- Multifunctional hydrogel based on ionic liquid with antibacterial performance
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Biocompatible antibacterial hydrogels as novel dressing materials have been a widely researched method in modern medical technology. Here, we designed and prepared a new type of multifunctional antibacterial hydrogels that used poly(vinyl alcohol) (PVA)-tetrahydroxyborate anion (B(OH)4 ?) hydrogel as a vector and pyrrolidinium ionic liquids (ILs) as antibacterial drugs. The formation of borate ester bonds between PVA and B(OH)4 ? as dynamic network junctions endows hydrogels with multiple functions. Moreover, the as-prepared hydrogel exhibited effective anti-microbial activity against Escherichia coli and Staphylococcus aureus. Our results indicated that the hydrogels containing ILs with longer alkyl chain exhibited more pronounced antibacterial properties. The moisture retention, self-healing, syringeability and multiresponse behavior together with the antibacterial properties of the hydrogels make them ideal candidates as multifunctional dressing materials for joint skin wound healing.
- Yu, Yang,Yang, Zeyu,Ren, Shujing,Gao, Yanan,Zheng, Liqiang
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Read Online
- Investigation of the N-butyl-N-methyl pyrrolidinium trifluoromethanesulfonyl-N-cyanoamide (PYR14TFSAM) ionic liquid as electrolyte for Li-ion battery
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A new asymmetrical anion, trifluoromethanesulfonyl-N-cyanoamide (TFSAM?), was paired with N-butyl-N-methyl pyrrolidinium (PYR14+) to prepare PYR14TFSAM. It has been investigated for Li-ion battery application and compared to its PYR14+ analogs paired with either the dicyanamide anion (DCA?) or other anions (i.e. bis(trifluoromethanesulfonyl) imide (TFSI?), bis(fluorosulfonly)imide (FSI?), trifluoromethanesulfonyl-fluorosulfonyl imide (FTFSI?)). The conductivity of PYR14TFSAM is not only higher than that of PYR14TFSI, but also higher than that of PYR14FTFSI with 3.8 mS cm?1 at 20 °C and 12.6 mS cm?1 at 60 °C. In addition, the ionic liquid does not crystallize and exhibits a viscosity similar to that of PYR14FSI (and even lower above 30 °C, which also results in a higher conductivity at high temperature). Compared to PYR14DCA, PYR14TFSAM has a higher anodic stability, more compatible with state-of-the-art cathodes such as NCM, even though the PYR14DCA electrolyte also allowed surprisingly good cycling results of NCM cathode considering its low anodic stability. PYR14TFSAM also allows Li+ (de-)/insertion into graphite, using vinylene carbonate as additive. When used in conventional Li-ion electrolyte solvents, it leads to moderate conductivity (as compared with LiFSI or LiTFSI), although much higher than LiDCA. Additionally, it is shown that, even in EC/DMC-based electrolyte, LiTFSAM does not induce Al corrosion at 4.2 V.
- Hoffknecht, Jan-Philipp,Drews, Mathias,He, Xin,Paillard, Elie
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Read Online
- Tuning ionic liquids for hydrate inhibition
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Pyrrolidinium cation-based ionic liquids were synthesized, and their inhibition effects on methane hydrate formation were investigated. It was found that the ionic liquids shifted the hydrate equilibrium line to a lower temperature at a specific pressure,
- Kim, Ki-Sub,Kang, Jeong Won,Kang, Seong-Pil
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Read Online
- Synergistic antimicrobial activity of N-methyl substituted pyrrolidinium–based ionic liquids and melittin against Gram-positive and Gram-negative bacteria
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Abstract: In pharmaceutical industry, the prodrug approaches and drug-drug conjugates are being now vastly used to optimize the efficacy of the drugs for multipurpose. The combination or conjugation of antimicrobials agents with natural antimicrobials may
- Saraswat, Juhi,Aldahmash, Badr,AlOmar, Suliman Yousef,Imtiyaz, Khalid,Rizvi, M. Moshahid Alam,Patel, Rajan
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Read Online
- Chemical Vapor Deposition of Ionic Liquids for the Fabrication of Ionogel Films and Patterns
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Film deposition and high-resolution patterning of ionic liquids (ILs) remain a challenge, despite a broad range of applications that would benefit from this type of processing. Here, we demonstrate for the first time the chemical vapor deposition (CVD) of ILs. The IL-CVD method is based on the formation of a non-volatile IL through the reaction of two vaporized precursors. Ionogel micropatterns can be easily obtained via the combination of IL-CVD and standard photolithography, and the resulting microdrop arrays can be used as microreactors. The IL-CVD approach will facilitate leveraging the properties of ILs in a range of applications and microfabricated devices.
- Ameloot, Rob,Arnauts, Giel,Calderon Gonzalez, Maider,Cruz, Alexander John,Hauffman, Tom,Marcoen, Kristof,Obst, Martin
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supporting information
p. 25668 - 25673
(2021/10/04)
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- Evaluation of ionic liquids as electrolytes for vanadium redox flow batteries
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Non-aqueous redox flow batteries (NARFBs) are promising electrochemical energy storage devices due to their wide electrochemical potential windows, generally >2 V of organic solvents. This study aims to investigate the suitability of ionic liquids (ILs) as electrolytes for NARFBs containing a vanadium metal complex. The electrochemistry of a single-component NARFBs employing vanadium (III) acetylacetonate (V(acac)3) was studied in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C4mim][NTF2], and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide, [C4mpyr][NTF2], electrolytes. The electrochemical kinetics of the anodic and cathodic reactions was measured using cyclic voltammetry. The VII/VIII and VIII/VIV couples were quasi-reversible and together yielded a cell potential of 2.2 V in both ILs. Charge/discharge characteristics show that a coulombic efficiency for cycles 1–50 ranged from 88 to 92% using a V(acac)3/[C4mpyr][NTF2] cell.
