Measurement of vapor–liquid equilibria (VLE) and excess enthalpies (H) of binary systems with 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and prediction of these properties and γ using modified UNIFAC (Dortmund)

Vapor–liquid equilibria (VLE) and excess enthalpies (H^E) were measured for a variety of alkanes, alkenes, aromatics, alcohols, ketones and water in several ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMIM]⁺[BTI]⁻, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [BMIM]⁺[BTI]⁻, 1-hexyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [HMIM]⁺[BTI]⁻ and 1-octyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide [OMIM]⁺[BTI]⁻, covering the temperature range from 323.15 to 413.15 K. The new data were used together with the already available experimental data for imidazolium compounds to fit the required group interaction parameters for modified UNIFAC (Dortmund). The results show that in the future modified UNIFAC (Dortmund) can be applied successfully also for systems with ionic liquids.     

Thermal stability of ionic liquid BMI(BF4) in the presence of nucleophiles

We have found that a common ionic liquid--one containing a N-N′-dialkylimidazolium cation--decomposes in the presence of nucleophiles at much lower temperatures than previously believed. The decomposition occurs through S_N2 attack of the nucleophile on the electrophilic alkyl groups attached to the imidazolium ring.     

Highly efficient C-H insertion reactions of hydrogen peroxide catalyzed by homogeneous and heterogeneous methyltrioxorhenium systems in ionic liquids

A convenient and efficient C-H insertion reaction of environment friendly H₂O₂ into representative hydrocarbon derivatives by homogeneous methyltrioxorhenium (MTO), heterogeneous poly(4-vinylpyridine)/methyltrioxorhenium (PVP/MTO) and microencapsulated polystyrene/methyltrioxorhenium (PS/MTO) systems in ionic liquids, is described. In some cases a higher activity was observed if compared with the same reaction in molecular solvents. The heterogeneous catalysts are stable systems under the reaction conditions and can be recycled for more transformations.     

Simultaneous Voltammetric Determination of Theophylline and Guaifenesin Using a Multiwalled Carbon Nanotube‐Ionic Liquid Modified Glassy Carbon Electrode

A glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes (MWCNTs) and a hydrophobic ionic liquid (IL), was used for the simultaneous voltammetric determination of theophylline (TP) and guaifenesin (GF). The results showed that the oxidations of TP and GF were facilitated at modified electrode and peak‐to‐peak separation at MWCNT? IL/GCE (252 mV) was larger than that observed at unmodified GCE (165 mV). Voltammetric signals for TP and GF exhibited linear ranges of 0.5 to 98.0 µM (R²>0.99) and 1.5 to 480.0 µM (R²>0.99), respectively. The method was used to estimate TP and GF contents in some real samples.     

Automatic flow methodology for kinetic and inhibition studies of reactions with poorly water-soluble substrates in ionic liquid systems

In the present work an automatic generic tool, based on sequential injection analysis (SIA) for kinetic and inhibition studies of reactions with poorly water-soluble compounds in ionic liquid (IL)-containing systems, is described.The oxidation of the poorly water-soluble phenolic compound, caffeic acid, catalyzed by the mushroom tyrosinase, in different 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄])/buffer mixtures as reaction media, was investigated. This determination was based on measuring depletion rate of the substrate caffeic acid at its maximum wavelength (λ_max 311 nm).The influence of several parameters such as substrate and enzyme concentration, temperature, pH, delay times and measurement periods on the sensitivity and performance of the SIA system were studied and the optimum reaction conditions subsequently selected.The obtained results showed that tyrosinase was active in oxidising caffeic acid in this water-miscible IL and the presence of an impaired tyrosinase activity with increase in [bmim][BF₄] concentration as an increase in the apparent Michaelis–Menten constant () was observed while the maximum reaction rate () remained fairly constant. The results were compared to those obtained when the assay was performed in water/methanol mixtures under the same conditions to substantiate [bmim][BF₄] as an alternative to conventional organic solvents.Additionally, it was shown that tyrosinase is effectively inhibited by the substrate analogues tested (trans-cinnamic acid and 3,4-dihydroxybenzoic acid) in the IL-containing aqueous system used.     

