Huiyong Wang

Structural Effects of Anions and Cations on the Aggregation Behavior of Ionic Liquids in Aqueous Solutions

The formation of ionic liquids aggregates in aqueous solution is of great importance to the future applications of ionic liquids. In this work, aggregation behavior of 1-alkyl-3-methylimidazolium salts [C8mim]X (X = Cl, Br, [NO3], [CH3COO], [CF3COO], [CF3SO3], and [ClO4]), 1-octyl-4-methylpyridinium bromide (4m-[C8pyr]Br), and 1-methyl-1-octylpyrrolidinium ([C8mpyrr]Br) has been investigated in aqueous solutions by conductivity, volume, fluorescence, dynamic light scattering, and transmission electron microscopy. The critical aggregation concentration (CAC), ionization degree of the aggregates alpha, the standard Gibbs energy of aggregation deltaG(m)degrees, the average aggregation number N, the apparent molar volumes at critical aggregation concentration V(phi,CAC), the apparent molar volumes in aggregation phase V(phi)mic, and the change of the apparent molar volumes upon aggregation deltaV(phi,m), have been derived from the experimental data for these ionic liquids. It is found that both nature of the anions and ring type of the cations significantly affect the aggregation in aqueous solution. The anionic effect basically follows the Hofmeister series, and the ability of anionic hydration is predominant for the aggregation behavior of the ionic liquids. Hydrophobicity and steric hindrance of the cations as well as binding strength of the cations with the anions are suggested to play important roles in the aggregation of [C8mim]Br, 4m-[C8pyr]Br, and [C8mpyrr]Br. The investigated ILs were found to form spherical aggregates. Structures of anions and cations have very weak effects on the morphology, but they do affect the aggregate sizes.

Salt Effect on the Aggregation Behavior of 1-Decyl-3-methylimidazolium Bromide in Aqueous Solutions

Understanding of the specific salt effect on the aggregation behavior of ionic liquids (ILs) is relevant to multiple applications. In this work, the influence of a series of 15 salts on the aggregation behavior of [C(10)mim]Br in aqueous solutions has been investigated by conductivity, fluorescence, and dynamic light scattering. It was shown that NaCl, NaBr, NaI, CH(3)CO(2)Na, NaSCN, NaNO(3), NaBrO(3), NaClO(3), C(6)H(5)COONa, Na(2)CO(3), Na(2)SO(4), Na(2)C(4)H(4)O(6), and Na(3)CH(5)O(7) have salting-out effect, whereas FeBr(3) and AlBr(3) have salting-in effect on the aggregation of [C(10)mim]Br in aqueous solutions. The effect of anions of the added sodium salts on the critical aggregation concentration (CAC), degree of anionic binding (beta), and aggregation number (N(agg)) of the IL basically follows the Hofmeister series, and the CAC values decrease but the beta and N(agg) values increase with increasing concentration of the salts. Hydrophobicity of the anions is suggested to play important roles in the salt effect on the aggregation of [C(10)mim]Br in aqueous solutions. Furthermore, the IL aggregates were found to grow slowly as the increase of the salt concentrations under studied static conditions, and resulting in the increased aggregation number of the IL. These results are expected to be useful in the applications of ionic liquids.

Reversible Hydrophobic–Hydrophilic Transition of Ionic Liquids Driven by Carbon Dioxide

Ionic liquids (ILs) with a reversible hydrophobic-hydrophilic transition were developed, and they exhibited unique phase behavior with H2O: monophase in the presence of CO2, but biphase upon removal of CO2 at room temperature and atmospheric pressure. Thus, coupling of reaction, separation, and recovery steps in sustainable chemical processes could be realized by a reversible liquid-liquid phase transition of such IL-H2O mixtures. Spectroscopic investigations and DFT calculations showed that the mechanism behind hydrophobic-hydrophilic transition involved reversible reaction of CO2 with anion of the ILs and formation of hydrophilic ammonium salts. These unique IL-H2O systems were successfully utilized for facile one-step synthesis of Au porous films by bubbling CO2 under ambient conditions. The Au porous films and the ILs were then separated simultaneously from aqueous solutions by bubbling N2, and recovered ILs could be directly reused in the next process.