- Bahadori, L.,Boyd, R.,Nockemann, P.,Shafeeyan, M. S.,Warrington, A.
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- Controlling the reactions of 1-bromogalactose acetate in methanol using ionic liquids as co-solvents
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The reactions of an acetobromogalactose in mixtures of methanol and one of seven different ionic liquids with varying constituent ions were studied. In general, small amounts of ionic liquid in the reaction mixture led to increases in the rate constant compared to methanol, whilst large amounts of ionic liquid led to decreases in the rate constant; this outcome differs significantly from previous reactions proceeding through this mechansim. Temperature dependent kinetic studies indicated that the dominant interaction driving these changes was between the ionic liquid and the transition state of the process. Through considering solvent parameters of ionic liquids, a relationship was found between the changes in the rate constant and both the hydrogen bond accepting ability and polarisability of the solvent, indicating that the interactions affecting reaction outcome are both specific and non-specific in nature; once more, these interactions were different to those observed in previous similar reactions. By changing the amount of ionic liquid in the reaction mixture, additional products not seen in the molecular solvent case were observed, the ratios of which are dependent on the anion of the ionic liquid and the proportion of ionic liquid in the reaction mixture. This demonstrates the importance of considering solvent effects on both the rate and product determining steps and the potential application of such changes is discussed.
- Gilbert, Alyssa,Haines, Ronald S.,Harper, Jason B.
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supporting information
p. 5442 - 5452
(2020/09/09)
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- Electrolyte and a battery with said electrolyte
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An electrolyte for a lithium-ion battery, and a battery incorporating the electrolyte. The electrolyte includes a lithium salt, a non-aqueous organic solvent which includes a carbonate-based solvent, a flame retardant, a film former, and a stabilizing medium. The flame retardant includes PYR1RPF6 (N-Methyl-N-alkylpyrrolidinium Hexafluorophosphate Salt).
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Page/Page column 7
(2020/09/13)
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- N, N - dialkyl pyrrolidine pressure concentrated water ion liquid preparation method and its application (by machine translation)
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The invention relates to a N, N - dialkyl pyrrolidine pressure concentrated water ion liquid preparation method and its application, the method to N - alkyl pyrrolidine and alkyl alcohol as raw material through the electrolysis mode, in the electrolytic cell is provided with a cation exchange membrane, cation exchange membrane into the cathode with the anode compartment of the electrolytic aluminum, electrolytic taken out after completion of the cathode electrolyte, separation and purification, to obtain N, N - dialkyl pyrrolidines pressure concentrated water ionic liquid, the preparation method is simple, mild condition, purity and high yield. The N, N - dialkyl pyrrolidine pressure concentrated water ionic liquid as solvent, in order to chlorine methyl pyridine hydrochloride and ammonia as raw material, synthetic three-pyridine methyl amine compound, the preparation of yield and high purity, without follow-up separation, low cost, environmental protection, the ionic liquid can be used repeatedly, is suitable for industrial production. (by machine translation)
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Paragraph 0027-0029
(2019/10/29)
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- Understanding the effects of ionic liquids on a unimolecular substitution process: Correlating solvent parameters with reaction outcome
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A unimolecular substitution process was studied in five different ionic liquids, with systematic variation of either the cation or anion, in order to determine the factors leading to the increase in the rate constant for the process relative to acetonitrile. It was found that both components of the ionic liquid, and the proportion of the salt in the reaction mixture, affect the rate constant. Activation parameters determined for the process suggest that there is a balance between interactions of the components of the ionic liquid with both starting material and transition state. A correlation was found between the rate constant and a combination of Kamlet-Taft solvent parameters; with the polarisability of the solvent being the most significant factor. As this reaction proceeds through both unimolecular and bimolecular pathways, competition experiments determined that the unimolecular pathway for the reaction can be favoured using small amounts of ionic liquid in the reaction mixture, demonstrating the potential to control reaction mechanisms using ionic liquids.
- Gilbert, Alyssa,Haines, Ronald S.,Harper, Jason B.
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supporting information
p. 675 - 682
(2019/01/24)
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- Correlating ionic liquid solvent effects with solvent parameters for a reaction that proceeds through a xanthylium intermediate
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A unimolecular nucleophilic substitution reaction that proceeds through a xanthylium carbocation was studied in seven ionic liquid solvents. It was found that the general trend in the rate constant with changing proportion of ionic liquid in the reaction mixture was different to that seen for other unimolecular processes, with the rate constant increasing as more ionic liquid was added to the reaction mixture. A significant correlation was found between the natural logarithm of the rate constant and a combination of the Kamlet-Taft solvent parameters. This relationship indicated that the principal interaction involved hydrogen bonding between the ionic liquid and some species along the reaction coordinate. Further, this correlation enables prediction of the effects that other ionic liquids will have on this, and other, reactions that proceed through a similar intermediate.
- Gilbert, Alyssa,Bucher, G?tz,Haines, Ronald S.,Harper, Jason B.
