- Anion amphiprotic ionic liquids as protic electrolyte matrices allowing sodium metal plating
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The sodium-ion battery (SIB) is proposed as a complementary technology to today's commercially dominant lithium-ion battery (LIB). While much know-how can be transferred from LIBs to SIBs, adjustments are still necessary, not the least for the electrolytes employed. Here the use of anion amphiprotic ionic liquid (AAIL) based electrolytes is proposed for SIB application. Two different AAILs, based on organic trifluoromethylsulfonylamide (TFSAm) and inorganic HSO4- anions, respectively, doped with NaTFSI salt have been studied, focusing on electrochemical stability and transport properties, complemented by studies of the ion-ion interactions, and final sodium-ion battery performance via stripping/plating vs. sodium metal electrodes.
- Jankowski, Piotr,Matuszek, Karolina,Treskow, Marcel,Armand, Michel,MacFarlane, Douglas,Johansson, Patrik
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- Zeolite structure direction by simple bis(methylimidazolium) cations: The effect of the spacer length on structure direction and of the imidazolium ring orientation on the 19F NMR resonances
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A series of doubly charged structure-directing agents based on two methylimidazolium moieties linked by a linear bridge of n = 3,4,5, or 6 methylene groups has been used in the synthesis of pure silica zeolites in the presence of fluoride. All of them yielded zeolite TON while only the one with n = 4 was able to produce also zeolite MFI at highly concentrated conditions. In this MFI zeolite, two distinct 19F MAS NMR resonances with about equal intensity were observed, indicating two different chemical environments for occluded fluoride. With the singly charged 1-ethyl-3-methylimidazolium cation, which can be formally considered as the monomer of the bis-imidazolium cation with n = 4, TON and MFI were also obtained, and again two 19F MAS NMR resonances now with largely dissimilar intensities were observed in MFI. Molecular mechanics simulations support a commensurate structure-direction effect for n = 4 in MFI, with each imidazolium ring, in two different orientations, sitting close to the [41526 2] cage. Periodic DFT calculations suggest that F in MFI resides always in the [415262] cages, with the different 19F resonances observed being due to the different orientation of the closest imidazolium ring.
- Rojas, Alex,Gomez-Hortigueela, Luis,Camblor, Miguel A.
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- Ionic parachor and its application II. Ionic liquid homologues of 1-alkyl-3-methylimidazolium Propionate {[Cnmim][Pro] (n = 2-6)}
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Five propionic acid ionic liquids (PrAILs) [Cnmim][Pro] (n = 2-6) (1-alkyl-3-methylimidazolium propionate) have been prepared by the neutralization method and characterized by 1H NMR spectroscopy and differential scanning calorimetry
- Tong, Jing,Ma, Xue,Kong, Yu-Xia,Chen, Yan,Guan, Wei,Yang, Jia-Zhen
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- Density, Viscosity, and Refractive Index of Ionic Liquid Mixtures Containing Cyano and Amino Acid-Based Anions
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In this work, mixtures of five ionic liquids (ILs) based on a common cation, 1-ethyl-3-methylimidazolium ([C2mim]+), and amino acid anions, namely glycinate ([Gly]a), l-alaninate ([l-Ala]a), taurinate ([Tau]a), l-serinate ([l-Ser]a), and l-prolinate ([l-Pro]a) with 1-ethyl-3-methylimidazolium tricyanomethane, [C2mim][C(CN)3], were prepared. The thermophysical properties, namely density, viscosity, and refractive index, of the neat ILs and their mixtures were measured in the temperature range of T = (293.15 up to 353.15) K. The thermal expansion coefficients were calculated for the neat ILs and were considered to be independent of temperature in the working temperature range. Overall, experimental density, viscosity, and refractive index data of the neat AAILs were in a good agreement with those reported in literature. A dramatic decrease in the viscosity was observed for the IL mixtures as the [C2mim][C(CN)3] content increased. The obtained results indicate that mixing [C2mim][C(CN)3] with amino acid-based ILs is a potential mean to further increase flexibility and the fine-tune capacity of the physical and chemical properties of amino acid-based ILs.
- Gouveia, Andreia S. L.,Tomé, Liliana C.,Marrucho, Isabel M.
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- Intrinsically electrochromic ionic liquids based on vanadium oxides: Illustrating liquid electrochromic cells
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Five intrinsically electrochromic ionic liquids based on vanadium oxides are obtained by a simple and efficient acid base neutralization of the cation hydroxide and ammonium vanadate. These novel ionic liquids play the role of the electrochrome and electrolyte in liquid electrochromic cells.
