Natalia V. Plechkova

Self-aggregation of ionic liquids: micelle formation in aqueous solution

Interfacial tension (using a drop-shape analysis technique), fluorescence (of a widely used spectroscopic molecular probe, pyrene), and 1H NMR measurements were used to monitor the adsorption at the aqueous solution–air interface and self-aggregation behaviour (critical micelle concentration, CMC) of room-temperature ionic liquids (ionic liquids) of the 1-alkyl-3-methylimidazolium family of cations, [Cnmim]+, with different linear alkyl chain lengths, CnH2n+1 (½n = 1–7), and different counter-ions, namely [Cnmim]Cl (n = 2–14), [Cnmim][PF6] (n = 4 or 10), and [C10mim][NTf2]. Only [Cnmim]Cl with n > 8 unambiguously form aggregates in solution and the nature of this self-aggregation is discussed in terms of the electrostatic vs. hydrophobic contributions of the isolated cation. In contrast, the shortest chains behave, as anticipated, as simple salts. In turn, the transitional ionic liquid, [C6mim]Cl is able to develop a monolayer at the aqueous solution–air interface but shows no noticeable self-aggregation in the bulk fluid. Moreover, the micellar characteristics of the well-studied sodium dodecyl sulfate (SDS) aqueous solutions as a function of the total concentration of [Cnmim]Cl (½n = 1–7) showed a clear change in the behaviour of the mixtures [Cnmim]Cl + SDS for n ≈ 6–8, with a characteristic mixed-micelle formation for the longer and a pure salt effect for the shorter chain lengths of [Cnmim]Cl.

On the self-aggregation and fluorescence quenching aptitude of surfactant ionic liquids.

The aggregation behavior in aqueous solution of a number of ionic liquids was investigated at ambient conditions by using three techniques: fluorescence, interfacial tension, and (1)H NMR spectroscopy. For the first time, the fluorescence quenching effect has been used for the determination of critical micelle concentrations. This study focuses on the following ionic liquids: [Cnmpy]Cl (1-alkyl-3-methylpyridinium chlorides) with different linear alkyl chain lengths (n=4, 10, 12, 14, 16, or 18), [C12mpip]Br (1-dodecyl-1-methylpiperidinium bromide), [C12mpy]Br (1-dodecyl-3-methylpyridinium bromide), and [C12mpyrr]Br (1-dodecyl-1-methylpyrrolidinium bromide). Both the influence of the alkyl side-chain length and the type of ring in the cation (head) on the CMC were investigated. A comparison of the self-aggregation behavior of ionic liquids based on 1-alkyl-3-methylpyridinium and 1-alkyl-3-methylpyridinium cations is provided. It was observed that 1-alkyl-3-methylpyridinium ionic liquids could be used as quenchers for some fluorescence probes (fluorophores). As a consequence, a simple and convenient method to probe early evidence of aggregate formation was established.

Structural properties of 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide ionic liquids: X-ray diffraction data and molecular dynamics simulations.

X-ray diffraction data for 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amides are reported as a function of the length of the alkyl chain on the imidazolium ring. The measured diffraction patterns have been compared with the theoretical patterns calculated (from the geometries obtained) with molecular dynamics simulations. This provides a detailed description (at the atomistic level) of the morphology in the liquid state of these salts, highlighting the role played by the alkyl chain length. An analysis of the behavior of the hydrogen bonds that are formed between the imidazolium acidic protons and the anion is presented.

Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid–liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

Speciation of chloroindate(III) ionic liquids

A range of chloroindate(iii) ionic liquid systems was prepared by mixing of 1-alkyl-3-methylimidazolium chloride with indium(iii) chloride in various ratios, expressed as the mol fraction of indium(iii) chloride, chi(InCl(3)). For chi(InCl(3))</= 0.50, the products were liquids, whereas for chi(InCl(3)) > 0.50, the products were biphasic (suspensions of a solid in an ionic liquid). Speciation of these chloroindate(iii) systems was carried out using a wide range of techniques: differential scanning calorimetry (DSC), polarised optical microscopy (POM), liquid-state and solid-state (115)In NMR spectroscopy, X-ray photoelectron spectroscopy (XPS) and extended X-ray absorption fine structure (EXAFS). Ionic liquids prepared using an excess of the organic chloride (chi(InCl(3)) < 0.5) contained [InCl(6)](3-), [InCl(5)](2-) and [InCl(4)](-) anions, in proportions dependent on the chi(InCl(3)) value. Equimolar mixtures yielded single compounds: 1-alkyl-3-methylimidazolium tetrachloroindates(iii). Systems containing an excess of indium(iii) chloride (chi(InCl(3)) > 0.5) contained indium(iii) chloride powder suspended in a neutral tetrachloroindate ionic liquid.