Effect of anionic structure on the phase formation and hydrophobicity of amino acid ionic liquids aqueous two-phase systems

Compared with the conventional ionic liquids, amino acid ionic liquids are more biodegradable and biocompatible, and can enhance stability of biomaterials. In this work, amino acid ionic liquids 1-butyl-3-methylimidazolium L-serine ([C(4)mim][Ser]), 1-butyl-3-methylimidazolium glycine ([C(4)mim][Gly]), 1-butyl-3-methylimidazolium L-alanine ([C(4)mim][Ala]) and 1-butyl-3-methylimidazolium L-leucine ([C(4)mim][Leu]) have been synthesized. These ionic liquids are found to form aqueous two-phase systems (ATPSs) by the salted-out of K(3)PO(4) in aqueous solutions. Phase diagram of the ATPSs and the Gibbs energies of transfer of methylene group from the bottom salt-rich phase to the top ionic liquid-rich phase have been determined at 298.15K and pH 14, and the effect of anionic structure of the ionic liquids on phase formation of the ATPSs and the relative hydrophobicity between the top and the bottom phases are then examined. In order to understand the effect of relative hydrophobicity of the phases in equilibrium in the ATPSs on the extraction/separation capability of biomolecules, the partition coefficients of cytochrome-c (as a model biomolecule) in the ATPSs are measured by spectrophotometry. It is suggested that hydrophobic interactions are mainly responsible for the higher partition coefficients of cytochrome-c in aqueous two-phase systems at pH 14, and the extraction and separation capacity of biomolecules can be improved by the modulation of the relative hydrophobicity of the phases and/or the pH of the system.

Anion-Based pH Responsive Ionic Liquids: Design, Synthesis, and Reversible Self-Assembling Structural Changes in Aqueous Solution

The creation of pH responsive materials that undergo morphological transitions between micelle and vesicle induced by solution pH change is of great importance for their potential application in drug delivery and biochemical engineering. Here, we have developed a series of 18 pH responsive ionic liquids composed of 1-alkyl-3-methylimidazolium cation, [C(n)mim](+) (n = 4, 6, 8, 10, 12, 14), and different pH responsive anions such as potassium phthalic acid ([C6H4COOKCOO](-)), sodium sulfosalicylic acid ([C6H3OHCOOSO3Na](-)), and sodium m-carboxylbenzenesulfonate ([C6H4COOSO3Na](-)). The aggregation behavior and self-assembly structures of the ILs in aqueous solution have been investigated by surface tension, dynamic light scattering, transmission electron microscopy, small-angle X-ray scattering, and nuclear magnetic resonance spectroscopy. It was found for the first time that single tail ionic liquids, [C(n)mim]X (n = 12 and 14, X = [C6H4COOKCOO], [C6H3OHCOOSO3Na], and [C6H4COOSO3Na]) could form vesicles without any additives, and reversible transition was observed between spherical micelles and vesicles with the change of solution pH value. The transition in self-assembly structures is suggested to be driven by the variation in molecular structure and hydrophilicity/hydrophobicity of anions of the ILs.

Is There Any Preferential Interaction of Ions of Ionic Liquids with DMSO and H2O? A Comparative Study from MD Simulation

Recently, some binary ionic liquid (IL)/cosolvent systems have shown better performance than the pure ILs in fields such as CO2 absorption, catalysis, cellulose dissolution, and electrochemistry. However, interactions of ILs with cosolvents are still not well understood at the molecular level. In this work, H2O and DMSO were chosen as the representative protic and aprotic solvents to study the effect of cosolvent nature on solvation of a series of ILs by molecular dynamics simulations and quantum chemistry calculations. The concept of preferential interaction of ions was proposed to describe the interaction of cosolvent with cation and anion of the ILs. By comparing the interaction energies between IL and different cosolvents, it was found that there were significantly preferential interactions of anions of the ILs with water, but the same was not true for the interactions of cations/anions of the ILs with DMSO. Then, a detailed analysis and comparison of the interactions in IL/cosolvent systems, hydrogen bonds between cations and anions of the ILs, and the structure of the first coordination shells of the cations and the anions were performed to reveal the existing state of ions at different molar ratios of the cosolvent to a given IL. Furthermore, a systematic knowledge for the solvation of ions of the ILs in DMSO was given to understand cellulose dissolution in IL/cosolvent systems. The conclusions drawn from this study may provide new insight into the ionic solvation of ILs in cosolvents, and motivate further studies in the related applications.

Relative hydrophobicity between the phases and partition of cytochrome-c in glycine ionic liquids aqueous two-phase systems.