- Branco, Aida,Belchior, Joao,Branco, Luis C.,Pina, Fernando
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- A non-phosgene process for bioderived polycarbonate with high molecular weight and advanced property profile synthesized using amino acid ionic liquids as catalysts
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The conversion of biomass and carbon dioxide to plastics is one of the key solutions to reduce the greenhouse effect and alleviate the petroleum resource depletion. However, there is still a lack of bioderived polymers with high molecular weights and excellent performance and their corresponding green synthesis processes, which limits the potential of bioderived polymers to replace petroleum-based polymers. In this study, an eco-friendly synthetic process for bioderived polycarbonate, catalyzed by amino acid ionic liquids, was developed by utilizing isosorbide (ISO) and diphenyl carbonate (DPC) as reactants, derived from a renewable resource and carbon dioxide, respectively. By using 1-ethyl-3-methylimidazole lysine ([Emim][Lys]) as a catalyst, poly(isosorbide carbonate) (PIC) with the weight average molecular weight of 150 000, the highest reported so far to the best of our knowledge, was synthesized, and the Tg of PIC was up to 174 °C. The reaction mechanism was investigated using nuclear magnetic resonance (NMR) spectroscopy, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF MS), and density functional theory (DFT) calculation. The remarkable catalytic performance was attributed to the fact that [Emim][Lys] could effectively activate the hydroxyl group of ISO and carbonyl group of DPC, and inhibit the formation of cyclic intermediates. Moreover, to overcome the brittleness of PIC, 1,4-butanediol (BD) and 1,4-cyclohexanedimethanol (CHDM) were introduced into PIC, and the copolycarbonate showed excellent Young's modulus, ultimate tensile strength, and elongation at break, which were 979 MPa, 57 MPa, and 145%, respectively, and were comparable to the commercial petroleum-based polycarbonates. Such a process provides further industrial prospects for the next generation of bioderived polycarbonate.
- He, Hongyan,Li, Chenhao,Li, Zengxi,Xu, Fei,Yang, Zifeng,Zhang, Yaqin,Zhang, Zhencai
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- Novel ionic liquids composed of only azole ions
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Novel ionic liquids (ILs) composed of azole type cation and anion were prepared. Triazole and tetrazole were coupled with 1-ethyl-3-methylimidazolium hydroxide. Obtained tetrazole salt was liquid at room temperature showing only glass transition temperature at -89°C. The ionic conductivity reached to 8.9 × 10-3 S cm-1 at room temperature reflecting low viscosity of 42.5 cP at 25°C. This is the first report on the ILs based on only azole type ions.
- Ogihara, Wataru,Yoshizawa, Masahiro,Ohno, Hiroyuki
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- Synthesis and characterization of imidazolium perrhenate ionic liquids
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A series of air- and water-stable imidazolium perrhenate-based room-temperature ionic liquids [(RT)ILs] of the type [Cnmim][ReO 4] (Cnmim = 1-CnH2n+1-3- methylimidazolium, n = 2, 4, 5, 6, 8, 10, 12) have been synthesized and characterized by 1H and 13C NMR spectroscopy, IR spectroscopy, electrospray ionization mass spectrometry (ESI-MS), and elemental analysis (EA). The effect of the variation of the alkyl chain length on physical properties such as melting point, thermal stability, density, and conductivity was examined.
- Yue, Shuang,Fang, Da-Wei,Li, Jun,Zang, Shu-Liang,Zhou, Ming-Dong,Zhang, Bo,Markovits, Iulius I.E.,Cokoja, Mirza,Kuehn, Fritz E.
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- 1-Ethyl-3-methylimidazolium tartrate chiral ionic liquids: preparation, characterization and opportunities thereof
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A unified acid/base synthetic access to tartrate-based chiral ionic liquids relying on the generation of cation hydroxide salts with AgOH was challenged with the preparation of sensitive 1-ethyl-3-methylimidazolium derivatives. Systematic variation of the starting tartaric acid stoichiometry and configuration led to eight stereoisomeric 1-ethyl-3-methylimidazolium hydrogen tartrate or di-(1-ethyl-3-methylimidazolium)tartrate entities. These salts were all characterised as proper ionic liquids. An unprecedented influence of the configuration ((2S,3S), or (2R,3R) vs. racemic or meso) on dynamic viscosity was observed. The relevance of such tartrate salts as task-specific ionic liquids was demonstrated in a synthetically useful base-promoted intramolecular cyclisation of a C2-symmetrical bis-epoxide en route to the total synthesis of phytofuran metabolites.
- Castellan, Tessa,Cuyamendous, Claire,Fitremann, Juliette,Galano, Jean-Marie,Oger, Camille,Durand, Thierry,Guillen, Frédéric,Génisson, Yves
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- Evaluation of imidazolium-based ionic liquids towards vermicidal activity: In vitro & in silico studies
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A series of six different ionic liquids (ILs) of the kind 1-alkyl-3-methylimidazolium bromide/hydroxide (IL-Br and IL-OH) tailored with different N-alkyl side chains (ethyl, butyl, octyl) were synthesized and evaluated for their vermicidal activity against the Indian earthworm, Pheretima posthuma. The percentage of paralysis and mortality of earthworms against ILs were recorded in a dose dependent (at different concentrations 2, 4, 8 and 16 mM) and time dependent manner. The ILs with hydroxide as the counter anion (IL-OH) showed higher vermicidal activity compared to their bromide counterparts (IL-Br). Moreover, the ILs with the longest alkyl chain (octyl) were observed to have significant vermicidal activity compared to the rest (ethyl and butyl) as well as the standard drug, Albendazole. Furthermore, theoretical modeling was carried out to visualize the preferential docking positions of these ILs into the active site of β-tubulin. Fascinatingly, it was found that the ILs with longest alkyl side chain showed remarkable vermicidal activity compared to the rest, and the molecular docking studies not only validated the experimental results, but also showed per-residue interaction analysis between the ILs and the different components of β-tubulin.
