Anion Of Ionic Liquid Research Articles

Determination of quinclorac by adsorptive stripping voltammetry in rice samples without sample pretreatment

A novel voltammetric method with practically no sample pretreatment was developed for determination of Quinclorac (QNC) in rice samples by using a working Carbon Paste Electrode (CPE) modified with ionic liquid, with deposition potential (ED) of −1.43 V for 30 s in NaOH 0.01 mol L−1. The systematic influence of cations and anions of imidazole ionic liquids on the composition of CPE has evaluated. The best electrode composition was 65% (w/w) of graphite powder, 30% (w/w) of mineral oil and 5.0% (w/w) of C4min+BF4 - ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate). The matrices analyzed were deionized water and extracts of upland rice: white, brown, peel and seed. The limits of quantification ranged between 0.954 mg kg−1 and 3.61 mg kg−1. The recovery percentages of QNC in rice samples ranged between 90% and 121%. The simplicity and good analytical frequency enable the proposed method to be used to obtain preliminary information on the presence of QNC, prior to the implementation of more detailed, costly and elaborate quantitative analyses. The technique can be applied in the study and evaluation of sorption mechanisms, metabolization of the herbicide in plants and its persistence and degradation in the environment.

Photoinduced electron transfer reactions in mixed micelles of a star block copolymer and surface active ionic liquids: Role of the anion

This work investigates the effect of different counter anions of ionic liquid (IL) co-surfactants, viz. [NTf2]−, [DCN]−, [PF6]−, [BF4]−, [Br]−, associated with the common cation (1-decyl-3-methylimidazolium, [DMIm]+), on the microenvironments of mixed micelles formed with a star block copolymer, T1304, through spectrofluorometric studies. The role of IL anions has been explored for modulating photoinduced electron transfer (PET) reactions between a series of coumarin dyes as the electron acceptors and N,N-dimethylaniline (DMAN) as the electron donor in different T1304-IL mixed micelles. It is revealed that IL co-surfactants increase the polarity in the corona region of micelles to different extents, depending on the nature of the IL anion. The PET reactions in all micellar systems follow the Marcus Inversion (MI) behavior, as predicted by Marcus electron transfer theory, but the rate constant of electron transfer and the onset of the MI along the reaction exergonicity scale, (−ΔG°)onset, varies with the IL anion. It is observed that rather than being correlated with their chaotropic/kosmotropic nature, the effect of the IL in T1304 micelles can be correlated with the hydrophobicity/hydrophilicity, and the steric bulkiness of the IL anions.

The anion of choline-based ionic liquids tailored interactions between ionic liquids and bovine serum albumin, MCF-7 cells, and bacteria

Choline-based ionic liquids (ILs) have been widely applied because of their good biocompatibility. Herein, the toxicity of choline-based ILs containing different anions was studied by UV–vis absorption spectra, fluorescence spectra, MTT assays and antibacterial experiments. The results explained that choline chloride ([Ch][Cl]) had no obvious effect on the conformation of bovine serum albumin (BSA), while the conformation could be slightly changed by choline bromide ([Ch][Br]). In the presence of choline iodide ([Ch][I]), choline bitartrate ([Ch][Bit]) and choline dihydrogen citrate ([Ch][Dhc]), the conformation of BSA changed significantly. The quenching mechanisms of [Ch][Bit] and [Ch][Dhc] were static quenching procedure, while there were charge transfer quenching and static quenching for [Ch][I]. ILs combined with BSA in spontaneous manner driven by hydrogen bond and van der Waals force, which was proved by thermodynamic constants and molecular docking. The toxicity of the five ILs to mammalian cells and bacteria came to a similar conclusion. [Ch][Cl] had little toxicity to cells, which was less than [Ch][Br] and [Ch][I]. [Ch][Bit] and [Ch][Dhc] were more toxic. These results provide more information to understand the effect of anions on choline-based ILs, in order to find low toxic choline-based ILs that can be used in biological and pharmaceutical fields.

