly related to IL selforganization, and can thus, in principle, be tuned by modulating the length of the N-alkyl imidazolium side chains, reaction temperature, anion volume, or anion coordination ability. Moreover, the advent of imidazolium ILs that possess very low vapor pressure and high thermal stability has opened the way for the investigation of processes in solution using physical methods, for example, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy, which require special conditions such as high vacuum. We report herein that, with the proper combination of N-alkyl imidazolium side chain, anion, and reaction conditions, ligand-free cobalt MNPs with either cubic or spherical shapes can be prepared. Moreover, we present the magnetic and catalytic properties of these naked ligand-free MNPs in 1-alkyl-3-methylimidazolium ILs.

The influence of the alkyl chain length and of the anion on the lubricating ability has been studied for the room-temperature ionic liquids (IL) 1-n-alkyl-3-methylimidazolium X − [X = PF 6 ; n = 6 (L-P106). X = BF 4 ; n = 2 (L102), 6 (L106), 8 (L108). X = CF 3 SO 3 ; n = 2 (L-T102). X = (4-CH3C6H4SO3); n = 2 (L-To102)]. Neat IL have been used for AISI 52100 steel-ASTM 2011 aluminium contacts in pin-on-disk tests under variable sliding speed. While all IL give initial friction values lower than 0.15, real-time sharp friction increments related to tribochemical processes have been observed for L102 and L-P106, at room-temperature and at 100 • C. Electronic microscopy (SEM), energy dispersive (EDS) and X-ray photoelectron (XPS) spectroscopies show that wear scar surfaces are oxidized to Al 2 O 3 and wear debris contain aluminium and iron (for L102) fluorides. For L-P106, the steel surface is covered with a P-containing tribolayer. A change of anion (L-T102; L-To102) reduces friction and wear, but the lowest values are obtained by increasing the alkyl chain length (L106; L108). When the more reactive L102 and L-P106 are used as 1 wt.% base oil additives at 25 • C, tribocorrosion processes are not observed and a friction reduction (69-75% for 1 wt.% L102) and a change from severe (10 −3 mm 3 m −1 ) to mild wear (10 −4 to 10 −6 mm 3 m −1 ) is obtained with respect to the neat IL. 1 wt.% IL additives also show good lubricating performance at 100 • C.

Ionic liquids are widely studied as alternative solvents in organic synthesis and catalysis, in electrochemistry and the separation sciences; with their many applications they will soon be produced on an industrial scale. Available toxicological data of ionic liquids have already suggested initial guidelines for the conscious design of safer chemicals. In this study a new group of such redesigned ionic liquids-1-alkoxymethyl-3-hydroxypyridinium cations+acesulphamate, saccharinate and chloride anions-was assayed with respect to their inhibitory activity towards acetylcholinesterase and their cellular toxicity towards the IPC-81 rat promyelocytic leukaemia cell line: the acute biological activity of these compounds is very low. Effective concentrations lie in the millimole range, which is well above possible intracellular concentrations. Only the compounds with the longest alkoxymethyl chain inhibit the enzyme at effective concentrations that are one order of magnitude smaller. No significant differences are observed when the anion compartment in the enzymatic assay is varied. However, the cytotoxicity data show EC 50 for acesulphamates and saccharinates to be higher than the values for the chloride analogues. Also, a slight alkoxymethyl chain length effect on the overall cytotoxicity is discernible. The biodegradability of the 1-alkoxymethyl-3-hydroxypyridinium salts varies from 21% to 72% and depends on the type of anion the cation is linked with. It improves with lengthening alkyl chain, but only in the range from 4 to 11 carbon atoms. r

Work relating to the electrodeposition of the Group I Alkali metals (Li, Na, K, Rb and Cs) from a range of ILs will be described, an extensive range of fundamental parameters briefly presented, and the electrochemical analysis and simulation methods utilised in their quantification discussed.