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supporting information
p. 9336 - 9342
(2019/11/13)
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- Complex-precipitation using functionalized chiral ionic liquids with L-proline anion and chromatographic analysis for enantioseparation of racemic amino acids
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As one kind of functionalized green medium, chiral ionic liquids (CILs) have been widely applied in fields of asymmetric catalysis, enantioseparation, and so on. In this study, four kinds of amino acid–based CILs were synthesized by using trimethylamine, N-methylpyrrolidine, N-methylimidazole, and tropine as cationic nucleus, respectively. Then their specific optical rotation and solubility in common solvents were determined for further resolution application. The effect of different cations in these CILs was explored on the separation of racemic phenylalanine in complex-precipitation way. Moreover, various factors were systematically investigated for their effects on resolution efficiency, including the type of additive copper salts, the molar ratio of Cu (II) to CIL, pH value, the amount of racemic phenylalanine, and temperature. Under the appropriate conditions, L-phenylalanine mainly existed in solid phase and could be separated from its enantiomers in liquid phase. Furthermore, the mechanism of resolution was studied by thermogravimetric analysis, infrared spectrum, and molecular simulation. The resolution system has characteristics of no organic solvent, fast separation speed, simple resolution process, and easy scale-up.
- Zang, Huimin,Yao, Shun,Luo, Yingjie,Tang, Dan,Song, Hang
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p. 1182 - 1194
(2018/09/12)
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- The impact of ionic liquids on the coordination of anions with solvatochromic copper complexes
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Solvatochromic transition metal (TM)-complexes with weakly associating counter-anions are often used to evaluate traditional neutral solvent and anion coordination ability. However, when employed in ionic liquids (IL) many of the common assumptions made are no longer reliable. This study investigates the coordinating ability of weakly coordinating IL anions in traditional solvents and within IL solvents employing a range of solvatochromic copper complexes. Complexes of the form [Cu(acac)(tmen)][X] (acac = acetylacetonate, tmen = tetramethylethylenediamine) where [X]- = [ClO4]-, Cl-, [NO3]-, [SCN]-, [OTf]-, [NTf2]- and [PF6]- have been synthesised and characterised both experimentally and computationally. ILs based on these anions and imidazolium and pyrrolidinium cations, some of which are functionalised with hydroxyl and nitrile groups, have been examined. IL-anion coordination has been investigated and compared to typical weakly coordinating anions. We have found there is potential for competition at the Cu-centre and cases of anions traditionally assigned as weakly associating that demonstrate a stronger than expected level of coordinating ability within ILs. [Cu(acac)(tmen)][PF6] is shown to contain the least coordinating anion and is established as the most sensitive probe studied here. Using this probe, the donor numbers (DNs) of ILs have been determined. Relative donor ability is further confirmed based on the UV-Vis of a neutral complex, [Cu(sacsac)2] (sacsac = dithioacetylacetone), and DNs evaluated via23Na NMR spectroscopy. We demonstrate that ILs can span a wide donor range, similar in breadth to conventional solvents.
- Kuzmina,Hassan,Patel,Ashworth,Bakis,White,Hunt,Welton
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supporting information
p. 12185 - 12200
(2017/09/25)
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- Physical-Chemical Characterization of Binary Mixtures of 1-Butyl-1-methylpyrrolidinium Bis{(trifluoromethyl)sulfonyl}imide and Aliphatic Nitrile Solvents as Potential Electrolytes for Electrochemical Energy Storage Applications
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In the scope of improving the energy and power densities of electrochemical double layer capacitors (EDLCs), the development of high performance electrolytes with enhanced operative voltages is imperative. The formulation of mixtures containing ionic liquids with organic molecular solvents is an important strategy in the pursuit of developing highly electrochemically stable and safe materials while retaining fast transport properties for high power applications. In this work, we report on the physical-chemical investigations into binary mixtures containing the ionic liquid 1-butyl-1-methylpyrrolidinium bis{(trifluoromethyl)sulfonyl}imide with one mononitrile solvent, butyronitrile, and two dinitrile solvents, glutaronitrile and adiponitrile, as potential electrolytes for EDLCs. The thermal, volumetric, and transport properties of the binary mixtures are investigated as functions of the electrolyte composition and temperature. Furthermore, the electrolyte composition which exhibits the highest conductivity for each of the binary mixtures was determined, and its electrochemical stability is reported using a glassy carbon macrodisk electrode. (Graph Presented).
- Neale, Alex R.,Schütter, Christoph,Wilde, Patrick,Goodrich, Peter,Hardacre, Christopher,Passerini, Stefano,Balducci, Andrea,Jacquemin, Johan
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p. 376 - 390
(2017/03/08)
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- Rationalising the effects of ionic liquids on a nucleophilic aromatic substitution reaction
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The nucleophilic aromatic substitution reaction between 1-fluoro-2,4-dinitrobenzene and ethanol was examined in a series of ionic liquids across a range of mole fractions. Temperature-dependent kinetic analyses were undertaken to determine the activation parameters for this reaction at the highest mole fraction. As the mole fraction of ionic liquid was increased, the rate constant of the reaction also increased, however the microscopic origin of the rate enhancement was shown to be different between different ionic liquids and also between different solvent compositions. These results indicate a balance between microscopic interactions that result in the observed solvent effects and a qualitative method for analysing such interactions is introduced.
- Hawker, Rebecca R.,Wong, Michaela J.,Haines, Ronald S.,Harper, Jason B.