Voltammetry of Mn(III) Porphyrin in Trihexyl(tetradecyl)‐phosphonium Tris(pentafluoroethyl)trifluorophosphate Supported Toluene in Contact with an Aqueous Electrolyte

Voltammetry of manganese tetraphenylporphyrinato chloride in trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate solution in toluene reveals its unexpectedly low diffusion coefficient. UV‐vis spectra confirm significant Cl^? exchange with large phosphate anion at the axial position of the complex. Experiments performed with a glassy carbon electrode covered by a liquid film of the same solution and immersed in an aqueous electrolyte solution show a peak potential dependence on the nature and concentration of the aqueous electrolyte anion described by a Nernst type equation. Electron transfer is followed by anion expulsion where the anion effect results from the lability of the axial coordination site of the porphyrin and from spontaneous ion exchange.     

Ionic liquid as a complexation and extraction medium combined with high-performance liquid chromatography in the evaluation of chromium(VI) and chromium(III) speciation in wastewater samples

A simple method has been proposed for the determination of chromium species by high-performance liquid chromatography (HPLC) after preconcentration by the ionic liquid, 1-butyl-3-methyimidazolium hexafluorophosphate ([C₄MIM][PF₆]). The simultaneous preconcentration of Cr(VI) and Cr(III) in wastewater was achieved with ammonium pyrrolidinedithiocarbamate (APDC) as the chelating agent and the ionic liquid [C₄MIM][PF₆] as the extractant. Baseline separation of the APDC chelates of Cr(III) and Cr(VI) was realised on a RP-C18 column using a mixture of methanol–acetonitrile–water (53:14:33, v/v) as the mobile phase at a flow rate of 1.0 mL min^{− 1}. The influences of several variables on the complexation and extraction were evaluated: pH, reaction time, APDC concentration and metal ion interference. Our results showed that when the linear concentration of Cr(VI) and Cr(III) ranged from 25 to 200 μg L^{− 1}, their linear correlation coefficients were between 0.9977 and 0.9978, their recoveries ranged from 91.8% to 95.8% and their relative standard deviations (n = 3) were between 0.31% and 1.8%. Common metal ions in water did not interfere with the determination. This method is a simple, fast, accurate, highly stable and selective method and has successfully been applied to the speciation of chromium in wastewater.     

Aqueous biphasic systems composed of ionic liquid and fructose

Liquid–liquid equilibria data of the [Bmim]BF₄ + fructose + water system were determined at 298.15, 308.15, 31815 K. It was found that the liquid–liquid equilibria can be formed over a wide component range and the effect of the temperature on the phase equilibria is obvious within the fructose concentration changing from 3 to 40%. The binodal curves were correlated using a five-parameter equation, and the tie lines were fitted the Othmer–Tobias and Bancroft correlations. Correlation coefficients for the equations exceeded 0.99.     

Highly sensitive determination of promazine in pharmaceutical and biological samples using a ZnO nanoparticle-modified ionic liquid carbon paste electrode

In this work we describe the first report for the determination of promazine using a nanostructuremodified ionic liquid carbon paste electrode in aqueous solutions. To achieve this goal, a novel modified carbon paste electrode using ZnO nanoparticles and 1-methyl-3-butylimidazolium bromide as a binder(ZnO/NPs/ILs/CPE) was fabricated. The oxidation peak potential of promazine at the surface of the ZnO/NPs/ILs/CPE appeared at 685 m V, which was about 65 m V lower than the oxidation potential at the surface of CPE under similar conditions. Also, the peak current was increased to about 4.0 times higher at the surface of ZnO/NPs/ILs/CPE compared to that of CPE. The linear response range and detection limit were found to be 0.08–450 and 0.04 mmol/L, respectively. The modified electrode was successfully used for the determination of promazine in real samples with satisfactory results.     

Columnar bis(pyridinium) ionic liquid crystals derived from 4-hydroxypyridine: synthesis,mesomorphism and emission properties

A series of flexibly linked bis(pyridinium) salts with various counterions (Br^?, PF₆^?, BF₄^? and OTf-) was designed and prepared starting from corresponding N-alkylated 4-pyridones precursors with mesogenic 3,4,5-tris(alkyloxy)benzyl moieties (alkyl = dodecyl or tetradecyl). These salts were investigated for their liquid crystalline properties by a combination of differential scanning calorimetry, polarising optical microscopy and temperature-dependent powder X-ray diffraction (XRD). Their thermal stability was checked by thermogravimetric analysis. All bis(pyridinium) salts, except the triflate salt with shorter terminal carbon chain, display an enantiotropic liquid crystalline behaviour with a hexagonal columnar (Col_h) phase assigned on the basis of its characteristic texture and XRD studies. It was found that these luminescent bis(pyridinium) salts show weak emission in dichloromethane solutions at room temperature and a pronounced red-shifted emission in solid state. The emission properties of these bis(pyridinium) salts do not depend significantly on the nature of counterion employed.     