- Charan, K. T. Prabhu,Ranjan, Prabodh,Manojkumar, Kasina,Pothanagandhi, Nellepalli,Jha, Prakash C.,Khedkar, Vijay M.,Sivaramakrishna, Akella,Vijayakrishna, Kari
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- Novel ascorbic acid based ionic liquids for the in situ synthesis of quasi-spherical and anisotropic gold nanostructures in aqueous medium
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A series of newly designed ascorbic acid based room temperature ionic liquids were successfully used to prepare quasi-spherical and anisotropic gold nanostructures in an aqueous medium at ambient temperature. The synthesis of these room temperature ionic liquids involves, first, the preparation of a 1-alkyl (such as methyl, ethyl, butyl, hexyl, octyl, and decyl) derivative of 3-methylimidazolium hydroxide followed by the neutralization of the derivatised product with ascorbic acid. These ionic liquids show significantly better thermal stability and their glass transition temperature (Tg) decreases with increasing alkyl chain length. The ascorbate counter anion of these ionic liquids acts as a reducing agent for HAuCl4 to produce metallic gold and the alkylated imidazolium counter cation acts as a capping/shape-directing agent. It has been found that the nature of the ionic liquids and the mole ratio of ionic liquid to HAuCl4 has a significant effect on the morphology of the formed gold nanostructures. If an equimolar mixture of ionic liquid and HAuCl4 is used, predominantly anisotropic gold nanostructures are formed and by varying the alkyl chain length attached to imidazolium cation of the ionic liquids, various particle morphologies can formed, such as quasispherical, raspberry-like, flakes or dendritic. A probable formation mechanism for such anisotropic gold nanostructures has been proposed, which is based on the results of some control experiments.
- Dinda, Enakshi,Si, Satyabrata,Kotal, Atanu,Mandal, Tarun K.
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- Synthesis and thermophysical properties of low viscosity amino acid-based ionic liquids
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Nowadays ionic liquids are in the focus of scientific interest owing to their attractive properties. In this context, a series of amino acid-based ionic liquids (AAILs; EmimGly, EmimAla, EmimPro, and EmimSer) were synthesized and characterized by NMR and elemental analysis. Thermophysical properties such as density and viscosity were measured in the temperature range of T = (293.15 to 353.15) K and refractive index in the temperature range of T = (293.15 to 333.15) K. The thermal expansion coefficient values were calculated from the acquired experimental density values for T = (293.15 to 363.15) K. A thermogravimetric analyzer (TGA) was used to investigate the thermal degradation behavior of synthesized ionic liquids.
- Muhammad, Nawshad,Man, Zakaria B.,Bustam, Mohamad Azmi,Mutalib, M. I. Abdul,Wilfred, Cecilia D.,Rafiq, Sikander
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- Extraction of polysaccharides from bran with phosphonate or phosphinate-derived ionic liquids under short mixing time and low temperature
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A novel series of 1-alkyl-3-methylimidazolium phosphonate and phosphinate-type ionic liquids is able to extract polysaccharides from bran, which is a renewable biomass. In particular, 1-ethyl-3-methylimidazolium phosphinate is a novel low viscosity polar ionic liquid with which one can extract a series of polysaccharides from bran without heating. The physico-chemical properties of a series of these salts are also determined, in a study of the ability of these ionic liquids to extract cellulose and other polysaccharides from bran. The Royal Society of Chemistry 2010.
- Abe, Mitsuru,Fukaya, Yukinobu,Ohno, Hiroyuki
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- Preparation method of halogen-free imidazolium hydroxide
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The invention discloses a preparation method of halogen-free imidazolium hydroxide. The preparation method comprises the following steps: firstly, preparing a crude product imidazolium alkyl sulfate from 1-methylimidazole or 1, 2-dimethylimidazole and excessive sulfuric acid diester compounds; adding a barium hydroxide solution with the mass concentration of 10% into the crude product imidazolium alkyl sulfate under the condition of continuous stirring; fully stirring, centrifugally filtering to remove white barium sulfate precipitate, and washing with n-pentane to obtain a clear imidazolium hydroxide solution. The preparation process is easy to operate, green and environment-friendly, high in yield and high in product purity, and can meet the raw material requirements of industries such as energy, materials, biological medicines and daily chemicals on preparation of the high-purity ionic liquid.
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Paragraph 0024-0026
(2021/11/21)
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- Synthesis and antibacterial activity of ionic liquids and organic salts based on penicillin g and amoxicillin hydrolysate derivatives against resistant bacteria
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The preparation and characterization of ionic liquids and organic salts (OSILs) that contain anionic penicillin G [secoPen] and amoxicillin [seco-Amx] hydrolysate derivatives and their in vitro antibacterial activity against sensitive and resistant Escherichia coli and Staphylococcus aureus strains is reported. Eleven hydrolyzed β-lactam-OSILs were obtained after precipitation in moderate-to-high yields via the neutralization of the basic ammonia buffer of antibiotics with different cation hydroxide salts. The obtained minimum inhibitory concentration (MIC) data of the prepared compounds showed a relative decrease of the inhibitory concentrations (RDIC) in the order of 100 in the case of [C2OHMIM][seco-Pen] against sensitive S. aureus ATCC25923 and, most strikingly, higher than 1000 with [C16Pyr][seco-Amx] against methicillin-resistant Staphylococcus aureus (MRSA) ATCC 43300. These outstanding in vitro results showcase that a straightforward transformation of standard antibiotics into hydrolyzed organic salts can dramatically change the pharmaceutical activity of a drug, including giving rise to potent formulations of antibiotics against deadly bacteria strains.