Ionic Liquids Uncoiled: Critical Expert Overviews

COIL Conferences vi Preface vii Acknowledgements ix Contributors xi Abbreviations xiii 1 Electrodeposition from Ionic Liquids: Interface Processes, Ion Effects, and Macroporous Structures 1 Frank Endres, Natalia Borisenko, Rihab Al Salman, Mohammad Al Zoubi, Alexandra Prowald, Timo Carstens, and Sherif Zein El Abedin 2 Interfaces of Ionic Liquids (1) 29 Werner Freyland 3 Interfaces of Ionic Liquids (2) 51 Robert Hayes, Deborah Wakeham, and Rob Atkin 4 Ionic Liquids in Separation Science 87 Christa M. Graham and Jared L. Anderson 5 Separation Processes with Ionic Liquids 119 Wytze (G. W.) Meindersma and Andre B. De Haan 6 Theoretical Approaches to Ionic Liquids: From Past History to Future Directions 181 Ekaterina I. Izgorodina 7 Ionic Liquids Derived from Natural Sources 231 Junko Kagimoto and Hiroyuki Ohno 8 Ionic Liquids Studied at Ultra-High Vacuum 251 Kevin R.J. Lovelock and Peter Licence 9 Pioneering Biological Processes in the Presence of Ionic Liquids: The Potential of Filamentous Fungi 283 Marija Petkovic and Cristina Silva Pereira 10 Use of Ionic Liquids in Dye-Sensitised Solar Cells 305 Jennifer M. Pringle 11 Phase Behaviour of Gases in Ionic Liquids 349 Mark B. Shifl ett and Akimichi Yokozeki Index 387

A novel recovery process for lipids from microalgæ for biodiesel production using a hydrated phosphonium ionic liquid

The use of a hydrated phosphonium ionic liquid, [P(CH2OH)4]Cl, for the extraction of microalgae lipids for biodiesel production, was evaluated using two microalgae species, Chlorella vulgaris and Nannochloropsis oculata. The ionic liquid extraction was compared to the conventional Soxhlet, and Bligh & Dyer, methods, giving the highest extraction efficiency in the case of C. vulgaris, at 8.1%. The extraction from N. oculata achieved the highest lipid yield for Bligh & Dyer (17.3%), while the ionic liquid extracted 12.8%. Nevertheless, the ionic liquid extraction showed high affinity to neutral/saponifiable lipids, resulting in the highest fatty acid methyl esters (FAMEs)-biodiesel yield (4.5%) for C. vulgaris. For N. oculata, the FAMEs yield of the ionic liquid and Bligh & Dyer extraction methods were similar (>8%), and much higher than for Soxhlet (<5%). The ionic liquid extraction proved especially suitable for lipid extraction from wet biomass, giving even higher extraction yields than from dry biomass, 14.9% and 12.8%, respectively (N. oculata). Remarkably, the overall yield of FAMEs was almost unchanged, 8.1% and 8.0%, for dry and wet biomass. The ionic liquid extraction process was also studied at ambient temperature, varying the extraction time, giving 75% of lipid and 93% of FAMEs recovery after thirty minutes, as compared to the extraction at 100 °C for one day. The recyclability study demonstrated that the ionic liquid was unchanged after treatment, and was successfully reused. The ionic liquid used is best described as [P(CH2OH)4]Cl·2H2O, where the water is not free, but strongly bound to the ions.

A greener, halide‑free approach to ionic liquid synthesis

Conventionally, ionic liquids with anions generated from simple organic acids are prepared following a metathetic procedure from a halide salt, usually a chloride. Here, we describe an efficient means of generating hydroxide solutions of the cations of interest, allowing many ionic liquids to be produced by simple acid–base reactions, completely avoiding the use of halides.

Carbon dioxide uptake from natural gas by binary ionic liquid–water mixtures

Carbon dioxide solubility in a set of carboxylate ionic liquids formulated with stoicheiometric amounts of water is found to be significantly higher than for other ionic liquids previously reported. This is due to synergistic chemical and physical absorption. The formulated ionic liquid/water mixtures show greatly enhanced carbon dioxide solubility relative to both anhydrous ionic liquids and aqueous ionic liquid solutions, and are competitive with commercial chemical absorbers, such as activated N-methyldiethanolamine or monoethanolamine.

Emerging Evidences of Mesoscopic-Scale Complexity in Neat Ionic Liquids and Their Mixtures

Ionic liquids (ILs) represent a blooming class of continuously developing advanced materials, with the aiming of a green chemical industry. Their appealing physical and chemical properties are largely influenced by their micro- and mesoscopic structure that is known to possess a high degree of hierarchical organization. High-impact application fields are largely affected by the complex morphology of neat ionic liquids and their mixtures. This Perspective highlights new arising research directions that point to an enhanced level of structural complexity in several IL-based systems, including mixtures. The latter represent a change in paradigm in the approach to formulate new, task-specific IL-based media, and the reported phenomenology has the potential to further expand their range of applications by calling for a revisitation of the nature of interactions in these exciting media.