A novel pyrrolidinium ionic liquid with 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoroethoxy)ethanesulfonate anion as a recyclable reaction medium and efficient catalyst for Friedel-Crafts alkylations of indoles with nitroalkenes

A series of pyrrolidinium-based salts with new fluorine-containing anions were synthesized. Different melting points could be obtained by changing the length of the fluoroalkyl chain of the anions. The pyrrolidinium 1,1,2,2-tetrafluoro-2-(1,1,2,2-tetrafluoroethoxy)ethanesulfonate ([C₄H₈NH₂][H(CF₂)₄O(CF₂)₂SO₃]) is highly fluid even below room temperature. It can be used both as a recyclable solvent and as an efficient catalyst for Friedel-Crafts alkylations of indoles with nitroalkenes.     

Theory of a reversible redox reaction in an ionic liquid that is coupled to an ion transfer across the aqueous electrolyte/ionic liquid interface

A theory is provided for a reversible electro-oxidation of a neutral redox probe dissolved in room-temperature ionic liquid, which is sandwiched between an electrode surface and an aqueous solution as a thin film. If the peak potentials in cyclic voltammetry depend on the bulk concentration of electrolyte in water, the oxidation is most probably coupled to the transfer of anions from water into ionic liquid; but if the peak potentials are independent of the electrolyte concentration, the transfers of anions from water into ionic liquid and cations from ionic liquid into water are equally probable. Dedicated to Professor Dr. Yakov I. Tur’yan on the occasion of his 85th birthday.     

Quick and Easy Modification of Glassy Carbon Electrodes with Ionic Liquid and Tetraruthenated Porphyrins for the Electrochemical Determination of Atrazine in Water

Atrazine is a pesticide used to control broadleaf weeds, however its wide distribution and its high persistence in the soil and in surface waters has resulted in a public and environmental health problem. Present results shows the design, construction and characterization of glassy carbon electrodes modified with tetrarutenated metalloporphyrin (M=Ni (II) and Zn (II)) and 1‐butyl‐3‐methylimidazolium bis (trifluoromethylsulfonyl) imide, BMIMNTF₂. The modification was reproducible and sensitive for the electrochemical detection of atrazine in neutral media. The detection limit was 230 nM when using GC/BMIMNTF₂/ZnTRP and 540 nM with GC/BMIMNTF₂/NiTRP, meaning that his methodology can be a feasible and inexpensive way to detect atrazine in trace levels.     

Functional ionic liquid from biorenewable materials: synthesis and application as a catalyst in direct aldol reactions

A new room temperature ionic liquid (IL) (2-hydroxyethyl)-trimethyl-ammonium (S)-2-pyrrolidinecarboxylic acid salt ([Choline][Pro]) has been synthesized from biorenewable and nontoxic raw materials (choline chloride and l(−)-proline) in a simple and relative green route. The IL has been demonstrated to be the efficient catalyst of the direct aldol reactions between ketones and aromatic aldehydes in water at room temperature. The aldol products can be obtained with good yields and the IL in aqueous phase can be separated easily and reused.     

Multi-component, 1,3-dipolar cycloaddition reactions for the chemo-, regio- and stereoselective synthesis of novel hybrid spiroheterocycles in ionic liquid

A library of novel 1-methyl-4-arylpyrrolo-(spiro[2.2′]indan-1′,3′-dione)-spiro[3.3″]-1″-methyl/benzyl-5″-(arylmethylidene)piperidin-4″-ones and 1-methyl-4-arylpyrrolo-(spiro[2.11′]-11H-indeno[1,2-b]quinoxaline)-spiro[3.3″]-1″-methyl/benzyl-5″-(arylmethylidene)piperidin-4″-ones have been synthesized via 1,3-dipolar azomethine ylide cycloaddition in the ionic liquid, 1-butyl-3-methylimidazolium bromide ([BMIm]Br), in excellent yields.     