- Branco, Luís C.,Dias, Ana Rita,Dias, Vitorino,Ferraz, Ricardo,Noronha, Jo?o Paulo,Petrovski, ?eljko,Pinheiro, Luís,Prudêncio, Cristina,Santos, Miguel M.,Silva, Dário
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- Antimicrobial activities of highly bioavailable organic salts and ionic liquids from fluoroquinolones
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As the development of novel antibiotics has been at a halt for several decades, chemically enhancing existing drugs is a very promising approach to drug development. Herein, we report the preparation of twelve organic salts and ionic liquids (OSILs) from ciprofloxacin and norfloxacin as anions with enhanced antimicrobial activity. Each one of the fluoroquinolones (FQs) was combined with six different organic hydroxide cations in 93–100% yield through a buffer-assisted neutralization methodology. Six of those were isomorphous salts while the remaining six were ionic liquids, with four of them being room temperature ionic liquids. The prepared compounds were not toxic to healthy cell lines and displayed between 47-and 1416-fold more solubility in water at 25 and 37 ?C than the original drugs, with the exception of the ones containing the cetylpyridinium cation. In general, the antimicrobial activity against Klebsiella pneumoniae was particularly enhanced for the ciprofloxacin-based OSILs, with up to ca. 20-fold decreases of the inhibitory concentrations in relation to the parent drug, while activity against Staphylococcus aureus and the commensal Bacillus subtilis strain was often reduced. Depending on the cation–drug combination, broad-spectrum or strain-specific antibiotic salts were achieved, potentially leading to the future development of highly bioavailable and safe antimicrobial ionic formulations.
- Alves, Celso,Branco, Luís C.,Costa, Alexandra,Florindo, Catarina,Marrucho, Isabel M.,Pedrosa, Rui,Petrovski, ?eljko,Santos, Miguel M.,Silva, Joana
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- Effect of anion in carboxylate-based ionic liquids on catalytic activity of transesterification with vinyl esters and the solubility of cellulose
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The role of 1-ethyl-3-methylimidazolium (Emim) carboxylate-type ionic liquid (IL) as the solvent and organocatalyst for transesterification reaction of cellulose was investigated. The reported method using Emim acetate and vinyl ester caused an undesired side reaction: the acetate anion derived from EmimOAc was introduced into cellulose ester. To improve the reaction system, ILs with a high cellulose solubility, a high degree of substitution (DS) value, and low side-reaction were systematically explored. Newly synthesized Emim p-anisate and a mixed solvent system achieved the transesterification reaction of cellulose with a high DS value derived from the employed vinyl esters (DS > 2.9), and a low DS value derived from side reaction (selectivity > 99%).
- Hirose, Daisuke,Wardhana Kusuma, Samuel Budi,Nomura, Shuhei,Yamaguchi, Makoto,Yasaka, Yoshiro,Kakuchi, Ryohei,Takahashi, Kenji
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p. 4048 - 4053
(2019/02/12)
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- Ionic Liquids and Salts from Ibuprofen as Promising Innovative Formulations of an Old Drug
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Herein we report the synthesis of novel ionic liquids (ILs) and organic salts by combining ibuprofen as anion with ammonium, imidazolium, or pyridinium cations. The methodology consists of an acid–base reaction of neutral ibuprofen with cation hydroxides, which were previously prepared by anion exchange from the corresponding halide salts with Amberlyst A-26(OH). In comparison with the parent drug, these organic salts display higher solubility in water and biological fluids and a smaller degree of polymorphism, which in some cases was completely eliminated. With the exception of [C16Pyr][Ibu] and [N1,1,2,2OH1][Ibu], the prepared salts did not affect the viability of normal human dermal fibroblasts or ovarian carcinoma (A2780) cells. Therefore, these ibuprofen-based ionic liquids may be very promising lead candidates for the development of effective formulations of this drug.
- Santos, Miguel M.,Raposo, Luís R.,Carrera, Gon?alo V. S. M.,Costa, Alexandra,Dionísio, Madalena,Baptista, Pedro V.,Fernandes, Alexandra R.,Branco, Luís C.
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supporting information
p. 907 - 911
(2019/04/17)
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- Method for synthesizing chalcone by solvent-free catalysis on basis of alkaline ionic liquid
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The invention relates to a method for preparing chalcone from benzaldehyde and acetophenone as raw materials by solvent-free catalysis on the basis of an alkaline ionic liquid, that is, acetophenone and benzaldehyde in a molar ratio of is 0.5:1-5:1 are mixed in the absence of a solvent, 1wt.%-10wt.% of an alkaline ionic liquid catalyst is added, a reaction is performed at 20-60 DEG C for 2-6 h, and chalcone is prepared, wherein the yield of chalcone can reach 86.7%-96.7%. The synthesis route (one-pot method) is simple, reaction conditions are mild, reaction time is shorter, the product yield is high, selectivity is good, pollution of the ionic liquid is low, the problems that traditional strong alkali catalysts are high in requirement for reaction devices and pollute the environment are solved, and green catalytic synthesis of chalcone is effectively realized.