Thermal degradation behavior of ionic liquid/ fluorinated polymer composites: Effect of polymer type and ionic liquid anion and cation

This work reports on the evaluation of the thermal degradation of poly(vinylidene fluoride) (PVDF) and PVDF co-polymer (PVDF-TrFE, PVDF-HFP and PVDF-CTFE) composite films with different imidazolium ionic liquids (ILs). The influence of the IL type, including cation and anion type, cation chain length and content up to 40 wt% were evaluated. Independently of the fluorinated polymer type, all neat samples present a single degradation step. Upon the incorporation of the IL [C2mim][TFSI] into the different polymers, a decrease in the thermal stability occurs, indicating the IL imidazolium interaction with the CH2-CF2 groups of the fluorinated matrix. Further, it was stablished that the thermal stability of the composite material decreases with increasing cation chain length. The Ozawa-Flynn-Wall and Kissinger models were applied to evaluate the activation energies of the samples during isothermal experiments, showing that the thermal degradation activation energy ranges from 161 ± 6 kJ mol−1 ([C2mim][TFSI]/PVDF) to 131 ± 14 kJ mol−1 ([C2mim][TFSI]/PVDF-CTFE). No large differences were observed on the effect of IL inclusion in PVDF, PVDF-TrFE, PVDF-HFP and PVDF-CTFE polymer matrices.

Ionic Liquid-Stabilized Single-Atom Rh Catalyst Against Leaching

Ionic Liquid-Stabilized Single-Atom Rh Catalyst Against Leaching

Effect of molecular structure of cation and anions of ionic liquids and co-solvents on selectivity of 5-hydroxymethylfurfural from sugars, cellulose and real biomass

The concept of biorefinery still requires advancements in process development for energy and materials. Ionic liquids have been successfully used for several biorefinery applications including high yield synthesis of biofuels and value added platform chemicals. Designing suitable ionic liquid that is efficient in terms of cost as well as product selectivity is still highly needed. This study is carried out to check the effect of different anions of Bronsted acidic ionic liquids (BAILs), Bronsted Lewis acidic ionic liquids (BLAILs), Lewis acidic ionic liquids (LAILs) as well as organic electrolyte solutions (OES) for 5-HMF selectivities from monosaccharides, polysaccharides as well as lignocellulosic composite. Different variables and parameters such as Lewis acidity of anions, alkyl side chain of ionic liquid, metal chloride type and loading, time, temperature, substrate loading, polar protic and aprotic solvents are thoroughly studied for process optimization. Polar protic solvents added in [C1C4SO3HPy] based ionic liquids with CH3COO− and Cl− anions yielded 94 and 80% 5-HMF from fructose and glucose respectively in the presence of AlCl3 as Lewis acid. C4SO3H side chain yielding high from fructose and glucose is inefficient for conversion of cellulose and lignocellulose. High product selectivity from these biopolymers is achieved using butyl side chain with 3-methylpyridinium cation and chlorochromate anion.

Control of retention mechanisms on an octadecyl-bonded silica column using ionic liquid-based mobile phase in analysis of cytostatic drugs by liquid chromatography

This study assesses the potential of using ionic liquids (ILs) as mobile phase additives to control the retention mechanism of four cytostatic drugs: doxorubicin hydrochloride (DOX), epirubicin hydrochloride (EPI), daunorubicin hydrochloride (DAU) and idarubicin hydrochloride (IDA). Chromatographic separations were performed on a C18 analytical column (Discovery C18 150 × 4.6 mm, 5 µm) using six IL anions and four methyl-substituted IL cations with different alkyl chain lengths (alone or with the additional methyl group on the aromatic ring), or with an allyl group added as a cationic substituent. Thus, a total of 17 different ILs were assessed. The aqueous formic acid solution and phosphate buffer were used to compare how mobile phase composition affected the behavior of the analyzed cytostatic agents in the presence of ILs. In addition, the impacts of IL concentration, phosphate buffer concentration, and phosphate buffer pH on the final results were also considered. The ability to change analyte retention without negatively impacting peak shape or analytical efficiency was also controlled via the tailing factor and number of theoretical plates. Based on the results, the tested ILs were classified as either effective or ineffective mobile phase additives for separation of anthracyclines and identification by LC-FL technique.