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supporting information
p. 6433 - 6440
(2017/08/10)
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- Ionic liquid-mediated deoxydehydration reactions: Green synthetic process for bio-based adipic acid
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A novel recyclable Re-catalyzed deoxydehydration (DODH) reaction was developed with an ionic liquid (IL) as a reaction medium for an efficient synthesis of adipic acid (1), one of the commercially important dicarboxylic acids, from biomass galactaric acid. The carefully designed solubility of ILs allowed a homogeneous DODH reaction to produce muconate 3 in excellent yields, a key intermediate for 1. Use of the IL also enabled an efficient separation of the DODH product 3 from the reaction mixture by simple decantation. The recovered IL layer containing the expensive Re catalyst was reused up to four times, yielding 3 without much decrease in yields. The target compound 1 was also produced in an excellent yield with the catalytic hydrogenation of 3 followed by the acidic hydrolysis. Thus, the overall process for bio-based adipic acid would become much more cost-effective, eco-friendly, and industrially viable, which could be applied to various biomass conversions.
- Shin, Nara,Kwon, Sohyun,Moon, Sojeong,Hong, Chae Hwan,Kim, Young Gyu
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supporting information
p. 4758 - 4765
(2017/07/17)
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- Comprehensive Insights into the Thermal Stability, Biodegradability, and Combustion Chemistry of Pyrrolidinium-Based Ionic Liquids
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The use of ionic liquids (ILs) as advanced electrolyte components in electrochemical energy-storage devices is one of the most appealing and emerging options. However, although ILs are hailed as safer and eco-friendly electrolytes, to overcome the limitations imposed by the highly volatile/combustible carbonate-based electrolytes, full-scale and precise appraisal of their overall safety levels under abuse conditions still needs to be fully addressed. With the aim of providing this level of information on the thermal and chemical stabilities, as well as actual fire hazards, herein, a detailed investigation of the short- and long-term thermal stabilities, biodegradability, and combustion behavior of various pyrrolidinium-based ILs, with different alkyl chain lengths, counteranions, and cations, as well as the effect of doping with lithium salts, is described.
- Eshetu, Gebrekidan Gebresilassie,Jeong, Sangsik,Pandard, Pascal,Lecocq, Amandine,Marlair, Guy,Passerini, Stefano
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p. 3146 - 3159
(2017/08/18)
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- Heterocyclic bismuth(III) compounds with transannular N→Bi interactions as catalysts for the oxidation of thiophenol to diphenyldisulfide
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The reactions between the diorganobismuth(iii) bromides [RCH2N(CH2C6H4)2]BiBr [R = C6H5 (1), C6H5CH2 (2)] and appropriate silver salts resulted in new diorganobismuth(iii) compounds of the general formula [RCH2N(CH2C6H4)2]BiX [R = C6H5, X = ONO2 (3), OSO2CF3 (4), OSO2C6H4 (CHCH2)-4 (5); R = C6H5CH2, X = ONO2 (6)], based on a butterfly-like tetrahydro-dibenzo[c,f][1,5]azabismocine heterocyclic framework. The new species were structurally characterized in solution by 1H, 13C{H} and 19F{H} NMR and in the solid state by IR spectroscopy and single-crystal X-ray diffraction. The nitrogen atom is intramolecularly coordinated to bismuth, thus resulting in hypercoordinated species of type 12-Bi-5 (3 and 6) and 10-Bi-4 (4 and 5). In addition, compound 4 shows bismuth?π arene and compounds 3 and 6 bismuth?oxygen intermolecular interactions, thus leading to dimers in the solid state. These compounds were investigated as catalysts for the oxidation of thiophenol to diphenyl disulfide by using air as an oxidizing agent, both in cyclohexane and in an ionic liquid (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide), at temperatures below 100 °C, affording high reaction rates (TON 34.8, with 100% conversion after 5 h) and a total selectivity to the targeted product.
- Toma, Ana M.,Ra?, Ciprian I.,Pavel, Octavian D.,Hardacre, Christopher,Rüffer, Tobias,Lang, Heinrich,Mehring, Michael,Silvestru, Anca,Parvulescu, Vasile I.
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p. 5343 - 5353
(2017/11/24)
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- Effect of cation structure on the oxygen solubility and diffusivity in a range of bis{(trifluoromethyl)sulfonyl}imide anion based ionic liquids for lithium-air battery electrolytes
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This paper reports on the solubility and diffusivity of dissolved oxygen in a series of ionic liquids (ILs) based on the bis{(trifluoromethyl)sulfonyl}imide anion with a range of related alkyl and ether functionalised cyclic alkylammonium cations. Cyclic voltammetry has been used to observe the reduction of oxygen in ILs at a microdisk electrode and chronoamperometric measurements have then been applied to simultaneously determine both the concentration and the diffusion coefficient of oxygen in different ILs. The viscosity of the ILs and the calculated molar volume and free volume are also reported. It is found that, within this class of ILs, the oxygen diffusivity generally increases with decreasing viscosity of the neat IL. An inverse relationship between oxygen solubility and IL free volume is reported for the two IL families implying that oxygen is not simply occupying the available empty space. In addition, it is reported that the introduction of an ether-group into the IL cation structure promotes the diffusivity of dissolved oxygen but reduces the solubility of the gas.