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Paragraph 0024-0026
(2019/09/17)
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- Cation-Anion Interactions in 1-Ethyl-3-methylimidazolium-Based Ionic Liquids with Aprotic Heterocyclic Anions (AHAs)
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Ionic liquids with aprotic heterocyclic anions (AHAs) have been developed for CO2 capture but have been considered for other applications as well. Previously, we have shown that AHA ILs, where the only site for reaction with CO2 is the anion, the CO2 capacity correlates with anion basicity. Moreover, we have shown that 1-ethyl-3-methylimidazolium ([Emim]+)AHA ILs can react with CO2 in two ways. The first is with the anion to form a carbamate. The second is by reaction of the deprotonated C2 of the imidazolium cation to form a carboxylate. Here we show that the amount of carboxylate formed when [Emim]+ AHA ILs are exposed to CO2 is not proportional to the anion basicity, contrary to expectations. Rather, it is roughly the same for all AHA ILs investigated, as long as the anion is able to readily deprotonate the C2. Moreover, the strength of the hydrogen bond between C2-H and the anion is not proportional to the anion basicity, once again contrary to expectations. In addition, we discovered that deuterium exchange occurs not only with the acidic proton on the C2 of the cation but also with the less acidic C4 and C5 protons of the imidazolium cation, when the anions are sufficiently basic. These conclusions were reached based on quantification of cation-CO2 and anion-CO2 complex formation, IR spectra, 1H NMR chemical shifts, and deuterium exchange equilibrium and kinetics.
- Oh, Seungmin,Morales-Collazo, Oscar,Brennecke, Joan F.
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p. 8274 - 8284
(2019/10/16)
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- Method for preparing alpha, alpha-dimethyl benzyl alcohol under dual catalyst and solvent-free conditions
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The present invention relates to a method for preparing alpha, alpha-dimethyl benzyl alcohol under dual catalyst and solvent-free conditions. The method comprises the following steps of 1) preparing an ionic liquid catalyst; 2) adding cumene, the ionic liquid catalyst and an inorganic salt catalyst into a reactor with a reflux device, introducing a certain amount of air into the reactor as an oxygen source, and enabling cumene to perform an oxidation reaction under a solvent-free condition; and 3) after the reaction is finished, performing standing, wherein after the material in the reactor islayered, the upper-layer material is a reaction product alpha-dimethyl benzyl alcohol and the lower-layer material is a mixed catalytic system formed by the ionic liquid catalyst and the inorganic salt catalyst; and 4) separating the upper-layer material to obtain the reaction product alpha-dimethyl benzyl alcohol. The method is a brand-new synthesis mechanism, is low in cost and is suitable forlarge-scale industrial production.
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Paragraph 0093; 0095; 0097
(2019/12/31)
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- A potential greener protocol for peptide coupling reactions using recyclable/reusable ionic liquid [ C 4-DABCO ] [ N(CN) 2 ]
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Abstract : Development of greener methodologies in synthetic organic chemistry has brought awareness in recent decades due to the ecological performance of green solvent media and catalytic systems. Here, we carried out the peptide bond formation reaction in one of the environmentally secure solvents, ‘ionic liquids’ in the presence of coupling reagent and in the absence of external base at room temperature, affording dipeptides in good to excellent yields. GRAPHICAL ABSTRACT: SYNOPSIS We carried out the peptide bond formation reaction in ionic liquids in the presence of a coupling reagent at room temperature, in the absence of an external base, affording dipeptides in good to excellent yields.
- Konwar, Manashjyoti,Khupse, Nageshwar D,Saikia, Prakash J,Sarma, Diganta
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- Deciphering the anthelmintic activity of benzimidazolium salts by experimental and in-silico studies
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Inspired from the facts that majority of the drug administrated in the form of salts and “poison is in the dose”; herein, we have synthesized and characterized 1-methyl-3-alkylbenzimidazolium and 1-methyl-3-alkylimidazolium derived ionic salts with varying N-alkyl chains and different anions. These ionic salts were evaluated for their vermicidal activity (VA) and cell viability test against the Pheretima posthuma and A549 cell lines (human alveolar basal epithelial cells), respectively. The morphological changes in the test organism were visualized by the Scanning Electron Spectroscopy (SEM) to get the mechanistic insight. Furthermore, results were compared with VA of 1-methyl-3-alkylimidazolium derivatives to establish their structure-activity-relationship (SAR) of the fused benzene ring in 1-methyl-3-alkylimidazolium. The current findings suggested that the activity of these salts depends on the nature of N-alkyl side-chain, anionic moieties, varying partial charge on quaternary nitrogen (due to different anions) lipophilicity and types of cationic core fused with imidazolium ring. These findings were complemented by the quantitative-structure-activity-relationship (QSAR), molecular docking approaches to unfold the features accountable for their activities and binding patterns of the ligand-receptor complex respectively. ADME/T assessment of the ionic salts shows that twelve compounds qualified the ADMET profiling test & encompasses the drug-likeness features.