Covalent organic frameworks with immobilized anions to liberate lithium ions: Quasi-solid electrolytes with enhanced rate capabilities

Ionic liquids (ILs) are promising candidates as fast Li+ conductors owing to their high ionic conductivity and admirable stability. However, the mobile ions in ILs will contribute to the overall ion conductivity which decreases Li ions transfer efficiency and rate capability of batteries. The improvemnt of Li ions transfer efficiency in ILs electrolyte materials is a great challenge. Covalent organic frameworks (COFs) with high porosity and aligned nanosize channels can offer free flowing pathways for Li+ migration as well as abundant active sites to anchor anions and liberate free Li+, which can maximize Li+ transfer efficiency. Herein we design a cationic COF and a neutral COF as porous hosts for immobilizing the anions of IL N,N-diethyl-N-(2-methoxyethyl)-N-methylammoniumbis(trifluoromethylsulphonyl)imide (DEME-TFSI) to enhance Li+ transference efficiency. The obtained quasi-solid COFs-IL electrolytes exhibit high IL loading amount owing to strong interactions between COFs and the IL. Moreover, COFs-IL electrolytes show good electrochemical stability and high ionic conductivity over 1×10−3 S cm−1, along with a 90% increase of Li+ transfer number in comparison to the bare IL electrolyte (IL/LiTFSI). Our research provides a general strategy for immobilizing mobile anions to liberate Li+ and improve Li+ transfer efficiency in IL-based electrolytes.

Structural and Dynamic Insights into the Conduction of Lithium-Ionic-Liquid Mixtures in Nanoporous Metal-Organic Frameworks as Solid-State Electrolytes.

Metal-organic framework (MOF)-based separators in Li-ion batteries (LIBs) have the potential to improve the battery performance. The mobility and conduction of lithium and organic ionic liquids (ILs) in these materials acting as (quasi) solid-state electrolytes are crucial for the battery power output. Here, we investigate the mobility of a Li-based IL in MOF nanopores and unveil the details of the conduction mechanism by molecular dynamics (MD) simulations. A complex conductivity depending on the Li-IL loading and on the IL composition is observed. Most importantly, the presence of Li prevents the collapse of the conductivity at high IL loadings. The fully atomistic MD simulations including guest-guest and guest-host interactions elucidate the competing mechanisms: Li follows a Grotthuss-like conduction mechanism with large mobility. While at small pore fillings, the Li conduction is limited by the large distance between the anions facilitating the Grotthuss-like conduction; the conduction at high pore fillings is governed by field-induced concentration inhomogeneities. Because of the small MOF pore windows, which hinders the simultaneous passage of the large IL cations and anions in opposite directions, the IL shows field-induced MOF pore blocking and ion bunching. The regions of low anion concentration and high cation concentration represent barriers for Li, decreasing its mobility. In comparison to Li-free IL, the IL bunching effect is attenuated by the formation of charge-neutral Li-anion complexes, resulting in a tremendously increased conductivity at maximum pore filling. The exploitation of this mechanism may enhance the development of advanced batteries based on IL and nanoporous separators.

Design of Graphene/Ionic Liquid Composites for Carbon Capture.