- Neale, Alex R.,Li, Peilin,Jacquemin, Johan,Goodrich, Peter,Ball, Sarah C.,Compton, Richard G.,Hardacre, Christopher
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p. 11251 - 11262
(2016/05/24)
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- Synthesis of traditional and ionic polymethacrylates by anion catalyzed group transfer polymerization
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The hydrophobic ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide was successfully used as solvent in group transfer polymerization of traditional methacrylates (methyl methacrylate, n-butyl methacrylate, and benzyl methacrylate) and of ionic liquid methacrylates (ILMAs). This demonstrates that this ionic liquid makes reaction conditions, which do not require the use of ultra-dried solvents. The ILMAs were N-[2-(methacryloyloxy)ethyl]-N,N-dimethyl-N-alkylammonium bis(trifluoromethylsulfonyl)imides bearing methyl, ethyl, propyl, butyl, or hexyl substituents. Increasing size of the alkyl substituent at the cation results in decreasing glass transition temperature in case of both ionic liquid methacrylates and polymers derived of them. Furthermore, the glass transition temperature is significantly higher for these polymers compared with the ionic liquid methacrylates, and the effect of glass transition temperature reduction with increasing size of the alkyl substituent is stronger for the polymers. A mechanism was proposed explaining the catalytic function of the ionic liquid used as solvent for polymerization.
- Strehmel, Veronika,Senkowski, Volker
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p. 2849 - 2859
(2016/01/12)
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- Electrodeposition of palladium from palladium(II) acetylacetonate in an amide-type ionic liquid
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The electrodeposition of palladium from palladium(II) acetylacetonate (Pd(acac)2) was investigated in an ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide at room temperature. Potentiostatic cathodic reduction was conducted using a glassy carbon electrode at - 2.0 V vs. Ag/Ag(I). Metallic palladium was deposited on the electrode and palladium nanoparticles were observed with dispersed state in the ionic liquid. The mean particle size of the obtained palladium nanoparticles was 2.8 ± 0.6 nm.
- Yoshii, Kazuki,Oshino, Yosuke,Tachikawa, Naoki,Toshima, Kazunobu,Katayama, Yasushi
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- Process for Producing Ionic Liquids
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The present invention provides a method for producing ionic liquids without the use of a volatile solvent and/or water. In some embodiments, methods of the invention allow a continuous process for producing ionic liquids.
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Paragraph 0075; 0077
(2014/09/03)
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- Water-based synthesis of hydrophobic ionic liquids for high-energy electrochemical devices
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In this work is described an innovative synthesis route for hydrophobic ionic liquids (ILs) composed of N-methyl-N-Alkylpyrrolidinium (or piperidinium) or imidazolium or tetralkylammonium cations and (perfluoroalkylsulfonyl)imide, ((CnF2n+
- Montanino, Maria,Alessandrini, Fabrizio,Passerini, Stefano,Appetecchi, Giovanni Battista
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p. 124 - 133
(2013/06/04)
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- Steric, hydrogen-bonding and structural heterogeneity effects on the nucleophilic substitution of N-(p-fluorophenyldiphenylmethyl)-4-picolinium chloride in ionic liquids
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The nucleophilic substitution of N-(p-fluorophenyldiphenylmethyl)-4- picolinium chloride was investigated using water and a range of alcoholic nucleophiles in ionic liquid solvents. The reactivity patterns across the nucleophiles examined could be attributed to steric factors, which mediated the relative nucleophilicities. Reducing the hydrogen-bond acidity of the ionic liquid cation was found to generally increase the rate of reaction, however, the magnitude of this rate effect could be influenced by the steric bulk of the nucleophile and the structural heterogeneity of the ionic liquid. Preferential solvation phenomena in binary mixtures of ionic liquids were examined and suggest that the mechanism behind the hydrogen-bond solvation phenomenon arises from direct cation-mediated, rather than indirect anion-mediated, effects. The Royal Society of Chemistry 2013.
- Weber, Cameron C.,Masters, Anthony F.,Maschmeyer, Thomas
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supporting information
p. 2534 - 2542
(2013/06/05)
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- Fluorosulfonyl-(trifluoromethanesulfonyl)imide ionic liquids with enhanced asymmetry
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New ionic liquids with an asymmetric anion, fluorosulfonyl- (trifluoromethanesulfonyl)imide (FTFSI), were prepared and their chemical-physical properties were investigated. The ionic liquids based on N-methyl-N-propylpyrrolidinium, PYR13, N-but
- Reiter, Jakub,Jeremias, Sebastian,Paillard, Elie,Winter, Martin,Passerini, Stefano
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p. 2565 - 2571
(2013/04/10)
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- Thermochemistry of the pyridinium- and pyrrolidinium-based ionic liquids
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We applied DSC for the determination of enthalpies of synthesis reactions of pyridinium- and pyrrolidinium-based ionic liquids (ILs) from pyridine (or N-methyl-pyrrolidine) and n-alkyl bromides (with n = 4, 5, 6, 7, and 8). The combination of reaction enthalpy measurements by DSC with modern high-level first-principles calculations opens valuable indirect thermochemical options to obtain values of enthalpies of the formation and vaporization enthalpies of ILs.