Initially a suitable IL had to be determined. Work relating to the electrodeposition of Na and Li from 12 ILs will be briefly discussed.1,2 Extension of the electrochemical window, alloy formation and underpotential deposition will also be noted.2,3 After demonstrating the applicability of [C4mPyrr][NTf2], the cyclic voltammetry for all five metals will be presented.4

The formal potential, Ef0, is the most fundamental thermodynamic parameter. This value, combined with kinetic parameters such as the electrochemical rate constant, k0, and the transfer coefficient, α, can be used to determine if a metal can be electrodeposited from an electrolyte of choice.

By combining cyclic voltammetry and simulation, the values of Ef0 (vs. Fc/Fc+), k0 and α for the M/M+ redox couples have been quantified for all five metals in the IL [C4mPyrr][NTf2] for the first time. The experimental conditions and simulation used to quantify these values will be discussed, as well as compared with the known values in more conventional solvents. Briefly, the simulation5 assumes the deposition and stripping processes follow Butler-Volmer kinetics and diffusion follows Fick’s Second Law, allowing the concentration gradients to be solved using a series of partial differential equations, and the current as a function of time can then be calculated. After metal deposition and prior to metal stripping the system is that of a defined M/M+ system, and the potential-current transient in this region is sufficiently sensitive to Ef0, α and k0 for their determination.

Detailed studies on Li and Na as a function of temperature provided a further range of fundamental thermodynamic parameters, namely the change in entropy (ΔS0), activation energy (Ea) and diffusional activation energy (Ea,D). The effect of temperature on the formal potential (dEf0/dT) and diffusion coefficient (D) were also quantified. Finally, the ΔGosolv (vs. Fc/Fc+) has been estimated for the five M+ ions.

Comparison of Ef0 (vs. Fc/Fc+) throughout the Group demonstrates that the trend in [C4mPyrr][NTf2] most closely resembles propylene carbonate in terms of increasing reactivity down the group, in comparison to solvents such as H2O, DMSO and DMF.


References

1 R. Wibowo, S. E.W. Jones and R. G. Compton, J. Chem. Eng. Data, 55 (3), 1374–1376, (2010).
2 R. Wibowo, L Aldous, E.I. Rogers, S.E.W. Jones, R.G. Compton, J. Phys. Chem. C, 114, 3618-3626, (2010).
3 R. Wibowo, S.E.W. Jones, R.G. Compton, J. Phys. Chem. B, 113, 12293-12298, (2009).
4 R. Wibowo, L Aldous, S.E.W. Jones, R.G. Compton, Chem. Phys. Lett., accepted, (2010).
5 S.E.W. Jones, F.G. Chevallier, C.A. Paddon, R.G. Compton, Anal. Chem., 79, 4110-19, (2007).

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Ionic liquids are emerging as important materials for applications in electrochemical devices, green chemistry etc. For device applications, ionic liquids are generally, either incorporated in polymer matrices or confined in porous matrices (giving rise to an interesting class of materials 'Ionogels'). This review deals with the science and technological applications of ionic liquids confined in nanopores. A comprehensive overview is given about the experimental studies dealing with the changes in the physico-chemical properties of ionic liquids like thermal phase transition, stability, dynamical behavior, optical properties etc. Recent theoretical studies highlighting the layering and structural heterogeneity of ionic liquids confined in nano-pores are also discussed. To make the review self-reading, basic ideas about ionic liquids and the phenomena of confinement are also briefly included.

Dispersive liquid–liquid microextraction (DLLME) has been proved to be a powerful tool for the rapid sample treatment of liquid samples providing at the same time high enrichment factors and extraction recoveries. A new, simple and easy to handle one step in-syringe set-up for DLLME is presented and critically discussed in this paper. The novel approach avoids the centrifugation step, typically off-line and time consuming, opening-up a new horizon on DLLME automation. The suitability of the proposal is evaluated by means of the determination of non-steroidal anti-inflammatory drugs in urine by liquid chromatography/ultraviolet detection. In the presented approach an ionic liquid is used as extractant. The target drugs can be determined in urine within the concentration range 0.02–10 μg mL−1, allowing their determination at therapeutic and toxic levels. Limits of detection were in the range from 8.3 ng mL−1 (indomethacin) to 32 ng mL−1 (ketoprofen). The repeatability of the proposed method expressed as RSD (n = 5) varied between 2.5% (for ketoprofen) and 8.6% (for indomethacin).

