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Continuous-flow rhodium-catalysed hydroformylation of long chain alkenes has been achieved with selectivities to the desired linear aldehyde of 92% and minimum rhodium loss, using a xantphos-derived ligand attached to an imidazolium salt in a supercritical fluid–ionic liquid system. The effect of oxygen in the system can be ameliorated to some extent by adding a simple sulfonated triphenylphosphine to the catalytic solution. [ABSTRACT FROM AUTHOR]

Both softwood (southern yellow pine) and hardwood (red oak) can be completely dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc) after mild grinding. Complete dissolution was achieved by heating the sample in an oil bath, although wood dissolution can be accelerated by microwave pulses or ultrasound irradiation. It has been shown that [C2mim]OAc is a better solvent for wood than 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) and that variables such as type of wood, initial wood load, particle size, etc.affect dissolution and dissolution rates; for example, red oak dissolves better and faster than southern yellow pine. Carbohydrate-free lignin and cellulose-rich materials can be obtained by using the proper reconstitution solvents (e.g., acetone/water 1 : 1 v/v) and approximately 26.1% and 34.9% reductions of lignin content in the reconstituted cellulose-rich materials (from pine and oak, respectively) have been achieved in one dissolution/reconstitution cycle. The regenerated cellulose-rich materials and lignin fractions were characterized and compared with the original wood samples and biopolymer standards. For pine, 59% of the holocellulose (i.e., the sum of cellulose and hemicellulose) in the original wood can be recovered in the cellulose-rich reconstituted material; whereas 31% and 38% of the original lignin is recovered, respectively, as carbohydrate-free lignin and as carbohydrate-bonded lignin in the cellulose-rich material. [ABSTRACT FROM AUTHOR]

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 have demonstrated the facile synthesis of stable gold nanoparticles (AuNPs) using imidazolium ionic liquids (ImILs) as a stabilizer as well as a surfactant and their surface plasmon resonance (SPR) in different molecular solvents with varying dielectric properties. The preparation of AuNPs capped with N,N′-dialkyl ImILs of different chain lengths (denoted as [C4,Cn-im]Br, n = carbon number of the alkyl chain) has been investigated. With one long alkyl chain (n≥ 14), these AuNPs could be stably dispersed in solution over a month. The amphiphilic nature of the imidazolium salt dictates the stability and dispersion of these AuNPs in organic or aqueous solvents. Alkyl chain lengths (n≥ 14) and the amount of ImILs have insignificant effect on the size of AuNPs and they possess an average size of 5 nm. These ionic liquid stabilized AuNPs were exploited to examine their optical properties when exposed to various solvent systems by measuring the change in the SPR spectrum. It was seen that the position of the SPR band of AuNPs is greatly influenced by the solvents under consideration. The shift in the SPR absorption band is observed to be in the range of 520 nm to 605 nm for AuNP@[C4,C16-im]Br from nonpolar to highly polar solvents. The considerable discovery presented here is that the λSPR of the SPR shifts to the blue with the increase of carbon atom in the alcohol chain from methanol to 1-decanol. Also for polyethylene glycols (PEGs), the λSPR shifts to the blue with the increase in molecular weight from PEG 200 to PEG 600. In above both cases, the variation in SPR of AuNPs is observed according to the dielectric properties of the medium in addition to the steric factor of alcohols and PEGs during their interaction with AuNP surfaces. [ABSTRACT FROM AUTHOR]

1-Methylimidazole (1-MIM) and 2-methylimidazole (2-MIM) are miscible in water and imidazolium based ionic liquids (ILs), and can coordinate with soft metal ions. This paper reports a novel solvent extraction process for trivalent lanthanides and yttrium from aqueous solutions into ILs, which was promoted by a hydrophilic 1-MIM or 2-MIM. Slope analysis confirmed that MIM in ILs formed a 1 : 1 complex with La3+ and Y3+ and a 1 : 4 complex with Eu3+ and Lu3+, depending on the atomic number of the metal and the metal-ligand interactions that have been characterized by FTIR spectroscopy and ESI-MS. The effect of nitrate concentration on the extraction of lanthanides with 1-MIM in ILs was analysed. It indicated that nitrate anions were involved in the extraction process. Under the same conditions, the extraction of lanthanides with MIM into n-pentanol was carried out. The extractability was by far lower than that obtained in ILs. Both cationic exchange and neutral solvation mechanisms occurred in ILs and only the neutral solvation mechanism occurred in n-pentanol, which were demonstrated by the extraction tests and the structure of extracted species determined by ESI-MS. The competitive extraction in ILs showed good selectivity for lanthanides compared to alkali metals and alkaline earth cations. After extraction, lanthanides could be stripped very easily from the ionic liquid phase with dilute nitric acid. From the temperature dependence data, the thermodynamic parameter values (ΔH, ΔS and ΔG) were calculated. The results indicated that the extraction reactions were spontaneous and went through an endothermic process. [ABSTRACT FROM AUTHOR]