- Ranjan, Prabodh,Athar, Mohd,Vijayakrishna, Kari,Meena, Lalit K.,Vasita, Rajesh,Jha, Prakash C.
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p. 156 - 168
(2018/07/25)
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- Induction of lignin solubility for a series of polar ionic liquids by the addition of a small amount of water
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Addition of a small amount of water was found to induce the lignin solubilizing ability in several polar ionic liquids which showed no lignin solubility in the absence of water. Similarly, addition of water was found to enhance lignin solubility in many polar ionic liquids. Though addition of water lowered the proton accepting ability of these ionic liquids, their proton donating ability was found to increase. The lignin dissolution by ionic liquids was newly found to be a function of both the proton accepting ability and proton donating ability of the ionic liquids. Water is a poor solvent for polysaccharides, and water addition has therefore been confirmed to be effective to improve the selective extraction yield of lignin from cedar powder under mild conditions.
- Akiba, Takashi,Tsurumaki, Akiko,Ohno, Hiroyuki
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supporting information
p. 2260 - 2265
(2017/07/24)
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- Method for preparing fructosazine by utilizing chitin-based biomass
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The invention relates to a method for preparing fructosazine by utilizing chitin-based biomass. The method comprises the following steps: adding a dry chitin-based biomass raw material, an imidazolium ionic liquid solution and an additive to dimethyl sulfoxide to obtain a mixture; uniformly mixing the obtained mixture to perform a reaction, wherein the mass ratio of the imidazolium ionic liquid to the chitin-based biomass raw material is 1: (2-100), and the mass ratio of the added chitin-based biomass raw material to an oxidant is 1: (1-50) to obtain an intermediate product; adding a crystallization solvent to the intermediate product, wherein the volume ratio of the intermediate product to the solvent is 1: 1 to 1: 10; completely dissolving the product; removing undissolved impurities to obtain a filter liquor; carrying out rotary evaporation concentration on the filter liquor; standing; and recrystallizing to prepare the final product. The method has the advantages of wide raw material resources, no pollution, simple preparation and high product purity.
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Paragraph 0038; 0039
(2016/10/07)
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- Extraction of polysaccharides from Japanese cedar using phosphonate-derived polar ionic liquids having functional groups
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Extraction of polysaccharides from Japanese cedar using ionic liquids has been demonstrated. To this aim, eleven types of phosphonate ionic liquids have been synthesized, their properties investigated, and applied to biomass processing. All ionic liquids prepared display strong hydrogen-bonding characteristics of Kamlet-Taft parameters (β > 1.1) which enabled the effective extraction of polysaccharides from Japanese cedar. In particular, 15wt% of polysaccharides was extracted from Japanese cedar powder using 1-(3-methoxypropyl)-3-methyl-imidazolium ethyl ethylphosphonate. Since the ionic liquid is easily prepared using conventional reagents and might be applicable to large-scale reactions, it is expected that practical polysaccharide extraction using the ionic liquid might be possible from a wide variety of biomass resources.
- Fukaya, Yukinobu,Asai, Ryo-Ichi,Kadotani, Shiho,Nokami, Toshiki,Itoh, Toshiyuki
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p. 879 - 886
(2016/10/12)
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- Nonaqueous lyotropic ionic liquid crystals: Preparation, characterization, and application in extraction
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A class of new ionic liquid (IL)-based nonaqueous lyotropic liquid crystals (LLCs) and the development of an efficient IL extraction process based on LC chemistry are reported. The nonaqueous LLCs feature extraordinarily high extraction capacity, excellent separation selectivity, easy recovery, and biocompatibility. This work also demonstrates that the introduction of self-assembled anisotropic nanostructures into an IL system is an efficient way to overcome the intrinsically strong polarity of ILs and enhances the molecular recognition ability of ILs. The distribution coefficients of IL-based LLCs for organic compounds with H-bond donors reached unprecedented values of 50-60 at very high feed concentrations (>100 mg mL-1), which are 800-1000 times greater than those of common ILs as well as traditional organic and polymer extractants. The IL-based nonaqueous LLCs combining the unique properties of ILs and LCs open a new avenue for the development of high-performance extraction methods. Putting order into ionic liquids: Ionic liquid (IL)-based nonaqueous lyotropic liquid crystals (LLCs) exhibit extraordinarily high extraction capacity, excellent separation selectivity, and easy recycling. The introduction of self-assembled nanostructures into IL systems is an efficient way to enhance the recognition ability for H-bond donor molecules. The IL-based LLCs successfully combine the unique properties of ILs and LCs and provide a new platform for high-performance separation.