Biodiesel, as an alternative fuel, is gradually receiving more popularity for use in internal combustion engines. However questions continue to arise with regard to its compatibility with elastomeric materials. The present work aims to investigate the comparative degradation of physical properties for different elastomers [e.g. ethylene propylene diene monomer (EPDM), silicone rubber (SR), polychloroprene (CR), polytetrafluroethylene (PTFE) and nitrile rubber (NBR)] upon exposure to diesel and palm biodiesel. Static immersion tests in B0(diesel), B10 (10% biodiesel in diesel), B20, B50 and B100(biodiesel) were carried out at room temperature (25 °C) for 1000 h. Different physical properties like, changes in weight and volume, hardness and tensile strength were measured at every 250 h of immersion time. Compositional changes in biodiesel due to exposure of different elastomers were investigated by Gas chromatography mass spectroscopy (GCMS). The overall sequence of compatible elastomers in palm biodiesel is found to be PTFE > SR > NBR > EPDM > CR.

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Biodiesel has been produced by transesterification of canola oil with methanol in the presence of highly Brønsted acidic ionic liquids based on 1-benzyl-1H-benzimidazole, and the effect of reaction temperature, type and amount of catalyst, molar ratio and reaction time investigated. The results show that the 4B ionic liquid has the highest catalytic activity and best recyclability under the optimised reaction conditions. Thus, this ionic liquid is able to catalyze the transesterification of canola oil to its methyl esters in 5 h with yields of more than 95%. Density functional calculations (B3LYP), using the 6-311G basis set, have been performed to have a better understanding on the reactivity of these catalysts. The catalytic activity of 4B for the transesterification of other vegetable oils and alcohols has also been studied.

A collaborative investigation has revealed new insight into how room temperature ionic liquids (RTILs) conduct electricity, which may have a great potential impact for the future of energy storage. [18] The phenomenon of ionic wind has been known about for centuries: by applying a voltage to a pair of electrodes, electrons are stripped off nearby air molecules, and the ionized air collides with neutral air molecules as it moves from one electrode to the other. [17]

Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications.
A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

A new 3-alkylpiperidine compound (À)-acanthocyclamine A (1) has been obtained from the methanolic extract of Acanthostrongylophora ingens (order Haplosclerida, family Petrosiidae) collected from Wakatobi Marine National Park in South East Sulawesi, Indonesia. The structure of 1 was investigated by extensive 1D-and 2D-NMR experiments. The absolute configuration of 1 was established by X-ray crystallography from anomalous dispersion effects using Cu radiation as C2 (R), C3 (R), C7 (R), and C9 (R). A plausible biosynthetic scheme leading to 1 is presented, and compared with the biosynthetic pathway proposed for the manzamine alkaloids.

Pretreatment technology is a prerequisite to facilitate the release of sugars from a lignocellulosic biomass prior to fermentation. Recently, some pretreatment methods have been tried with ionic liquids, but they were still expensive and unpractical. In this study, an efficient pretreatment method using ammonia and ionic liquid was developed for the recovery of bio-digestible cellulose from a lignocellulosic byproduct, rice straw, and the increase of ionic liquid utilization. The combined use of ammonia and ionic liquid ([Emim]Ac) treatment exhibited a synergy effect for rice straw with 82% of the cellulose recovery and 97% of the enzymatic glucose conversion. This cooperative effect showed over 90% of the glucose conversion even with a reduced enzyme usage and incubation time. The ionic liquid was successfully recycled more than 20 times. The 20th-recycled ([Emim]Ac) showed 74% of the cellulose recovery and 78% of the glucose conversion to rice straw. Compared with the conventional pretreatment, our combined method for lignocellulosic biomass pretreatment was an economical and eco-friendly.