Pore size is a crucial factor impacting gas separation in porous separation materials, but how to control the pore size to optimize the separation performance remains a challenge. Here, we propose a design of graphene/ionic liquid composites with tunable slit pore sizes, where cations and anions of ionic liquids are intercalated between graphene layers. By varying the sizes of the ions, we show from first-principles density functional theory calculations that the accessible pore size can be tuned from 3.4 to 6.0 Å. Grand canonical Monte Carlo simulations of gas sorption find that the composite materials possess high CO2 uptake at room temperature and 1 bar (up to ∼8.5 mmol/g). Further simulations of the sorption of gas mixtures reveal that high CO2/N2 and CO2/CH4 adsorption selectivities can be obtained when the accessible pore size is <5 Å. This work suggests a new strategy to achieve tunable pore sizes via the graphene/IL composites for highly selective CO2/N2 and CO2/CH4 adsorption.

Ionic Liquids in Drug Delivery

Ionic liquids (ILs) are molten salts composed of a large organic cation and an organic/inorganic anion. Due to their ionic character, most ILs present advantageous properties over conventional solvents, such as negligible volatility at atmospheric conditions and high thermal and chemical stabilities. The wide variety of IL anion–cation combinations allows these solvents to be designed to display a strong solvation ability for a myriad of active pharmaceutical ingredients (APIs) and (bio)polymers. Given these properties, ILs have been used as solvents and as formulation components in different areas of drug delivery, as well as novel liquid forms of APIs (API-ILs) applied in different stages of development of novel drug delivery systems. Furthermore, their combination with polymers and biopolymers has enabled the design of drug delivery systems for new therapeutic routes of administration.

Riveting Hydroxyl Ionic Liquids onto Melem Oligomers for CO2 Cycloaddition into Cyclic Carbonates

AbstractThe product of cyclic carbonates from carbon dioxide (CO2) and epoxides under solvent‐free and co‐catalyst‐free conditions is an environmental‐friendly and economical route. However, the core of this route lies in the design and preparation of efficient and low‐cost catalysts. In this work, hydroxyl ionic liquids (HEIMBr) modified melem oligomers (CN‐HEIMBr) was fabricated and used for the cycloaddition of CO2 into cyclic carbonates. The characterizations for these catalysts, such as XPS, TGA, SEM, FT‐IR, etc, all confirmed that HEIMBr was successfully grafted onto melem oligomers. The synergistic effects of edge defects (−NH and −NH2) of melem oligomers, hydroxyl groups and halogen anions of ionic liquids were conductive to promoting CO2 cycloaddition. The influences of CO2 pressure, catalyst dosage, reaction time and temperature on the conversion and yield were investigated in detailed. In the conditions of co‐catalyst‐free and solvent‐free, the conversion of epichlorohydrin (ECH) was 99 % and the yield of chloropronene carbonate (CPC) was 97 % under optimal conditions (140 °C, 2.0 MPa, 2 h, catalyst 0.1 g, ECH 30 mmol). Moreover, the catalyst was reused at least five runs without any significantly loss of catalytic performance. Furthermore, a credible multi‐synergetic catalytic mechanism was proposed. An originality idea was provided for designing high‐efficiency catalysts for coupling of CO2 and epoxides, and put forward the multi‐synergistic effects of catalysts on CO2 conversion.

Design of absorption process for CO2 capture using cyano based anion ionic liquid

Ionic liquids are regarded as potential candidate for CO2 absorption because of their tunable properties, wide liquid range, negligible vapor pressure and their high CO2 solubility. This work aimed to study the feasibility of CO2 separation from gas containing methane and carbon dioxide using a cyano based anion ionic liquid “1-hexyl-3-methylimidazolium tetracyanoborate” [hmim][TCB] as physical absorbent due to its high CO2 capacity and its low viscosity comparing to the organic solvent DEPG called Selexol. A comparative study among different proposed case studies for CO2 absorption in the both cases of solvent has been carried out to improve the performance of the separation process. Results show that for feed gas containing between 20 and 40mol.% of CO2, it is well favorable to use the IL instead of DEPG. At 5mol.% of CO2 in feed gas it was found that lower solvent flow rate is required for the absorption with [hmim][TCB] than DEPG and the solvent can be regenerated by combining both the pressure and temperature swing process.