- Liu, Xianxian,Yang, Qiwei,Bao, Zongbi,Su, Baogen,Zhang, Zhiguo,Ren, Qilong,Yang, Yiwen,Xing, Huabin
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p. 9150 - 9156
(2015/06/16)
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- Bronsted acids in ionic liquids: How acidity depends on the liquid structure
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Gutmann Acceptor Number (AN) values have been determined for Bronsted acid-ionic liquid mixtures, over a wide compositional range. Four systems of general formula [C2mim][A]-HA (A- = bistriflamide, [NTf2]-; triflate, [OTf]-; mesylate, [OMs]-; or acetate, [OAc]-, [C2mim]+ = 1-ethyl-3-methylimidazolium cation) were studied. A library of Bronsted acidic systems of varying acidity was constructed and the AN parameter was found to be a convenient approach for quantifying their acidity. HOAc, HOMs and HOTf, when dissolved in ionic liquids, were found to associate with the respective anions to form hydrogen-bonded anionic clusters, [A(HA)x]-. In contrast, HNTf2 was solubilised as a discrete, undissociated molecule. AN values were sensitive to the presence of anionic clusters; acidity could be buffered to a particular AN by binding the solubilised acid in the anionic cluster form. Overall, a simple way to manipulate and quantify the Bronsted acidity of acid-ionic liquid mixtures was demonstrated, and measured AN values were related to liquid speciation. This journal is
- McCune, Jade A.,He, Peizhao,Petkovic, Marina,Coleman, Fergal,Estager, Julien,Holbrey, John D.,Seddon, Kenneth R.,Swadba-Kwasny, Malgorzata
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p. 23233 - 23243
(2015/01/08)
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- Physical properties and CO2 reaction pathway of 1-ethyl-3-methylimidazolium ionic liquids with aprotic heterocyclic anions
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Ionic liquids (ILs) with aprotic heterocyclic anions (AHA) are attractive candidates for CO2 capture technologies. In this study, a series of AHA ILs with 1-ethyl-3-methylimidazolium ([emim]+) cations were synthesized, and their physical properties (density, viscosity, and ionic conductivity) were measured. In addition, CO2 solubility in each IL was determined at room temperature using a volumetric method at pressures between 0 and 1 bar. The AHAs are basic anions that are capable of reacting stoichiometrically with CO2 to form carbamate species. An interesting CO2 uptake isotherm behavior was observed, and this may be attributed to a parallel, equilibrium proton exchange process between the imidazolium cation and the basic AHA in the presence of CO2, followed by the formation of "transient" carbene species that react rapidly with CO2. The presence of the imidazolium-carboxylate species and carbamate anion species was verified using 1H and 13C NMR spectroscopy. While the reaction between CO2 and the proposed transient carbene resulted in cation-CO2 binding that is stronger than the anion-CO2 reaction, the reactions of the imidazolium AHA ILs were fully reversible upon regeneration at 80 °C with nitrogen purging. The presence of water decreased the CO2 uptake due to the inhibiting effect of the neutral species (protonated form of AHA) that is formed.
- Seo, Samuel,Desilva, M. Aruni,Brennecke, Joan F.
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p. 14870 - 14879
(2015/02/19)
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- Thermal decomposition of carboxylate ionic liquids: Trends and mechanisms
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The thermal stability of a series of dialkylimidazolium carboxylate ionic liquids has been investigated using a broad range of experimental and computational techniques. Ionic liquids incorporating fluoroalkyl carboxylate anions were found to have profoundly differing thermal stabilities and decomposition mechanisms compared with their non-fluorinated analogues. 1-Ethyl-3-methylimidazolium acetate was observed to largely decompose via an SN2 nucleophilic substitution reaction when under inert gas conditions, predominantly at the imidazolium methyl substituent. The Arrhenius equations for thermal decomposition of 1-ethyl-3-methylimidazolium acetate, and the C2-methylated analogue 1-ethyl-2,3-dimethylimidazolium acetate, were determined from isothermal Thermogravimetric Analysis experiments. The low thermal stability of 1-ethyl-3-methylimidazolium acetate has important implications for biomass experiments employing this ionic liquid. For these two ionic liquids, ion pair and transition state structures were optimised using Density Functional Theory. The activation barriers for the SN2 nucleophilic substitution mechanisms are in good agreement with the experimentally determined values.
- Clough, Matthew T.,Geyer, Karolin,Hunt, Patricia A.,Mertes, Juergen,Welton, Tom
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p. 20480 - 20495
(2013/12/04)
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- Ionic amino acids: Application as organocatalysts in the aza-Michael reaction
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The ethyl methyl imidazolium salts of amino acids, [emim][AA], have been used as catalysts in the aza-Michael reaction. Furthermore, when chiral amino acids were used, a stereoselective reaction was achieved. The mechanism of the transformation was verified by the detection of a key intermediate by electrospray ionization mass spectroscopy (ESI-MS).
- Morimoto, Naoki,Takeuchi, Yasuo,Nishina, Yuta
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- Tartrate-based ionic liquids: Unified synthesis and characterisation
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A convenient and general preparative approach for tartrate-derived organic salts with bulky non-coordinating cations is described. This route is based on neutralisation of tartaric acid with cation hydroxides in aqueous solution. A series of 24 tartrate salts was prepared by systematic variation of the hemi- or bis-tartrate anion and the nature of the organic cation. Chirality of the anion was also explored as a vector for structural modification. Complete characterisation, including X-ray crystallography, was carried out. This comparative study of the physicochemical properties of these salts led to the identification of several informative trends useful for designing proper tartrate-based chiral ionic liquids.