The aim of this work is to investigate extraction of ruthenium(III) from acidic aqueous solutions with such phosphonium ionic liquids as: trihexyl(tetradecyl)phosphonium chloride (Cyphos IL 101), trihexyl(tetradecyl)phosphonium bis(2,4,4-trimethylpentyl)phosphinate (Cyphos IL 104) and tributyl(tetradecyl)phosphonium chloride (Cyphos IL 167) as extractants. The influence of HCl content in the feed solutions on extraction of Ru(III) was investigated. The research was performed for model solutions containing Ru(III) and a mixture of waste solutions containing Ru(III) and Rh(III). Also, investigation of the type of extractant and its concentration in the organic phase on extraction of Ru(III) was carried out. Co-extraction of protons to the organic phase was determined. To the best of our knowledge, the extraction of Ru(III) with Cyphos IL 167 (tributyl(tetradecyl)phosphonium chloride) as an extractant has not yet been described in the scientific literature.

A new technology to form nanoparticles of hydrophobic organic actives at high concentration and yield, as well as methods to characterize the process, are presented. In Flash NanoPrecipitation, an organic active and an amphiphilic diblock copolymer are molecularly dissolved in an organic phase and mixed rapidly with a miscible anti-solvent to afford precipitation of the active with a tunable, narrow submicron particle size distribution from 1 µm to 80 nm. The enabling components are a novel 'analytical' (quantified mixing time) confined impinging jets (CIJ) mixer for millisecond stream homogenization and amphiphilic diblock copolymers which alter the organic nucleation and growth, provide steric stabilization for the particles, and offer a functional surface for the particle. Applications in enhanced pharmaceutical delivery, dye preparation, and pesticide formulation are specifically targeted.

The ionic liquid 1-butyl-3-methylimidazolium acetate proves to be an excellent reaction medium for the acetylation of alcohols and phenols, providing better conditions than the acidic 1-butyl-3-methylimidazolium bisulfate. Reactions were carried at room temperature, with only a 10% excess of acylating agent and with no other solvent or catalyst added.

Biodiesel production from abundant bio-sources has drawn the attention of the academic as well as the industrial communities in recent years. However, one of the most serious obstacles for using biodiesel as an alternative fuel is the complicated and costly purification processes involved in its production. The difficulties involved in the separation of glycerine and other un-reacted reactants and by-products necessitate the development of new competent low cost separation processes for this purpose. In this work, a low cost quaternary ammonium salt–glycerine-based ionic liquid is proposed as a solvent for extracting glycerine from the transesterification biodiesel product. The separation technique was tested on palm oil-based produced biodiesel with KOH as a reaction catalyst. The study investigated the effect of DES:biodiesel ratio and the DES composition on the efficiency of the extraction process. The lab scale purification experiments proved the viability of the separation technique with a best DES:biodiesel molar ratio of 1:1 and a DES molar composition of 1:1 (salt:glycerine). The purified biodiesel fulfilled the EN 14214 and ASTM D 6751 standard specifications for biodiesel fuel in terms of glycerine content. A continuous separation process is suggested for industrial scale application.

Anionic complexes of iridium(IV) were extracted from acidic solutions of HCl using ionic liquids (IL). The influence of the cationic structure of IL and of the aqueous phase pH on the distribution coefficients of IrCl 6 2À was investigated. Liquid--liquid extraction and precipitation of iridium(IV) were studied. Iridium(IV) was precipitated from aqueous solutions using water-soluble ionic liquids by forming a water-insoluble salt composed of two cations from the ionic liquid. Pyridinium cations appear to be the most efficient at precipitating iridium(IV). Iridium(IV) was found to be efficiently extracted using simple hydrophobic ionic liquids, exhibiting D values ranging up to 71. Investigations on the extraction mechanism tend to show that iridium(IV) is exchanged with two [NTf 2 ] À anions from the IL phase. Finally, elution of iridium(IV) from ionic liquids towards aqueous solutions was carried out from [BMIM][NTf 2 ], [OMIM][NTf 2 ] or [OdMIM] [NTf 2 ] into solutions containing high amounts of hydrochloric acid or nitric acid.