Economic Optimization of Carbon Capture Processes Using Ionic Liquids: Toward Flexibility in Capture Rate and Feed Composition

Aprotic heterocyclic anion ionic liquids (AHA ILs) have received significant recent attention as potential absorbents for next-generation carbon capture processes. In this paper, we describe a rate...

Understanding Electric Field‐Dependent Structure Variation of Functional Ionic Liquids at the Electrode Interface

AbstractUnderstanding the electric field‐dependent structure variation of ionic liquids (ILs) near electrodes is crucial to the rational design of ILs‐based electrochemical applications. In the present work, the number density and ionic orientation show that anions in imidazole ILs accumulate first and then are pulled out while that in sulfonic imidazole ILs changes little as the electric field strengthens. Meanwhile, the evolution of layered structure of cation and anion leads to a stronger interfacial polarization compared to that in the bulk for various ILs. Moreover, the elongation and sulfonic modification of the side chain can further respectively strengthen and weaken the interfacial polarization. These quantitative relations among structure change, side‐chain length, sulfonic group, and the electric field can provide practical guidelines in the ionic liquid design and management of the related electrochemical processes.

Experimental and theoretical studies of chitosan dissolution in ionic liquids: Contribution ratio effect of cations and anions

Typical hydrogen bonding information (hydrogen bonds, hydrogen bond lengths, and average bond lengths) and weak interaction energy (ΔH) of four ionic liquids (ILs), anion/chitobiose, cation/chitobiose, and IL/chitobiose complexes were determined using density functional theory (DFT) calculations to elucidate the contribution ratio effect of ions (cations or anions of ILs) upon chitosan dissolution.For [Emim]Ac and [Bmim]Ac with same acetate anion, contribution ratio (Rc) values of cations in [Bmim]Ac and [Emim]Ac increased from 37.88% to 38.14%. For [Bmim]Cl and [Etmim]Cl with same chloride anion, contribution ratio (Rc) values of cations increased slightly from 39.39% to 41.65%. As for [Bmim]Cl and [Bmim]Ac with same cation, contribution ratio (Rc) values of Cl- anion in [Bmim]Cl (60.61%) was lower than that of acetate anion in [Bmim]Ac (62.12%).These changes revealed that cations of ILs played more important role in chitosan dissolution.Hydrogen-bond basicity values (β values) of ILs were closely related to the DFT simulation results (weak interaction energy and average hydrogen bond length values) of ILs. Chitosan dissolved faster in acetate based imidazolium ILs ([Emim]Ac and [Bmim]Ac) than the chloride based ILs ([Bmim]Cl and [Etmim]Cl). The chitosan dissolution performance in ILs was consistent with DFT simulation results (weak interaction energy values and average hydrogen bond length values) of IL/chitobiose and hydrogen-bond basicity values of ILs.

Biomass-Derived Ionic Liquids Based on a 5-HMF Platform Chemical: Synthesis, Characterization, Biological Activity, and Tunable Interactions at the Molecular Level

A new family of protic ammonium ionic liquids (ILs) with various inorganic anions was synthesized from bio-derived 5-HMF. Starting with cellulose biomass, a complete preservation of the C₆ unit was achieved throughout the synthetic sequence (no carbon loss). Evaluation of green metrics showed a significant advantage of the developed bio-derived pathway to access ILs from a natural renewable source, depending on feasible routes to 5-HMF manufacturing. The reduced number of synthetic steps and availability of the starting materials were the key advantages. Experimental physicochemical and biological studies, as well as computational modeling revealed a unique multifunctional intrinsic organization of these bio-derived ILs. The nature of interactions between the cations and anions of the novel ILs was mapped at the molecular level. The substituents in the cationic core and the nature of the original building blocks had a prominent impact on cytotoxicity of the novel ILs. The obtained results suggest possible sustainable applications of the least toxic ILs, while the regulation of biological activity of the ILs via the corresponding structural adjustments can find biological and medicinal applications. The 5-HMF-derived IL with a sulfate anion demonstrated potentially useful properties in dissolution of microcrystalline cellulose.