A series of novel ionic liquids comprising two asymmetric phosphate-derived anions, namely dimethyl phosphorothioate and dimethyl phosphoroselenoate, and several imidazolium and non-imidazolium-based cations was prepared viaa facile synthetic route. Thermal degradation was studied by dynamic thermogravimetric analysis (TGA) revealing a slightly higher stability of the imidazolium ionic liquids and an overall low thermal stability for the phosphoroselenoate salts. Long-term moisture sorption analysis showed correlation with the polarity of the cation and differences in absorption and desorption kinetics. Finally, a Eucalyptus globuluskraft paper grade pulp was dissolved and subsequently regenerated to assess the degradation of the various molecular weight fractions by size exclusion chromatography. In addition, pre-extracted xylan was subjected to the same dissolution procedure to examine the degradation of low-molecular weight components in more detail. [ABSTRACT FROM AUTHOR]

This paper reports on a detailed study of the influence of salinity on the biological activity of 1-alkyl-3-methylimidazolium chlorides on two green algae Oocystis submarinaand Chlorella vulgaris, one diatom Cyclotella meneghinianaand one blue-green alga Geitlerinema amphibium. All these organisms inhabit the Baltic Sea, an environment naturally varying greatly in salinity. The toxicity effects of ILs towards cyanobacterial and algal organisms were tested in fresh water and in water of four different salinities—8, 16, 24 and 32 PSU—reflecting the whole range encountered in the Baltic Sea. Increasing the salinity was found to exert a significant influence on ionic liquid toxicity in all cases. The lower toxicity is probably due to the reduced permeability of ionic liquid cations through the algal cell walls. Higher chloride concentrations offer a good ion-pairing environment for imidazolium cations, which therefore compete with hydroxyl or silanol functional groups in cell-wall structures. The results of this work indicate that at higher salinities algal growth is inhibited to a significantly lesser extent. With the same IL concentration, the toxicity decreases by eight–ten times in the algae or about three times in the cyanobacterium in the 0–32 PSU salinity range. [ABSTRACT FROM AUTHOR]

This paper reports on an investigation into the toxicity of 1-alkyl-3-methylimidazolium ionic liquids (ILs) towards two green algae (Chlorella vulgarisand Oocystis submarina) characteristic of freshwater and brackish environments, as well as two brackish and marine diatoms (Cyclotella meneghinianaand Skeletonema marinoi). The test kit of IL compounds consisted of five 1-alkyl-3-methylimidazolium chlorides (from -ethyl to -decyl) for evaluating the expected alkyl chain length effect, together with 1-butyl-3-methylimidazolium tetrafluoroborate, dicyanamide, trifluoromethanesulfonate, methyl sulfate an α-methyl[poly(oxy-1,2-ethanediyl)]sulfate for investigating the influence of the anion on IL toxicity towards various algal species. A pronounced alkyl chain effect was confirmed with all the organisms studied. EC50values were linearly very well correlated with the number of carbon atoms in the IL alkyl chains. The results indicate that diatoms are far more sensitive than green algae to ILs. Cell size also plays an important part in the intoxication process: a tenfold difference in cell size results in a 100% more sensitive reaction to ionic liquids in both the green algae and diatoms. No significant differences were observed between alkylimidazolium salts and an alkylpyridinium compound of similar lipophilicity. It was also found that the use of tetrafluoroborate and trifluoromethanesulfonate as counteranions in the IL structure gave rise to the most pronounced toxic effects in comparison with the other anions tested. In the case of tetrafluoroborate this is probably caused by the potential hydrolysis of this entity, which leads to the formation of fluoride and a further increase in toxicity. Whereas in the case of trifluoromethanesulfonate it is likely caused by relatively high lipophilicity of this anion, additionally known to be strongly associated with alkylimidazolium cations, that in turn may enhance cell wall penetration. [ABSTRACT FROM AUTHOR]

This paper reports the synthesis and the physical characterization of a new family of chelating ionic liquids carrying a terpyridine fragment suitable for metal extraction. [ABSTRACT FROM AUTHOR]

Lignocellulosic biomass composite fibers (southern yellow pine and bagasse) were successfully prepared directly from the ionic liquid, 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc) with a dry-jet wet spinning process using short dissolution times (10–30 min) and temperatures above the glass transition temperature of lignin. Fibers could not be spun at all from solutions of pine dissolved using previously reported dissolution methods (110 °C, 16 h), while bagasse fibers spun using the higher temperature/shorter time method were stronger than those obtained using the lower temperature/longer time method. [ABSTRACT FROM AUTHOR]