Electronic structure theory (density functional and Møller−Plesset perturbation theory) and vibrational spectroscopy (FT-IR and Raman) are employed to study molecular interactions in the room-temperature ionic liquid 1-ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide. Different conformers of a cation−anion pair based on their molecular interactions are simulated in the gas phase and in a dielectric continuum solvent environment. Although the ordering of conformers in energy varies with theoretical methods, their predictions for three lowest energy conformers in the gas phase are similar. Strong C−H---N interactions between the acidic hydrogen atom of the cation imidazole ring and the nitrogen atom of the anion are predicted for either the lowest or second lowest energy conformer. In a continuum solvent, different theoretical methods yield the same ion-pair conformation for the lowest energy state. In both phases, the density functional method predicts that the anion is in a trans conformation in the lowest energy ion pair state. The theoretical results are compared with experimental observations from Raman scattering and IR absorption spectroscopies and manifestations of the molecular interactions in the vibrational spectra are discussed. The directions of the frequency shifts of the characteristic vibrations relative to the free anion and cation are explained by calculating the difference electron density coupled with electron density topography.

Phosphonium cation-based ionic liquids (ILs) are a readily available family of ILs that often offer superior properties compared to ammonium cation-based ILs. Recently investigated applications include extraction solvents, electrolytes in batteries and super-capacitors, and corrosion protection. At the same time, the range of cationeanion combinations available commercially has also increased in recent years. Polymerized ionic liquids and polyelectrolytes play major roles in a broad range of biological applications including antimicrobials, non-viral gene delivery, synthetic enzymes, metal chelation, and drug delivery. Ammonium-and phosphonium-containing macromolecules will be reviewed with a focus on structure eproperty relationships of these polyelectrolytes and ionic liquids. Phosphonium-containing macromolecules often display enhanced performance compared to ammonium analogs.

Deprotection of various substituted alkyl and phenolic TBDMS ethers were carried out using prepared silver
exchanged silicotungstic acid (AgSTA) salt as heterogeneous catalyst in methanol at room temperature.
The Brönsted acidic protons of silicotungstic acid were substituted by Lewis acidic silver molecule
and prepared heterogeneous AgSTA catalyst which characterized using different spectroscopic and analytical
methods. 0.2 equiv. of AgSTA catalyst showed tremendous catalytic activity in the desilylation of
alkyl and phenolic TBDMS ethers under mild reaction condition in methanol to produce respective alcohol
in excellent yield. On screening, 100% conversion of reactants and up to 92.0% yield of respective alcohol
in 40 min reaction time was achieved using 0.2 equiv. of AgSTA catalyst. The solid AgSTA catalyst was
separated from the reaction mixture by simple filtration process at the end of reaction and reused for several
times without significant loss of catalytic activity. The present eco-friendly catalytic system is found
to be very convenient, high yielding, fast and clean method for desilylation of alkyl as well as phenolic
silyl ethers even in existence of other sensitive organic functional groups such as aldehyde, methoxy,
and acetate under mild reaction condition.

Ionic liquids (ILs) have been used as solvents or materials, or both, in many applications, including pharmaceutics and medicine due to their exceptional properties consisting of the combination of “green” properties with tunable physicochemical and biological properties. The use of ILs in the pharmaceutical industry can address many challenges associated with the use of conventional organic solvents or water. ILs have been established as potential solvents to solubilize many insoluble or sparingly soluble drugs for formulations or delivery. The use of ILs can also address many of the drawbacks of solid-state drugs, including polymorphism and low solubility, stability, and bioavailability. However, many ILs are inherently toxic, which is the main challenge toward developing IL-based drug formulations and drug delivery systems. The use of second- and third-generation ILs comprising more biocompatible cations and anions, compared with the first-generation ILs, has considerably addressed the toxicity issue. A wide range of biocompatible ILs have been designed to improve the pharmacokinetic and pharmacodynamic properties, as well as the biological activity, of drugs. This review describes the advances in the area of green IL-related research and emphasizes the new conceptual development of ILs in pharmaceutics and medicine. Particular attention is given to the mechanistic knowledge in the synthesis of ILs, as well as to the ecotoxicological and biological impact of biocompatible ILs, stimulating the understanding of innovative technologies in IL-based drug delivery systems.