- Verevkin, Sergey P.,Ralys, Ricardas V.,Emel'Yanenko, Vladimir N.,Zaitsau, Dzmitry H.,Schick, Christoph
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p. 353 - 358
(2013/06/04)
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- Asymmetry effect of novel per(fluoroalkylsulfonyl)imide anions in pyrrolidinium ionic liquids
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Ionic liquids based on the N-butyl-N-methylpyrrolidinium, (PYR 14)+, cation and different per(fluoroalkylsulfonyl)imide anions, having symmetric, (IM11)-, moderately asymmetric, (IM24)-, highly asymmetric, (IM14)- and (IMT4)-, and cyclic, (IM3)- structures, were properly synthesized. A few of the presented per(fluoroalkylsulfonyl)imide ions have never been reported in the literature as ionic liquid anions. The thermal and transport properties of the ionic liquid materials, having a common cation, were investigated and correlated with the structure of the per(fluoroalkylsulfonyl)imide anion. The results have indicated that the symmetry as well as the steric hindrance of the anion affect the melting point and the crystallization kinetics as well as the ion conduction and the self-diffusion coefficient of the ionic liquids. The conductivity data are in good agreement with the thermal measurements. The Royal Society of Chemistry.
- Jeremias, Sebastian,Carewska, Maria,Conte, Lino,Passerini, Stefano,Appetecchi, Giovanni Battista
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p. 17755 - 17761
(2013/10/01)
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- Activity coefficients at infinite dilution for organic solutes dissolved in three 1-alkyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids bearing short linear alkyl side chains of three to five carbons
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In this work, we report the infinite dilution activity coefficients (γ1,2∞) of 39 to 43 diverse organic solutes dissolved in three 1-alkyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids (IL) homologues bearing propyl, butyl, and pentyl n-alkyl side chains, respectively, as determined by inverse gas chromatography at temperatures from 323 K to 343 K. The organic solutes include various (cyclo)alkanes, alkenes, alkynes, aromatic hydrocarbons, alcohols, thiophene, ethers, nitroalkanes, and ketones. The measured retention data were further transformed to gas-to-IL and water-to-IL partition coefficients using established thermodynamic approaches based upon the corresponding gas-to-water partition coefficients of the test solutes. Both sets of partition coefficients were interpreted with a modified form of the basic Abraham general solvation parameter model. The mathematical correlations obtained by regression analysis back-calculated the observed gas-to-IL and water-to-IL partition coefficient data to within average standard deviations of 0.104 and 0.136 log units, respectively.
- Mutelet, Fabrice,Hassan, El-Sayed R. E.,Stephens, Timothy W.,Acree, William E.,Baker, Gary A.
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p. 2210 - 2218
(2013/09/02)
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- Standard pKa scales of carbon-centered indicator acids in ionic liquids: Effect of media and structural implication
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Energetics of bond dissociation, especially the R-H bond heterolysis free energy (pKa), has played a central role in promoting chemistry to become a rational science. Despite the oceans of acidity studies in the literature, the current knowledge is limited to that in the classical molecular solvents and is unable to be extended to anticipate the acidity changes in ionic media. As the latter is now very popular for replacing volatile organic solvents, it becomes highly desirable to know how the driving force of bond cleavage is varied as the medium composition is switched from neutral molecules to the charged ions. Here we describe a general approach to measure absolute pKa's in pure ionic liquid (IL). The standard conditions warranting accurate measurement were outlined. The pKa's of the selected 18 C-H type indicator acids in four ILs were determined and a convenient indicator platform was constructed for easy expansion of acidity scales. These absolute pKa's make possible, for the first time, direct comparisons of bond energies in IL with those in molecular solvent and in the gas phase and should be able to serve as the standard parameters for calibrating computational methods suitable for the studies in ionic media. The effect of cation and anion in IL in relation to structure was analyzed.
- Deng, Hui,Li, Xin,Chu, Yuan,He, Jiaqi,Cheng, Jin-Pei
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p. 7291 - 7298
(2012/11/07)
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- H2O2/NaHCO3-mediated enantioselective epoxidation of olefins in NTf2-based ionic liquids and under ultrasound
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The bicarbonate-activated peroxide (BAP) system has been shown to constitute an excellent and versatile combination for the epoxidation of olefins. Herein, we demonstrate that the benign H2O 2/NaHCO3 oxidative combination can be used for the enantioselective epoxidation of olefins using a chiral manganese porphyrin as a catalyst. This unprecedented result was made possible by the use of an ionic liquid with ultrasound, which leads to the activation of Mn-porphyrin catalysis.
- Chatel, Gregory,Goux-Henry, Catherine,Mirabaud, Anais,Rossi, Thomas,Kardos, Nathalie,Andrioletti, Bruno,Draye, Micheline
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experimental part
p. 127 - 132
(2012/08/13)
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- Ionic-liquid-mediated active-site control of MoS2 for the electrocatalytic hydrogen evolution reaction
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The layered crystal MoS2 has been proposed as an alternative to noble metals as the electrocatalyst for the hydrogen evolution reaction (HER). However, the activity of this catalyst is limited by the number of available edge sites. It was previously shown that, by using an imidazolium ionic liquid as synthesis medium, nanometre-size crystal layers of MoS2 can be prepared which exhibit a very high number of active edge sites as well as a de-layered morphology, both of which contribute to HER electrocatalytic activity. Herein, it is examined how to control these features synthetically by using a range of ionic liquids as synthesis media. Non-coordinating ILs with a planar heterocyclic cation produced MoS2 with the de-layered morphology, which was subsequently shown to be highly advantageous for HER electrocatalytic activity. The results furthermore suggest that the crystallinity, and in turn the catalytic activity, of the MoS2 layers can be improved by employing an IL with specific solvation properties. These results provide the basis for a synthetic strategy for increasing the HER electrocatalytic activity of MoS2 by tuning its crystal properties, and thus improving its potential for use in hydrogen production technologies. Copyright
- Lau, Vincent Wing-Hei,Masters, Anthony F.,Bond, Alan M.,Maschmeyer, Thomas
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experimental part
p. 8230 - 8239
(2012/08/29)
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- MATERIAL FOR ELECTROLYTIC SOLUTIONS AND USE THEREOF
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It is an object of the present invention to provide a material for electrolytic solutions suited for use as material in electrolytic solutions serving as ionic conductors in electrochemical devices, such as large-capacity cells or batteries. The present invention is related to a material for electrolytic solutions which comprises, as an essential constituent, an anion represented by the general formula (1): wherein X represents at least one element selected from among B, N, O, Al, Si, P, S, As and Se; M1 and M2 are the same or different and each represents an organic linking group; a is an integer of not less than 1, and b, c and d each independently is an integer of not less than 0.