Selective extraction/isolation of hemoglobin with ionic liquid 1-butyl-3-trimethylsilylimidazolium hexafluorophosphate (BtmsimPF6)

Ionic liquid was for the first time employed for selective isolation of heme-protein species. Direct extraction of hemoglobin into ionic liquid without using any concomitant reagent or extractant was carried out. Hemoglobin at the level of 100 ng μL⁻¹ could readily be quantitatively extracted into ionic liquid (IL) 1-butyl-3-trimethylsilylimidazolium hexafluorophosphate (BtmsimPF₆) in the absence of any co-existing extractants/additives at pH 7, at the same time; however, the other protein species do not interfere and remain in the aqueous phase. A back extraction efficiency of ca. 80% for 20 ng μL⁻¹ hemoglobin in ionic liquid phase was achieved with sodium dodecyl sulfate (SDS) solution as stripping reagent. ⁵⁷Fe Mossbauer spectra and circular dichroism (CD) spectra indicated that the penta-coordinated ferrous atom in hemoglobin provide a vacant or free coordinating position, which could be occupied by the cationic Btmsim⁺ moiety. The interaction/coordination reaction between the iron atom in the heme group of hemoglobin and the cationic ionic liquid moiety furnishes the driving force for facilitating fast transfer of hemoglobin into BtmsimPF₆. The present system was applied for selective isolation of heme-protein, i.e., hemoglobin from human whole blood without any pretreatment, giving rise to satisfactory results.     

Selective detection of dopamine in the presence of ascorbic acid and uric acid by a carbon nanotubes-ionic liquid gel modified electrode

The electrochemistry of dopamine (DA) was studied by cyclic voltammetry at a glassy carbon electrode modified by a gel containing multi-walled carbon nanotubes (MWNTs) and room-temperature ionic liquid of 1-octyl-3-methylimidazolium hexafluorophosphate (OMIMPF₆). The thickness of gel on the surface of the electrode has to be controlled carefully because the charging currents increase with the modified layer being thicker. The anodic peaks of DA, ascorbic acid (AA) and uric acid (UA) in their mixture can be well separated since the peak potential of AA is shifted to more negative values, while that of UA is shifted to more positive values due to the modified electrode. At pH 7.08 the three peaks are separated ca. 0.20 and 0.15 V, respectively; hence DA can be determined in the presence of UA and more than 100 times excess of AA. Under optimum conditions linear calibration graphs were obtained over the DA concentration range 1.0 × 10⁻⁶ to 1.0 × 10⁻⁴ M. The detection limit of the current technique was found to be 1.0 × 10⁻⁷ M based on the signal-to-noise ratio of 3. The modified electrode has been successfully applied for the assay of DA in human blood serum. This work provides a simple and easy approach to selectively detect dopamine in the presence of ascorbic acid and uric acid.     

Triethylammonium acetate (TEAA): a recyclable inexpensive ionic liquid promotes the chemoselective aza- and thia-Michael reactions

A new, highly efficient, inexpensive, recyclable, mild, convenient, and green protocol for chemoselective aza/thia-Michael addition reactions of amines/thiols to α,β-unsaturated compounds using triethylammonium acetate (TEAA) ionic liquid was developed. The catalyst can be recycled ten times and obviate the need for toxic and expensive catalysts. Correspondence: Akhilesh K. Verma, Green Organic Chemistry Research Laboratory, Dr. B.R. Ambedkar Center for Biomedical Research, University of Delhi, Delhi 110007, India.     

Interfacial tension and wetting behavior of air/oil/ionic liquid systems

We measured the interfacial tension and the density of air/n-hexane, n-decane, 1-perfluorohexane/1-hexyl-3-methyl-imidazolium hexafluorophosphate systems as a function of temperature. From the air/ionic liquid surface tension values, it was suggested that Coulombic interaction between imidazolium cations and counter anions are not so much different between the surface and bulk. The density values indicated that the decrease of surface tension by saturating organics was closely correlated to the mutual solubility between ionic liquid and organics. Interfacial tension at the oil/ionic liquid interfaces suggested that ionic liquid molecules were more ordered at the oil/ionic liquid interfaces compared to the air/ionic liquid interfaces, but the decrease of the entropy due to the interfacial orientation of ionic liquid was compensated by the increase of the entropy due to the contact of different chemical species. The initial spreading coefficients and the Hamaker constants indicated that all the oil phases spread at the air/ionic liquid interfaces spontaneously, and form the complete wetting films.