- Rouch, Anne,Castellan, Tessa,Fabing, Isabelle,Saffon, Nathalie,Rodriguez, Jean,Constantieux, Thierry,Plaquevent, Jean-Christophe,Genisson, Yves
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p. 413 - 426
(2013/03/29)
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- Study on enthalpy and molar heat capacity of solution for the ionic liquid [C2mim][OAc] (1-Ethyl-3-methylimidazolium acetate)
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An acetic acid ionic liquid (AcAIL) [C2mim][OAc] (1-ethyl-3-methylimidazolium acetate) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar enthalpies of solution, δsolHm, for the ionic liquid [C 2mim][OAc] with different molalities were measured in the temperature range from (288.15 to 308.15 ± 0.01) K with an interval of 5 K. In terms of Archer's method, the standard molar enthalpies of solution, δsolHmθ, for [C2mim] [OAc] were obtained in the temperature range of (288.15 to 308.15 ± 0.01) K. Plotting δsolHmθ against (T - 298.15) K, a good straight line was obtained, with the slope of the line being the standard molar heat capacity of solution, δCp,m θ = 411 J·K-1·mol-1, for [C2mim][OAc], and the specific heat capacity of solution, δCpθ = 2.4 J·g -1·K-1, was also obtained.
- Ma, Xiao-Xue,Li, Long,Wei, Jie,Duan, Wen-Bin,Guan, Wei,Yang, Jia-Zhen
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p. 3171 - 3175
(2013/01/15)
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- A quick and green approach to prepare [Rmim]OH and its application in hydrophilic ionic liquid synthesis
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A quick and green process to prepare [Rmim]OH solutions is developed based on fast ion exchange between OH- and halide ions (halide = Cl - or Br-) in ethanol. Five ionic liquids were synthesized by neutralizing the obtained [Rmim]OH solution with acids to verify the feasibility of the whole process. The halogen content in the finally obtained ionic liquids and the experimental factors influencing the content are mainly discussed. Moreover, two other alcohols besides ethanol, propanol and iso-propanol, were further examined as solvents. The results show that this process, together with the alkylation and hydroxide anion route, is simple and efficient for preparing various ionic liquids, and that the process is a complementary synthetic route to existing strategies to prepare various ILs.
- Gao, Jian,Liu, Jianguo,Li, Bo,Liu, Wenming,Xie, Yun,Xin, Yuchen,Yin, Ying,Jie, Xiao,Gu, Jun,Zou, Zhigang
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experimental part
p. 1661 - 1666
(2011/10/08)
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- Revolutionary phosgene-free synthesis of α-amino acid N-carboxyanhydrides using diphenyl carbonate based on activation of α-amino acids by converting into imidazolium salts
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The phosgene-free synthesis of α-amino acid n-carboxyanhydrides using diphenyl carbonate based on activation of α-amino acids by converting into imidazolium salts was reported. 1-Ethyl-3-methylimidazolium bromide (4.77 g, 25.0 mmol) was dissolved in water (25 mL) and was passed through a column of Amberlite IRA 400 CL (50 cm3) using 250 mL of water as an eluent to synthesize amino acid imidazolium salt. A solution of L-phenylalanine imidazolium salt (550 mg, 2.0 mmol) in acetonitrile (15 mL) was added dropwise to a solution of diphenyl-carbonate (427 mg, 2.00 mmol) in acetonitrile (5 mL) at room temperature, and the reaction mixture was stirred at room temperature to synthesize urethane derivative. The results showed that all of the obtained imidazolium salts were soluble in chloroform, dichloromethane, 2-butanone acetonitrile, and not soluble in tetrahydrofuran.
- Koga, Koichi,Sudo, Atsushi,Endo, Takeshi
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experimental part
p. 4351 - 4355
(2011/11/30)
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- Amino acid ionic liquids as chiral ligands in ligand-exchange chiral separations
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Recently, amino acid ionic liquids (AAILs) have attracted much research interest. In this paper, we present the first application of AAILs in chiral separation based on the chiral ligand exchange principle. By using 1alkyl-3-methylimidazolium L-proline (L-Pro) as a chiral ligand coordinated with copper(II), four pairs of underivatized amino acid enantiomers - DLphenylalanine (DL-Phe), DL-histidine (DL-His), DL-tryptophane (DL-Trp), and DL-tyrosine (DL-Tyr) - were successfully separated in two major chiral separation techniques, HPLC and capillary electrophoresis (CE), with higher enantioselectivity than conventionally used amino acid ligands (resolution (Rs) = 3.26-10.81 for HPLC; Rs = 1.34-4.27 for CE). Interestingly, increasing the alkyl chain length of the AAIL cation remarkably enhanced the enantioselectivity. It was inferred that the alkylmethylimidazolium cations and L-Pro form ion pairs on the surface of the sta-tionary phase or on the inner surface of the capillary. The ternary copper complexes with L-Pro are consequently attached to the support surface, thus inducing an ion-exchange type of retention for the DL-enantiomers. Therefore, the AAIL cation plays an essential role in the separation. This work demonstrates that AAILs are good alternatives to conventional amino acid ligands for ligand-exchange-based chiral separation. It also reveals the tremendous application potential of this new type of task-specific ILs.
- Liu, Qian,Wu, Kangkang,Tang, Fei,Yao, Lihua,Yang, Fei,Nie, Zhou,Yao, Shouzhuo
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supporting information; experimental part
p. 9889 - 9896
(2010/04/06)
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