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- Melting behavior and ionic conductivity in hydrophobic ionic liquids
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Four room-temperature ionic liquids (RTILs) based on the N-butyl-N-methyl pyrrolidinium (Pyr14 +) and N-methyl-N-propyl pyrrolidinium cations (Pyr13 +) and bis(trifluoromethanesulfonyl)imide (TFSI-) and bis(fluorosulfonyl) imide (FSI-) anions were intensively investigated during their melting. The diffusion coefficients of 1H and 19F were determined using pulsed field gradient (PFG) NMR to study the dynamics of the cations, anions, and ion pairs. The AC conductivities were measured to detect only the motion of the charged particles. The melting points of these ionic liquids were measured by DSC and verified by the temperature-dependent full width at half-maximum (FWHM) of the 1H and 19F NMR peaks. The diffusion and conductivity data at low temperatures gave information about the dynamics at the melting point and allowed specifying the way of melting. In addition, the diffusion coefficients of 1H (DH) and 19F (DF) and conductivity were correlated using the Nernst-Einstein equation with respect to the existence of ion pairs. Our results show that in dependence on the cation different melting behaviors were identified. In the Pyr14based ILs, ion pairs exist, which collapse above the melting point of the sample. This is in contrast to the Pyr 13-based ILs where the present ion pairs in the crystal dissociate during the melting. Furthermore, the anions do not influence the melting behavior of the investigated Pyr14 systems but affect the Pyr 13 ILs. This becomes apparent in species with a higher mobility during the breakup of the crystalline IL.
- Kunze, Miriam,Montanino, Maria,Appetecchi, Giovanni B.,Jeong, Sangsik,Schoenhoff, Monika,Winter, Martin,Passerini, Stefano
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experimental part
p. 1776 - 1782
(2010/08/04)
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- Effects of acetonitrile on electrodeposition of Ni from a hydrophobic ionic liquid
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The effects of addition of acetonitrile (ACN) on electrodeposition of nickel were investigated in a hydrophobic room-temperature ionic liquid, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide (BMPTFSA) containing Ni(TFSA)2. Addition of ACN resulted in the change of the color of the ionic liquid. The UV-vis and FT-IR spectra of the electrolyte showed the coordination environment of Ni(II) changed gradually from [Ni(TFSA)3]- to [Ni(ACN)6]2+ with an increase in the concentration of ACN. The diffusion coefficient of Ni(II) in BMPTFSA was increased and the reduction potential of Ni(II) shifted to the more positive side in the presence of ACN. The nucleation/growth process of Ni was not affected by the change in the coordination environment of Ni(II) from the chronoamperometric results although the more nuclei formed on the electrode surface. SEM showed smoother deposit was obtained in Ni(TFSA) 2/BMPTFSA with ACN.
- Zhu, Yan-Li,Katayama, Yasushi,Miura, Takashi
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experimental part
p. 9019 - 9023
(2011/02/24)
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- Ag(I)/Ag electrode reaction in amide-type room-temperature ionic liquids
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Ag(I)/Ag electrode reaction was investigated in some amide-type room-temperature ionic liquids composed of different cations. The morphology of silver deposits and the electrochemical behavior were not sensitive to the difference in the cations of ionic liquids. On the other hand, it was suggested that the adsorption of bis(trifluoromethylsulfonyl)amide (TFSA-) is more important for electrodeposition of silver in both ionic liquids and aqueous solutions. The diffusion coefficients of silver cation in the ionic liquids indicated the silver cation is surrounded by TFSA- to form a bulky species. The rate of crystal growth of silver particles in the ionic liquids by electrochemical Ostwald ripening was much slower than that in a nitrate aqueous solution, suggesting the charge transfer in the ionic liquids is slower than that in the aqueous solution.
- Serizawa, Nobuyuki,Katayama, Yasushi,Miura, Takashi
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experimental part
p. 346 - 351
(2011/03/17)
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- A recyclable triethylammonium ion-tagged diphenylphosphine palladium complex for the Suzuki-Miyaura reaction in ionic liquids
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Suzuki-Miyaura reactions of aryl bromides and arylboronic acids proceed in good to excellent yields in a pyrrolidinium ionic liquid by using a preformed air stable and easily handled triethylammonium-tagged diphenylphosphine palladium(ii) complex (2). The reaction requires short reaction times and mild temperature conditions and does not show any tendency towards the formation of palladium black. After extraction of the product, the catalyst containing ionic liquid phase is easily recycled for 6 times, with no significant loss of catalytic activity.
