Jean-Marc Lévêque

Efficient removal of gold complexes from water by precipitation or liquid–liquid extraction using ionic liquids

Extraction of tetrachloroaurate or tetrabromoaurate anions has been carried out at acidic pHs (1 and 4) with several ionic liquids bearing halide or bis(trifluoromethanesulfonyl)imide NTf2− anions and cations 1-octyl-3-methylimidazolium, 1-octylpyridinium or 1-methyl-1-octylpyrrolidinium. The removal of gold anionic moieties from water was first studied by mixing aqueous solutions containing gold complexes and water soluble halide (chloride or bromide) ionic liquids. This lead to the formation of either a solid precipitate or a liquid phase corresponding to a hydrophobic ionic liquid based on a tetrahalogenoaurate anion. Values below 10−6 for the solubility products of gold-bearing ionic liquids were obtained. Liquid–liquid extraction of anionic gold complexes with hydrophobic ionic liquids was also carried out. Gold was successfully extracted from water whatever the pH and the ionic liquid used. Distribution coefficients ranged from 3 × 102 to 3 × 104. Investigation on the extraction mechanism revealed an anion exchange between one anionic gold complex and one NTf2− anion.

An improved preparation of ionic liquids by ultrasound

The use of ionic liquids (ILs) as a novel class of environmentally friendly solvents is now of topical interest among the chemical community, worried about the environmental impact of chemicals. Many reactions of organic chemistry have thus been re-examined since the 1990s. Nevertheless, even if a given preparation of ILs does not represent any particular difficulty, the reaction times appear to be long and the use of large amounts of classical solvents for the synthesis and the purification steps is crucial. This article presents preliminary work performed for the ultrasound assisted preparation of several 1-butyl-3-methylimidazolium salts (BF4, PF6, CF3SO3 and BPh4). In all cases a clear yield increase results and a dramatic reduction of the reaction time accompanied by an improved quality of the products occurs. After a short and simple work-up, the ILs are ready to use without a further purification step. Moreover, an original and simple analytical way to follow the reaction in real time is also presented.

Preparation of Second Generation Ionic Liquids by Efficient Solvent-Free Alkylation of N-Heterocycles with Chloroalkanes

Non-conventional techniques, such as microwave (MW) and power ultrasound (US) as well as combined MW/US irradiation, have been used to promote one-pot synthesis of second-generation ionic liquids (ILs), cutting down reaction times and improving yields. However, the use of chloroalkanes in the alkylation of N-heterocycles requires more drastic conditions if results are to match those obtained with more reactive alkyl halides. The present paper describes a series of MW- or MW/US-promoted IL preparations starting from chloroalkanes and classic heterocycles (1-methylimidazole, pyridine and 1-methylpyrrolidine). When reactions were carried out under conventional heating in an oil bath they required longer reaction times and gave poorer yields. 1H-NMR analysis and ion-exchange chromatography showed that the present solventless procedure afforded ILs of satisfactory purity. The observed high yields (usually 70-98% isolated), and short reaction times showed that a straightforward access to ILs can be also achieved with the use of alkyl chlorides, resulting in a considerable reduction of costs.

Effect of sonication conditions: solvent, time, temperature and reactor type on the preparation of micron sized vermiculite particles.

The effects of temperature, time, solvent and sonication conditions under air and Argon are described for the preparation of micron and sub-micron sized vermiculite particles in a double-jacketed Rosett-type or cylindrical reactor. The resulting materials were characterized via X-ray powder diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Fourier Transform Infrared (FTIR) Spectroscopy, BET surface area analysis, chemical analysis (elemental analysis), Thermogravimetry analysis (TGA) and Laser Granulometry. The sonicated vermiculites displayed modified particle morphologies and reduced sizes (observed by scanning electron microscopy and laser granulometry). Under the conditions used in this work, sub-micron sized particles were obtained after 5h of sonication, whereas longer times promoted aggregation again. Laser granulometry data revealed also that the smallest particles were obtained at high temperature while it is generally accepted that the mechanical effects of ultrasound are optimum at low temperatures according to physical/chemical properties of the used solvent. X-ray diffraction results indicated a reduction of the crystallite size along the basal direction [001]; but structural changes were not observed. Sonication at different conditions also led to surface modifications of the vermiculite particles brought out by BET surface measurements and Infrared Spectroscopy. The results indicated clearly that the efficiency of ultrasound irradiation was significantly affected by different parameters such as temperature, solvent, type of gas and reactor type.

Effect of imidazolium-based ionic liquids on bacterial growth inhibition investigated via experimental and QSAR modelling studies

Tuning the characteristics of solvents to fit industrial requirements has currently become a major interest in both academic and industrial communities, notably in the field of room temperature ionic liquids (RTILs), which are considered one of the most promising green alternatives to molecular organic solvents. In this work, several sets of imidazolium-based ionic liquids were synthesized, and their toxicities were assessed towards four human pathogens bacteria to investigate how tunability can affect this characteristic. Additionally, the toxicity of particular RTILs bearing an amino acid anion was introduced in this work. EC50 values (50% effective concentration) were established, and significant variations were observed; although all studied ILs displayed an imidazolium moiety, the toxicity values were found to vary between 0.05 mM for the most toxic to 85.57 mM for the least toxic. Linear quantitative structure activity relationship models were then developed using the charge density distribution (σ-profiles) as molecular descriptors, which can yield accuracies as high as 95%.