Ionic liquid (IL) surfactants have attracted great interest as promising substitutes for conventional surfactants owing to their exceptional and favorable physico-chemical properties. However, most IL surfactants are not eco-friendly and form unstable micelles, even when using a high concentration of the surfactant. In this study, we prepared a series of halogen-free and biocompatible choline–fatty-acid-based ILs with different chain lengths and degrees of saturation, and we then investigated their micellar properties in aqueous solutions. Characterization of the synthesized surface-active ILs (SAILs) was performed by 1H and 13C nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, and elemental analysis. The surface-active properties of the SAILs were investigated by tensiometry, conductometry, and dynamic light scattering measurements. The critical micelle concentration of the SAILs was found to be 2–4 times lower than those of conventional surfactants. The thermodynamic properties of micellization (DG0 m, DH0m, and DS0
m) indicate that the micellization process of the SAILs is spontaneous, stable, and entropy-driven at room temperature. The cytotoxicity of the SAILs was evaluated using
mammalian cell line NIH 3T3. Importantly, [Cho][Ole] shows lower toxicity than the analogous ILs with conventional surfactants. These results clearly suggest that these environmentally friendly SAILs can be used as a potential alternative to conventional ILs for various purposes, including biological applications.

Green production of glycerol 1,2-carbonate with an environmentally friendly catalyst was proposed. Screening and optimisation of the catalysts were comprehensively performed. The basic ionic liquid (emim[Ac]) showed best catalytic activity and recyclability. Detail understanding on the glycerol-catalysts and glycerol 1,2-carbonate-catalysts interactions has been well explored. a b s t r a c t The rapid growth of biodiesel industry has led to a large surplus of its major unintentional byproduct particularly glycerol. Thus, finding a new application is necessary to convert glycerol to value added products. In this study, glycerol has been subjected to a transesterification reaction to synthesis glycerol carbonate (GC) over several selected ammonium and imidazolium-based ionic liquids (ILs) as catalysts. It is believed that the variation of catalytic performance between ILs was due to the anion strength of ILs. The glycerol conversion, yield and selectivity of GC were followed the anion order of [Ac] > [Dca] > [Fmt] > [DMP] > [NO 3 ] > [Cl] > [BF 4 ]. Effects of reaction temperature, time, diethyl carbonate (DEC)/glyc-erol molar ratio and catalyst loading on glycerol conversion and GC yield have been analysed. The IL, 1-ethyl-3-methylimidazolium acetate (emim[Ac]) shows best performance under solvent-free with conversion of glycerol and GC yield reached highest at 93.50% and 88.70%, respectively under reaction temperature of 120 °C reaction time of 2 h, DEC/glycerol molar ratio of 2 and catalyst loading of 0.5 mol%. Also, this emim[Ac] can be reused as catalyst at least three times without any significant reduction in conversion, yield and selectivity. Reaction mechanism of the transesterification reaction catalysed by emim[Ac] has been proposed in this study.

A B S T R A C T A molecular screening of 64 ionic liquids (IL's) for the solubility of monosaccharides such as D-(+)-Glucose, D-(+)-Xylose, D-(À)-Fructose and D-(+)-Galactose were performed by continuum solvation model (COSMO-RS) over the temperature range of 303.15-373.15 K. The IL data set consisted of 31 cations and 23 anions comprising of cations such as imidazolium, ammonium, pyridinium, pyrrolidinium, phosphonium, sulfonium and piperidinium. The imidazolium and ammonium based IL's gave the highest solubility for cations possessing lesser number of carbon side chains. Based on the screening studies, the following two IL's were chosen: 1-ethyl-3-methylimidazolium thiocyanate ([EMIM][SCN]) and Tris(2hydroxyethyl)methyl ammonium methylsulfate [TMA][MeSO 4 ] to experimentally study the solubility of monosaccharides in the two IL's. The experimentally obtained solid-liquid equilibria (SLE) values were then compared with COSMO-RS predicted values. The root mean square error (RMSE) values of monosaccharides such as D-(+)-Glucose, D-(+)-Xylose, D-(À)-Fructose and D-(+)-Galactose in [EMIM][SCN] were 3.11%, 3.12%, 2.32% and 1.83% respectively while the corresponding figures in [TMA][MeSO 4 ] is 1.47%, 1.20%, 2.94% and 0.70%. The overall solubility ranking in two IL's was: D-(À)-Fructose > D-(+)-Xylose > D-(+)-Glucose > D-(+)-Galactose.