In this work, glycine ionic liquids tetramethylammonium glycine ([N1111][Gly]), tetraethylammonium glycine ([N2222][Gly]), tetra-n-butylammonium glycine ([N4444][Gly]), tetra-n-butylphosphonium glycine ([P4444][Gly]) and tetra-n-pentylammonium glycine ([N5555][Gly]) were synthesized and used to prepare aqueous two-phase systems (ATPSs) in the presence of K2HPO4. Binodal curves of such ATPSs and partition coefficients of a series of dinitrophenylated (DNP) amino acids in these ATPSs were determined at 298.15K to understand the effect of cationic structure of the ionic liquids on the phase-forming ability of glycine ionic liquids, relative hydrophobicity between the phases in the ionic liquids ATPSs, and polarity of the ionic liquids-rich phases. With the attempt to correlate the relative hydrophobicity of the phases in the ATPSs with their extraction capability for proteins, partition coefficients of cytochrome-c in the ATPSs were also determined. It was shown that partition coefficients of cytochrome-c were in the range from 2.83 to 20.7 under the studied pH conditions. Then, hydrophobic interactions between cytochrome-c and the ionic liquid are suggested to be the main driving force for the preferential partition of cytochrome-c in the glycine ionic liquid-rich phases of the ATPSs. Result derived from polarity of the ionic liquids-rich phases supports this mechanism.

Efficient Ionic‐Liquid‐Promoted Chemical Fixation of CO2 into α‐Alkylidene Cyclic Carbonates

The efficient conversion of CO2 into value-added chemicals under metal-free conditions is of significant importance from the viewpoint of sustainable chemistry. In this work, ionic liquids (ILs) with different properties were used to promote the reaction between CO2 and propargylic alcohol for the synthesis of α-alkylidene cyclic carbonates. The protic IL 1,8-diazabicyclo-[5.4.0]-7-undecenium 2-methylimidazolide ([DBUH][MIm]) was prepared by simple neutralization of the superbase with a weak proton donor and could efficiently promote the reactions in high yields. After the reactions, the IL was separated from the reaction mixtures by simply adding water, and then reused after drying without an observable decrease in the catalytic activity and selectivity. NMR spectroscopy and detailed density functional theory analysis were used to propose a reaction mechanism. Both the cation and anion of the IL played a key synergistic role in promoting the reaction. These findings may be useful for the rational design of novel metal-free and recyclable routes for the reaction between CO2 and propargylic alcohols.

Tuning the Hydrophilicity and Hydrophobicity of the Respective Cation and Anion: Reversible Phase Transfer of Ionic Liquids.

The separation and recycling of catalyst and cocatalyst from the products and solvents are of critical importance. In this work, a class of functionalized ionic liquids (ILs) were designed and synthesized, and by tuning the hydrophilicity and hydrophobicity of cation and anion, respectively, these ILs could reversibly transfer between water and organics triggered upon undergoing a temperature change. From a combination of multiple spectroscopic techniques, it was shown that the driving force behind the transfer was originated from a change in conformation of the PEG chain of the IL upon temperature variation. By utilizing the novel property of this class of ILs, a highly efficient and controllable CuI-catalyzed cycloaddition reaction was achieved wherein the IL was used to entrain, activate, and recycle the catalyst, as well as to control the reaction.

Recovery of Ionic Liquids with Aqueous Two-Phase Systems Induced by Carbon Dioxide

Recovery is a very important factor for the industrial application of ionic liquids (ILs). In this work, a novel method is presented for the recovery of ILs by using carbon dioxide (CO₂-induced formation of aqueous two-phase systems (ATPSs). It was found that, in the presence of amines, introduction of CO₂ into aqueous IL solutions leads to the formation of ATPSs at 25 °C and atmospheric pressure, in which the upper phase is ammonium-salt-rich and the lower phase is IL-rich. Thus, the ILs in aqueous solutions can be significantly enriched, and the amines can be regenerated by heating and bubbling Ar or N₂ in the salt-rich phase. To better understand the recovery of ILs, the phase diagrams of the ATPSs were measured at 25 °C, and the effects of the molecular structure of the ILs and the amines and temperature of the systems on the recovery efficiency of the ILs were investigated. It was shown that the single-step recovery efficiency of the ILs could be as high as 99 % in the presence of primary or secondary amines. Therefore, this new method could potentially be sustainable, efficient, and attractive to industry.