1-octyl-3-methylimidazolium-hexafluorophosphate and 1-butyl-3-methylimidazolium-hexafluorophosphate

Three hydrophobic ionic liquids (ILs) including 1-butyl-3-methylimidazole hexafluorophosphate ([BMIM]PF6), 1-hexyl-3-methyl-imidazole hexafluorophosphate ([HMIM]PF6), and 1-octyl-3-methylimidazole hexafluoro-phosphate ([OMIM]PF6) coated Fe3O4@SiO2 nanoparticles with core-shell structure to prepare magnetic solid phase extraction agent (Fe3O4@SiO2@ILs) and establish a new method of magnetic solid phase extraction (MSPE) coupled with UV spectrometry for separation/analysis of linuron. The results showed that linuron was adsorbed rapidly by Fe3O4@SiO2@[OMIM]PF6 and eluanted by ethanol. Under the optimal conditions, preconcentration factor of the proposed method was 10-fold. The linear range, detection limit, correlation coefficient (R) and relative standard deviation (RSD) were found to be 0.04-20.00 μg mL(-1), 5.0 ng mL(-1), 0.9993 and 2.8% (n=3, c=4.00 μg mL(-1)), respectively. The Fe3O4@SiO2 nanoparticles could be used repeatedly for 10 times. This proposed method has been successfully applied to the determination of linuron in food samples.

Topics: Adsorption; Ferrosoferric Oxide; Food Analysis; Food Contamination; Fruit; Hydrogen-Ion Concentration; Imidazoles; Ionic Liquids; Linuron; Magnetite Nanoparticles; Osmolar Concentration; Silicon Dioxide; Solid Phase Extraction; Spectrophotometry, Ultraviolet; Temperature; Thermogravimetry; Vegetables

A simple, rapid and efficient method, ionic liquid based dispersive liquid-liquid microextraction (IL-DLLME), has been developed for the first time for the determination of 18 polycyclic aromatic hydrocarbons (PAHs) in water samples. The chemical affinity between the ionic liquid (1-octyl-3-methylimidazolium hexafluorophosphate) and the analytes permits the extraction of the PAHs from the sample matrix also allowing their preconcentration. Thus, this technique combines extraction and concentration of the analytes into one step and avoids using toxic chlorinated solvents. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, extraction time, dispersion stage, centrifuging time and ionic strength, were optimised. Analysis of extracts was performed by high performance liquid chromatography (HPLC) coupled with fluorescence detection (Flu). The optimised method exhibited a good precision level with relative standard deviation values between 1.2% and 5.7%. Quantification limits obtained for all of these considered compounds (between 0.1 and 7 ng L(-1)) were well below the limits recommended in the EU. The extraction yields for the different compounds obtained by IL-DLLME, ranged from 90.3% to 103.8%. Furthermore, high enrichment factors (301-346) were also achieved. The extraction efficiency of the optimised method is compared with that achieved by liquid-liquid extraction. Finally, the proposed method was successfully applied to the analysis of PAHs in real water samples (tap, bottled, fountain, well, river, rainwater, treated and raw wastewater).

Topics: Analytic Sample Preparation Methods; Chromatography, High Pressure Liquid; Imidazoles; Ionic Liquids; Microchemistry; Osmolar Concentration; Polycyclic Aromatic Hydrocarbons; Rain; Reproducibility of Results; Rivers; Solvents; Time Factors; Water; Water Pollutants, Chemical

Photoinduced electron transfer in two room-temperature ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF(6)) and 1-octyl-3-methylimidazolium hexafluorophosphate (OMIM-PF(6)), has been investigated using steady-state fluorescence quenching of 9,10-dicyanoanthracene with a series of single electron donors. From these fluorescence quenching rates, reorganization energy (lambda) values and k(diff) values can be derived from a Rehm-Weller analysis. In many cases, these fluorescence quenching reactions occur at rates larger than what would be expected based on the Smoluchowski equation. In addition, lambda values of 10.1 kcal/mol and 16.3 kcal/mol for BMIM-PF(6) and OMIM-PF(6), respectively, have been determined.

Topics: Anthracenes; Electrons; Fluorescence; Imidazoles; Ionic Liquids; Microscopy, Fluorescence; Molecular Structure; Nitriles; Oxidation-Reduction; Photochemistry; Sensitivity and Specificity; Temperature; Viscosity

A comparative study of peak shape, elution behavior, elution strength and resolution of seven beta-blockers (acebutolol, alprenolol, labetalol, metoprolol, nadolol, pindolol and propranolol) chromatographed with aqueous-organic mobile phases containing additives such as the ionic liquid (IL) 1-butyl-3-methylimidazolium (BMIM BF(4)) or triethylamine (TEA) is performed using a conventional reversed-phase Kromasil C(18) column and isocratic elution. The efficiencies and asymmetry factors achieved for the group of beta-blockers in the Kromasil C(18) column improve when the cationic modifiers are added to the aqueous-organic mobile phase as competing additives for the silanol active sites. BMIM BF(4) is a significantly better additive compared to TEA. The improvement is more notably for the asymmetry factor, BMIM BF(4) allowing to obtain higher plate numbers than TEA at the same concentration. The effects of both modifiers on elution strength and retention factors are, however, different. TEA decreases the solute retention factors when BMIM BF(4) does not change them significantly. Using other additives taken in the IL family such as 1-butyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium tetrafluoroborate (OMIM BF(4)), it is shown that the silanol screening effect is always observed, due to the IL cation, when it is possible to increase or to decrease the solute retention factors playing with the hydrophobic nature or chaotropic character of its anion.

Topics: Adrenergic beta-Antagonists; Borates; Chromatography, High Pressure Liquid; Ethylamines; Imidazoles; Ions

The transesterification reaction of N-acetyl-L-phenylalanine ethyl ester with 1-propanol catalyzed by alpha-chymotrypsin was examined in the ionic liquids 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF(6)]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([omim][PF(6)]), and in combination with supercritical carbon dioxide (SC-CO(2)). The activity of alpha-chymotrypsin was studied to determine whether trends in solvent polarity, water activity, and enzyme support properties, observed with this enzyme in conventional organic solvents, hold for the novel environment provided by ionic liquids. alpha-Chymotrypsin freeze-dried with K(2)HPO(4), KCl, or poly(ethylene glycol) demonstrated no activity in [bmim][PF(6)] or [omim][PF(6)] at very low water concentrations, but moderate transesterification rates were observed with the ionic liquids containing 0.25% water (v/v) and higher. However, the physical complexation of the enzyme with poly(ethylene glycol) or KCl did not substantially stimulate activity in the ionic liquids, unlike that observed in hexane or isooctane. Activities were considerably higher in [omim][PF(6)] than [bmim][PF(6)]. Added water was not necessary for enzyme activity when ionic liquids were combined with SC-CO(2). These results indicate that [bmim][PF(6)] and [omim][PF(6)] provide a relatively polar environment, which can be modified with nonpolar SC-CO(2) to optimize enzyme activity.

Topics: 1-Propanol; Carbon Dioxide; Catalysis; Chymotrypsin; Esterification; Freeze Drying; Imidazoles; Kinetics; Phenylalanine; Solutions