- Lombardo, Marco,Chiarucci, Michel,Trombini, Claudio
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supporting information; experimental part
p. 574 - 579
(2010/04/23)
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- IONIC LIQUID, METHOD FOR PRODUCING SAME, DOUBLE LAYER CAPACITOR COMPRISING SAME, AND LITHIUM BATTERY
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The present invention relates to ionic liquids comprising at least one organic ammonium ion and at least one member selected from the group consisting of anions represented by [BF3(CnF2n+1)]- wherein n represents 2, 3 or 4.
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Page/Page column 7-8
(2008/06/13)
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- Cyclic quaternary ammonium ionic liquids with perfluoroalkyltrifluoroborates: Synthesis, characterization, and properties
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New cyclic quaternary ammonium salts, composed of N-alkyl(alkyl ether)-N-methylpyrrolidinium, -oxazolidinium, -piperidinium, or -morpholinium cations (alkyl = nC4H9, alkyl ether = CH 3,OCH2, CH3,OCH2CH2) and a perfluoroalkyltrifluoroborate anion ([RFBF3] -, RF = CF3, C2F5, nC3,F7, nC4F9), were synthesized and characterized. Most of these salts are liquids at room temperature. The key properties of these salts - phase transitions, thermal stability, density, viscosity, conductivity, and electrochemical windowswere measured and compared to those of their corresponding [BF4] and [(CF3SO 2)2N]- salts. The structural effect on all the above properties was intensively studied in terms of the identity of the cation and anion, variation of the side chain in the cation (i.e., alkyl versus alkyl ether), and change in the length of the pertluoroalkyl group (RF) in the [RFBF3,]- ion. The reduction of Li + ions and reoxidation of Li metal took place in pure N-butyl-N-methyl pyrrolidinium pentafluoroethyltrifluoroborate as the supporting electrolyte. Such comprehensive studies enhance the knowledge necessary to design and optimize ionic liquids for many applications, including electrolytes. Some of these new salts show desirable properties, including low melting points, high thermal stabilities, low viscosities, high conductivities, and wide electrochemical windows, and may thus be potential candidates for use as electrolytes in high-energy storage devices. In addition, many salts are ionic plastic crystals.
- Zhou, Zhi-Bin,Matsumoto, Hajime,Tatsumi, Kuniaki
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p. 2196 - 2212
(2008/01/27)
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- Ultrafast dynamics of pyrrolidinium cation ionic liquids
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We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N -butyl- N -methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P 14 + NTf2-), N -methoxyethyl- N -methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P 1EOE + NTf2-), N -ethoxyethyl- N -methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P 1EOE + NTf2-), N -ethoxyethyl- N -methylpyrrolidinium bromide P 1EOE +, and N -ethoxyethyl- N -methylpyrrolidinium dicyanoamide P 1EOE + DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P 14 +, P 1EOM +, and P 1EOE + paired with the NTf2- anion. The other group of liquids consists of the P 1EOE + cation paired with each of the three anions NTf2-, Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast (~2 ps) and intermediate (~20 ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750 cm-1 are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150 cm-1 are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape.
- Shirota, Hideaki,Funston, Alison M.,Wishart, James F.,Castner Jr., Edward W.
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- Fluorescence studies of protein thermostability in ionic liquids
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Using the single tryptophan residue in the sweet protein monellin as a spectroscopic handle, we show the extreme thermodynamic stabilization offered by an ionic liquid; Tun ~ 105°C in [C4mpy][Tf 2N] compared to 40°C in bulk water.
- Baker, Sheila N.,Mark McCleskey,Pandey, Siddharth,Baker, Gary A.
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p. 940 - 941
(2007/10/03)
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- Low-melting, low-viscous, hydrophobic ionic liquids: N-alkyl(alkyl ether)-N-methylpyrrolidinium perfluoroethyltrifluoroborate
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A series of new hydrophobic ionic liquids comprising N-alkyl (alkyl ether)-N-methylpyrrolidinium and perfluoroethyltrifluoroborate were prepared and characterized. The new [C2F5BF3] --based salts show lower melting points than the corresponding [BF4]--based ones. Of these new salts, five are liquids at room temperature and show very low viscosities (37-71 cP at 25°C), high ionic conductivities (3.0-6.8 mScm-1) and wide electrochemical windows. Copyright
- Zhou, Zhi-Bin,Matsumoto, Hajime,Tatsumi, Kuniaki
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p. 1636 - 1637
(2007/10/03)
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- Nucleophilicity in ionic liquids. 2.1 Cation effects on halide nucleophilicity in a series of bis(trifluoromethylsulfonyl)imide ionic liquids
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In this work, the nucleophilicities of chloride, bromide, and iodide have been determined in the ionic liquids [bmim] [N(Tf)2], [bm2im][N(Tf)2], and [bmpy][N(Tf)2] (where bmim = 1-butyl-3-methylimidazolium, bm2im = 1-butyl-2,3-dimethylimidazolium, bmpy = 1-butyl-l-methylpyrrolidinium, and N(Tf)2 = bis(trifluoromethylsulfonyl)imide). It was found that in the [bmim]+ ionic liquid, chloride was the least nucleophilic halide, but that changing the cation of the ionic liquid affected the relative nucleophilicities of the halides. The activation parameters ΔH?, ΔS?, and ΔG? have been estimated for the reaction of chloride in each ionic liquid, and compared to a similar reaction in dichloromethane, where these parameters were found for reaction by both the free ion and the ion pair.
- Llewellyn Lancaster,Salter, Paul A.,Welton, Tom,Brent Young
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p. 8855 - 8861
(2007/10/03)
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