Removal of platinum from water by precipitation or liquid–liquid extraction and separation from gold using ionic liquids

Precipitation and liquid–liquid extraction of PtX62− (X = Cl−, Br−, SCN−) in acidified aqueous solutions ranging from 0.1 M to 9 M HBr or 11 M of HCl have been studied using water-soluble or hydrophobic ionic liquids. Divalent hexachloroplatinate(IV) anions appear to be extracted much less efficiently than tetrachloroaurate(III) complexes. At a concentration of 11 M HCl, values of 15 and 800 for the distribution coefficients of PtCl62− and PtBr62− in [OMIM][NTf2] have been obtained accordingly. The presence of a labile hydrogen on the imidazolium ring has been found to play a specific role in the extraction of platinum(IV) complexes in concentrated HCl or HBr. Pt(SCN)62− appears to be very efficiently extracted at pH 1 using [OMIM][NTf2], exhibiting a distribution coefficient of 6150. Finally, two methods for quantitative separation of gold and platinum in water using in each method two extraction steps have been proposed. The back extraction of platinum(IV) during the second separation process was also discussed.

A Speedy One-Pot Synthesis of Second-Generation Ionic Liquids Under Ultrasound and/or Microwave Irradiation

The present work describes an efficient one-pot synthesis of second-generation ionic liquids (ILs), combining in one step the Menshutkin reaction and anion metathesis. Working in a closed vessel under microwaves, or better still under simultaneous ultrasound and/or microwave irradiation, in a few minutes a series of ILs with 1-methylimidazole or pyridine cores were obtained in high yields (80–97% isolated). Under conventional heating, ILs could not be prepared in one pot in acceptable times and yields, whereas our protocol, carried out with commercially available equipment, was highly effective and reproducible. Moreover, 1H NMR analysis and ion-exchange chromatography showed that the present solventless procedure afforded satisfyingly pure ILs.

Synthesis and anti-microbial potencies of 1-(2-hydroxyethyl)-3-alkylimidazolium chloride ionic liquids: Microbial viabilities at different ionic liquids concentrations

Three 1-(2-hydroxyethyl)-3-alkylimidazolium chloride room temperature ionic liquids (ILs) [2OHimC(n)][Cl]; (n=0, 1, 4) have been synthesized from the appropriate imidazole precursors and characterized by IR and NMR spectroscopies and elemental analysis. Their anti-microbial activities were investigated using the well-diffusion method. The viabilities of Escherichia coli, Aeromonas hydrophila, Listeria monocytogenes and Salmonella enterica as a function of IL concentrations were studied. The minimal inhibitory concentrations (MICs) and EC₅₀ values for the present ILs were within the concentration range from 60 to 125 mM and 23 to 73 mM. The anti-microbial potencies of the present ILs were compared to a standard antibiotic, gentamicin. The finding affords additional perspective on the level of ILs toxicity to aquatic lifeforms and yet, this characteristic can be readily harnessed to detect microbial growth and activity.

Hydrodynamic sono-voltammetry of ferrocene in [Tf2N]- based ionic liquid media.

The present work deals with the hydrodynamic behavior of several room-temperature ionic liquids presenting the same bis(trifluoromethanesulfonyles)imide anion, associated with four different cations: 1-butyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, N-trimethyl-N-propylammonium and 1-butyl-1-methylpyrrolidinium cations. Steady state voltammetry was used as an electrochemical technique to characterize mass transfer in both silent and sonicated conditions, using a rotating disk electrode. Results obtained in RTILs media are compared to those acquired in synthetic solutions of controlled viscosity, in order to develop a better understanding of the phenomena involved in such media.

A rosette cooling cell: more effective container for solubilization of single-walled carbon nanotubes under probe-type ultrasonic irradiation.

Probe-type ultrasonication has been employed for surfactant-aided solubilization, or individualization, of single-walled carbon nanotubes (SWNTs). The resulting solution can be used not only for spectroscopic analyses such as absorption, photoluminescence, and circular dichroism, but also for separation by density gradient ultracentrifugation, dielectrophoresis, chromatography, and polymer wrapping. In spite of its importance, the sonochemical processing of SWNTs has not been considered seriously. Herein, we report on a more efficient cooling cell for probe-type ultrasonication. As compared with a conventional cylindrical cell, the concentration of the SWNTs solubilized in water was found to be almost double in a rosette cooling cell after ultracentrifugation. The efficiency of a rosette cell can be attributed to the higher efficiency in circulation and cooling of the SWNT dispersion as well as enhancement of the cavitation process.