Interplay of Acidity and Ionic Liquid Structure on the Outcome of a Heterocyclic Rearrangement Reaction.

The study of suitable probe reactions is a powerful tool to investigate the properties of nonconventional solvents such ionic liquids (ILs). In particular, we studied the acid-catalyzed mononuclear rearrangement of heterocycles (MHR) of the Z-phenylhydrazone of 5-amino-3-benzoyl-1,2,4-oxadiazole into the relevant 1,2,3-triazole, in solution of ILs by means of kinetic measurements. We chose as solvents six ILs differing both in the cation and anion, in the presence of five carboxylic and sulfonic acids as catalysts. For a useful comparison, the reaction was also performed in 1,4-dioxane and methanol. In general, the reaction occurs faster in ILs, compared to conventional solvents, according to the weaker solvation interactions operating in the former media. The effect of IL anion and cation on the reactivity and on the acidic strength of the catalysts was analyzed. To this aim, we measured the acidic strength of the sulfonic acids in each IL, estimated by the equilibrium formation constant of each acid with 4-nitroaniline. We found that the trend of reactivity as a function of the IL anion mainly reflects the larger difference in acidic strengths of the catalyst. Conversely, acidic strength spans a narrower range as a function of the IL cation. As a result, other factors come into play, such as the π-π interactions involving aromatic IL cations, substrate, and transition states, leading to a more articulate trend.

Ionic Liquid Vapors in Vacuum: Possibility to Derive Anodic Stabilities from DFT and UPS.

Ultraviolet photoelectron spectroscopy (UPS) investigations of several gas-phase ionic liquid (IL) ion pairs have been conducted. [EMIM][OTF], [PYR14][OTF], [EMIM][DCA], [PYR14][DCA], [PYR14][TCM], [PYR14][FSI], [PYR14][PF6], [S222][TFSI], [P4441][TFSI], and [EMMIM][TFSI] vapor UPS spectra are presented for the first time. The experimental low-binding-energy cutoff value (highest occupied molecular orbital, HOMO energy) of the ionic liquid ion pairs, which is of great interest, has been measured. Many studies use calculated gas-phase electronic properties to estimate the liquid-phase electrochemical stability. Hybrid density functional theory (DFT) calculations have been used to interpret the experimental data. The gas-phase photoelectron spectra in conjunction with the theoretical calculations are able to verify most HOMO energies and assign them to the cation or anion. The hybrid M06 functional is shown to offer a very good description of the ionic liquid electronic structure. In some cases, the excellent agreement between the UPS spectra and the M06 calculation validates the conformer found and constitutes as a first indirect experimental determination of ionic liquid ion-pair structure. Comparisons with recent theoretical studies are made, and implications for electrochemical applications are discussed. The new data provide a much-needed reference for future ab initio calculations and support the argument that modeling of IL cations and anions separately is incorrect.

Homogeneous and Heterogeneous Ionic Liquid System: Promising “Ideal Catalysts” for the Fixation of CO2 into Cyclic Carbonates

AbstractMassive emissions of CO2 have caused environmental problems all over the world. The fixation of CO2 into cyclic carbonates is regarded as an effective way of capturing and utilizing CO2. Ionic liquid catalysts (ILCs) have received great attention and been employed for catalyzing the above reaction in recent years due to their unique properties. However, there are still a few problems requiring solutions in order to finally find the “ideal catalyst”. Herein, we reviewed a number of recent related literature. The progresses of both homogeneous and heterogeneous ILCs were discussed to find out where we are and which directions to work on. The effects of cations and anions of ionic liquids (ILs), functional groups, reaction phase states, structures of supports, preparation methods of supported ionic liquids (SILs), and interactions between the ILs and supports were investigated systematically. Accordingly, basic principles of designing ILCs for the title reaction are summarized and directions of future investigations are highlighted.